Resources, Conservation & Recycling xxx (xxxx) xxx

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Resources, Conservation & Recycling

journal homepage: www.elsevier.com/locate/resconrec

Environmental and economic assessment of gasification wastewater

treatment by life cycle assessment and life cycle costing approach
Valentina Innocenzi a, *, Federica Cantarini b, Svetlana Zueva a, Alessia Amato c,
Barbara Morico b, Francesca Beolchini c, Marina Prisciandaro, Conceptualization and
Supervision a, Francesco Vegliò a
a
Department of Industrial and Information Engineering and Econmics - University of L’Aquila, Piazzale Ernesto Pontieri, Monteluco di Roio 67100, L’Aquila Italy
b
NextChem srl, Via Guido Polidoro 1, 67100 L’Aquila, Italy
c
Department of Life and Environmental Sciences, Università Politecnica delle Marche, Via Brecce Bianche, 60131 Ancona, Italy

A R T I C L E I N F O A B S T R A C T

Keywords: This study compared the sustainability of six alternatives for the treatment of industrial wastewater from a
Industrial wastewater gasifier, considering both environmental and economic aspects by the approaches of: uses Life Cycle Assessment
Gasifier (LCA) and Life Cycle Cost (LCC). The processes have been developed under the zero liquid discharge approach
Process design
and included a chemical removal of pollutants by using Fenton and neutralization, evaporation and crystalli­
Life cycle assessment
Life cycle cost
zation to concentrate salts and stripping for the removal of ammonia from distillate of evaporation step and
Zero liquid discharge recover water useful for industrial reuses. The scenarios differed for the type of utilities used for the operation
(steam and hot water from thermal waste) and from an optimization of the crystallization that provided a
reduction of the amount of waste and an energy recovery from distillate. LCA indicated that the six scenarios
produced comparable results, since the common chemical treatment (raw material and waste disposal) causes the
highest contribution. The optimal scheme used hot water as utilities and had an optimization of the crystalli­
zation section (scenario B2), this options allowed a decrease of emission to air of 25% and reduction of 15% of
deposited goods. Scenario B2 is much more financially attractive than the other proposed treatment, having a
total cost of 123 €/t, with a reduction of 17% respect to the current disposal of 150 €/t.
LCA and LCC results prove the effectiveness of thermal waste use as utilities for the wastewater treatment
operations and the optimization of crystallization unit is the most environmentally and economically favourable
alternative.

1. Introduction variation and complexity of composition and the difficult to achieve

emission standards.
Nowadays coal and biomasses, as well as solid wastes, are important Many researchers are paying more attention to the development of a
raw material useful for producing a variety of high-value chemicals via treatment process useful to overcome the problems associated to the
gasification process. This treatment includes a thermal conversion of coal or biomasses gasification wastewater, analyzing causes and possible
carbonaceous feedstocks by using oxygen and/or steam into syngas solutions to this issue.
composed mainly of hydrogen and carbon monoxide. The obtained The gasification wastewater is expected to have a variable compo­
syngas is suitable for different applications as a chemical feedstock or as sition due to feedstock characteristics (coal, wood, coconut shell, agri­
a fuel gas used for electricity generation (gas reciprocating engines or cultural refuse, etc.), gasifier types (up-draft or down-draft) (Jeswani
gas turbines). Syngas from gasification is treated to remove impurities and Mukherji, 2012) and also due to operating conditions. It contains
and it is fed into a cleaning section using water (as a function of selected phenolics, polynuclear aromatic hydrocarbons (PAHs) and heterocyclic
technology); this in turn, leads to the generation of wastewater. The compounds which have toxic, mutagenic and carcinogenic properties
gasification wastewater (i.e. from quench, contactors, cyclones steps) is (Jeswani and Mukherji, 2012). Chemical oxygen demand (COD) for
one of the most important problems to be managed due to extremely wastewater from biomasses gasification is between 920 - 160,000 mg/L

* Corresponding author.
E-mail address: valentina.innocenzi1@univaq.it (V. Innocenzi).

https://doi.org/10.1016/j.resconrec.2020.105252
Received 8 April 2020; Received in revised form 30 October 2020; Accepted 30 October 2020
0921-3449/© 2020 Elsevier B.V. All rights reserved.

Please cite this article as: Valentina Innocenzi, Resources, Conservation & Recycling, https://doi.org/10.1016/j.resconrec.2020.105252
V. Innocenzi et al. Resources, Conservation & Recycling xxx (xxxx) xxx

(Jeswani and Mukherji, 2013) as these effluents contain a relevant Fenton and precipitation with lime, evaporation, crystallization and
concentration of organic compounds, while for coal gasifier wastewater stripping. The residual solid from crystallization is rich in chlorides and
the COD typical range is 300–5000 mg/l (Zhao al., 2017). Moreover the could valorized and sold. In the analysis this residual solid has been
presence of refractory organic species makes it necessary to adopt treated in a conservative way as a waste. The main advantage of the
complicated treatment operations. proposed process scheme, unlike for example biological degradation, is
The coal gasification wastewater contains substances as phenols, related to the total water recovery from both evaporation, crystallization
ammonia nitrogen, volatile acids and ions as fluorides, sulfides and and stripping section. The recovered water can be used for industrial
chlorides (Ji et al., 2015). The composition of the effluents depends on purpose reducing the fresh water supply from industries.
the quality of the coal and but also on the gasification process that could The high utilities consumption for the solution concentration
be divided into two mainly categories: high temperature gasifier and low (evaporation and crystallization) is reduced as a result of an energy
temperature gasifier. Wastewater from low temperature gasification recovery from crystallization phase and replacing the low pressure
contains polycyclic aromatic compounds (benzene and phenols), het­ steam with hot water coming from a thermal recovery section.
erocyclic compounds and many refractory organics (Zhao al., 2017). In this context, the scope of the present work is the assessment of the
Due to the low operating temperature, the organic matter decomposition proposed wastewater treatment to prove the techno- economic and
is not complete, and the results is a complex wastewater composition. environmental sustainability. With this aim, both the life cycle assess­
The ammonia concentration and COD are higher than those obtained ment (LCA) and the life cycle costing (LCC) analysis are performed. The
during a gasification process at high temperature (NH3 200–400 mg/l vs research activities are carried out within STREAM project (Wastewater
150–220 mg/l; COD 3500–5000 mg/l vs 300–350 mg/l). Low temper­ treatment system with energy water and material recovery PON
ature gasification wastewater also has higher chromaticity, total dis­ 2014–2020 FESR, F/050,203/01–02/X32 Program) focused on the in­
solved solids and salinity (Zhao et al., 2017). dustrial wastewater treatment in agreement with the zero liquid
Wastewater generated from biomasses gasifier process contains discharge (ZLD) approach.
organic (tar) and inorganic. Tar is a mixture of several acidic, basic and
other substances (i.e. nitrogen compounds, polyaromatic species -PAHs) 2. Materials and methods
(Mehta and Chavan, 2009).
Although it is widely reported that biological treatment may provide 2.1. Chemicals and solutions
more cost effective solution using a specific microbial consortium (Jes­
wani and Mukherji, 2012 and 2013; Tian et al., 2006), the residual The experimental tests have been performed with residual effluents
organic contaminant concentration may still pose a risk due to the collected from gasification plant located in central Italy. Hydrochloric
toxicity of that contaminants. The phenolic and recalcitrant substances acid (36%) has been used for pH adjustments, hydrogen peroxide (Carlo
contained in the coal gasifier wastewater inhibit the biological activities Erba, 30% w/v H2O2), iron chloride (Sigma Aldrich, 98%) have been
of the bacteria, for that the biological process is widely used to treat this used for Fenton process, instead sodium hydroxide (Fluka Chemika,
type of waste after a preliminary treatment for ammonia stripping and >97%) has been used to increase the solution pH after Fenton and
phenol solvent removal by extraction (Ji et al., 2016). For wastewater precipitate the impurities. All solutions, FeCl3 (40% w/v) and NaOH
from biomasses gasification, ammonia-based components and also small (20% w/v), were prepared by dissolving the reagents in distilled-
quantity of H2S and chlorides are toxic to microorganism and resist to deionized water.
biological degradation (Mehta and Chavan, 2009). But those compounds Ion concentrations (i.e. chloride, sulfates, sulfur, ammoniacal nitro­
are amenable to be removed through physical or chemical methods. gen) and total organic carbon (TOC) have been measured with Dr.
The treatment of biomass gasifier wastewater includes phys­ Lange’s kit, cuvette-test.
ico–chemical treatment as coagulation with alum or lime followed by A quantitative analysis for the concentration of metals have been
adsorption with activated carbon (PAC) that guarantee an high removal performed by atomic absorption spectroscopy (AAS) (spectrometer
of phenolics, COD, ions as fluorides (Jeswani and Mukherji, 2012; Spectro AA 200, Varian).
Ippolito et al., 2016; Wan et al., 2021) and also for color, total suspended Total suspended solids (TSS) were measured according to Standard
solid (TSS) and total dissolved solid (TDS) (Mehta and Chavan, 2009). Method 2540 for solid determination in water and wastewater treatment
The disadvantage of processes is the production of large volume of (Eaton et al., 1998).
hazardous sludge (Jeswani and Mukherji, 2012).
The residual wastewater treatment process from gasification poses a 2.2. Experimental procedure
serious challenge on the sustainable development of this industrial
sector. The biological treatment has been considered as an environment- Advanced oxidation Processes (AOPs) and precipitation experiments
friendly and cost-effective method if compared to physico-chemical were carried out to evaluate the efficiency of physical chemical pre­
approaches (Zhao and Liu, 2016; Wan et al., 2021). Furthermore a treatment of the studied wastewater.
combination of biological treatment process and advanced one could Among AOPs, the most common is the Fenton reaction which in­
achieve the desired results (Zhao and Liu, 2016). Several research ac­ cludes the use of a catalyst (i.e. FeSO4) and hydrogen peroxide (H2O2) as
tivity has been performed on the various technologies for the treatment oxidizing agent (see reaction 1 and 2):
of coal and biomass gasifier wastewater (Zhao and Liu, 2016; Mehta and
Fe2+ + H2 O2 →Fe3+ + OH− + •OH (1)
Chavan, 2009; Jeswani and Mukherji, 2012 and 1013; Tian et al., 2006)
in order to meet the urgent need to identify the better treatment to deal
Fe3+ + H2 O2 →Fe + HO2 • +H+ (2)
with the international organizations and strict requirements of envi­
ronmental regulations. Fenton like experiments were suggested to avoid re-contamination of
In a world where the industrialization and also the continuous in­ wastewater with Ca and sulfate ions. The Fenton-like was carried out
crease in population lead to the gradual reduction of the availability of with iron chlorides as a source of Fe3+ according to optimal conditions
fresh water, an innovative wastewater management approach appears found in previous work: ratio [COD]:[H2O2] = 1:9; ratio [H2O2]:[Fe2+]
necessary: wastewaters can be used as a valuable resource of water after = 4.5:1 and pH 3–3.5 (Bianco et al., 2011). Samples of the wastewater
specific treatment. were heated up to the desired constant temperature (40 ◦ C). After FeCl3
In the present research activity, an integrated process to treat gasifi­ and hydrogen peroxide solution were added to the mixture for Fenton
cation wastewater is proposed with the aim to valorize and recover water reactions (see Eqs. (1)-2) . The solutions were stirred (200 rpm) for 120
for its possible reuse. The scheme includes a chemical pretreatment by min at a temperature of 20 ◦ C. After reaction time, precipitation of the

2
V. Innocenzi et al. Resources, Conservation & Recycling xxx (xxxx) xxx

Fig. 1. The block diagram of the pretreatment process performed at lab scale.

oxidized iron as Fe(OH)3 was performed in two steps (Fig. 1): Step 1, chlorides from water, for that the chloride ions concentration is rela­
Adjusting the pH up to 8 by neutralization with NaOH (40% w/v) for 1 h tively high (See Table S1, Supplementary materials).
and following filtration; and Step 2, Adjusting the pH up to 11 by A wastewater treatment has been proposed with the aim to treat this
neutralization with NaOH (40% w/v) for 1 h and following filtration. residual effluent after chemical treatment to: a) reduce the chlorides
The pH of the solutions, the concentrations of sulfate, sulfide, chlo­ concentration and other impurities from water after chemical pre-
ride, ammonium and metals were measured before and after the Fenton treatment; b) maximize the water recovery and; c) produce a final
and chemical precipitation experiments. solid rich in sodium chlorides that could be analysed for a possible reuse.
Anyway, in this study the concentrate of salts is considered as solid
waste. The overall treatment included: chemical pre-treatment, evapo­
2.3. Scope definition and background on process for LCA and LCC
ration, crystallization and stripping section. Mass and energy balances
analysis
have been described considering that the proposed plant can work in
continuous mode with a capacity of the plant of 8900 kg/h. This value
The results of the experimental activity (as described in Section 3.1)
was chosen considering the capacity of the real gasification plant located
showed that chemical treatment with Fenton and basification with so­
in central Italy. The final products were a residual solid from chemical
dium hydroxide was efficient to remove pollutants from wastewater.
pre-treatment, a concentrate of salts and cleaned water that can be
The treated water mainly contained sodium chloride, this effluent
reused from concentration sections.
cannot be discharged because the concentration of substances as chlo­
ride, and ammonium and sodium exceeds the legal limits to the
2.3.1. Functional unit and system boundary
discharge (Italian Legislative Decree 152/2006). The chemical
A production of 8900 kg/h of wastewater has been chosen as func­
pre-treatment has been performed adding iron chloride and the
tional unit for the treatment comparison in the life-cycle inventory. The
following neutralization with sodium hydroxide is not able to remove

Fig. 2. System boundaries for the proposed gasification wastewater treatment.

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Table 1 Mass and energy balances (M&E) of the various scenarios have been
Scenarios considered for the process analysis. reported in Table S2 (Supplementary materials).
Utilities Optimization process The final concentrate from crystallization is rich in sodium chloride
Scenario Low Thermal Filtration Energy recovery with traces of other salts: in the present study it has been considered as
stream waste(for system after (80%) from waste to disposal. Fig. S1 (Supplementary Materials) shows the final
pressure example crystallization distillate of
composition of salt for scenarios A and scenarios B.
(0.3 barg) hot water crystallization
at 70 ◦ C)
Scenario A
2.3.2. Methodology
A1 X The mass and energy balances have been used to carry out LCA and
A2 X
A3 X X
LCC analysis with the aim to assess both the enviromental and the
economic impact of the considered options. The implementation of the
Scenario B
environmental sustainability analysis, by LCA way, aimed at the quan­
B1 X X tification of impacts due to the six scenarios described in the present
B2 X X
work, following the approach described by Innocenzi et al. (2020). The
B3 X X X
evaluation allowed the identification of the most critical steps, sup­
porting the lowest impact choice, among the six options. The additional
system boundaries of the system are shown in Fig. 2. combination with the LCC was essential to identify the most sustainable
The description of the proposed wastewater treatment process is scenario considering environmental and the economic aspects (Amato
reported below. et al., 2019). The functional unit chosen for the assessment was 8900
kg/h of the initial wastewater. This unit ensured the characteristics
i) In the first phase of the chemical pre-treatment as suggested by required by the LCA ISO standard 14,040 and 14,044:2006: simple
the experimental results, wastewater has been treated by Fenton definition, measurability and reproducibility (ISO14044:2006). These
process followed by chemical precipitation adding sodium hy­ standards were taken into account for the implementation of the whole
droxide to reduce the amount of pollutants. Experimental data analysis. Overall, the system boundaries included four blocks: chemical
has been used to define the mass balance for the chemical pro­ pre-treatment, evaporation, crystallization and stripping sections, in
cess. Moreover, an energy balance has been estimated consid­ agreement with Fig. 2. More in detail, the first step (common to the six
ering that the treatment is performed in a reactor that needs scenarios) involves the use of: hydrogen peroxide, hydrochloric acid,
energy for mixing system and filter press for separating residual ferric chloride and sodium hydroxide, with the production of a solid
solid and solution. This last has been sent to evaporation system, waste, classified as hazardous. Low pressure steam was supplied to the
instead the solid needs to be disposed of. other stages of the process, except for scenarios A2 and B2. A solid waste
ii) In the second step, the treated solution is fed into a multiple effect (classified as not hazardous) results from the crystallization step. The
evaporator with three effects (vertical falling film). The inlet European grid mix electricity was assumed for energy supply to the
flowrate was 10,000 kg/h with an initial concentration (%wt) of process. Tables S2 summarizes both the raw material and energy bal­
2% sodium, 3% chlorides, 0.12% calcium, 0.012% ammonium ances considered for the assessment. The thinkstep GaBi
chloride and 0.05% of ammonia. The outputs from the last effect software-System and Database for Life Cycle Engineering (compilation
were a distillate (7575 kg/h) that was condensed by using cooling 7.3.3.153; DB version 6.115) were chosen for the quantification of the
water at 20 ◦ C, and a concentrate (2345 kg/h) rich in sodium environmental impacts of the six scenarios. The assessment study
chloride with traces of other substances and having 250 kg/m3 of comprised the life cycle inventory (LCI) and the mandatory steps of life
salts. This last current was fed into the crystallization section, cycle impact assessment (LCIA): classification and characterization. The
instead the distillate was sent to stripping section to remove Environmental Footprint 3.0 method was selected for the assessment,
ammonia and recover purified water. including all the recommended impact categories: acidification terres­
iii) Outputs from crystallization were a mixture of salts (1280 kg/h), trial and freshwater (mole of H+ eq.), cancer human health effects
mainly sodium chloride with a concentration of 500 kg/m3 and (CTUh), climate change (kg CO2 eq.), ecotoxicity freshwater (CTUe),
water (around 1000 kg/h) that was condensed with cooling water eutrophication freshwater (kg P eq.), eutrophication marine (kg N eq.),
at 20 ◦ C. eutrophication terrestrial (Mole of N eq.), ionizing radiation - human
iv) The last operation was the stripping with air to remove any traces health (kBq U235 eq.), land Use (Pt), non-cancer human health effects
of ammonia contained in the distillate from evaporation. The (CTUh) (European Commission-JRC, 2012). An uncertainty analysis was
concentration of ammonium was near to 600 ppm, higher than carried out to study the effect of the variability of the mass and energy
the limit law for discharge into water surface (Italian Legislative balances on the LCA results (Barjoveanu et al., 2018; Zampori et al.,
Decree 152/2006). Sodium hydroxide was added to increase the 2016). This aspect is very interesting in the perspective of process
pH until 11.5 before that the distillate was fed into stripping optimization on a real scale. With this aim 500 simulations for each
column. The recovered water can be used as process water (i.e. scenario were carried out by Monte Carlo method implemented in
cooling water) RStudio software, assuming a maximum variability of input/output
flows of 10% (Barjoveanu et al., 2018).
Low pressure steam (0.3 barg) and as alternative hot water (70 ◦ C) The economic analysis of the different scenarios has been performed
intended as a thermal waste available in the site have been considered as by using the LCC method (Dhillon, 2010; Theregowda et al., 2013;
utilities for the operation of evaporation, crystallization and stripping. Innocenzi et al., 2020), considering the Eq. (3):
Table 1 shows the scenarios considered in this study. LCC = RC + NRC (3)
Scenarios B (B1, B2 and B3) differs from Scenarios A (A1, A2 and A3)
because a filtration system is added to separate the liquid and solid to Where RC include annual labor costs, operational energy costs and
reduce the amount of waste to disposal. The case studies A3 and B3 maintenance (repair) cost, purchase cost for the raw materials and
include an energy recovery of 80% from the crystallization section: 80% disposal costs (operating Expense, OPEX). Non recurring costs (NRC)
of the distillate is recirculated for heating of the concentrate inlet to are the capital investment (equipment cost, PEC, piping, engineering)
crystallization, this optimization reduces low pressure steam consump­ amortized in X years. Capital Expenditure (CAPEX) has been deter­
tion and the cooling water for condensing and cooling of the distillate. mined from PEC, on the basis of which total costs (direct and indirect)

4
V. Innocenzi et al. Resources, Conservation & Recycling xxx (xxxx) xxx

have been estimated (FCI-fixed Capital Investment) contributing to the pressure steam, cooling water and hot water have been considered as
determination of the TCI. PEC were obtained from vendors using if utilities, instead “Waste Management” and “Maintenance and repairs”
necessary the formula (4): have been considered in the Others. Consumables, Raw Materials, Util­
( )x ities come from M&E of the simulated processes, while the Maintenance
Sn
Cn = C0 (4) and Repairs has been considered 3% of FCI. The total amount of variable
S0
operating cost (Table S4) has been obtained multiplying the consump­
tion (per ton of wastewater) of chemicals, utilities and waste manage­
Where Cn = cost of the equipment of interest, C0 = know cost of existing
ment by unit cost reported in Table S5 and Table S6 (Supplementary
equipment; Sn = size of the equipment of interest, S0 = size of existing
materials). The costs are related to the Italian market provided by
equipment and X is the exponent function on type of equipment (Peter
several suppliers.
et al., 2004). 2002 was the reference year for the PEC estimation and the
The cost of personnel has been estimated considering three labor
values have been discounted by using the CEPCI – Chemical Engineering
shifts/day of 8 h, each shits has two workers (25 €/h). The total labor
Plant Cost Index (Calculation Methodology for Cost Goals).
costs has been calculated adding the operating supervision (5% of the
For the estimation of the total fixed investment, the other cost items
labor cost).
related to equipment erection, piping, instrumentation, buildings, stor­
To make a comparison between the scenario, Payback Period (PBP)
ages, design and engineering, contractor’s fee and contingency set to be
and Return on Investment (ROI) have been calculated (Chen, 2020). A
10% of PCE have been added. Moreover, a working capital (15% of total
preliminary sensitivity analysis has been performed varying utilities
project capital costs) was considered and added to the capital costs that
input flows of 10% (electricity, low pressure steam and cooling water)
was finally amortized to define the annual capital costs (Table S3,
coming from mass and energy balances to investigate their effect on the
Supplementary materials). Straight line depreciation over 10 years is
economic feasibility.
considered with an index of 7.7.
Table S2 (Supplementary materials) summarizes the RC for the
various scenarios. 3. Results and discussions
RC is estimated by the contribution of chemicals necessary for the
wastewater treatment, utilities and Other cost items. These data from 3.1. Chemical pretreatment
M&E have been calculated for each section: (a) for chemical pre-
treatment; b) for evaporation; c) for crystallization and; d) for strip­ The aim of this work was to reduce concentrations of the pollutants
ping. It is possible to observe that chemicals have been considered for as metals, organic substances and suspended solids in wastewater in
the pre-treatment (hydrochloric acid, hydrogen peroxide, sodium hy­ order to make it suitable for the subsequent evaporation and crystalli­
droxide, ferric chloride) and for stripping operation (sodium hydroxide) zation treatment by combined AOPs – precipitation process. It can be
since other sections does not need require reagents. Electricity, low seen from the Table S1 (Supplementary materials) that oxidation by
Fenton like reaction was efficient to remove organic pollutants in the

Fig. 3. Total cost (€/t) for the studied process schemes (Scenario A1, A2, A3 and Scenario B1, B2, B3) to treat gasification wastewater. Annual plant capacity =
70,488 t of effluent).

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V. Innocenzi et al. Resources, Conservation & Recycling xxx (xxxx) xxx

studied wastewater with a TOC removal of 99%. The results of experi­

ments showed that three stages treatment process (AOPs - precipitation
at pH=8 - precipitation at pH=11) allowed to achieve the effect of metal
and TSS removal of 99%. The results of the experimental study sug­
gested that advance oxidation with FeCl3 instead of FeSO4 and precip­
itation with NaOH instead of lime was an effective technique for the
wastewater and make it suitable for subsequent evaporation and crys­
tallization steps. These preliminary data have been used to propose a
wastewater treatment as described in the following sections.

3.2. LCA analysis results

LCI is a mandatory step of LCA which allows the compilation and the
complete quantification inputs and outputs (Torres-Carrillo et al., 2020).
In addition to the energy and mass balances, used for the system
boundary building (Table S2), data summarized in Table S7 (Supple­ Fig. 4. Total and net total annualized cost (€) compared to the current
mentary materials) took into account the aspects of: used resources, disposal cost.
produced waste (specified as deposited goods), and emissions in both air
and water environmental compartments. Overall, the six scenarios including also 2% of FCI for insurance and taxes, raw materials, elec­
produced comparable results, since the common chemical pre-treatment tricity, personnel cost, maintenance and repairs, utilities and waste
causes the highest contribution. The main reasons can be identified in disposal. Moreover, Operating supplies (15% of maintenance), Labora­
both the production process of sodium hydroxide, used in the first step of tory charges (10% of labor cost), Plant overhead cost (30% of the total
process, and the management of the resulting hazardous waste. More in labor cost) and General expenses (25% of plant overhead cost) and
detail, the first aspect caused the 45% of resources consumption and research and development cost (1.4% of annual net treatment cost, NPC)
emissions in freshwater produced by the pre-treatment block. On the have been added.
other hand, the hazardous waste showed the highest effect on the In all studied cases, the chemical purchase necessary for the treat­
deposited goods (80% of the pre-treatment block contribution) and ment was the major component of the total cost. The raw material cost
emissions to air (45%). The option A2 allows a decrease of emissions to was 78.45 €/t, followed by waste disposal cost equal to 29 €/t and 20.90
air of about 20%, which reaches the 25% in the B2 case, thanks to the €/t for Scenarios A and Scenarios B, respectively. This difference was
avoided contribution of low pressure steam production. The positive due to the fact that in the Scenarios B, a centrifugation system down­
effect of the further filtration, at the end of crystallization, is translated stream of the crystallization step has been added to reduce the amount of
into the reduction of about 15% of deposited goods. solid waste to disposal.
The classification and characterization steps produced the results in OPEX (€/t of wastewater) are shown in the Fig. S3 (Supplementary
Figure S2 (A-N, Supplementary materials). Overall, the main advan­ materials). It is possible to confirm that the raw materials is the main
tages, in environmental terms, were achieved by both the use of hot voice on operating cost followed by the disposal cost of the solid waste
water available in the site from thermal recovery (evaporation step) and coming from chemical pre-treatment and crystallization. The disposal
the waste reduction thanks to the further filtration system (crystalliza­ cost was reduced by 28% in the Scenario B in which the centrifugation
tion step). The combination of the two aspects can be translated into the after crystallization was included. A reduction of the utilities (low-
lowest impact of scenario B2. This result (not affected by the data un­ pressure steam consumption) about 18%, has been reported for the
certainty) is highlighted in all the selected categories, mainly in climate Scenario A3 and B3 as a result of crystallization process optimization.
change, where an emission saving of about 45% was obtained, compared Fig. S4 (Supplementary materials) shows the details for the utilities
to scenario A1 (Figure S2). The benefit of the reduced quantity of waste costs. The use of hot water available in the site allows a reduction of the
to dispose (classified as not hazardous) from the crystallization treat­ costs. Low pressure steam was used for the Scenario A1/B1 and A3/B3
ment, is emphasized in the category of eutrophication freshwater, in and the optimization process of the crystallization allowed for the
which the emissions decreases over 60% (Figure S2D). The chemical reduction of utilities costs.
pre-treatment is the reason of about 80% of the environmental burden in The first phase of the processes, chemical pre-treatment, required
all the categories, except for the eutrophication freshwater. The result­ greater consumption of raw materials. Fig. S5 (Supplementary mate­
ing hazardous waste represents the main criticality, with a contribution rials) shows the incidence of the various chemicals on raw material
between 40% and 60% of the whole pre-treatment environmental load. costs: sodium hydroxide and hydrogen peroxide have the higher impact
Furthermore, a significant contribution on the impact of pre-treatment on the total chemical cost.
block was due to the hydrogen peroxide, around 30% in the categories
of climate change, cancer/ non cancer human health effects, eutrophi­
3.4. Economic feasibility
cation freshwater, land use, ozone depletion and resource uses. On the
other hand, the negative effect of sodium hydroxide use (higher than
A comparison between the total annualized treatment cost for the
30%) was assessed in the category of ecotoxicity freshwater, land use
proposed processes and the disposal cost of the wastewater off -site in a
and ozone depletion. The significant impact of both chemicals is
specific plant has been analysed (150 €/t, actual quotation obtained by
consistent with that reported in the literature (González-García et al.,
consulting specific treatment plants).
2011; Hong et al., 2014). Further observations are related to the weight
For each scenario, once estimated the annual treatment as described
of energy consumption on ionizing radiation category (around 27% of
above, the net annual treatment cost i.e., net of the positive contribution
the whole wastewater treatment). Nevertheless, the possibility of an
related to water recovery from process (around 0.9 kg of recovered
energy supply by a photovoltaic system, to replace the conventional grid
water/ kg of treated wastewater) has been considered. The treated water
mix, could reduce the impact up to thirty times, in this category.
from concentration sections can be recycled within the plant of gasifi­
3.3. LCC analysis results cation (as water process) avoiding having to supply fresh water from the
water network. Fig. 4 summarizes the results of the study.
Fig. 3 summarizes the results of the life cycle costs analysis. It is possible to observe that Scenarios A were scarcely competitive
The total cost (€/t of initial wastewater) are divided into capital cost, against the Current disposal cost, the process cost of the Scenarios B was

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V. Innocenzi et al. Resources, Conservation & Recycling xxx (xxxx) xxx

Table 2
Financial parameters estimated for the studied processes.
Scenario A1 Scenario A2 Scenario A3 Scenario B1 Scenario B2 Scenario B3

Net annualized cost (€/y) 9850,416 9216,024 9705,281 9335,607 10,128,605 10,673,507
Revenue (€/y) 10,573,200 10,573,200 10,573,200 10,573,200 12,307,680 12,307,680
Net profit 722,784 1357,176 867,919 1237,593 2179,075 1634,173
PBP 5.8 3.1 4.9 3.4 1.9 2.6
ROI 17% 32% 21% 29% 52% 39%

below 150 €/t. Scenario B2 was the most economical process with a total in the site) was used as alternative to the steam for the operations of
cost of 123 €/t, and a reduction of 17% respect to the current disposal. concentration and stripping. Moreover among all proposed processes,
Table 2 shows the financial indicators for the each scenario. B2 was the cheapest, having a total cost of around 123 €/t, with a
Sensitivity analysis performed varying input/output flows of 10% in reduction of 17% respect to the current disposal assumed to be 150 €/t.
terms of utilities consumption (electricity, low pressure steam and The LCA and LCC studies allow an overall evaluation of the six sce­
cooling water) showed that there is not a significant effect on economic narios and allow to make the best decision from economic and envi­
feasibility of the proposed processes. ronmental sustainability point of view. In the specific case, any effort to
reduce the steam consumption, even better if replaced with thermal
4. Conclusions waste, is seen as a good opportunity for the implementation of the
wastewater treatment, in particular to decrease their environmental and
An innovative process for the treatment of gasification wastewater economic impact.
has been described under the zero-liquid discharge, ZLD, approach.
Experimental activity has been performed in order to evaluate the pos­ CRediT authorship contribution statement
sibility to pre-treat wastewater by Fenton with ferric chloride and
neutralization with sodium hydroxide. The results showed that the Valentina Innocenzi: Conceptualization, Methodology, Formal
effluent, that had a high concentration of chlorides, can be treated with analysis, Writing - original draft, Writing - review & editing. Federica
ferric chloride to removal pollutants and increase the chloride concen­ Cantarini: Conceptualization, Methodology, Formal analysis, Writing -
tration that produced sodium chloride after adding sodium hydroxide to original draft. Svetlana Zueva: Formal analysis, Investigation. Alessia
neutralize the solution. These preliminary results suggested a possible Amato: Methodology, Formal analysis, Writing - original draft, Writing -
process that included a chemical pre-treatment by Fenton and neutral­ review & editing. Barbara Morico: Conceptualization, Supervision,
ization with sodium hydroxide, after that the treated wastewater can be Project administration. Francesca Beolchini: Conceptualization, Su­
sent to a series of thermal processes, evaporation and crystallization to pervision. Marina Prisciandaro: . Francesco Vegliò: Conceptualiza­
concentrate sodium chloride. The outputs of crystallization are water tion, Supervision, Project administration.
and a concentrate of salts (sodium chloride with traces of calcium sul­
phates, chlorides). The last operation was the stripping with air to Declaration of Competing Interest
remove any traces of ammonia contained in the distillate from evapo­
ration. The concentration of ammonium was near to 600 ppm, higher The authors declare that they have no known competing financial
than the limit law for discharge into water surface. interests or personal relationships that could have appeared to influence
In this context, it has been considered that the water can be recov­ the work reported in this paper.
ered as process water for internal uses of the site, while the residual salts
are disposed of as waste. Several scenarios have been studied: Scenarios Acknowledgement
A and Scenarios B. The main difference between the two scenarios is that
in the second case (scenarios B), a filtration system has been added after Authors wish to thank Eng. Alessandra Battista and Eng. Silvano
crystallization to reduce the amount of solid to disposal. Moreover, as Cimini for their precious collaboration on design of evaporation system.
regards the utilities for the concentration and stripping operations, low The research activities were founded by Italian project, STREAM
pressure steam (for Scenario A1, B1 and A3, B3) and alternatively hot (acronym for Wastewater treatment system with energy water and
water from thermal waste available in the site (for Scenario A2 and B2) material recovery), developed inside the PON 2014-2020 FESR, F/
have been considered. Finally another case has been considered: sce­ 050203/01-02/X32 Program.
narios A3, B3 in which steam is used as utility and include a reduction of
80% of the steam consumption thanks to an energy recovery from the Supplementary materials
distillate of crystallization.
The sustainability of the processes have been studied by LCA and LCC Supplementary material associated with this article can be found, in
analysis considering the mass and energy balances obtained from pro­ the online version, at doi:10.1016/j.resconrec.2020.105252.
cess analysis. A reduction of the environmental impacts has been veri­
fied for the two improvement actions hypothesized for the process: the References
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