chemengineering

Article
An Integrated Approach to the Hydrothermal Carbonization
of Sewage Sludge: Simulation, Modeling, and Life
Cycle Assessment
Riccardo Bacci di Capaci 1 , Andrea Luca Tasca 1 , Riccardo Gori 2 , Sandra Vitolo 1 , Monica Puccini 1, *
and Gabriele Pannocchia 1

1 Department of Civil and Industrial Engineering, University of Pisa, 56122 Pisa, Italy;
riccardo.bacci@ing.unipi.it (R.B.d.C.)
2 Department of Civil and Environmental Engineering, University of Firenze, 50139 Firenze, Italy
* Correspondence: monica.puccini@unipi.it

Abstract: Sewage sludge management at wastewater treatment plants is becoming a more and more
challenging task. Here, an innovative integrated modeling approach is developed to investigate the
optimization of a municipal wastewater treatment plant (MWWTP) by the inclusion of hydrothermal
carbonization (HTC). To this aim, two alternative plant layouts have been considered: (i) a conven-
tional activated sludge-based treatment plant, i.e., based on thickening, stabilization, conditioning,
and dewatering; (ii) additional hydrothermal carbonization and integrated treatment of the spent
liquor in the sludge line. An Italian MWWTP has been selected as a case study, and three different
scenarios have been implemented in the process simulation software World Wide Engine for Sim-
ulation Training and Automation (WEST) by considering the effect of the different digestion times
in the aerobic reactor. Then, according to the Design of Experiment (DoE) methodology applied
both on simulated and experimental data, and by the use of a Python code, the desired models
have been developed and compared. Finally, a Life Cycle Assessment (LCA) study has been carried
out to estimate the impacts on human health, ecosystems, and resources. The integration of HTC
corresponds to the generation of a valuable product (the hydrochar), whereas the conventional layout
Citation: Bacci di Capaci, R.; Tasca,
is associated with high disposal costs of the sewage sludge. According to LCA results, a sludge age of
A.L.; Gori, R.; Vitolo, S.; Puccini, M.;
40 days is recommended due to the lowest impacts estimated, both with and without a HTC section.
Pannocchia, G. An Integrated
Approach to the Hydrothermal
This has been ascribed mainly to the electricity demand of the sludge line, which increases with the
Carbonization of Sewage Sludge: excess sludge flow rate, i.e., as the sludge age decreases.
Simulation, Modeling, and Life Cycle
Assessment. ChemEngineering 2023, 7, Keywords: design of experiments; hydrothermal carbonization; integrated modeling; municipal
44. https://doi.org/10.3390/ wastewater treatment; sewage sludge
chemengineering7030044

Academic Editor: Alírio E. Rodrigues

Received: 19 January 2023 1. Introduction

Revised: 21 March 2023
Conventional municipal wastewater treatment plants (MWWTPs) include pretreat-
Accepted: 21 April 2023
ments, such as bar screening and degassing, followed by primary and secondary treat-
Published: 4 May 2023
ments, i.e., air flotation, primary sedimentation, a biofilm process/activated sludge process,
and secondary sedimentation. To further improve the effluent quality, tertiary treatments
(e.g., membrane filtration, advanced oxidation) can be carried out [1]. The raising of the
Copyright: © 2023 by the authors.
population, together with ever more demanding regulations, result in an increased produc-
Licensee MDPI, Basel, Switzerland. tion of sewage sludge, which is the main by-product of wastewater treatment plants [2].
This article is an open access article Sewage sludge is a solid/liquid heterogeneous suspension with an initial solid content of
distributed under the terms and 1–4% by weight. Regardless of the primary source and the MWWTP layout, it generally
conditions of the Creative Commons comprises a nontoxic organic fraction, nutrients, and a hazardous fraction (pathogenic
Attribution (CC BY) license (https:// microorganisms, organic contaminants and heavy metals).
creativecommons.org/licenses/by/ Among the wide range of technologies available for treatment and disposal, resource
4.0/). recovery, and power generation, hydrothermal carbonization (HTC) is emerging as a

ChemEngineering 2023, 7, 44. https://doi.org/10.3390/chemengineering7030044 https://www.mdpi.com/journal/chemengineering

ChemEngineering 2023, 7, 44 2 of 19

promising technique able to meet all of these process objectives [3]. Indeed, HTC does
not require preliminary drying, as it operates with sub-critical water and autogenous
pressure, converting the feedstock into a solid carbonaceous fraction, named hydrochar,
and a water-soluble organic fraction, the spent liquor [4,5]. The main transformations
occurring during the process are the hydrolysis and dehydration of cellulose, hemicellulose,
and lignin to monosaccharides and disaccharides, which are then dehydrated, hydrolyzed,
and decarboxylated to intermediate fragments, which are finally re-condensate into the
hydrochar matrix.
While the conventional process layout implies high disposal costs of sewage sludge,
the integration of HTC with a traditional wastewater plant corresponds to the generation of
a valuable product [6,7]. As a matter of fact, hydrochar can be employed in several fields [8]:
in industry, as a combustible from a renewable source [9–11]; agriculture, as fertilizer [12];
wastewater treatment itself, as an adsorbent material [13]; and soil remediation [14,15].
Several studies have applied different models into wastewater management, by involv-
ing different process technology including HTC [16]. In [17], the role of process simulation
in designing, evaluating, and optimizing wastewater treatment facilities was discussed.
In particular, alternatives for controlling VOC emissions from plants and removing dis-
solved solids from clarified effluent streams were evaluated. Later, an artificial neural
network to model the activated sludge process of two different MWWTPs was developed
by [18]. More recently, in [19], a hybrid model of a MWWTP was designed, which is
meant to improve the quality of effluent prediction, by combining mechanistic, i.e., an
activated sludge model, and data-driven models. In [20], the influence of solid loading
on characteristics of hydrochar, process water, and plant energetics was investigated. In
detail, by modeling an experimental facility with Aspen Plus, the authors showed that
the integration of anaerobic digestion with HTC provides a significant positive energy
balance when process water and hydrochar are considered as fuel sources for cogeneration.
Finally, in [21], HTC was evaluated as a possible treatment for sewage sludge, by including
phosphorus recycling. In particular, Aspen Plus modeling was used to show the posi-
tive impact of implementing HTC in a WWTP: the mechanical dewaterability of sewage
sludge increases, enabling energy savings by means of subsequent thermal drying. A
phenomenological-based semi-physical model (PBSM) was developed by [22] to predict
and describe the dynamic behavior of the oxygen transfer in a diffused aeration process of
a WWTP by means of a formal modeling methodology. The authors of [23] showed how
sewage systems can be modeled and controlled within the framework of model predictive
control (MPC). Several MPC-based strategies were proposed, accounting for the inherently
complex dynamics and the multi-objective nature of the control required. Finally, in [24],
different structures and configurations of artificial neural networks were used for the
prediction of influent biological oxygen demand and WWTP performance.
Life Cycle Assessment (LCA) is a well-established technique to quantify the impacts
associated with a product, service, or process by using a cradle-to-grave perspective. LCA
was first applied in the 1990s in the field of wastewater treatment [25], and it nowadays
proves to be a key tool to estimate impacts of design and operation decisions, as demon-
strated by the many works available in the literature [26–28]. LCA has been also applied to
investigate hydrothermal carbonization processes. In [29], the case of HTC from olive mill
waste was investigated, while in [30] the general scenario of food wastes was considered.
In [31], a process simulation model in Aspen Plus was developed to obtain the main data
for the required input-output inventories to perform both techno-economic and life cycle
assessment study. In addition, in [32], the processes of HTC were investigated with and
without sewage sludge digestion as well as energetic and agricultural utilization, examin-
ing twelve different valorization concepts of sewage sludge on the basis of empirical and
literature data. More recently, in [33], a LCA analysis of hydrothermal carbonization of
sewage sludge from an Italian plant and its produced valorization pathways was presented;
while in [34], a study was conducted on urban organic solid waste in comparison with a
gasification process in southern Chile.
ChemEngineering 2023, 7, 44 3 of 19

Based on all these premises, the aim of the present study is the integration of a
HTC section into the layout of a conventional MWWTP, evaluating the feasibility and
the efficiency of the proposed solutions. Firstly, process data were obtained from a set
of experiments performed on a WEST rigorous simulator. Then, according to the DoE
methodology, these data were used to obtain input-output correlation models in Design
Expert software for the wastewater and sludge line of the analyzed processes (Figure 1).
These relations were then integrated with mass and energy balances written for the HTC
section, and other input-output correlation models were obtained for an HTC reactor from
lab scale experimental data, and hence solved altogether within a Python software code.
The resulting highly integrated models were employed to evaluate the efficiency of different
operating scenarios. Finally, a LCA was carried out on SimaPro to estimate the expected
impacts on human health, ecosystems, and resources. Note that an Italian MWWTP was
adopted as a case study: the historical plant data were previously used as a reference to test
and validate the WEST models, while a set of actual effluent sludge were here employed
for laboratory tests for the HTC section. Note that the proposed modeling approach is
highly integrated both in terms of software and in terms of data type, which gives novelty
to the work and flexibility to the methodology.

Figure 1. The integrated approach for simulation, modeling and life cycle assessment.

The reminder of the paper is as follows: Section 2 describes the case study used to
apply the proposed approach; the methodology is illustrated in detail in Section 3, showing
how the different software and the various data types are highly integrated. The results
are then presented in Section 4, where different plant layouts and process scenarios are
compared. Finally, conclusions are given in Section 5.

2. Case Study
The studied MWWTP is the urban plant of San Colombano, near Florence (Italy). The
plant has a potential of 600,000 Population Equivalent (PE), i.e., 250,000 m3 /d, and it is
divided into three units operating in parallel of 200,000 PE each. Table 1 summarizes the
main characteristics of inlet and outlet streams.
ChemEngineering 2023, 7, 44 4 of 19

Table 1. Features of the wastewater treated in the MWWTP under study.

Parameter Unit Input Output

Chemical Oxygen Demand (COD as O2 ) g/m3 141.0 ± 54.2 27.1 ± 6.4
Total Suspended Solids (TSS) g/m3 65.1 ± 18.4 3.6 ± 0.6
Ammonia nitrogen (as NH4 + ) g/m3 18.2 ± 5.4 0.95 ± 0.65
Nitrous nitrogen (as N) g/m3 0.28 ± 0.12 0.07 ± 0.02
Nitric nitrogen (as N) g/m3 2.6 ± 1.6 7.4 ± 2.0
Total nitrogen (as N) g/m3 21.3 ± 6.8 8.6 ± 2.0
Total phosphorus (as P) g/m3 2.6 ± 0.8 0.96 ± 0.27
pH - 7.77 ± 0.05 7.89 ± 0.13

Each of the three units consists of two main sections: (a) the wastewater treatment
line and (b) the sludge treatment line, equipped with an anaerobic digester for the pro-
duction of biogas. The wastewater line consists of: (i) pretreatments: coarse and very fine
screening, sand removal, and oil removal; (ii) primary sedimentation, carried out by biolog-
ical treatment with activated sludge with both anoxic and aerobic section; (iii) secondary
sedimentation; (iv) disinfection. The aerators of the aerobic reactors are of the fine bubble
type, with micro-perforated PIK300 discs and EPDM membranes. Totally, 1305 diffusers
are installed; the number of discs decreases along the flow direction.
As a result of the HTC implementation, the layout of the considered MWWTP would
appear as represented in the simplified flow diagram of Figure 2. The unit operations
modeled in this work are shown as different blocks and material and energy streams,
and the main process variables are also represented.

Figure 2. Flow diagram of the MWWT process integrated with the HTC section.

3. Methodology
As said, both existing sections—wastewater line and sludge line—were modeled using
the WEST platform, then analyzed by the DoE approach to build regression correlation
models, which were finally implemented in Python for quantitative assessments.

3.1. Modeling in WEST

The WEST software is a sophisticated tool released by MIKE DHI [35], generally
used for modeling and simulating various chemical-physical processes as wastewater
purification, river pollution phenomena, and degradation processes occurring in sewers.
Nevertheless, it can be easily extended to any system described by algebraic and differential
equations. Here, the Activated Sludge Model No.3 (ASM3) of WEST was chosen as a
rigorous model for the wastewater line, as extensively tested and discussed by [36]. The
HTC section was instead modeled both by mass and energy balances based on the process
flow scheme directly in Python and by a DoE study obtained from experimental data on
the actual sludge, including the yield of the carbonization reactor, in order to find optimal
operating conditions. The HTC treatment was assumed to take place at 220 °C, with a
residence time of 4 h and an inlet solid/liquid ratio of 1/15 by weight.
ChemEngineering 2023, 7, 44 5 of 19

Overall, six different scenarios have been investigated, three based on the conventional
layout (named WWTP-i) and three with the integration of a HTC section (WWTP-i/HTC),
by considering three different Solids Retention Times (SRTs) in the oxidation tank of
primary treatments; i.e., sludge age ‘i’ of 40, 20 and 10 days, respectively. It is worth noting
that a SRT of 40 days is not conventionally applied in MWWTPs, which may result in
high concentration of suspended solids and induce problems in pollutant removal and
sludge sedimentation. Nevertheless, the treatment plant of San Colombano considered
in this study actually operates with a very long retention time, around 40 days, since
the inlet wastewater is very diluted (compare the values of Table 2). Therefore, to get a
processable sludge leaving the secondary sedimentation tank, the corresponding SRT has
to be particularly high.
Overall, the modeled scenarios are comprehensive of: (i) wastewater line, with fine
and very fine screening, sand and oil removal, Modified Ludzak-Ettinger (MLE) biological
treatments, and secondary sedimentation; (ii) eventual hydrothermal treatment, comprising
mechanical thickening by centrifugation, hydrothermal carbonization (HTC), mechanical
dewatering by filter press, and drying; (iii) sludge line, with mechanical thickening by cen-
trifugation, anaerobic digestion, pumping via a sludge pipeline to a delocalized treatment
section, and mechanical dewatering by centrifugation. The simulation of the current state
of the real plant was extended to a one-year period (from June to May) to allow suitable
calibration and validation of the WEST models.

3.2. Test Plans with DoE

The software Design Expert, released by Stat-Ease Inc., is here used for the application
of the Design of Experiments (DoE) methodology [37]. Design Expert is a statistical analysis
and modeling tool useful for planning, running and analyzing experiments, and building
input-output correlation models. It also allows comparative testing, screening, charac-
terization, optimization, robust parameter design, and combined designs. The statistical
significance of the input factors is established by the analysis of variance (ANOVA). A
Response Surface Model (RSM) can be used to map a design space, providing an immediate
visualization of the effects of the variation of the input factors on the responses of interest.
For the three conventional scenarios, that is, layouts without the HTC section, named
WWTP-10, WWTP-20, and WWTP-40, five input factors were considered for the wastewater
treatment line (Table 2). A low and high level was chosen for each factor, identified on the
basis of an extensive set of real process data. The excess sludge flow rate (Qex ) separated
from the secondary sedimentation and pumped back to the oxidation tank was chosen
according to the different scenarios obtained by modeling in WEST the recirculation of the
sludge. The overall inlet flow rate includes both the fresh inlet (Qin ) and the supernatant
liquid, recirculating from the sludge line (Qsup ).

Table 2. Input factors considered for the wastewater treatment line.

Low High
Factor Description Unit
Level Level
Qin Inlet flow rate 15,000 350,000 m3 /d
CODin Inlet Chemical Oxygen Demand 60 270 g/m3
N-NH4,in Inlet ammonia nitrogen content 10 40 g/m3
Tox Temperature in the oxidation tank 13 27 °C
Qex Excess sludge flow rate from secondary sedimentation 1440 7200 m3 /d

A total of 18 responses were evaluated as output variables, listed in Table 3. The first 12
variables are strictly related to the wastewater line, while the last 6 are related to the sludge
line. A Full-Factorial plan was chosen for the DoE methodology, with 5 factors, 2 levels
(high/low), 1 replication each, and 1 single central point, for a total of 25 + 1 = 33 trials.
Hence, 33 different simulation scenarios were performed by the WEST platform.
ChemEngineering 2023, 7, 44 6 of 19

Table 3. Output responses of the wastewater and sludge treatment lines (WWTP-i scenarios).

Response Description Unit Notes

Wastewater line
TSSox Total suspended solids in oxidation tank kg/m3 -
TSSex Total suspended solids in excess sludge t/y ASM3-HTC inlet
SRT Solids Retention Time in oxidation tank d energy and process parameters
VSS/TSSox Ratio Volatile—Total Suspended Solids % w/w energy and process parameters
O2,ox Oxygen demand in oxidation tank kg/d energy and process parameters
ECox Energy Consumption of oxidation tank kWh/d energy and process parameters
CODout COD of clear liquid g/m3 ASM3-clear liquid
TSSout Total Suspended Solids in clear liquid g/m3 ASM3-clear liquid
N-NH4,out Ammonia nitrogen in clear liquid g/m3 ASM3-clear liquid
N-NO3,out Nitric nitrogen in clear liquid g/m3 ASM3-clear liquid
TNout Total Nitrogen g/m3 ASM3-clear liquid
DOout Dissolved Oxygen in clear liquid g/m3 ASM3-clear liquid
Sludge Line
Qex,th Flow rate of excess sludge after thickening m3 /d -
Qbg Flow rate of biogas exiting the sludge line m3 /d -
Qdew Flow rate of dewatered sludge exiting the sludge line m3 /d -
CODsup COD of liquid supernatant exiting the sludge line g/m3 -
TNsup Total Nitrogen in supernatant liquid g/m3 -
Qsup Flow rate of supernatant liquid m3 /d -

DoE was performed with a single central point, thus favoring linear relationships
between input and output variables. The choice of a single central point is also motivated
by the fact that responses are actually originated from the WEST simulation model and not
from experimental laboratory tests or from real plant data; i.e., repetitions of the central
point would give the same result.
Concerning the responses of Table 3, the Design Expert software returns, by the
analysis of variance (ANOVA), a set of parametric linear equations, related to the five input
factors listed in Table 2 and, eventually, their linear interactions. For instance, the solids
retention time, energy consumption of oxidation tank, and flow rate of supernatant liquid
were modeled, respectively, as follows:

1/SRT = 0.000659 + 3.61 × 10−9 Qin + 1.52 × 10−5 Qex + 1.089 × 10−12 Qin · Qex (1)

ln( ECox ) = 6.5917 + 4.163 × 10−6 Qin + 0.0057 CODin + 0.045940 N-NH4,in +
+0.0074 Tox − 0.000026 Qex − 0.00011 CODin · N-NH4,in + (2)
−8 −7
−4.745 × 10 CODin · Qex + 3.59869 × 10 N-NH4,in · Qex

Qsup = −4.28585 + 0.000031 Qin + 0.009340 CODin + 1.00072 Qex +

(3)
−1.86558 × 10−6 Qin · CODin − 5.396712 × 10−9 Qin · Qex
It is worth noting that, in order to decrease residuals in the data, the software suggests
adopting inverse and logarithmic transformation for the correlation of SRT and ECox ,
respectively. The correlations for the other outputs are not reported for the sake of brevity.
With regard to the three integrated scenarios (WWTP-i/HTC), a different experimental
plan was established. The wastewater line was modeled as for three WWTP-i scenarios,
with the five factors listed in Table 2 as inputs, and the first 12 variables of Table 3 as outputs.
The three specific input factors of Table 4 and the five responses of Table 5 were instead
considered for the HTC section. Note that the yield in hydrochar (ηhc ) was defined as
the percentage ratio between the mass of the dry hydrochar and the mass of dry sludge,
while the yield in Carbon (ηC ) as the percentage ratio between the carbon content of dry
hydrochar and of dry sludge.
ChemEngineering 2023, 7, 44 7 of 19

Table 4. Input factors of the HTC section.

Factor Description Low Level High Level Unit

Tr Carbonization temperature 190 220 °C
τr Carbonization residence time 85 240 min
SCts Solid Content in thickened sludge 5 12 % w/w

Table 5. Output responses for the HTC section.

Response Description Unit

ηhc Yield in hydrochar %
ηC Yield in carbon C %
HHVhc High Heating Value of hydrochar MJ/kg
Dew Dewaterability of hydrochar m/kg
Ash Ash content in hydrochar % w/w

A rotatable Central-Composite plan of RSM type was chosen as the DoE, with 3 factors,
2 levels (high/low) and 1 replication each, 6 repetitions of the central point, and 6 axial
points, resulting in 23 + 6 + 6 = 20 trials. As said, trials involving the HTC section were not
simulated in the WEST platform, but carried out on a lab scale; therefore, the repetitions of
the central point were set to take into account measurement errors in the experiments. In
detail, laboratory trials were carried out with an AISI 316 stainless steel autoclave, with a
volume of 300 mL, equipped with a conventional electric heating system (thermoman-
thus). The autoclave head was equipped with mechanical stirring, a thermocouple for
temperature control and a pressure gauge with a full scale of 1000 psi for pressure con-
trol. The temperature control (220 °C) inside the reactor was carried out with a manual
controller (PARR 4842) and the sludge was introduced directly into the autoclave, filled to
about 2/3 [38], so that a coupled temperature and pressure hydrothermal treatment was
performed (Figure 3). Nevertheless, note that the decoupled temperature and pressure
treatment of [39] provides a novel promising method to produce sustainable carbon mate-
rials from cellulose with a carbon-negative effect; as a matter of fact, by using a different
carbonization mechanism, even lower temperatures (200 °C) can be achieved [40].

Figure 3. Lab apparatus for the hydrothermal carbonization of the sewage sludge.

Hydrochar yield and the high heating value have been modeled as follows:

ηhc = 74.28 − 0.099 Tr − 0.015 τr + 0.978 SCts (4)

ChemEngineering 2023, 7, 44 8 of 19

HHVhc = 8.972 + 0.137 SCts (5)

Again, the other correlations are omitted for the sake of brevity.
Selected responses from the HTC model were then used as input factors for the sludge
treatment line. Through simulation in Python, it was indeed possible to identify the suitable
input levels for the DoE plan to be finally implemented into the WEST platform. To this
aim, three input factors were employed, as shown in Table 6.

Table 6. Input factors of the sludge line (integrated scenarios WWTP-i/HTC).

Factors Description Low Level High Level Unit of Measure

COD pw Chemical Oxygen Demand of inlet process water 10,000 43,350 g/m3
N-NH4,pw Ammonia nitrogen content of inlet process water 529 1850 g/m3
Q pw Flow rate of inlet process water 50 850 m3 /d

Five responses were established as outputs, which correspond to the last five variables
considered for the three WWTP-i scenarios listed in Table 3, that is, Qex,th was excluded. A
simple Full-Factorial plan was chosen as the DoE, with 3 factors, 2 levels (high/low) and
1 replication each, and 4 repetitions of the central point, corresponding to 23 + 4 = 12 trials.
For the sake of brevity, only two correlations are reported below; the outlet flow rate of
biogas and dewatered sludge were modeled as follows:

Qbg = 7.79518 + 0.000307 COD pw − 9.44372 × 10−16 Q pw

(6)
+0.000239 COD pw · Q pw

Qdew = −0.041613 − 1.63787 × 10−6 COD pw − 0.000739 Q pw

(7)
+1.114202 × 10−7 COD pw · Q pw

3.3. Integration in Python

In order to assess and quantify the six different scenarios under study, additional
material and energy balances have been implemented and solved in Python along with the
parametric correlations obtained by DoE methodology. Table 7 lists the major input data
used for the six considered scenarios. Note that the excess sludge flow rate (Qex ) varies
according to the established Solids Retention Time in the aerobic digester.

Table 7. Major input data for Python modeling.

Input Variable Value Scenarios

Qin Inlet flow rate [m3 /d] 212,697 all six
CODin Inlet Chemical Oxygen Demand [g/m3 ] 141 all six
N-NH4,in Inlet ammonia nitrogen content [g/m3 ] 18 all six
Tox Temperature of the oxidation tank [°C] 19 all six
1547 WWTP-40; WWTP-40/HTC
Qex Excess sludge flow rate leaving the secondary sedimentation [m3 /d] 3187 WWTP-20; WWTP-20/HTC
6465 WWTP-10; WWTP-10/HTC
Tr Carbonization temperature [°C] 220 3 WWTP-i/HTC
τr Carbonization residence time [min] 240 3 WWTP-i/HTC
SCts Solid Content in thickened sludge [%] 15 3 WWTP-i/HTC
Uhc,out Humidity of hydrochar leaving the dryer [-] 0.10 3 WWTP-i/HTC

Figure 4 shows the block diagram of the additional HTC section adopted for the
integrated WWTP-i/HTC scenarios with material and energy streams.
ChemEngineering 2023, 7, 44 9 of 19

Figure 4. Flow diagram of HTC section with material and energy streams implemented in Python.

Tables 8 and 9 list all the other variables used for the material and energy balances
related to the HTC section and the corresponding utilities, respectively. Note that variables
are separated in fixed parameters and unknowns. The material and energy balances
implemented in Python are reported below in detail.

Table 8. Variables involved in material and energy balances for WWTP-i/HTC scenarios—HTC section.

Symbol Description
Parameters
Uhc,in Humidity of hydrochar at dryer inlet [0.45]
Tth,0 Temperature before preheating E1 [80 °C]
Tth,1 Temperature post preheating E1 [120 °C]
Tth,2 Temperature post preheating E2 [180 °C]
Unknowns
ηhc Yield in hydrochar [%]
Qhc Flow rate of hydrochar leaving the dryer [kg/d]
Qws Flow rate of wet solid leaving the filter press [kg/d]
Qsl Flow rate of slurry leaving the HTC reactor [kg/d]
Q pw Flow rate of process water leaving the filter press [m3 /d]
∆vap Condensed vapor inside the HTC reactor [kg/d]
Q gas Flow rate of gas required for drying the hydrochar [kg/d]

Table 9. Variables involved in material and energy balances of the WWTP-i/HTC scenarios-Utilities.

Symbol Description
Parameters
Tf m Temperature of the fumes leaving the boiler [245 °C]
Rta, f Ratio between theoretical air and fuel [17.31]
Rra,ta Ratio between real air and theoretical air [1.5]
TH2 O Temperature of evaporator inlet water [23 °C]
Tair Temperature of air to be mixed with the fumes for the dryer [90 °C]
Tgas Temperature of gas entering the dryer [115 °C]
Tb Temperature of combustion in the boiler [1950 °C]
Twg,1 Temperature of water-glycol before preheating E1 [180 °C]
Twg,2 Temperature of water-glycol after preheating E1 [100 °C]
ChemEngineering 2023, 7, 44 10 of 19

Table 9. Cont.

Symbol Description
Unknowns
Q air Flow rate of air to be mixed with the fumes for the dryer [kg/d]
Qfm Flow rate of fumes leaving the boiler [kg/d]
Qvap Flow rate of steam leaving the evaporator [kg/d]
Tmix Temperature of evaporator outlet water [°C]
Qvap1 Flow rate of steam entering the second preheater [kg/d]
Qvap2 Flow rate of steam entering the HTC reactor [kg/d]
Q air,c Flow rate of effective air for combustion [kg/d]
QCH4 Flow rate of fuel required for combustion [kg/d]
Q H2 O Flow rate of water to be sent to the evaporator [kg/d]
Qwg Flow rate of water-glycol to be sent to the preheater [kg/d]
Tsl Temperature of the slurry leaving the reactor exchanger (E3) [°C]
Q f m1 Flow rate of fumes sent to the dryer [kg/d]
Q f m2 Flow rate of fumes sent to energy recovery and to disposal [kg/d]

Concerning the HTC section, the following set of equations (S1 ) was defined:
• Evaluation of flow rate of thickened sludge Qth (in kg/d) from the WEST model ASM3
by using TSSex (in t/y):
( TSSex 1000
365 )
Qth = 100 (8)
SCts
• Hydrochar yield in HTC section:

ηhc
(1 − Uhc,out ) Qhc = SCts Qth (9)
100
where ηhc is expressed by Equation (4).
• Material balance of the dryer:

(1 − Uhc,in ) Qws = (1 − Uhc,out ) Qhc (10)

• Material balance of the filter press:

Qsl = Qws + Q pw (11)

• Material balance of the HTC reactor:

Qth + ∆vap = Qsl (12)

• Energy balance of the reactor:

∆vap λ H2 O = Qth c pth ( Tr − Tth,2 ) (13)

Concerning the utilities, the following second set of equations (S2 ) is defined:
• Material balance of gas at node (N1 ) at dryer inlet:

Q air + Q f m1 = Q gas (14)

• Energy balance at the evaporator:

Q f m c p f ( Tb − T f m ) = Qvap (c p H O ( Tr − Tmix ) + λ H2 O ) (15)

2

• Material balance of the vapor at node (N2 ):

Qvap = Qvap1 + Qvap2 (16)

ChemEngineering 2023, 7, 44 11 of 19

• Effective air for combustion in the boiler:

Q air,c = Rra,ta Rta, f QCH4 (17)

• Material balance at the boiler:

Q f m = QCH4 + Q air,c (18)

• Material balance of water at system composed of evaporator and HTC reactor

Q H2 O = Qvap1 + ∆vap (19)

• Energy balance of water at node (N3 ) at evaporator inlet:

Q H2 O c p H TH2 O + ( Qvap2 − ∆vap ) c p H Tr = Qvap c p H Tmix (20)

2O 2O 2O

• Energy balance of water-glycol at pre-heater E1:

Qwg c pwg ( Twg,1 − Twg,2 ) = Qth c pth ( Tth,1 − Tth,0 ) (21)

• Energy balance of pre-heater E2:

Qvap1 λ H2 O = Qth c pth ( Tth,2 − Tth,1 ) (22)

• Energy balance at the HTC reactor outlet heat exchanger (E3):

Qwg c pwg ( Twg,1 − Twg,2 ) = Qsl c psl ( Tr − Tsl ) (23)

• Energy balance of gas at node (N1 ) at dryer inlet:

Q gas c p gas Tgas = Q air c pair Tair + Q f m1 c p f T f m (24)

• Mass balance at node (N4 ) on fumes line:

Q f m = Q f m1 + Q f m2 (25)

• Constraint on the steam (Qvap2 ) sent to the HTC reactor:

Qvap2 = 1.5 ∆vap (26)

• Energy balance at the dryer (approximated):

( Qws Uhc,in − Qhc Uhc,out ) λ H2 O = Q gas c pgas ( Tgas − Tgas,out ) (27)

The resolution of these two nonlinear systems (S1 , S2 ) was performed through the fsolve
function in Python. In addition to material and energy balance equations, direct equations
were considered to establish the main features of the output products, including carbon
yield, high heating value, and the ash content of the produced hydrochar, all previously
obtained by the DoE model of the HTC reactor.

3.4. Life Cycle Assessment

Finally, the models obtained from the integrated approach WEST-DoE-Python have
been analyzed by the LCA methodology. The study followed the guidelines of the UNI
EN ISO 14040 and 14044 standards. The analysis was indeed carried out according to the
conventional four-stage structure: (i) scope definition, (ii) inventory analysis, (iii) impact
assessment, and (iv) interpretation of the results. As a functional unit, 1 m3 of wastewater
entering the plant was set.
ChemEngineering 2023, 7, 44 12 of 19

The process boundaries included: (a) the wastewater line, (b) the sludge line, and (c)
the HTC section. All the sludge ages (40, 20, and 10 days) were considered. In addition,
the production process of defecation gypsum, one of the possible options for the sludge
disposal processes, was also modeled. The estimation of the impacts on the environment
and on human health was carried out according to the ReCiPe 2016 midpoint (H) Europe
method with 18 different categories and then implemented in the software SimaPro 9.2.

4. Results and Discussion

The implementation of the parametric equations in Python allowed one to define and
quantify the material and energy streams used for the inventory phase of the LCA analysis.
The six different scenarios with three different sludge ages, such as Solids Retention Time
(SRT) in the oxidation tank, are here compared. In detail, the following key performance
indicators are examined: (i) energy consumption; (ii) operating conditions; (iii) effluent
quality; (iv) impact on greenhouse gas (GHG) emissions.
Table 10 summarizes the various results of modeling in Python obtained from three
WWTP-i scenarios.

Table 10. Results of modeling in Python for three WWTP-i scenarios.

Output Variable WWTP-40 WWTP-20 WWTP-10

Clear liquid
CODout Outlet Chemical Oxygen Demand [g/m3 ] 27.37 27.00 25.92
TSSout Total Suspended Solids [g/m3 ] 2.254 1.514 0.674
N-NH4,out Ammonia nitrogen content [g/m3 ] 1.139 1.512 2.633
N-NO3out Nitric nitrogen content [g/m3 ] 5.054 5.180 5.228
TNout Total Nitrogen content [g/m3 ] 6.467 6.962 8.120
DOout Dissolved Oxygen [g/m3 ] 0.528 0.928 1.728
Qout Flow rate of outlet clear liquid [m3 /d] 212,643 212,642 212,641
Thickened sludge
TSSex Total Suspended Solids in excess sludge [t/y] 5578 5904 6492
Qth Thickened sludge flow rate [kg/d] 15,282 16,176 17,787
Anaerobic
digester
Qbg Biogas flow rate [Sm3 /d] 2641 3147 4130
Qdew Flow rate of dewatered sludge [m3 /d] 53.94 54.80 56.00
Mdew Dewatered sludge amount [kg/d] (∗ ) 54,747 55,657 56,827
CODsup COD of supernatant liquid [g/m3 ] 264.7 183.0 86.19
TNsup Total Nitrogen in supernatant liquid [g/m3 ] 129.9 102.5 62.83
Qsup Flow rate of supernatant liquid [m3 /d] 1493 3132 6409
Energy and process variables
TSSox Total suspended solids in oxidation tank [kg/m3 ] 4.508 3.027 1.348
SRT Solids Retention Time [d] 40 20 10
VSS/TSSox Ratio Volatile—Total Suspended Solids [-] 0.581 0.595 0.626
O2,ox Oxygen demand in oxidation tank [kg/d] 19,967 19,458 18,004
ECox Energy Consumption of oxidation tank [kWh/d] 7748 7550 6986
ECwl Energy Consumption of wastewater line [kWh/d] 35,770 36,043 36,591
ECsl Energy Consumption of sludge line [kWh/d] 4667 9615 19,505
(∗ ): Mdew = Qdew ρsl , being ρsl = 1.015 kg/m3 the sludge density.

Moreover, the results obtained for three integrated WWTP-i/HTC scenarios are re-
ported in Tables 11 and 12.
ChemEngineering 2023, 7, 44 13 of 19

Table 11. Results of the modeling in Python for three WWTP-i/HTC scenarios—part 1.

WWTP- WWTP- WWTP-

Output Variables
40/HTC 20/HTC 10/HTC
Clear liquid
CODout Outlet Chemical Oxygen Demand [g/m3 ] 30.35 30.00 29.27
TSSout Total Suspended Solids [g/m3 ] 2.523 1.698 0.769
N-NH4,out Ammonia nitrogen content [g/m3 ] 1.166 1.536 2.668
N-NO3,out Nitric nitrogen content [g/m3 ] 5.505 5.514 5.544
TNout Total Nitrogen content [g/m3 ] 6.974 7.350 8.505
DOout Dissolved Oxygen [g/m3 ] 0.528 0.928 1.728
Qout Flow rate of outlet clear liquid [m3 /d] 212,687 212,687 212,686
Thickened sludge
TSSex Total suspended solids in excess sludge [t/y] 6162 6545 7332
Qth Thickened sludge flow rate [kg/d] 16,882 17,931 20,089
HTC section—extensive variables
Qhc Flow rate of hydrochar leaving the dryer [kg/d] 11,878 12,616 14,134
Q pw Flow rate of process water leaving the filter press [m3 /d] 103.25 109.7 122.9
Qws Flow rate of wet solid leaving the filter press [kg/d] 112,548 119,541 133,927
Q gas Flow rate of outlet gas required for drying the hydrochar [kg/d] 279,813 297,199 332,966
Q gas,out Flow rate of outlet gas [kg/d] 287,372 305,227 341,961
∆vap Condensed vapor inside the HTC reactor [kg/d] 10,134 10,764 12,059
Qsl Flow rate of slurry leaving the reactor [kg/d] 122,682 130,305 145,987
Utilities—extensive variables
Q air Flow rate of air to mix with the fumes for the dryer [kg/d] 240,619 255,570 286,327
Qcond1 Flow rate of condensed vapour [kg/d] 15,202 16,146 18,089
Q air,c Flow rate of effective air for combustion [kg/d] 39,720 42,188 47,265
QCH4 Flow rate of fuel required for combustion [kg/d] 1529 1625 1820
Q H2 O Flow rate of water to be sent to the evaporator [kg/d] 25,336 26,910 30,149
Qwg Flow rate of water-glycol to be sent to the preheater [kg/d] 60,186 63,926 71,619
Tsl Temperature of the slurry leaving the reactor exchanger (E3) [°C] 183.3 183.3 183.3
Q f m1 Flow rate of fumes sent to the dryer [kg/d] 39,194 41,629 46,639
Q f m2 Flow rate of fumes sent to energy recovery and to disposal [kg/d] 2055 2183 2446

Table 12. Results of the modeling in Python for three WWTP-i/HTC scenarios—part 2.

Output Variable WWTP-40/HTC WWTP-20/HTC WWTP-10/HTC

Hydrochar features
ηhc Yield in hydrochar [%] 63.30 63.30 63.30
ηC Yield in carbon C [%] 54.62 54.62 54.62
HHVhc High heating Value [MJ/kg] 11.03 11.03 11.03
Dew Dewaterability [m/kg] 761.2 × 109 761.2 × 109 761.2 × 109
Ash Ash content [% w/w] 59.19 59.19 59.19
Sludge line after HTC section
Qbg Biogas flow rate [Sm3 /d] 1518 1611 1801
Qdew Flow rate of dewatered sludge [m3 /d] 0.836 0.896 1.021
Mdew Dewatered sludge amount [kg/d] 849.0 909.0 1036
CODsup Chemical Oxygen Demand in supernatant liquid [g/m3 ] 35,665 35,665 35,665
TNsup Total Nitrogen in supernatant liquid [g/m3 ] 6909 6909 6909
Qsup Flow rate of supernatant liquid [m3 /d] 102.9 109.2 122.4
ChemEngineering 2023, 7, 44 14 of 19

Table 12. Cont.

Output Variable WWTP-40/HTC WWTP-20/HTC WWTP-10/HTC

Energy and process variables
TSSox Total suspended solids in oxidation tank [kg/m3 ] 5.045 3.395 1.539
SRT Solids Retention Time in the oxidation tank [d] 40 20 10
VSS/TSSox Ratio Volatile—Total Suspended Solids [-] 0.582 0.596 0.626
O2,ox Oxygen demand in oxidation tank [kg/d] 22,373 21,608 20,182
ECox Energy Consumption of oxidation tank [kWh/d] 8682 8385 7831
ECwl Energy Consumption of wastewater line [kWh/d] 35,777 36,051 36,598
ECth Energy Consumption of thickening [kWh/d] 533.0 721.0 1097
EChc Energy Consumption of HTC [kWh/d] 8188 8697 9743
ECsl Energy Consumption of sludge line [kWh/d] 311.0 331.0 371.0

In particular, energy consumption is evaluated by the total electrical energy demand

(TEED), considered as sum of energy for oxidation tank (ECox ), energy for the other units of
wastewater treatment line (ECwl ), energy for hydrothermal carbonization (only for WWTP-
i/HTC scenarios, composed of HTC term EChc and thickening term ECth ), and energy for
sludge treatment line (ECsl ). The results for the different scenarios are summarized in
Figure 5.

Figure 5. Total electrical energy demand of the six different scenarios.

Note that the integrated WWTP-i/HTC scenarios are demonstrated to be almost

independent from the Solids Retention Time of the aerobic digester. In detail, a linear
correlation can be fitted with a proportionality constant one order of magnitude smaller
than the one obtained for the simple WWTP configurations, that is, −65 vs.−460. Moreover,
a significant reduction in the energy demand of the integrated layout with respect to the
corresponding traditional plant seems feasible only for a low sludge age (SRT = 10 d).
The operating conditions of the various scenarios were compared in terms of the
amount of solid effluents, i.e., sewage sludge to be disposed (Mdew ) and hydrochar to be
sold (Qhc ), expressed in tons per year (Figure 6). Integrated plants produce very lower
amount of sewage sludge if compared with the conventional layouts, around two order of
magnitude less. In addition, the sludge produced by traditional WWTPs has typically a
high humidity rate, around 80%, leading to a considerable disposal cost (around 200 €/t).
Conversely, the hydrochar obtained after hydrothermal carbonization and suitable drying
process has very lower humidity content (10%), and its added value would be currently
remarkable (around 80 €/t).
ChemEngineering 2023, 7, 44 15 of 19

Figure 6. Amount of solid effluents of the different scenarios.

Effluent quality and impact on greenhouse gas (GHG) emissions were evaluated by
the LCA methodology. In a nutshell, it has been found that the process scenario with
the lowest impacts is the one associated with sludge age of 40 days, both without and
with the implementation of HTC treatment. This is mainly due to a reduced electricity
consumption of the sludge line, which instead increases with the excess sludge flow rate,
i.e., as the sludge age decreases. Since the analyzed treatment plant actually operates with
a SRT = 40, the adopted configuration proves to be the optimal one.
In detail, considering the three scenarios without hydrothermal carbonization (WWTP-
10, -20, -40), the largest contributor to environmental impacts is the wastewater line, due to
the high consumption of energy and chemical additives. Figure 7 shows the results for the
WWTP-40 scenario, in terms of the relative impacts of wastewater line and sludge line.

Figure 7. Estimated impacts: comparison between wastewater and sludge lines in the WWTP-
40 scenario.
ChemEngineering 2023, 7, 44 16 of 19

In addition, Figure 8 shows the contributions to the environmental impacts of the three
sections (wastewater line, HTC unit, and sludge line) for the WWTP-40/HTC scenario.
Wastewater line confirms to be the largest contributor in 15 out of 18 impact categories.
Note that similar results have been obtained also for the other two integrated scenarios
(WWTP-20/HTC and WWTP-10/HTC), which are not here presented for the sake of brevity.

Figure 8. Estimated impacts: comparison between wastewater and sludge treatment lines in the
WWTP-40/HTC scenario.

Finally, Figure 9 shows the comparison between the two best operating scenarios
associated with a 40-day sludge age: WWTP-40 and WWTP-40/HTC.

Figure 9. Comparison in terms of environmental impacts between the WWTP-40 and WWTP-
40/HTC scenarios.

This comparison results in a higher environmental impact associated with the inte-
grated WWTP-40/HTC layout only in the following four categories: stratospheric ozone
depletion, freshwater ecotoxicity, marine ecotoxicity, and non-carcinogenic human toxicity,
due to the incineration of the obtained hydrochar. The overall reduced impact of the inte-
grated scenario has to be ascribed to the avoided sludge disposal; indeed, notwithstanding
ChemEngineering 2023, 7, 44 17 of 19

the emission associated with the hydrochar incineration, this operation does not affect
significantly most of the impact categories here analyzed.

5. Conclusions
In this paper, the analysis of the municipal wastewater purification process was carried
out by developing an integrated mathematical modeling of two alternative treatments:
(i) actual layout of the considered activated sludge plant, i.e., thickening, stabilization,
conditioning, and dewatering; (ii) additional hydrothermal carbonization of the excess
sludge and treatment of the liquid fraction in the sludge line.
Design Expert software was used to obtain a parametric modeling of the considered
alternatives starting from the rigorous modeling obtained on the WEST simulation platform
and on the basis of experimental lab scale data for the HTC section. The implementation of
parametric correlations in Python allowed the definition of material and energy streams
related to three scenarios corresponding to different sludge ages. Finally, environmental
impacts were estimated by LCA analysis.
The energy consumption obtained from the integrated layout has been shown to be
almost insensitive to variations of the Solids Retention Time, and it compares favourably
with respect to the existing conventional MWWTP in the case of low SRT values. The
integrated process WWTP/HTC generates a valuable product, whereas the traditional
solution produces a considerable amount of sewage sludge to be disposed. In terms of
environmental impacts, LCA analysis denoted the wastewater line as the greatest con-
tributor to most of the considered impact categories. Additionally, operating with a high
sludge age (of forty days, which is the actual SRT of the considered plant) proved to be
associated with the lowest impact, especially due to the reduced energy demand. The
comparison between the two scenarios—WWTP-40 and WWTP-40/HTC—reflects in a low
environmental impact associated with the integrated layout, designing HTC-integration as
a promising solution to a more sustainable management of sewage sludge.

Author Contributions: Conceptualization, R.G., M.P. and G.P.; methodology, R.G., M.P. and G.P.;
software, R.B.d.C., R.G. and G.P.; validation, R.G., S.V. and M.P.; formal analysis, R.B.d.C., R.G.
and G.P.; investigation, R.G., S.V. and M.P.; resources, S.V. and M.P.; data curation, R.B.d.C., R.G., S.V.,
M.P. and G.P.; writing—original draft preparation, R.B.d.C. and A.L.T.; writing—review and editing,
R.B.d.C., A.L.T., M.P. and G.P.; visualization, R.B.d.C. and A.L.T.; supervision, R.G., M.P. and G.P.;
project administration, R.G., M.P. and G.P.; funding acquisition, R.G., M.P. and G.P. All authors have
read and agreed to the published version of the manuscript.
Funding: This work has been supported by Regione Toscana through the POR FESR (2014–2020)
funding program within the research and development strategic project SLUDGE 4.0.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available upon request from the
corresponding author.
Acknowledgments: Authors greatly acknowledge Publiacqua S.p.A., and in particular Eng. Simone
Caffaz, for providing the data of the San Colombano plant and for improving this study with
constructive criticisms.
Conflicts of Interest: The authors declare no conflict of interest.

Abbreviations
The following abbreviations are used in this manuscript:

DoE Design of Experiments

HTC Hydrothermal Carbonization
HC Hydrochar
LCA Life Cycle Assessment
ChemEngineering 2023, 7, 44 18 of 19

MWWTP Municipal Wastewater Treatment Plant

PE Population Equivalent
RSM Response Surface Model
SRT Solid Retention Time
TEED Total Electrical Energy Demand
TSS Total Suspended Solids
WEST World Wide Engine for Simulation Training and Automation

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