Hydrothermal Carbonization

Special Issue Reprint
Hydrothermal Carbonization
Edited by
M. Toufiq Reza
www.mdpi.com/journal/energies
Editor
M. Toufiq Reza
Basel • Beijing • Wuhan • Barcelona • Belgrade • Novi Sad • Cluj • Manchester

Editor
M. Toufiq Reza
Department of Biomedical
and Chemical Engineering
and Sciences,
Florida Institute
of Technology,
Melbourne, FL, USA
Editorial Office
MDPI
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4052 Basel, Switzerland
This is a reprint of articles from the Special Issue published online in the open access journal
Energies (ISSN 1996-1073) (available at: https://www.mdpi.com/journal/energies/special issues/
hydrothermal carbonization).
For citation purposes, cite each article independently as indicated on the article page online and as
indicated below:
Lastname, A.A.; Lastname, B.B. Article Title. Journal Name Year, Volume Number, Page Range.
ISBN 978-3-0365-8456-0 (Hbk)

ISBN 978-3-0365-8457-7 (PDF)
doi.org/10.3390/books978-3-0365-8457-7
Cover image courtesy of M. Toufiq Reza.
© 2023 by the authors. Articles in this book are Open Access and distributed under the Creative
Commons Attribution (CC BY) license. The book as a whole is distributed by MDPI under the terms
and conditions of the Creative Commons Attribution-NonCommercial-NoDerivs (CC BY-NC-ND)
license.
Contents
About the Editor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
M. Toufiq Reza
Reprinted from: Energies 2022, 15, 5491, doi:10.3390/en15155491 . . . . . . . . . . . . . . . . . . . 1
Manfredi Picciotto Maniscalco, Maurizio Volpe and Antonio Messineo

Hydrothermal Carbonization as a Valuable Tool for Energy and Environmental Applications:
A Review
Fabio Merzari, Jillian Goldfarb, Gianni Andreottola, Tanja Mimmo, Maurizio Volpe and
Luca Fiori
Hydrothermal Carbonization as a Strategy for Sewage Sludge Management: Influence of
Process Withdrawal Point on Hydrochar Properties
Louise Delahaye, John Thomas Hobson, Matthew Peter Rando, Brenna Sweeney, Avery
Bernard Brown, Geoffrey Allen Tompsett, et al.
Experimental and Computational Evaluation of Heavy Metal Cation Adsorption for Molecular
Design of Hydrothermal Char
Taina Lühmann and Benjamin Wirth

Sewage Sludge Valorization via Hydrothermal Carbonization: Optimizing Dewaterability and
Phosphorus Release
Kyoung S. Ro, Judy A. Libra and Andrés Alvarez-Murillo

Comparative Studies on Water- and Vapor-Based Hydrothermal Carbonization:
Process Analysis
Md Rifat Hasan, Nepu Saha, Thomas Quaid and M. Toufiq Reza

Formation of Carbon Quantum Dots via Hydrothermal Carbonization: Investigate the Effect of
Precursors
Reprinted from: Energies 2021, 14, 986, doi:10.3390/en14040986 . . . . . . . . . . . . . . . . . . . . 111
Md Tahmid Islam, Nepu Saha, Sergio Hernandez, Jordan Klinger and M. Toufiq Reza
Integration of Air Classification and Hydrothermal Carbonization to Enhance Energy Recovery
of Corn Stover
Gabriel Gerner, Luca Meyer, Rahel Wanner, Thomas Keller and Rolf Krebs
Sewage Sludge Treatment by Hydrothermal Carbonization: Feasibility Study for Sustainable
Nutrient Recovery and Fuel Production
Gabriella Gonnella, Giulia Ischia, Luca Fambri and Luca Fiori

Thermal Analysis and Kinetic Modeling of Pyrolysis and Oxidation of Hydrochars
Reprinted from: Energies 2022, 15, 950, doi:10.3390/en15030950 . . . . . . . . . . . . . . . . . . . . 147
v
About the Editor
M. Toufiq Reza
M. Toufiq Reza, Ph.D., is an Assistant Professor of Chemical Engineering at the Department of
Biomedical and Chemical Engineering and Sciences of Florida Institute of Technology. He received
his M.S. and Ph.D. in Chemical Engineering from the University of Nevada, Reno, in 2011 and 2013,
respectively. He has published more than ninety peer-reviewed journal articles, five patents, two book
chapters, and more than one hundred oral and poster presentations. Dr. Reza was named as one of
recipients of the I&EC Research 2021 Class of Influential Researchers. He has also contributed to the
AIChE Journal 2022 Futures Issue. He was the recipient of the 2022 New Holland Young Researcher
award from American Society of Agricultural and Biological Engineers (ASABE) and 2022 FASABE
Young Researcher Award. He is also listed in the “World Ranking of Top 2% Scientists” in the 2021
and 2022 database published by Stanford University. Dr. Reza leads the Biofuels Research Lab at
Florida Tech, with primary research interest on upcycling wastes via hydrothermal carbonization.
His current research projects have been funded by the National Science Foundation, U.S. Department
of Agriculture, U.S. Environmental Protection Agency, American Chemical Society, Florida Sea Grant,
U.S. Agency for International Development, Sugarbush Foundation, and other agencies. Dr. Reza is a
member of the American Institute of Chemical Engineers, American Chemical Society, and American
Society of Agricultural and Biological Engineers. He is the secretary of PRS-707 Food & Organic
Waste Management & Utilization at the ASABE. He is an Associate Editor of Frontiers in Fuels, a
Section Editor of the Energies journal, and an Editorial Board member of the Biomass Conversion and
Biorefinery journal.
vii
energies
Editorial
M. Toufiq Reza
Department of Biomedical and Chemical Engineering and Sciences, Florida Institute of Technology,
150 West University Blvd, Melbourne, FL 32901, USA; treza@fit.edu
Over the past decade, hydrothermal carbonization (HTC) has emerged as a promising
thermochemical pathway for treating and converting wet wastes into fuel, materials, and
chemicals. Many of the earlier studies have been carried out to understand HTC reaction
mechanisms and reaction kinetics using model compounds [1,2]. More recently, HTC
studies have shifted from model compounds to researching lignocellulosic biomasses [3–5];
however, these works remain focused on solid biofuel production in the form of hydrochar.
Perhaps the real potential for HTC lies in wet wastes (such as sewage sludge, agricultural
wastes, animal wastes, etc.) and their conversion to fertilizer, high value materials, and
sustainable chemicals [1]. However, the kinetics and reaction mechanism of the real wet
wastes often deviate from those of the model compounds [6]. Therefore, studying the
reaction kinetics of real wet waste is an important step towards revealing the viability of
HTC in the commercial process.
This Special Issue titled, “Hydrothermal Carbonization” has invited researchers from
around the World to contribute to these issues in the field of HTC research. Including
the editorial, ten papers are listed in this Special Issue. Researchers from eight different
countries have contributed their research to this Special Issue. The highlights of the Special
Issue are as follows:
• Maniscalco et al. [7] reviewed the recent progress made towards using HTC as a
valuable tool for energy and environmental applications. The review identified that
pristine hydrochar from organic wastes such as food waste are suitable for combustion
or soil amendment based on feedstock. However, the review also reported recent pro-
gresses with respect to further activating hydrochar for energy storage and pollutant
Citation: Reza, M.T. Hydrothermal
adsorption applications.
Carbonization. Energies 2022, 15, 5491.
• Three articles are reported aspects of HTC related to sewage sludge. Merzari et al. [8]
https://doi.org/10.3390/en15155491
have evaluated HTC systems at various points in wastewater treatment plants to treat
Received: 19 July 2022 various type of sludges (e.g., primary, secondary, and digestate sludge) for different
Accepted: 27 July 2022 applications. Meanwhile, Luhmann and With have optimized the dewaterability and
Published: 29 July 2022 phosphorus release from sewage sludge during HTC [9]. Sewage sludge is one of
Publisher’s Note: MDPI stays neutral the major sources of phosphorus and recovering phosphorus effectively from sewage
with regard to jurisdictional claims in sludge may enhance the success of HTC. Finally, Gerner et al. [10] have reported
published maps and institutional affil- the nutrient recovery and fuel production potentials from sewage sludge. The study
iations. reveals that the HTC process could be much cheaper than the current practice of
sewage sludge treatment in Switzerland; therefore, fuel production and nutrient
recovery from sewage sludge are economically viable.
• Ro et al. [11] have compared the HTC process with vapothermal carbonization (VTC).
Copyright: © 2022 by the author. When feedstock does not have an adequate volume of water to create subcritical water
Licensee MDPI, Basel, Switzerland. conditions, the thermochemical conversion is called VTC. There are distinct product
This article is an open access article formations for HTC and VTC [12]. This study reveals the minimum amount of water
distributed under the terms and
required in the feedstock to be considered conducive to HTC. This fundamental study
conditions of the Creative Commons
will clarify future research directions and ensure the practice of HTC.
Attribution (CC BY) license (https://
• Islam et al. [13] reported an approach integrating air classification with HTC. In
creativecommons.org/licenses/by/
the study, air classification separated high-ash-fraction (waste) corn stover from the
4.0/).
Energies 2022, 15, 5491. https://doi.org/10.3390/en15155491 https://www.mdpi.com/journal/energies

1
Energies 2022, 15, 5491
light ash fraction type [14]. This paper reported that the HTC of waste products can
be performed and the hydrochar can be used to enhance the pelletization of clean
corn stover.
• Gonnella et al. [15] have studied the thermal analysis and kinetics modelling of both
the pyrolysis and oxidation of hydrochar. Although hydrochar has been reported as
solid fuel, few sources have reported the combustion of hydrochar.
• Delahaye et al. [16] evaluated the cationic heavy metal adsorption of hydrochar both
experimentally and computationally. Confirmed via density functional theory (DFT)
simulation, this fundamental study reveals that hydrochar possesses superior binding
sites for copper (II) ions compared to ion exchange resins.
• Finally, Hasan et al. [17] reported how various precursors affect the carbon quantum
dot (CQD) properties via HTC. CQDs are very high-value materials with a variety
of applications, such as bioimaging, photocatalysis, and energy storage. This paper
demonstrates the possibility of separating CQDs from HTC process liquid. The utiliza-
tion of HTC process liquid has always been a concern for HTC commercialization and
this paper reveals a potential application for this very liquid.
Overall, HTC has shown tremendous potential toward commercialization. We hope
that readers will find this Special Issue informative and inspiring. The editor is thankful
to the authors for submitting their HTC research. The Energies editors and the review-
ers are also acknowledged for reviewing the manuscripts, which have made significant
improvements to this Special Issue.
Funding: The work is partially funded by USDA NIFA AFRI grant no. 2019-67019-31594 and grant
no. 2021-67022-34487.
Conflicts of Interest: The author declares no conflict of interest.
References
1. Román, S.; Libra, J.; Berge, N.; Sabio, E.; Ro, K.; Li, L.; Ledesma, B.; Álvarez, A.; Bae, S. Hydrothermal Carbonization: Modeling,
Final Properties Design and Applications: A Review. Energies 2018, 11, 216. [CrossRef]
2. Libra, J.A.; Ro, K.S.; Kammann, C.; Funke, A.; Berge, N.D.; Neubauer, Y.; Titirici, M.-M.; Fühner, C.; Bens, O.; Kern, J.; et al.
Hydrothermal carbonization of biomass residuals: A comparative review of the chemistry, processes and applications of wet and
dry pyrolysis. Biofuels 2011, 2, 71–106. [CrossRef]
3. Islam, M.T.; Sultana, A.I.; Saha, N.; Klinger, J.L.; Reza, M.T. Pretreatment of Biomass by Selected Type-III Deep Eutectic Solvents
and Evaluation of the Pretreatment Effects on Hydrothermal Carbonization. Ind. Eng. Chem. Res. 2021, 60, 15479–15491.
[CrossRef]
4. Reza, M.T.; Yang, X.; Coronella, C.J.; Lin, H.; Hathwaik, U.; Shintani, D.; Neupane, B.P.; Miller, G.C. Hydrothermal Carbonization
(HTC) and Pelletization of Two Arid Land Plants Bagasse for Energy Densification. ACS Sustain. Chem. Eng. 2015, 4, 1106–1114.
[CrossRef]
5. Saba, A.; Saha, P.; Reza, M.T. Co-Hydrothermal Carbonization of coal-biomass blend: Influence of temperature on solid fuel
properties. Fuel Process. Technol. 2017, 167, 711–720. [CrossRef]
6. Reza, M.T.; Yan, W.; Uddin, M.H.; Lynam, J.G.; Hoekman, S.K.; Coronella, C.J.; Vasquez, V.R. Reaction kinetics of hydrothermal
carbonization of loblolly pine. Bioresour. Technol. 2013, 139, 161–169. [CrossRef] [PubMed]
7. Maniscalco, M.P.; Volpe, M.; Messineo, A. Hydrothermal Carbonization as a Valuable Tool for Energy and Environmental
Applications: A Review. Energies 2020, 13, 4098. [CrossRef]
8. Merzari, F.; Goldfarb, J.; Andreottola, G.; Mimmo, T.; Volpe, M.; Fiori, L. Hydrothermal Carbonization as a Strategy for Sewage
Sludge Management: Influence of Process Withdrawal Point on Hydrochar Properties. Energies 2020, 13, 2890. [CrossRef]
9. Lühmann, T.; Wirth, B. Sewage Sludge Valorization via Hydrothermal Carbonization: Optimizing Dewaterability and Phosphorus
Release. Energies 2020, 13, 4417. [CrossRef]
10. Gerner, G.; Meyer, L.; Wanner, R.; Keller, T.; Krebs, R. Sewage Sludge Treatment by Hydrothermal Carbonization: Feasibility
Study for Sustainable Nutrient Recovery and Fuel Production. Energies 2021, 14, 2697. [CrossRef]
11. Ro, K.S.; Libra, J.A. Alvarez-Murillo, Comparative Studies on Water- and Vapor-Based Hydrothermal Carbonization: Process
Analysis. Energies 2020, 13, 5733. [CrossRef]
12. Funke, A.; Reebs, F.; Kruse, A. Experimental comparison of hydrothermal and vapothermal carbonization. Fuel Process. Technol.
2013, 115, 261–269. [CrossRef]
13. Islam, M.T.; Saha, N.; Hernandez, S.; Klinger, J.; Reza, M.T. Integration of Air Classification and Hydrothermal Carbonization to
Enhance Energy Recovery of Corn Stover. Energies 2021, 14, 1397. [CrossRef]
2
Energies 2022, 15, 5491
14. Lacey, J.A.; Aston, J.E.; Westover, T.L.; Cherry, R.S.; Thompson, D.N. Removal of introduced inorganic content from chipped
forest residues via air classification. Fuel 2015, 160, 265–273. [CrossRef]
15. Gonnella, G.; Ischia, G.; Fambri, L.; Fiori, L. Thermal Analysis and Kinetic Modeling of Pyrolysis and Oxidation of Hydrochars.
Energies 2022, 15, 950. [CrossRef]
16. Delahaye, L.; Hobson, J.T.; Rando, M.P.; Sweeney, B.; Brown, A.B.; Tompsett, G.A.; Ates, A.; Deskins, N.A.; Timko, M.T.
Experimental and Computational Evaluation of Heavy Metal Cation Adsorption for Molecular Design of Hydrothermal Char.
17. Hasan, M.R.; Saha, N.; Quaid, T.; Reza, M.T. Formation of Carbon Quantum Dots via Hydrothermal Carbonization: Investigate
the Effect of Precursors. Energies 2021, 14, 986. [CrossRef]
3
energies
Review
Hydrothermal Carbonization as a Valuable Tool for
Energy and Environmental Applications: A Review
Manfredi Picciotto Maniscalco, Maurizio Volpe and Antonio Messineo *
Faculty of Engineering and Architecture, Kore University of Enna, Cittadella Universitaria, 94100 Enna, Italy;
manfredi.maniscalco@unikore.it (M.P.M.); maurizio.volpe@unikore.it (M.V.)
* Correspondence: antonio.messineo@unikore.it
Received: 6 July 2020; Accepted: 4 August 2020; Published: 7 August 2020
Abstract: Hydrothermal carbonization (HTC) represents an efficient and valuable pre-treatment

technology to convert waste biomass into highly dense carbonaceous materials that could be used
in a wide range of applications between energy, environment, soil improvement and nutrients
recovery fields. HTC converts residual organic materials into a solid high energy dense material
(hydrochar) and a liquid residue where the most volatile and oxygenated compounds (mainly
furans and organic acids) concentrate during reaction. Pristine hydrochar is mainly used for direct
combustion, to generate heat or electricity, but highly porous carbonaceous media for energy storage
or for adsorption of pollutants applications can be also obtained through a further activation stage.
HTC process can be used to enhance recovery of nutrients as nitrogen and phosphorous in particular
and can be used as soil conditioner, to favor plant growth and mitigate desertification of soils.
The present review proposes an outlook of the several possible applications of hydrochar produced
from any sort of waste biomass sources. For each of the applications proposed, the main operative
parameters that mostly affect the hydrochar properties and characteristics are highlighted, in order to
match the needs for the specific application.
Keywords: HTC; waste biomass; energy recovery; environmental remediation; nutrients recovery;
activated carbon
1. Introduction
The increasing need of finding new renewable energy alternatives to fossil fuels together with
the need to safely dispose of organic waste has pushed, in the last few years, the investigation for
more efficient and reliable technologies for waste biomass energy exploitation and conversion towards
valuable materials. Indeed, the constant rise in the global energy consumption together with the
parallel decrease in the fossil fuel reservoirs, has driven the scientific community toward the research of
more sustainable sources [1]. Waste biomass, and in particular the organic fraction of municipal solid
waste (OFMSW) and industrial and sewage sludges are among the most studied residual feedstocks to
produce energy and valuable carbonaceous materials [2–6].
One of the major drawbacks of choosing waste biomass for energy production, is the need for
one or more pre-treatments before use [7]. The low energy density due to the high moisture content
of waste biomass, makes it often not suitable for a direct energy conversion by combustion and/or
gasification [8–10]. The high moisture in residual biomass raises significantly the operational cost of
transportation and energy consumption for drying [11]. However, due to its great abundance, globally
availability, carbon neutrality and the necessity to find efficient and valuable technologies to treat
and convert it into sustainable energy sources and exploitable materials, waste biomasses has gained
increasing attention and investigation [12].
Between different valuable alternative treatments for waste biomass, wet thermochemical
technologies for their flexibility and, principle, their low investment and operating costs are receiving
Energies 2020, 13, 4098; doi:10.3390/en13164098 www.mdpi.com/journal/energies
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Energies 2020, 13, 4098
increasing attention in the last years [13,14]. In particular, hydrothermal carbonization (HTC),
also known as wet pyrolysis, is a thermochemical process performed in the presence of sub-critical
water at temperature usually between 180 and 280 ◦ C and autogenous saturated vapor conditions
(10–80 bars). Residence time is varied from minutes up to several hours [3,15,16]. At high temperature
and pressure, even at subcritical conditions, water undergoes a dramatic properties change acting more
as an organic solvent and its increased ion product favors reactions that are typically catalyzed by acids
or bases, promoting biomass decomposition through hydrolysis, dehydration and decarboxylation
reactions [17,18]. By means of these reactions, it is possible to increase the carbon content of the initial
feedstock, by removing most of the more volatile oxygenated compounds (furans and low molecular
fatty acids) that are typically moved to the aqueous phase [19]. It is also well documented in the
literature that, during HTC, part of the inorganics are moved to the liquid phase [19–21] thus, on the
one hand, reducing in the solid residue (hydrochar), minerals and ash formation during combustion,
and on the other hand, increasing the high heating values (HHV) [17,22]. This behavior leads to
a reduced risk of slugging and fouling phenomena during combustion of hydrochars in boilers if
compared to the use of pyrochars [2,23,24]. Hydrochar can be used in numerous applications, as a bio
fuel for energy production [1,13,25], as a source of carbon and nutrients in soil application [19,26,27] or
even as starting material for further advanced utilization in supercapacitors or a porous matrix for the
adsorption of pollutants [28,29]. Moreover, the possible scalability of the process up to the industrial
level [30], as well as relatively mild process conditions, make HTC a valid solution for the near future
for the transformation of a wide range of raw biomass into valuable materials [13,30]. In Figure 1
is reported a flowchart of hydrochar production from waste biomass and its possible energetic and
environmental applications.
Since HTC is performed under wet conditions, this technology can find its best application for
biomasses that present high initial moisture content. Indeed, when dealing with direct combustion,
a detrimental overall efficiency was shown when the starting biomass presents high moisture
content [10]. The main reaction pathways involved in the hydrothermal carbonization process
are still under discussion among the scientific community [31]. One possible route was discussed
by Jatzwauck and Schumpe [32], according to which the HTC process is essentially divided into
three steps. The first one is mainly related to the hydrolyzation of cellulose, hemicellulose and part
of the lignin. During the second step, the generated intermediates endure further re-arrangement
resulting in the generation of gaseous products. As an alternative to the formation of the gas phase,
intermediate products can conglomerate to form secondary char, during the third step. The other
mostly discussed route, regarding the evolution of HTC reactions, involves two main pathways:
a solid–solid transformation, according to which hydrochar is directly generated from the dehydration
of the initial biomass, and a vapor–solid reaction in which the dissolved organics present in the solution,
back polymerize to form again a solid material, often named coke or secondary char [33–35].
The present work attempted to review the most relevant research on HTC of the last 5 years,
in order to derive the best operative conditions for the production of valuable hydrochar materials.
Moreover, whenever possible, the present review was integrated with a further pyrolysis or gasification
process in order to evaluate how HTC behaves as a thermo-chemical pre-treatment for the production
of porous material or precursor for energy application purposes.
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Energies 2020, 13, 4098
Figure 1. Waste biomass hydrochar potential applications.
2. Effect of HTC Operating Conditions

It is well established that the HTC treatment induces some major transformations inside the
biomass particles, in accordance with the severity of the process that is performed. From an operative
point of view, the three main parameters that can be varied in a HTC process are temperature, residence
time and biomass-to-water ratio. It was found that each of these variables can differently influence the
intermediate reaction and the output products in terms of yields and composition [33,36]. The evolution
of the main biomass components (lignin, cellulose and hemicellulose) in relation to the reaction severity
was recently studied and modelled [37,38]. Heidari et al. [37] found almost negligible interactions
between lignin, cellulose and hemicellulose on the final hydrochar properties, while cellulose was
mostly affected by reaction severity. Authors also conducted an evaluation on the optimal proportion
between biomass components to increase carbon content and calorific value of hydrochar, finding
that a cellulose, hemicellulose and lignin content respectively of 40%, 35% and 25%, represents the
optimal starting conditions. Another main parameter that can significantly influence the composition
of the final hydrochar is the origin of the biomass. It is well known that ligno-cellulosic biomass is
mainly composed of lignin, cellulose and hemicellulos, but the extent of their proportion in the overall
biomass composition is strictly related to the nature of the material considered. At the same time
each of these components undergoes degradation processes at different extent in accordance to the
process conditions [39,40]. The first component that is subjected to hydrolyzation is hemicellulose,
which starts to degrade at temperatures of 180–200 ◦ C [41], followed by cellulose depolymerization
(above 210 ◦ C) [40] and softening of lignin [42]. Complete conversion of hemicellulose for reaction
temperature of 180 ◦ C and residence time of 4 h was reported by Olszewski et al., when treating brewer’s
spent grains [43]. Cellulose was found to be the most difficult component to be degraded, as reported
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Energies 2020, 13, 4098
by Titirici [31]. According to the author, cellulose starts to be converted above 210 ◦ C according to
two different pathways, as depicted in Figure 2 [31]. In their experiments, Olszewski et al. [43] and
Volpe et al. [40] reported a complete cellulose conversion at a reaction temperature of 260 ◦ C.
Figure 2. Cellulose conversion pathways, as proposed in Titirici, 2012.
Due to its very complex structure, lignin undergoes decomposition under a wider temperature
range with respect to hemicellulose and cellulose [44]. The deterioration starts at around 200 ◦ C, leading
to the disruption of highly reactive alkyl-aryl-ether bonds, which further react with other intermediate
compounds to form highly stable products [45]. Volpe et al. [19], when performing thermos gravimetric
analysis (TGA) on olive mill waste hydrochar, found that while cellulose peak is significantly reduced
for HTC temperature of 250 ◦ C, the peak associated to lignin increases [44]. Through the same analysis,
authors also confirmed the production of lower molecular compounds and/or tarry products coming
from the decomposition of lignin. Indeed, a new peak in TGA curve at around 250 ◦ C was found for
the sample produced at 220 and 250 ◦ C. From these considerations, it can be deduced that different
reaction temperatures lead to different compositions in terms of cellulose, hemicellulose and lignin.
The study conducted by Kim et al. [46] reported the energy retention efficiency (ERE) for each of these
components in relation to reaction temperature. Indeed, as previously reported, as HTC temperature is
raised, the calorific value increases as well, but the mass yield is reduced. It is therefore of paramount
importance to define the best conditions to maximize the ERE, in order to obtain a valuable biochar for
energy purposes. The results of this study showed that ERE for lignin and cellulose was maximized,
respectively, at 200 ◦ C and 220 ◦ C, while the best temperature for the conversion of biomass into high
energetic medium appeared to be 220 ◦ C.
The higher thermal stability of lignocellulosic against non-lignocellulosic biomass was also
confirmed by Zhuang et al. [47], testing herb tea waste (lignocellulosic) and penicillin mycelial
waste (non-lignocellulosic). The analysis performed on the hydrochars produced showed a superior
thermal stability for the tea waste, due to the presence of hemicellulose and lignin which start to
degrade above 210 ◦ C, while polysaccharide and protein present in the penicillin mycelial waste were
hydrolyzed at temperatures lower than 180 ◦ C. Finally, some considerations should be addressed
regarding the influence of pressure, particle size, and the possibility of water recirculation within
the system. With respect to the first parameter, the autogenous pressure that is developed inside the
reactor maintains the water in the liquid state, favoring its ability to dissolve polar compounds [48].
Higher pressure levels result in smaller hydrochar dimensions and higher pore volume, together with
a mild increase in the HHV. Only when pressure is raised above 100 MPa, significant increases in the
HHV can be achieved, but the higher cost of the reactor can limit the application [48]. Regarding
particle size and water recirculation, Heidari et al. [49] found that when biomass dimension was raised
from <0.25 mm to within the range of 1.25–3 mm, a slight increase in the mass yield was observed,
8
Energies 2020, 13, 4098
but the calorific value was lower. This condition is explained by the more severe conversion that
biomass endures since water can more easily penetrate and reach the inner core of the biomass particle.
Water recirculation affects almost only the mass yield, increasing it after the first recycle of about 12%,
while the contribution to HHV is almost negligible, since it was raised by just 2%.
Proximate and ultimate analysis have been widely used to characterize the hydrochars properties.
Proximate analysis is used to get an overall picture of the char composition in terms of fixed carbon
(FC), volatile matter (VC), ash and moisture content (M), while the ultimate analysis give the weight
percentages of their major elements (C, H, N, S, O). Although not all the reactions involved in HTC
treatment are well known, the general evolution pathways of the main biomass elements are fairly well
understood. As long as reaction severity is increased, most of the volatile compounds are released,
increasing carbon content and heating value. The main reactions occurring are dehydration and
de-hydrogenation which imply, respectively, the removal of hydroxyl groups and the rupture of the
of the long chain carboxylic acids [50]. Different studies evaluated the effect of residence time and
reaction temperature on the final hydrochar yields and properties [4,17,51,52]. The results of the studies
assert that the main contribution to biomass degradation and increase in the calorific value is reaction
temperature rather than residence time [53]. Lucian et al. [51] reported an increase in the heating value
of olive trimming from 22.6 to 27.8 MJ kg−1 when reaction temperature was raised from 180 to 250 ◦ C.
At the same time, increasing the residence time from 1 to 6 h led to a maximum increase in HHV of
+2 MJ kg−1 , at the temperature of 220 ◦ C, passing from 24.7 to 26.7 MJ kg−1 . The increase in the calorific
value is mainly due to the combined effect of the removal of oxygen and volatile compounds and the
parallel rise in carbon content. The evolution of the concentration of carbon, oxygen and hydrogen
is usually represented through the van Krevelen diagram in H/C and O/C ratios which are plotted.
It is fairly stated that an increase in the hydrothermal carbonization temperature boosts dehydration
reactions, removing oxygen from the initial biomass structure, resulting in a decrease in the O/C ratio.
The evolution of the hydrochar composition is represented in the van Krevelen diagram through
a shift toward lower values of O/C, characteristic of highly carbonaceous fuels like lignite or coals.
Ulbrich et al. stated that the removal of oxygen for low HTC temperature is only mildly affected by
residence time, while in the temperature range of 230–280 ◦ C a more pronounced connection between
oxygen reduction and residence time was observed [52]. Figure 3 displays the van Krevelen diagrams
for three biomass sources reported in the literature: a sugar rich waste, namely rotten apples and
coming from the fruit industry, a lignocellulosic residue (olive trimming) and a protein based biomass
(Penicillin mycelial waste) [1,51,54]. It can clearly be seen that each waste endures a specific evolution
pathway, in relation to its initial structure and composition. Evidences of the different transformations
that biomass endures during HTC, in relation to its origin process parameters, are reported in Table 1.
Lignocellulosic material, like olive trimming, presents higher thermal stability than proteins and
polysaccharides, resulting in higher mass yield (approx. 50%) and fixed carbon (9%) with respect to
fruit and protein-based wastes.
Hydrochar produced from fruit wastes resulted in an increase in fixed carbon as long as reaction
temperature is raised, due to the conversion of glucose which starts at around 225 ◦ C [1]. Different
research groups showed that mass yield is mainly affected by reaction temperature, rather than
residence time. For low reaction temperature, residence time can even have a positive effect on the
final mass yield. Chen et al. [55], as well as Lucian et al. [51], reported an increase in mass yield when
reaction temperature was set respectively at 190 and 180 ◦ C for a reaction time of 6 h, when compared
to mass yields obtained at 1-h reaction time. The increase in hydrochar mass is associated with a
re-arrangement and back polymerization of organic compounds from liquid to solid phase [55].
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Figure 3. van Krevelen diagram of hydrothermal carbonization (HTC) treatment of rotten apples,
Penicillin mycelial and olive trimming.
As previously reported, the last parameter that can be varied when performing HTC treatment is
the biomass-to-water ratio (B/W). Volpe et al. [17] found that when biomass is increased in the mix up to
a B/W ratio equal to 0.2, the share of secondary char production is increased as well, boosting the HHV
of the hydrochar. In terms of ash content, HTC presents a huge advantage over other pre-treatment
process such as pyrolysis. In fact, although during “dry” pre-treatment all the inorganics are kept
inside the biomass structure, increasing their content in the final product due to the mass loss during
the heating, in HTC some of the ash forming elements are removed from the biomass and washed
away with the process water [24].
10
Table 1. Effect of HTC reaction parameters on hydrochar composition, calorific value and mass yield, together with coal properties as reference.
FC VM C H O HHVraw HTC Res. Time FC_HTC VM_HTC C_HTC H_HTC O_HTC HHV_HC MY Ash_HC
Biomass Ref.
[%] [%] [%] [%] [%] [MJ/kg] Temp [◦ C] [h] [%] [%] [%] [%] [%] [MJ/kg] [%] [%]
Pine 13.1 87.8 48.1 6.6 45.1 19.2 220 4.0 30.8 68.8 66.0 5.9 27.5 25.9 76 0.4 [56]
Straw 14.8 80.9 48.2 6.5 40.6 18.2 220 4.0 25.2 72.6 57.9 5.0 34.4 22.4 56 2.2 [56]
150 0.5 15.3 68.8 54.9 6.9 34.8 19.8 84 15.8
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180 0.5 16.0 65.8 58.6 6.9 31.6 20.5 69 18.1

Herb tea waste 17.2 69.4 45.1 5.9 32.7 19.3 [54]
210 0.5 16.6 63.4 62.6 6.9 27.6 22.1 63 20.0
240 0.5 19.1 58.4 68.4 6.5 22.1 26.3 53 22.5
150 0.5 14.3 76.9 50.2 7.3 34.4 21.3 71 8.7
Penicillin mycelial 180 0.5 15.9 73.6 53.3 7.1 31.6 23.6 38 10.5
14.0 78.3 44.8 6.1 33.4 19.1 [54]
waste 210 0.5 17.1 68.2 64.5 7.1 20.6 27.4 29 14.6
240 0.5 18.9 63.8 69.2 7.0 16.5 29.2 23 17.2
150 0.5 3.1 31.6 50.4 8.4 33.5 10.4 79 65.4
180 0.5 2.8 24.7 57.1 8.3 27.2 10.2 75 72.5
Sewage sludge 3.51 39.9 21.5 3.7 14.2 9.3 [54]
210 0.5 2.4 19.6 66.4 9.4 16.7 8.1 72 77.9
240 0.5 2.2 16.8 71.5 9.9 11.0 7.7 68 81
180 2.0 17.8 74.9 60.3 7.1 27.8 26.5 68 4.3
200 2.0 20.8 71.9 62.0 7.0 26.4 27.2 64 4.3
Brewer spent grains 220 2.0 23.7 69.0 65.8 7.3 22.1 29.2 58 4.3
16 76.2 51.3 6.9 36.5 22.3 [4]
(80% moisture) 180 4.0 26.7 72.8 62.9 7.0 25.2 27.6 67 4.2
11
200 4.0 23.0 70.5 61.2 7.1 27.2 26.9 63 4.1
220 4.0 29.6 66.2 67.1 6.9 21.1 29.3 55 4.2
180 2.0 22.4 74.2 60.2 7.4 28.3 26.7 66 3.4
200 2.0 25.1 71.7 62.3 7.2 26.2 27.5 62 3.2
Brewer spent grains 220 2.0 28.7 68.0 66.5 7.3 21.9 29.6 52 3.2
16 76.2 51.2 6.9 36.5 22.3 [4]
(90% moisture) 180 4.0 23.7 73.1 59.9 7.0 29.1 26.2 65 3.1
200 4.0 26.5 70.3 63.5 7.2 24.9 28.0 60 3.2
220 4.0 31.9 64.8 66.6 6. 9 21.8 29.1 51 3.3
190 0.25 34.2 65.5 62.4 5.4 30.8 24.8 36 0.3
Rotten apples 14.8 83.6 43.5 6.2 47.5 17.5 225 0.25 35.9 63.9 64.2 5.3 29.4 25.7 36 0.2 [1]
260 0.25 37.9 61.6 66.8 5.0 26.8 26.0 39 0.4
Table 1. Cont.
FC VM C H O HHVraw HTC Res. Time FC_HTC VM_HTC C_HTC H_HTC O_HTC HHV_HC MY Ash_HC
Biomass Ref.
[%] [%] [%] [%] [%] [MJ/kg] Temp [◦ C] [h] [%] [%] [%] [%] [%] [MJ/kg] [%] [%]
190 0.25 28.8 68.6 55.7 5.5 34.5 21.8 38 2.6
Grape pomace 11.6 87.5 44.1 6.2 41.9 17.5 225 0.25 35.4 62.8 61.4 5.1 29.9 24.5 40 1.7 [1]
260 0.25 35.0 60.6 64.9 5.0 24.9 24.8 45 4.3
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0.25 40.5 52.4 59.5 4.8 34.1 25.2 74 7.1

Peat moss 27.4 65.9 51.1 5.4 42.0 21.3 240 0.5 42.4 51.4 61.5 5.0 31.8 25.3 73 6.2 [57]
0.75 41.8 51.5 62.1 4.9 31.3 25.8 70 6.8
180 1.0 20.3 76.1 54.3 6.1 34.3 22.6 72 3.5
180 3.0 23.2 72.9 56.7 6.2 31.4 23.4 70 3.9
180 6.0 21.9 73.8 58.9 5.9 29.2 24.1 73 4.3
220 1.0 25.1 70.6 59.4 6.2 28.3 24.7 63 4.3
Olive trimming 17.6 78.4 48.3 6.1 40 19.8 220 3.0 31.4 64.4 63.0 6.3 24.4 26.4 58 4.2 [51]
220 6.0 28.4 66.9 65.5 6.0 21.8 26.7 57 4.6
250 1.0 29.2 66.8 65.3 6.2 22.2 27.8 52 4.0
250 3.0 35.7 59.6 68.9 6.3 17.6 29.0 48 4.7
250 6.0 39.9 56.3 70.6 5.9 17.5 29.6 50 3.8
Sub-bituminous Coal 35.1 33.1 60.8 5.7 15.6 28.2 8(*) [58]
FC = fixed carbon; VM = volatile matter; MY= mass yield. (*) the value of ash for sub-bituminous coal is referred to the raw material and not the hydrothermally carbonized one.
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3. HTC of Waste Biomass for Energy Production and Storage

Hydrothermal carbonization has been proven to be an effective tool for waste biomass pre-treatment,
to produce highly carbonaceous materials that can be used for energetic applications [59–62]. In the last
5 years, research projects have focused their attention on the possible energetic use of the HTC products as a
carbon-rich material for direct combustion or as a precursor for the realization of supercapacitors [63–66].
Prior to any of its further use, hydrochar must be dried to remove all the moisture.
3.1. Direct Combustion

Hydrochar has shown better energetic properties with respect to the raw original biomass. In fact,
the increased heating value and the reduced volatile content ensure a better combustion and exploitation
of the calorific properties of the biomass. Moreover, the lower ash content due to the removal in
the liquid phase of part of the inorganics, reduce fouling and slagging phenomena that can lead to
inefficacy and increased maintenance of the boiler [16,67,68].
Numerous studies investigated the possible use of hydrochar from HTC of sludge for direct
combustion in a boiler. Most of the researches involve sludge from municipal waste water treatment
plants, but recently also industrial sludge, like from a paper mill plant was proposed [69]. Merzari et al.
studied the HTC as a strategy for sewage sludge management [70,71]. Peng et al. [72] tested various
temperatures and residence times for the pre-treatment of sewage sludge from a waste water treatment
plant, before its combustion. Temperature was varied in the range of 180-300 ◦ C, with a 40 ◦ C interval
with a residence time of 30 min, while, to evaluate the contribution of reaction time authors kept the
temperature fixed at 260 ◦ C for 30, 60, 90, 360 and 480 min. Authors found that 260 ◦ C and a residence
time between 30 and 90 min, led to the highest increase in the higher heating value (2–10%). A further
prolongation of reaction time up to 360 min, induced only an increment in the ash content up to 69.26%.
The ash-related problems are common issues when dealing with sludges from waste water treatment
plants. Wang et al. [73] studied the behavior of high-ash municipal sewage sludge when subjected
to HTC in the temperature range of 170–350 ◦ C. Raw sludge presented poor energetic properties,
due to the very high ash and volatile matter (VM) content and the low fixed carbon amount. Similarly
to what was reported previously by Peng et al. [72] and by Chen et al. [74], a mild HTC treatment
with temperatures below 260 ◦ C determines the best hydrochar properties for the further combustion
stage. Indeed, the reduced ash content, the higher dewaterability and the greater HHV with respect
to the other pre-treatment conditions, make this temperature the optimum one at which to process
sludges. A valid practice to obtain hydrochar with better combustion performances, is to perform a
co-HTC with carbon rich biomass, in order to raise the carbon content and the calorific value [57,75,76].
Zheng et al. [77] tested co-HTC of food waste (FW) and municipal sludges (MS) under different ratios
and carbonization temperatures. The share of food waste in the mix was varied between 30, 50 and
70%, while the temperatures tested were 180 ◦ C, 230 ◦ C and 280 ◦ C. The addition of food waste can
partly mitigate the drawbacks related to poor combustion properties of sewage sludge hydrochar by
raising the HHV and the carbon content, while lowering at the same time the ash amount. As long as
the amount of food waste was raised in the feedstock mix, authors reported a drastic increase in the
HHV which passed from 9.62 MJ kg−1 for the hydrochar prepared at 230 ◦ C from only MS to 19 and
23 MJ kg−1 when the amount of FW was, respectively, 50 and 70%. At a temperature of 230 ◦ C, HTC of
only food waste produced a good quality solid fuel with a HHV of 31 MJ kg−1 and an ash content
of 6%. Another perspective on the possible use of food waste as feedstock for HTC conversion was
presented by Wang et al. [78] and McGaughy et al. [79]. Wang et al. [78] found a similar trend in the
evolution of the calorific value of the hydrochar, with a peak of 31.7 MJ kg−1 when FW was treated at
260 ◦ C for 1 h. In addition, fouling and slagging phenomena were reduced. Indeed, as long as reaction
temperature increases, the removal of inorganics like Cl, S and N, together with a great share of alkali
metals, is enhanced which contribute the most to slagging and fouling problems. However, when the
carbonization temperature was raised above 220 ◦ C, authors encountered an increased emission of
NOx, which should be avoided during combustion. McGaughy and Reza [79], on the basis of HTC
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experiments with food waste, proposed a simulation model of a plant processing 1 ton of fresh refuse
per day, resulting in a positive net energy balance for the whole process.
Food waste in the form of digestate from biogas plants, was experimented by Cao et al. [80].
The digestion significantly reduced the potential for energy conversion, since it converted a great share
of the carbonaceous content to methane and carbon oxides and increased the ash amount with respect
to the raw material. HTC treatment did not show significant improvement in terms of combustion
potential. Poor energetic properties were also reported in [81] when dealing with the wet fraction of
municipal solid waste digestate, but mostly due to the scarce potential of the initial feedstock.
A good potential for solid fuel conversion was proposed in [82,83] for the lignocellulosic material.
In [82] authors tested the efficacy of a 220 ◦ C, 90 min HTC treatment on six different biomasses, namely:
olive pomace, walnut shell, hazelnut shell, apricot seed, tea stalk and wood sawdust. Each of the
biomasses studied, presented better combustion properties with respect to the initial feedstock, in terms
of heating value, carbon content and ignition conditions. The best energetic properties were found to
be related to the olive pomace with an increase in the HHV of up to 25.6 MJ kg-1 and an ash content of
5.5%, while hazelnut husks showed the poorest properties with a HHV of 20.6 MJ kg−1 and an ash
percentage of approximately 12%. Moreover, all the hydrochar presented higher ignition temperatures
with respect to the raw biomasses, which significantly improve the handling and storage properties
of the fuels, reducing the risk of self-ignition and combustion. Similar properties of the obtained
hydrochar were also reported by Chen et al. when dealing with HTC of sweet potato peels [84].
3.2. Supercapacitors & Batteries Application

The research on possible use of biomass-derived material as source for electrode fabrication has
recently increased the attention on the use of HTC pre-treatment. The present review will consider
only the methods involving the use of waste biomass as starting material. This consideration is due to
the fact that some studies had focused the attention mostly on the activation step, using synthetized
glucose or lignin as starting material, while in the present work only the biomass-derived precursors
were considered. Agricultural wastes, as well as plant wastes or high lignocellulosic materials were
reported as suitable for energy storage applications [85–88]. Application for supercapacitors has been
more and more studied in recent years. Supercapacitors can deliver great power output, ensuring
at the same time long life and great efficiency after hundreds of cycles [86]. Supercapacitors store
charge reversibly through ions immobilization in the electric double layer, on which non-faradaic and
pseudocapacitive reaction occurs [87]. Hence, carbon-based material for supercapacitors applications
must ensure good electric conductivity, great surface area with possible hierarchical pore distribution,
together with a reasonable cost. For such reason, biomass material represents a greatly attractive
option in this field [87].
Soybean root was tested by Guo et al. [89], resulting in a great electrode capacitance and cycling
stability. Authors performed an acid HTC treatment at 180 ◦ C for 18 h by using a 5% w/w H2 SO4
solution. The obtained hydrochars were further active with KOH at 800 ◦ C for 3 h, under a N2
atmosphere. The Brunauer–Emmet–Teller (BET) and Scanning Electron Microscope (SEM) analysis
showed the formation of a hierarchical interconnected porous structure composed of large macro
and meso-pores on the external surface, which further develop into a capillary net of micropore sites.
These latter spots are the ones that mainly contribute to ions storage [90]. Cyclic voltammetry (CV)
showed great electrical response even at a high scanning rate, reporting an almost rectangular trend of
the curve even at 800 mV s−1 , as well as a significant capacitance of 328 F g−1 for a current density of
1 A g−1 .
Tests on bamboo shells were reported by [65], resulting in a lower capacitance with respect to the
ones reported by Gou et al. [89], and equal to 209 F g−1 at 0.5 A g−1 . Similarly in this case, authors
performed an acid HTC treatment with 1% w/w H2 SO4 solution and the obtained hydrochars, before
being activated in KOH at 600–800 ◦ C, were carbonized with melamine under N2 at a temperature
of 600 ◦ C, with a char-to-melamine ratio of 1:4 w/w. To better understand the effect of melamine
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treatment on the final product, a blank assay was also conducted. The results showed a remarkable
increase in surface area and pore development, as well as in the capacitance properties of the hydrochar.
Melamine for hydrochar activation was also studied by Sevilla et al. [91], mixing it with K2 C2 O4 and
the hydrochar obtained from eucalyptus sawdust produced at 250 ◦ C for 4 h. The use of K2 C2 O4 ,
instead of the more frequently used potassium hydroxide, according to the authors, is due to three main
reasons: its lower corrosive potential, the higher obtainable product yield and its less disruptive action
on the morphology of chars. The use of K2 C2 O4 instead of KOH can almost double the char production,
for the same amount of reactant adopted, while increasing at the same time the electrical properties.
Hydrochar from pine cones, hemp waste, tobacco rods, peony pollen and argy worm-wood were
successfully tested as precursors for supercapacitors application through KOH activation [63,92–95].
Excellent capacitance properties were found by Zhao et al. [63] when working with hydrothermally
carbonized tobacco rods. In this work, authors firstly treated the biomass through HTC at 200 ◦ C for
12 h and then activated it at 800 ◦ C for 1 h with a char-to-KOH ratio of 1:3 in mass. Results showed
that the activation stage increased the specific surface area up to 2115 m2 g−1 , raising significantly
also the specific capacitance. Indeed, the produced electrodes showed superb electrical properties
with a capacitance as high as 286 and 212 F g−1 , when the current density was, respectively, 0.5 and
30 A g−1 . Higher capacitance was recorded when using malva nut as biomass precursor by Ye et al. [96].
HTC was performed at 200 ◦ C for 18 h and hydrochars were further activated at 700 ◦ C in a ratio of 3:1
with KOH. Capacitance up to 279 and 219 F g−1 were achieved for current densities of 1 and 20 A g−1 ,
respectively. Acid HTC with KOH activation resulted in lower performance when pine cones were
used as starting biomass [93]. Manyala et al. tested the addition of 0.5 ml of sulfuric acid into 80 ml of
de ionized (DI) water, as medium for the HTC reaction. The further activation was performed for 1 h at
the temperatures of 600, 700, 800 and 900 ◦ C, with a KOH-to-char ratio of 1:1 (w/w). When temperature
reached 900 ◦ C a significant reduction in porosity and electrical properties of the char was observed.
This condition is probably due to pore walls collapsing at higher temperature, which enlarge their
average dimensions, reducing at the same time the amount of micropores which act as a storage site
during charging. A wider inspection of the possible activating agent was conducted by Jain et al. [97]
on coconut shells. Biomass was firstly treated in autoclave with H2 O2 or ZnCl2 , testing different
dosages and temperatures, and further activated under CO2 at 800 ◦ C for 2 h. Three different HTC
conditions were tested in this work:
1. Temperature of 315 ◦ C, 20 min with a ZnCl2 -to-shell ratio of 1:1 (w/w);

2. Temperature of 275 ◦ C, 20 min with a ZnCl2 -to-shell ratio of 3:1 (w/w);
3. Temperature of 200 ◦ C, 20 min in a 10% H2 O2 solution with a successive stage at 275 ◦ C for 20 min
with a ZnCl2 -to-shell ratio of 3:1 (w/w).
Each set of tests was further proposed under a wide range of biomass concentrations in the
solution, ranging from 0.05 to 0.66 mg L−1 . For the case of ZnCl2 -to-shell ratio of 1:1, authors reported
a decrease in the specific surface area as long as biomass concentration was raised, passing from
1700 m2 g −1 for a biomass concentration of 0.05 mg L−1 , to 1350 m2 g −1 when the concentration was
raised to 0.22 mg L−1 . The tests using H2 O2 presented a similar trend, with an increase in surface area
from 1750 to 2450 m2 g−1 when the biomass concentration was raised from 0.16 to 0.5 mg L−1 , but a
further increase up to 0.66 mg L−1 led to an almost 20% reduction in specific surface area. In terms of
electrical properties, the highest energy density as well as the highest capacitance was found to be
related to carbon produced with H2 O2 and ZnCl2 with a biomass concentration of 0.5 mg L−1 , with a
capacitance of 246 and 221 F g−1 for a current density of 0.25 and 5 A g−1 , respectively. Impressive
performances were also reported in [98] when testing ZnCl2 -activated hydrocar produced from Coca
Cola® . Authors found one of the highest capacitances ever recorded for waste precursors, equal to
352.7 F g−1 for a current density of 1 A g−1 . Table 2 summarizes some of the studies reported above
with also some reference values for synthetized materials used for supercapacitor applications.
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Table 2. Performances of biomass-derived hydrochar for supercapacitors application.
HTC Activation Activation Max

HTC HTC Temp. Activation
Biomass Res. Time Temp. Time Capacitance Ref.
Medium [◦ C] Agent
[h] [◦ C] [h] [F g−1 ]
5% H2 SO4
Soybean root 180 18 KOH 800 3 328 * [89]
solution
1% H2 SO4 KOH+
Bamboo shell 200 24 600–800 1 209 ** [65]
solution melamine
Tobacco rods H2 O 200 12 KOH 800 1 287 ** [63]
Malva nuts H2 O 200 18 KOH 700 1.5 279 * [96]
1% H2 SO4
Pine cones 160 12 KOH 600–800 1 78 ** [93]
solution
Self-stacked solvated graphene - - - 245 ** [99]
PANI nanowires through electrochemical deposition - - - 818 ** [100]
* Capacitance calculated at 0.5 A g−1 . ** Capacitance calculated at 1 A g−1 .
Aside from applications for supercapacitors, hydrochar has been successfully used for the
production of electrode material in lithium or sodium ion batteries as well as in the vanadium redox
ones [101–104]. In [101], authors used corn stalk as substrate for the production of a bio-based
lamellar molybdenum disulfide electrode to be used as anode in a lithium ion battery. To obtain the
desired material, a thiourea and ammonium molybdate solution was used as reaction medium for the
hydrothermal carbonization of cornstalks. Hydrochars were further treated in a furnace at 1000 ◦ C in
N2 atmosphere and then placed into an ammonium chloride solution at 60 ◦ C, to separate the excess of
calcium. The obtained material presented a discharge capacity, after 100 cycles, for a current density of
0.1 and 1 A g−1 of, respectively, 1129 and 339 mAh g−1 . A lithium ion battery anode was also produced
from a cellulose-derived carbon nanosphere obtained from corn straw by Yu et al. [102]. A sulfuric
acid bath and a following sodium hydroxide bath were used to extract cellulose from corn straw.
The obtained products were hydrothermally carbonized at 200 ◦ C for 24, 36, 48 and 60 h before being
further carbonized at 600 ◦ C in Ar, to obtain carbon nanospheres. Authors found that if reaction time
is too long, it can induce particles agglomeration, reducing the available specific area and, therefore,
the storage capacity. The best carbonization time was found to be 36 h, which showed a specific
discharge capacity after 100 cycles of 577 mA g−1 for a current density of 74 mA g−1 . Aside from lithium
ion, also applications for sodium ion batteries were studied. In [103], authors tested lath-shaped carbon
made through HTC followed by a 800 ◦ C carbonization step produced from peanut shells, to be used as
anode in Sodium ion battery. In this case, the discharge capacity was found to be equal to 265 mA g−1
at 30 mA g−1 after 100 cycles. Moreover, tests for a possible cathode material were performed by
Palomares et al. [105], using waste from vine shoots and eucalyptus wood as precursor to realize a
sodium vanadium fluorophosphate electrode. Authors found that when hydrochar is further subjected
to a flash thermal treatment (700 ◦ C, 10 min in N2 ), its electrochemical properties reached a specific
capacity of more than twofold that of pristine hydrochar.
Promising results were also achieved in vanadium redox flow batteries when testing activated
hydrochar [104] as electrode material.
4. Environmental Remediation
4.1. Adsorption of Contaminants

Waste biomass has been widely experimented for the realization of activated carbons for air or
water remediation [106]. Indeed, as already seen for the preparation of supercapacitors, biomass can
be transformed into a highly carbonaceous porous media, with superior properties in term of specific
area and surface composition. Contaminants are adsorbed within the carbon matrix both through
physical trapping on the internal surface or chemical bonding on the charged surface of the porous
material. Moreover, depending on the characteristics needed for the final material, the HTC treatment
and activation step can be further tailored by adjusting the operative parameters.
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Two studies involving the use of digestate material as precursor for the realization of activated
carbon for the adsorption of contaminants were found in the literature [107,108]. The research
conducted by Bernardo et al. [108] on the use of hydrochar from digestate of municipal solid waste,
showed a promising perspective for its application on the removal of phosphate from waste water.
Digestate was hydrothermally carbonized at 250 ◦ C for 1 h, in acid (with addition of H2 SO4 ) or native
conditions, before being activated at 600 ◦ C for 2 h with a KOH-to-hydrochar ratio of 3:1 in mass.
Despite the reduction in specific surface area when biomass is subjected to acid treatment, the two
sets of chars present the same adsorption capacity of 12 mg of orthophosphate for each gram of
carbon. Results indicate that morphological properties do not play a significant role in orthophosphate
adsorption. According to the authors, the presence of Al3+ , Ca2+ , Fe2+/3+ and Mg2+ ions in the acid
hydrochar, can boost the formation of mineral complexes with phosphate ions, reducing its content.
Similar behaviors were also reported in [109–111], when operating with bio-chars for the removal of
phosphate from aqueous streams.
Hydrochars were also successfully used to remove CO2 from gaseous streams by using
agro-industrial waste or Coca Cola® [98,107,112]. Bio chars from agro-industrial waste were produced
at different temperatures (190–250 ◦ C), carbonization times (3 and 6 h) and pH levels (5 and 7),
in order to evaluate the optimal reaction conditions [107]. Activated carbons were then realized by
mixing hydrocarbons (HCs) with KOH in a mass ratio of 1:4 and then heated up to 600 ◦ C for 2 h.
Activation considerably boosted surface area and micro-meso porosity of the material. When testing the
adsorption capacity, authors found a much greater affinity toward CO2 than CH4 , with an adsorption
capacity of 8.8 molCO2 kg−1 , for the carbon produced at 250 ◦ C for 6 h at a pH of 5. Tests on the
adsorption of CO2 were also performed with activated carbons realized from the HTC of garlic peel
and Coca Cola® [98,112]. Hydrochar from garlic peels [112] were activated under different activation
temperatures (600, 700 and 800 ◦ C) and KOH-to-char ratios (0:1; 2:1 and 4:1) in order to investigate their
effect on porosity development and adsorption capacity. Tests revealed that an increase in activation
temperature and KOH amount led to a rise in specific surface area and pore volume. However,
CO2 adsorption is mainly driven by micropores availability, resulting in lower adsorption capacity
as long as temperature and potassium hydroxide increases. Indeed, too severe activation conditions
can induce pore enlargement, as well as pore walls collapse, reducing the possible sites for CO2
immobilization. Superior performances were achieved when using Coca Cola® as precursor in the
HTC treatment [98]. The work conducted by Boyjoo et al. showed outstanding capacity when Coca
Cola® was hydrothermally carbonized at 200 ◦ C for 4 h and further activated either with ZnCl2 or
KOH. This latter condition induced the highest increment in the adsorption ability, leading to an
adsorption capacity of 5.22 mmol g−1 at 25 ◦ C and 1 Atm, which is one of the highest ever recorded for
biomass precursors.
Bernardo et al. produced activated carbon by hydrothermal carbonization of digested sludge
and tested their activity toward phosphorous adsorption. They demonstrated that the high porosity
together with a high concentration of cations as in Ca, Al, Fe etc., favored phosphates removal from
wastewater [108].
Experiments for heavy metals removal were also conducted starting from agro-industrial wastes
as reported in [113–115]. In [114], authors tested the removal capacity of Antimony (III) and Cadmium
(II) on pyro-char and hydrochar realized from animal manure. The results of the adsorption tests
showed higher yields when pyrolytic chars were used, as well as an increase in the removal capacity as
long as pH was raised from 3 to 6. The total adsorption potentials for Antimony were 2.24–3.98 and
4.44–16.28 mg g−1 , respectively, for hydrochar and pyrochar, while higher capacities were reported
for the case of Cadmium, achieving a removal of 19.80–27.18 and 33.48–81.32 mg g−1 . Aside from
Cadmium removal, promising results on the adsorption of heavy metals contaminants such as
lead (Pb) [116,117], copper (Cu) [118–120], Zinc (Zn) [55,113,115] as well as pharmaceutical and
chemical waste were obtained in different researches [106,121–124]. For copper removal, different
studies proved that surface charge, pH and adsorbent dosage were the main parameters affecting
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Energies 2020, 13, 4098
the adsorption capacity, while for lead superior efficiency (>99.5%) was achieved with Ni/Fe-doped
hydrochar [125]. Additionally, organic compounds like methylene blue, methyl orange and Congo
red were removed from contaminated solutions through the adsorption on hydrochar produced from
biomass waste [126–132]. Up to 655.7 mg of methylene blue for each gram of hydrochar was absorbed
when bamboo sawdust was carbonized into 1 M hydrochloric acid solution, before being further
treated with NaOH for 1 h. Acid modification led to 100%–200% increase in the adsorption capacity
when the solution was kept in the pH range of 10–12 [127].
The removal of Congo red and 2-naptol was studied by Li et al. in two following works,
using bamboo sawdust as starting material [133,134]. Both the two pollutants can have toxic effects on
both aquatic life and human organisms and, therefore, need to be removed from the water stream.
Moreover, due to their recalcitrant behavior to biological and thermal treatment, the use of adsorbent is
more and more studied. In both the studies published by the authors, they found that pore development
and the presence of oxygen functional groups on the surface can positively influence the adsorption
capacity of the activated carbon. HTC reaction was conducted according to three main procedures:
with pure water, with acid medium (HNO3 , H2 SO4 and H3 PO4 ) or through a two-stage operation with
a first hydrothermal carbonization in a 5% weight NaOH solution followed by an acid one in HNO3 ,
H2 SO4 or H3 PO4 . The two-stage process was used to perform a first delignification in order to favor
the penetration of the acid inside the material and enhance pore development. The results showed
that, among all, the best adsorption performances were achieved in a two-stage process, with H2 SO4
or H3 PO4 as acid medium and were equal to 90.51 and 72.93 mg g−1 , respectively, for Congo red
and 2-naphtol.
Adsorption of crystal violet (C25 H30 IN3 ) and malachite green was also investigated in
biomass-derived hydrochar in [135–137]. For both contaminants, pH represents a key factor for
adsorption since it is responsible for the surface charge modification of the hydrochars and the ionic
charge modification of the contaminants. It was found that for crystal violet, the optimum pH was 10,
while for malachite green it was found to be 7. Food leftovers were also transformed in adsorbent
material to remove rare earth ions [138] and toluene [139] from contaminated streams.
Magnetic modified hydrochar, produced from different biomasses through the addition of iron
compounds in the reaction media, were also used to remove tetracycline, roxarsone and persistent
free radicals from waste water [140–142]. The magnetic properties of the obtained material can reduce
the whole purification process time, by shortening the time needed to remove the adsorbent from
the solution and saving costs of operation. In Table 3, some of the presented works are reviewed,
according to the starting biomass, HTC condition and contaminant removed.
Table 3. Biomass type and HTC condition for removal of contaminants from waste waters.
HTC Reaction HTC Modifying Contaminant

Biomass Reference
Conditions Agent Removed
Digestate 250 ◦ C, 1 h H2 SO4 Orthophosphate [108]
Coca Cola® 200 ◦ C, 4 h KOH, ZnCl2 CO2 [98]
Anthimony
Animal manure 250 ◦ C - (III), Cadmium [114]
(II)
Bamboo sawdust 200 ◦ C, 24 h HCl + NaOH Methylene blue [127]
To sum up, the last five years of studies on the possible use of hydrochar material as precursor for
the realization of the adsorption of different contaminants, showed interesting potential for the further
development of substrates with enhanced capacities that could represent, in the near future, cheaper
and more environmentally friendly options with respect to artificially synthetized materials.
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Energies 2020, 13, 4098
4.2. Phosphorous Recovery

Waste biomass as OFMSW and sewage and agro-industrial sludge contain large amounts of
phosphorous. Phosphorous (P) is a “critical raw material” for Europe [143] meaning that this element
is of strategical importance but reserves of P rock are limited and mostly concentrated in Morocco,
USA and China. As stated above, European legislation is pushing and financing for an increase in
recovery of P from waste streams [144]. Hydrothermal carbonation of waste biomass, and in particular
of sewage sludge containing up to 4% by weight on a dry basis, has demonstrated the possibility
of recovering up to 95% of the total phosphorous content [70,145–147]. It has been demonstrated
that during HTC, the phosphorous element segregates into the solid phase and treatment of the
recovered hydrochar by an acidic leaching leads to the removal of P which moves to the aqueous
phase. Phosphorous element in sewage sludge could be found in different forms depending on the
reaction conditions [148]. P can be then precipitated by alkalization of the aqueous solution by adding
CaO [145] or sodium hydroxide solution[146]. The addition of magnesium chloride and ammonium to
the acidic phosphorous solution prior to alkalization led to the precipitation of struvite directly usable
as solid fertilizer [146].
4.3. Soil Conditioning

Char addition in soil has been widely recognized as an good practice to favor plant growth,
enhancing soil properties in terms of available nutrients, soil porosity and water retention
capacity [149–153]. In terms of plant growth, positive outcomes regarding roots nodulation and
biomass production were reported in [154,155]. Moreover, different studies demonstrated also the
positive effect of hydrochar on the retention of pesticides, allowing an optimized utilization and
reducing the possible risk of leakage and contamination of ground waters [156–158]. The fast
mineralization of the carbon contained in the char leads to a short-term release of nutrients in the soil,
reducing the carbon content by 30–40% within the first 12–19 months [159–161].
The nature of the biomass used to produce the biochar, as well as the operating conditions,
can significantly influence the final char composition and, therefore, the possible interaction with the
soil [162,163]. A possible drawback of hydrochar addition can be represented by the release of organic
compounds that can have toxic effects on soil. To minimize this effect, simple washing, aerobic or low
temperature thermal treatment had been reported as further options to reduce the phytotoxic effect
of pristine hydrochar [164,165]. Particular attention must be paid also when using HC from sewage
sludges, due to the high content and release of heavy metal in the soil [166].
Tests to control ammonia volatilization and optimize nitrogen use for plant growth were proposed
in [167–169]. Chu et al. tested the addition of algae-derived hydrochar to increase yield and
mitigate N2 O and NH3 emission [167]. Conversely to the main goal of the work, results showed a
significant increase in grain yield up to approximately 25%, together with a rise in N2 O emission
and ammonia volatilization. The increased released of nitrogen compounds could be due to the low
C/N ratio of the biomass and hydrochar, which could further prompt microbial activities, facilitating
nitrogen gasification. Similar results related to emission of N-containing compounds were reported by
Subedi et al. [169], as well as by Andert and Mumme [170] when adding pyro or hydro char into soil.
On the same aspect, good results with high nitrogen retention, together with a significant decrease
in ammonia volatilization was reported in [168] when using acid-modified hydrochar obtained from
sewage sludge. Magnesium citrate or magnesium citrate with sulfuric acid were tested as potential
additives in the reaction media for the HTC process. In the author’s opinion, the acidity of the
chars could reduce the ammonia volatilization, while the high porosity of the carbons can favor the
adsorption of NH4 + . Moreover, the presence of surface functional groups rich in anion exchange sites
can further reduce the nitrification rate, increasing N retention.
Base-modified hydrochars were also successfully tested on the removal of heavy metals like Lead
(Pb) and Cadmium (Cd) [171,172]. In [171], authors evaluated the possible addition of 0, 10, 20 and
30% (w/w) of lime in the solution, before the HTC treatment. The obtained hydrochars were mixed
19
Energies 2020, 13, 4098
with the contaminated soil in a proportion equal to 1, 2.5 and 5% by weight to evaluate the effect on
leaching and contaminants immobilization. Results of the trials showed a remarkable increase in the
removal of contaminants as long as the share of hydrochar was raised, achieving an improvement
in the immobilization efficiency of 95.1% (Pb) and 64.4% (Cd), with respect to pristine hydrochar.
Indeed, as long as hydrochar amount and lime content were raised, pH of soil shifted toward basic
values, increasing electrostatic interaction between positively charged metals ions and the anions in
hydrochar. Moreover, the formation of precipitates like metal (hydr)oxide or carbonate at high soil pH
helped to further reduce the amount of Pb and Cd ions in the samples. Copper was also successfully
removed from contaminated soil by Xia et al. [172], by using amino-functionalized hydrochar derived
from pinewood sawdust. Authors reported an efficiency in Cu removal from the soil equal to 96.2%,
together with a reduction of 98.1% in Cu amount in the leachate.
5. Hydrochar for Biorefinery

HTC products were recently proposed, from lab scale up to pilot plant unit, as precursor for the
production of many organic compounds that were traditionally synthetized from fossil fuel-derived
hydrocarbons [173–176]. Most of the efforts are focused on the production of ethanol, furfural
compounds and glucose. During HTC, biomass endures significant modifications leading to the
production of a vast amount of different chemical components, both in solid or liquid forms. Ethanol
was successfully produced from the cellulose extracted from agave and sugarcane bagasse hydrochar
in [177] and [178], achieving a production up to 145 L of ethanol from 1 ton of raw sugarcane
bagasse. In order to maximize cellulose production, low temperature HTC (180–190 ◦ C) is preferred.
The obtained hydrochar is further treated trough enzymatic hydrolysis and fermentation to obtain
ethanol. Through the enzymatic hydrolysis of both liquid and solid products of the HTC, glucose was
produced from palm oil waste by Zakaria et al. [179].
Furfural and 5-hydroxymethylfurfural (HMF) were also produced from Miscanthus, corncob
wastes and hemp [180–183]. HMF was successfully generated from both hydrolyzed cellulose or
hemicellulose contained in the original biomass. In both cases, acid treatment through H2 SO4 or
catalytic conversion were necessary to produce HMF.
6. Conclusions
HTC represents a valid pre-treatment technology to convert waste biomass into new valuable
products which could find applications in a wide range of fields, from energy production to environment
remediation and soil conditioning. Since HTC operates in aqueous medium, it is perfectly suitable to
convert wet biomass, without any drying step. The most common waste biomass materials include
those produced by agro-industries, municipalities (organic fraction of municipal solid waste and
sewage sludge) but also from forestry and paper mill industries. The removal of part of the volatile
compounds and ashes increases the combustion properties of the hydrochar, making them suitable for
direct combustion in energy production applications. Chemical and physical activation, by using KOH
or CO2 , respectively, were successfully proposed to increase the surface area and internal porosity
of the material. By modifying the morphology and chemical surface, activated hydrochar can be
successfully used for the production of energy storage devices for the immobilization of pollutants
in gaseous or liquid streams. Pores development as well as elemental and surface composition can
be tailored by changing the carbonization and activation parameters. Finally, the addition in soil can
induce important benefits on pant growth, increasing water retention and reducing at the same time
possible leaching of contaminants into ground water.
Recently, some researchers focused their attention on how to mitigate the energetic impact of
the hydrothermal carbonization process by coupling it with renewable energy production systems.
Indeed, biochar can represent a valuable product to increase the efficiency of co-digestion systems,
with respect to its pristine composition. HC produced from coffee spent, rice straw or microalgae,
as well as the liquid phase produced from the hydrothermal carbonization, induced higher biogas
20
Energies 2020, 13, 4098
production as well as an increased methane content [184–188]. In such a way, the energy content of the
produced biogas can be used to run the HTC reactor, ensuring cleaner combustion with respect to the
hydrochar itself. Another option that has recently been studied is to couple the HTC reactor with a
solar concentration system which can satisfy the thermal load. Linear parabolic and parabolic disc
concentrators ensured a carbonization temperature up to 200 and 250 ◦ C respectively, ensuring heating
conditions of traditional systems [189,190].
Nevertheless, there are still some mechanisms in the HTC process that need further study to be
completely understood, in order to gain a stronger control over the process parameters, their influence
on the final product properties and thus their possible applications. Depending on the HTC operating
conditions and the nature of the feedstock, the technology still presents some limitations for its full
development. Between them, the correct process liquid treatment and management often present
challenges due to the presence of toxic hydrocarbons (such as polycyclic aromatic hydrocarbons (PHAs)
and high heavy metals concentrations. The presence of toxic compounds severely limits the possibility
to use such residue (as for example in agriculture as a possible source of nutrients) increasing the
overall costs of the HTC process. Investigations related to toxic hydrocarbons removal and heavy
metals recovery represent a necessary step for further development of the HTC technology.
Author Contributions: Conceptualization, M.P.M., M.V. and A.M.; Writing-Original Draft Preparation, M.P.M.;
Writing-Review & Editing, M.P.M., M.V. and A.M.; Supervision & final review, A.M. All authors have read and
agreed to the published version of the manuscript.
Funding: This research received no external funding.
Conflicts of Interest: The authors declare no conflict of interest.
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© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).
30
energies
Article
Hydrothermal Carbonization as a Strategy for Sewage
Sludge Management: Influence of Process
Withdrawal Point on Hydrochar Properties
Fabio Merzari 1 , Jillian Goldfarb 2 , Gianni Andreottola 1 , Tanja Mimmo 3 , Maurizio Volpe 1,4 and
Luca Fiori 1, *
1 Department of Civil, Environmental and Mechanical Engineering, University of Trento, via Mesiano 77,
38123 Trento, Italy; fabio.merzari@unitn.it (F.M.); gianni.andreottola@unitn.it (G.A.);
maurizio.volpe@unikore.it (M.V.)
2 Department of Biological and Environmental Engineering, Cornell University, 226 Riley-Robb Hall, Ithaca,
NY 14853, USA; jlg459@cornell.edu
3 Faculty of Science and Technology, Free University of Bolzano, Piazza Università 5, 39100 Bolzano, Italy;
tanja.mimmo@unibz.it
4 Faculty of Engineering and Architecture, University of Enna Kore, Cittadella Universitaria, 94100 Enna, Italy
* Correspondence: luca.fiori@unitn.it; Tel.: +39-0461-282692
Received: 29 April 2020; Accepted: 1 June 2020; Published: 5 June 2020
Abstract: Conventional activated sludge systems, still widely used to treat wastewater, produce
large amounts of solid waste that is commonly landfilled or incinerated. This study addresses the
potential use of Hydrothermal Carbonization (HTC) to valorize sewage sludge residues examining the
properties of hydrochars depending on HTC process conditions and sewage sludge withdrawal point.
With increasing HTC severity (process residence time and temperature), solid yield, total Chemical
Oxygen Demand (COD) and solid pH decrease while ash content increases. Hydrochars produced
from primary (thickened) and secondary (digested and dewatered) sludge show peculiar distinct
properties. Hydrochars produced from thickened sludge show good fuel properties in terms of
Higher Heating Value (HHV) and reduced ash content. However, relatively high volatile matter and
O:C and H:C ratios result in thermal reactivity significantly higher than typical coals. Both series
of carbonized secondary sludges show neutral pH, low COD, enhanced phosphorous content and
low heavy metals concentration: as a whole, they show properties compatible with their use as
soil amendments.
Keywords: sewage sludge; hydrothermal carbonization; hydrochar; solid biofuel; soil amendment
1. Introduction
In 1991, the European Union (EU) Directive 91/271/EEC set new benchmarks for the collection,
treatment and monitoring of wastewater in urban areas [1]. In 2000, the EU produced over 10 million
dry tons of sewage sludge (latest available official EU data [2]). Since then, production has steadily
increased, increasing burdens on municipal wastewater treatment systems [3]. In 2017, the global
sewage sludge production reached approximately 45 million of dry tons per year [4]. In Italy alone,
over 1100 kilotons of dry sludge matter were produced in 2010, with almost 40% going to landfills and
less than 30% used in agricultural applications [2]. In 2016, the European Commission reported that
the 1991 directive was successful in terms of current improvements seen in EU water quality despite
an increasing population growth. However, the European Commission also underlined the need to
develop “innovative solutions to increase resource efficiency, such as solutions for energy recovery,
nutrient recovery, and processing to marketable products and water re-use” [5]. Beyond the EU, global
urbanization and the growth of the middle class, combined with stricter environmental regulations,
31
Energies 2020, 13, 2890
have forced municipalities to re-examine their sludge management practices—transitioning away from
traditional disposal via incineration, landfilling, or discharge to oceans/waterways—to favor beneficial
reuse [6,7].
Sludge is a complex, heterogeneous mixture comprised of organic compounds such as proteins,
peptides, polysaccharides, phenols, aliphatic, aromatic and furan compounds, as well as inorganic
materials such as nutrients (phosphorous, potassium, nitrogen), silica, and heavy metals [8] and
pathogens and other microbiological pollutants [9]. In a typical wastewater treatment process, primary
sludge is characterized as the sludge following mechanical processing (screening, grit removal,
sedimentation) containing between 93 and 99.5 wt% water, with a high content of suspended and
dissolved organics. Secondary sludge (also known as Waste Activated Sludge, WAS) follows from
biological treatment and contains a high amount of microbial cells with a total solids concentration
ranging between 0.8 and 1.2 wt% depending on the type of process used [10].
Anaerobic Digestion (AD) is the most widely used sludge management technique. AD converts
the organic solids to biogas (predominantly CH4 and CO2 ) via hydrolysis, acidogenesis, acetogenesis,
and methanogenesis [11,12]. Despite its popularity, a considerable amount of solid remains after AD;
as little as 20–30 wt% of the total organic matter is mineralized [9]. While these solids were once
thought to be environmentally benign, their use into the soil may well be a potentially large source of
greenhouse gas emissions and point pollutant sources for mercury, lead, cadmium, and copper on
arable land, contributing to environmental acidification [13] and posing a toxicological risk in terms
of pathogens present [9]. The microbiological processes occurring on land-applied sludge (mainly
anaerobic decomposition, nitrification, and denitrification) lead to considerable emissions of methane
and nitrous oxide, as well as ammonia and nitrate. While land application of sludge offsets the
use of industrial nitrogen-containing fertilizers and represents a considerable net reduction of N2 O,
NH3 , and NO3 − emissions, CH4 emissions are still estimated to be 6.3 kgton−1 of applied sludge [13].
As such, direct land application of secondary sludge may not be the optimal nutrient recovery pathway
and may well represent a waste of a renewable energy source.
Hydrothermal Carbonization (HTC) is a process to concentrate the carbon in a given biomass,
occurring in water at elevated temperatures in the range of 160–280 ◦ C [14], above saturated vapor
pressure, where water’s dielectric constant decreases so drastically that it catalyzes the carbonization of
biomass while acting as an organic solvent [15,16]. HTC proceeds via a series of mechanisms, including
hydrolysis, dehydration, decarboxylation, decarbonylation, and demethanation. HTC is performed
in 80–95 vol% water [17–20], making it an ideal processing pathway for wet biomasses [21,22] such
as sewage sludge. As well recognized in the literature, HTC not only leads to reduced volume and
energy densification of the solid residue, considerably improving its dewaterability [23,24], but also
significantly increases its solid fuel properties while stabilizing and disinfecting the sludge [25,26].
Interestingly, HTC of sludge enhances NO + NH3 reactions during solid combustion, significantly
reducing NOx emissions across combustion modes [27].
While multiple studies focused on nutrients recovery such as phosphorous [28–30] or probed
the impact of processing conditions on the solid and energy yields of hydrochars produced from the
HTC of sludge from one withdrawal point in the wastewater treatment (WWT) process [23,31–39],
the impact of upstream WWT processes on hydrochars is often not part of the experimental design.
Thus, a primary goal of the present work was to determine the most viable point in the WWT process
to employ HTC for sludge treatment from a solid fuel production and potential nutrient recovery
standpoint. There are two sets of variables of interest in the present work: (1) feedstock withdrawal
point from the WWT process; (2) hydrothermal reaction conditions on the composition and oxidation
properties of resulting hydrochars. While some research has been done to quantify the environmental
and economic benefits of using HTC to treat sewage sludge, understanding the impact of both feedstock
and processing conditions on resulting hydrochars is critical to enable better optimization of this
waste-to-energy conversion pathway [40].
32
Energies 2020, 13, 2890
2. Materials and Methods

Three kinds of samples were collected at different process points from the municipal Wastewater
Treatment Plant (WWTP) of Trento, Italy, which uses a Conventional Activated Sludge (CAS) and
Membrane BioReactor (MBR) system (more information about CAS/MBR systems in recent prior works
in the field: [41,42]). The primary sludge extracted from the primary settler is sent to a static thickener
and mixed with secondary sludge coming from the MBR system (Pipe 1 of Figure 1). The thickened
sludge exiting the static thickener (Pipe 3) is the first sample taken for the present work. The secondary
sludge coming from the CAS system is sent to a dynamic thickener (Pipe 2). After thickening, both
streams are sent to the anaerobic digester. Anaerobic digestion lasts 21 days at 33 ◦ C, after which the
digested sludge (Pipe 4) is sent to a dewatering system. The effluent from Pipe 4 is the second sample
taken for this work. To the digested sludge from Pipe 4 polyelectrolyte is added; this stream is sent
to the dewatering system (centrifuge) where it reaches about 25 wt% solids content to enable solid
handling. This dewatered sludge after the centrifuge (Pipe 5) is the third sample used in this work.
Each of the three samples taken was characterized and stored in a fridge at 4 ◦ C until use.
Figure 1. Schematic of wastewater treatment plant in Trento, Italy, identifying three sludge samples
(Thickened—Pipe 3; Digested—Pipe 4; Dewatered—Pipe 5) used in the present work.
2.1. Feedstock Characterization

The three feedstocks used were characterized in accordance with accepted environmental practices.
All measurements were conducted in triplicate and the average and standard deviation of each data is
reported. The total solids content of each sludge was measured by drying in an oven at 105 ◦ C for at
least 8 h until constant weight was reached.
The pH of the raw and carbonized samples was measured using a Profi-Line pH 3310 (WTW,
Milan, Italy) portable pH-meter by placing 1 g of solids in 20 g of deionized water, shaking for at least
90 min, allowing the mixture to settle for 15 min, and then reading the pH. The total Chemical Oxygen
Demand (COD) was measured using a closed reflux titration method [43] using potassium dichromate
digestion solution, sulfuric acid reagent, ferroin indicator solution, and a standard ferrous ammonium
sulphate titrant according to standard procedures. The same method was used for soluble COD
following filtration of the sample through a 0.45 μm filter [43]. Organic nitrogen in the trinegative state
was measured via the semi-micro Kjeldahl method. Ammonium nitrogen was measured [43] by first
buffering the sample at pH 9.5 with a borate buffer (to decrease hydrolysis), then distilling in a solution
of boric acid, and determining the concentration via acid titration with H2 SO4 . To measure the total
phosphorous, samples were first digested in H2 SO4 , forming molybdophosphoric acid, which was then
reduced by stannous chloride to molybdenum blue. The concentration was measured photometrically
at 690 nm and compared against a calibration curve [43].
33
Energies 2020, 13, 2890
Ultimate analysis to determine elemental composition of C, H, N, S, and O (by difference)

was conducted on a LECO 628 analyzer (LECO, Moenchengladbach, Germany) equipped with
Sulphur module for CHN (ASTM D-5373 standard method) and S (ASTM D-1552 standard method)
determination. Proximate analyses were done on a LECO Thermogravimetric Analyzer TGA 701
(LECO Corporation, St. Joseph, MI, USA). Samples were heated at 20 ◦ C min−1 to 105 ◦ C in air and
held until constant weight (< ±0.05%) to provide a dry baseline. They were subsequently heated at
16 ◦ C min−1 from 105 ◦ C to 900 ◦ C in nitrogen with a hold time of 7 min, where the mass loss was
attributed to Volatile Matter (VM). Finally, samples were held at 800 ◦ C in air to oxidize the Fixed
Carbon (FC) until the mass change stay within ±0.5% by weight. Mass remaining after this was
considered to be ash (inorganic matter) content. The Higher Heating Value, HHV, was measured using
an IKA 200C isoperibolic calorimeter (IKA-Werke GmbH, Staufen, Germany) according to the CEN/TS
14918 standard.
Inductively coupled plasma-optical emission spectroscopy (Arcos Ametek, Spectro, Germany) was
used to determine the inorganic concentration of the sludge samples. Briefly, samples were oven-dried
at 105 ◦ C until constant weight and then acid-digested in concentrated nitric acid (650 mL−1 ; Carlo Erba,
Milano, Italy) using a single reaction chamber microwave digestion system (UltraWAVE, Milestone
Inc., Sheldon CT USA) and Teflon-lined vials to prevent interference. Elements were quantified using
certified multi-element standards (CPI International).
2.2. Hydrothermal Carbonization and Product Analysis

Hydrothermal carbonization typically occurs between 180 and 250 ◦ C under autogenous pressure
(up to 50 bar) but below the critical point [18]. The present work utilized a 50 mL stainless steel batch
HTC reactor rated to withstand 300 ◦ C and 140 bar, with temperature and pressure monitoring and
temperature control, as previously described [44,45]. The thickened and digested sludges were used
as-received. The reactor was loaded with 35.0 mL ± 0.1 mL biomass, which maintained a biomass
(dry biomass)-to-water ratio of about 0.03:1. The dewatered sludge had a solid content of 25 wt%
and needed to be diluted to ensure that the biomass was fully submerged. The reactor was filled
with 20.00 g ± 0.01 g of dewatered sludge and 15.00 g ± 0.01 g of deionized water to cover the sludge,
resulting in a biomass-to-water ratio of 0.17:1. Prior to each run, the reactor was sealed and purged with
nitrogen gas; then it was heated up to the desired reaction temperature (190 ◦ C, 220 ◦ C and 250 ◦ C) and
held at the set point for the desired reaction time (30 min and 60 min). At least three experimental runs
for each of the temperature/time combinations were performed for each of the three sludge samples.
After the reaction time, the reactor was cooled by placing a cold (−25 ◦ C) stainless steel disk under
its bottom and by blowing compressed air into its outer walls. The reactor was cooled to ambient
temperature in less than 15 min, at which point the produced gas was measured by flowing it into a
graduate cylinder filled with water [45]. As reported in the literature, where the CO2 content is always
greater than 90 vol.%, the produced gas was assumed to be comprised entirely of CO2 [45,46]. The gas
yield was estimated according to the ideal gas law under the assumption of standard temperature and
pressure as:
MassCO2
Y gas = (1)
MassSludge, dry
The liquid and solid HTC products were filtered through a pre-dried and weighed piece of
cellulose filter paper. The filter paper was then put in the oven overnight at 105 ◦ C and weighed to
calculate the solids produced. The solid yield of the hydrochar, Yhydrochar , was calculated as:
Masshydrochar,dry
Yhydrochar = (2)
MassSludge,dry
The liquid yield was computed as the complement to 1 of the gas and solid yields.
34
Energies 2020, 13, 2890
The solid hydrochar was characterized according to the same methods described in Section 2.1.
for Higher Heating Value (HHV), proximate, and ultimate analyses. The hydrochar’s relative solid
reactivity was measured using a Mettler-Toledo Thermogravimetric Analyzer–Differential Scanning
Calorimeter (TGA-DSC-1, Mettler-Toledo LLC, Columbus, Ohio, USA) in an oxidative atmosphere.
The TGA-DSC was calibrated with NIST-traceable gold, indium, and aluminum and the mass was
measured to ±0.1 μg and temperature to ±0.1 ◦ C. Approximately 10 mg of sample was loaded into a
70 μL alumina crucible. Samples were heated at 20 ◦ C min−1 up to 110 ◦ C in air flowing at 50 mL min−1
and held for 30 min to drive off any residual moisture. They were subsequently heated at 20 ◦ C min−1
up to 950 ◦ C and held for 30 min to oxidize all material. The mass fraction of sample converted (X) at
any time, t, was calculated as:
m − mt
X= i (3)
mi − m f
where mi is the initial mass, mt is the mass at any time, t, and mf is the final mass after the hold at
950 ◦ C. Derivative thermogravimetric (DTG) curves were plotted as dX/dt (s−1 ) versus temperature.
Differential scanning calorimeter (DSC) data was normalized as heat flow per sample mass at any
given instant (mt ). DTG curves are compared to those from an in-house sample of Illinois No. 6 coal,
a high volatile bituminous coal from the Illinois #6 (Herrin) seam from the Argonne Premium Coal
Bank [47]. The coal sample is well characterized in the literature and is often used as a standard on
which to compare solid fuel oxidation [47–49].
Dewaterability—and the improvement due to HTC was determined by measuring the Capillary
Suction Time (CST) required for water to be separated from sludge across a filter paper (Whatman 17
CHR, VWR International, Milan, Italy) using a Triton Electronics Ltd. capillary suction timer type 304B
according to standard methods [43]. CST provides a quantitative assessment of how readily sludge
releases water.
The liquid phase remaining after hydrothermal carbonization was characterized by measuring
pH, COD, organic nitrogen, ammonia nitrogen, and phosphorous as described above. Measurements
of Readily Biodegradable COD (RBCOD) were performed following the procedure described in
literature [50]. To measure NH4 + nitrogen and soluble COD, samples were screened through a 0.45 μm
filter [43].
3. Results
To assess the optimal point to withdraw sludge from the wastewater treatment process for
hydrothermal carbonization in terms of resulting hydrochar properties, three samples were pulled
from various points along the process: Thickened, Digested, and Dewatered (Figure 1). The feedstocks
characteristics are presented in Tables 1 and 2. These three samples were subjected to hydrothermal
carbonization at three temperatures (190 ◦ C, 220 ◦ C, 250 ◦ C) and two residence times (30 min, 60 min)
each, producing a total of 18 hydrochar samples for analysis.
Looking at the data of the different raw sludges, it is clear that they differ substantially. Thickened
sludge contains about 46 wt% elemental carbon and 15 wt% ash. In digested sludge, the carbon
decreases to about 26 wt%, and the ash content increases to 45 wt%, due to stabilization during
anaerobic digestion. Dewatered sludge contains 36 wt% carbon and about 28 wt% ash. Thus, even if
dewatering is a mechanical process, it greatly modifies the sludge characteristics. The supernatant from
sludge dewatering has high concentrations of inorganic compounds such as N-NH4 + , P compounds,
CaCO3 , Mg, K, Na, and other minerals that contribute to the ash content [51]. The dewatering unit
washes away these inorganics strongly decreasing the ash content of the dewatered sludge: this reflects
on an increase in elemental C, H, N, and O, and also in FC and VM. VM variation is extremely
significant, passing from a value of 50 wt% in the digested sludge to about 66 wt% in the dewatered
sludge. These differences are also due to the fact that the digested sludge, immediately upstream
of the dewatering operation, is chemically conditioned with organic polyelectrolyte (1–10 g/kg dry
solids [52]) that is quickly adsorbed on the sludge particles.
35
Table 1. Characteristics of raw thickened sludge, raw digested sludge, and raw dewatered sludge and products of hydrothermal carbonization of thickened, digested,
and dewatered sludge.
Property Thickened Sludge Digested Sludge Dewatered Sludge

Moisture Content (wt%) 97.1 ± 0.1 97.1 ± 0.3 74.9 ± 0.1
Total Solids (g/L) 29.1 ± 0.4 29.0 ± 2.3 n.a.
Energies 2020, 13, 2890
Fixed + Volatile Solids (g/L) 26.7 ± 0.4 15.4 ± 0.9 n.a.

HTC Temp (◦ C) 30 min HTC 60 min HTC 30 min HTC 60 min HTC 30 min HTC 60 min HTC
Raw 28.1 ± 1.4 18.0 ± 0.9 193.2 ± 0.3 a
190 14.1 ± 2.0 15.3 ± 0.7 9.1 ± 0.2 9.3 ± 0.4 55.3 ± 1.4 56.3 ± 2.7
Total COD (g/L)
220 15.4 ± 1.4 15.1 ± 1.1 11.3 ± 1.2 9.9 ± 0.1 56.7 ± 8.2 54.1 ± 0.3
250 18.4 ± 0.7 18.4 ± 1.8 10.4 ± 0.7 8.8 ± 0.4 64.9 ± 8.2 57.5 ± 0.3
Raw 2.3 ± 0.1 0.4 ± 0.1 47.2 ± 2.4 a
190 10.5 ± 1.0 13.4 ± 0.4 6.4 ± 0.3 6.7 ± 0.5 49.8 ± 0.4 55.1 ± 2.8
Soluble COD (g/L)
220 11.9 ± 1.5 13.5 ± 0.5 6.7 ± 0.3 6.7 ± 0.5 44.8 ± 3.4 45.7 ± 5.5
250 15.3 ± 0.9 13.7 ± 0.1 8.3 ± 0.8 5.7 ± 0.2 57.5 ± 9.8 46.8 ± 0.6
Raw 7.21 ± 0.1 8.42 ± 0.01 7.0 ± 0.0
190 6.0 ± 0.0 5.3 ± 0.0 7.1 ± 0.2 6.8 ± 0.0 6.0 ± 0.1 6.0 ± 0.0
pH
220 6.0 ± 0.0 6.1 ± 0.0 6.8 ± 0.0 6.2 ± 0.1 6.0 ± 0.0 5.9 ± 0.0
250 5.8 ± 0.1 6.0 ± 0.0 7.3 ± 0.6 6.9 ± 0.1 6.0 ± 0.0 5.5 ± 0.0
36
Raw 175.00 ± 9.00 187.00 ± 9.00 10.00 ± 1.00 a
190 32.5 ± 0.1 38.4 ± 0.1 19.6 ± 0.3 22.7 ± 0.1 0.3 ± 0.0 0.4 ± 0.0
Total Phosphorous in Liquid (mg/L)
220 20.2 ± 0.1 16.4 ± 0.2 19.8 ± 0.3 17.8 ± 0.1 0.2 ± 0.0 0.2 ± 0.0
250 16.1 ± 0.1 11.1 ± 0.2 19.3 ± 0.3 12.2 ± 0.1 0.2 ± 0.0 0.2 ± 0.0
Raw 5.22 ± 0.10 5.81 ± 0.13 9.22 ± 0.33
190 6.2 ± 0.7 6.8 ± 0.4 7.2 ± 0.7 7.4 ± 1.4 9.2 ± 0.5 9.4 ± 0.4
Total Phosphorous in Solid (mg/g)
220 7.8 ± 0.3 9.4 ± 0.2 7.5 ± 0.5 7.5 ± 1.5 10.5 ± 0.2 10.6 ± 0.2
250 9.9 ± 0.5 10.2 ± 4.6 7.4 ± 0.9 6.7 ± 1.2 10.8 ± 0.8 10.9 ± 0.9
Raw 0.470 ± 0.230 0.880 ± 0.010 11.023 ± 0.551 a
190 0.1 ± 0.0 0.1 ± 0.0 1.3 ± 0.0 1.2 ± 0.0 4.5 ± 1.0 4.1 ± 0.2
Organic Nitrogen in Liquid (g/L)
220 0.1 ± 0.0 0.1 ± 0.0 1.4 ± 0.0 0.9 ± 0.0 2.4 ± 0.6 1.5 ± 0.1
250 0.1 ± 0.0 0.1 ± 0.0 1.3 ± 0.0 1.5 ± 0.0 1.7 ± 0.3 1.4 ± 0.7
Raw 0.490 ± 0.010 0.880 ± 0.010 0.598 ± 0.030 a
190 0.4 ± 0.0 0.6 ± 0.0 0.7 ± 0.0 0.7 ± 0.0 2.7 ± 0.1 3.8 ± 0.2
Ammonia Nitrogen in Liquid (g/L)
220 0.4 ± 0.0 0.5 ± 0.0 0.8 ± 0.0 1.0 ± 0.0 4.4 ± 0.3 4.6 ± 0.6
250 0.6 ± 0.0 0.6 ± 0.0 1.0 ± 0.0 0.8 ± 0.0 6.9 ± 0.4 6.5 ± 0.4
aras received, n.a.—not applicable, a Based on 1g of dry biomass dissolved in one liter of distilled water, HTC—Hydrothermal Carbonization.
Table 2. Products yields and analysis of solid fuel characteristics of raw feedstocks and hydrochars from thickened, digested, and dewatered sludge.
HTC Temp Thickened Sludge Digested Sludge Dewatered Sludge

Property
(◦ C) 30 min HTC 60 min HTC 30 min HTC 60 min HTC 30 min HTC 60 min HTC
Process Yields (dry basis)
190 77.2 ± 4.7 67.0 ± 11.0 82.8 ± 8.9 81.5 ± 8.9 88.2 ± 2.0 85.6 ± 0.0
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Solid Yield (wt%) 220 60.6 ± 8.8 57.2 ± 3.4 64.6 ± 6.4 70.6 ± 3.4 75.1 ± 1.0 75.2 ± 0.3
250 49.4 ± 4.8 52.0 ± 6.2 78.1 ± 7.8 64.9 ± 3.7 67.6 ± 2.5 66.8 ± 0.2
190 2.5 ± 0.0 2.7 ± 0.2 3.7 ± 0.9 4.7 ± 0.3 2.1 ± 1.4 2.6 ± 0.2
Gas Yield (wt%) 220 4.1 ± 0.7 4.2 ± 0.4 5.1 ± 1.3 5.6 ± 1.0 3.7 ± 0.1 4.3 ± 0.6
250 6.3 ± 1.6 7.2 ± 1.3 6.1 ± 2.1 7.6 ± 1.9 5.1 ± 0.2 5.9 ± 0.1
190 20.3 ± 2.4 34.9 ± 5.4 43.2 ± 4.9 43.1 ± 4.6 45.2 ± 1.7 44.1 ± 0.1
Liquid Yield (wt%) 220 35.3 ± 4.7 30.7 ± 1.9 34.8 ± 3.9 38.1 ± 2.2 39.4 ± 0.6 39.7 ± 0.4
250 44.3 ± 3.2 29.6 ± 3.8 42.1 ± 5.0 36.3 ± 2.8 36.4 ± 1.3 36.4 ± 0.2
Ultimate Analysis (dry basis)
Raw 45.96 ± 0.20 45.96 ± 0.20 25.60 ± 0.33 25.60 ± 0.33 35.91 ± 0.25 35.91 ± 0.25
190 44.56 ± 0.39 46.11 ± 0.39 19.22 ± 1.37 14.16 ± 2.57 36.61 ± 0.02 35.07 ± 0.23
C (wt%)
220 44.86 ± 0.51 43.15 ± 0.19 11.70 ± 0.64 10.21 ± 0.58 35.19 ± 0.17 35.75 ± 0.31
37
250 41.68 ± 0.29 41.21 ± 0.52 12.51 ± 0.26 12.02 ± 0.05 35.30 ± 0.18 35.57 ± 0.08
Raw 6.57 ± 0.02 6.57 ± 0.02 3.96 ± 0.06 3.96 ± 0.06 5.42 ± 0.00 5.42 ± 0.00
190 6.24 ± 0.08 6.46 ± 0.06 2.63 ± 0.16 2.00 ± 0.29 4.92 ± 0.02 4.61 ± 0.03
H (wt%)
220 5.95 ± 0.01 5.69 ± 0.02 1.61 ± 0.08 1.37 ± 0.07 4.32 ± 0.01 4.36 ± 0.03
250 5.03 ± 0.05 5.01 ± 0.03 1.65 ± 0.01 1.56 ± 0.02 4.11 ± 0.00 4.05 ± 0.01
Raw 4.26 ± 0.00 4.26 ± 0.00 3.59 ± 0.10 3.59 ± 0.10 5.81 ± 0.02 5.81 ± 0.02
190 2.23 ± 0.07 2.10 ± 0.07 1.58 ± 0.07 1.07 ± 0.17 4.27 ± 0.06 3.95 ± 0.01
N (wt%)
220 1.87 ± 0.24 1.86 ± 0.07 0.80 ± 0.08 0.66 ± 0.01 3.48 ± 0.02 3.45 ± 0.02
250 1.89 ± 0.05 1.99 ± 0.04 0.70 ± 0.00 0.69 ± 0.02 3.16 ± 0.04 3.12 ± 0.02
Raw 27.61 ± 4.86 27.61 ± 4.86 21.16 ± 0.79 21.16 ± 0.79 23.52 ± 0.52 23.52 ± 0.52
190 28.52 ± 6.69 25.97 ± 4.63 18.43 ± 3.50 15.67 ± 6.89 18.55 ± 0.17 19.33 ± 0.58
O (wt%)
220 25.51 ± 6.34 26.43 ± 5.06 12.35 ± 1.03 18.93 ± 1.10 16.53 ± 0.33 15.34 ± 0.49
250 22.47 ± 6.44 21.59 ± 3.83 11.72 ± 2.00 7.17 ± 2.53 14.07 ± 0.44 14.12 ± 2.18
Table 2. Cont.
HTC Temp Thickened Sludge Digested Sludge Dewatered Sludge

Property
(◦ C) 30 min HTC 60 min HTC 30 min HTC 60 min HTC 30 min HTC 60 min HTC
Proximate Analysis (dry basis)
Raw 12.56 ± 1.43 12.56 ± 1.43 4.76 ± 3.78 4.76 ± 3.78 5.90 ± 0.62 5.90 ± 0.62
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190 4.25 ± 2.50 4.58 ± 1.75 1.70 ± 0.09 2.06 ± 0.34 5.37 ± 0.23 9.94 ± 6.93
Fixed Carbon (wt%)
220 5.37 ± 4.00 5.23 ± 3.97 1.26 ± 0.07 0.13 ± 0.01 4.04 ± 2.06 9.83 ± 5.58
250 5.31 ± 5.85 6.12 ± 5.93 0.62 ± 0.05 1.38 ± 0.09 6.27 ± 0.61 7.02 ± 0.03
Raw 72.48 ± 3.19 72.48 ± 3.19 50.25 ± 3.51 50.25 ± 3.51 65.67 ± 0.50 65.67 ± 0.50
190 70.84 ± 6.65 71.03 ± 5.36 41.09 ± 3.22 30.84 ± 4.20 58.98 ± 0.29 53.02 ± 6.61
Volatile Matter (wt%)
220 66.05 ± 5.56 63.57 ± 7.81 26.17 ± 1.59 31.99 ± 0.90 55.48 ± 2.19 49.07 ± 5.72
250 60.06 ± 2.19 56.70 ± 3.95 25.97 ± 1.68 21.65 ± 4.68 50.37 ± 0.39 49.85 ± 2.03
Raw 14.96 ± 2.31 14.96 ± 2.31 44.99 ± 3.65 44.99 ± 3.65 28.43 ± 0.56 28.43 ± 0.56
190 24.91 ± 4.57 24.40 ± 3.56 57.21 ± 1.61 67.10 ± 2.27 35.66 ± 0.26 37.05 ± 6.77
Ash (Inorganic) (wt%)
220 28.58 ± 4.78 31.20 ± 5.89 72.57 ± 0.80 67.88 ± 0.45 40.48 ± 2.13 41.10 ± 5.65
250 34.63 ± 4.02 37.18 ± 4.94 73.42 ± 0.86 76.97 ± 2.34 43.36 ± 0.50 43.14 ± 1.03
Combustion Analysis
38
Raw 20.50 ± 0.14 20.50 ± 0.14 10.66 ± 1.79 10.66 ± 1.79 16.02 ± 0.09 16.02 ± 0.09
190 19.45 ± 0.64 20.71 ± 0.03 9.27 ± 1.73 7.97 ± 1.77 16.30 ± 0.19 15.96 ± 0.07
HHV (MJ/kg)
220 20.06 ± 0.90 18.72 ± 0.03 8.96 ± 1.77 7.86 ± 0.39 15.70 ± 0.09 15.47 ± 0.37
250 18.66 ± 0.26 19.17 ± 0.61 8.59 ± 1.78 9.37 ± 1.39 15.98 ± 0.11 15.33 ± 0.26
Energies 2020, 13, 2890
3.1. Hydrochar Properties Depend on Sludge Withdrawal Point and Carbonization Conditions
Solid hydrochar yields and properties are strongly influenced by both sewage sludge feedstock
and HTC temperature and residence time, as shown in Table 2 (see also Supplementary Materials
Figure S1). In general, as the harshness of carbonization increases, the solid hydrochar yield decreases,
as is the case with biomasses across the literature [53]. The one exception to this general trend was
the digested sludge sample carbonized at 220 ◦ C for 30 min, which had a lower solid yield than
its 250 ◦ C and 190 ◦ C counterparts. This anomaly was observed for multiple experimental runs.
Such behavior could be attributed to potential re-condensing of tarry materials onto the hydrochar
matrix, increasing the observed “solid” yield at 250 ◦ C. Such materials were previously identified on
the surface of heterogeneous biomasses that can be maximized at carbonization conditions specific to
each biomass [17]. As the solid hydrochar is collected on a 10–100 μm filter, any particles smaller than
this size range would be considered part of the liquid yield, which may also explain this anomaly.
As a result of the carbonization process, which releases organic compounds from the solid matrix
and forces them into the water phase while generating CO2 , the total COD present substantially
decreased upon carbonization (at any time, temperature) of the dewatered sludge sample, with a
similar behavior noted for the thickened and digested samples (the effect on these two samples is less
pronounced given the lower initial concentration in the raw samples) as shown in Table 1 and Figure S2
in Supplementary Materials. Conversely, soluble COD increased with increasing severity, most notably
for the thickened and digested samples, with a significantly higher soluble COD that is maintained
throughout carbonization for the dewatered samples. Such behavior has been described in the literature
for other biomasses, including sludge, secondary sludge, wood waste, and dairy waste [54]. Given
the nature of the carbonization process, where water acts as both a solvent and transport medium,
simultaneously drawing organics into the water phase and generating CO2 , this COD mass balance
suggests that indeed the insoluble fraction is being converted to CO2 (and lesser amounts of CO and
other non-condensable gases) while the soluble portion is retained in the process water.
The decrease in hydrochar pH for increasingly severe carbonization of the thickened sludge is
to be expected; Volatile Fatty Acids (VFAs) present in primary sludge and formed via hydrolysis of
triacylglycerols [55], especially acetic acid, are known to remain stable in the liquid phase, only breaking
down at higher carbonization temperatures [54]. It was found here that the pH for the thickened
sludge dropped from 7.2 (raw) to 6.0 for both the 190 ◦ C and 220 ◦ C conditions and to 5.8 for the
250 ◦ C condition of the 30 min HTC samples and to 5.3, 6.1, and 6.0 for the 190 ◦ C, 220 ◦ C, and 250 ◦ C
60 min samples, respectively (Table 1; plotted in Figure S3 in Supplementary Materials). This suggests
that carbonization is able to release some VFAs from the primary matrix, but that the overall acidic
nature of the hydrochar increases slightly. It should be noted that these measurements were taken in
the same manner used to measure biochar pH, by equilibrating the hydrochar with deionized water
and reading the pH of the liquid following settling. Anecdotally, when the pH of the process water is
measured immediately following carbonization, the pH increases slightly upon severe carbonization,
which would indicate hydrolysis of released VFAs occurs in the process water. For the digested
samples, carbonization at 250 ◦ C yields hydrochars with slightly higher pH than their 190 ◦ C and
220 ◦ C counterparts, suggesting a reduced acid content of the char. For the dewatered secondary
sludge, the pH decreases with increasing carbonization but is overall lowest to begin with, suggesting
that the acid content decreased during anaerobic digestion.
The proposed loss of semi-volatile compounds from the sludge matrices upon carbonization is
further supported by the proximate analysis (Figure 2; Table 2; data of Table 2 plotted in Figure S4 in
Supplementary Materials). The sludge treatment of WWTP results in a decrease in fixed carbon and
volatile matter content upon digestion, with a slight increase in both upon dewatering. Changes in
proximate analysis as a function of carbonization conditions versus the raw sludge withdrawn at each
point are given in Figure 2. Figure 2 reports the percentage change in value of the various variables
(FC, VM, Ash, all data on a dry basis) due to HTC, in respect to the raw biomasses. As compared
to the raw sludge sample from each withdrawal point, the volatile matter content decreased with
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increasingly harsh carbonization. The fixed carbon content also decreases upon HTC, shifting the
balance of the hydrochar composition to the inorganic (loosely termed “ash” phase). The change
in proximate analysis appears to be more heavily temperature dependent than time dependent for
the thickened samples. In this case, the ash content increased by 50 wt%, 100 wt%, and 150 wt%
over the raw thickened sample as the carbonization temperature increased from 190 ◦ C to 220 ◦ C to
250 ◦ C, respectively. This increase in inorganic content is offset more so by decreases in fixed carbon
than volatile matter. For the digested samples, the increase in ash content—ranging from 25 wt% to
50 wt% as temperature increases—is offset by decreases in both VM and FC, with a slightly higher
decrease in FC than VM across HTC conditions. The behavior of the dewatered samples is somewhat
different. While for HTC at 30 min there is a slight increase in ash (especially at 220 ◦ C and 250 ◦ C
carbonization), the 220 ◦ C 30 min sample is offset more by changes in FC, whereas the 250 ◦ C 60 min
sample’s higher ash content is due to a decrease in VM. The dewatered 60 min HTC samples show
even further divergent behavior; for all temperatures, the FC and ash contents increase, offset by
a decrease in VM content. For the 190 ◦ C and 220 ◦ C samples, the change in FC weight percent is
actually greater than that of the ash, whereas the 250 ◦ C sample has a larger increase in ash than fixed
carbon. This is likely due to the preparation of the samples. Both thickened and digested samples were
used as received. The dewatered samples had too low of a moisture content to ensure all solids were
submerged in the reactor, such that deionized water was added to the samples prior to carbonization.
It is possible that some of the inorganics migrated into the water phase (to establish a concentration
equilibrium), and thus, the relative change in ash content was lower for these samples.
Figure 2. Changes in volatile matter, fixed carbon, and ash composition as a result of hydrothermal
carbonization: (a) Thickened sludge, 30 min of Hydrothermal Carbonization (HTC); (b) Thickened
sludge, 60 min HTC; (c) Digested sludge, 30 min HTC; (d) Digested sludge, 60 min HTC; (e) Dewatered
sludge, 30 min HTC—note 190 ◦ C Fixed Carbon (FC) and Volatile Matter (VM) data points overlap; (f)
Dewatered sludge, 60 min HTC.
This behavior is echoed by the ultimate analysis, whereby HTC temperature has a greater impact
on organic element composition than time (Figure 3; Figure 4; Table 2; data of Table 2 plotted in Figure S5
in Supplementary Materials). As expected, the biological transformations of the primary sludge lead
to overall lower oxygen and carbon contents of the raw digested and dewatered samples [56]. Figure 3
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reports the percentage change in content of atomic species C, H, N, and O (all data on a dry basis)
due to HTC, in respect to the raw biomasses. As shown in Figure 3, in general the weight percent of
the organic elements decrease upon carbonization of the sludge samples, the balance made up by an
increasing (relative) inorganic content. The elemental carbon contents for the thickened 190 ◦ C 30 min
and 60 min and all dewatered samples remain constant within statistical significance. Interestingly,
the relative percent changes of C, H, and O were fairly minimal for the thickened sludge carbonized at
190 ◦ C and 220 ◦ C, suggesting minimal decarboxylation and dehydration, both of which would lower
the O:C and H:C ratios, respectively [57]. However, this is not to imply a stagnant system; for the
thickened (and indeed all sludge samples) the nitrogen content of the solids decreases considerably
upon even mild carbonization, ranging from hydrochars with 40 wt% to those with 80 wt% lower N
content than their raw counterparts (Figure 3). This loss of nitrogen supports the hypothesis that there
is significant hydrolysis of fat and protein components present in the sludge. The organic nitrogen in
the process liquid tends to decrease by 15–85 wt% upon carbonization of all samples. The ammonia
nitrogen present in the liquid varies in a certain range, without any clear trend with time or temperature,
as shown in Table 1. Given the substantial elemental decrease in N of the hydrochar, and liquid-phase
organic nitrogen upon carbonization, closure of a mass balance would suggest either production of
nitrogen gases (N2 , NOx ) or formation of nitrate or nitrite in the liquid phase, which could precipitate
out as salts onto the hydrochar. As reported by Kruse and co-workers, this concentration would be too
low to detect with N content measurements [58].
Figure 3. Changes in ultimate analysis as a result of hydrothermal carbonization: (a) Thickened sludge,
30 min HTC; (b) Thickened sludge, 60 min HTC; (c) Digested sludge, 30 min HTC; (d) Digested sludge,
60 min HTC; (e) Dewatered sludge, 30 min HTC; (f) Dewatered sludge, 60 min HTC.
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Figure 4. Van Krevelen diagram of raw and hydrothermally carbonized sludge samples with:
(a) all samples; (b) thickened sludge; (c) dewatered sludge; (d) digested sludge.
The carbon and fixed carbon values reported in Table 2 and the trends of the same variables
shown in Figures 2 and 3 testify to the peculiarity of these kinds of substrates which behave differently
during HTC in respect to the vast majority of the other biomasses. While HTC applied to agro-waste,
lignocellulosic feedstock, organic fraction of municipal solid waste, or compost [20,45,53,59,60] results
in an increase in the values of C and FC, this is not the case for the majority of the sludge samples
here investigated. The FC content decreases after HTC for thickened and digested sludges (Figure 2).
The C content in the hydrochars is equal to or lower than C content in the raw sludges (Figure 3).
This apparently strange behavior depends on the very high ash content of the sludge samples and
was also previously reported in the literature [31,57,61]: in all these cases, the C and FC contents were
expressed on a dry basis. Reverse C and FC trends were reported when the data was expressed on a
dry ash free (daf) basis [23]. Here, on a daf basis, thickened and dewatered sludge increase their C
content after HTC, and this applies to the digestate treated at the highest HTC temperature of 250 ◦ C,
too; FC data, conversely, even on a daf basis, remain still lower in the hydrochars in respect to the
parent biomasses. To summarize, the organics in the sludge carbonized as should be expected in an
HTC process: the increase in C content is evident when the basis of calculation is represented by the
organics themselves (i.e., data on a daf basis), and the HTC was sufficiently severe. On a dry basis,
conversely, the relative increase in ash content often prevails over the relative increase in C, as recently
also discussed by Ferrentino et al. [62].
3.2. Distribution of Nutrients and Inorganics: Potential for Use as Soil Amendment
As shown in Table 1, the total phosphorous concentrated in the solid hydrochar
(all samples/processing conditions) from 5 wt% in the raw samples to up to 10 wt% in the carbonized
samples, with the thickened and dewatered 250 ◦ C 30 min and 60 min samples having the highest
amounts. The thickened sludge (all times/temperatures) showed lower organic nitrogen concentrations
in the liquid phase, suggesting it remains in the solid phase or exits as a gas, as mentioned previously.
This, coupled with the higher FC and VM contents of the thickened and dewatered hydrochars,
suggests they would make better soil amendments than the digested sludge hydrochars [63–65].
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Thermally treated biomasses tend to show enhanced P fertilizer values as a result of various
mechanisms, including structural surface changes and improved association of P to inorganics such
as Mg, Ca, and Al [66]. In the present work, the type of sludge sample had a larger impact on the
retention and concentration of these nutrients than the carbonization conditions. As shown in Figure 5,
the dewatered samples had higher overall Al concentrations—from 4 mgAl /gsludge for the raw sample
as compared to ~ 2 mgAl /gsludge for the thickened and digested raw samples. Carbonization at 220
and 250 ◦ C for both 30 min and 60 min doubled all of these concentrations, to 8 mgAl /gsludge for the
carbonized dewatered sample and ~ 4 mgAl /gsludge for the others. Conversely, the digested sludge
had almost twice the concentration of magnesium than the thickened or dewatered samples (which
again almost doubled upon carbonization at 220 ◦ C and 250 ◦ C). The calcium concentration was quite
similar for all sludge samples at 23, 33, and 28 mgCa /gsludge , for the thickened, digested, and dewatered
raw samples, respectively. Upon carbonization at 250 ◦ C for 30 min, the Ca content increased by over
100% for the thickened sample but only by 39% and 43% for the digested and dewatered raw samples,
respectively. While soil incubation studies are beyond the scope of the present work, prior work by
Thomsen and co-workers [66] suggests that the more heavily oxidized hydrochar samples (e.g., those
that released more CO2 and thus had higher gas yield) containing more Mg, Ca, and Al would have
a higher P availability. This corresponds to the digested 250 ◦ C 60 min and dewatered 220 ◦ C and
250 ◦ C for 30 min and 60 min samples. Future work will investigate the degree to which hydrothermal
carbonization plays a role in P plant availability, as well as the impact of HTC processing conditions
itself on the volatilization and re-condensation of P species on the hydrochar surfaces.
Figure 5. Impact of hydrothermal carbonization on nutrient and heavy metals concentrations for:
(a) Al; (b) Ca; (c) Mg; (d) K; (e) Ag; (f) V; (g) Cr; (h) Ni; (i) Co; (j) Mo; (k) As; (l) Pb.
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The concentrations of a series of additional inorganic elements in the sludges and hydrochars were
measured. Figure 5 shows a representative set of these elements (all data available in Supplementary
Materials: Tables S1 and S2, Figures S6 and S7). Silver was included in the analysis, given its
increasing prevalence in consumer materials as an incorporated nanomaterial and resulting detection
in wastewater treatment systems [67]. Prior work indicates that silver will more likely accumulate
in the biosolids than in the WWTP effluent [68]. Here, considerably higher levels of silver in the
digested sludge are found as compared to the thickened or dewatered sludge, suggesting that the
digestion indeed concentrates the silver in the biosolid, but that the dewatering process shifts the
silver to the liquid phase. The silver concentration in the digested hydrochar decreases with increasing
carbonization. Both of these indicate that the silver is in an easily mobile state in the digested sludge,
equilibrating with its aqueous phase to lower solid concentration.
Arsenic and vanadium were included in this analysis given their high prevalence in Italian
drinking water sources; the acceptable limit for arsenic in the Trentino-Alto Adige region increases
to 50 μg L−1 over the nationwide 10 μg L−1 limit due to natural lithology [69]. As seen in Figure 5,
the arsenic concentrations in the solid samples decreased with increasing harshness for the thickened
and digested samples (with the exception of the 190 ◦ C and 250 ◦ C, 60 min digested samples). All other
hydrochars had arsenic concentrations below 2 μg g−1 . The International Biochar Initiative (IBI) [70]
suggests an acceptable range for As in biochars of between 13 and 100 μg g−1 if they are to be applied
as a soil amendment.
In Sicily, concentrations of V in drinking water sources are routinely above E.U. and U.S. maximum
contaminant levels (MCLs) due to the underlying geology [71–73]. As such, it is important to ensure
that concentrations of these metals were below MCLs before considering the potential for hydrochars to
be land-applied, which could exacerbate the metal contamination issue. The vanadium concentration
was slightly increased upon carbonization, but never exceeded 10 μgg−1 ; the MCL for drinking water
in Italy is 50 μgL−1 . V is known to co-precipitate with iron (III) [74]; while the oxidation states
are not known here, the concentrations of iron in all solids exceeded 2 mgg−1 (therefore higher by
several orders of magnitude), such that it is possible that V is present in the hydrochars in an iron
(hydr)oxide precipitate.
As shown in Figure 5, the concentrations of chromium, cobalt, nickel, molybdenum, and lead
(and a series of additional inorganics, as given in SI) are only modestly affected by carbonization and
sludge withdrawal point. The cobalt concentration of the digested sludge was notably higher than
the thickened or dewatered, but upon carbonization reached the same levels as the other samples of
hydrochars, all at less than 3 μgg−1 . The concentrations of all of these metals are below IBI maximum
allowable thresholds [70], making them reasonable candidates for use as soil amendments on the basis
of heavy metal content.
3.3. Energy Content and Oxidative Reactivity: Potential for Use as Solid Fuel
As Table 2 shows, the solid hydrochars have similar higher heating values to their raw counterparts.
In this case, HTC has not substantially improved the “energy density” of the solid fuel. However,
HTC does enable a more efficient solid–liquid separation and dewaterability. For the raw dewatered
sludge, CST was not complete after 60 min, while it was complete for the 190 ◦ C 60 min hydrochar
after only 380 s. With an increase in HTC temperature, CST was 209 and 90 s at 220 ◦ C and 250 ◦ C
(60 min), respectively. Images of the CST trials are available in Supplementary Materials Figure S8.
This improved dewaterability demonstrates a reduction of volume for transport of the solid waste and
reduced moisture content for potential combustion applications.
Figure 6 plots the DTG curves of the hydrochar samples produced at each of the three carbonization
temperatures at 30 min, alongside an Illinois No. 6 coal sample. As can be seen, the hydrochar
sludge samples are considerably more reactive than the coal sample. Their peak DTG temperatures
(highest conversion rates) occur at hundreds of degrees less than the coal sample and at higher
conversion rates. The highest peak mass loss rates occur for all three hydrochars produced from
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the thickened sludge, prior to any anaerobic digestion. Post-digestion, while the shape of the DTG
curves changes, the peak rates are quite similar for both the thickened and dewatered sludge. For all
three samples, the 190 ◦ C carbonized hydrochars display the highest reactivity compared to the other
HTC temperatures. Especially at such mild conditions, HTC does not significantly carbonize the
sample—oftentimes, the original materials microstructure is preserved, whereas higher temperatures
lead to a more complete destruction of the carbon matrix [53,75].
Figure 6. Derivative thermogravimetric curves of oxidation: (a) thickened sludge and hydrochars;
(b) digested sludge and hydrochars; (c) dewatered sludge and hydrochars, produced at 30 min alongside
Illinois No 6. Coal.
Given the relatively high reactivity of any of the sludge hydrochars, it may be difficult to combust
them for electricity generation in current boilers designed for solid fuels such as coal [76]. While the
higher heating values of especially thickened sludge (18–21 MJ kg−1 ) are suitable for such combustion
schemes, their lower ignition and peak reactivity temperatures are considerably lower than that of
most bituminous coals, and therefore may lead to loss of efficiency in boilers [77]. That, combined with
the higher ash content that could result in slagging and fouling, suggests that the sludge hydrochars
may perform better in co-combustion scenarios [78].
It was previously shown that blending biofuels with similar characteristics at ratios less than 20 wt%
with coal mitigates fuel segregation and efficiency loss issues while increasing the share of renewables
in energy generation portfolios [48,49,76]. Recent work in the literature suggests that hydrochars can
be co-combusted with a variety of coals in economically, environmentally, and energetically viable
schemes in existing infrastructure [79–81] and may even improve the emissions profile at optimized
blending ratios [82]. It was recently demonstrated that hydrochars with similar reactivities can be
oxidized with Illinois No. 6 coal at ratios of 10 wt% hydrochar, balance coal, without causing significant
fuel segregation [83]. In summation, the high reactivity and ash content (though high HHV) of the
thickened and dewatered hydrochars temper enthusiasm for their use as a combustible fuel. The low
HHV of the digested sludge—below low-rank coals—makes it difficult to envision a combustion
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scenario where this would be a valuable solid fuel. As such, the potential for using sludge-based
hydrochars as a drop-in solid fuel is likely minimal, though this could be accomplished without the
need for anaerobic digestion of the sludge if used in a co-fired fuel scenario.
3.4. Further Considerations

This work examined the impact of WWTP withdrawal point and hydrothermal carbonization
conditions on resulting hydrochar properties. Table S3 in Supplementary Materials provides a summary
of the overall results discussed. While there is considerable potential to use HTC to convert sewage
sludge to renewable fuels and/or use the hydrochars for nutrient recovery redistribution, several
questions about the feasibility of implementing such a process remain unanswered.
One question is what to do with the process water remaining after treatment, which contains
unreacted feedstock and/or chemical intermediates that are potentially hazardous [84]. While this
is beyond the scope of the present work, others have previously demonstrated several potential
management options. Process liquors remaining after hydrothermal treatments have been shown to
be suitable feedstocks for aerobic, anoxic, and anaerobic processes [85–87]. The experimental data
of the present investigation testify that RBCOD (readily biodegradable COD) for HTC performed
at 190 ◦ C reached values above 85% of total COD, while increasing the temperature led to values
below 15 % at 250 ◦ C. While wet air oxidation liquors have shown some inhibitory behaviors for
strictly anaerobic treatments [86], this has not been the case for some studies of HTC liquors [87,88],
although others suggest methanogenesis inhibition at high inoculum concentrations (>25 gCOD L−1 ) [89].
As demonstrated by Qiao and co-workers [90], HTC process water may actually increase the efficiency
of the solid hydrolysis step, a rate-limiting step in the digestion process [91,92], and enhance methane
production in the digester [93]. The use of nitrates as oxidants can catalyze COD and dissolved organic
carbon removal [94], and, as it was recently demonstrated, hydrochars themselves can be used to
enhance anaerobic digestion [95].
Second, the fate of some heavy metals during HTC, especially Cu and Cr, may complicate the
use of these materials as a soil amendment, as successive WWT and carbonization concentrates them
within the hydrochar. While it was not found here that heavy metal concentrations were above
recommended IBI limits in the hydrochars, the concentrations of heavy metals in wastewater solids
and effluents vary widely across the globe and can pose health risks in certain areas [96]. To address
this potential concern, Shi and co-workers [97] demonstrated that Cd in sludge hydrochars can be
immobilized by the synergistic nature of apatite P present in the chars and addition of hydroxyapatite.
However, as both acid and alkaline leaching have been shown to dissolve phosphate in sludges and
sludge ashes [98], the long-term stability of the Cd immobilized by the method of hydroxyapatite
addition is not clear. Prior work by Yoshizaki and Tomida [99] demonstrated that such heavy metals
could be removed by phosphoric acid and hydrogen peroxide for downstream reuse and recovery.
Their method had enhanced recovery and was more environmentally and economically viable than
treatment with hydrochloric acid or sulfuric acid, opening a potential pathway for extraction of the
metals from hydrochars. Such treatment would likely act as a porogen to increase the surface area of
the hydrochars [100], increasing their ability to retain water and slow-release nutrients when used as
a solid amendment [101], and may open up possibilities for conversion of the materials to activated
carbons for use in water treatment, battery electrodes, and other high-value materials [102–105].
4. Conclusions
The present study probed the impact of hydrothermal processing conditions and sewage sludge
withdrawal point on resulting hydrochars. The hydrothermal carbonization (HTC) of sludge proceeds
similarly to many other wet biomasses; as harshness (time and temperature) of the process increases,
the solid yield decreases, the ash (inorganic) content increases, total COD decreases but soluble COD
increases, and solid pH decreases. However, there are distinct differences between the hydrochars
produced from primary (thickened) versus secondary (digested and dewatered) sludge. Thickened
46
Energies 2020, 13, 2890
sludge carbonized at moderate conditions (220 ◦ C, 30 min) produced the most viable solid fuel with
the highest HHV, moderate ash content, and high volatile matter content. However, with O:C and
H:C ratios higher than typical bituminous coals of similar heating content, the thermal reactivity of
the hydrochar was significantly higher than coals typically combusted. This suggests that sludge
hydrochars could be co-fired with coal but are not ideal solid fuels. On the other hand, hydrochars
produced from secondary sludge are more viable as potential soil amendments. The carbonized
digested sludges show relatively neutral pH, low COD, and enhanced phosphorous, along with
enhanced Ca, Mg, and Al concentrations to help mobilize P. Their heavy metal composition is well
below International Biochar Initiative standards, though the elemental oxygen content and lower
volatile matter content warrant future inquiry into this pathway.
Supplementary Materials: The following are available online at http://www.mdpi.com/1996-1073/13/11/2890/s1,

Figure S1: Product distribution among solid, gas and liquid (by difference) phases following hydrothermal
carbonization of three sludge samples, Figure S2: Impact of hydrothermal carbonization on total COD (top)
and soluble COD (bottom) of three sludge samples, Figure S3: pH of raw and hydrothermally carbonized
sludge samples, Figure S4: Proximate analysis of hydrothermally carbonized sludge samples with black circles
indicating fixed carbon, red squares are volatile matter, and blue plus symbols are ash content (a: Thickened
sludge, 30 min HTC; b: Thickened sludge, 60 min HTC; c: Digested sludge, 30 min HTC; d: Digested sludge,
60 min HTC; e: Dewatered sludge, 30 min HTC; f: Dewatered sludge, 60 min HTC), Figure S5: Ultimate analysis
of hydrothermally carbonized sludge samples, Figure S6: Inorganic element distribution in raw sludge samples
with: a high concentrations and b: low concentrations; error bars indicate 95% confidence interval, FigureS7:
Inorganic elements as a function of sludge sample and carbonization conditions, Figure S8: Visual evidence of
hydrochar dewaterability, Table S1: ICP-OES analysis of inorganics present in three sludge feedstocks, Table S2:
ICP-OES analysis of inorganics present in hydrothermally carbonized sludge samples, Table S3: Summary of
observations of sludge hydrochars.
Author Contributions: Conceptualization, J.G., G.A. and L.F.; methodology, F.M., J.G., G.A. and L.F.; validation,
F.M., M.V. and T.M.; formal analysis, F.M., J.G., T.M. and M.V.; investigation, F.M.; resources, J.G., G.A. and L.F.;
data curation, F.M., J.G. and M.V.; writing—original draft preparation, F.M. and J.G.; writing—review and editing,
J.G., M.V. and L.F.; visualization, F.M. and J.G.; supervision, G.A. and L.F.; project administration, G.A. and L.F.;
funding acquisition, G.A. and L.F. All authors have read and agreed to the published version of the manuscript.
Funding: This work was partially supported by Atzwanger Spa http://www.atzwanger.net/.
Acknowledgments: The authors appreciate the help of Lihui Gao and Giulia Ischia in running the
thermogravimetric analysis and of Fabio Valentinuzzi and Stefano Cesco for inductively coupled plasma-optical
emission spectroscopy. J. Goldfarb acknowledges support of the U.S.-Italy Fulbright Commission.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design of the
study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to
publish the results.
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sludge-based biochar for the adsorption of methylene blue from aqueous solutions. J. Mol. Liq. 2014, 198,
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52
energies
Article
Experimental and Computational Evaluation of
Heavy Metal Cation Adsorption for Molecular Design
of Hydrothermal Char
Louise Delahaye 1,† , John Thomas Hobson 1,† , Matthew Peter Rando 1 , Brenna Sweeney 1 ,
Avery Bernard Brown 1 , Geoffrey Allen Tompsett 1 , Ayten Ates 2 , N. Aaron Deskins 1 and
Michael Thomas Timko 1, *
1 Department of Chemical Engineering, Worcester Polytechnic Institute, Worcester, MA 01609, USA;
lcdelahaye@wpi.edu (L.D.); jthobson@wpi.edu (J.T.H.); mprando@wpi.edu (M.P.R.); bes117@pitt.edu (B.S.);
abbrown@wpi.edu (A.B.B.); gtompsett@wpi.edu (G.A.T.); nadeskins@wpi.edu (N.A.D.)
2 Department of Chemical Engineering, Engineering Faculty, Sivas Cumhuriyet University,
58140 Sivas, Turkey; aytates@gmail.com
* Correspondence: mttimko@wpi.edu
† These authors contributed equally to this work.
Abstract: A model hydrochar was synthesized from glucose at 180 ◦ C and its Cu(II) sorption
capacity was studied experimentally and computationally as an example of molecular-level adsorbent
design. The sorption capacity of the glucose hydrochar was less than detection limits (3 mg g−1 ) and
increased significantly with simple alkali treatments with hydroxide and carbonate salts of K and
Na. Sorption capacity depended on the salt used for alkali treatment, with hydroxides leading to
greater improvement than carbonates and K+ more than Na+ . Subsequent zeta potential and infrared
spectroscopy analysis implicated the importance of electrostatic interactions in Cu(II) sorption to the
hydrochar surface. Computational modeling using Density Functional Theory (DFT) rationalized
the binding as electrostatic interactions with carboxylate groups; similarly, DFT calculations were
consistent with the finding that K+ was more effective than Na+ at activating the hydrochar.
Based on this finding, custom-synthesized hydrochars were synthesized from glucose-acrylic acid
and glucose-vinyl sulfonic acid precursors, with subsequent improvements in Cu(II) adsorption
capacity. The performance of these hydrochars was compared with ion exchange resins, with the
finding that Cu(II)-binding site stoichiometry is superior in the hydrochars compared with the resins,
offering potential for future improvements in hydrochar design.
Keywords: hydrochar; alkali treatment; copper ions; adsorption; computational
1. Introduction
According to the World Health Organization (WHO), approximately 785 million people lack access
to clean drinking water, mainly in poor countries [1], but also in some rural and even highly urbanized
areas [2] in the developed world. Heavy metal contamination of the water supply is a persistent
problem that dates back to antiquity [3], and some researchers speculate that lead contamination of
the water supply may have played a role in the downfall of the Roman empire [3]. More recently,
Fernández-Luqueño et al. [4] summarized the health effects of heavy metals, listing their contributions
to disease ranging from cancer to lung failure. Despite widespread acknowledgement of these negative
human health outcomes, providing uniform access to drinking water free of heavy metal contamination
has proven remarkably difficult to achieve, as evidenced by recent widely reported examples [2].
Different technologies have been developed to remove heavy metals from water [5] including
precipitation [5–7], sedimentation [8], flotation [8,9], membrane processes [8,10–12], electrochemical
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Energies 2020, 13, 4203
processes [13–15], adsorption [16,17], and ion exchange [18,19]. Most of these technologies are
either costly, wasteful, reliant on non-renewable resources, energy inefficient, or unable to achieve
sufficiently low levels of metal concentration on their own. Of the available options, adsorption and
the kindred technique of ion exchange are energy efficient and capable of achieving suitably low
metal concentrations [20]. However, commercial adsorbents and ion exchange resins are derived
from non-renewable resources, either petrochemicals or coal, meaning that their use has associated
negative environmental impacts, creating a tradeoff between clean drinking water and mitigating
climate change [21]. Accordingly, development of renewable, cost-effective, and high-capacity metal
adsorbates has potential to greatly expand access to clean drinking water while minimizing other
negative environmental impacts [22,23].
Recently, pyrolysis biochar has emerged as a renewable sorbent for heavy metal removal [24,25].
Unlike most activated carbons, which are produced from coal, pyrolysis biochar is produced from
biomass or agricultural wastes [26]. In some cases, heavy metal capacity on biochar can reach
40 mg g−1 , which is comparable with activated carbons (20–80 mg g−1 ) [25] or ion exchange resin
capacity (20–30 mg g−1 ) [25]. Surface precipitation and electrostatic interactions are thought to be
the key adsorption mechanisms onto biochar, and abundant oxygenated functional groups (OFG)
are associated with effective cation adsorption [27,28]. Unfortunately, pyrolysis at typical conditions
(>400 ◦ C) tends to be ineffective for OFG formation, meaning that biochar must usually be activated to
increase its adsorption capacity [29]. Various activation procedures can increase the sorption capacity
of biochar, but only by adding cost, energy use, or waste generation [30]. Lastly, pyrolysis is performed
in the vapor phase and requires a dry feedstock, negatively impacting the process energy balance for
utilization of abundant wet wastes [31,32].
Hydrothermal carbonization (HTC) [33–35] of carbon-rich feeds, including carbohydrates, biomass,
and food waste, at moderate temperature (130–250 ◦ C) and autogenous pressures is a versatile,
low-energy, and renewable way to produce carbon-rich materials with abundant OFGs that are
known as hydrothermal chars (hydrochars) [36,37]. Possibly due to the abundance of OFGs present in
hydrochars, they have greater metal sorption capacity than most pyrolysis biochars, making them
especially attractive for drinking water purification [5,38,39]. For example, Regmi et al. [33] reported a
hydrochar with greater Cu(II) sorption capacity than conventional activated carbon (4.8 compared
with 1.8 mg g−1 ) [39]. Similarly, HTC compatibility with wet feeds eliminates the need for drying,
benefiting process-level energy balance especially for agricultural and food waste streams [40,41].
Although HTC is a promising technology, process costs and uncertainties must be reduced to
de-risk further investment [42]. Similarly, HTC can benefit by maximizing its value, which in the
case of sorbent manufacture, can be accomplished by maximizing hydrochar sorption capacity [16].
Accordingly, a persistent mystery in the field of hydrochar sorption is the high capacity that the material
has for metal cations despite its relatively low (<10 m2 g−1 ) measurable surface area. For this reason,
many reports describe methods to increase hydrochar surface area [29,37,43]. Unfortunately, hydrochar
activation to increase surface area again produces wastes and requires energy; moreover, the resulting
capacity of the activated material often decreases on a per area basis; for example, Jain et al. [44]
reported that the phenol capacity of activated carbon produced from hydrochar decreased with
increasing surface area, from 0.16 to 0.13 mg g−1 [16].
While pyrolytic treatment and various chemicals can increase hydrochar sorption capacity,
immersion in an alkali solution at room temperature reportedly increases OFG abundance and heavy
metal adsorption capacity with minimal energy requirements while generating minimal amounts of
waste [28,33,37]. The mechanism of the alkali-treatment promotion effect is not clear since mild alkali
treatment does not increase hydrochar surface area [45], and the conditions are not sufficient to make
or break covalent bonds. Moreover, alkali treatment is sometimes reported as a necessary step for
hydrochar to exhibit any heavy metal sorption capacity [29,37], while for others, alkali treatment is not
reported [33]. Understanding alkali treatment is, therefore, one goal of this work.
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Complicating analysis further, hydrochar OFG abundance, and sorption capacity vary depending
on the properties of the feed and reaction conditions. Guo et al. [46,47] have shown that, starting with a
lignocellulosic raw material, a hydrochar can be produced with greater OFG abundance than produced
from carbohydrate precursors. For example, HTC from wood (initially consisting of 52.7 wt% C)
produces a hydrochar with 77 wt% C [48], whereas the carbon content of hydrochar produced from
glucose typically contains 53–62 wt% C [49]. Hydrochar OFG abundance tends to decrease with
increasing reaction conditions such as reaction time, temperature, and water-to-biomass ratio [46–48].
For many feeds [50–54], HTC can be performed over the temperature range from 160–180 ◦ C and
at reaction times <12 h to promote formation of OFGs. More aggressive conditions (≥200 ◦ C) are
preferred for other applications [55].
The relationship between feed properties, reaction conditions, and sorption capacities provides
an opportunity to synthesize a hydrochar tailor-made for a specific application, such as heavy metal
adsorption. For example, Demir-Cakan et al. [56] reported that co-HTC of glucose and acrylic acid
produced a hydrochar with exceptionally high OFG abundance; the resulting materials exhibited
sorption capacities up to 350 mg g−1 for Pb(II) and 90 mg g−1 for Cd(II). In comparison, Xue et al. [16]
reported peanut-hull based hydrochar sorption capacity for Cd(II) as 12.38 mg g−1 .
Ideally, hydrochars could be designed for a specific application at the molecular level.
Computational methods have proven effective at understanding sorption mechanisms and thereby
enabling the molecular level design of metal-organic frameworks for sorption of perfluoroalkyl
substances [57], nanopores for CO2 adsorption [58], and ion exchange resins and activated carbon
for heavy metal sorption [59,60]. Density Functional Theory (DFT) is an especially valuable tool for
studying the geometry and energetics of sorbate binding to the active site, provided that molecular
structures are known that can be used as targets of rational design. Unfortunately, the structural
models of hydrochar have only recently converged [61–63], making attempts at molecular level design
or computational modeling of sorbate-sorbent binding difficult until now.
Recent work by Brown et al. [61] reconciled several disparate models proposed for the structure of
hydrochar synthesized from glucose. Previous models inferred from infrared spectroscopy and Raman
microscopy [62,64] indicated that hydrochar structures resembled activated carbon and consisted of
fused aromatic cores, comprised of many aromatic rings and with OFGs present primarily as side chains.
In contrast, solid-state Nuclear Magnetic Resonance (NMR) [65] and Near-Edge X-ray Absorption
Fine Structure (NEXAFS) [63] indicate a structure consisting primarily of individual furan and arene
groups, polymerized via short alkyl chains, and decorated with OFGs. Brown et al. [61] recognized that
previously reported Raman spectra of hydrochar contained artifacts due to laser-induced pyrolysis of
the hydrochar material, causing it to collapse into a condensed aromatic structure. DFT simulation of
hydrochar Raman vibrations [61] then indicated that artifact-free Raman spectra were indeed consistent
with the furan-arene polymer previously inferred from NMR and NEXAFS [62–64,66]. This paves the
way for a molecular-level study of metal binding to hydrochar as a furan-rich polymer, thereby enabling
rational design of hydrochar.
The objective of this work was molecular-level design of a hydrochar adsorbent using both
experiments and simulation. To focus on generalizable mechanisms, we studied a model hydrochar
synthesized from glucose for sorption of a model heavy metal, Cu(II) cations. Sorption capacity
was studied before and after alkali treatment and compared with capacities measured for several
activated carbon materials. Similarly, the hydrochar was characterized for OFG type and density
using Fourier transforms-infrared spectroscopy (FT-IR), solid-state titration, and zeta potential
measurement. Metal-hydrochar binding interactions and geometries were evaluated using DFT
simulations. Chars with different types and/or densities of OFGs and other metal binding groups
were custom synthesized for comparison with glucose hydrochar. The experimental and simulation
results described here establish a new method for the rational design of hydrochar sorbents at the
molecular level.
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2.1. Materials
All reagents were analytical grade, including: D-(+)-glucose (≥99.5%-Sigma Aldrich), acrylic acid
monomer (≥99.0%-TCI chemicals), vinyl sulfonic acid (≥99.0%-TCI Chemicals), hydrochloric acid
(0.1 M, ≥99.0%-Acros), sodium hydroxide (0.1 M, ≥95.0%), and the anhydrous salts sodium carbonate
(≥99.5%-Sigma Aldrich), sodium hydroxide (≥97.0%-EM Science), potassium carbonate (≥99.0%-Alfar
Aesar), and potassium hydroxide (≥85%-Sigma Aldrich). The carbon materials were donations from
Norit (since acquired by Cabot) and MeadWestvaco. Specific activated carbon samples included
wood-based carbons, Norit Darco® KB-G, Norit Darco® KB-WJ and Nuchar® (MeadWestvaco), and a
peat-based carbon, Norit® SX-1. Amberlyst® 15 was used in its hydrogen form and AG® 50 W-X4 in its
hydrogen form was purchased from Bio-Rad. Cu(NO3 )2 · 2.5 H2 O and elemental standards, 5% HNO3 ,
10 μg/mL were acquired from PerkinElmer. Deionized (DI) water was purified to a minimum resistivity
of 17.9 MΩ cm prior to use.
2.2. Hydrochar Synthesis

Hydrochar was prepared from a precursor solution formed by dissolving 28.152 g of D-(+)-glucose
in 100 mL of DI water. The solution was loaded into a 160 cm3 PTFE-lined, stainless-steel autoclave,
which was then placed in a room-temperature oven that was heated to 180 ◦ C at a heating rating of
approximately 10 ◦ C min−1 , held at 180 ◦ C for 8 h, before allowing to cool for 12 h. The reaction protocol
was selected to replicate those that favor OFG generation, as reported previously by Brown et al. [61]
and others [46]. After reaction, the resulting slurry was mixed first with a solution of 100 mL of ethanol
and 100 mL of water, and then filtered to remove soluble organic materials from the solid hydrochar.
The solid hydrochar was recovered by filtration and rinsed again with ethanol and water. The washing
and filtering steps were repeated twice. The hydrochar was then placed in a crucible, dried in an oven
at 65 ◦ C for 24 h, and stored in airtight vials before further analysis or use.
Functionalized hydrochars were custom synthesized by preparing a precursor solution consisting
of glucose and either acrylic acid or vinyl sulfonic acid and subjecting it to a modified HTC treatment.
For the synthesis of acrylic acid-hydrochars (AA-hydrochar), the precursor solution consisted of
10 g of glucose, 10 g of acrylic acid, and 80 g of DI water. The HTC reaction time was extended to
16 h for AA-hydrochar synthesis (at 190 ◦ C), as 8 h reaction time yielded a material that could not
be recovered by filtration [56]. For synthesis of vinyl sulfonic acid-hydrochars (VSA-hydrochar),
the precursor solution consisted of 36.1 g of glucose, 7.22 g of vinyl sulfonic acid, and 150 mL of water.
After some preliminary trials to evaluate the effects of reaction temperature and time on hydrochar
yield, the synthesis of VSA-hydrochar was performed at 190 ◦ C for 24 h to yield a solid that could be
recovered by filtration. As described previously for hydrochar, both AA-hydrochar and VSA-hydrochar
were recovered by filtration, with ethanol and water washing, and oven drying at 65 ◦ C.
Hydrochars were activated by mixing 2.0 g of the synthesized material with 500 mL of alkali
solution (2 N). The effects of alkali solutions of Na2 CO3 , K2 CO3 , NaOH, KOH were evaluated.
After several hours at room temperature, the material was recovered by filtration, and placed in DI
water where the pH was neutralized by dropwise addition of HCl (1 N) and NaOH (1 N) until the
pH stabilized. The final product was washed 3 times with DI water, dried in a 100 ◦ C oven, ground,
and stored in airtight glass vials.
2.3. Hydrochar Characterization

The surface areas of the samples were determined by N2 physisorption at 77 K on a Micromeritics
ASAP 2000 apparatus, using N2 as adsorbate. N2 physisorption on similar instruments has been reported
in more detail elsewhere [67]. Surface areas were determined using the Brunauer–Emmett–Teller (BET)
model [68]. Prior to adsorption-desorption experiments, all the samples were degassed at 120 ◦ C for
12 h.
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Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) was performed on powder
samples using a Thermo-Fisher FT-IR 6700 with DRIFTS accessory, described previously in the
literature [69]. The spectral resolution was 2 cm−1 and all samples were purged with N2 gas for 2 min
before analysis to exclude atmospheric CO2 and H2 O from the sample space. A background spectrum
was obtained prior to each measurement and results were obtained by scanning 1024 times and taking
their average. Spectra were analyzed using MagicPlot software and plotted by normalization with
the baseline.
Zeta potential measurements were determined using a zeta meter (Malvern Zetasizer-Nano-Z)
that has been previously described elsewhere [70]. For each test, 0.005 g of the solid sample was
suspended in 100 cm3 of de-ionized water containing 0.1 N NaCl followed by homogenization for
2 h in an ultrasonic bath. After ultrasonication, the aqueous suspension was equilibrated at different
pH values for 30 min. Zeta potential results are reported as the average and standard deviation of
three measurements.
The combined densities of strong and weak acid groups were determined using the Boehm
titration method, described previously in the literature [29,71,72]. In brief, a carbon sample (0.5 g) was
placed in NaHCO3 solution (20 mL, 0.1 N), agitated for 48 h, and the carbon was removed by filtration.
The resulting filtrate was degassed for at least 30 min using N2 to remove CO2 and was then titrated to
determine the acid site density of carbon-rich materials [73].
2.4. Hydrochar Adsorption Tests

For single-point Cu(II) cation adsorption tests, 0.2 g of sorbent was suspended in 10 mL of an
aqueous solution of Cu(II) (0.08 M) and placed within an high density polyethylene sample vial
(Celltreat). Initially, the supernatant liquid was clear and pale blue, a consequence of the Cu(II) present
in the mixture. The resulting slurry was agitated at room temperature using a wrist-action shaker
(Burrell) for 24 h. Preliminary tests indicated that adsorption equilibrium was reached after 12 h.
After shaking and centrifugation, the supernatant liquid remained clear and the pale blue coloration was
visibly fainter. The hydrochar was discarded and Cu(II) concentrations in the supernatant liquid were
measured using a Perkin Elmer, Nexion 350 × Inductively Coupled Plasma (ICP) spectrometer. The ICP
response was calibrated using standard solutions. Samples were diluted prior to each measurement to
ensure that the concentration fell within the pre-determined calibration range. Adsorption capacity
was then estimated using the initial (masscopper,i ) and final (masscopper,f ) Cu(II) concentrations and the
mass of sorbate (masssorbent ):
masscopper,i − masscopper,f
Adsorption Capacity mg g−1 = ∗ 1000
masssorbent
Each adsorption measurement was performed at least in duplicate and ICP concentration
measurements were performed in triplicate. Average values are reported here. Control runs were
performed in the absence of sorbent and the loss to the vial was equivalent to <1 mg g−1 of sorbent.
2.5. Computational Modeling

DFT simulations were performed to study cation-hydrochar binding energies and geometries.
The proposed hydrochar structures were modeled using DFT with the Gaussian 09 program [74] run
via WebMO [75]. All the geometries were optimized using the Becke, 3-parameter, Lee–Yang–Parr
(B3LYP) [76,77] hybrid functional, with the 6–311+G(d,p) basis set. Because the physical experiments
included a water solvent, the polarizable continuum model (PCM) [78] was chosen to implicitly include
the solvent in these calculations, assuming its dielectric constant was equal to 78. Model adsorption
reactions were modeled and compared with one another to determine their energies and relative
favorability. For each adsorption reaction, the products were hydrochar with a bound copper
atom, and the respective ion, either hydrogen, sodium, or potassium, in solution. Multiple initial
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Energies 2020, 13, 4203
configurations were studied to confirm that the final geometry captured a global minimum, rather than
a local one.
3. Results and Discussion

The objective of this study development of rational methods to design hydrochar for heavy metal
adsorption at the molecular level [79]. The study consists of several components: (1) measurements of
sorption capacity of glucose hydrochar and comparison with activated carbon; (2) characterization
and DFT modeling of glucose hydrochar; (3) custom-synthesis of hydrochars with tailored heavy
metal capacity.
3.1. Glucose Hydrochar Sorption Capacity and Characterization

As a starting point, hydrochar was synthesized from a glucose precursor solution. The base
structure of glucose hydrochar was recently reconciled between several models [61–63], with the
finding that it consists of a furan-rich polymer decorated with OFG groups. Accordingly, and following
previous reports, we hypothesized that the OFG groups would encourage heavy metal sorption.
Unfortunately, glucose hydrochar exhibited negligible Cu(II) sorption capacity, <3 mg g−1 , as shown in
Table 1. The negligible Cu(II) capacity measured for glucose hydrochar seemingly contradicted previous
literature descriptions of hydrochar absorption capacity [80–82], thus, motivating further examination.
Table 1. Adsorption Capacity and Surface Area of Hydrochar and Activated Carbon. BET =
Brunauer–Emmett–Teller model.
Material Post Treatment Adsorption Capacity (mg Cu g−1 ) BET Surface Area (m2 g−1 )
None <3
Na2 CO3 20.0 ± 0.4
Glucose Hydrochar K2 CO3 29 ±5 4±2
NaOH 35 ±4
KOH 40 ±4
None 19 ±4
Norit® SX1 KOH 21 ±6
800 ± 100
None 29 ±3
Nuchar® KOH 11 ±7
1700 ± 200
Activated Carbons
None 9 ±0.1
Darco® KB-G KOH 5 ±0.8
1500 ± 100
Darco® None 6 ±0.2
1600 ± 100
KB-WJ KOH 21 ±4
Sun et al. [37] reported that alkali treatment increased the sorption capacity of hydrochar by
2–3 times, motivating the study of alkali treatment in the current study. As shown in Table 1,
alkali treatment greatly increased the Cu(II) capacity, by at least an order of magnitude compared with
the original glucose hydrochar. Several different bases were evaluated, with the finding that strong
bases (hydroxides) outperformed weak ones (carbonates) and that bases featuring the potassium cation
outperformed ones possessing sodium.
We compared the capacity of alkali-activated glucose hydrochar with several different activated
carbons (Table 1), selected to cover a range of properties [83]. Interestingly, the activated carbons
exhibited much greater sorption capacity than glucose hydrochar without activation, but less capacity
than their alkali-activated forms. Alkali treatment was evaluated for two of the activated carbons,
and it was found that the treatment either had no effect (Norit® SX1) or even negative effect (Nuchar® )
on sorption capacity. The different response to alkali treatment observed for activated carbon and
hydrochar clearly points to differences in the mechanism that must be understood for molecular-level
hydrochar design.
To understand the adsorption results presented in Table 1, surface areas were measured using N2
sorption and the BET isotherm fitting method. Consistent with previous reports [29,37,43], the measured
BET surface area of hydrochar was <10 m2 g−1 . Alkali treatment had no effect on the measured
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hydrochar surface area, allowing us to reject the hypothesis that the effect of the treatment was to
open up the hydrochar pore structure [82,84]. Similarly, consistent with previous reports [83], the BET
surface areas of the activated carbons were >800 m2 g−1 and not affected by the dilute alkali treatment.
Accordingly, while the capacity of glucose hydrochar is comparable to activated carbon on a mass
basis, on a surface area basis the capacity is orders of magnitudes greater. This observation clearly
points to a specific hydrochar-sorbate interaction that can be engineered to maximize adsorption.
The strongest common sorbate-hydrochar interaction is electrostatic [85], which can be understood
as the interaction between the positively charged metal cation and negatively charged functional
groups on the hydrochar surface. Accordingly, as a way to understand and quantify hydrochar surface
charge, we measured hydrochar zeta potential before and after alkali activation and over a wide
range of pH, from 2–12. Figure 1 presents the results, showing that zeta potential of alkali activated
hydrochar was much more negative in the pH range of interest (pH < 7) than the parent hydrochar.
Under strongly alkali pH, the zeta potential of the parent and the alkali treated material are the same
to within the limits of experimental uncertainty, which is consistent with expectations given that the
alkali treatment is simply immersion in an alkali solution with pH > 9.
Figure 1. Comparison of zeta potential of different sorbent materials as a function of pH.
Zeta potential measurements support electrostatic interaction as the primary basis of cation
sorption to the hydrochar, providing a valuable clue for rational design. For further comparison,
we measured the zeta potential of one of the aforementioned activated carbons (Norit® SX-1) and
include these data in Figure 1. The zeta potential of the activated carbon was much less negative than
glucose hydrochar, even before alkali treatment. Again, this points to a qualitatively different sorption
mechanism for activated carbon compared to hydrochar, with cation sorption to activated carbon likely
occurring due to cation-π interactions, which appear to be less important than electrostatic interactions
for cation binding to hydrochar [86].
Rational sorbent design requires understanding the molecular binding sites. Figure 1 clearly
implicates the importance of groups that ionize on alkali treatment, which naturally suggests carboxylic
acids, acid anhydrides, and strongly acidic aromatic alcohols, such as phenol [16,24,73]. The fact that
strong bases were more activating than weak ones (Table 1) seems consistent with de-protonation of
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weak acids but does not provide sufficient molecular detail for sorbent design. Accordingly, glucose
hydrochar was analyzed using FT-IR for identification of ionizable OFGs. Figure 2 provides FT-IR
spectra divided into the fingerprint region, 1000–2000 cm−1 (Figure 2a) and the C−H and O−H
stretching region, 2400–4000 cm−1 (Figure 2b). Prior to alkali treatment, glucose hydrochar exhibits
bands attributable to carbonyl (1720 cm−1 ) and hydroxyl (3200–3400 cm−1 ) groups associated with
carboxylic acids. Other features at 2900, 1600, and 1200 cm−1 are attributable to C−H stretches,
arenes/furans breathing modes, and C−O stretches, respectively [65] These spectroscopic attributions
are broadly consistent with the structural models previously inferred from NMR [65], Raman [61],
and NEXAFS [62–64,66]. Interestingly, the C−H and O−H stretches are sufficiently differentiated to
suggest that carboxylic acid exists in its free, rather than dimerized, state [87].
(a) (b)
Figure 2. FT-IR spectra of glucose hydrochar as synthesized and after activation by various bases.
(a) the fingerpint region (1000–2000 cm−1 ) (b) the O−H and C−H stretch region (2500–4000 cm−1 ).
After alkali treatment, the intensities of the hydroxyl band at 3200–3400 cm−1 and carbonyl band
at 1720 cm−1 become much less intense. Simultaneously with these changes, the intensity of the band
at 1600 cm−1 increases and the feature broadens noticeably. The C−O stretch present at approximately
1200 cm−1 becomes less intense and broader after alkali treatment. The effects are more noticeable for
treatment with the hydroxides than the carbonates, consistent with their relative basicities and with
the observed effects on sorption capacity, noted in Table 1.
All of the aforementioned changes observed in the FT-IR spectra of glucose hydrochar after alkali
treatment are attributable to deprotonation of carboxylic acid groups to form carboxylates [37,88].
Specifically, deprotonation involves a shift of the main carbonyl band from approximately 1700 to
about 1600 cm−1 ; [84] a reduction of intensity of the C−O stretch at 1200 cm−1 ; and a reduction of the
intensity of the O−H stretch at 3200–3400 cm−1 . The last of these is consistent with partial removal of
the H atoms involved with O−H stretches, as expected for de-protonation. The carboxylate feature at
1600 cm−1 overlaps with the furan/arene breathing mode that is characteristic of hydrochar [61,63,89].
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The fact that alkali treated hydrochar still exhibits an O−H stretching band is consistent either with
incomplete de-protonation of acid groups or with the presence of multiple forms of O−H in the
structure (i.e., alcohol groups that are not sufficiently acidic to be deprotonated).
Since the carboxylic acid groups present in glucose hydrochar appear to be primarily in their
protonated forms (Figure 1) and since the pH of the HTC reaction mixture is about 3 [90], the pKa of
these acid groups must be greater than approximately 3–otherwise, they would be present in hydrochar
in their deprotonated forms. Alkali treatment then deprotonates these groups, resulting in formation
of the alkali carboxylate. Because hydrochar is a complex material and because localized induction
and steric effects can influence pKa [91], carboxylic acids present in hydrochar likely possess a range of
pKa’s. In fact, this assertion is supported from the broad zeta potential curve observed for glucose
hydrochar and shown in Figure 1. Treatment with carbonates may therefore deprotonate only the
strongest carboxylic acids present in hydrochar, while treatment with hydroxides deprotonates both
strong and weak carboxylic acids.
We considered the possibility of alternative ionizable groups, aside from carboxylic acid.
Treatment with hydroxide would partially deprotonate any strongly acidic alcohol groups (e.g., phenols)
present in the hydrochar structure; however, the FT-IR spectra show no direct evidence to support
the formation of phenolate ions, nor do reported structural models suggest the presence of
phenol in hydrochar [24,61,63]. Accordingly, metal-carboxylate binding appears to be the primary
cation adsorption mechanism underlying glucose hydrochar sorption, providing a clear target for
molecular simulation.
Hydrochar is thought to be composed of furan/arene polymers connected by alkyl spacers.
Mild alkali treatment is insufficient to break or form covalent bonds present in this structure [82],
which is consistent with the negligible change in surface area associated with alkali treatment
(see Table 1). That stated, Mihajlovic et al. [92] proposed that hydrolytic degradation of OFGs can
sometimes occur during alkali treatment, and re-arrangement of the hydrochar structure from its
hypothesized form would complicate attempts to model the binding site. Accordingly, we searched for
evidence of bond breaking in the spectra shown in Figure 2. Inspection of the FT-IR spectra suggests
that important hydrochar features [28,29] at 1020 cm−1 (C−OH alcohol and/alkyl-substituted ethers
groups), 1600 cm−1 (furan/arene breathing modes), and 2900–3000 cm−1 (C−H stretch) are not affected
by alkali treatment, consistent with the main effect of alkali treatment being confined to deprotonation
rather than making and/or breaking of covalent bonds. This observation permits use of published
hydrochar structural models to recreate the local environment of the metal-carboxylate binding site for
DFT simulation.
3.2. DFT Simulations of the Metal-Carboxylate Interactions

Zeta potential measurements and FT-IR analysis clearly implicate metal-carboxylate binding.
DFT simulations of the metal-carboxylate complex were performed to examine this hypothesis in more
detail. In particular, we sought to answer three questions: (1) since a metal cation should be able to
displace protons from carboxylic acid, why is alkali treatment required to activate the hydrochar?
(2) Why do potassium salts outperform sodium salts? (3) What is the geometry of the binding site?
Simulating cation-carboxylate binding requires recreating a plausible local environment.
The hydrochar molecule, pictured in Figure 3a, was created as a composite structure based on
previous literature. Titirici et al. [93] demonstrated via NMR that the majority of the aromatic
functionality of hydrochars synthesized from glucose at temperatures less than 200 ◦ C can be attributed
to furan groups. Latham et al. [63] supported this via NEXAFS while showing that carbonyl groups
are also important. The previously mentioned IR spectra also indicate the presence of carbonyl groups
and are in agreement with the model proposed by Latham et al. [63]. Accordingly, we recreated
the local adsorption environment as a furanic dimer configuration to be consistent with published
hydrochar structures [61]. The carboxylic acid/carboxylate group resides as a side chain on the alkyl
linker between adjacent furan rings, consistent with the observation using FT-IR and the importance
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of carboxylate groups inferred from sorption capacity measurements presented here. The local
environment experienced by a metal cation during adsorption also includes water solvent molecules.
Here, we recreated the water solvation effect using an implicit cavity model of the appropriate dielectric
constant (taken as 78). Future work can improve the accuracy of our calculations by including explicit
water molecules in the simulation.
D
E
F

Figure 3. Carboxylate-containing hydrochar structures optimized using Density Functional Theory

(DFT). (a) Model of the base hydrochar molecule. The different structures in (b) involve carboxylate
binding with hydrogen, potassium, and sodium, respectively, with the carboxylate, which make up
the reactants of the modeled adsorption reactions. (c) Illustrates the interaction between Cu(II) and
the carboxylate group. Estimated adsorption energies are provided as shown. Legend: carbon;
hydrogen; oxygen; potassium; sodium; copper.
We then simulated a series of possible cation-carboxylate structures, starting with the hydrochar
model shown in Figure 3a. The focus of these calculations was to answer the aforementioned questions
that focus on elucidation of trends, rather than quantitative energy estimates. We then simulated cation
binding, shown stoichiometrically in Figure 3b, by replacing either H+ , K+ , or Na+ with the Cu(II)
cation to form the final structure shown in Figure 3c.
Consistent with experimental observations (Table 1), we find that replacing H+ with Cu(II) is
energetically unfavorable, whereas replacing K+ and Na+ is energetically favorable. The simulated
energies are consistent with the observation that glucose hydrochar requires alkali treatment prior to
activation. Moreover, DFT simulations predict that replacing K+ is energetically more favorable than
replacing Na+ by 10.72 kJ mol−1 , which is consistent with the observation that KOH is a more effective
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activating salt than NaOH and K2 CO3 is more effective than Na2 CO3 . That stated, the calculated
energy difference between K+ and Na+ substitution is relatively modest, which is again consistent with
experimental observation. Note that for these reactions the cations in solution may not be properly
modeled by implicit solvation, which is why for instance the replacement of a hydrogen by Cu(II) is so
endothermic. Nonetheless the trends in cation exchange are captured by the DFT calculations.
Figure 3c shows the optimized geometry of a Cu-hydrochar structure. Here, the Cu-carboxylate
bond length is approximately 1.85 Å, slightly longer than that associated with the distance between the
proton and carboxylate group in carboxylic acid. The longer bond is consistent with the size of the
Cu(II) ion compared with the proton [37].
The DFT simulations summarized in Figure 3 explain that alkali treatment removes the proton to
activate the sorption capacity of glucose hydrochar. Physically, the proton is more tightly bonded to
the carboxylate group than the metal cations, owing to the differences in ionic radii and the strong
effect of ion-ion distance on the strength of electrostatic interactions [94]. Similarly, the differences
observed between potassium and sodium can be ascribed to their relative ionic radii.
Interestingly, alkali treatment is not always reported as a necessary step for observation of
hydrochar sorption capacity. This may be due to differences in the reaction mixture pH for different
precursors and/or the presence of alkali salts in many hydrochar starting materials [95,96]. Accordingly,
subtle differences in the reaction mixture and the composition of the precursor may decide whether
or not alkali treatment is required to activate a given hydrochar for metal adsorption. Alternatively,
the alkali step may not be uniformly reported, even when it is required. We recommend more consistent
reporting of alkali treatment and reaction mixture pH in future work in this area.
3.3. Custom-Synthesis of Hydrochar for Heavy Metal Adsorption

Experiments and DFT simulations clearly implicate the importance of metal-carboxylate
interactions in hydrochar adsorption of Cu(II). Accordingly, our next step was custom synthesis
of a hydrochar for heavy metal adsorption. Following the work of Demir-Cakan et al. [56], we elected to
synthesize a hydrochar by co-processing glucose and acrylic acid. Acrylic acid possesses a polymerizable
double bond, which can form covalent linkages with the alkyl linker groups in the hydrochar
structure, thereby increasing the density of carboxylate groups in the resulting material. We term the
resulting material acrylic acid-hydrochar, or simply AA-hydrochar. Demir-Cakan et al. [56] reported
synthesis of a series of AA-hydrochars, starting with different amounts of acrylic acid in the precursor
mixture. Here, we selected a precursor mixture with composition similar to the optimum reported by
Demir-Cakan et al. [56] as a proof of concept.
Table 2 provides the sorption capacity and surface area measurements for AA-hydrochar.
As expected from DFT simulations, without activation the Cu(II) sorption capacity of AA-hydrochar
is negligible. Interestingly, Demir-Cakan et al. [56] did not report alkali activation of their materials,
which might be attributable to their study of Pb(IV) and Cd(II) whereas we studied Cu(II) or the
aforementioned impact of subtle differences in reaction mixture pH on hydrochar protonation and
subsequent sorption capacity. Regardless, after alkali activation, sorption capacity increases by at least
an order of magnitude for the AA-hydrochar, and strong bases are again more effective than weak
bases. AA-hydrochar capacity for Cu(II) sorption is greater than that observed for standard glucose
hydrochar (50 ± 4 compared with 40 ± 4 mg g−1 ). Again, the effect is not as pronounced as reported by
Demir-Cakan et al. [56], but it is consistent with the design concept.
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Table 2. Adsorption capacity and surface area of custom-synthesized hydrochar and ion exchange resins.
Material Post Treatment Adsorption Capacity (mg Cu g−1 ) BET Surface Area (m2 g−1 )
None <3
Acrylic Na2 CO3 30 ±7
acid-hydrochar K2 CO3 26 ±6 5–10
(AA-hydrochar) NaOH 50 ±4
Hydrochars
KOH 45 ±7
Vinyl sulfonic acid
None <2
(VSA-hydrochar)
<1
NaOH 34 ±5
KOH 51 ±3
Amberlyst® None 128 ±4 53 [97]
Resins
AG® 50W-X4 None 109 ±7 <1
The effect of AA and glucose co-processing to produce hydrochar was consistent with our
expectations, but consistency does not imply confirmation and we considered alternative hypotheses.
Table 2 shows that the surface area of AA-hydrochar was similar to the glucose hydrochar, eliminating
surface area changes as a major difference between these materials. To understand further, we studied
the OFGs of AA-hydrochar using FT-IR. Figure 4 provides the FT-IR spectra obtained for AA-hydrochar
before and after KOH treatment. The FT-IR of glucose hydrochar is included in Figure 4 for direct
comparison to show that the AA-hydrochar spectrum exhibits much more intense bands associated
with carboxylic acids at 1720 (carbonyl) and 1200 cm−1 (C-O stretch) than glucose hydrochar. In fact,
the carboxylic acid bands dominate the AA-hydrochar spectrum and appear as the most prominent
features. The band at 1600 cm−1 , which is characteristic of furans and arenes, appears only as a minor,
though distinct, feature in the AA-hydrochar spectrum. In comparison, the furan/arene band is one
of the most prominent features in the glucose hydrochar spectrum. Similarly, after alkali treatment,
the carbonyl band shifts to approximately 1550 cm−1 and becomes the most prominent feature in the
AA-hydrochar spectrum. Correspondingly, the C-O stretch feature shifts and broadens. Taken together,
these observations clearly indicate that AA-hydrochar has abundant carboxylic acid groups that
deprotonate after alkali treatment.
Figure 4. FT-IR spectra of AA-hydrochar before and after KOH treatment. G-hydrochar is synthesized
entirely of glucose precursor, shown before alkali treatment. AA-hydrochar synthesized from co-feed
of acrylic acid and glucose, shown before and after alkali treatment using KOH.
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The performance of hydrochar sorbents is often compared with activated carbon [25,39]. However,
our findings indicate that hydrochar adsorption is mediated by metal-carboxylate binding interactions
that are more similar to what occurs on an ion exchange resin, rather than activated carbon. Accordingly,
we measured Cu(II) sorption capacity of two commercial ion exchange resins, Amberlyst® -15 and
AG® 50W-X4. Capacity results for these resins are provided in Table 2. Interestingly, these resins far
outperform activated carbon (Table 1) and outperform by about a factor of two the AA-hydrochar.
Moreover, the ion exchange resins did not require alkali activation, unlike the hydrochars. Since the
resins outperform hydrochar, even AA-hydrochar, we sought to understand the differences between
the resins and the hydrochar as part of our rational design approach.
An obvious potential difference between the resins and the hydrochar is surface area. Table 2
provides N2 sorption-based BET surface areas for Amberlyst® -15 and AG® 50W-X4. Interestingly,
Amberlyst® -15 exhibits much greater surface area than any of the hydrochars, which could explain its
superior performance. However, the surface area measured for AG® 50W-X4 was less than any of the
other materials (<1 m2 g−1 , the instrument detection limit), meaning that surface area considerations
alone cannot explain the performance of the resins–at least not the surface area measured by N2
sorption and estimated by BET analysis of the isotherm. In fact, the swelling behavior of ion exchange
resins has been studied carefully in water and other solvents [98–100]; swelling in the presence of water
likely opens the pore structure of AG® 50W-X4 (and possibly the other sorbents), accounting for its
sorption capacity despite negligible N2 sorption surface area. Understanding the effects of hydrochar
swelling on surface area available for cation sorption is an area that should be studied in the future.
The binding site in both Amberlyst® -15 and AG® 50W-X4 is a sulfonate group [101], whereas the
findings presented here indicate that carboxylate groups are mainly responsible for binding in glucose
hydrochar and especially AA-hydrochar. The sulfonic acid group is at least 1000× stronger than the
carboxylic acid group, meaning that this difference could explain sorption behavior and the need for
alkali activation. Accordingly, we modified the acrylic acid synthesis procedure for incorporation
of a sulfonate group into the hydrochar structure by co-processing glucose and vinyl sulfonic acid.
Like acrylic acid, vinyl sulfonic acid possesses a polymerizable double bond that can be incorporated
in the hydrochar-alkylated backbone. Unlike acrylic acid, though, vinyl sulfonic acid can introduce
a sulfonate group into the hydrochar instead of the carboxylic acid introduced by acrylic acid.
Accordingly, we term this new char vinyl sulfonic acid-hydrochar, or VSA-hydrochar.
Table 2 provides the Cu(II) cation sorption capacity of VSA-hydrochar. Interestingly, despite the
strength of the vinyl sulfonic acid precursor (pKa < 1 compared with 4.35 for acrylic acid) [98,102],
we observed negligible Cu(II) sorption capacity for VSA-hydrochar before treatment with alkali.
After treatment with KOH, the Cu(II) capacity of VSA-hydrochar increased substantially to
51 ± 3 mg g−1 . Interestingly, NaOH was much less effective at increasing Cu(II) sorption capacity than
KOH, consistent with the aforementioned trend observed and simulated for carboxylate binding.
As before, the measured BET surface area of VSA-hydrochar was in the same range as the
other hydrochars and <10 m2 g−1 . Similarly, Figure 5 shows the FT-IR spectrum of VSA-hydrochar.
Unlike carboxylic acid and carboxylate groups that have intense and well-differentiated vibrational
bands, sulfonic acid and sulfonate give rise to weak and broad bands that are not easily differentiated
from other features [103]. That stated, the FT-IR VSA-hydrochar spectrum contains bands in the range
expected for sulfonic acid (1100–1300 cm−1 ). The carboxylate/carboxylic acid bands are less intense in
VSA-hydrochar than glucose hydrochar, indicating substitution of the weak acid in AA-hydrochar for
the strong acid in VSA-hydrochar.
Cu(II)-sulfonate structures were simulated using DFT methods, similar to those previously
presented for carboxylate binding. Figure 6a shows the sulfonic acid- hydrochar geometry,
which consisted of two furan groups bonded to a sulfonic acid group. As before, binding was
simulated as an exchange of Cu(II) for H+ , K+ , and Na+ . Despite the strength of the sulfonic acid,
DFT calculations found that replacing H+ with Cu(II) was thermodynamically unfavorable, consistent
with the need to activated VSA-hydrochar with alkali. Figure 6b summarizes this result. Similarly,
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the distance of the Cu−O bonded to sulfonate (shown in Figure 6c) is 1.95 Å, somewhat greater than the
Cu−O bond in carboxylate hydrochar (1.85 Å). As before, the cations in solution may not be properly
modeled by implicit solvation, which is why some energies may be so large, despite DFT identifying
the trends in cation exchange.
Figure 5. FT-IR spectrum of VSA-hydrochar, before and after KOH treatment. Vertical lines mark the
carboxylic acid and carboxylate vibration bands. The region where sulfonic acid vibrations appear is
indicated. The spectrum of glucose hydrochar is reproduced from Figure 4 as a point of reference.
Surface area, FT-IR, and DFT simulations provide further evidence of cation-sulfonate binding
in the VSA-hydrochar, but do not explain why the performance of neither VSA-hydrochar nor
AA-hydrochar can match the commercial ion exchange resins. As a final hypothesis, we quantified
the density of surface acids present on the various sorbents, with the expectation that differences
in the density of surface acids might explain observed differences in sorption capacity. For these
experiments, hydrochars were first treated with strong acid (HCl) to protonate fully all available acid
groups. Then, the acid group density was measured of the protonated sorbent using Boehm titration
methods [29,71,72].
Table 3 summarizes the carboxylic acid site density measurements. As expected, the density
of acid functional groups on the glucose hydrochar is much greater than on the activated carbons
considered here, consistent with the different adsorption mechanisms for the two materials (primarily
electrostatic vs. primarily π-cation). The ion exchange resins have much greater acid concentrations
than any of the other sorbents, consistent with their superior performance and indicating that the AA-
and VSA-hydrochars function as designed, albeit with fewer acid binding groups than are available on
the ion exchange resins tested here. Nonetheless, the Cu(II) adsorption performance of the designer
hydrochars is comparable to the ion exchange resins (to within a factor of two) and superior to activated
carbon, meaning that strategies to increase acid functional group density can be effective for synthesis
of task-specific hydrochar sorbents.
Table 3 provides qualitative evidence of the importance of acid group density on sorption
performance and permits analysis of a critical parameter: the binding stoichiometry of the metal-acid
complex formed during adsorption. Binding stoichiometry is important for quantifying sorbent
performance since the ideal absorbent will possess high density of binding sites and utilize them as
efficiently as possible. Simultaneously achieving high binding site density and binding site utilization
may not be possible, since densely spaced binding sites may promote bidentate binding instead of
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monodentate binding, which is less efficient binding site utilization. We analyzed the sorption and
acid site density data to evaluate these effects in hydrochar, activated carbon, and ion exchange resins.
D
E
F
Figure 6. Sulfonate-containing hydrochar structures optimized using DFT. The structure in (a) is
the sulfonated hydrochar molecule. (b) Depicts the reactants which are the interactions between the
sulfonate group and either hydrogen, potassium, or sodium, respectively. Structure (c) shows binding
of Cu(II) to the sulfonated hydrochar molecule. Adsorption energies are provided as shown. Legend:
carbon; hydrogen; oxygen; sulfur; potassium; sodium; copper.
Table 3. Titration results of sorption materials.
Carboxylic Acid Density Carboxylic Acid Density b

Material
(mmol g−1 ) (mmol m−2 )
glucose-hydrochar 1 ±0.07 0.15 ±0.02
Hydrochars VSA-hydrochar 0.9 ±0.1 0.12 ±0.01
AA-hydrochar 2.8 ±0.3 0.4 ±0.1
Norit® SX1 <0.1 a
Activated Carbons Norit® SX Ultra <0.1 a <0.0001
Nuchar® <0.1 a
Amberlyst-15® 5 ±0.01 0.1 ±0.0002
Resins
AG® 50W-X4 1.71 ±0.1 2.6 ±0.1
a the estimated acid site detection limit. b based on estimated BET surface area.
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To use Table 3 data to understand stoichiometry, we plotted Cu(II) sorption capacity as a function of
measured acid group density, converting both to molar quantities, as shown in Figure 7. For comparison,
lines of constant ion-binding site stoichiometry (two Cu ions per acid, 1:1, and 1:2) are shown. Data for
the activated carbons cluster around the origin and fall entirely off the stoichiometric trend lines,
as expected given that the sorption mechanism to activated carbons is likely cation-π interactions and
is, therefore, independent of acid site density. In contrast, sorption for the hydrochars falls between the
1:1 and 1:2 stoichiometry lines, indicating that—on average—each acid group binds approximately
0.75 Cu ions. This again is further quantitative evidence of the importance of electrostatic interactions
for binding to hydrochar.
Figure 7. Measured Cu(II) adsorption capacity plotted as a function of measured carboxylate group
density. Lines of constant cation-anion stoichiometry are shown as dotted lines at 2 Cu(II) ions per
binding site (2:1), 1 Cu(II) ions per binding site, and 1 Cu(II) ion for every two binding sites. Legend:
depicts activated carbon, ion exchange resins, hydrochar.
The stoichiometry inferred from Figure 7 shows that the designer hydrochars outperform
Amberlyst® -15 on a per acid site basis. This is an important finding since increasing binding site
utilization efficiency is an effective means of increasing sorption capacity, along with increasing
the density of binding sites themselves. Interestingly, AG® 50W-X4 far exceeds all other sorbents
on effectiveness per acid site, with nearly two Cu ions associated with every acid site (Figure 6).
The difference between AG® 50W-X4 and Amberlyst® -15 is noteworthy as both sorbents are described
in the literature as polymerized styrene backbones with periodic sulfonic acid group substitution [101].
The difference in their performance must be due either to (1) the ability of the sorbent to hold charge,
which could be saturated for Amberlyst® -15 limiting its sorption capacity, (2) differences in acid site
accessibility in the swollen resins and hydrochars, or (3) differences in the spatial proximity of the
acid binding groups in the different sorbents. The performance of AG® 50W-X4 suggests further
engineering of the hydrochar structure to optimize sorption capacity.
To understand the origins of stoichiometry between Cu(II) ions and carboxylate or sulfonate
groups, we performed simulations to compare monodentate with bidentate binding of Cu(II) to
carboxylate and sulfonate groups. To make the calculation accessible using DFT, we simplified the
structure previously used in Figures 3 and 6 to remove the furan groups. Figure 8a shows the optimized
geometry for the monodentate binding structures, and Figure 8b shows the optimized geometry for
the bidentate binding structures. As expected, bidentate binding is much more energetically favorable
than binding to a single acid functional group. For the sulfonate site, bidentate binding is more
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Energies 2020, 13, 4203
stable by 201 kJ mol−1 , and for the carboxylate site, bidentate binding is more stable by 126 kJ mol−1 .
These values indicate a clear thermodynamic preference for bidentate binding. As measured by the
Cu−O distance, the Cu(II) ion is roughly equidistant between the two sulfonate groups; as a result,
the Cu−O distance in bidentate binding complex is greater than found in the geometry optimized
for single Cu-acid stoichiometry (shown previously in Figure 6). This clearly shows that Cu(II) (and
presumably other double charged cations) will prefer bidentate binding, when such an option is
available. Since bidentate binding is a less efficient use of sites than monodentate binding, rational
design of hydrochars should attempt to achieve uniform acid spacing to minimize acid-acid interaction
and the ability of cations to bind simultaneously to multiple acid sites.
Figure 8. Optimized geometries of monodentate (a) and bidentate (b) binding of Cu(II) to hydrochar
carboxylate and sulfonate groups simulated using DFT. Oxygen-Cu(II) distances are shown for reference.
Legend: carbon; hydrogen; oxygen; sulfur; copper.
When functional group precursors with polymerizable double bonds are co-fed to the HTC
reactor with glucose, the functional group bearing molecules will polymerize primarily with each
other, rather than with groups present in the hydrochar. Because they are formed by co-feeding
glucose and vinyl groups, VSA-hydrochar is not engineered to achieve the desired spacing, which may
explain why it falls short of the desired 1:1 Cu-binding site stoichiometry. More uniform spacing of
the binding groups has potential to improve binding site utilization by forcing binding to occur via
the preferred monodentate arrangement rather than via the thermodynamically preferred bidentate
geometry. Furthermore, utilization of vinyl sulfonic acid as a source of binding groups detracts
from the renewable and green characteristics of hydrochar. Accordingly, future work in this area
should seek to utilize feeds that are naturally abundant in anionic binding sites and/or functional
groups that are converted into anionic binding sites during HTC. Questions of binding site access
and cooperative effects should be addressed for hydrochars synthesized from renewable or waste
resources, using similar methods as shown here for rational sorbent design.
As a final analysis, we evaluated cation-π binding to the furan backbone itself in the absence
of acid groups, as a comparison with the arene backbone present in commercial exchange resins.
By providing a secondary stabilizing interaction, optimizing the cation-π binding interaction can
potentially improve the utilization efficiency of the anionic binding sites—a desired goal as explained
previously. In particular, we were interested to understand the effect of locating the cation between
nearby rings as compared with interacting with a single ring individually—in the absence of
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anionic binding groups, such as sulfonate or carboxylate. Figure 9 provides the results of these
calculations; Figure 9a,b depict arene binding and Figure 9c,d depict furan binding, respectively.
In both cases, locating the Cu(II) between two nearby aromatic rings (either furan or arene) is more
stable than interaction with a single aromatic ring. Interestingly, the energy difference is greater for
furan-cation interactions (Figure 9c,d) than arene-cation interactions (Figure 9a,b), by approximately
23 kJ mol−1 . Accordingly, a final design consideration for custom-synthesis of hydrochar sorbents is
inclusion of geometries, which permit formation of furan “pockets” for optimized cation-π interaction.
When combined with electrostatic interactions, cation-π interactions can provide a secondary stabilizing
force to optimize hydrochar sorption capacity.
Figure 9. Optimized geometries calculated for arene, (a,b), and furan, (c,d), cation-π binding, in the
absence of anionic binding groups. Legend: carbon; hydrogen; oxygen; sulfur; copper.
Differences in energy are shown directly in the Figure.
Figures 3 and 6–9 describe a combined experimental and simulation approach for rational design
of hydrochar sorbents to exploit electrostatic interactions between anionic functional groups and metal
cations. Maximizing the effectiveness of each functional group can be achieved by spacing them
uniformly throughout the material, thus emphasizing monodentate binding over bidentate binding.
Presumably, highly effective hydrochar sorbents, such as those reported by Demir-Cakan et al. [56],
who first demonstrated the acrylic acid co-HTC approach, and Xue et al. [16], who activated peanut
hull hydrochar using hydrogen peroxide, already exploit these principles. Likewise, the accuracy
of the computational approach in particular will benefit as hydrochar structure is further resolved,
especially for materials produced from precursors other than glucose. The result of the rational
design approach will be hydrochars with maximized value; thus, making them as competitive as
possible with sorbents obtained from non-renewable resources. Although not within the scope of
this work, computational modeling should be appropriate for guiding selection of conditions for
hydrochar regeneration, for example by using alkali solutions to remove the heavy metal adsorbates.
Applying our adsorption capacity results directly to metals other than Cu(II) is not recommended;
however, the combined experimental and computational approach should be amenable to any metal
cation of interest. Similar analysis can be applied in the future to understand the adsorption of organic
substances to hydrochar, as organic pollutants will exhibit different hydrochar interactions than metal
cations [104].
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4. Conclusions
Glucose hydrochar was studied as a model renewable sorbent for heavy metals, using Cu(II) as a test
case for custom-designing a hydrochar sorbent. Glucose hydrochar required alkali activation to exhibit
Cu(II) sorption capacity; a strong base (hydroxide) was more effective than a weak base (carbonate)
and K+ counter ions were more effective than Na+ for activation. In comparison, activated carbon
sorption was less than observed for activated glucose hydrochar, despite significant differences in
their measured BET surface areas (<10 m2 g−1 compared with >800 m2 g−1 ). Similarly, activated
carbon did not require alkali treatment to promote cation sorption, consistent with entirely different
sorption mechanisms for these two common sorbents. Zeta potential measurements indicated that
Cu(II) sorption to hydrochar was due to electrostatic interactions and FT-IR analysis implicated a key
role for carboxylate groups. DFT simulations provided further information on Cu-hydrochar binding
to the carboxylate site, suggesting beneficial synergy with nearby furan groups.
These results were used as the basis for molecular level design of two hydrochars bearing either
carboxylate or sulfonate groups. The designer hydrochars exhibited approximately 50 m2 g−1 Cu(II)
sorption capacity, consistent with the role of carboxylate and sulfonate groups in cation binding.
Nonetheless, the capacity of the hydrochar sorbents failed to yield the expected increase in sorption
capacity. In accordance with the electrostatic binding mechanism, sorption capacity of two ion
exchange resins, Amberlyst® -15 and AG® 50W-X4, was studied for comparison with hydrochar.
The ion exchange resins outperformed hydrochar on a per mass basis. Interestingly, the hydrochars
bound approximately 0.75 Cu ions per acid site, whereas Amberlyst® -15 bound only 0.5 Cu ions per acid
site. The superior performance of Amberlyst® -15 compared with hydrochar was therefore attributable
entirely to differences in acid site density. AG® 50W-X4, on the other hand, bound nearly 2 Cu ions per
acid site, which accounted for its superior performance compared with hydrochar. DFT simulations
confirmed that bidentate binding is preferred whenever possible, meaning, uniform spacing of the
binding groups will maximize their binding efficiency on a per site basis. Similarly, cooperative
effects from nearby aromatic groups (either furan or arene) can promote cation-π interactions that
improve binding and acid site utilization. The combination of experimental investigation and computer
simulation provide a clear starting point for molecular-level design of hydrochar for use as sorbents,
that can be used in future work.
Author Contributions: Conceptualization, M.T.T. and N.A.D.; Methodology, A.B.B., and G.A.T.; Validation, L.D.
and B.S.; Formal Analysis L.D. and M.P.R.; Investigation J.T.H., L.D., A.A., and M.P.R.; Data Curation, L.D.; Writing
(original draft), Writing (review and editing), N.A.D., M.T.T., A.B.B., A.A, J.T.H. and G.A.T.; Visualization, B.S.,
L.D., M.T.T.; Supervision, M.T.T., N.A.D.; Project Administration, M.T.T., A.B.B., N.A.D.; Funding Acquisition,
M.T.T. All authors have read and agreed to the published version of the manuscript.
Funding: The work was funded by the U.S. National Science Foundation (ENG/CBET 1605916).
Acknowledgments: Rediet Tegegne and Maksim Tyufekchiev supported experimental efforts by synthesizing
and titrating several of the hydrochars.
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76
energies
Article
Sewage Sludge Valorization via Hydrothermal
Carbonization: Optimizing Dewaterability and
Phosphorus Release
Taina Lühmann and Benjamin Wirth *
Biorefineries Department, Deutsches Biomasseforschungszentrum Gemeinnützige GmbH, Torgauer Straße 116,
04347 Leipzig, Germany; taina.luehmann@ru.nl
* Correspondence: benjamin.wirth@dbfz.de; Tel.: +49-341-2434-449
Abstract: As the use of sewage sludge as a fertilizer in agriculture is increasingly restricted in the
European Union, other ways to utilize this waste stream need to be developed. Sewage sludge
is an ideal input material for the process of hydrothermal carbonization, as it can convert wet
biomass into a solid energy carrier with increased mechanical dewaterability. Digested sewage sludge
was hydrothermally carbonized at 160–200 ◦ C for 30–60 min with initial pH levels of 1.93–8.08 to
determine optimal reaction conditions for enhanced dewaterability and phosphorus release into
the liquid phase. Design of experiments was used to develop response surface models, which can
be applied to optimize the process conditions. For optimal dewaterability and phosphorus release,
low initial pH values (pH 1.93) and mild temperatures around 170 ◦ C are favorable. Because holding
time had no statistically relevant effect, a dependency of reaction time was investigated. Though it
did not yield substantially different results, it could be included in investigations of short reaction
times prospectively. Low reaction temperatures and short holding times are desirable considering
economic reasons for scale-up, while the high acid consumption necessary to achieve these results
is unfavorable.
Keywords: dry matter; moisture; dewatering; sewage sludge; hydrothermal treatment; phosphorus;
RSM; DoE; optimization; regression model
1. Introduction
Sewage sludge is widely used in agriculture because high contents of phosphorus, nitrogen,
and potassium, as well as organic carbon make it a favorable organic fertilizer [1,2]. Because of
concerning substances, such as heavy metals, organic residues, microplastics, and various pathogens,
stronger regulations regarding the use as fertilizer have been passed. This has been combined with a
requirement to recover phosphorus from sewage sludge in countries such as Germany [3,4], so that
new ways for valorization are sought after. After landfilling became restricted in the European
Union (EU) in 1999, incineration has become the preferred solution in the EU-15 countries [5]. During
incineration, sewage sludge can be mono-combusted in specifically designed furnaces, co-combusted in
existing waste incineration plants or added in small quantities in cement kilns [6]. Thermal dewatering,
an energy intensive process, is the major drawback of incineration [6].
Hydrothermal carbonization (HTC) is a process that can convert sewage sludge into a more
easily mechanically dewaterable substance by breaking up the cell structure, thereby releasing bound
water [7–10]. Essentially, it is a process that converts biomass in hot pressurized water yielding an
upgraded solid biofuel [11,12]. Typical reaction conditions reported in literature are 180 to 250 ◦ C for
1 to 12 h holding time [11] at an elevated pressure due to water saturation pressure and additional
pressure by gaseous compounds formed during the reaction. To measure the dewaterability of
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sewage sludge, different approaches such as filtration and mechanical dewatering were examined.
Danso-Boateng et al. [8] used a filtration cell and calculated the specific cake resistance as a measure
for dewaterability. They found that the reaction temperature was the defining factor for dewaterability,
especially when compared to holding time. When Escala et al. [9] mechanically dewatered hydrochar
(HC) from stabilized sewage sludge that was acidified, they were able to reach dry matter contents
of 52 ± 5.5%, compared to the dry matter content of sewage sludge of 30%. Besides improved
dewaterability, another advantage of applying HTC to sewage sludge is the opportunity for phosphorus
recovery, the most valuable component of wastewater. Distribution of phosphorus in liquid and solid
phase as well as chemical composition has been increasingly studied [13–16]. Shi et al. [14] investigated
the effect of initial pH and reaction temperature on the distribution of phosphorus. They found that
higher temperatures caused phosphorus to be more present in the solid phase while adding large
amounts of acid could shift phosphorus into the liquid phase.
The aim of this study is to investigate the dewaterability and phosphorus release of hydrothermally
treated sewage sludge as minimum required reaction conditions are yet to be determined. A method
to investigate the optimal reaction conditions in a defined reaction space is facilitated by a Design
of Experiments (DoE)/Response Surface Model (RSM) approach. For HTC, this has been already
utilized frequently [13,17–20] and for sewage sludge dewatering after HTC by Danso-Boateng et al. [8].
While they tested the filterability as an indicator for dewatering, the objective of this study was to take
a more practical approach by investigating mechanical dewatering using a screw press at lab-scale.
This experimental set-up was implemented to reflect a possible industrial application. Sewage sludge
was used as received (without any pre-treatment) from a wastewater treatment plant (WWTP) to
identify if mild HTC conditions are suitable for valorization.
Although the process parameters reaction temperature, holding time and initial pH all play a
role on phosphorus release and dewaterability, they have only been investigated individually so far.
To also consider interaction effects, a DoE approach was taken. This allowed for the development of
regression models to predict the above-mentioned parameters as well as typical HTC characteristics.
Reaction conditions that are close to industrial applicability, for which low reaction temperatures and
short holding times are of interest, were investigated.
2.1. Digested Sewage Sludge

Digested sewage sludge (DSS) was collected from a municipal WWTP in Leipzig, Germany,
where the wastewater undergoes mechanical (screening, grit removal, primary sedimentation), chemical
(phosphate precipitation) and biological treatment (aeration reactor, secondary sedimentation). Sludge
stabilization includes sludge thickening, digestion, and mechanical dewatering, reaching a dry matter
content of 24.3%. The composition of the sample used in this study can be found in Table 1. A sample
of approximately 30 L was homogenized and separated into 27 subsamples, which were stored at 4 ◦ C.
Before being used in the experiments, they were left to warm up at room temperature.
Table 1. Properties of the tested samples with standard deviations given in parentheses.
C‡ H‡ N‡ S‡ O‡ Ash † HHVmeas † HHVcalc

(%db ) (MJ kgdb −1 )
32.5 4.7 5 1.7 15.2 40.9 14.3
13.4
(±0.24) (±0.05) (±0.04) (±0.01) (±0.33) (±0.11) (±0.10)
‡ †
= triplicates; = duplicates; HHV = higher heating value; meas = measured; calc = calculated; db = dry basis.
The calculated higher heating value (HHV) is slightly lower than the actual measured one as high
ash contents of a sample can severely impact the results of various calculation formulas [21]. However,
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the correlation of ultimate analysis data and HHV used here is reported to fit measured HHVs of HCs
very well and the value for DSS was added as a comparison.
2.2. Experimental Method

The DoE included the variation of reaction temperature, holding time, and initial pH.
A face-centered central composite design (FCCD) was chosen. Corner points were carried out
in duplicate and the center point in triplicate, resulting in 27 experiments. The reaction conditions were
(i) reaction temperature: 160, 180, 200 ◦ C, (ii) holding time (starting when the reaction temperature was
reached): 30, 60, 90 min, and (iii) initial pH: 2, 4.5, 7. Though holding time only accounts for part of the
timespan during which reactions take place, it is the common measure for comparison of HTC studies.
For sewage sludge, Escala et al. [9] used the timespan above 180 ◦ C for each experiment. Wang et al. [22]
concluded that the conversion of sewage sludge starts at around 130–150 ◦ C, observed by a rapid
rise of the organic load found in process water. However, they did not observe decomposition of
these organic compounds below 180 ◦ C. In this study, it was investigated if using the timespan above
140 ◦ C instead of holding time for analysis would yield substantially different regression models,
in accordance to the values provided by Wang et al. [7].
A graphical illustration of the design space can be found in Figure 1 and the randomized
experimental design in Table A1 in Appendix A.
Figure 1. Design space of the face-centered central composite design (FCCD), red dots indicate
triplicates, green dots duplicates, and blue dots single repetitions.
In preparation for the pH adjustment, the amount of acid needed for the targeted pH levels
was determined according to DIN EN 15933 [23]. After homogenizing a mixture of 10 g of sludge
and 100 mL of deionized water on a vibrating plate for 10 min at 130 rpm, concentrated sulfuric
acid (18 M) was added whilst stirring until the desired pH levels were reached and held constant for
30 min. The amount of acid needed for the actual amount of sludge could then be extrapolated from
these results.
For each experiment, around 350 g of DSS were weighed out and the calculated amount of sulfuric
acid (18 M) was added. Of that mixture, 290 g were used for the HTC experiment and 10 g for pH
measurement of the acidified sample. The measured pH was later used for regression modeling instead
of the targeted pH. Except for the addition of acid, the DSS was not further diluted with water but
utilized as received from the WWTP. The experiments were conducted in a 500 mL high-pressure
stirred-tank reactor made of stainless steel (BR-500, Berghof Products + Instruments GmbH, Eningen
unter Achalm, Germany). The stirrer was set to 100 rpm and the reactor was heated up electrically
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with a heating rate of 2 K min−1 . After reaching the desired temperature, the reactor temperature was
kept constant over the holding time. Then, the heater of the reactor was switched off and the reactor
was allowed to cool down to room temperature by the environment.
After the process, the HC-water-slurry was separated with a screw press with an integrated scale.
The screw press was tightened until a pressure of 300 kg (which corresponds to 2.2 bar) was applied
and retightened when the weight dropped by 10 kg. Pressing was stopped when there was no liquid
flow for more than one minute. After the pressing process was completed, the HC was divided into
two homogeneous samples according to DIN EN ISO 14780 [24] by coning and quartering. The HC
was dried and the process water was stored at 4 ◦ C until further use.
2.3. Analytics
In all solid samples (DSS and HC), dry matter content, elemental composition (C, H, N, S) and ash
content was analyzed. Additionally, HHV of DSS was measured and the concentrations of phosphorus
analyzed in DSS as well as process water.
Dry matter content was determined by placing the samples in a drying oven at 105 ◦ C overnight
referring to DIN EN ISO 18134-3 [25]. Elemental carbon, hydrogen, nitrogen, and sulfur (C, H, N, S)
were measured according to DIN EN 15104 [26] with an elemental analyzer (vario MACRO CUBE,
Elementar Analysensysteme GmbH, Langenselbold, Germany). Ash content was determined by
incineration at 550 ◦ C according to DIN EN 14775 [27] and the oxygen content was calculated by
difference. HHV was determined by combustion with oxygen in a bomb calorimeter (Parr Instrument
GmbH, Moline, IL, USA), according to DIN EN ISO 18125 [28]. Phosphorus was determined according
to DIN EN ISO 11885 [29] with a spectrometer (ICP-OES Icap 6300, Thermo Fisher Scientific, Waltham,
MA, USA). Every sample was analyzed three times.
2.4. Calculations
Solid yields based on dry matter (DM) were calculated according to Equation (1) with respect to
the mass of DSS put into the reactor and the mass of HC after the reaction:
mchar × DMchar
Solid yield (%db ) = × 100% (1)
minput × DMinput
For the calculation of carbon yields, Equation (1) was supplemented by the carbon contents of
DSS and HC and calculated as follows:
mchar × DMchar × Cchar
Carbon yield (%db ) = × 100% (2)
minput × DMinput × Cinput
Higher heating value (HHV) was calculated from the elemental analysis according to Channiwala
and Parikh [30]:

HHV MJ kgdb −1 =
(3)
0.3491 × C + 1.1783 × H − 0.1005 × S − 0.1034 × O − 0.0051 × N − 0.0211 × Ash
The calculated HHV from Equation (3) can be then used to determine the energy yield:
mchar × DMchar × HHVchar

Energy yield (%db ) = × 100% (4)
minput × DMinput × HHVinput
To determine the share of phosphorus in the liquid phase (Pliquid ), the concentrations of phosphorus
(cP ) in the DSS and HC are put into relation as follows:
mliquid × cP,liquid
Pliquid (%) = × 100% (5)
minput × DMinput × cP,input
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2.5. Regression Modeling

Because the relationship between certain output variables from HTC reaction conditions was to be
determined, a DoE/RSM approach was chosen to obtain the most information out of a limited number
of experiments. Regression modelling was performed as described by Montgomery [31]. The FCCD
was chosen to aim at fitting a second order model through the following equation:
y = β0 + βT xT + βt xt + βpH xpH + βTt xT xt + βTpH xT xpH + βtpH xt xpH + βT2 xT 2

(6)
+βt2 xt 2 + βpH2 xpH 2 + ε
in which T denotes the reaction temperature, t the holding time after the reaction temperature was
reached and pH the initial pH.
Equation (6) can also be expressed as:
y = Xβ + ε (7)
where y is a vector of the measured responses (e.g., dry matter content), X is a matrix containing
information about the levels of the variables at which the responses were obtained, β is the vector of
regression coefficients, and ε is a vector of random errors. With the aim to find the values of the β’s
that minimize the sum of squares of ε, the least squares estimates are calculated by:
β̂ = (X X)−1 X y (8)
The regression model can now be estimated as:
ŷ = X β̂ (9)
and the difference between measured responses (y) and fitted values (ŷ) is given in the vector of
residuals:
e = y − ŷ (10)
Analysis of variance was used to refine the regression model by testing the significance of each
of the terms in Equation (6) by conducting an F-test. The F-value of a term (e.g., temperature) was
calculated by comparing the mean squares of the evaluated term (MSTerm ) and the remaining residuals
(MSResidual ):
MSTerm SSTerm/dfTerm
F0 = = (11)
MSResidual SSResidual/dfResidual
with SS denoting the sum of squares and df the degrees of freedom. F0 was tested against FStat (α, dfTerm ,
dfResidual ) on a significance level of α = 0.1 and if F0 > Fstat , it was concluded that there are significant
effects caused by the evaluated term. After the model was refined to include only statistically relevant
terms, it was further improved by testing to exclude outliers (results from one or more experiments)
from the model. For each term, a t-value was calculated for each run, according to Weisberg [32]:
ê i
ti = (12)
MSResidual,i 1 + xi (X i Xi )−1 xi
The designation i denotes that data from the ith run was excluded during the calculation and x is
essentially a vector containing the first row of X. The t-value was compared with tStat (α/2, n – p − 1),
where n denotes the total number of runs and p the number of parameters in the model. If |ti | < tStat ,
the run was excluded from regression modelling.
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To give the reader an impression of the regression model quality, the metrics predictive and
adjusted R2 are provided. R2 , the coefficient of determination, expresses how much variation around
the mean is explained by the model and is calculated as follows:
SSResidual
R2 = 1 − (13)
SSModel + SSResidual
where SSModel denotes the sum of squares of the model, which is calculated by adding up all SSTerm
of the terms included in the model. If the model captures all variation around the mean, R2 equals
one, and if the model cannot account for any variation, R2 equals zero. R2 is closest to one when all
terms are still in the model and can thus mislead to include terms in the model that do not contribute
a statistically significant effect. An adjusted R2 (R2 adj ) accounts for this and, therefore, decreases as
the number of model terms increases if the additional terms do not improve the model. Additionally,
predictive R2 (R2 pred ) expresses the predictive ability of the model. It takes into account the variation
that arises when excluding one run from the model and using it to predict this value [31].
Regression modeling and data plotting were performed with the software packages Design Expert
12 (Stat-Ease, Inc., Minneapolis, MN, USA) and Origin 2020 (OriginLab Corp., Northampton, MA, USA).
3.1. Regression Modeling

For the parameters of interest, dewaterability, and phosphorus release, as well as general HC
characteristics energy, carbon, and solid yield, regression models were developed and are presented in
Table 2. The calculation of the F-test (Equation (11)) indicated which model coefficients are statistically
relevant, which means that they are adding more information than noise to the model. Factors that
were not included in any model (xT × xt and xt × xpH ) were excluded from the table.
Table 2. Coded regression model coefficients for hydrochar (HC) and process water properties.
Coded Regression Model Coefficients Metrics

Target Value
xT xt xpH xT × xpH xT 2 xt 2 xpH 2 R2 adj R2 pred
Hydrochar Characteristics
Dry matter (%) 2.70 −3.90 2.22 −1.87 0.89 0.84
Carbon content (%daf ) 2.12 0.61 2.52 1.31 −0.90 0.92 0.90
HHV (MJ kgdb −1 ) −0.23 −0.16 0.31 0.63 0.53
Solid yield (%db ) −3.36 5.19 −4.09 0.72 0.69
Carbon yield (%db ) −4.39 4.62 −3.40 0.72 0.69
Energy yield (%db ) −4.95 4.04 −4.01 0.78 0.74
Process Water Properties
P content (mg L−1 ) −159.55 −2260.21 163.81 1720.72 0.99 0.99
P share (%) −2.56 −31.46 3.64 24.97 0.99 0.98
Final pH (-) 0.10 0.11 2.17 0.32 −0.87 0.99 0.99
daf = dry and ash-free basis; db = dry basis; P = phosphorus.
The displayed models were further refined by the exclusion of outliers by conducting a t-test
(Equation (12)). Because of the experimental design (FCCD) and the repetitions of corner and central
points, outliers could be excluded without having to limit the order of the model, which led to
regression models with good predictive and adjusted R2 in most cases. The coded regression model
coefficients indicate by how much the response is expected to change when the input parameter is
changed by one unit. By default, the coded units range from −1 for the lowest level and +1 for the
highest level. In this study, the change by one unit relates to a temperature change of 20 ◦ C, holding
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time change of 30 min or a pH change of 3.1. The comparison of the coefficient’s magnitude within a
response allows for an estimation of the relative impact that each input parameter has.
Table 2 shows that reaction temperature and initial pH have a statistically significant (at least
p < 0.05) influence on the output parameters in all models while holding time is only included in two
models. As the absolute values of the coefficients of reaction temperature and initial pH are of similar
magnitude for HC characteristics, it can be assumed that the effect of changing the temperature by
20 ◦ C is similar to a pH change of 3.1. Even though holding time is included for carbon content, its
value is the smallest, which relates to a small influence on the actual model. These trends are different
for the investigated process water properties where pH has 12–21 times higher effects compared to
temperature. In addition, the final pH is equally influenced by reaction temperature as by holding
time. In comparison with other RSM publications, Álvarez-Murillo et al. [19] observed a similar effect
of temperature on the solid yield of olive stone (−5.56 × xT whereby a temperature change of one
unit corresponds to 30 ◦ C). Holding time was included in the model, because their tested maximum
duration of 10 h yielded a statistically relevant effect. Mäkelä et al. [17] encountered a much stronger
influence on the solid yield (daf) treating industrial mixed sludge from a pulp and paper mill (−27 × xT
whereas a temperature change of one unit corresponds to 40 ◦ C). This can be attributed to the higher
temperatures that were investigated (180–260 ◦ C) and the exclusion of the observed high ash contents
for the calculation of the solid yields. Hence, greater differences in yield can be observed. A more in
depth analysis of the investigated output parameters is included in the following sections.
3.2. Holding Time vs. Reaction Time

Because holding time does not cover the whole timespan during which reactions take place, a
more inclusive measure was used to investigate if this would cause time to become statistically relevant.
The time during which temperature in the reactor exceeded 140 ◦ C was chosen as Wang et al. [7]
implicated that reactions start taking place between 130 and 150 ◦ C. Reaction time will now be referred
to by t140 in this study. It should be noted that this value only applies to sewage sludge and should be
carefully chosen depending on the input material. Holding time and reaction time for each experiment
can be found in Table A1 in Appendix A.
Regression modeling was carried out analogous to the procedure described in the previous
sub-chapter. The output parameters for which reaction time is statistically relevant and, thus, included
in the regression model are shown in Table 3. Carbon content is still mainly dependent on reaction
temperature and initial pH, but the influence of time increased by using reaction time instead of
holding time in the model. A comparison of contour plots is provided in Figure A1 in Appendix A and
the use of reaction time shows the expected trend that with increasing reaction time and temperature,
the carbon content increases. This becomes not that clear when holding time is used for the model.
While the model for HHV does not include holding time, it does so with reaction time. The general
trends that were described in the previous subsection remain as can be observed in the comparison in
Figure A2 in Appendix A. For the final pH, reaction temperature is now excluded from the model,
but the influence of time is still marginal, compared to initial pH as would be expected. Not much
changes when comparing the contour plots in Figure A3 in Appendix A.
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Table 3. Coded regression model coefficients for hydrochar (HC) and process water properties with
t140 reaction time instead of holding time.
Coded Regression Model Coefficients Metrics

Target Value
xT xt,140 xpH xT *xpH xt140 *xpH xT 2 xpH 2 R2 adj R2 pred
Hydrochar characteristics
Carbon content (%daf ) 1.72 1.04 2.56 1.34 −0.93 0.91 0.89
HHV (MJ kgdb −1 ) −0.17 −0.15 −0.17 0.16 0.35 0.73 0.61
Process water properties
Final pH (-) 0.24 2.17 −0.59 0.99 0.99
daf = dry and ash-free basis; db = dry basis.
The refined data analysis with reaction time instead of holding time did not yield significantly
different results. This shows that for batch experiments, variation of holding time does not have a
significant influence on most output parameters. It could be considered to be kept constant in future
DoEs, unless parameters such as carbon content, HHV, and final pH are of major interest and holding
or reaction time will be varied in a much wider range. However, holding time is clearly important
when developing continuous processes as it will alter the size of the equipment for a certain targeted
mass flow. This has to be addressed with corresponding equipment in lab-scale to allow for a smaller
difference between holding time and time above a certain reaction temperature.
3.3. Hydrochar Properties

To verify the results and to form a basis for comparison, a van-Krevelen-diagram was created
(Figure 2) and common HC properties such as solid, carbon, and energy yield were calculated (Table 4).
For reasons of clarity and comprehensibility, only a selection of HCs as well as DSS is shown in these
illustrations. The HCs produced at the mildest (160 ◦ C, 30 min, pH 7) and harshest conditions (200 ◦ C,
90 min, pH 2) are shown to illustrate the range of reaction severity. To estimate the individual effect of
the different reaction parameters, each parameter was varied from the mildest to the harshest condition
while the other two remained at the mildest.
Figure 2. van-Krevelen-diagram of selected hydrochars (HC) and digested sewage sludge (DSS) at
different process conditions.
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Table 4. Hydrochar (HC) properties in relation to reaction conditions.
T t pH C Content N Content HHV Solid Yield C Yield Energy Yield

(◦ C) (min) (-) (%daf ) (%daf ) (MJ kgdb −1 ) (%db ) (%db ) (%db )
160 30 7.5 ± 0.23 57.3 ± 0.04 4.6 ± 0.16 13.7 ± 0.27 90.0 ± 0.88 86.4 ± 2.02 92.1 ± 2.71
200 30 7.9 ± 0.23 63.8 ± 0.63 3.7 ± 0.19 13.0 ± 0.52 76.9 ± 0.69 71.9 ± 2.32 74.9 ± 3.68
160 90 7.7 ± 0.07 58.3 ± 1.02 4.4 ± 0.04 13.6 ± 0.00 85.8 ± 7.44 82.2 ± 6.94 87.5 ± 7.58
160 30 2.2 ± 0.14 55.5 ± 0.13 3.6 ± 0.09 14.5 ± 0.62 62.7 ± 18.60 62.4 ± 15.93 67.4 ± 17.24
200 90 2.1 ± 0.05 57.9 ± 0.45 3.1 ± 0.08 13.3 ± 0.07 74.2 ± 1.77 68.1 ± 1.46 73.5 ± 1.37
T = reaction temperature; t = holding time; C = carbon; N = nitrogen; HHV = higher heating value.
By visualizing the atomic H/C versus O/C ratios of DSS and HCs in Figure 2, insights into the
governing reactions can be gained. Generally, carbonization decreases both H/C and O/C ratios and,
depending on how the ratios change in relation, an assumption about the major governing reaction can
be made. In this case, the atomic ratios of the HCs primarily follow dehydration, which confirms the
finding of Wang and Li [33] that reactions at temperatures below 180 ◦ C are governed by dehydration.
When comparing the HCs that were both produced at 160 ◦ C and pH 7, but at differing holding times
of 30 and 90 min, it becomes apparent that varying the holding time between these time intervals does
not have a noticeable effect. Contrarily, the variation of pH or temperature leads to a more severe
conversion of the feedstock. The pH variation resulted in HCs with lower H/C ratios than caused by
dehydration reactions only.
Considering the lower nitrogen contents of pH-adjusted HCs (Table 4), it seems like the pH
adjustment favored deamination, which is besides decarboxylation the major conversion mechanism
for proteins [22]. This causes the additional removal of hydrogen, resulting in a lower H/C ratio.
When analyzing the influence of temperature variation, HC produced at 200 ◦ C possesses almost the
same atomic ratios as the HC produced at the harshest combined conditions (200 ◦ C, 90 min, pH 2).
It can be seen from the data that the initial calculated HHV based on dry matter of DSS is
slightly higher (13.4 MJ kgdb −1 , Table 1) than the HHV of some of the produced HCs (12.7–15.0 MJ
kgdb −1 ). This is due to the accumulation of ash in HC (increasing ash content from 40.9%db in DSS
to 39.2–53.4%db in HC). Calculating HHV on a dry and ash free basis (daf) results in the expected
increase when comparing the resulting chars (26.0–30.9 MJ kgdaf −1 ) with the initial DSS (22.6 MJ
kgdaf −1 ). The HC characteristics solid, carbon, and energy yield were calculated according to the
described approach (Equations (1), (2), and (4), respectively). They follow the expected trajectory that
more severe reactions result in lower yields. Conducting an analysis of variance for the respective
yields showed for reaction temperature (p < 0.01), initial pH (p < 0.001), and their interaction (p < 0.05)
to have statistically significant effects on the yields. The regression models in terms of actual factors
(T in ◦ C, t in min and pH) are as follows:
Solid yield (%db ) = 40.14 + 0.16xT + 13.64xpH − 0.066xT × xpH (14)
Carbon yield (%db ) = 56.28 + 0.057xT + 11.45xpH − 0.055xT × xpH (15)
Energy yield (%db ) = 59.31 + 0.079xT + 13.04xpH − 0.065xT × xpH (16)
In contrast to the majority of studies, holding time was found not to be statistically relevant in
these experiments. This is because others investigated a much longer time span [18,19]. Therefore,
it can be concluded that for solid, carbon, and energy yield, a variation of holding time between 30 and
90 min does not cause statistically different results, and the time could be minimized. Danso-Boateng
et al. [34] developed a regression model for the solid yield of primary sewage sludge (SY = 118.49 −
0.26xT − 0.04xt , actual factors, range of 140–200 ◦ C and 15–240 min) and it compares quite well with
Equation (14) when set at a neutral pH of 7 (SY = 135.62 − 0.30xT , actual factors). Though holding time
is included, the main effect comes from temperature, as found in this study.
The regression model of the solid yield is displayed as a contour plot in Figure 3 as a representative
for the other yields, as they follow the same trend. It shows that mild conditions (low reaction
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temperature and neutral pH) lead to higher solid, carbon, and energy yields. While Mäkelä et al. [18]
found no effect of the addition of acid on the yields when investigating industrial mixed sludge from a
pulp and paper mill, these experiments show a clear effect. This is likely to occur because a wider range
of pH with a more concentrated acid was tested. Unlike Reza et al. [35], who found that mass yield
was more affected by reaction temperature than initial pH when converting wheat straw, the opposite
is indicated here with pH having 1.5 times the effect compared to that of reaction temperature.
Figure 3. Regression model contour plot showing the influence of initial pH and reaction temperature
on the solid yield (%db ).
The dry matter content after mechanical dewatering was used as a measure of the increase in
sludge dewaterability. Analysis of variance has shown that only the influence of reaction temperature
(p < 0.001) and initial pH (p < 0.001) was statistically relevant (see Table 2). Furthermore, their interaction
(p < 0.001) as well as the quadratic term of temperature (p < 0.01) are included in the model due to
their high significance level, resulting in the following equation with actual factors:
Dry matter content (%) = −91.48 + 1.64xT − 7.74xpH + 0.036xT × xpH − 0.0047xT 2 (17)
The resulting response contour, plotted in Figure 4, shows the general trend that low pH and
higher temperatures favor dewaterability. Initial pH has a clear and strong influence, as a more acidic
initial pH yields increasing dry matter contents. A deviation from the expected trend exists at low
pH levels, where an increase in reaction temperature does not result in ever increasing dry matter
contents. This trend is caused by the quadratic term xT 2 in the regression model, which causes the
slight curvature. However, when determining to what extent this term contributes to the model by
comparing the SS of the term xT 2 to the total SS, it becomes clear that it contributes only with 5% to the
model and should not be emphasized.
The regression model of the dry matter content is in agreement with Danso-Boateng et al. [8],
Gao et al. [36], and Wang et al. [37], who also found a strong influence of temperature on dewaterability,
but not of holding time. When the threshold time of 30 min is exceeded, there is no longer any
holding time dependency according to Wang et al. [37]. At the selected temperatures, the typical
HTC reactions already take place sufficiently and another increase in temperature will yield even
faster reactions. Because dehydration and decarboxylation cause a decrease in hydrophilic functional
groups, such as hydroxyl and carboxyl groups [38], the product is more easily dewatered already by a
simple mechanical press. The effect of acidic pH on improved dewaterability can be explained by the
enhancement of dehydration reactions, caused by sulfuric acid [39], which adds to the temperature
effect. Dewaterability is additionally improved by the floc structure disintegration, which releases the
bound water as free water [22]. Escala et al. [9], who conducted a comparable experiment, achieved
similar dry matter contents. They were able to reach a dry matter content of 52 ± 5.5% after applying a
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pressure of 40 bar to HC produced at 205 ◦ C and 24 min. This is higher than the 45.6 ± 2.24% achieved
in this study at comparable reaction conditions (200 ◦ C, 30 min, pH 2 and 7) and is very likely due to a
much lower dewatering pressure.
Figure 4. Regression model contour plot showing the influence of initial pH and reaction temperature
on the dry matter content (%) after mechanical dewatering.
3.4. Phosphorus Release

For the phosphorus distribution, the pH value is the most significant driver and the variation of
holding time showed no statistically relevant effect again, resulting in the following regression models
with actual factors:

Phosphorus content mg L−1 = 12.97 − 0.021xT − 3.03xpH + 0.027xT × xpH + 0.18xT 2 (18)
Phosphorus share (%) = 204.32 − 0.42xT − 47.22xpH + 0.059xT × xpH + 2.63xT 2 (19)
A lower initial pH generally leads to a lower pH value after the reaction (Figure 5a). This lower
pH value favors the solution of phosphorus from the solid and the phosphorus concentration in the
process water increases. The influence of the pH value is particularly evident in a range of the initial
pH of 2–5 (Figure 5b).
Figure 5. Regression model contour plots showing (a) the dependence of process water pH and (b) the
dependence of liquid phase phosphorus release (% of total P) on reaction temperature and initial pH.
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Energies 2020, 13, 4417
At neutral pH, not much phosphorus will be dissolved by varying holding time and reaction
temperature. As others already found, most of the phosphorus is retained in the solid phase [9,13,22].
However, the variation of the initial pH has a major influence on the transfer of phosphorus into the
liquid phase. When Shi et al. [14] reached an initial pH of 0.24 and applied HTC conditions of 170 ◦ C
and 30 min, they were able to transfer 83% of phosphorus into the liquid phase. The results of this
study confirm their findings, as the maximum phosphorus share achieved in these experiments is 78%
at 160 ◦ C and an initial pH of 1.93. An even higher share of 88% was achieved in an experiment at
160 ◦ C and an initial pH of 2.25 but was excluded as an outlier from the model as a result from the
t-test according to Equation (12). It is, thus, possible to transfer phosphorus into the liquid phase to
be potentially recovered by precipitation, e.g., as magnesium ammonium phosphate (struvite) [14],
though this comes at the cost of high acid consumption. Additionally, precipitation of phosphorus in
HTC process water brings additional challenges due to the huge variety of other components found in
the process water.
The future upscaling of this process requires considerations regarding holding time, mixing
behavior and heat transfer, especially because a continuous process is desired. While the results of
this study show that the holding time can be minimized to 30 min for maximum dewaterability and
phosphorus release in a batch process, this time needs to be assessed anew for the application in a
continuous process. During the heating time in a batch process, the conversion of sewage sludge
already begins and, therefore, the holding time of a batch cannot be directly transferred to a continuous
process. More severe reaction conditions (higher reaction temperature and longer holding time) would
be necessary, if energy densification and a further increase in HHV are desired [17].
4. Conclusions
The results of this study provide useful information for the design and optimization of HTC
systems for sewage sludge treatment. It aimed at finding the optimal HTC reaction conditions for a
maximized mechanical dewaterability and phosphorus release in the liquid phase. In the investigated
design space (160–200 ◦ C, 30–90 min, pH 1.93–8.09), low initial pH levels are desirable and holding
time can be minimized as it had no statistically relevant effect. The influence of reaction temperature
is not completely clear. While low temperatures are somewhat more advantageous for phosphorus
release, medium temperatures are favorable for dewaterability.
It was investigated if using reaction time as an input parameter instead of holding time would
cause different results. Though only minor changes were observed, some models were more refined.
However, with regard to future experimental plans using batch reactors, aiming at identifying the
impact of HTC process parameters on several product characteristics, it could be considered to exclude
holding time from the parameter variation. Residence time is of course a main factor in the design of
larger plants, but can only be addressed sufficiently in lab-scale using equipment allowing continuous
operation to minimize actual heating and cooling times.
A numerical optimization to maximize mechanical dewaterability and phosphorus release yielded
achievable dry matter contents of 48.6% and a phosphorus share of 70.3% in the liquid phase at 170 ◦ C
and an initial pH of 1.93. This would be accompanied by an HHV of 13.95 MJ kgdb −1 .
Author Contributions: Conceptualization, T.L. and B.W.; Formal analysis, T.L.; Funding acquisition, B.W.;
Investigation, T.L.; Methodology, T.L. and B.W.; Project administration, T.L.; Supervision, B.W.; Validation, T.L.
and B.W.; Visualization, T.L.; Writing—original draft, T.L.; Writing—review and editing, B.W. All authors have
read and agreed to the published version of the manuscript.
Funding: This research received funding by the Federal Ministry of Food and Agriculture of Germany (BMEL)
and by the Sächsische Aufbaubank (SAB) financed by the European Regional Development Fund (ERDF) under
grant no. 100283030.
Acknowledgments: The authors would like to thank all of the laboratory and technical staff at DBFZ for conducting
the experiments and analyses. Furthermore, the authors would like to thank L. Prokot for her contributions to the
experimental part of this study.
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Energies 2020, 13, 4417
Appendix A
Table A1. Experimental design (temperature, holding time, and pH) as well as reaction time and
measured pH.
T T t140 pH, DoE pH, Measured

Experiment
(◦ C) (min) (min) (-) (-)
1 160 90 275 7.0 7.8
2 180 60 251 4.5 5.6
3 200 90 411 7.0 8.1
4 160 30 130 2.0 2.1
5 160 90 274 7.0 7.7
6 200 30 247 2.0 2.3
7 160 30 144 7.0 7.7
8 200 30 207 7.0 7.8
9 200 90 365 7.0 7.1
10 160 30 147 7.0 7.4
11 180 60 221 7.0 7.3
12 180 30 178 4.5 5.3
13 160 90 274 2.0 2.2
14 200 30 236 2.0 2.2
15 180 60 264 2.0 2.1
16 160 90 280 2.0 1.9
17 180 90 352 4.5 5.5
18 200 60 324 4.5 5.5
19 160 60 194 4.5 5.3
20 200 90 398 2.0 2.1
21 180 60 251 4.5 5.4
22 180 60 272 4.5 5.4
23 180 60 241 4.5 5.4
24 160 30 155 2.0 2.3
25 200 30 242 7.0 8.1
26 200 90 413 2.0 2.0
Figure A1. Regression model contour plots showing the dependence of carbon content (%daf ) on
reaction temperature and (a) holding time and (b) reaction time.
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Energies 2020, 13, 4417
Figure A2. Regression model contour plots showing the dependence of the higher heating value (MJ
kgTS −1 ) on reaction temperature and initial pH based on a model referring to (a) holding time and (b)
reaction time (contours shown at the respective time at the corresponding center point).
Figure A3. Regression model contour plots showing the dependence of the process water pH (-) on
initial pH and (a) holding time and (b) reaction time.
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Article
Comparative Studies on Water- and Vapor-Based
Hydrothermal Carbonization: Process Analysis
Kyoung S. Ro 1, *, Judy A. Libra 2, * and Andrés Alvarez-Murillo 3
1 USDA-ARS Coastal Plains Soil, Water & Plant Research Center, Florence, SC 29501, USA
2 Leibniz Institute for Agricultural Engineering and Bioeconomy, 14469 Potsdam, Germany
3 Department of Applied Physics, School of Industrial Engineering, University of Extremadura, 06006 Badajoz,
Spain; andalvarez@unex.es
* Correspondence: kyoung.ro@usda.gov (K.S.R.); jlibra@atb-potsdam.de (J.A.L.);
Tel.: +1-843-669-5203 (K.S.R.); +49-331-5699-866 (J.A.L.)
Received: 7 August 2020; Accepted: 29 October 2020; Published: 2 November 2020
Abstract: Hydrothermal carbonization (HTC) reactor systems used to convert wet organic wastes
into value-added hydrochar are generally classified in the literature as liquid water-based (HTC) or
vapor-based (VTC). However, the distinction between the two is often ambiguous. In this paper,
we present a methodological approach to analyze process conditions for hydrothermal systems.
First, we theoretically developed models for predicting reactor pressure, volume fraction of liquid
water and water distribution between phases as a function of temperature. The reactor pressure
model predicted the measured pressure reasonably well. We also demonstrated the importance of
predicting the condition at which the reactor system enters the subcooled compression liquid region
to avoid the danger of explosion. To help understand water–feedstock interactions, we defined a
new solid content parameter %S(T) based on the liquid water in physical contact with feedstock,
which changes with temperature due to changes in the water distribution. Using these models,
we then compared the process conditions of seven different HTC/VTC cases reported in the literature.
This study illustrates that a large range of conditions need to be considered before applying the label
VTC or HTC. These tools can help in designing experiments to compare systems and understand
results in future HTC research.
Keywords: hydrothermal carbonization (HTC); vapothermal carbonization (VTC); reactor pressure;

process conditions; phase distribution of water; solid contents; hydrochar
1. Introduction
The process of hydrothermal carbonization (HTC) is used to carbonize organic residues and
wastes for diverse applications ranging from fuels to soil amendments. In HTC, subcritical water is
used as a solvent and reactant to transform a wide variety of organic feedstocks to solid carbonaceous
products (hydrochar), which usually contain higher carbon contents, heating values and degrees of
aromaticity than the original feedstocks [1–4]. Diverse types of reactors have been used, ranging from
batch [3,5–12], semi-batch [2,9,10] to continuous reactors [13], with and without mixing, using direct
heating through steam injection or through the reactor walls with controlled heating rates, or indirectly
in muffle ovens. The pressurized reaction system usually consists of all three phases (gas, liquid, solid)
and is heated to temperatures from 160 to 280 ◦ C with pressures between 0.6 and 6.4 MPa due to
the water vapor and gases produced in the reactions. Water is initially introduced into the reaction
system via the moisture content of the feedstock and/or through the addition of water as a liquid or
as steam. Common HTC process variations are differentiated according to how the water initially
contacts the feedstock. When the feedstock is immersed in bulk liquid water, it is often called HTC.
Where the feedstock is in direct contact with only steam, it is often called steam HTC, vapor HTC or
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Energies 2020, 13, 5733
vapothermal carbonization (VTC) [2,7,10,11]. Here, feedstock can be held in baskets away from liquid
water, transported in and out on conveyor belts with little to no post-processing dewatering steps
necessary. However, the dividing line between the two process types often does not remain sharp over
the operating time, since the distribution of water between the liquid and vapor phases will change
as temperature rises in batch systems, or as more steam is added in semi-batch systems. Usually we
cannot see inside high-pressure reaction systems to gain visual insights, so the extent of the phase
change is often unknown. Process comparisons between HTC vs. VTC based on the state of the initial
water phase may be misleading. The phase changes may play an important role in causing structural
variations in the hydrochars produced, their biodegradability, stability, and functionality in various
applications [5].
Only a few studies comparing hydrochars produced by HTC vs. VTC have been reported in the
literature. Cao et al. [5] found that biomass was more carbonized under liquid water in HTC than
through steam in VTC. They determined that more aromatic and less alkyl groups were formed in the
sugar beet and bark hydrochars made from HTC than in those from VTC under the same operating
conditions (200 ◦ C for 3 h). The hydrochars made from HTC also were less biodegradable than those
from VTC as indicated by the lower values of the ratio BOD/COD for HTC-hydrochars. The lower
biodegradability of hydrochar from HTC was probably due to its higher aromaticity produced during
the reactions taking place in liquid water. In this case, the hydrochar made from HTC should be
more stable in the environment than that made from VTC, which would have consequences for its
use, e.g., as a soil amendment. On the other hand, comparisons between hydrochars from HTC vs.
VTC for use as fuels have produced mixed results on how the phase of the reaction medium affects the
important energy parameters: solid yield, higher heating value (HHV) and energy yield [10,11,14].
Comparing HTC vs. VTC for two feedstocks, digestate and straw, at 230 ◦ C, 6 h, Funke et al. [11] found
no clear trend in HHV: VTC-chars had a higher HHV than HTC-chars from digestate, but for straw,
the order was reversed. However, VTC produced higher solid yields and, therefore, higher energy
yields than HTC for both feedstocks. In contrast, Shafie et al. and Yeoh et al. reported mostly lower
solid yields and higher HHV from the VTC process compared to HTC process (both at 220 ◦ C, 1 h;
two feedstocks [10,14], three feedstocks [14]). Again, as in [11], the combination of these two trends in
the energy yield showed that the VTC process was more efficient for energy yield. We suspect that the
reason for these conflicting trends in HHV and solid yield arise from the fact that a clear picture of
how the water was distributed between gas and liquid phases was not given, nor to which extent the
feedstocks were exposed to the liquid water phase. For instance, the VTC experimental setup used
by Yeoh et al. (two concentric chambers with water filled in the outside chamber and the biomass in
the inner chamber) was assumed to avoid the liquid water directly contacting the biomass feedstock.
Yet it is not clear from their description that the liquid water was contained in the outside chamber
throughout the reaction, since liquid water expands at higher temperature, possibly causing overflow
into the biomass chamber. It appears that the transition between HTC/VTC reported in the literature is
fuzzy at best because it can be changed by small variations in the same reactor system. How much
water is present in each phase depends not only on the reactor temperature and pressure, but also on
the total amount of water in the system relative to the volume of the reactor system.
As more knowledge is gained on the beneficial applications of hydrochars and HTC for waste
and residue processing, more work on reactor designs for diverse settings (ranging from high to
low tech systems) will be carried out. The variety of process variations may increase, with process
configurations and conditions utilizing the unique transport properties of each medium, e.g., the higher
thermal conductivity of bulk liquid water or the higher diffusivity of steam to penetrate the porous
structure of the feedstock [7,15]. These changes in transport properties can affect reactions and product
characteristics [15]. Therefore, knowledge on what influences the distribution of water between the
reaction phases is essential for the production of the desired hydrochar quality. Especially if we want
to replicate process conditions in various reactor types and scales to produce a desired hydrochar
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Energies 2020, 13, 5733
quality, we must be able to predict the distribution of water between the vapor and liquid phases at the
design HTC reaction conditions.
Furthermore, reactor designs must consider how the HTC reactor pressure will change in response
to operating conditions to ensure process safety. All reactors must be able to withstand the high
temperatures and pressures that can develop during the process. As a rigid HTC reactor partially filled
with water and feedstock is heated, the increase in the saturated water vapor and gases produced by
the chemical reactions cause the reactor pressure to rise. At the same time, the density of the bulk
liquid water decreases and consequently the volume of liquid water increases, decreasing the volume
of the reactor headspace. When the liquid volume in the HTC reactor completely fills the headspace,
it can no longer expand if the reactor temperature is increased further. The reactor water then enters
a subcooled liquid compression region. In this region, pressure increases very rapidly with small
increases in reactor temperature. To avoid the reactor pressure exceeding the tensile strength of reactor
material, it is very important that the reactor system has a working safety disk or valve that can release
pressure at a preset value. Without the use of proper rupture disks, the reactor can explode. Therefore,
in order to maintain safe operating conditions, we need to predict the reactor pressure at the chosen
process conditions. This requires understanding the relationship between the HTC reactor conditions
(temperature, water volume, feedstock) and pressure.
The aim of this work is to present a methodological approach to analyze process conditions
for hydrothermal systems in the framework of the hydrothermal carbonization reactions. In the
paper, we first theoretically develop models for predicting reactor pressure, the distribution of water
between phases, and the liquid water volume fractions as a function of reactor temperatures. Then,
the evaluation is expanded to water and feedstock. Finally, using these new models, we analyze and
compare process conditions for VTC and HTC systems reported in the literature.
2.1. Theoretical Development

For a reactor without any HTC reaction (i.e., without any feedstock inside reactor), we can estimate
the HTC autogenic pressure with that of pure water at the HTC reaction temperature. This information
is often visualized for hydrothermal systems with a pressure-temperature (P-T) phase diagram for water,
showing the regions for the different types of processes, e.g., gasification, liquefaction, carbonization.
However, to help us understand the process conditions during a hydrothermal reaction, the use of the
temperature-volume (T-v) phase diagram for water is a powerful tool which provides information on
P and T as well as the distribution of water between phases as a function of the overall specific volume
of water (liquid and steam) in the reactor vR (Figure 1). Using this diagram, one can understand the
thermodynamic equilibrium at the chosen process conditions of the reactor system, e.g., temperature,
pressure and mass of water in the system. In Figure 1, the saturation line represents the boundary
condition for the phase change. For most HTC/VTC reactor systems, the reaction zone is usually
located within the saturation curve, where steam and liquid phases coexist. The operating path for
a batch system can be followed from the starting process conditions until the target conditions are
met and the holding time begins. The closer the target point is to the steam or liquid saturation lines,
the higher the amount of that phase. Since a log scale is used for the x-axis, the ratio between the two
phases cannot easily be determined visually from the figure. The calculation procedure is developed in
the following section.
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Energies 2020, 13, 5733
Figure 1. Temperature-volume (T-v) diagram for water showing the common operating region for
vapor and hydrothermal carbonization reactions.
Total mass of water in the reactor is
MH2O = xL MH2O + xV MH2O (1)
where
MH2O = total mass of liquid and vapor water in the reactor (kg);
xL = mass fraction of liquid water;
xV = mass fraction of vapor water (or steam quality);
xL + xV = 1.
As the HTC reactor is heated beyond the boiling temperature, the reactor volume is mostly filled
with liquid water and steam, and the following relationship can be developed assuming both liquid
water and steam are in equilibrium (i.e., for the saturated liquid–vapor region; Figure 1).
VR = xL MH2O vL + xV MH2O vV (2)
where
VR = reactor volume (m3 );
vL = specific volume of saturated liquid water (m3 /kg);
vV = specific volume of saturated steam (m3 /kg).
Combining Equations (1) and (2), the mass fraction of vapor water (xv ) can be calculated by
knowing the thermophysical properties of water at those conditions, the mass of water in the reactor
and the reactor volume:
vR − v L
xV = (3)
vV − vL
where
vR = VR /MH2O , overall specific volume of reactor water and steam mixture (m3 /kg).
As the liquid-steam mixture in the reactor is heated, the volume of liquid water expands due to
the decrease in water density ρL. Using Equation (3) along with values for saturated vapor and liquid
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Energies 2020, 13, 5733
specific volumes [16], the fraction of liquid-water occupying the reactor volume VFw can be estimated
at the HTC reaction temperature:
Vw ( 1 − xV ) v L
VFw = = (4)
VR vR
where
Vw = volume of liquid water in the reactor at temperature T (m3 );
VFw = volume fraction of liquid water in the reactor at temperature T (-).
As long as the reactor volume is larger than the bulk liquid water volume (i.e., VFw < 1), we can
assume the liquid and vapor water phases are in equilibrium and the autogenic pressure can be
estimated from the saturation properties of water using saturated steam tables [16–18].
If the temperature is further increased so that the liquid volume completely fills the reactor due
to the decrease in its density (i.e., VFw = 1, and xL = 1), the liquid water will enter the subcooled
liquid compression region. This region can be seen in the T-v phase diagram, left of the saturated
vapor curve (Figure 1). There is no longer any headspace in the reactor and the water density in
the reactor system at this point (also called overall reactor water density) becomes constant and can
be calculated from D = MH2O /VR . As the rigid reactor walls are suppressing the tendency of the
liquid volume to increase in response to the decrease in liquid water density, the reactor pressure
increases rapidly as the water expands with the increase in temperature. When VFw > 1 calculated
from Equation (4) (i.e., physically impossible unless the reactor explodes), the reactor pressure in this
range can be estimated with liquid compressibility factor for subcooled water:
P = ZL × D × RT/MWH2O (5)
where
P = reactor pressure (MPa);
ZL = liquid compressibility factor for subcooled water (-);
D = overall reactor water density, MH2O /VR (kg/m3 );
R = universal gas constant (8.31451 × 10−3 m3 -MPa/kmol-K);
T = reactor temperature (K);
MWH2O = molecular weight of water (kg/kmol).
To illustrate the danger of a potential reactor explosion if the liquid fills the reactor completely,
example calculations to estimate the reactor pressure at three common HTC temperatures using
Equation (5) are reported in Table 1. The values of liquid compressibility factor of the subcooled water
reported by Lemmon et al. (2018) were used. A value for D was chosen that is slightly higher than the
saturated liquid water density at 200 ◦ C. This simulates the reactor pressure for the case when the
liquid water fills the reactor completely at 200 ◦ C. A further increase in T to 250 ◦ C will rapidly increase
P from 2 to 81.6 MPa, a pressure that many HTC reactors are not made to withstand. For instance,
maximum allowable pressures for common laboratory reactors range from 13.3 to 34.5 MPa [19].
In contrast, if there is less liquid water added and more headspace in the reactor so that the liquid
water-vapor equilibrium can exist at all operating temperatures, the pressure increase would follow
the saturation pressure, increasing only from 1.6 to 4.0 MPa.
In order to avoid the subcooled compressible region, some manufacturers of pressure equipment
recommend calculating the maximum allowable water mass using a safety factor and the ratio of
ρL or its inverse vL at the desired T to that at room temperature [20]. It is also important to note
that the actual HTC pressure will be higher than that from the pure water because of gas production
(predominantly CO2 ) from HTC reactions.
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Table 1. Example calculations for the effect of increasing the hydrothermal carbonization (HTC)
temperature on reactor pressure for D = 865 kg/m3 (values for saturated water properties taken from
Lemmon et al. (2018).
Saturated Water (i.e., VFw < 1)

200 ◦ C 230 250
Specific volume of liquid water (vl ) (m3 /kg) 0.00116 0.00121 0.00125
Specific volume of vapor water at (vv ) (m3 /kg) 0.12721 0.07151 0.05008
Saturation pressure (Psat ) (MPa) 1.55 2.80 3.98
Subcooled Water (i.e., VFw > 1)
Liquid compressibility factor (-) 0.010606 0.24601 0.39023
Reactor pressure (P) for D = 865 m3 /kg (MPa) 2.00 49.44 81.55
2.2. HTC Reactor System

Three laboratory-scale HTC reactor systems were used to measure pressure change with
temperature increase and validate the predicted values with experimental set-ups. Two sealed high
pressure and temperature reactors made of Alloy C276 with valves and fittings made of T316 Stainless
Steel (500-mL, Model 4575A and 1-L, Model 4680 HT, Parr Instrument Co., Moline, IL, USA) were
used with various initial fillings with distilled water. A 1500-watts heater surrounding the outside
reactor wall along with a programmable temperature controller was used to heat the reactants at
a designed temperature. This reactor system was modified to improve control and data logging
capability. In addition, a 18.75-L reactor system (Model 4555, T 316 Stainless Steel, Parr Instrument Co.,
Moline, IL, USA) with a similar heating system (6000 watts) and temperature controller (Model 4848BM)
using SpecView data acquisition software was used to study the effect of initially pressurizing the
system with nitrogen.

Understanding and replicating process conditions to produce a desired hydrochar quality require
that we can estimate how much liquid water is in contact with the feedstock. Maintaining safe
operating conditions requires that we can predict pressure increases during the reaction. In pressurized
hydrothermal batch and semi-batch conversion systems, process conditions in the reaction system can
be difficult to measure as well as to predict. The volume of liquid water and the distribution between
the liquid and vapor phase change with temperature. Reactor pressure can increase with temperature
due to (1) rising water vapor pressure, (2) the expansion of the liquid water, and (3) the production of
process gas. In the following sections, the focus is on the effects caused by changes in the physical state
of water. First, the relationships between temperature, pressure, the volume fraction of liquid water
VFw and the distribution of water between the liquid and vapor phase are shown for a reactor system
filled only with water. Then, the evaluation is expanded to water and feedstock. Finally, the effect of
these process conditions for VTC and HTC systems reported in the literature are discussed.
3.1. HTC Reactor Filled with Water Only
3.1.1. Estimating VFw at Various Temperatures and VFo

In HTC and VTC experiments, a wide range of initial water amounts can be used. For HTC
experiments, high values of VFo are commonly chosen. It is important, however, to choose process
conditions so that the liquid water does not fill the reactor volume at the holding temperature
(i.e., VFw = 1) to avoid entering the subcooled liquid compression region. The higher the initial VFo ,
the lower the reactor temperature at which VFw becomes 1, because smaller headspace volumes cannot
accommodate much expansion of liquid water as its density decreases with temperature. This behavior
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is shown in Figure 2 for a reactor filled with water only. Values for VFw were estimated at various
temperatures and VFo using Equation (4). For a reactor initially filled with water at 90% (i.e., VFo = 0.9),
the liquid volume expands to the reactor volume (i.e., VFw = 1) when the reactor temperature reaches
165 ◦ C. Fortunately, this critical temperature, at which VFw =1, increases rapidly as VFo is decreased,
e.g., 305 ◦ C for VFo = 0.7 and 365 for VFo = 0.5, so that process conditions can be chosen to remain
well below the critical temperature. When the reactor is initially filled with water to less than half its
volume (i.e., VFo < 0.5), the liquid does not fill the reactor even when the temperature approaches the
critical point of water around 374 ◦ C. Interestingly, for experiments with low values of VFo common to
VTC operating conditions, VFw can actually decrease with temperature. When the reactor is initially
filled with a very low volume of water, such as VFo = 0.1, the liquid volume decreases to zero at
T = 340 ◦ C. This happens when there is so much headspace that the liquid water completely vaporizes,
i.e., the molecular collision frequency of H2 O molecules in the headspace is so small that condensation
does not happen in this high headspace situation.

9)R
9)R
9)R

9)R

9)R

R
7 &
Figure 2. Change in volume fraction of reactor filled with liquid water VFw (Vw /VR ) as a function of
temperature for various initial liquid water volume fractions (VFo ).
3.1.2. Estimating Pressure and VFw under Process Conditions

For a batch reactor system starting with only water at atmospheric pressure, the reactor pressure
at the holding temperature can be easily estimated using the simple saturation water vapor pressure at
T as long as 0 < VFw < 1. However, when VFw = 1 or higher, if the temperature is further increased,
the reactor pressure will now follow the subcooled water pressure, which rises rapidly. The pressure
increase must then be estimated using Equation (5) with the liquid compressibility factor Z and the
overall reactor water density D. This approach can then be used to predict the increase in reactor
pressure as a function of the reactor temperature at various VFo . The results are illustrated in Figure 3.
When VFo = 0.3, the liquid volume does not reach the reactor volume (i.e., VFw < 1) even at the highest
temperature simulated at 370 ◦ C. Therefore, the reactor pressure follows the saturation water vapor
pressure shown as the lower curve in Figure 3. For a reactor system with a high initial volume of water,
e.g., VFo = 0.8, the reactor pressure also follows the saturation pressure line below 250 ◦ C, similar
to the behavior at VFo = 0.3. However, at T = 250 ◦ C, VFw becomes unity and the water enters the
subcooled compression region. In this region, a small increase in temperature of only 5◦ can cause a
rapid increase in pressure from 4.9 to 11.7 MPa (Figure 3).
The application of this approach to predict VFw and pressure for experimental runs at various
temperatures was evaluated by comparing the predicted pressures with the observed pressures
in HTC reactors initially filled with three different amounts of water. As most researchers have
discovered, determining the actual volume of an HTC reactor with cavity volume in the reactor head
due to connections to the pressure gauge and sampling ports is difficult. Based on reactor volume
estimations from simple geometric dimensions, the added water resulted in VFo = 0.3, 0.63, and 0.67.
For VFo = 0.3, the observed pressures as the reactor was heated followed the saturation water vapor
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line at temperatures up to 349 ◦ C (Figure 3). However, for VFo = 0.67 at temperatures higher than
349 ◦ C, the pressure increased much more rapidly than the saturation vapor pressure, indicating that
the water entered the subcooled compression region. According to the predicted pressure line for the
estimated VFo , it should have entered the subcooled region at a lower temperature of 320 ◦ C. Instead,
the observed pressure followed the predicted pressure line of VFo = 0.6 (Figure 3). We suspect that this
discrepancy can be attributed to the fact that the actual reactor volume was larger than the estimated
volume, (e.g., 1.1 L instead of 1 L for 0.67 L water initially filled). These results show that the approach
is adequate to estimate VFw at various reactor temperatures in practical applications, however, if the
actual reactor volume is not known accurately, there will be some deviation from the predicted values.
3 03D
Figure 3. Comparison of measured and estimated reactor pressure at different initial liquid water
volume fractions (VFo ).
Another important question to consider in deciding upon operating conditions and evaluating
experimental results is: How does a higher initial pressure affect the pressure development and phase
distribution of water in the reactor? For example, some experimenters pressurize the system initially
using an inert gas such as N2 or Ar. The answer in short is that the addition of pressure to the reactor
headspace does not change the behavior of water. If enough water and time are available, water will
vaporize to the gas phase to reach the saturation water vapor pressure at which liquid water and
vapor water are in equilibrium. This pressure is a function of temperature only and independent of
the presence of other gases. The added inert gas does not change the relationships for VFw and the
distribution of water between the liquid and vapor phases. However, the total reactor pressure will be
higher in the reactor initially filled with N2 or Ar than that without the initial inert gases. The total
pressure P(total) can be estimated by summing the partial pressures of all individual non-reacting gases
as stated in Dalton’s law. The increase in the partial pressure for each component with temperature
can be calculated independently and added together. This can be seen in Figure 4 for two experimental
runs in an 18.75-L Parr reactor in which water was heated to 220 ◦ C (VFo = 0.63): one starting at
atmospheric pressure and the second one with N2 addition to achieve an initial pressure of 1.4 MPa.
The measured values from the nonpressurized run (Po = 0.1 MPa) are compared to the saturation water
vapor pressure P(sat) from [2] in the lower curve. For the run at Po = 1.4 MPa, the partial pressure
increase for N2 P(N2 ) was estimated using the ideal gas law, combined with Equation (4) to calculate
the changes in headspace volume (1-VFw ) as temperature increases.
Comparison of the measured and theoretical values shows clearly that the contribution of the
saturated water vapor to the total pressure is not affected by the initial addition of N2 gas. The small
deviation between the calculated pressure and the measured can be due to inaccuracies in the pressure
measurement or in estimating the reactor volume, and the assumption that N2 behaves as an ideal
gas with no solubility in the liquid. Nevertheless, the difference does not mask that the fact that the
addition of pressure to the reactor headspace does not change the behavior of water.
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Figure 4. Comparison of the theoretical total pressure P(total) calculated from the partial pressures
for N2 P(N2 ) and saturated water vapor P(sat) to the measured values for pressure P and P(sat) in the
reactor for VFo = 0.63.
3.2. HTC Reactor Filled with Water and Feedstock
3.2.1. Estimating the Distribution of Water between Phases as a Function of Temperature and Its Effect
on Solid Content
In their comparison of hydrochars from VTC and from HTC systems, Cao et al. (2013) postulated
that the amount of liquid water in contact with the feedstock in the reaction system may determine the
degree of carbonization and influence which reactions take place and their sequence [5]. However,
they did not quantify how much liquid water was in contact with the feedstock in their reaction
systems. This is a common problem in most of the literature on HTC/VTC systems. Often the label
used for the system is defined by the initial conditions. For instance, when the feedstock is initially
completely submerged in bulk liquid water, it is commonly called an HTC system. Whereas, when dry
or wet feedstock is placed separately from the bulk liquid water, it is called a VTC system. However,
the volume of liquid water and the distribution of water between the liquid and vapor phase change
with temperature, which can change the amount of water contacting the feedstock. In addition,
the feedstock characteristics such as moisture content, particle size, bulk density, as well as structural
changes during the reaction can affect how water interacts with the feedstock. In VTC, carbonization
reactions can take place between a wet feedstock and water within its cells or present as a film on its
surface [10,11]. Ref. [11] Even with completely dried feedstock, the feedstock can be wetted during the
process by absorbing water vapor or water vapor condensing on its surface.
The parameters often used to describe the relationship between water and feedstock in a reaction
system do not differentiate between the bulk liquid water added to the process and the liquid water
in contact with the feedstock. The nominal solid content at the start of the run is usually reported in
published studies as:
Mbiomass
%So = × 100 (6)
MH2O + Mbiomass T=To
where
%So = nominal solid content;
Mbiomass = initial feedstock dry mass;
MH2O = total mass of water in the reactor.
A similar parameter R which describes the initial ratio of feedstock dry mass to total mass of
water is also often used. These parameters only describe the initial conditions based on the initial
filling masses of water and feedstock, but do not provide critical information on the extent to which
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feedstock is exposed to liquid water in the HTC or VTC systems to promote important hydrothermal
carbonization reactions. In order to provide useful information on the degree of physical contact
between the feedstock and liquid water throughout the process, we propose reporting the following
solid content parameter:
Mbiomass
%S(T ) = × 100 (7)
mH2O + Mbiomass T=T
where
%S(T) = actual solid content based on liquid water in contact with feedstock;
mH2O = mass of liquid water in contact with feedstock;
T = reactor temperature.
With these new definitions, one can systematically distinguish various HTC/VTC process
conditions in terms of fraction of liquid water physically in contact with feedstock. For HTC
systems, where the feedstock is assumed to be completely submerged in the bulk liquid water over
the whole reaction time, mH2O = xL . MH2O . Using Equations (3) and (4), these assumptions can
be checked for the reaction temperature and the solid content values adjusted with Equation (7).
For example, the change in the distribution of water between the two phases can be seen in Figure 5a.
For temperatures below 250 ◦ C and VFo larger than 0.3, less than 4% of the water will be vaporized.
The expansion of VFw, as seen in Figure 2, should offset the small loss of liquid water to the vapor phase
and submerged feedstocks should remain submerged at these conditions. Therefore, the actual solid
content will be approximately the same as the nominal solid content at the initial reactor temperature
To (i.e., %S(T) = %So ). Only for systems with VFo closer to 0.1, more common to VTC systems,
will approximately 20% of the water be present as vapor at 250 ◦ C.
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Figure 5. Changes in process parameters at various initial VFo as the operating temperature increases
for (a) mass fractions of water in liquid xL and vapor xV , (b) the ratio of actual to nominal solid content
in the reactor system, %S(T) at T to %So at the initial temperature.
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In VTC systems, wetted or completely dried feedstock can be suspended without any physical
contact with bulk liquid water. The bulk liquid water can be placed either at the bottom of the reactor
or in a separate interconnected chamber, or steam can be injected to heat the reactor. The value
reported for %So for such systems often includes the bulk water. However, this can be misleading,
especially for dried feedstock, where the actual initial solid content %S(To ) = 1 because m2O = 0.
Although %S(To ) = 1 initially, %S(T) will become less than one over time because water vapor will be
volatilized from the physically separated bulk liquid as the VTC reactor temperature increases and will
condense on the surface of the dry feedstock. The extent to which the vaporized water condenses onto
the feedstock depends on the kinetics of condensation and vaporization at the reaction temperature,
but %S(T) will rarely reach %So . The condensed water will promote typical hydrolysis and other
important carbonization reactions as in HTC systems. For VTC systems with initially wetted feedstock,
bulk liquid water may or may not be added to the reactor. If no bulk liquid water is added similar to
that of Funke et al. [11], %S(To ) = %So , where the moisture content (MC) determines the value of the
initial solid content. As the temperature increases, liquid water is lost to vaporization, reducing the
water content of the feedstock. %S(T) can then be calculated with Equation (7) and:
Mbiomass × MC
mH2O = xL × MH2O = xL × (8)
1 − MC
Using these equations for the new solid content parameters, the ratios of actual to nominal solid
content are plotted against the reactor temperatures in Figure 5b for various initial volume fractions
of liquid water. For HTC systems with VFo larger than 0.3 and temperatures below 250 ◦ C, there is
little difference between the two values. At 250 ◦ C, only a 4% increase is seen in %S(T), and after the
reactor is half-filled (i.e., VFo > 0.5), no differences are noticeable. In contrast, for systems with low
values of VFo (e.g., VFo = 0.1), %S(T) becomes 20% higher than %So . Less liquid water is in contact
with the solids to participate in reactions. For VTC systems with wet feedstocks where the liquid
water is associated in or on the feedstock, the transfer of water to the vapor would change the %S(T)
in the reactor significantly. For wetted feedstock suspended over bulk liquid water, the situation is
more complicated, since water can vaporize from the wet feedstock or bulk liquid water, mass transfer
within and in-between feedstock, and the kinetics of condensation and vaporization all play roles in
the location of the liquid water. This is beyond the scope of this paper. Moreover, the implications of
the reduction in the mass of bulk liquid water on the potential of reducing physical contact between
feedstock with a bulk volume larger than that of liquid water and subsequent carbonization reactions
need to be further studied.
3.2.2. Estimating VFw and Pressure under Process Conditions with Feedstock
Up until now. we have analyzed the changes in volume fractions due to changes in the physical
properties of water. The addition of feedstock to the reactor can reduce the headspace volume available
to accommodate the expansion of liquid water. To adjust the volume fractions for the presence of
feedstock, the reactor volume must be reduced by the volume occupied by the feedstock. To strictly
determine this volume, we need to know the true density of the material, i.e., the ratio between the
feedstock mass and its volume excluding the cavities, pores and gaps in the material where water and
air could be trapped. In addition, the loss of solid mass and structure during HTC reactions would
have to be taken into consideration. For practical purposes, simple estimates of the initial volume of
feedstock can be made with liquid displacement methods and used to adjust the calculation of VFw .
HTC reactions with the feedstock can also change the gas composition and pressure of the
headspace. The composition and amount of the produced gases is closely tied to the process conditions
and feedstock material. In general, most HTC reactions with biomass produce predominantly CO2
(~>80%) with minor percentages of N2 , H2 S, O2 , CH4 , H2 , etc., in the gas besides water vapor. Explosive
gas mixtures are not expected in HTC, unlike hydrothermal gasification where reactor temperatures
are near or above the critical temperature of water (i.e., ~374 ◦ C) and produce approximately 1:1 of CH4
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and CO2 . However, an in-depth analysis about gas production and compositions is beyond the scope
of this paper. The impact of the product gas on the total reactor pressure and its partition between
water and gas phases need to be further investigated as gas solubility changes with temperature and
pressure. The results of this study provide a theoretical framework for further experimental and
modeling research on this aspect of HTC.
3.3. Comparison of Process Conditions for Hydrothermal Treatment (HTC and VTC) Reported in the Literature
The results from published HTC/VTC studies that have been made at various scales, ranging
from 1 L to 10 m3 , and with different modes of operation, e.g., batch and semi-batch with respect to the
steam, are analyzed in this section. As summarized in the introduction, few studies comparing HTC
and VTC systems have been published and some results are contradictory. The goal here is to identify
the effect of process conditions on the distribution of the water between the phases to understand what
is behind the labels—HTC and VTC—and develop criteria on how to label systems, either HTC or
VTC. This is necessary especially for cases in which we want to replicate process conditions used to
produce a desired hydrochar quality in other reactor types and/or scales. The results are structured
into seven cases for the discussion here and an overview of the process conditions and feedstocks is
given in Table 2.
Table 2. Overview of the process conditions and feedstock for the seven cases with VTC/HTC processes.
Case Reactor Feedstock Water in System Literature
T VR MC Mbiomass MH2O vR
Type Heating Mixed Type
(◦ C) (L) (%) (gDM) (g) (m3 /kg)
bark 7 23.5 101.6 0.010
1 Batch HTC 200 1 heating band No
sugar beet 7 37.6 162.9 0.006
Cao et al. [5]
Semi- batch steam, condensate bark 40–70 n.r. n.r. 0.013 *
2 200 70 No
VTC removal sugar beet 40–70 n.r. n.r. 0.012 *
start start
Semi- batch
steam, no condensate 1998.1 0.005
3 VTC 200 10,000 Yes MSW 53 1771.9 Safril et al. [9]
removal end end
3398.1 0.0029
wheat straw 0 450 8550 0.00219
4 Batch HTC 230 18.75 heating band No
digestate 0 630 11,970 0.00157
Funke et al. [11]
wheat straw 25 450 1350 0.01390
5 Batch VTC 230 18.75 heating band No
digestate 25 630 1890 0.00995
bagasse 67.2 16.6–28.8 1495.5 0.003
6 Batch HTC 220 4.6 heating band No
lime peel 78 14.4–44.0 1495.5 0.003
Shafie et al. [10]
Semi- batch heating band, bagasse 67.2 n.r. n.r. 0.041–0.053 @
7 220 4.6 No
VTC condensate separated lime peel 78 n.r. n.r. 0.022–0.044 @
n.r.—not reported. MC – moisture content. * Assumed 50% reactor volume filled with bark or sugar beet feedstock
(MC = 55%) suspended in baskets with bulk density of 0.267 kg/L for bark [21] and 0.298 kg/L for sugar beet pulp [22].
@ Assumed the same amount of feedstock as in Case 6 with biomass bulk density of 0.616 kg/L for bagasse [23] and
0.490 kg/L for lime peel [24].
In Cases 1 and 2, a comparison of batch HTC (Case 1) with semi-batch VTC (Case 2) using the
same feedstocks was made in different reactor systems [5]. For Case 1, the feedstock was dried, ground,
and water added to the 1 L reactor, submerging the feedstock. In Case 2, the wet feedstock was
suspended in baskets and steam (1.6 MPa) was injected to heat the 70 L reactor. As water condensed
over the heating up and holding time, it was removed except for that which remained on the feedstock.
Therefore, there was no increase in the mass of condensed water in the reactor over time (Revatec
GmbH, DE 10 2009 010 233.7). The feedstock was reported to have a moisture content between 40 and
70%. For the calculations here, the mass of water in the system was estimated from the overall specific
volume of saturated water vapor at 200 ◦ C in the 70 L reactor and an average moisture content of
the feedstock (55%) during the HTC reaction. As feedstock loading information is not available,
we assumed 50% of the reactor volume was filled with bark or sugar beet pulp suspended in baskets
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inside the reactor. The mass of water was estimated using bulk densities of bark and sugar beet pulp
reported in the literature [21,22].
In Case 3, a commercial-scale hybrid system with municipal solid waste (MSW) in a 10 m3 reactor
system was used [9]. The semi-batch system was fed saturated steam (2.5 MPa) to heat the feedstock
and held at 180–230 ◦ C for 30 min. The system started similar to a VTC system with only wet feedstock,
but as the condensed steam was mixed with the feedstock over time, the system became more similar
to HTC. A mid-range temperature of 200 ◦ C was assumed for further analyses here. In Cases 4 and
5, Funke et al. compared VTC and HTC for two feedstocks in the same batch reactor system [11].
For VTC, the dried feedstock was first soaked in water and then suspended in a basket without any
additional liquid water added to the reactor. For HTC, the dried feedstock was submerged in water.
In Cases 6 and 7, Shafie et al. used bagasse with MC of 67.16% (cut into less than 10 mm) and lime peel
with MC of 78.04% (size as received) as feedstock [10]. For HTC, the feedstock was fully submerged
inside the water in a reactor. For VTC, saturated steam was supplied to the reactor with the feedstock
suspended in order to avoid contact with condensed liquid water accumulated at the bottom of the
reactor. As feedstock loading information was not reported for the VTC experiments, we assumed
the mass of feedstock was the same as that used in HTC experiments, along with bulk densities from
the literature (bagasse [23]; lime peel (value for lemon peel was used [24]). The process conditions
and feedstock for each case are summarized in Table 2, along with the respective vR, overall specific
volume of reactor liquid water and steam mixture.
3.3.1. Change in Process Conditions in Batch HTC (Cases 1, 4, 6) or VTC Processes (Case 5)
In batch reactors, the solids and liquids are introduced at the beginning of the run and the reactor
is sealed before heating starts. The initial VFo and %So can be easily calculated and are usually reported
(Table 3). Feedstock initially submerged in water can unequivocally be called HTC when VFw at the
holding temperature remains as large or larger than VFo . This is true for all batch HTC cases (1, 4,
6) analyzed here. Each case includes results for two feedstocks under slightly differing conditions.
In Case 4, with a relatively large amount of initial water (VFo = 0.46 and 0.64, for wheat straw and
digestate, respectively), the expansion of water at 230 ◦ C causes VFw to increase by approximately 20%.
As only 0.5 to 1.4% (m/m) of the initial liquid water is transferred to the vapor phase, there is little to
no change in %S(T). Similarly, very little increase in solid content is observed in Case 6. In contrast,
Case 1 at 200 ◦ C has a low degree of initial water filling for both feedstocks (i.e., VFo = 0.1 and 0.16),
and VFw is very similar to VFo . Between 4 and 7% of the water is transferred to the vapor, causing a
corresponding increase in the value of %S(T). The values for %S(T) ranged from 1.0 to 19.9% for all
batch HTC cases, ensuring adequate contact with liquid water to promote HTC reactions. Despite
the loss of liquid water due to vaporization, the filling volume (VFw ) slightly increases because the
volume of water expands with the reactor temperature, guaranteeing that the feedstock is completely
submerged in the liquid water throughout the reaction period. Therefore, hydrothermal reactions will
take place between the feedstock and liquid water and the process can be called batch HTC in Cases 1,
4, and 6.
If the solids are suspended in the reactor in baskets or on trays so that they are not submerged in
water, the process is commonly called VTC (Cases 5). If the feedstock has a high moisture content such
as the dried feedstock soaked in water (Case 5, MC = 75% or %So = %S(To ) = 25%), or it is made up of
intact microorganisms or fresh plant material, the actual %S(T) slightly increases compared to %So
(27.6 or 28.9 vs. 25%) due to the small loss of liquid water in the feedstock to vapor (Table 3).
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Table 3. Overview of process conditions and water distribution for the seven cases of VTC/HTC.
Case Reactor Feedstock vR Mass Fraction in Vapor xv VFo VFw %So %S(T)
Type Type (m3 /kg) (-) (-) (-) (%) (%)
bark 0.010 0.069 0.1 0.11 18.8% 19.9%
1 Batch HTC
sugar beet 0.006 0.04 0.16 0.18 18.8% 19.4%
bark 0.013 * 0.051 * n.r. - 45%# 45% #
2 Semi-batch VTC
sugar beet 0.012 * 0.046 * n.r. - 45%# 45% #
start 0.005 start 0.03 0.2 47.0%
3 Semi-batch VTC MSW
end 0.0029 end 0.0142 0.34 34.6%
wheat straw 0.00219 0.014 0.46 0.54 5.0% 5.1%
4 Batch HTC
digestate 0.00157 0.0051 0.64 0.77 5.0% 5.0%
wheat straw 0.01390 0.1804 0.07 0.07 25.0% 28.9%
5 Batch VTC
digestate 0.00995 0.1239 0.1 0.11 25.0% 27.6%
bagasse 0.003 0.03 0.33 0.378 1.1–1.9% 1.1–2.0%
6 Batch HTC
lime peel 0.003 0.03 0.33 0.378 1.0–2.9% 1.0–3.0%
bagasse 0.041–0.053 @ 0.473–0.609 @ n.r. - 32.8% 32.8%
7 Semi-batch VTC
lime peel 0.022–0.044 @ 0.251–0.510 @ n.r. - 22.0% 22.0%
n.r.—not reported. * Assumed 50% of reactor volume filled with bark or sugar beet suspended in baskets. # Averaged
value for feedstock. @ Assumed the same amount of feedstock as in Case 6.
3.3.2. Change in Process Conditions for Semi-Batch VTC Process with Steam Injection (Cases 2 and
7 with Condensate Removal or Separation, and Case 3 without Condensate Removal)
For reactors in Cases 2 and 3 with a semi-batch mode of operation where saturated steam is
introduced over time to first heat the reactor and then to maintain the desired operating temperature,
the calculations for how much mass of the water is present as liquid or vapor are not as straightforward.
The steam condenses as it heats the feedstock to the targeted operating temperature, and more will
condense over the targeted holding time. As steam is introduced, the reactor pressure will remain
constant at the saturation pressure if there are no reaction products entering the vapor phase. However,
gases are normally produced by the hydrothermal reactions and the pressure rises as the gases, mainly
CO2 , enter the headspace.
For systems with condensate removal, as in Case 2, or condensate separation, as in Case 7,
the mass of bulk liquid water in contact with feedstock comes from moisture already present within
the feedstock and water condensation on the surface of feedstock. Wet feedstocks will retain most
of their moisture. For dried feedstock, the majority of the water in the system will be in the vapor,
with some steam condensing on the feedstock surface, especially in the heating phase. Assuming that
the amount of steam condensed on the feedstock surface is negligible, the overall specific volume vR is
mostly that of the saturated water vapor and the moisture content of the feedstock. In such systems,
the process can be labeled VTC without much ambiguity. The amount of liquid water that can react
with the feedstock for VTC systems mainly depends on the moisture content of the original feedstock
and the condensed water on the feedstock surface. It is very difficult to quantify this amount of water.
For these two cases, %S(T) was assumed to remain the same as the initial value. The condensed water
is sometimes flashed off at the end of the run (e.g., for energy recovery (Revatech, 2012)), so that the
solids come out about as wet as they went in. This is helpful in reducing dewatering requirements,
but this hinders easily assessing how much water was in contact with the feedstock.
In systems without condensate removal, as in Case 3, the continuous injection of steam will build
up the total mass of water in the system, with the majority present in the form of liquid water. The VTC
process then approaches the HTC process. In this hybrid VTC–HTC commercial-scale unit, the reaction
system is well-mixed and liquid water is mixed into the feedstock, gradually lowering the value of
%S(T) in the reactor from the initial %So value 47% to 34.6%. The volume fraction of vapor water (xV )
changes somewhat. Starting with 3% of the water present as vapor, it reduces to 1.4% at the end of the
run (Table 3). In general, it is important to measure the mass of steam introduced in systems without
106
Energies 2020, 13, 5733
condensate removal, so that the mass of accumulated condensed water can be monitored as a safety
precaution. Steam injection must stop before VFw approaches 1 to avoid rupture of the reactor.
It is interesting to note that the solid content %S(T) of feedstock for all seven cases was less than
45% at the reaction temperature. The solid content for HTC systems ranged from 1.0 to 19.9%, while
that for VTC systems from 27.6 to 45%. It means that 55% or more of the total water mass was present
as liquid water and had direct physical contact with feedstock promoting carbonization reactions.
According to Cao et al., the lower the %S(T), the more the product was carbonized. The highest solids
content for VTC was 45% in Case 2 because of the water already present within the raw feedstock even
though additional water was not supplied. This leads to questions on what will happen if we conduct
VTC with completely dried feedstock, such as: Is it possible to carbonize the dried feedstock with
steam alone? For such reaction systems, the initial value of %S(To ) equals one. The value of %S(T) will
become less than one as some of the steam condenses on the surface of feedstock promoting the HTC
reactions. In such a system, the extent of carbonization will be determined by the extent of the wetting
of the feedstock by steam. More detailed study is needed to understand the relationship between the
degree of wetting by steam and carbonization.
3.4. Comparison of the Processes Using the T–v Diagram

To graphically illustrate the process conditions for each case at its reaction temperature, the values
for the seven cases are plotted on a T-v phase diagram (Figure 6). Their locations in relation to the
saturation curve show whether steam or liquid water predominates at the specific process conditions.
Due to the log scale for the x-axis, the ratio between the two phases cannot easily be determined
visually from the figure. Nevertheless, this visualization may help us to understand why some results
from these studies comparing HTC and VTC systems are contradictory. The operating conditions in the
HTC vs. VTC comparative studies are very different. The thermodynamic conditions in Cases 4 and
6 result in water being present mainly as a liquid for the HTC reactions as expected (i.e., toward the left
side of the dome), while Case 5 is mid-range and Case 7 is located nearer the vapor saturation curve
with a predominant steam phase. Process conditions for Case 1 (HTC) are to the left of Case 2 (VTC)
on the 200 ◦ C and 1.5 MPa isobaric line, suggesting more HTC reactions in Case 1, but the locations are
closer together than the other pairs. Thus, this diagram visualizes the differences in the reaction phases,
and allows us to subsequently interpret whether the system can be characterized more as HTC or VTC.
When the conditions result in the same overall specific volume but with different process temperatures,
the amount of water present as steam will change. This is true for Case 1-bark and Case 5-digestate
(Table 3 and Figure 6). Both have a similar vR , but Case 5-digestate at 230 ◦ C has almost double the
amount of water present as steam (xv = 0.1239) than that for Case 1-bark at 200 ◦ C (xv = 0.069).
Figure 6. Comparison of the process conditions for the seven cases in the T–v diagram for water.
107
Energies 2020, 13, 5733
Furthermore, the diagram helps visualize the safety aspects. It is easy to see that the target
conditions in Cases 1, 2, 5, and 7 are well away from entering the subcooled liquid compression region,
where pressure increases rapidly with an increase in reactor temperature. For the semi-batch system
in Case 3, the overall specific volume vR decreases from 0.005 to 0.0029 m3 /kg due to the increase in
the total mass of water as steam is injected into the reactor, and we move from the right to the left on
the isobaric line at 1.6 MPa (Figure 6). For such semi-batch systems, it is important to make sure the
start and end points remain far enough away from the subcooled compression region. Temperature
increases above the initial target conditions due to use of superheated steam or exothermic reactions
could move the system diagonally upwards towards the subcooled compression region and high
pressure as steam is added. In the subcooled compression region, if a safety rupture disk valve is not
present to release at a preset pressure, the reactor pressure can exceed the tensile strength of reactor
material, and the reactor can explode.
4. Conclusions
There are many types of hydrothermal reactor systems being used with many process variations
in the literature. The analysis presented in this paper illustrates that a large range of conditions
need to be considered before labeling a reactor system VTC and HTC. The analysis of the process
conditions of seven different HTC/VTC cases reported in the literature through the use of the models
developed in this paper and a T-v phase diagram showed that the distinction between HTC and VTC
is often ambiguous. The models developed in this study for predicting pressure, the volume fraction
of liquid water and the distribution of water between phases as a function of reactor temperature
can be used to systematically analyze various HTC/VTC process conditions. Furthermore, this study
also demonstrates the importance of predicting the condition at which the reactor system enters the
subcooled compression liquid region to avoid the danger of explosion. Comparison of the reactor
pressures predicted by the models to the actual pressure for reactors filled with varying amounts
of water with and without initial pressurization showed reasonable agreement. However, higher
pressures can be expected with the addition of feedstock due to the production of CO2 and other
gases by the hydrothermal reactions and the decrease in headspace volume occupied by the feedstock.
In order to describe the amount of liquid water in physical contact with feedstock, we defined a new
solid content parameter %S(T) which changes with reaction temperature due to changes in the water
distribution between phases. This parameter is more useful in describing the solid content than the
nominal parameter %So typically reported in the literature. While the models developed here can help
determine whether steam or liquid water predominates at the specific process conditions, more research
and modeling on hydrothermal systems with feedstock present are required to understand the effect
of the water phase on the hydrothermal reactions. The tools presented here can help in designing
experiments to compare systems and in understanding results in future HTC research.
Author Contributions: K.S.R. conceived the original idea, conducted W-HTC experiments, analyzed the data,
and participated in manuscript writing. J.A.L. conducted experiments using an 18.75-L reactor system, and both
J.A.L. and A.A.-M. participated in all phases of the research, analyzed the data, simulated T-v diagrams,
and participated in manuscript writing. All authors have read and agreed to the published version of
the manuscript.
Funding: Financial help for A.A.M. came from the Junta de Extremadura and FEDER (Fondo Europeo de
Desarrollo Regional “Una manera de hacer Europa”) project IB16108, and also from the program “Ayudas a grupos
de la Junta de Extremadura” GR18150. The open access journal fee was supported by the Leibniz Association’s
Open Access Publishing Fund.
Acknowledgments: The authors would like to acknowledge the technical support provided by Melvin Johnson
of the USDA-Agricultural Research Service (ARS), Coastal Plains Soil, Water and Plant Research Center, Florence,
SC, and Marcus Fischer of the Leibniz Institute of Agricultural Engineering and Bioeconomy. This research was
supported by the USDA-ARS National Program 212 Soil and Air. Mention of trade names or commercial products
is solely for the purpose of providing specific information and does not imply recommendation or endorsement
by the U.S. Department of Agriculture.
108
Energies 2020, 13, 5733
Glossary
Symbol Description Unit
D overall reactor water density, MH2O /VR kg/m3
Mbiomass mass of feedstock in the reactor as dry matter (DM)
MH2O total mass of water as liquid and vapor water in the reactor kg
MC moisture content %
MWH2O molecular weight of water kg/kmol
P reactor pressure MPa
Po initial reactor pressure MPa
Psat saturated vapor pressure -
R universal gas constant (8.31451 × 10-3 m3 -MPa/kmol-K) -
% solid in reactor—ratio of mass of feedstock in DM to (total mass of
%S water + mass of feedstock in DM in reactor), -
Mbiomass /(MH2O + Mbiomass )
T reactor temperature ◦C
VFo volume fraction of liquid water in the reactor at initial temperature To -

VFw volume fraction of liquid water in the reactor at temperature T -
VR reactor volume m3
Vw volume of liquid water in the reactor at temperature T m3
overall specific volume of reactor liquid water and steam mixture,
vR m3 /kg
VR /MH2O
vL specific volume of saturated liquid water m3 /kg
vv specific volume of saturated steam m3 /kg
xL mass fraction of liquid water -
xv mass fraction of vapor water or steam (or also called steam quality) -
Z compressibility factor for liquid or vapor -
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affiliations.
110
energies
Article
Formation of Carbon Quantum Dots via Hydrothermal
Carbonization: Investigate the Effect of Precursors
Md Rifat Hasan 1 , Nepu Saha 2 , Thomas Quaid 2 and M. Toufiq Reza 2, *
1 Department of Chemical and Biomolecular Engineering, Ohio University, Athens, OH 45701, USA;
mh919116@ohio.edu
2 Department of Biomedical and Chemical Engineering and Sciences, Florida Institute of Technology,
Melbourne, FL 32901, USA; nsaha2019@my.fit.edu (N.S.); tquaid2018@my.fit.edu (T.Q.)
* Correspondence: treza@fit.edu; Tel.: +1-321-674-8578
Abstract: Carbon quantum dots (CQDs) are nanomaterials with a particle size range of 2 to 10 nm.
CQDs have a wide range of applications such as medical diagnostics, bio-imaging, biosensors,
coatings, solar cells, and photocatalysis. Although the effect of various experimental parameters,
such as the synthesis method, reaction time, etc., have been investigated, the effect of different
feedstocks on CQDs has not been studied yet. In this study, CQDs were synthesized from hydrox-
ymethylfurfural, furfural, and microcrystalline cellulose via hydrothermal carbonization at 220 ◦ C
for 30 min of residence time. The produced CQDs showed green luminescence behavior under
the short-wavelength UV light. Furthermore, the optical properties of CQDs were investigated
using ultraviolet-visible spectroscopy and emission spectrophotometer, while the morphology and
chemical bonds of CQDs were investigated using transmission electron microscopy and Fourier-
transform infrared spectroscopy, respectively. Results showed that all CQDs produced from various
precursors have absorption and emission properties but these optical properties are highly dependent
Citation: Hasan, M.R.; Saha, N.;
on the type of precursor. For instance, the mean particle sizes were 6.36 ± 0.54, 5.35 ± 0.56, and
Quaid, T.; Reza, M.T. Formation of 3.94 ± 0.60 nm for the synthesized CQDs from microcrystalline cellulose, hydroxymethylfurfural,
Carbon Quantum Dots via and furfural, respectively, which appeared to have similar trends in emission intensities. In addition,
Hydrothermal Carbonization: the synthesized CQDs experienced different functionality (e.g., C=O, O-H, C-O) resulting in different
Investigate the Effect of Precursors. absorption behavior.
Energies 2021, 14, 986.
https://doi.org/10.3390/en14040986 Keywords: carbon quantum dots; hydrothermal carbonization; hydroxymethylfurfural; furfural;
microcrystalline cellulose
Academic Editor: David Chiaramonti
Received: 17 January 2021

Accepted: 11 February 2021
1. Introduction
Published: 13 February 2021
Carbon quantum dots (CQDs) are a new class of carbon nanomaterials sized below
Publisher’s Note: MDPI stays neutral
10 nm [1,2]. CQDs have attracted tremendous attention in the research community due
with regard to jurisdictional claims in
to their unique photoluminescence (PL) properties, biocompatibility, electrochemical lu-
published maps and institutional affil- minescence properties, and low toxicity [3–5]. These properties enable them to be used
iations. in bio-imaging, biosensor, drug delivery, and photo-catalysis applications [6–13]. CQDs
are mainly synthesized via two approaches: top-down and bottom-up. The top-down
approach refers to the breakdown of larger carbon particles by laser ablation, electrochemi-
cal oxidation, chemical oxidation, and ultrasonic synthesis [14–17], while the bottom-up
Copyright: © 2021 by the authors.
approach synthesizes the CQDs from molecular precursors through microwave synthe-
Licensee MDPI, Basel, Switzerland.
sis, thermal decomposition, and hydrothermal treatment [4,18–20]. Among all synthesis
This article is an open access article
methods, hydrothermal carbonization (HTC) has been considered as the most promising
distributed under the terms and method due to high quantum efficiency, lower cost, environmentally friendly nature, and
conditions of the Creative Commons non-toxicity [4,5,20–22].
Attribution (CC BY) license (https:// HTC is an emerging technology that converts carbohydrates into high-value materials,
creativecommons.org/licenses/by/ fuels, and chemicals [23–26]. HTC is typically performed at 180 to 260 ◦ C for 5 min to 12 h
4.0/). under water saturation pressure, depending on the application [27]. In this conditions,

111
Energies 2021, 14, 986
water is more reactive and behaves as a non-polar solvent because of high ionic product
and low dielectric constant [28]. Therefore, carbohydrates undergo for hydrolysis and
the hydrolyzed products then undergo for simultaneous dehydration, decarboxylation,
condensation, and polymerization to make cross-linked polymeric materials [29]. The
particle sizes of the solid product, often referred as hydrohcar, are generally between 10 nm
to 100 μm [30]. As HTC is a bottom-up approach, the particles smaller than 10 nm remain
in the liquid phase (known as process liquid). HTC process liquid is referred to as the
waste product from a HTC process; thus far, it is considered as a liability for the HTC
development, as it requires expensive treatment. Various treatment technologies including
anaerobic digestion (AD), wet air oxidation (WAO), and membrane distillation (MD) have
been proposed to treat HTC process liquid [31–33]. However, the lack of value-added
product separation along with the additional cost of treatment often prohibits the adoption
of these aforementioned technologies for HTC process liquid.
In the recent past, various researchers have tried to separate the CQDs from the
liquid phase of the HTC process [3,4,34–36]. For instance, Mehta et al. produced highly
fluorescent CQDs from sugarcane via hydrothermal treatment at 120 ◦ C for 3 h [4]. The
obtained the CQDs were about 3.0 nm in size with highly blue fluorescence. On the other
hand, Sahu et al. reported highly photoluminescent CQDs with sizes 1.5 to 4.5 nm from
orange juice via HTC at 120 ◦ C for 2.5 h [34]. Papaioannou et al. studied the effect of
HTC residence time from 2 to 12 h at 200 ◦ C on the properties of CQDs produced from
D -(+)-glucose [35]. They reported that the sizes of CQDs decreased and their level of
crystallinity increased with an increase in reaction time.
From the above discussed literature, it is clear that various parameters such as reaction
time, residence time, etc. have been examined to understand their effect on the properties of
CQDs. Although researchers studied different feedstocks at various conditions, to the best
of the authors’ knowledge, no study has been reported about how the properties of CQDs
change with the variation of feedstock at the same experimental conditions (temperature
and residence time). The hypothesis was that simultaneous evolutions of amorphous
hydrochar and semi-crystalline CQDs occur during HTC reactions. The amorphous hy-
drochar agglomerates into micro-meter-sized supramolecules, whereas, nano-sized CQDs
remain in the liquid phase due to their high aqueous solubility. As various biopolymers
react differently under HTC conditions, the authors’ expectation was that the presence
and properties of CQDs will be different as well. Therefore, the objectives of the project
were to investigate the effect of feedstock on the properties of CQDs. To achieve this
goal, HTC of three organic precursors (i.e., furfural, 5-hydroxymethyl furfural (HMF),
and microcrystalline cellulose) have been performed at 220 ◦ C for 30 min of residence
time. In this study, the HTC experiments were conducted at a relatively low temperature
and residence time as they are reported to be favorable for CQD production. HMF and
furfural might react at temperatures lower than 220 ◦ C under an HTC environment, but the
literature indicates that microcrystalline cellulose starts to react at around 220 ◦ C [29,37].
As the purpose of this study was to investigate the effect of precursor, the authors wanted
to choose the lowest temperature where all the precursors could react under the HTC
environment. Multi-staged filtration was performed on the process liquids to remove
supramolecules. The presence of CQDs was confirmed by investigating the optical (lumi-
nescence, ultraviolet-visible absorption, and emission), morphology (transmission electron
microscopy), and chemical (Fourier Transform Infrared Spectroscopy) properties.

2.1. Materials
In this study, CQDs were produced from three different biomass precursors. Of them,
5-hydroxymethylfurfural (HMF) was purchased from Carbosynth LLC. (San Diego, CA,
USA). Meanwhile, furfural was purchased from Sigma-Aldrich (St. Louis, MO, USA).
On the other hand, microcrystalline cellulose (extra pure, avg. particle size 90 μm) was
112
Energies 2021, 14, 986
purchased from Acros Organics (Fair Lawn, NJ, USA). Analytical-grade ethanol was
purchased from Fisher Scientific (Waltham, MA, USA).
2.2. Methods
2.2.1. Hydrothermal Carbonization and Separation of CQDs from HTC Process Liquid
HTC experiments of different precursors were performed in a glass-lined 100 mL Parr
batch reactor (reactor series 4590, Moline, IL, USA). A Parr proportional-integral-derivative
(PID) controller (model 4590) with an accuracy of ±2 ◦ C was used to control the reaction
temperature. The pressure was not controlled but was monitored during the experiment
with a pressure transducer and a gauge. HTC experiments were conducted at 220 ◦ C for
a residence time of 30 min. The reactor was loaded with 45 mL solution contained 10%
(w/v) of precursor and the rest was deionized (DI) water. The reactor was closed and
heated at a constant rate of 10 ◦ C/min until it reached the set temperature and then it
was maintained at isothermal conditions for 30 min. At the end of the residence time, the
heater was turned off, heating elements were removed from the reactor, and the reactor
was rapidly cooled to room temperature (~30 ◦ C) by placing it in an ice-water bath. Once
the reactor reached room temperature, the gaseous products produced during the reaction
were vented in a fume hood by opening the vent valve. Finally, the lid of the reactor was
opened and HTC process liquid was filtered by Whatman 41 filter paper. Dark brown HTC
process liquid samples were collected in centrifuge tubes and stored in the refrigerator
for further synthesis. As the major goal of this study was to evaluate the variation of
optical, morphological, and chemical properties of CQDs with precursors, the hydrochar
and gaseous products were not further characterized. However, the mass balance and
physico-chemical characterization of hydrochars can be found elsewhere [23]. All the
experiments were completed in duplicate to check reproducibility.
The dark brown HTC process liquid was centrifuged at 10,000 rpm for 15 min by
a Sorvall BIOS 16-series centrifuge from Thermo Fisher Scientific (Waltham, MA, USA)
to separate the larger particles from the liquid phase. The fluorescent CQD containing
liquid phase was then filtered with a standard syringe filter (0.22 μm). The filtered CQD
containing solution was then evaporated under reduced pressure by vacuum distillation.
The concentrated product from vacuum distillation was kept in the high vacuum freeze
dryer for 24 h to obtain powdered CQDs. The powdered CQDs were collected and
refrigerated in glass vials for further investigations. A schematic of the CQD synthesis and
characterization strategy is shown in Figure 1.
Feedstocks Synthesis Process Characterizations
DI Water
Uv-Vis Absorbance
Centrifuged at 10,000 Vacuum distillation
Filtered out the rpm for 15 minutes Freeze dry
solids Emission
Emission
HTC process CQD containing Spectrometer
Powdered CQD
liquid liquid phase
10 % (w/v) TEM Morphology
precursor Separate the
larger particles
HTC @ 220 °C for 30 FTIR Functional Groups

minutes
Figure 1. A schematic of the CQD synthesis and characterization strategy.
113
Energies 2021, 14, 986
2.2.2. Optical, Morphological, and Chemical Characterizations of CQDs

To investigate the fluorescent properties of the synthesized CQDs, short-wavelength
(254 nm) UV light was used. Although the produced CQDs appeared as light brown in
color under the day light, it showed a green luminescence under UV light (see graphical
abstract). The green luminescence under the UV light provided hints about the presence of
quantum particles in the produced solution. This finding encouraged the authors to further
investigate the optical properties of CQDs.
A Perkin Elmer Lambda LS 35 UV-visible spectrometer (Waltham, MA, USA) was
used to observe the absorption behavior of the CQDs. The syringe-filtered CQD containing
liquid phase was used in this analysis. The absorption capacity of those CQDs containing
liquid phase were beyond the maximum limit (2.5) of the UV-vis spectrometer. As a
result, all the original samples were diluted 5000 times with DI water. For each run, 10 mL
of diluted sample was taken in a quartz cuvette and absorption was monitored for a
wavelength range of 200 to 700 nm. The absorption capability of the CQDs was observed
relative to the DI water blank run.
A Horiba FluoroMax-4 emission spectrometer (Irvine, CA, USA) was used to investi-
gate the fluorescence emission capability of the synthesized CQDs at a certain excitation
wavelength. For a clear comparison of the emission capacity of different CQDs, all the CQD
samples were diluted to an absorbance value of 0.2 at 350 nm wavelength. A quartz cuvette
(considered for better light transmission) was used for obtaining the fluorescence emission
spectra. A slit width of 3 mm was used for the excitation and fluorescence emission spectra
of aqueous CQD solution. For 360 nm of excitation wavelength, emission spectra were
recorded for a wavelength range of 375 to 700 nm. Emission spectra were compared to DI
water blank run at the same condition.
To observe the morphologies and obtain size images of CQDs, transmission electron
microscopy (TEM) was performed on a Tecnai F20 system (Hillsboro, OR, USA). The
powdered CQDs were dispersed into ethanol and sonicated for 6 h. One drop of the
ethanol dispersed CQDs was placed on a copper grid coated with amorphous carbon, dried
at room temperature, and analyzed in TEM. The instrument was operated at 200 kV with
an X-TWIN lens and high-brightness field emission electron gun (FEG). The TEM images
were then processed with Image J software to determine the particle size distribution of
the CQDs.
To observe the changes in functional groups, Fourier-transform infrared spectroscopy
(FTIR) analysis was performed in Bruker Optics Vertex 80 FTIR (Billerica, MA, USA). For
the analysis, CQDs particles were dispersed in DI water. FTIR transmittance spectra were
obtained for the wavenumber range of 4000 to 500 cm−1 with respect to the reference of DI
water run.
All the above-mentioned characterizations were completed in duplicate to check
reproducibility.
3. Results and Discussions

3.1. Absorption Properties
The optical characteristics of CQDs were investigated in terms of their absorption and
emission properties. From the UV-vis spectra (absorption properties) shown in Figure 2, it
was observed that all CQDs exhibit a broad range of absorption in the UV region, with the
tails of the spectra in the near-visible region. Although all of the CQD samples started to
show absorption behavior at the same wavelength (240 nm), their peak intensities were
different. For instance, the cellulose peak showed the highest intensity of 2.35 while HMF
and furfural showed peaks of 1.45 and 0.7, respectively. Additionally, the cellulose derived
CQDs showed normal distribution while the furfural showed average distribution. This
phenomenon indicates that the CQDs produced from furfural can absorb wide wavelengths
while cellulose CQDs can adsorb more specific wavelengths among the three studied
precursors. This variation of the absorption properties could be further supported by the
FTIR spectra (see Figure 3). In the cellulose spectrum, only a carbonyl (C=O) peak was
114
Energies 2021, 14, 986
observed at 1670 cm−1 . On the other hand, both HMF and furfural showed various other
peaks, such as medium alcohol (O-H) peaks between 1330 and 1420 cm−1 , aromatic ester
(C-O) peaks between 1200 and 1300 cm−1 , and a sharp alkyl ether (C-O) peak at 1027 cm−1 .
Due to the presence of additional functionality, HMF and furfural could exhibit broader
absorbance compared to cellulose. In addition to the broad peaks, CQDs showed tails in
the visible region. These tails are typically related to nanoparticle functionalization and are
reported as lower energy surface centers [38]. These tails are also attributed the presence of
various π→π* (C=C) and n→π* (C=O and/or others) transitions [2]. As the aromatic rings
increase with the hydrothermal treatment, the energy gaps between π states gradually
decreased [15]. On the other hand, functional groups (i.e., carbonyl) with electron lone pairs
could be bonded with aromatic carbon that allows electron transition from n states [39].
2.5
Cellulose
HMF
2.0
Furfural
Absorbance
1.5
1.0
0.5
0.0
200 300 400 500 600 700
Wavenlength (nm)
Figure 2. UV-Vis spectra for carbon quantum dots derived from various precursors.
Aromatic ester/ether @1200−1300
Conjugated ketone @1666−1680
Transmission
Carboxylic monomar @1760
Cellulose
Alcohol @1330−1420
Furfural
HMF
3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000
Wavenumber (cm-1)
Figure 3. FTIR spectra of the CQDs synthesized from various precursors.
3.2. Emission Properties

In addition to the adsorption properties, fluorescence emission properties of the CQDs
were investigated. The emission spectra of the CQDs are shown in Figure 4, where it can
115
Energies 2021, 14, 986
be seen that the emission wavelength (360 nm) is longer than the excitation wavelength
(240 nm) shown in the absorbance spectra (Figure 2). This observation is in line with previous
literature, where the researchers reported the reason behind this is mainly due to bandgap
of the conjugated π domains and/or the presence of defects in the structures [39–41]. The
spectra also show that the emission capacity of cellulose-based CQDs is the highest among
the studied feedstocks, where furfural-derived CQDs show the least emission capacities. As
the absorbance intensity of the furfural-derived CQDs was the least, it was expected to have
the highest emission properties. However, the emission properties showed the similar trend
as absorption capacity. This could be due to the combined effect of functional groups, ligand
chain length, surface defects, and morphology of the CQDs [42].
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Figure 4. Emission spectra of carbon quantum dots derived from various precursors.
3.3. Morphology of the CQDs

The morphology and particle size of the produced CQDs were obtained from TEM
analysis which are shown in Figure 5. It is observed that these CQD particles are spherical
in shape and most of the particles are separated from each other. Size distribution results
revealed that the spherical nanoparticles diameter ranged from 2 to 9 nm. Although the
CQDs were synthesized under the same hydrothermal conditions, the sizes of the CQDs
were different. This could be due to the various degradation temperatures of the precursors
allowing them to nucleate at different conditions, thus forming different-sized CQDs [43,44].
In addition, the agglomeration of the particles could be the reason for getting various mean
sizes [43]. A general trend between CQD emission capacity and mean size was observed.
For instance, the highest emission capacity was attributed to the mean particle diameter
of 6.36 ± 0.54 nm for the cellulose-derived CQDs, while the lowest emission intensity
occurred with the mean particle diameter of 3.94 ± 0.60 nm from the furfural-derived
CQDs. This could be attributed to the increased surface area of the particles, allowing more
light-emitting functional groups to be present and active.
The CQDs produced in this study contain remarkably similar characteristics, as found
by the Zhao et al. and Gao at al., where they produced CQDs from pine wood and alkali
lignin, respectively, via HTC treatment [45,46]. The similarities include but are not limited
to the absorption range of 225 to 300 nm, the emission range of 435 to 450 nm, and the size
2 to 5 nm. With these characteristics, the CQDs were successfully used as a nanosensor to
detect the iron (Fe3+ ) and ascorbic acid. It has been determined that the functionalization
of the CQDs with groups containing oxygen are crucial to the success of the detection of
the ions as they are chelated by these groups to induce a fluorescent quenching [45,46]. The
CQDs produced in this study all share this vital characteristic as well. Although the dots in
this study fall within those ranges in every respect except for the size of the cellulose dots,
these CQDs could be used for similar purposes as well.
116
Energies 2021, 14, 986
(A)
(B)
(C)
Figure 5. TEM size images along with the particle size distribution of the different types of CQDs synthesized from:
(A) HMF; (B) Furfural; (C) Cellulose.
117
Energies 2021, 14, 986
4. Conclusions
In this study, CQDs were produced from HMF, furfural, and microcrystalline cellulose
via HTC at 220 ◦ C for 30 min. The optical and morphological properties of the produced
CQDs were investigated. It was observed that CQDs showed green luminescence under
short-wavelength UV light (254 nm). Additionally, they can absorb light in a broad range.
The variation of the absorption range was justified from the FTIR spectra where CQDs
from different precursors showed different chemical bonds (e.g., alcohol, ketone, etc.).
Although all the studied CQDs were within two to nine nm in diameter, the mean diameter
varied with the precursor. Depending on the particle size, the CQDs showed different
emission capacities. Finally, this study provides an insight into the effect of precursor on
the CQD properties. So, the precursors for the CQDs should be selected based on the
targeted applications.
Author Contributions: Conceptualization, M.R.H., N.S., M.T.R.; methodology, M.R.H., N.S.; formal
analysis, M.R.H., N.S., T.Q.; investigation, M.R.H., N.S., M.T.R.; writing—original draft preparation,
M.R.H., N.S., T.Q.; writing—review and editing, M.R.H., N.S., T.Q., M.T.R. All authors have read and
agreed to the published version of the manuscript.
Funding: The research is partially funded by the United States Department of Agriculture (USDA)
grant (2019-67019-2928) through M.T.R.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: The authors acknowledge Travis A. White from the Department of Chemistry
and Biochemistry at Ohio University for allowing to use emission spectrofluorometer. The authors
are also thankful to Kyle McGaughy from the biofuels lab at the Florida Institute of Technology for
his laboratory efforts in this project.
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energies
Article
Integration of Air Classification and Hydrothermal
Carbonization to Enhance Energy Recovery of Corn Stover
Md Tahmid Islam 1 , Nepu Saha 1 , Sergio Hernandez 2 , Jordan Klinger 2 and M. Toufiq Reza 1, *
1 Department of Biomedical and Chemical Engineering and Sciences, Florida Institute of Technology,
150 W University Boulevard, Melbourne, FL 32901, USA; islamm2019@my.fit.edu (M.T.I.);
nsaha2019@my.fit.edu (N.S.)
2 Biomass Characterization Department, Idaho National Laboratory, 2525 Fremont Ave, Idaho Falls,
Idaho, ID 83402, USA; sergio.hernandez@inl.gov (S.H.); jordan.klinger@inl.gov (J.K.)
* Correspondence: treza@fit.edu; Tel.: +1-321-674-8578
Abstract: Air classification (AC) is a cost-effective technology that separates the energy-dense light
ash fraction (LAF) from the inorganic-rich high ash fraction (HAF) of corn stover. HAF could be
upgraded into energy-dense solid fuel by hydrothermal carbonization (HTC). However, HTC is a
high-temperature, high-pressure process, which requires additional energy to operate. In this study,
three different scenarios (i.e., AC only, HTC only, and integrated AC–HTC) were investigated for
the energy recovery of corn stover. AC was performed on corn stover at an 8 Hz fan speed, which
yielded 84.4 wt. % LAF, 12.8 wt. % HAF, and 2.8 wt. % below screen particles. About 27 wt. % ash
was reduced from LAF by the AC process. Furthermore, HTC was performed on raw corn stover
and the HAF of corn stover at 200, 230, and 260 ◦ C for 30 min. To evaluate energy recovery, solid
products were characterized in terms of mass yield, ash yield, ultimate analysis, proximate analyses,
and higher heating value (HHV). The results showed that the energy density was increased with
Citation: Islam, M.T.; Saha, N.;
the increase in HTC temperature, meanwhile the mass yield and ash yield were decreased with the
Hernandez, S.; Klinger, J.; Reza, M.T. increase in HTC temperature. Proximate analysis showed that fixed carbon increased 18 wt. % for
Integration of Air Classification and original char and 27 wt. % for HAF char at 260 ◦ C, compared to their respective feedstocks. Finally,
Hydrothermal Carbonization to the hydrochar resulting from HAF was mixed with LAF and pelletized at 180 bar and 90 ◦ C to densify
Enhance Energy Recovery of Corn the energy content. An energy balance of the integrated AC–HTC process was performed, and the
Stover. Energies 2021, 14, 1397. results shows that integrated AC with HTC performed at 230 ◦ C resulted in an additional 800 MJ/ton
https://doi.org/10.3390/en14051397 of energy recovery compared to the AC-only scenario.
Academic Editor: Byong-Hun Jeon Keywords: corn stover; air classification; hydrothermal carbonization; pelletization; energy recovery
Received: 28 January 2021

Accepted: 1 March 2021
Published: 4 March 2021
1. Introduction
More than one billion tons of biomass will be available for bioenergy production in
the USA by 2030 [1–3]. Among other resources, corn stover (CS) has a huge potential to
published maps and institutional affil- contribute to the renewable energy portfolio, as more than 250 million dry tons of CS are
iations. produced annually in the USA [1,4]. With proper feedstock handling and preprocessing,
CS could become an abundant source of bioenergy [5,6]. However, a significant amount of
agricultural waste, including CS, is burnt or left unprocessed in the field due to high logis-
tical costs. This results in serious environmental problems and economic forfeiture [7,8].
Copyright: © 2021 by the authors.
Therefore, the utilization of potential bioenergy from waste biomass sources such as CS
Licensee MDPI, Basel, Switzerland.
needs to be considered with urgency.
This article is an open access article
Air classification (AC) is a low-cost preprocessing technology that has been developed
distributed under the terms and particularly in agricultural processing and mining applications. In AC, the separations
conditions of the Creative Commons are performed based on a combination of material size, density, and drag properties,
Attribution (CC BY) license (https:// utilizing screens and air streams to effectively separate high-density fractions from low-
creativecommons.org/licenses/by/ density fractions. In general, large amounts of soil, rocks, and other foreign matters are
4.0/). incorporated into the feedstock during harvest and collection. The inorganics, dirt, rocks,

121
Energies 2021, 14, 1397
and foreign materials are mostly dense materials compared to the lignocellulosic structure
of biomass. Therefore, AC separates a significant amount of these exogenous inorganics
and creates an enriched stream of biomass (often called the light ash fraction, LAF) and a
soil-laden reject stream (also known as the high ash fraction, HAF) [9–11]. Lacey et al. [11]
showed such separations for chipped forest residues after AC and reported remarkable
ash (wt. %) reductions (>32 wt. %) in the final throughputs. Emerson et al. [9] also found
quite reasonable reductions in ash (wt. %) for hybrid poplar (from 2.34 wt. % to 1.67 wt. %)
and shrub willow (from 2.60 wt. % to 2.14 wt. %). Recently, Thompson et al. [2] showed
that AC can effectively upgrade CS by removing 30 wt. % ash at a mild 7.5 Hz fan speed,
or approximately 2.1 m/s counter-stream air flow of AC. It has also been reported that a
large fraction of HAF byproduct is produced during AC, accounting for more than 12 wt.
% of the initial CS. This HAF of CS contains more than 80 wt. % organic content that can be
further utilized [2]. Instead, an estimated HAF disposal cost of USD 28.86 per ton has been
suggested by Reza et al. [12] and Humbird et al. [13], accounting for 2.5 cents of the USD
2.15 per gallon minimum ethanol selling price. In order to make AC more economically
viable, the further utilization of HAF needs to be implemented in conjunction with AC
technologies and system-wide economics and sustainability for full material utilization.
However, to the best of the authors’ knowledge, no work has been done to date to utilize
the waste energy in value-added fuel. Therefore, to make use of the vital unrecovered
energy from this solid waste and integrate it with the AC technology, the HAF could be
converted into essential products.
Hydrothermal carbonization (HTC) is a promising thermochemical process that trans-
forms biomass, such as CS, into a carbon-rich solid product called hydrochar [5,14,15]. The
reaction temperature varies between 180 and 260 ◦ C, and the pressures are maintained
above the saturation pressure. The ionic products of water increase three orders of magni-
tude (KH2O (573K) /KH2O (298K) = 103 ) [5,15,16] and the dielectric constant of water reduces
from 78.5 (298 K, 0.1 MPa) to 27.1 (523 K, 5 MPa) [15,17]. As a result, biomass undergoes a
series of reactions, i.e., hydrolysis, decarboxylation, dehydration, condensation polymeriza-
tion, and aromatization, in subcritical water due to the increased reactivity and solvent-like
properties [18,19]. For agricultural residues, the HTC reaction products can be divided into
three streams: 41–90 wt. % solids with 80–95 wt. % of the original calorific value; 2–10 wt.
% gas consisting mainly of CO2 ; the rest is process liquid [20–24]. The energy-dense solid
hydrochar can be pelletized to improve the mass and energy density of the feedstock and
reduce the cost of transportation, handling and storage [25–27].
During HTC, the low density and low viscosity of subcritical water, in combination
with the acidic process liquid and the modification of the biomass structure, aid in the
leaching of inorganics from biomass structures [18,28–31]. The reduction of ash is partic-
ularly important for hydrochars’ application as fuel, as this can significantly reduce the
ash-fusion temperatures, leading to slagging in fuel boilers [1]. Therefore, HTC could be
used to recover the energy in the HAF stream while reducing ash from the hydrochar.
However, HTC is an energy-intensive process as it requires high temperatures and high
pressure. Therefore, an energy balance in the integrated AC–HTC is warranted to evalu-
ate the net energy recovery from the integrated process compared to the individual AC
and HTC processes. Therefore, the main goal of this work was to study the feasibility of
three different scenarios, to determine the energy recovery from CS: 1. AC-only process;
2. HTC-only process; 3. Integrated AC–HTC process. First, the AC of CS was performed
to separate LAF and HAF. Then HTC on HAF was performed at various temperatures
and the hydrochars were pelletized with LAF. The energy recovery from the integrated
AC–HTC process was compared with AC-only and HTC-only, wherein the original (ORG)
CS was used for both technologies.
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2.1. Materials
A raw corn stover bale from Kadolph Farms in Hardin, Iowa was deconstructed in the
process development unit (PDU) of the Idaho National Laboratory’s Biomass Feedstock
National User Facility (BFNUF). The bale was harvested in the fall of 2018 using an 8-
row stripper header and raked using rotary tedder prior to baling. Bales were stored
immediately after baling in stacks at the field edge with a six-high by three-length stacking
position. Size reduction in the BFNUF was accomplished using a Vermeer prototype
horizontal bale grinder (BG480, Pella, Iowa) with a 15.24 cm screen. This mill was powered
by two 200 HP electric motors with 96 swinging hammers on each of the two grinding
drums. The sample, referred to as ORG CS hereafter, was dried below 10 wt. % moisture
content prior to AC and HTC treatments.
2.2. Methods
2.2.1. Air Classification of Corn Stover
The ORG CS intended for HTC were sampled using mechanical sampling procedures
and equipment according to Solid Biofuels Sampling ISO 18135:2017. A super sack of the
deconstructed CS bale was divided using a custom rotary splitter that consists of a conveyor
and eight bins mounted on a rotating table. In this unit, a feed hopper accommodates
approximately 120 L of sample and a live-bottom style belt feeder slowly dispenses the
samples to 8 sample bins below. The 45 L bins rotate over 100 times during each splitting
operation and make at least one full rotation for each belt flight to ensure the samples
are representative of the original bulk solid. Both the belt feeder and the rotary table are
equipped with speed control devices (variable frequency drive and/or DC potentiometer)
to adjust the processing parameters according to the sample feed behavior to ensure
analytical splitting (an image of AC can be found in the supplementary information
(Figure S1)). AC separates the samples into two fractions as the material is passed over a
screen-covered fan: LAF and HAF. The HAF is blown upward and removed while the LAF
(air classified material) remains. Air classification was performed on CS feedstocks using
a 2× Air Cleaner equipped with an Iso-flo dewatering infeed shaker (Key Technologies,
Walla Walla, WA, USA). CS was air classified using a fan speed of 1.8 m/s. Both light and
heavy fractions were collected after classification for downstream processing and analyses.
2.2.2. Hydrothermal Carbonization (HTC)

HTC was carried out in the 300 mL Parr reactor (Moline, IL, USA) for 30 min at three
different temperatures 200, 230, and 260 ◦ C (an image of the HTC reactor system is shown
in the supplementary section (Figure S2)). In a typical HTC run, 20 g of dry CS (HAF or
ORG CS) was mixed with 180 mL of deionized (DI) water inside the reactor vessel. The
reactor was stirred at 150 ± 5 rpm throughout the HTC experiment. The temperature
of the reactor was controlled using a proportional integral derivative (PID) controller.
The heating rate was maintained at 10 ◦ C min−1 . The pressure was not controlled but
monitored throughout the HTC, which was found to be 210 ± 20 psi, 380 ± 20 psi, and
620 ± 20 psi for the 200 ◦ C, 230 ◦ C and 260 ◦ C operating temperatures, respectively. When
the reactor reached the desired HTC temperature, it was kept isothermal for 30 min. At
the end of the HTC reaction time, the heater was turned off and the reactor was quenched
by an ice water bath. It took 15 ± 5 min to cool down the reactor below 50 ◦ C. The gas
produced during HTC was not the focus of this work and was vented in a fume hood.
The slurry was then filtered using Whatman 41 filter paper in a vacuum filtration system.
The hydrochar was first washed with approx. 200 mL deionized (DI) water to remove the
HTC liquid products that adhered to the hydrochar, and then dried at 105 ◦ C for 24 h in an
oven. The dried hydrochar was stored in a ziplock bag for further analysis. The solid mass
yield (MY) was calculated using Equation (1). Each hydrochar referred to in this work is
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labeled according to the HTC temperature. For instance, CS ORG HTC200 represents the
hydrochar produced from ORG CS at 200 ◦ C.
Mass of dried post(g) − process solid(g)

MY(wt. %) = × 100% (1)
Mass of untreated dry feedstock (g)
2.2.3. Pelletization of Hydrochar with Corn Stover

Samples (LAF, ORG hydrochar, and hydrochar–LAF mix) were pelletized using a
24 ton benchtop single-press pellet press (Across International, model # MP24A, Livingston,
NJ) (an image of the pellet press can be found in the supplementary information (Figure S3)).
About 1.5 g of dry sample was powdered using mortar pestle to make it homogeneous.
From the homogeneous powdered sample, 0.50 g of dry was taken out and put in the die
sleeve of the 13 mm circular pressing die. A compressive force of 7.5 MT was applied at
the top surface of the sample by the lever. The temperature was set at 90 ◦ C (beyond the
glass transition temperature for CS) [32] using a band heater and the holding time was set
at 30 s for each pellet. Pellets were stored in sealed bags for further characterizations.
2.3. Product Characterization

2.3.1. Higher Heating Value (HHV)
An IKA C 200 bomb calorimeter (Staufen, BW, Germany) was used to determine
higher heating values (HHV) of the raw and hydrochar pellets by following the ASTM
D240 method. Energy yield (EY) was calculated by Equation (2). Triplicates were performed
for each sample to report reproducibility.

HHV of dried hydrochar MJ kg
EY(%) = MY(wt. %) × (2)
HHV of untreated dry feedstock MJ kg
2.3.2. Ash
The ASTM D1102 method was followed to determine the ash content of the dry solid
samples by using a muffle furnace (Thermo Scientific, Model # FB1415M, Waltham, MA) at
575 ◦ C for 5 h 30 min. The ash yield (AY) was calculated by using Equation (2). Triplicates
were performed for each sample to report reproducibility.
Ash in hydrochar (wt. %)

AY (wt. %) = MY(wt. %) × (3)
Ash in raw feedstock (wt. %)
2.3.3. Thermogravimetric Analysis (TGA)

The volatile matter (VM) and fixed carbon (FC) of samples were determined by TGA
using a TGA Q5000 (TA instruments, New Castle, DE, USA). The experimental procedure
was taken from the literature [33]. Experiments were carried out under inert atmosphere
using a constant flowrate (10 mL/min) of nitrogen to avoid any possible oxidation and to
continuously purge the VM. The sample was first heated to 105 ◦ C and kept isothermal
for 5 min. The mass loss at this temperature accounts for the moisture content (MC). The
sample was then heated to 900 ◦ C at a ramp rate of 20 ◦ C/min and kept isothermal for
5 min. The mass loss from 105 ◦ C to 900 ◦ C accounts for VM. Finally, the FC (wt. %) was
then calculated from Equation (3):
FC (wt. %) =100 wt. % − MC (wt. %) − VM (wt. %) − ash (wt. %) (4)
2.3.4. CHNS/O Analysis

A FLASH EA 1112 Series (Thermo Scientific, Waltham, MA, USA) elemental analyzer
was used to quantify the elemental carbon (C), hydrogen (H), nitrogen (N), and sulfur (S)
content in the sample using the method described in the literature [34]. For the analysis, 2,
5-Bis (5-tert-butyl-benzoxazol-2-yl) thiophene (BBOT) was used as a calibration standard
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and vanadium oxide (V2 O5 ) as a conditioner for the samples, which were combusted
around 950 ◦ C in ultra-high purity oxygen with helium carrier gas and passed over copper
oxide pellets and then electrolytic copper. The produced gases were then analyzed by a
thermal conductivity detector (TCD), with the peak areas of detection being compared to
those of BBOT standards. The oxygen (O) content was found by subtraction method. The
following equation was used to find the oxygen wt. %.
O (wt. %) = 100 wt. % − C (wt. %) − H (wt. %) − N (wt. %) − S (wt. %) − ash (wt. %) (5)

3.1. Characterization of Air Classified CS
The AC of ORG CS led to an LAF or “clean” fraction and an HAF or “dirty” fraction.
All the separations were conducted under the fan speed and frequency of 1.8 m/s and
8 Hz, respectively. These conditions were chosen for optimum separation as reported in
the literature [2,9,11,35]. As seen in Figure 1, the separated LAF contains more low ash
plant tissue fractions such as cobs, stalks, and husks, while the HAF contains more of
the undesired plant fractions (leaves, pith, rind) that usually contain higher ash values
as well as soil entrained during plant growth or picked up and baled with the CS during
harvest. Table 1. Proximate and ultimate analysis of ORG and separated CS. Measurements
made using ASTM D7582, ASTM D5373, and ASTM D4239.shows the results from the
three materials for comparison, detailing the proximate and ultimate analysis of each
fraction. The elemental carbon and moisture content increased more in the LAF than the
HAF because of the tissue types and sizes that are preferentially separated into the heavy
stream (cob and stalk) after AC. Meanwhile, the elemental oxygen content and volatile
content also increased in LAF after AC. On the other hand, the nitrogen and ash content
were increased in the HAF after AC. In fact, the LAF fraction from the air classification
resulted in a 27 wt. % reduction (from 7.13 wt. % to 5.24 wt. %) in total ash compared
with the original as-received CS material, whereby the trend is also in compliance with
Lacey et al. [11] and Thompson et al. [2]. The HAF resulted in a higher ash fraction, with
19.10 wt. % total ash that resulted from the higher portion of fines, leaves, and contaminants
such as plastic, twine, and introduced dirt typical of harvesting methods. Similar result
was also found in other reports in the literature [2]. This indicates a significant reduction in
inorganics that are non-convertible and lead to excessive equipment wear [2]. This material
beneficiation creates an enhanced feedstock for conversion, but also generates an alternate
biomass fraction that requires utilization. As discussed in this work, we investigate HTC
as a method of utilization. The conversion and analysis results further considered in this
study are focused around the HAF.
Figure 1. Photo of the original (ORG) prepared corn stover (CS) and the air classified separated CS with high ash fraction
(HAF) and light ash fraction (LAF) divisions.
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Table 1. Proximate and ultimate analysis of ORG and separated CS. Measurements made using
ASTM D7582, ASTM D5373, and ASTM D4239.
Sample Name CS ORG CS LAF 8 Hz CS HAF 8 Hz

Moisture (wt. %) 6.5 ± 0.0 6.7 ± 0.0 3.1 ± 0.0
VM (wt. %) 77.2 ± 0.2 78.9 ± 0.1 67.6 ± 0.2
Ash (wt. %) 7.1 ± 0.2 5.2 ± 0.0 19.1 ± 0.1
FC (wt. %) 15.7 ± 0.2 15.9 ± 0.2 13.3 ± 0.1
H (wt. %) 5.5 ± 0.0 5.3 ± 0.4 4.9 ± 0.0
C (wt. %) 46.2 ± 0.1 47.2 ± 0.3 40.4 ± 0.2
N (wt. %) 0.6 ± 0.0 0.5 ± 0.0 1.1 ± 0.0
O (wt. %) 40.4 ± 0.2 41.7 ± 0.2 34.4 ± 0.2
S (wt. %) 0.2 ± 0.0 0.2 ± 0.0 0.2 ± 0.0
3.2. Characterization of Hydrochars Prepared from HAF of CS

HTC experiments were conducted to determine the effect of HTC temperature
on the physiochemical properties of hydrochar. Table 2 shows the MY, EY, proximate
and ultimate analyses of the ORG CS and hydrochar samples. The MY decreased with
the increase in HTC temperature for both ORG and HAF hydrochars. For ORG, the
MY was 61.7 ± 3.9 wt. % at HTC200, while it was decreased to 43.1 ± 2.8 wt. % at
HTC260. For HAF, the MY was 62.2 ± 1.9 wt. % at HTC200 and then it decreased to
50.1 ± 0.4 wt. % at HTC 260. It was previously reported that MY decreased with increasing
HTC temperature [20,22,24]. The attenuation in MY between the lower and higher temper-
ature HTC treatments could be primarily due to the degradation of different components
at successively higher temperatures [28]. For example, hemicellulose starts degrading at
a lower temperature at approximately 180 ◦ C, cellulose starts breaking down at approxi-
mately 230 ◦ C, and the lignin starts decaying significantly with temperatures at and above
260 ◦ C. All these are responsible for the lower MY at higher temperatures [19,24,28,36–38].
Previous studies also suggest that the hydrolysis reaction, which requires the lowest activa-
tion energy compared to other decomposition reactions, occurs below 200 ◦ C and results in
high MY [36,39]. On the other hand, HTC temperature elevation releases volatile matters,
which enhance the dehydration and elimination reactions. This phenomenon takes part
in dropping the MY with the increase in HTC temperature [39]. It might be anticipated
that the transformation from CS to hydrochars entailed a high proportion of organic degra-
dation, and inorganics solubilization and removal from the solution. It could be possible
that when the HTC temperature increased from 200 ◦ C to 260 ◦ C, the dehydration reaction
became more prominent than hydrolysis reaction (see Figure 2). The dehydration reaction
might synthesize more organic acids (lowering the pH of process liquid), which could
potentially catalyze the decomposition of biomass, meaning that more process liquid and
gas were being produced and resulted in a low mass yield at high temperatures. Although
the MY values at 230 ◦ C for both feedstocks were similar, at 260 ◦ C, HAF showed the
highest value. This could be due to the relatively higher content of inorganic dirt and
foreign materials in the HAF compared to the ORG.
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Table 2. Proximate and ultimate analysis of air classified CS hydrochars. DB is dry basis.
Thermogravimetric Analysis Ultimate Analysis

Sample Sample MY EY HHVDB AY
Type Condi- (wt. %) (%) (MJ/kg) (wt. %) MC Ash VM FC C H N S O
tion (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %)
100.0 ± 100.0 ± 100.0 ±
raw 18.3 ± 0.2 5.9 ± 1.2 5.7 ± 0.9 76.9 ± 0.8 13.3 ± 1.6 45.3 ± 0.9 5.5 ± 0.1 0.6 ± 0.04 BD** 42.8 ± 1.0
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0.0 0.0 0.0

HTC 200 61.7 ± 3.9 66.4 ± 4.2 19.7 ± 0.2 50.4 ± 4.5 1.8 ± 0.0 4.7 ± 0.4 75.5 ± 0.7 17.9 ± 0.7 48.1 ± 0.4 5.7 ± 0.0 0.3 ± 0.1 BD** 41.2 ± 0.4
ORG
HTC 230 54.1 ± 0.6 60.9 ± 0.7 20.7 ± 0.2 72.1 ± 6.4 1.4 ± 0.3 7.6 ± 0.7 69.2 ± 0.8 21.8 ± 1.0 50.9 ± 0.1 5.4 ± 0.1 0.4 ± 0.0 BD** 35.6 ± 0.1
85.9 ±
HTC 260 43.1 ± 2.8 52.0 ± 3.3 22.1 ± 0.2 1.2 ± 0.1 11.3 ± 1.6 55.9 ± 0.5 31.6 ± 0.4 55.5 ± 0.0 2.6 ± 2.6 0.5 ± 0.2 BD** 30.0 ± 2.4
11.6
100.0 ± 100.0 ± 100.0 ± 38.51 ±
LAF raw 18.8 ± 0.2 5.6 ± 1.6 4.5 ± 0.1 71.2 ± 3.9 17.5 ± 2.2 51.3 ± 0.0 5.5 ± 0.0 0.1 ± 0.0 BD**
0.0 0.0 0.0 0.0
100.0 ± 100.0 ± 100.0 ±
raw 16.8 ± 0.1 7.9 ± 0.2 10.3 ± 1.1 64.9 ± 0.4 17.1 ± 0.7 40.6 ± 0.3 5.1 ± 0.2 0.9 ± 0.1 BD** 42.9 ± 0.4
0.0 0.0 0.0
HAF HTC 200 62.2 ± 1.9 68.9 ± 2.8 18.6 ± 0.2 64.1 ± 3.8 2.3 ± 0.1 10.6 ± 0.6 69.5 ± 0.4 17.6 ± 0.3 43.9 ± 0.2 5.1 ± 0.1 0.9 ± 0.2 BD** 39.4 ± 0.2
64.9 ±
HTC 230 76.7 ± 2.6 19.9 ± 0.1 67.1 ± 1.3 1.9 ± 0.4 10.6 ± 0.2 66.9 ± 1.5 20.5 ± 1.9 47.5 ± 1.9 4.7 ± 0.3 1.1 ± 0.2 BD** 35.9 ± 1.9
1.9 *
50.1 ±
HTC 260 66.4 ± 0.4 22.2 ± 0.2 69.7 ± 1.7 1.1 ± 0.2 14.3 ± 0.4 40.3 ± 0.2 44.4 ± 0.0 51.1 ± 0.5 3.5 ± 0.1 1.7 ± 0.2 BD** 29.4 ± 0.5
0.4 *
* values refer to duplicate experiments. All other experiments were triplicated; ** below detection limit.
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Figure 2. Van-Krevelen diagram.
The AY showed slight changes in their values (Table 2) for HAF hydrochars, but
these changes were significant for ORG hydrochars. AY showed remarkable reductions
of ~50 wt. % and ~36 wt. % from raw ORG to ORG HTC200 and raw HAF to HAF
HTC200, respectively, but it increased for successive HTC temperatures. Qadi et al. [40]
and Chen et al. [41] found that HTC aids in the removal of loose minerals from the biomass.
One possible explanation is that CS can be accompanied by large amounts of loose dirt
during harvesting, depending on method, and this portion was removed significantly
during the HTC200 process. It is likely that this agronomic practice contributed to the
trapped soil in this sample, as discussed on the previous section. On the other hand,
the ORG HTC260 and HAF HTC260 showed the highest AY values of ~86 wt. % and
~70 wt. %, respectively. This could be due to the adsorption of the inorganics from the
liquid phase to the solid phase (hydrochar) at elevated temperatures. The oversaturation
with minerals in the liquid phase at high temperatures could be responsible for this
precipitation phenomenon. Several researchers found that HTC enhances the degradation
process with higher temperatures, and produces sugar monomers, furfurals, and organic
acids, which leave porous structures of hydrochar. As such, some entrapped/loosely
bonded inorganics in the crosslinked matrix might have been adsorbed into the pores of
hydrochar during HTC [18,24,40]. Since cellulose and lignin start degrading at around
230 ◦ C and 260 ◦ C, respectively, and create porous structures, they might permit the
insoluble inorganics to be absorbed from the process liquid into the hydrochar surface,
resulting in higher AY.
The ultimate analysis shown in Table 2 indicates that with the increase in HTC temper-
ature, the carbon content was increased by ~10 wt. % for ORG HTC260 and ~11 wt. % for
HAF HTC260 from raw ORG and HAF, respectively, wherein the oxygen content dropped
about 13 wt. % and 14 wt. %. Regarding hydrogen, although ORG chars showed essentially
no change, HAF chars showed a slight drop (~1.5 wt. %) for HTC 260 from raw HAF. The
nitrogen showed insignificant changes in the hydrochars with respect to the feedstock.
The higher carbon content and lower oxygen content rationalized the rising HHV with
the increase in HTC process temperature. The fuel quality was also analyzed with the
van-Krevelen diagram (Figure 2). The van-Krevelen diagram depicts that the closer to
the origin of the data the points are, the better the fuel is [33]. The HAF fuel quality was
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very low compared to the LAF quality, as expected due to the higher concentration of
non-combustible species. Even considering this on an inorganics-free basis, there is a small
discrepancy with a lower calorific value in the HAF. As mentioned above, this is attributed
to the partitioning of tissues during AC. In addition to having higher inorganics content,
these HAF tissues (larger portions of leaf, sheaths) have higher amounts of extractives
(cutin resin, protein, etc.). With the increase in HTC temperature, the hydrochar fuel quality
(calorific value, and carbon, oxygen, and hydrogen content) increases (up to 32 wt. % in the
HAF). Hydrochars produced at 260 ◦ C showed the best fuel quality among all the chars,
and this agrees with prior studies undertaken in these condition ranges [5]. As the rise in
HTC temperature favored the dehydration and decarboxylation reactions (see Figure 2),
this could justify the increase in elemental C and decrease in elemental O content during
the carbonization process.
The TGA of the ORG chars showed a decreasing trend (Table 2) of VM and a rising
trend of FC. The ORG HTC260 showed ~21 wt. % VM decrease and ~19 wt. % FC increase
from the raw ORG, whereas HAF HTC260 showed a significant decrease (~25 wt. %)
in VM and increase (~27 wt. %) in FC compared to raw HAF. However, a minimum
change in both FC and VM was observed for both feedstocks at 200 ◦ C. Previous studies
suggested that the degradation of cellulose at around 220 ◦ C might be responsible for
this phenomenon [36,42,43]. Sharma et al. [39] and Titirici et al. [44] further explained
cellulose degradation via two routes: (1) cellulose > glucose > 5-hydroxymethyl furfural >
carbonized structure; (2) cellulose > aromatic structure. In this study, a possible explanation
for receiving higher FC for both ORG and HAF HTC260 is the cellulose carbohydrate’s
degradation into more carbonaceous particles at successively higher temperatures.
The highest energy content was observed at the 260 ◦ C hydrochars for both ORG and
HAF (about 22 MJ/kg), as shown in Table 2, which was almost 4 MJ/kg and 5 MJ/kg higher
than with the ORG CS (~18 MJ/kg) and HAF (~17 MJ/kg), respectively. Earlier studies
demonstrated that with the increasing HTC temperature, the HHV and corresponding
EY showed upward and downward trends, respectively [20,22,24]. The EY reported in
Table 2 showed a descending trend for ORG chars, but a more complex pattern for HAF
hydrochars. A possible explanation for the discrepancies between the hydrochar EY values
is that the HAF HTC230 had higher MY, which could be due to the retention of cellulose in
the hydrochar due to partial degradation. In addition, the enriched energy content and
mass yield is convolved with the reduction in inorganics to create a potentially complex
optimization for the energy yield of the HAF.
3.3. Energy Recovery by Integrating AC–HTC Process

Figure 3 shows three different proposed scenarios: the AC-only process, the HTC-only
process, and the integrated AC–HTC process. The main objective of these processes was to
determine the energy recovery from CS. For all processes, the basis was arbitrarily taken
as 100 kg dry ORG feed. In the AC-only process, the throughputs were LAF and HAF,
as the below-screen particles were assumed to be negligible. The HAF was considered
as waste and discarded from the process for AC. The LAF was the only throughput that
was pelletized and the HHV was determined. In the HTC-only process, dry ORG was
directly fed into the HTC reactor at three different temperatures (200, 230, and 260 ◦ C),
and then corresponding hydrochars were pelletized to find out the energy recovery of the
HTC process. The last process was considered as the integrated AC–HTC process, which
comprised the AC followed by the HTC process. As mentioned earlier, the AC process had
two main throughputs: LAF and HAF. The HAF waste was fed into the HTC process at
three different temperatures (200, 230, and 260 ◦ C). The hydrochars were then mixed with
LAF at their corresponding weight ratios and pelletized to find out the energy recovery
from the integrated process.
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Figure 3. AC, HTC, and integrated AC–HTC process.
The overall energy balances for the three scenarios were calculated using Equation (6)–(11).
For process units, the specific energy consumptions (SECs) were found from [45,46] and
shown in Table 3. Specific energy consumption for each process unit. The SEC of AC
was calculated as 0.0036 MJ/kg by INL and the basis was taken as per kg dry LAF. The
pellet press SEC was found to be 0.4 MJ/kg dry feed for the raw LAF and LAF–HTC
mixtures and 0.2 MJ/kg dry hydrochar for the ORG chars [45]. Earlier, it was demonstrated
that the pellet press SEC increases with a higher feed rate, feed moisture (wt. %), and
length-to-diameter (L/D) ratio of pellet die, etc. [47]. For example, the moisture (wt. %) in
the biomass feed is higher than in the hydrochar feed due to the higher hydrophilicity [48],
which can increase the overall SEC of biomass pelletization. Here, the SEC for biomass and
biomass–hydrochar mixtures under pelletization (Table 3. Specific energy consumption
for each process unit) was considered higher than the hydrochar SEC due to the higher
feed, moistures (wt. %), and/or L/D ratio. For the case of SEC of HTC, the required
SEC was found to be 5.9, 6.3, and 6.7 MJ/kg dry feed for HTC200, HTC230, and HTC260,
respectively (for both ORG and HAF chars) [46]. As higher temperatures require higher
energy consumption [46], HTC260 has the highest SEC (6.7 MJ/kg dry feed) among all the
chars. Table 4 shows the overall energy balance of the processes.
As per the AC process (Table 4), the overall net energy in was 1833.6 MJ (Equations (6),
(7), and (11) and Table 4) and the energy out was 1588.3 MJ (Equation (8), Table 4). The
recoverable energy of the HAF was found by the difference between the ORG and LAF
energies, which was ~245 MJ (Equation (9), Table 4). Since the HAF waste was not processed
and eliminated after AC, the recoverable energy was 0 MJ for the AC-only
In the case of the HTC-only process (Table 4), the overall energy in was 2439.6 MJ,
2474.1 MJ, and 2507.9 MJ for ORG HTC200, 230 and 260, respectively (Equations (6), (7) and
Table 4). The overall energy out was 1217.6 MJ, 1116.4 MJ and 953.8 MJ for HTC200, 230 and
260, respectively (Equation (8) and Table 4). The energy consumptions for the bulk quantity
of HTC of ORG significantly elevated the process’ overall energy demand. Since the HTC
process was highly energy-intensive, the energy recovery was not feasible. process.
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Table 3. Specific energy consumption for each process unit.
Process Units Specific Energy Consumption (SEC) Unit Reference Paper

AC 0.0036 MJ/kg dry LAF This study
Pellet press for LAF 0.4 MJ/kg dry feed [45]
HTC for ORG200 5.9 MJ/kg dry feed [46]
Pellet press for ORG200 0.2 MJ/kg dry hydrochar [45]
HTC for HAF200 5.9 MJ/kg dry feed [46]
Pellet press for LAF:HAF HTC200 0.4 MJ/kg dry feed [45]
Table 4. Energy extracted from HAF waste.
Energy in (MJ) Energy out (MJ) Potential Energy

Energy (MJ) Recovery
Process Type HTC ORG HTC Pellet LAF ORG LAF:HAF
AC in HAF Waste (MJ) from
Feed of HAF Press Pellet Pellet HTC Pellet HAF Waste
AC Process 1833.3 0.3 - 37.1 1588.3 - 245.0 0
ORG
1833.3 - 594.0 12.3 - 1217.6 - 245.0 -
HTC 200
HTC Process ORG

1833.3 - 630.0 10.8 - 1116.4 - 245.0 -
HTC 230
ORG
1833.3 - 666.0 8.6 - 953.8 - 245.0 -
HTC260
LAF: HAF
1833.3 0.3 76.0 40.6 - - 1736.5 245.0 68.7
HTC200
Integrated LAF: HAF
AC–HTC Process 1833.3 0.3 80.6 40.8 - - 1752.6 245.0 80.0
HTC230
LAF: HAF
1833.3 0.3 85.3 40.0 - - 1727.4 245.0 51.0
HTC260
As per the integrated AC–HTC process (Table 4), the HAF waste was hydrothermally
carbonized to utilize the recoverable energy present (~245 MJ) in the product, and further
mixed with the LAF stream for taking advantage of AC preprocessing (Equation (10),
and Table 4). The results in Table 4 show that the energy recovery was the maximum
(~80 MJ) for LAF:HAF under HTC230, which was about ~11 MJ and ~29 MJ higher than
LAF:HAF HTC200 and LAF:HAF HTC260, respectively (using Equations (6)–(8), (10), (11),
and Table 4). The higher FC and elemental carbon for HAF HTC230 than HAF HTC200
could contribute as a better solid fuel compared to LAF: HAF HTC200. On the other hand,
although HAF HTC260 has higher FC and elemental carbon than HAF HTC230, due to
the higher volatile matters as well as the elemental oxygen in HAF HTC230, this could
enhance the energy content of the LAF:HAF HTC230. Since volatiles are mainly made of
short chain hydrocarbons, long chain hydrocarbons and aromatic hydrocarbons that are
easy to distill off, it might be possible that the heavier hydrocarbons break into lighter gases
during combustion and react with limited oxygen via partial oxidation, releasing more
131
Energies 2021, 14, 1397
energy as heat [49]. In this context, integrating the LAF and HAF HTC230 process streams
might give a better energy recovery out of the AC reject stream. Moreover, in this mode,
the HTC process energy consumptions were significantly less than the HTC-only mode,
which might impact the overall energy recovery in a positive dimension. On the other
hand, the final product energy value was much higher than the AC-only mode, which bears
the importance of combining the AC and HTC processes together. Overall, the integrated
AC–HTC could become a better option to take the advantage of the potential waste energy
as valuable utilizable energy, and minimize the overall energy lost.
Equations used:
Energy in (MJ) of feed = HHV of feed×Total mass of feed (6)
Energy in (MJ) of process unit = Specific energy consumption of

the unit×Total mass of feed or product (7)
Energy out (MJ) of product = HHV×Total mass of product (8)

Potential energy (MJ) in HAF waste = LAF pellet-ORG feed (9)
Energy recovery (MJ) from HAF waste for the integrated AC-HTC process
= LAF:HAF HTC pellet-HTC of HAF-pellet press for LAF:HAF HTC
(10)
pellet-net energy of LAF pellet
Net energy (MJ) of LAF pellet = LAF pellet-Pellet press for LAF (11)
4. Conclusions
This study investigated an integrated AC–HTC process to recover the energy from
corn stover. An air classifier was used to beneficiate CS into a purified biomass stream with
27 wt. % reduction in ash content from LAF with 84.4 wt. % mass recovery. The waste from
this fractionation technique was used as a feedstock for HTC to produce a high-energy fuel
pellet (19–22 MJ/kg). When CS was hydrothermally carbonized, both MY and AY were
decreased with the HTC temperature; meanwhile, the energy content of the hydrochar was
increased. This study showed that the AC and HTC processes cannot recover any energy
from the HAF stream individually. On the other hand, along with the high-energy densified
hydrochar, the integrated AC–HTC process further showed significant energy recovery
(~800 MJ/tonne) from the HAF. Therefore, this study provides evidence of an HTC that can
be integrated with AC to reduce the inorganic content and recover energy. Adopting HTC
with AC could potentially transform CS into an advanced biorefinery feedstock, while
still utilizing the otherwise lost organics from the AC process. Further sustainability and
technoeconomic assessment of AC and HTC are needed to justify the economic viability
of the integrated process. However, the energy consumption of this study was calculated
based on the laboratory-scale data, which could vary at a large scale. Process economics
with large-scale data could reveal additional data that might assist technology maturation.
Supplementary Materials: The following are available online at https://www.mdpi.com/1996-107

3/14/5/1397/s1, Figure S1: Air classification technology, Figure S2: Hydrothermal Carbonization
(HTC) reactor system, Figure S3: Pellet press for pelletization.
Author Contributions: Conceptualization, M.T.I. and M.T.R.; methodology, M.T.I., N.S., S.H., J.K.;
formal analysis, M.T.I., N.S., S.H.; investigation, M.T.I., S.H.; resources, J.K., M.T.R.; data curation,
M.T.I., M.T.R.; writing—original draft preparation, M.T.I., S.H.; writing—review and editing, N.S.,
M.T.R., J.K.; supervision, M.T.R., J.K.; funding acquisition, M.T.R. All authors have read and agreed
to the published version of the manuscript.
Funding: This research was funded by United States Department of Agriculture, grant number
2019-67019-31594. This work was authored in part by the Idaho National Laboratory under USA
Department of Energy (DOE) Idaho Operations Office with Contract no. DE-AC07-05ID14517.
132
Energies 2021, 14, 1397

Acknowledgments: The authors are grateful for the air classification technology of the Biomass
Feedstock National User Facility (BFNUF) at Idaho National Laboratory. The authors acknowledge
laboratory assistances from Kyle McGaughy, Cadianne Chambers, and Travis Rembrandt from
Biofuels Lab at Florida Institute of Technology for their laboratory efforts in this project.
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energies
Article
Sewage Sludge Treatment by Hydrothermal Carbonization:
Feasibility Study for Sustainable Nutrient Recovery and
Fuel Production
Gabriel Gerner 1, *, Luca Meyer 1 , Rahel Wanner 1 , Thomas Keller 2 and Rolf Krebs 1
1 Institute of Natural Resource Sciences, Campus Grüental, Zurich University of Applied Sciences (ZHAW),
CH-8820 Wädenswil, Switzerland; luca.meyer@zhaw.ch (L.M.); rahel.wanner@zhaw.ch (R.W.);
rolf.krebs@zhaw.ch (R.K.)
2 Institute of Chemistry and Biotechnology, Campus Reidbach, Zurich University of Applied Sciences (ZHAW),
CH-8820 Wädenswil, Switzerland; thomas.keller2@zhaw.ch
* Correspondence: gabriel.gerner@zhaw.ch; Tel.: +41-58-934-5588
Abstract: Phosphorus recovery from waste biomass is becoming increasingly important, given that
phosphorus is an exhaustible non-renewable resource. For the recovery of plant nutrients and
production of climate-neutral fuel from wet waste streams, hydrothermal carbonization (HTC) has
been suggested as a promising technology. In this study, digested sewage sludge (DSS) was used as
waste material for phosphorus and nitrogen recovery. HTC was conducted at 200 ◦ C for 4 h, followed
by phosphorus stripping (PS) or leaching (PL) at room temperature. The results showed that for PS
and PL around 84% and 71% of phosphorus, as well as 53% and 54% of nitrogen, respectively, could be
recovered in the liquid phase (process water and/or extract). Heavy metals were mainly transferred
to the hydrochar and only <1 ppm of Cd and 21–43 ppm of Zn were found to be in the liquid phase
Citation: Gerner, G.; Meyer, L.; of the acid treatments. According to the economic feasibility calculation, the HTC-treatment per dry
Wanner, R.; Keller, T.; Krebs, R. ton DSS with an industrial-scale plant would cost around 608 USD. Between 349–406 kg of sulfuric
Sewage Sludge Treatment by acid are required per dry ton DSS to achieve a high yield in phosphorus recovery, which causes
Hydrothermal Carbonization: additional costs of 96–118 USD. Compared to current sewage sludge treatment costs in Switzerland,
Feasibility Study for Sustainable
which range between 669 USD and 1173 USD, HTC can be an economically feasible process for DSS
Nutrient Recovery and Fuel
treatment and nutrient recovery.
Production. Energies 2021, 14, 2697.
https://doi.org/10.3390/en14092697
Keywords: hydrothermal carbonization; phosphorus recovery; digested sewage sludge; hydrochar;
Academic Editor: M. Toufiq Reza
nutrient recovery; climate-neutral fuel; energy efficiency; economic feasibility
Received: 10 March 2021

Accepted: 30 April 2021
Published: 8 May 2021 1. Introduction
To meet global food demand, the utilization of mineral fertilizer in agriculture has
Publisher’s Note: MDPI stays neutral become indispensable. While the production of phosphorus (P) and nitrogen (N) fertilizer
with regard to jurisdictional claims in cause a negative environmental impact, phosphate rock is also a limited resource and since
published maps and institutional affil- 2014 it has been on the list of Critical Raw Materials for the European Union (EU) [1,2].
iations. Phosphorus as an essential plant nutrient represents a considerable environmental burden
due to its production from phosphate ores. According to Binder et al. [3] and Daneshgar
et al. [4], easily accessible phosphorus will only last for the next 300 years, while we could
reach the phosphorus peak already by 2070 [5]. In addition to huge mining areas, the
Copyright: © 2021 by the authors. production of phosphoric acid from phosphate ore leaves behind hundreds of millions
Licensee MDPI, Basel, Switzerland. of tons of phosphogypsum, some of which is radioactive [6]. Radioactive material such
This article is an open access article as uranium as well as heavy metals (HM) like cadmium can be transferred from the ore
distributed under the terms and to the mineral P fertilizer [7–12]. A study by the Braunschweig Federal Research Center
conditions of the Creative Commons for Cultivated Plants JKI (Julius Kühn-Institute) found in triple superphosphate 52–232
Attribution (CC BY) license (https:// mg/kg of uranium [6]. Recycling of phosphorus from waste streams offers a sustainable
creativecommons.org/licenses/by/
alternative to conserve phosphorus deposits and reduce impurities in plant fertilizer. In
4.0/).

135
Energies 2021, 14, 2697
contrast to phosphorus, which relies on a definite source, nitrogen fertilizer can be synthe-
sized as ammonia from air by the Haber–Bosch process [13]. The negative aspect of this
process is that to produce ammonia fertilizer, it consumes between 1–2% of global energy
and produces around 1.4% of global CO2 emissions [14]. Countries like Switzerland and
Germany approved new regulations to reduce the dependency on phosphorus imports.
It will be mandatory to recycle phosphorus from sewage sludge by 2026 in Switzerland
and by 2029 in Germany [15]. This attempt to reduce mismanagement of this exhaustible
resource and the need for high-quality fertilizer has increased the necessity of a phosphorus
recycling process with high nutrient recovery and low environmental burden. Hydrother-
mal carbonization (HTC) is a thermochemical process allowing the direct usage of wet
feedstock without drying them and converting it under high pressure and temperature
to a coal slurry, which can be separated into an energy-rich solid phase (hydrochar) and
nutrient-rich liquid phase (process water) [16]. The conversion leads to reduced NO emis-
sion in the hydrochar combustion [17] and simultaneously improves dewaterability of
the carbonized sludge [18,19], which is crucial for an energy-efficient separation. In this
process, phosphorus is mainly incorporated in the hydrochar and has to be removed by
acid leaching [20–22]. Other processes use sewage sludge ash for P-leaching [23], where the
sludge’s fuel property is mainly used as process energy for the incineration. Therefore, it is
lost to industrial processes like the cement industry or coal power plants as climate-neutral
fuel.
Modern wastewater treatment plants (WWTP) employ biological and/or chemical
phosphorus removal technologies to transfer around 90% of the input phosphorus load
into the sewage sludge [24]. Larger WWTPs utilize the sludge as a feedstock for anaerobic
digestion (AD) producing methane, which can be converted to electricity and heat to cover
energy demands. Implementing an HTC plant on-site allows the methane yield to be
increased by feeding the AD with HTC process water (PW), as a supplemental feedstock
with high organic carbon content [20,25–30]. Recovered energy can at the same time be
utilized for the HTC process and increase the energy efficiency.
Different studies show the potential of P-recovery by applying acids before or after
the HTC treatment [20,22,31,32] and the need for using digested sewage sludge. For the
acid application, digested sludge has a higher P availability compared to raw sludge, while
with raw sludge only 50% of P can be recovered at pH 2 [23]. For a profitable application
of the process a cost-effective usage of acid must be achieved.
The aim of this study was to investigate the recovery of plant nutrients (phosphorus
and nitrogen) from digested sewage sludge for a sustainable fertilizer and fuel production
with the main focus on minimizing the acid usage and increasing the PW utilization.
Two paths of P-recovery are investigated in lab-scale experiments, with immediate acid
application before and after liquid–solid separation and without prior drying to simulate
industrial processing. Process liquids are analyzed for their nutrient and heavy metal
content and hydrochars are examined for their fuel properties as possible substitutes for
fossil fuels. Furthermore, the economic feasibility of the process in an industrial-scale
HTC-plant is evaluated.

2.1. Digested Sewage Sludge
For this study anaerobically digested sewage sludge was used as a raw material. The
digested sewage sludge (DSS) was collected at a WWTP in Switzerland (ARA Rietliau,
Waedenswil, Switzerland), with an initial dry matter content of 22.30% (dried at 105 ◦ C).
The WWTP consists of four treatment trains, two with membrane bioreactors (MBR) and
microfiltration (0.35 μm pore size) and two with conventional activated sludge (CAS)
treatments. It was built for a population equivalent of 44,000 and treats communal and
industrial wastewater. For chemical phosphorus precipitation, iron (III) chloride and poly
aluminum chloride (PAC) are used by the WWTP. The collected DSS was immediately
transferred to a convection oven and dried at 40 ◦ C for 86 h (BINDER GmbH, Tuttlingen,
136
Energies 2021, 14, 2697
Germany). The slowly dried stock was homogenized by grinding to a fine powder (GM200,
Retsch GmbH, Haan, Germany) and stored in airtight 1 L glass bottles (DURAN® GLS
80® laboratory wide mouth bottle, DURAN Group GmbH, Mainz, Germany) for HTC
trials. These sludge pre-treatments are conducted to achieve a better reproducibility of
the lab-scale experiments. In large-scale HTC-treatments sewage sludge will be treated
directly after dewatering, without previous drying step.
2.2. Hydrothermal Carbonization

HTC lab experiments were carried out using a 1 L pressure vessel made from Hastelloy®
C22® (Büchi AG, Uster, Switzerland). All trials were run in duplicates. The reactor vessel
was loaded with 600 g of a mixture of dried DSS and deionized (DI) water. The input
amount of DSS (dried at 40 ◦ C) was adjusted by its remaining moisture content (mea-
sured at 105 ◦ C) to obtain a final dry matter (DM) content of 20%. The reactor head space
contained a small amount of air. Reaction time was set at 4 h after reaching a reaction
temperature of 200 ◦ C. The residence time was selected in accordance with the parameters
from the industrial-scale reactor from GRegio Energie AG, Chur, Switzerland. During the
reaction a maximum pressure of 18.8 bar (±0.2) was reached. The reactor jacket contained
an electric heating mantle and water-cooling coil for short heating and cooling phases.
Heating up from room to the set temperature took around 30 min and the cooling below
50 ◦ C around 13 min. The mixture was stirred continuously at 200 rpm. All trials were
monitored in situ for temperature and pressure. The resulting product of HTC is a mixture
(HTC-slurry) of a solid (hydrochar) and liquid (process water) fraction. The HTC-slurry
was transferred into a 1 L glass bottle (DURAN® GLS 80® laboratory wide mouth bottle)
and afterwards vacuum filtered through a Buchner funnel with a Whatman filter paper
(pore size 11 μm, Cat No 1001 125). The PW was stored until analysis at 6 ◦ C and the
hydrochar was, without a washing step, dried at 40 ◦ C overnight. Dewaterability of the
hydrochar was calculated based on the DM content (dried at 105 ◦ C), achieved after simple
vacuum filtration.
2.3. Phosphorus Extraction

Figure 1 shows the flow charts of experimental set-ups with and without acid addition.
To optimize the acid dose achieving maximum P recovery by minimizing the PW contami-
nation with acid and heavy metals, the following three experimental set-ups were tested:
(i) HTC-C (control): direct liquid–solid separation without any acid addition; (ii) HTC-PS
(phosphorus stripping): acid addition to the slurry followed by L/S-separation; and (iii)
HTC-PL (phosphorus leaching): Short-time sedimentation of hydrochar particles followed
by decantation of surplus process water and acid addition to remaining hydrochar. The last
set-up was conducted to reduce the amount of acidified process water, while concentrating
the leached nutrients in the extract. Because of the hydrophobic characteristics of the
hydrochar [18], the sedimentation took place immediately. Acid extractions (leaching or
stripping) were carried out directly after HTC in the 1 L glass bottle, without any intermedi-
ate step. All slurries were stirred continuously at 600 rpm with a magnetic stirrer (Big Squid,
IKA, Breisgau, Germany). Initial pH value was recorded, followed by a stepwise addition
of 1 mL concentrated sulfuric acid (93–98%, Hiperpur, PanReac AppliChem, Darmstadt,
Germany) to the mixture until a pH of 2 was reached. After reaching the desired pH value
the reaction time of 2 h started [33]. During the reaction, the glass bottle was covered with
aluminum foil to minimize the loss from evaporation and the pH value was measured
every 15 min and adjusted with 0.5–1 mL acid addition. After 2 h the mixture was vacuum
filtered through a Buchner funnel with a Whatman filter paper (pore size 11 μm, Cat
No 1001 125). The liquid samples were stored at 6 ◦ C and hydrochars were, without a
washing step, directly transferred to the convection oven and dried at 40 ◦ C over night.
Remaining PW (incl. nutrients) on char was considered as a loss, to keep the treatment for
industrial-scale applications simple and cost effective.
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Energies 2021, 14, 2697
Figure 1. Flow charts of experimental set-ups with and without acid addition. (HTC = Hydrothermal carbonization, C =
Control, PS = P-Stripping, PL = P-Leaching, DSS = Digested sewage sludge, PW = Process water, Ext = Leaching extract, VF
= Vacuum filtration).
2.4. Characterization of Feedstock and HTC-Products

DSS and hydrochars were analyzed for DM and ash content. To avoid losses of
mercury due to volatilization, all samples were previously dried at 40 ◦ C [34] for further
analyses and the initial DM content (% DM40C ) was recorded. As a second step, subsamples
were taken and dried at 105 ◦ C until constant weight was reached (% DM105C ). The effective
DM content (% DM) was then calculated by Equation (1):
DM (wt.%) = DM40C (wt.%) × DM105C (wt.%) ÷ 100 (1)
After determination of the DM105C , samples were incinerated in a muffle furnace

(L 40/11 BO, Nabertherm GmbH, Lilienthal, Germany) and the ash content was mea-
sured according to DIN EN 14775. Ultimate analyses for carbon (C), hydrogen (H) and
N were undertaken with a CHN-analyzer (TruSpec Macro, LECO Instrumente GmbH,
Mönchengladbach Germany) and sulfur was measured at an external lab with a CHNS-
analyzer (vario EL cube, Elementar Analysensysteme GmbH, Langenselbold, Germany).
All samples for ultimate analyses were dried at 105 ◦ C. Oxygen content was calculated by
difference (Equation (2)):
O (wt.%) = 100 − C (wt.%) − H (wt.%) − N (wt.%) − S (wt.%) − Ash content (wt.%) (2)
Total content of HM (Cd, Cu, Ni, Pb and Zn) and phosphorus (P) was measured for
liquid and solid samples spectroscopically by ICP-OES (Agilent 5100, Agilent Technologies,
CA, USA). 2 mL of liquid sample or 0.35 g of solid sample (dried at 40 ◦ C) was added
to 8 mL of aqua regia and microwave digested (Speedwave Four, Berghof Products +
Instruments GmbH, Eningen, Germany) for 35 min at 175 ◦ C (in dependence on SN EN
13346, protocol C). After the acid digestion samples were transferred to a 25 mL volumetric
flask and diluted with ultrapure water. Final results for solid samples were corrected
by the remaining water content (% DM105C ). Acid digestion using aqua regia did not
lead to a complete digestion for solid char samples. Therefore, measurement results were
utilized for material balance and recovery efficiency was determined. The results showed
good overall recovery with >83% for HM (excl. Pb, Cd and Hg) and nutrients. Dilution
effects in liquid samples faced detection limitations, especially for elements with low
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Energies 2021, 14, 2697
concentrations as Pb, Cd and Hg. Phosphorus contents for hydrochars were calculated by
difference. All samples were digested in triplicates and average results are reported. For
the determination of mercury (Hg) samples dried at 40 ◦ C were measured according to DIN
EN 1483: 08.97. Mercury was analyzed using a cold vapor atomic absorption spectrometer
(CV-AAS) (novAA® 350, Analytik Jena GmbH, Jena, Germany) equipped with a hydride
generator (HS 60A, Analytik Jena GmbH, Jena, Germany).
Liquid samples (process water and leaching extract) were analyzed for total organic
carbon (TOC), measured as non-purgeable organic carbon (NPOC), according to ASTM
D7573 and total bound nitrogen (TNb) according to DIN EN 12260 with a TOC-LCSH
analyzer equipped with a TNM-L unit (Shimadzu, Kyoto, Japan). For TOC measurements
the samples were automatically acidified with HCl to pH < 3 and sparged with purified air
to remove inorganic carbon. Purgeable organic carbon (POC) may also be lost during this
sample treatment. The pH values of fresh process water and leachate were measured with
a portable multi-parameter meter (HQ40d, Hach Lange, Düsseldorf, Germany).
Hydrochars were further characterized for its fuel properties. Regarding energy con-
tent, the higher heating value (HHV) of the raw material and the hydrochar was measured
using a calorimeter (IKA C 200, Breisgau, Germany). The volumetric emissions of CO2 and
SO2 were calculated according to Equations (3) and (4) adapted from Kaltschmitt [35], on
the assumption of a complete combustion. Weight percentage of carbon (c) and sulfur (s)
are given by the elemental analysis:

m3 CO2 c
CO2 emission = 22.41 (3)
kg DM 12

m3 SO2 s
SO2 emission = 22.41 (4)
kg DM 32
The hydrochar yield and energy efficiency (EE) were calculated by Equations (5) and
(6), respectively [36–38].

DMhydrochar (kg)
Hydrochar yield (%) = × 100 (5)
DMraw material (kg)
⎛ ⎞
MJ
HHVhydrochar kg
Energy efficiency (%) = (Hydrochar yield) × ⎝ ⎠ (6)
MJ
HHVraw material kg
2.5. Economic Feasabiliy of Hydrothermal Carbonization (HTC)

For the economic calculation, on-site treatment at a WWTP with anaerobic sludge
digestion was presumed. Therefore, transport and PW treatment costs were neglected.
The investment costs and annul fixed costs were obtained by the HTC-company GRegio
Energie AG, Switzerland. All Swiss franc (CHF) amounts are reported in US dollars
(USD) and were converted at the exchange rate of 1.1 USD/CHF. The costs include the
HTC-process, liquid–solid separation with a hydraulic filter press (HPS, Bucher Unipektin
AG, Switzerland), as well as drying and briquetting of the hydrochar. Annual fixed costs
are based on Swiss rates and include electrical and thermal energy (electricity rate 0.22
USD/kWh; heating rate 0.066 USD/kWh), rent (198.00 USD/m2 a), labor, maintenance,
provision and contingency insurance, as well as capital costs. Labor costs are based on a
full time-position. Capital costs were calculated based on a payback period of 10 years
with 2% annual interest. Annual provision and insurance costs are 1% and maintenance
costs are 2.5% of the investment. Costs for the P-extraction were calculated based on the
acid consumption in the lab experiments, and do not include industrial scale plant costs
and/or fertilizer production. An average market price of 275 USD per ton of industrial
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Energies 2021, 14, 2697
grade H2 SO4 98% was applied. Specific overall costs per dry ton DSS were determined by
Equation (7).

Annual fixed cos ts (CHF per year)
Specific overall cos ts (CHF per ton DSS) = (7)
Annual troughput (tons per year)
The industrial scale HTC-plant from GRegio Energie AG is operating continuously
with a reactor volume of 5.6 m3 . The maximum flow rate of the current system is 2 m3 /h
and is limited by the heating system and heat recovery unit. The optimal DM content
of the sludge input material is around 15%. For the calculation of the disposal fees the
throughput was set at 11,200 tons dewatered sewage sludge (15%DM) per year. With a
carbonization time of 4 h and a yearly operation time of 8000 h, the flow rate was set to
1.4 m3 /h.

3.1. Carbonization and Separation
For the characterization of hydrochars and liquid phases extensive analysis were
conducted. Higher heating values of the raw material and hydrochars are shown in Table 1.
HTC of DSS causes a slight decrease in HHV for the control (HTC-C_HC) and hydrochar
after P leaching (HTC-PL_HC). The HHV declined around 11% from 12.7 MJ/kg (DSS)
to 11.3 MJ/kg (HTC-C_HC and HTC-PL_HC), which is comparable to reported heating
values of other studies with DSS [8,14]. After P stripping the hydrochar (HTC-PS_HC)
showed with 13.3 MJ/kg a slight increase of 4.5% compared to the starting material and
was in average 17.7% above the HHV of HTC-C_HC and HTC-PL_HC.
Table 1. Ultimate analysis and higher heating values (HHV) of digested sewage sludge (DSS) and its
derived hydrochars (HTC-xx). (C = Control; PS = P stripping; PL = P leaching; HC = Hydrochar) (n =
2).
C H N S Odiff Ash H/C O/C HHV

[wt.%] [wt.%] [wt.%] [wt.%] [wt.%] [wt.%] MJ/kg
DSS 30.2 4.4 4.2 1.0 17.3 42.8 1.7 0.4 12.7
HTC-C_HC 27.4 3.5 2.4 0.9 10.1 55.6 1.5 0.3 11.3
HTC-PS_HC 30.8 3.9 3.1 8.7 8.4 45.1 1.5 0.2 13.3
HTC-PL_HC 27.0 3.7 2.7 9.2 9.6 47.7 1.6 0.3 11.3
Table 1 summarizes the results from ultimate analyses, as well as gross calorific values
on raw material and hydrochar samples. The ash content of the hydrochars decreased by
10% after the acid treatment, with a minimum ash content of 45.1% after P stripping. Volu-
metric carbon dioxide and sulfur dioxide emissions c are shown in Figure 2. Hydrochars
after acid addition show an increase in sulfur content by 9–10 times, which has a direct
influence on the SO2 emissions. Hydrochars from HTC-PS and HTC-PL contained more
than 6 wt.% sulfur which, according to the Swiss Clean Air Act (LRV, Annex 5 Number 2),
is 3% above the recommended value for coal, coal briquettes and cokes [39]. The carbon
content of the chars as well as the CO2 emissions are very stable and did not show any
major changes (Table 1, Figure 2).
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Figure 2. Volumetric carbon dioxide and sulfur dioxide emission per kg dry matter (DM) (Error bars
show standard deviation of n = 2).
3.2. Nutrient Recovery

The aim of this study was to recover P and N from sewage sludge into the process
water with minimal heavy metal contamination. Figure 3 shows the recovery of nutrients
to the liquid phase. PS achieved with 84% a 13% higher P recovery than PL. The difference
between the two methods in N recovery is even greater, because for PL it is divided into
two liquid fractions. N recovery efficiencies of 53% for PS_PW and 22% for PL_Ext were
reached. While for PL 32% of N were in the PW fraction. Compared to the control with
49% N recovery, even without additional treatment considerable amount of N could be
recovered directly into the PW.
Figure 3. Recovery of main nutrients in the process water (PW) and leaching extract (Ext) (Error bars
show standard deviation of n = 2).
Tables 2 and 3 show the nutrient and heavy metal contents in the raw material,
hydrochars and liquid phase. Regarding heavy metal contaminations in the liquid phase,
only cadmium and zinc could be detected and quantified. The appearance of Cd could
141
Energies 2021, 14, 2697
not be explained by the authors, as it was not found in the raw material and must have
accumulated in the PW. A release of Zn was also observed by Becker et al. [22]. Elemental
analysis confirmed that most HM stayed in the hydrochar. An explanation for the high
selectivity is the sorption property of the char [22] and the reduction of HM solubility after
the HTC-treatment [40].
Table 2. Content analysis of raw material and hydrochars (HC). (C = Control; PS = P stripping; PL = P leaching; BLD =
bellow limit of detection) (n = 2).
Nutrient Content Heavy Metal Content

P [mg kg−1 ] N [wt.%] Pb [mg kg−1 ] Cd [mg kg−1 ] Cu [mg kg−1 ] Ni [mg kg−1 ] Zn [mg kg−1 ] Hg [mg kg−1 ]
DSS 34,128 4.2 24.3 BLD 262.8 21.9 700.8 0.9
HTC-C_HC 49,505 * 2.4 20.8 BLD 337.5 33.2 900.5 0.5
HTC-PS_HC 9100 * 3.0 39.0 BLD 433.5 38.9 1031.9 1.0
HTC-PL_HC 14,745 * 2.7 25.9 BLD 367.8 43.5 894.0 1.0
* P content calculated by difference.
Table 3. Content analysis of process water (PW) and leaching extract (Ext). (C = Control; PS = P stripping; PL = P leaching; BLD =
bellow limit of detection) (n = 2).
Nutrient Content Heavy Metal Content pH

P [mg L−1 ] N [mg L−1 ] Pb [mg L−1 ] Cd [mg L−1 ] Cu [mg L−1 ] Ni [mg L−1 ] Zn [mg L−1 ] Hg [mg L−1 ]
HTC-C_PW 208 6900 BLD BLD BLD BLD BLD BLD 7.1
HTC-PS_PW 8113 6386 BLD BLD BLD BLD 21.3 BLD 2.1
HTC-PL_Ext 16,050 6195 BLD 0.9 BLD BLD 42.9 BLD 2.0
HTC-PL_PW BLD 6960 BLD BLD BLD BLD BLD BLD 7.3
Because of high sulfur and heavy metal content in the hydrochar, it can only be used
for energy production in industrial-scale plants (e.g., cement industry, coal-fired power
plant, mono-incineration) with appropriate fume cleaning systems. To decrease the sulfur
content in the char, sulfuric acid could be substituted with nitric or organic acids (e.g., citric
acid) for the P-recovery treatment. However, other mineral and organic acids can increase
the leaching costs [22].
While the N concentrations were for all four liquid samples (PW and Ext) in a similar
range (6195–6960 mg N/L), differences in P concentration could be observed. The PW after
acid stripping contained 8113 mg P/L, whereas the highest P concentration was achieved
in the leachate extract (HTC-PL_Ext) with 16,050 mg P/L. The acid consumption was for
both methods (HTC-PS and HTC-PL) at around 14.2 kg (±0.3 kg) H2 SO4 per kg P.
3.3. Feasability of Application

Figure 4 shows hydrochar dewaterability and yield, as well as energy efficiency.
Normally, sewage sludge is difficult to separate to a high DM content, because of the
microbial cell membranes strongly bound to water [41]. With conventional technologies
like a decanter centrifuge or filter press, which are used in WWTPs, a DM content of 20–35%
or 28–45%, respectively, can be obtained [42]. After HTC it was observed that the solid
phase settles very quickly and with simple vacuum filtration a DM content of around 40%
could be achieved. This is consistent with other findings, showing the positive effect on the
dewaterability of biomass and sewage sludge [18,43]. The acid leaching treatment even
increased the dewaterability slightly by 6%. All treatments included a single liquid–solid
separation by vacuum filtration. It is assumed that the decantation, as an intermediate
separation step, had no impact on the dewaterability of PL, as the process water was not
removed completely. According to Chen et al. [44], an increase in acidity can improve the
dewaterability of activated sludge. This would also explain the improvement in the PL
treatment.
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Energies 2021, 14, 2697
Figure 4. Dewaterability (DW), hydrochar (HC) yield and energy efficiency of the raw material (DSS
as received), the control and acid treated hydrochars (Error bars show standard deviation of n = 2).
3.4. Profitability
Calculations for annual fixed costs are presented in Table 4. The specific costs per ton
DSS for the HTC treatment depend on the DM content of the delivered sludge and can
range between 91 USD and 183 USD with 15% and 30% DM content, respectively. On a dry
basis, the specific overall costs are 608 USD per ton DM. In Switzerland average disposal
costs (incl. transportation) per dry ton sewage sludge amounted in 2001 to: (i) 827 USD
for sewage sludge incineration plant; (ii) 882 USD for municipal solid waste incineration
plant; and (iii) 669 USD for cement plant (including drying) [45]. The WWTP Werdhölzli in
Zurich is one of the biggest WWTPs in Switzerland and operates its own sludge incinerator.
The sludge capacity of the plant is designed so that external WWTPs can also deliver their
sewage sludge for disposal. The disposal of sludge at the WWTP Werdhölzli costs currently
1173 USD per dry ton [46]. Besides the disposal costs, by 2026 the acid treatment will be an
important cost factor for WWTPs. In the current study the acid usage per dry ton DSS was
for PS 406 kg and for PL 349 kg, which adds additional costs of 111 USD and 96 USD per
dry ton DSS, respectively. Based on the acid usage per kg P recovered, both methods are
equal with acid costs of 3.96 USD per kg P.
Table 4. Calculation of net costs for the HTC process from GRegio Energie AG (amortization time 10
years, interest rate 2%; db = dry basis; DSS = digested sewage sludge).
Tons (15%DM) 11,200

Annual Throughput of DSS
Tons (db) 1680
Investment costs USD 4,332,460.00
Annual fixed costs USD/a 1,022,674.00
Capital costs USD/a 482,317.00
Operation costs USD/a 540,357.00
Electrical energy USD/a 88,704.00
Heat energy USD/a 72,441.00
Rent USD/a 74,250.00
Labor costs 1 Person (USD) 110,000.00
Maintenance 2.5% of Invest. (USD) 108,312.00
Provision 1% of Invest. (USD) 43,325.00
Contingency insurance 1% of Invest. (USD) 43,325.00
Specific overall costs USD per ton DSS (db) 608.00
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Energies 2021, 14, 2697
4. Conclusions
Two methods for the nutrient recovery and fuel production were evaluated. For
the treatments PS and PL the acid consumption per kg P recovered were, at around 14.2
kg (±0.3 kg) H2 SO4 , equal, whereas for PL an advantage was the reduction of acidified
PW and doubling the P-concentration in the extract. The additional treatment step with
sedimentation and decantation and the reduced P-recovery efficiency compared to PS are
the only drawbacks of this treatment. In comparison, PS produced a char with a slightly
higher HHV, which could be favorable as a fuel substitute for industrial-scale plants. Both
treatments exceed the regulatory requirements for P recovery and additionally transfer
around 50% of N into the liquid phase, while leaving the main part of heavy metals in
the hydrochar. A reduction in char-N content improves as well the combustion emissions
regarding NOx . Regarding the high char-S content, only industrial plants with appropriate
exhaust gas treatments are applicable. Therefore, sewage sludge will be still available as a
climate-neutral fuel for the cement industry and coal power plants.
HTC can compete with current costs for sewage sludge disposal and offers an advan-
tageous alternative to mono-incineration as a sludge treatment, regarding fuel and nutrient
recovery. For an implementation in current WWTP infrastructures plants with AD are
favored because of their sludge property and the possibility of PW fermentation for higher
methane recovery. To promote the P recovery from waste streams like sewage sludge,
further investigations in a sustainable and economically feasible fertilizer production are
needed.
Author Contributions: Conceptualization, G.G. and L.M.; methodology, G.G.; validation, G.G.
and T.K.; formal analysis, G.G., L.M. and T.K.; investigation, G.G., L.M., R.W. and T.K.; resources,
G.G., L.M., R.W. and T.K.; data curation, G.G. and L.M.; writing—original draft preparation, G.G.;
writing—review and editing, G.G. and R.K.; visualization, G.G.; supervision, G.G. and R.K.; project
administration, G.G.; funding acquisition, G.G. All authors have read and agreed to the published
version of the manuscript.
Funding: This research was funded by cemsuisse, the Association of the Swiss Cement Industry. The
article processing charges for the open access publication was funded by ZHAW Zurich University
of Applied Sciences.
Acknowledgments: The authors would like to thank for the financial support received from cemsu-
isse, the Association of the Swiss Cement Industry and ZHAW Zurich University of Applied Sciences
for funding the open access publication. The authors would also like to thank Samuel Solin and
Simon Kaiser, Institute of Bioenergy and Resource Efficiency at the FHNW University of Applied
Sciences and Arts Northwestern Switzerland, for the help with the elemental analysis.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript.
The project funders agreed to publish the results.
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energies
Article
Thermal Analysis and Kinetic Modeling of Pyrolysis and
Oxidation of Hydrochars
Gabriella Gonnella 1 , Giulia Ischia 1 , Luca Fambri 2 and Luca Fiori 1, *
1 Department of Civil, Environmental and Mechanical Engineering, University of Trento, 38123 Trento, Italy;
ga.gonnella@gmail.com (G.G.); giulia.ischia-1@unitn.it (G.I.)
2 Department of Industrial Engineering, University of Trento, Via Sommarive 9, 38123 Trento, Italy;
luca.fambri@unitn.it
* Correspondence: luca.fiori@unitn.it
Abstract: This study examines the kinetics of pyrolysis and oxidation of hydrochars through thermal
analysis. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques
were used to investigate the decomposition profiles and develop two distributed activation energy
models (DAEM) of hydrochars derived from the hydrothermal carbonization of grape seeds produced
at different temperatures (180, 220, and 250 ◦ C). Data were collected at 1, 3, and 10 ◦ C/min between
30 and 700 ◦ C. TGA data highlighted a decomposition profile similar to that of the raw biomass for
hydrochars obtained at 180 and 220 ◦ C (with a clear distinction between oil, cellulosic, hemicellulosic,
and lignin-like compounds), while presenting a more stable profile for the 250 ◦ C hydrochar. DSC
showed a certain exothermic behavior during pyrolysis of hydrochars, an aspect also investigated
through thermodynamic simulations in Aspen Plus. Regarding the DAEM, according to a Gaussian
model, the severity of the treatment slightly affects kinetic parameters, with average activation
energies between 193 and 220 kJ/mol. Meanwhile, the Miura–Maki model highlights the distributions
of the activation energy and the pre-exponential factor during the decomposition.
Citation: Gonnella, G.; Ischia, G.; Keywords: hydrothermal carbonization; modeling; kinetics; thermal analysis; Aspen Plus; biomass;
Fambri, L.; Fiori, L. Thermal Analysis hydrochar
and Kinetic Modeling of Pyrolysis
and Oxidation of Hydrochars.
Energies 2022, 15, 950. https://
doi.org/10.3390/en15030950
1. Introduction
Academic Editors: M. Toufiq Reza The global increase in energy demand, driven mainly by the growing global popula-
and Javier Fermoso tion, urbanization, and economic growth, is depleting the world’s reserves of fossil fuels,
Received: 30 December 2021
already strained by their high consumption rate, heightening environmental concerns, re-
Accepted: 24 January 2022 source depletion, and rising costs. To face the problem, different renewable energy sources
Published: 27 January 2022 have been investigated, like wind, solar, hydropower, geothermal, and biomass. Among
the different biomasses, those deriving from waste or agricultural residues, agro-industrial,
horticulture, and wood processing, are cheap and convenient [1,2]. Besides, the use and
valorizing of waste biomass are part of a circular economy context, where residues become
published maps and institutional affil-
the input for a new process [3]. At present, most of the waste produced in Europe is dis-
iations.
posed of without any further treatment resulting in wastefulness of energy and resources
and in serious environmental impact. A high-efficient use of waste not only increases its
economic value but also results in environmental benefits [4].
Copyright: © 2022 by the authors. In the last decades, biomass waste treatment and management have seen an increasing
Licensee MDPI, Basel, Switzerland. interest from the research community. Currently, biomass waste has characteristics that limit
This article is an open access article its use, including a low heating value, low fixed carbon content, high moisture content, low
distributed under the terms and grindability, and non-uniformity. Studies on the conversion of biomass into high-quality
conditions of the Creative Commons biofuels have been performed to avoid the problems caused by direct combustion and
Attribution (CC BY) license (https:// find more effective methods of utilization, such as pyrolysis, gasification, torrefaction, and
creativecommons.org/licenses/by/ hydrothermal carbonization [5,6].
4.0/).

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Energies 2022, 15, 950
Despite pyrolysis, gasification, and torrefaction processes reducing moisture con-

tent and increasing fixed carbon content and heating value, all of them have a problem
concerning high energy consumption and high pollutant emissions [6,7].
Hydrothermal carbonization (HTC) is a promising technique that can turn lignocellu-
lose biomass into carbon-rich, solid, lignite-like fuel.
HTC is a thermochemical treatment able to recover energy from biomass wastes and
eliminate organic contaminants and pollutants [8]. Similar to the natural coalification
process, HTC lowers both the oxygen and hydrogen content of the feedstock, obtaining
a final coal-like product referred to as hydrochar [9]. The process consists of subjecting
the feedstock to mild temperatures (180–250 ◦ C) and autogenous pressure in liquid water,
ensuring a wide range of applicability for substrates with high moisture, up to 95 wt.% [10].
Hydrochar is endowed with higher calorific value and higher fixed carbon content com-
pared to its precursor biomass [11]. Due to its potential, HTC is a mindful tool to treat
biomass waste, recover materials, and provide an energy source. Hydrochar can be used as
solid fuel and integrating HTC with other processes (like gasification, pyrolysis, anaerobic
digestion [12], and composting [13]) can face shortcomings related to the single-stage, and
improve the overall process efficiency. For example, HTC as a pre-treatment can affect the
pyrolysis performance [1]. This last factor is important to control because it is the primary
stage during the combustion and gasification processes (in view of using hydrochar as a
fuel) and because it is a standalone process to produce biofuels (i.e., char, oil, syngas). In this
framework, HTC can be used for the pre-conditioning of high moisture content biomass,
making it hydrophobic (and thus allowing for a much cheaper dewatering/drying [2]),
and then the biomass can undergo the dry pyrolysis treatment [14]. How much HTC could
affect the pyrolysis rate depends on the type of feedstock involved [15,16].
In this context, understanding the kinetics of pyrolysis and oxidation of hydrochar
could help in designing a thermochemical conversion process.
Even though the application of hydrochar is important in boilers and burners, the
kinetics and combustion performance of hydrochar have been poorly studied. Sharma
et al. [17] showed that adding hydrochar to pulverized coal helps to decrease pollutant
gas emissions. Moreover, the study of process kinetics and the modeling of its control in
the industrial field is weak. Different models (e.g., the Kissinger–Akahira–Sunose method
and the Coats–Redfern method) have also been adopted to investigate the combustion
kinetics of hydrochar [18,19], but the results obtained did not lead to quantitative data that
fit well with the experimental values. Due to the importance of the kinetic behavior of
hydrochar combustion, additional studies are needed. Actually, the distributed activation
energy model (DAEM) is the most comprehensive model to investigate the thermal reaction
kinetics of biomass. Bach et al. [20] employed DAEM to study the kinetic performance of
combustion of wet-towered forest residues, while Chen et al. [6] applied DAEM to study
the kinetic performance of pyrolysis of five lignocellulosic biomasses. Still, Zhang et al. [21]
used a multi-Gaussian DAEM to investigate the decomposition characteristics of cellulose,
hemicellulose, and lignin in different atmospheres. Therefore, the DAEM offers a higher
quality of fit to the experimental data and can provide more information about the kinetics
of biomass pyrolysis. DAEM was proposed originally by Vand [22] to model coal pyrolysis
and is based on the hypothesis that the decomposition occurs through an infinite number
of parallel reactions characterized by a certain distribution of activation energy. The energy
distribution is often modeled through a continuous function, like the Gaussian, Weibull, or
Boltzmann function [23]. Despite the diffusion of DAEMs to predict kinetics parameters
of biomass and coal pyrolysis and oxidation [24–28], studies on the hydrochars are still
very rare in the literature [20]. Therefore, this study used thermogravimetric analysis
(TGA) to investigate the pyrolytic and oxidative behavior of hydrochars derived from an
agro-industrial residue (grape seeds [29]).
In particular, TGA is a technique commonly adopted to analyze and examine biomass
degradation in oxidation or pyrolysis patterns, and can be used to deduce kinetics pa-
rameters and mechanisms [30,31]. TGA data under inert and oxidative atmosphere were
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Energies 2022, 15, 950
collected and used to determine kinetic parameters through two DAEMs (Gaussian and
Miura–Maki DAEM). To do this, TGA data at different heating rates were collected, and
activation energies and pre-exponential factors were computed. Analyses were also per-
formed on the raw biomass and the oil contained inside the seeds. To investigate more
in-depth the decomposition, derivative conversion curves were deduced, and the heat
involved during the pyrolysis or oxidation was determined through differential scanning
calorimetry (DSC). A simple thermodynamic model was also developed in Aspen Plus to
compare experimental outputs with thermodynamic predictions. Through the software,
pyrolysis and oxidation of the hydrochars were simulated and the outputs were compared
with experimental measures from DSC to understand if this modeling approach can be
used as a preliminary study of the heat of reactions.

2.1. Starting Samples: Grape Seeds and Hydrochars
The starting substrate consists of grape seeds and their corresponding hydrochars
produced and characterized in previous work by our group [32]. Grape seeds are a residue
of the winemaking industry and were provided by an alcohol producer company in the
North of Italy (province of Trento). Hydrochars were obtained at 180, 220, and 250 ◦ C
through a solar HTC reactor, at a residence time of two hours, and a dry biomass to water
weight ratio (B/W) of 0.3 [32]. Table 1 summarizes the main properties of the samples.
Table 1. Grape seeds and hydrochar (HC) properties, from the literature [32] (C: carbon, H: hydrogen,
O: oxygen, N: nitrogen, S: sulfur, HHV: higher heating value).
Ultimate Analysis (wt.%) HHV

Sample Ash (wt.%)
C H O N S (MJ/kg)
Grape seeds 53.2 6.7 36.2 1.7 0.3 1.9 22.5
HC 180 ◦ C 59.7 6.7 29.4 1.5 0.4 2.3 24.9
HC 220 ◦ C 64.0 6.4 25.3 1.7 0.4 2.2 27.2
HC 250 ◦ C 69.2 6.5 19.4 2.0 0.3 2.5 30.5
2.2. Sample Characterization

Grape seeds and hydrochars were characterized through thermogravimetric analy-
sis (TGA), differential scanning calorimetry (DSC), and Fourier-transform infrared spec-
troscopy (FTIR).
TGA was performed in a thermobalance Mettler TG50 under non-isothermal condi-
tions. 15 mg of whole dried samples (i.e., the entire raw and carbonized grape seeds) were
placed into a 70 μL alumina crucible. Runs were performed between 40 and 700 ◦ C at a
heating rate of 1, 3, and 10 ◦ C/min, under 100 mL/min of nitrogen or air (20.95% O2 and
78.08% N2 ). The thermobalance has a sensitivity of ±1 × 10 −3 mg and 0.1 ◦ C. The extent
of conversion α at any time t was computed as:
m0 − m(t) v(t)
α(t) = = (1)
m0 − mf v∞
where m0 , m(t), and mf are the mass at time zero (dry), at a given time t, and final time,
respectively. This corresponds to the ratio between v(t), which represents the amount of
volatiles evolved up to a certain time t, and v∞ , which represents the amount of volatiles
that evolved up to the end of the process.
DSC was performed in a Mettler DSC20 calorimeter between 40 and 600 ◦ C, at a
heating rate of 10 ◦ C/min, under nitrogen or air at a flow rate of 100 mL/min. About 15 mg
of material was placed into a 40 μL aluminum crucible. The heat released/absorbed was
computed by integrating the measured heat flow over time in the 40–600 ◦ C range, while
the sample mass variation was recorded after every run.
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Energies 2022, 15, 950
FTIR spectra of samples were acquired using PerkinElmer FT-IR spectrometer Spec-
trum One. Spectra were obtained over a wavenumber range of 4000–650 cm−1 . Dried
samples were ground to be compacted into a thin film and a flat top-plate Zinc Selenide
crystal was used for the detection.
2.3. Distributed Activation Energy Models (DAEMs)

Two types of DAEMs (the Gaussian and the Miura–Maki [33]) were developed in
software codes to model the decomposition of hydrochars, grape seeds, and grape seed oil.
In particular, when a first-order reaction is assumed to model biomass degradation,
the variation of α vs. time can be expressed as the product between the reaction rate k and
the conversion function f:
dα
= k(T)f(α) (2)
dt
By adopting the Arrhenius theory, k(T) can be expressed by Equation (3):

E
k(T) = k0 exp − (3)
RT
where k0 represents the pre-exponential factor, E is the activation energy, and R is the
universal gas constant.
To deduce the kinetic parameters, f(α) is usually assumed in advance (in the so called
model-fitting methods) and then forced to fit experimental data [23]. In particular, non-
isothermal models usually adopt a constant heating rate β equal to dT/dt, allowing the
re-arrangement of Equation (3) into (4), which can be solved using thermogravimetric
data [23].
dα ∼ dα dt dα 1 k(T) k0 E
= = = f(α) = exp − f(α) (4)
dT dt dT dt β β β RT
Among model-fitting methods, DAEM assumes that pyrolysis can be described
through an infinite number of irreversible first-order parallel reactions, with different
rate parameters, which occur simultaneously [23,34]. In particular, the DAEM for a reaction
order equal to 1 can be obtained by re-arranging Equations (2)–(4) as:
∞
T

k0 E
1−α = exp − exp − dT f(E)dE (5)
0 T0 β RT
Equation (5) does not have an analytical solution and there are two families of methods
to solve it. One is referred to as distribution-fitting method and the other as isoconver-
sional methods. The distribution-fitting method assumes f(E) (like a Gaussian, Weibull, or
Boltzmann distribution) and forces to fit the TGA data by applying a certain numerical
method [23]. Meanwhile, isoconversional methods do not assume f(α), but adopt a series of
thermogravimetric data at different heating rates to directly compute the activation energy.
The reaction rate at a certain α is a function of temperature. Among these distribution-free
methods, the Miura–Maki integral method is a common one [35].
2.3.1. Gaussian Model

In the Gaussian DAEM, the distribution function f(E) is assumed to be a Gaussian
distribution with mean activation energy E0 and standard deviation σ, which is:
1 (E − E0 )2
f(E) = √ exp (6)
σ 2π 2σ2
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Energies 2022, 15, 950
Applying the Coats–Redfern [36] and Fisher et al. [37] approximations, Equation (7)
is obtained.

∞ k0 RT2 E 1 ( E − E0 ) 2
1−α = exp − exp − √ exp dE (7)
0 βE RT σ 2π 2σ2
To solve Equation (7), the authors applied the simplification reported by Anthony
and Howard [38], which consists in keeping k0 constant and equal to 1.67 × 1013 s−1 , and
the minimization procedure proposed by Güneş and Güneş [39] that solves the integral
using the Simpson’s 1/3 rule. To avoid oscillations in the results, dE was kept constant
at 50 kJ/mol, while the extremes of integration were iteratively adjusted according to E0 .
Then, the best solution was calculated by iterating the solution of the integral for several
values of E0 and σ and minimizing h, i.e., the root mean quadratic error between the model
output and the experimental data:
2
∑nj=1 αTGA,j − αDAEM,j
h= (8)
n
where αTGA,j and αDAEM,j are the experimental and calculated extent of conversion, respec-
tively, and n is the number of available data points.
The code was developed in MATLAB and a direct search technique was adopted [39].
The code is reported in Supplementary Materials. Firstly, a larger grid procedure was used
for both E0 and σ, with a step size equal to 5. The first three values minimizing h were
obtained. Then, for these last three values, an iteration process using E0 ± 5 and σ ± 5 with
a step equal to 1 was set. Finally, final values were used to solve the integral of Equation (7)
and to calculate αDAEM .
2.3.2. Miura–Maki Model

The Miura–Maki model adopts some assumptions to determine f(E) and k0 without
any a priori assumption on the energy distribution [33]. In particular, Miura and Maki
approximated [33,35] the so called Φ function (Equation (9)) to a step-function E = Es for a
selected temperature T.
t
T

E k0 E
Φ(E, T) = exp −k0 exp − dt ∼
= exp − exp − dT (9)
0 RT β 0 RT
Thus, Equation (5) can be written as:

∞ Es
α∼
= 1− f(E)dE = f(E)dE (10)
Es 0
with Es so that Φ(Es ,T) ∼

= 0.58.
By the Miura and Maki approach, only a reaction having an activation energy Es
occurs at a given T and β—the model simplifies an actual reaction system by a set of N
reactions, characterized by their own activation energy and pre-exponential factor.
Approximating the function Φ(E,T) as:

k0 RT2 E
Φ(E, T) ∼
= exp − exp − (11)
βE RT
the extent of conversion for the j-th reaction is expressed by Equation (12):

Δv ∼ k0 RT2 E
1− = exp − exp − (12)
Δv∞ βE RT
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Energies 2022, 15, 950
where Δv and Δv∞ represent the amount of volatiles evolved and the effective volatile
content for the j-th reaction.
After some mathematical steps [35], and after imposing 1 − Δv/(Δv∞ ) = Φ(E, T) ∼ =
0.58, the representative equation of the Miura–Maki model is given by Equation (13).

β k0 R E
ln 2 = ln + 0.6075 − (13)
T E RT
Compared to the Gaussian DAEM, the approach of Miura [35] and Miura and Maki [33]
relies on the dependence of k0 on E. In particular, they proposed a simple procedure to
estimate f(E) and k0 , consisting of the following steps:
(1) measurement of α vs. T relationship for at least three heating rates;
(2) calculation of β/T2 at selected α values from the α vs. T relationship obtained in
(1) for each heating rate;
(3) plotting of ln (β/T2 ) vs. −1/(RT) at the selected α values, and determination of E
and k0 from the Arrhenius plot at different α values using the relationship represented by
Equation (13): E can be estimated by the slope, and k0 by the intercept of each line with the
y axis; and
(4) plotting the α value against the activation energy E, as calculated in (3), and
differentiating the α vs. E relationship to obtain f(E).
2.4. Aspen Plus Model

The energy aspects of pyrolysis were thermodynamically investigated by performing
some Aspen Plus simulations reproducing the pyrolysis of hydrochars. The model is
based on thermodynamic equilibrium and the minimization of the Gibbs energy, without
considering any kinetic phenomena. In particular, the thermodynamic properties of the
conventional components were calculated by adopting the Peng–Robinson method.
Simulations were performed on grape seeds, hydrochars, and a commercial coal.
Table 2 reports a summary of all input data, while Figure 1 shows the general Aspen
scheme. The stream REACTANT represents the input feedstock entering the process,
defined through a non-conventional stream characterized by its ultimate analysis and
HHV (grape seeds and hydrochar in Table 1, coal Illinois No. 6 from literature [40]).
Then, the RYIELD reactor, which is fictitious, splits the non-conventional stream into a
conventional one (ELEMENTS) based on its elemental distribution. This stream enters the
RGIBBS reactor, which computes the product distribution as a function of the operating
conditions (i.e., temperature and pressure) by minimizing the Gibbs energy of the product
mixture. The final products considered in the model are carbon graphite, carbon dioxide
(CO2 ), carbon monoxide (CO), water (H2 O), hydrogen (H2 ), oxygen (O2 ), methane (CH4 ),
acetylene (C2 H2 ), ethylene (C2 H4 ), and ethane (C2 H6 ), to ensure a good model performance.
Then, the net heat required/produced by the process is given by stream QOUT, while QIN
represents the heat required to sustain RYIELD. Runs were performed between 300 and
900 ◦ C (every block and stream were kept isotherm to avoid any sensible heat contribution)
to deduce the amount of heat involved during the reaction. The product distribution at
different temperatures was also investigated. Data were referred per gram of dry feedstock
entering the process.
Table 2. Summary of parameters used in the Aspen Plus simulations.
Feedstock Grape seeds, HC 180 ◦ C, HC 220 ◦ C, HC 250 ◦ C, Coal

Products (at equilibrium) C (graphite), CO2 , CO, H2 , O2 , H2 O, CH4 , C2 H2 , C2 H4 , C2 H6
Equation of state Peng–Robinson
Pyrolysis temperature 300–900 ◦ C
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Energies 2022, 15, 950
Figure 1. Aspen Plus scheme used to model pyrolysis.

3.1. Derivative Thermogravimetric Curves
Figure 2 shows the derivative thermogravimetric curves (DTGA) of grape seeds and
hydrochars under pyrolytic and oxidative conditions, at different heating rates. Table 3
shows a sum of the position of local peaks, with their temperatures and intensities.
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153
Energies 2022, 15, 950

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Figure 2. Derivative thermogravimetric (DTGA) curves: (a) during pyrolysis at 10 ◦ C/min; (b) during
oxidation at 10 ◦ C/min; (c) effect of the heating rate during pyrolysis of hydrochar 180 ◦ C; (d) effect
of the heating rate during pyrolysis of hydrochar 220 ◦ C; (e) effect of the heating rate during pyrolysis
of hydrochar 250 ◦ C. HC: hydrochars, dα/dt: derivative conversion curve of the extent of conversion
α with respect to time t.
Table 3. DTGA peak temperature and decomposition rate of pyrolysis and oxidation (10 ◦ C/min).
Pyrolysis Oxidation
DTGA Peak Grape HC HC HC Grape HC HC HC
Oil
Seeds 180 ◦ C 220 ◦ C 250 ◦ C Seeds 180 ◦ C 220 ◦ C 250 ◦ C
T (◦ C) - 280 - - - 280 - - -
1 dα/dt
- 5.9 × 10−4 - - - 4.4 × 10−4 - - -
(s−1 )
T (◦ C) - 343 353 358 - 346 334 336 -
2 dα/dt
- 8.2 × 10−4 1.0 × 10−3 1.1 × 10−3 - 7.4 × 10−4 6.6 × 10−4 5.7 × 10−4 -
(s−1 )
T (◦ C) 423 421 424 428 400 415 415 406 409
3 dα/dt
2.0 × 10−3 6.6 × 10−4 7.8 × 10−4 7.7 × 10−4 8.2 × 10−4 4.6 × 10−4 6.2 × 10−4 5.8 × 10−4 5.3 × 10−4
(s−1 )
T (◦ C) - - - - - 502 502 482 480–523
4 dα/dt
- - - - - 1.1 × 10−3 1.3 × 10−3 1.4 × 10−3 1.6–1.1 × 10−3
(s−1 )
Overall, both grape seeds and hydrochars mostly decompose between 200 and 500 ◦ C,
indicating that most of the volatile matter is removed in this range. Grape seeds present
three main decomposition peaks, occurring at 280, 343, and 421 ◦ C under a pyrolytic atmo-
sphere. These peaks can be attributed to the overlapped decomposition of hemicellulose,
lignin plus cellulose, and oil, which are the main constituents of grape seeds (around 7%
cellulose, 31% hemicellulose, 44% lignin, and 10–15% oil [41,42]). Indeed, it is well known
that under pyrolytic conditions, due to its amorphous and little polymerized structure,
hemicellulose is very reactive at low temperatures (in the range of 250–300 ◦ C [21,43]). In
the DTGA curves, this reactivity translates into the first decomposition peak. Meanwhile,
the second peak can be attributed to the overlapped decomposition of lignin and cellulose,
which both generally decompose in the 300–350 ◦ C range [43]. Considering the low content
of cellulose (around 7% [41,42]), lignin clearly dominates at this temperature. Beyond this
decomposition, lignin also contributes by forming a decomposition “baseline” to the profile,
overlapping the other components. Indeed, due to its high polymerized structure and
higher heterogeneity, it decomposes also (less intensively than at 300–350 ◦ C) in a broad
range of temperatures, from around 230◦ up to 600 ◦ C [43]. Therefore, during the pyrolysis
of grape seeds, its decomposition could overlap to that of the other constituents, forming a
“baseline” to the overall profile. Meanwhile, comparing the measured curve with that of
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Energies 2022, 15, 950
grape seed oil from previous work by our group [28], it is clear that the peak occurring at
423 ◦ C can be attributed to the decomposition of the oil. Regarding the hydrochars, through
HTC, grape seeds undergo carbonization, decreasing their atomic O/C and H/C ratios
with a natural reduction of the volatile matter as the harshness of the process increases [32].
In DTGA curves, this translates in flattening the first decomposition peak at around 280 ◦ C,
which is indeed absent for all the hydrochars. Therefore, the authors can affirm that
hemicellulosic compounds are mostly degraded during HTC. Interestingly, the 250 ◦ C
hydrochar exhibits a broad and not intense decomposition between 200 and 300 ◦ C. Since
hemicellulose degrades during HTC, this reactivity can be explained by the presence of
re-polymerized compounds from the aqueous phase. Indeed, during HTC, sugar-derived
compounds dissolved in the aqueous phase (like 5-HMF) can undergo condensation and
re-polymerization, forming a solid phase called “secondary char” [44]. Beyond this, fatty
acids formed during the hydrolysis of the oil could also be embedded in the solid phase,
conferring to the sample an extra-reactivity at low temperatures. Both grape seeds and 180
and 220 ◦ C hydrochars show their highest reactivity at around 350 ◦ C, attributable to the
degradation of lignin and cellulosic derived compounds. Differences can be due to both the
heterogeneity of the feedstock and the synergistic behavior among the constituents, which
are present in different ratios in the various samples. Conversely, the 250 ◦ C hydrochar,
after the initial slow decomposition at 200–300 ◦ C, shows only one main decomposition
peak at 400 ◦ C. Therefore, while the 180 and 220 ◦ C hydrochars tend to follow the feedstock
profile (2nd and 3rd peaks), the 250 ◦ C hydrochar highly deviates from that, highlighting
the impact of the HTC operating temperature on the devolatilization profile. Overall, it is
important to highlight to positive effect of the HTC treatment: after HTC, curves tend to
shift towards the right region of the graph, demonstrating a higher thermal stability during
the degradation process.
Regarding oxidative conditions (Figure 2b), as expected by typical combustion profiles
of biomass fuels [20], all the profiles can be divided into two regions: a first phase during
which the feedstock devolatilizes to char, and a second phase where char oxidation occurs.
The first phase, between 250 and 450 ◦ C, resembles the pyrolytic behavior: hemicellulose,
lignin plus cellulose, and oil volatilize in the same temperature ranges as during pyrolysis.
Then, the second phase, 480–520 ◦ C, corresponds to the oxidation of the char formed during
the first phase. This phase is predominant with respect to the previous phase. As for
pyrolysis, the 180 and 220 ◦ C hydrochars resemble the behavior of grape seeds, exhibiting
three main DTGA peaks. Meanwhile, the 250 ◦ C hydrochar presents only two DTGA peaks,
demonstrating the harshness of severe HTC conditions on the feedstock structure and
composition. Oxidation and pyrolysis TGA curves where (1-α) is plotted vs. T are reported
in Supplementary Materials Figure S1.
Figure 2c–e show the effect of the heating rate on DTGA curves. The heating rate
does not affect the shape of the decomposition profile. Meanwhile, the DTGA peak moves
towards higher temperatures at increasing heating rates, which can be due to heat and
mass transfer phenomena and intrinsic devolatilization kinetics. Indeed, at higher rates, the
mismatch between the temperature in the furnace and the particle is higher, and therefore
there is a delay between the temperature measured and the decomposition stage [45]. In
addition, the dα/dt is higher at higher rates because, at a fixed α, dt is smaller. In addition,
higher rates cause a bigger gradient between the surface and core temperature of the
sample [45].
3.2. DSC Curves

Figure 3 shows DSC curves under nitrogen and oxidative atmosphere. Under an
inert atmosphere, both grape seeds and hydrochars show an initial endothermic phase
followed by an exothermic one at higher temperatures. The transition from an endo-
to an exothermic behavior occurs in a temperature range between 200 and 290 ◦ C. The
heat request comprises both the heat necessary to evaporate water and that to trigger
endothermic reactions. Water derives from both some residual moisture and some produced
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during condensation reactions occurring at the beginning of pyrolysis. Meanwhile, after

the transition temperature, heat is released during pyrolysis. This behavior was already
observed in literature with hydrochars derived from other feedstock [40,46] and can be
attributed to the presence of non-oxidized oxygen on the hydrochar, like in the form of
carboxylic groups. Indeed, this oxygen is enough to oxidize the elemental carbon, leading to
a heat release. As shown in Table 4, the net energy balance along the temperature spectrum
40–600 ◦ C is positive for all the samples, highlighting that overall pyrolysis releases thermal
energy. Not surprisingly and consistently with elemental analysis (Table 1), a higher heat
release is associated with a higher volatile matter loss (Table 4). Details on the progressive
integration of DSC data are given later in the paper (namely, in Section 3.5).

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Figure 3. Differential scanning calorimetry (DSC) curves of grape seeds and hydrochars (HC) at
10 ◦ C/min: (a) under inert and (b) oxidative atmosphere (> 0 exothermic, < 0 endothermic); per
grams of dry feedstock.
Table 4. Details of DSC curves: integrals, mass loss, and transition point from endothermic to
exothermic behavior; per kilograms of dry feedstock. The positive values of “Net energy” correspond
to exothermal behavior during thermal treatments.
Pyrolysis Oxidation
Raw HC 180 ◦ C HC 220 ◦ C HC 250 ◦ C Raw HC 180 ◦ C HC 220 ◦ C HC 250 ◦ C
Endothermic 1
118 90 67 23 98 54 31 19
(J/g)
Exothermic 1 (J/g) 705 587 585 598 4406 4928 6678 7533
Net energy 1 (J/g) 587 497 518 575 4309 4874 6647 7514
Mass loss 1 (%) 61.2 56.2 55.4 43.7 73.7 69.0 73.3 69.0
1 Integral and mass losses computed/measured in the range 40–600 ◦ C.
As for DTGA curves, samples show heat profiles with local peaks. Indeed, grape seeds
show three main peaks, at 280, 352, and 410–425 ◦ C, in correspondence with the degradation
of hemicellulose, lignin plus cellulose, and oil. The 180 and 220 ◦ C hydrochars show two
peaks, while the 250 ◦ C shows only one at 420 ◦ C. A comparison between DTGA and DSC
curves under pyrolytic atmosphere is reported in Supplementary Materials Figure S2.
As expected from the nature of the process, under oxidative conditions (Figure 3b),
the amount of heat released increases as the carbonization degree of the sample increases.
All the samples show a slight endothermic behavior at low temperature, justified by the
absence or low presence of oxidative reactions at this condition. Overall, the heat release
profile is broad and rises to the final observed temperature. Indeed, at 600 ◦ C, a certain
quantity of matter that undergoes oxidation is still present. Even if less sharp than under
an inert atmosphere, all the samples show a peak at 350–450 ◦ C that can be associated with
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Energies 2022, 15, 950
the oxidation of lignin-like compounds. Grape seeds also show a small inflection at 280 ◦ C,
probably due to the oxidation of hemicellulosic compounds.
3.3. FTIR
Figure 4 reports the FTIR spectra of the samples. The deflection at 3300 cm−1 indicates
the stretching of the hydroxyl group, occurring generally in the range 3700–3200 cm−1 [47].
Increasing HTC temperature results in a decreasing intensity in O-H stretching, because
dehydration phenomena occur during HTC treatment. The peak at 3010 cm−1 represents
=C-H group stretch, which tends to gradually disappear in the hydrochars. This fact can
be related to double bonds present in the oil, which degrades, and it is even not present
in HC 250 ◦ C. Purnomo et al. [48] identified hydrogen bonded to the unsaturated carbon
chain (C-H), whereas peaks at lower wavelength represent attachment to the saturated
carbon chain. The peak at 1744 cm−1 indicates a typical bending of carbonyl group >C=O,
possibly in the form of aldehyde [5], and/or the ester group in glyceride compounds. It
tends to attenuate by increasing HTC treatment severity. Whereas grape seeds and HC
180 ◦ C still present a peak, the HC 220 ◦ C spectrum moves toward a lower wavelength. In
the HC 250 ◦ C spectrum the peak disappeared, confirming degradation and formation of
new compounds during the hydrothermal treatment. Furthermore, Diaz et al. [41] state
that peaks around 1030 cm−1 indicate C-O and C-O-C stretching, confirming that both
decarboxylation and dehydration occurred. The grape seed spectrum exhibits a shoulder
at a wavelength equal to 1655 cm−1 , attributed to stretching of double bond >C=C< [47],
that tends to flatten out in hydrochars. Unsaturated double-bound >C=C< could be related
to the presence of oil [6]—grape seed oil is mainly composed of linoleic acid [48,49], having
two double bonds C=C in position 9 and 12. In general, functional groups act a stretch
toward the region at a shorter wavelength.

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Figure 4. Fourier transform infrared spectroscopy (FTIR) curves of grape seeds and hydrochars (HC).
3.4. Kinetic Models

3.4.1. Gaussian Model
Table 5 shows E0 , σ, and h computed through the Gaussian model at different heating
rates for the various substrates, while Figure 5 shows the experimental data compared with
the modeling curves for pyrolysis (data and curves relevant to oxidation are available in
Supplementary Materials Figure S3). Experimental data are the starting point to compute
DTGA curves reported in Figure 2.
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Table 5. Values of E0 and σ for the Gaussian model for the different substrates and heating rates; per
moles of dry feedstock. k0 is let constant and equal to 1.67 × 1013 s−1 .
Grape Seeds Oil HC 180 ◦ C HC 220 ◦ C HC 250 ◦ C

1◦ C/min - - 205 207 209
E0 (kJ/mol) 3 ◦ C/min - - 203 202 206
10 ◦ C/min 193 218 200 200 204
σ 1 ◦ C/min - - 15 16 17
Pyrolysis
(kJ/mol) 3 ◦ C/min - - 14 15 16
10 ◦ C/min 16 11 15 15 16
1 ◦ C/min - - 0.083 0.090 0.089
h (-) 3 ◦ C/min - - 0.061 0.072 0.073
10 ◦ C/min 0.084 0.022 0.064 0.062 0.076
1 ◦ C/min - - 211 214 219
E0 (kJ/mol) 3 ◦ C/min - - 215 215 220
10 ◦ C/min 213 - 214 213 221
σ 1 ◦ C/min - - 14 15 15
Oxidation 3 ◦ C/min - - 15 14 15
(kJ/mol)
10 ◦ C/min 17 - 16 15 15
1 ◦ C/min - - 0.057 0.065 0.065
h (-) 3 ◦ C/min - - 0.071 0.066 0.066
10 ◦ C/min 0.102 - 0.084 0.077 0.077
Data demonstrate that for both pyrolysis and oxidation, the effect of the heating rate
on E0 and σ is negligible. Therefore, every substrate can be associated with one single pair
of E0 and σ, regardless of the heating rate, which agrees with previous studies performed
on other biomass substrates [28]. Under both inert and oxidative atmospheres, the Gaussian
DAEM adopted does not highlight the effects of both HTC and its severity on the starting
feedstock (their maximum relative difference is 3.7%). This is not surprising: the model
basis on the assumption of approximating the entire decomposition profile, which includes
more stages, through a one-step profile characterized by a Gaussian distribution. Therefore,
the final values of E0 and σ can be considered as a sort of weighted average among the
values of the single components (biomass constituents), i.e., hemicellulosic, lignin-like
plus cellulosic compounds, and oil. Probably, the difference in the relative composition
of the hydrochars is not enough to affect the final values. In particular, under an inert
atmosphere, E0 passes from 193 kJ/mol of grape seeds to 200–209 kJ/mol of hydrochars,
while σ ranges between 14 and 17 kJ/mol. Values agree with those reported in the literature
on the single components. For example, during pyrolysis, the activation energies usually
range in 80–116 kJ/mol for hemicellulose, 195–286 kJ/mol for cellulose, and 176–300 kJ/mol
for lignin [35,42]. The pyrolysis of oil alone has an E0 of 218 kJ/mol. With values between
211 and 215 kJ/mol, the activation energy of oxidation is the same for grape seeds and
hydrochars obtained at 180 and 220 ◦ C. Meanwhile, it slightly increases at 220 kJ/mol for
the 250 ◦ C hydrochar.
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Figure 5. 1-α vs. temperature: comparison between experimental data (dots) and predicted data
(lines) computed through the Gaussian model, during pyrolysis of different samples. (a) hydrochar
180 ◦ C; (b) hydrochar 220 ◦ C; (c) hydrochar 250 ◦ C.
3.4.2. Miura–Maki Model

Figure 6 shows the values of E, while Tables S1 and S2 (Supplementary Materials)
report the values of both E and k0 with the correlation coefficient R2 . Figure 7 shows the plot
of ln(β/T2 ) vs. −1/RT at different values of α. Each line corresponds to a certain α, while
the three points on each line correspond to different heating rates. Each α corresponds
to a certain temperature and the sequence Tβ=1 ◦ C/min < Tβ=3 ◦ C/min Tβ=10 ◦ C/min has to be
respected. The maximum value of conversion for which the correct sequence of temperature
was respected is defined with αmax < 1. This was found in the range of α 0.1–0.8 for pyrolysis
and 0.1–0.9 for oxidation. Then, for the valid range of α, E and k0 were determined
graphically using the schemes in Figure 7; E is given by the slope of each line for each α,
while k0 is obtained from the intercept and by applying Equation (13).
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Figure 6. Distribution of E at different α of hydrochars, computed through the Miura–Maki model

during (a) pyrolysis and (b) oxidation; per mol of dry feedstock.
Figure 7. Miura–Maki diagrams of pyrolysis of: (a) hydrochar 180 ◦ C; (b) hydrochar 220 ◦ C;
(c) hydrochar 250 ◦ C.
Under pyrolysis, the fitting is satisfactory, with a R2 always higher than 0.95, except
for one outlier at α = 0.7 for the 220 ◦ C hydrochar. Results show that α hugely affects
the kinetic parameters. All the hydrochars present an E that increases with the degree
of conversion: it rapidly passes from 100–147 kJ/mol (at α = 0.1) to 371–386 kJ/mol in a
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range of α 0.6–0.7. This phenomenon can be explained by the progressive increase of the
degree of carbonization with temperature. As pyrolysis proceeds, the biomass undergoes
volatilization and is converted into a high-carbon content matrix. This char is more difficult
to degrade than the volatile matter and therefore causes a higher E. Generally, values are
considerably higher than those commonly found in literature for biomass substrates (for
example, for lignin it is 237–267 kJ/mol, and for pine wood it is 186–271 kJ/mol [27]),
which can be explained by the nature of the substrate. Meanwhile, k0 reaches its maximum
at an α of 0.5–0.6, with maximum values of 1024–27 for the 180 and 250 ◦ C hydrochars and
1038 for the 220 ◦ C one.
Figure 6b shows how E of different hydrochars vary during oxidation. For the 180 and
220 ◦ C hydrochars, E increases up to α = 0.3–0.5 to values of 357–379 kJ/mol. Meanwhile,
the 250 ◦ C hydrochar shows a very similar trend to the 220 ◦ C one up to an α of 0.35, and
then stabilizes at much lower values of 221–225 kJ/mol. The 180 ◦ C hydrochar shows higher
values of E at the beginning of the conversion. Therefore, the HTC severity decreases the
kinetic parameters of both volatile matter and char produced during the process. Similar
trends were observed by Bach et al. [20] on hydrochars produced from wood residues.
Meanwhile, pre-exponential factors k0 show a very similar trend to E (they reach their
maxima in correspondence of the maximum of α, arriving up to 1024–27 for the 180 and
220 ◦ C hydrochars, and 1014 for the 250 ◦ C one).
3.4.3. Comparison and Suggestions for Future Work

Table 6 reports a comparison table with the average values of E, σ, and k0 , computed
through the Gaussian and Miura–Maki models.
Table 6. Average values of E, σ, and k0 computed through the Gaussian and Miura–Maki models (k0
constant and equal to 1.67 × 1013 s−1 for the Gaussian model).
Hydrochar
Model Atmosphere Parameter Grape Seeds Oil
180 ◦ C 220 ◦ C 250 ◦ C
E (kJ/mol) 193 218 203 203 206
Pyrolysis
σ (kJ/mol) 16 11 15 15 16
Gaussian
E (kJ/mol) 213 - 213 214 220
Oxidation
σ (kJ/mol) 17 - 15 15 15
E (kJ/mol) - - 265 339 239
Pyrolysis
k0 (s−1 ) - - 7.6 × 1027 6.0 × 1038 9.8 × 1024
Miura-Maki
E (kJ/mol) - - 222 215 181
Oxidation
k0 (s−1 ) - - 3.4 × 1026 1.0 × 1026 2.9 × 1013
Due to its starting hypothesis, i.e., approximating the profile with a single Gaussian
curve, the Gaussian model does not highlight the effect of the severity of the HTC pro-
cess on E, which ranges between 193 and 206 kJ/mol for pyrolysis. This does not occur
for the Miura–Maki model, which assumes a distribution of E that varies on the entire
range leading to more diverse average values. Indeed, the Gaussian approach models a
decomposition involving several stages through a single decomposition stage character-
ized by a Gaussian profile of the activation energy. Therefore, this assumption “averages”
the profiles, canceling the differences among the samples obtained at different severities.
Meanwhile, the Miura–Maki model avoids this averaging since it does not impose a similar
strong assumption on the distribution.
Since the literature lacks the modeling of the kinetics of pyrolysis of hydrochar derived
from grape seeds, the comparison of the results obtained was possible considering typical
values of activation energy for decomposition of the main constituents of lignocellulosic
materials. In particular, cellulose decomposition activation energy ranges between 175
and 279 kJ/mol [21,27,50] hemicellulose is in the range 132–186 kJ/mol [27,51,52], whereas
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lignin ranges from 62 to 271 kJ/mol [27,50–52], with the broadest range. These values seem
to prove the consistency of the results obtained in the present work.
In general, the Gaussian model has the advantage of being valid over the entire range
of conversion, while the Miura–Maki model requires always that the temperature sequence
must be satisfied, an aspect that is not obvious (in this study this occurs only for α in the
range of 0.1–0.8). Overall, both the models suffer from a strong starting hypothesis: k0
fixed for the Gaussian model and a strong integral simplification in the Miura–Maki model
that can lead to an overestimation of the average values of the kinetics parameters [53].
To improve the prediction, the authors suggest extending the single Gaussian model
to a Multi Gaussian, in which the entire decomposition profile is divided into single
decomposition peaks, each one approximated by a Gaussian curve [21]. Indeed, the
single approach suits well homogeneous substrates (like the oil) characterized by a single
decomposition peak, but seems too simple for complex substrates like biomasses. As a
result, future works should include a comparison with other kinetics models.
Then, applying other DAEMs (like Kissinger–Akahira–Sunose method and the Coats–
Redfern method) on the same feedstock could help to validate the results. Apart from
contributing to understanding the mechanisms behind the decomposition, kinetic parame-
ters can help in technological design and optimization. Moving to a larger scale, integration
with other modeling techniques is necessary. Among these, it is worth mentioning models
that consider the effects of particle distribution and geometry on heat transfer phenomena
(like fractal models [54,55]), statistical models [56], and comprehensive computational
models [57].
3.5. Aspen Plus Model

Figure 8a,c show the trend of heat produced/required as computed by Aspen Plus
under pyrolytic and oxidative atmosphere.
Regarding pyrolysis, all samples follow a similar trend, characterized by an exother-
mic behavior at low temperatures and an endothermic one at high temperatures. Figure 9
reports the trends of the products at different pyrolysis temperatures resulting from the
180 ◦ C hydrochar (the other samples present the same qualitative trends) and can help
to interpret the heat trends. At low temperatures, thermodynamics favors exothermic
reactions like char oxidation to CO2 and CO, oxidation of hydrogen, and methanation.
Conversely, higher temperatures enhance endothermic reactions, like the Boudouard reac-
tion (and therefore the conversion of CO2 into CO), and methane steam reforming (thus
the conversion of CH4 and H2 O to CO and H2 ). At low temperatures, more carbonized
substrates show a higher exothermic behavior due to a higher carbon partial oxidation
and methane production (they present a higher C/H ratio than less carbonized substrates).
Conversely, at higher temperatures, less carbonized samples show a higher endothermic
behavior, probably due to the higher production of CO. As expected from its high C/O
ratio and low volatile matter content, the profile of coal is flatter than hydrochar, and it
is always endothermic. The different starting points can be explained by the higher ash
content of coal than hydrochars (13.7% vs. 1.9–2.5%): ash, being not reactive, lowers the
energy input/output per unit of mass involved. The slight difference in the coal profile
with the previous work of our group [40] is due to the different inlet temperatures (isotherm
to the reactors here vs. at ambient temperature in [31]).
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Figure 8. Energy released (> 0) or absorbed (< 0) by the samples computed from: (a) Aspen Plus
during pyrolysis; (b) DSC data during pyrolysis at 10 ◦ C/min; (c) Aspen Plus during oxidation;
(d) DSC data during oxidation at 10 ◦ C/min; per grams of dry feedstock.
Figure 9. Aspen Plus results: main products from pyrolysis of hydrochar 180 ◦ C.
Besides, Figure 8b shows the progressive integration of pyrolytic DSC data; comput-
ing the energy integral is necessary because DSC measures the instantaneous heat flow
absorbed or released (which depends on the “history” of the sample due to the thermal
program), while thermodynamics considers the energy absorbed or released when convert-
ing all the reactants into products at that determined temperature (and therefore the values
obtained from thermodynamics do not depend on the thermal history of the sample). Over-
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all, DSC data show a trend towards a cumulative exothermic behavior, whose final value
corresponds to the integral reported in Table 4. The different behavior concerning Aspen
data can be due to the nature of the thermodynamic approach. Indeed, real systems do not
behave as predicted by thermodynamics at low temperatures because of reaction kinetics
constraints. Moreover, as previously mentioned, thermodynamics does not consider the
“history” of what happened before a certain condition. Indeed, inside the DSC, the starting
material progressively undergoes pyrolysis, and the material at every time is the result of
what happened before (i.e., the thermal program). In addition, thermodynamics does not
consider typical “out of equilibrium” products, like tarry compounds, always present in
real systems. Therefore, the thermodynamic approach requires particular attention and
criticism before being used.
Regarding oxidation, both thermodynamic and DSC curves are clearly exothermic,
with values that progressively increase with temperature. Under both atmospheres, ab-
solute values differ between the Aspen and DSC approaches. This is due to the mass
involved: DSC curves measure the energy absorbed/released by an amount of material
that progressively decreases with time (the process is occurring), while Aspen predicts
the energy absorbed/released by the same mass at every temperature. Since the energy
is normalized by the amount of starting feedstock (and not the mass measured at every
temperature), the amount of heat computed through the DSC approach is smaller than
the Aspen one. Finally, it is interesting to note that in an oxidative environment, and
for the whole range of temperature investigated, the thermodynamic approach foresees
the complete oxidation of the biomass with the production essentially of CO2 , H2 O, and
residual ash (equal to about 2% of the biomass fed to the reactor, Table 1). Conversely, in an
oxidative environment in DSC, at the maximum temperature reached of 600 ◦ C, there is
still a substantial mass of non-oxidized carbon: the residual mass at 600 ◦ C is of the order
of 30% (Table 4). Through this critical comparison, the two approaches, thermodynamic
and DSC, turn out to actually be very distant from each other, which is an aspect worthy
of interest.
4. Conclusions
This work investigated the kinetic behavior during pyrolysis and oxidation of hy-
drochars derived from an agro-industrial residue (grape seeds). The topic was approached
through experimental techniques (TGA and DSC) that were used to develop two different
DAEMs for biomass decomposition. Indeed, there is a certain lack in the literature regard-
ing hydrochar decomposition, especially for the computation of the kinetic parameters.
Therefore, this work covers both the experimental aspects and the comparison of two
DAEMs using a critical approach. Thermogravimetric analysis and differential scanning
calorimetry highlighted the importance of the HTC severity on the decomposition profiles.
Indeed, hydrochars obtained at 180 and 220 ◦ C still decompose with two/three stages
(pyrolysis/oxidation) due to the presence of lignocellulosic constituents and oil that only
partially degraded during HTC. Meanwhile, the 250 ◦ C hydrochar shows a more stable
profile, with one/two decomposition peaks, highlighting that HTC temperature hugely af-
fected the structure of the biomass. Interestingly, all hydrochars show a certain exothermic
behavior during pyrolysis.
DAEMs predicted the kinetic parameters involved during the pyrolysis and oxida-
tion processes, i.e., the activation energy and the pre-exponential factor. The single-stage
Gaussian model does not highlight differences among the various hydrochars obtained
at different HTC temperatures, with average values of activation energy in the range
203–206 kJ/mol for pyrolysis and 213–220 kJ/mol for oxidation. Actually, the Gaussian
DAEM turned out to be unsatisfactory to model complex feedstock such as hydrochars
characterized by multi-decomposition peaks. Meanwhile, the Miura–Maki model, even if
not applicable over the entire decomposition region, enabled the determination of the dis-
tribution of activation energies: the more severe the HTC process, the lower the activation
energy values.
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Energies 2022, 15, 950
Supplementary Materials: The following supporting information can be downloaded at: https:
//www.mdpi.com/article/10.3390/en15030950/s1, Figure S1: (1-α) at different temperatures of
feedstock during: (a) pyrolysis; (b) oxidation. Heating rate: 10 ◦ C/min.; Figure S2: Comparison
between DTGA and DSC curves during pyrolysis at 10◦ C/min of: (a) grape seeds and hydrochar
180 ◦ C; (b) hydrochars 220 and 250 ◦ C; Figure S3: Comparison between experimental and predicted
data (1-α vs temperature) computed through the Gaussian model, during oxidation of different
samples: (a) hydrochar 180 ◦ C; (b) hydrochar 220 ◦ C; (c) hydrochar 250 ◦ C; Table S1: Details of
Miura-Maki model, pyrolysis (on a dry basis); Table S2: Details of Miura-Maki model, oxidation (on a
dry basis); Gaussian DAEM – MATLAB code.
Author Contributions: G.G.: methodology, software, data curation, writing—original draft prepara-
tion; G.I.: data curation, visualization, writing—original draft preparation; L.F. (Luca Fambri): exper-
imental planning, writing—review and editing, supervision, project administration; L.F. (Luca Fiori):
writing—review and editing, supervision, project administration. All authors have read and agreed
to the published version of the manuscript.
Funding: This research received no external funding.
Informed Consent Statement: Informed consent was obtained from all subjects involved in the study.
Acknowledgments: All the authors acknowledge Claudia Gavazza for thermal analysis. G.I. ac-
knowledges the financial support provided by the ERICSOL project of the University of Trento, which
partially covered her Ph.D. scholarship. All individuals included in this section have consented to
the acknowledgement.
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Basel • Beijing • Wuhan • Barcelona • Belgrade • Novi Sad • Cluj • Manchester

ISBN 978-3-0365-8456-0 (Hbk)

Cover image courtesy of M. Touﬁq Reza.

About the Editor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii

Manfredi Picciotto Maniscalco, Maurizio Volpe and Antonio Messineo

Taina Lühmann and Benjamin Wirth

Kyoung S. Ro, Judy A. Libra and Andrés Alvarez-Murillo

Md Rifat Hasan, Nepu Saha, Thomas Quaid and M. Touﬁq Reza

Gabriella Gonnella, Giulia Ischia, Luca Fambri and Luca Fiori

Energies 2022, 15, 5491. https://doi.org/10.3390/en15155491 https://www.mdpi.com/journal/energies

Received: 6 July 2020; Accepted: 4 August 2020; Published: 7 August 2020

Abstract: Hydrothermal carbonization (HTC) represents an eﬃcient and valuable pre-treatment

Energies 2020, 13, 4098; doi:10.3390/en13164098 www.mdpi.com/journal/energies

Figure 1. Waste biomass hydrochar potential applications.

2. Eﬀect of HTC Operating Conditions

Figure 2. Cellulose conversion pathways, as proposed in Titirici, 2012.

180 0.5 16.0 65.8 58.6 6.9 31.6 20.5 69 18.1

0.25 40.5 52.4 59.5 4.8 34.1 25.2 74 7.1

3. HTC of Waste Biomass for Energy Production and Storage

3.1. Direct Combustion

3.2. Supercapacitors & Batteries Application

1. Temperature of 315 ◦ C, 20 min with a ZnCl2 -to-shell ratio of 1:1 (w/w);

Table 2. Performances of biomass-derived hydrochar for supercapacitors application.

HTC Activation Activation Max

4.1. Adsorption of Contaminants

HTC Reaction HTC Modifying Contaminant

4.2. Phosphorous Recovery

4.3. Soil Conditioning

5. Hydrochar for Bioreﬁnery

Received: 29 April 2020; Accepted: 1 June 2020; Published: 5 June 2020

Energies 2020, 13, 2890; doi:10.3390/en13112890 www.mdpi.com/journal/energies

2. Materials and Methods

2.1. Feedstock Characterization

Ultimate analysis to determine elemental composition of C, H, N, S, and O (by diﬀerence)

2.2. Hydrothermal Carbonization and Product Analysis

Property Thickened Sludge Digested Sludge Dewatered Sludge

Fixed + Volatile Solids (g/L) 26.7 ± 0.4 15.4 ± 0.9 n.a.

HTC Temp Thickened Sludge Digested Sludge Dewatered Sludge

HTC Temp Thickened Sludge Digested Sludge Dewatered Sludge

3.4. Further Considerations

Supplementary Materials: The following are available online at http://www.mdpi.com/1996-1073/13/11/2890/s1,

Received: 16 July 2020; Accepted: 10 August 2020; Published: 14 August 2020

Keywords: hydrochar; alkali treatment; copper ions; adsorption; computational

Energies 2020, 13, 4203; doi:10.3390/en13164203 www.mdpi.com/journal/energies

2. Materials and Methods

2.2. Hydrochar Synthesis

2.3. Hydrochar Characterization

2.4. Hydrochar Adsorption Tests

2.5. Computational Modeling

3. Results and Discussion

3.1. Glucose Hydrochar Sorption Capacity and Characterization

Figure 1. Comparison of zeta potential of diﬀerent sorbent materials as a function of pH.

3.2. DFT Simulations of the Metal-Carboxylate Interactions

Figure 3. Carboxylate-containing hydrochar structures optimized using Density Functional Theory

3.3. Custom-Synthesis of Hydrochar for Heavy Metal Adsorption

Table 3. Titration results of sorption materials.

Carboxylic Acid Density Carboxylic Acid Density b

Received: 25 July 2020; Accepted: 26 August 2020; Published: 26 August 2020

Energies 2020, 13, 4417; doi:10.3390/en13174417 www.mdpi.com/journal/energies

β̂ = (X X)−1 X y (8)

9)R

[/ 9)R