Fuel 327 (2022) 124986

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Fuel
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Designing and integrating NOx, SO2 and CO2 capture and utilization process
using desalination wastewater
Jonghun Lim a, b, Junghwan Kim a, *
a
Green Materials and Processes R&D Group, Korea Institute of Industrial Technology, 55, Jonga-ro, Ulsan 44413, Republic of Korea
b
Department of Chemical and Biomolecular Engineering, Yonsei University, 50, Yonsei-ro, Seoul 03722, Republic of Korea

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

Keywords: Numerous industries are facing serious environmental contamination, because of the significant emission of
Process design nitrogen oxide (NOx), sulfur dioxides (SO2), and carbon dioxide (CO2) and it has become imperative to reduce
Desalination these gaseous emissions. To reduce pollution caused by gaseous emissions, desalination wastewater is possible to
NOx, SO2 and CO2 utilization
be used because it contains highly concentrated useful mineral ions such as Ca2+, Mg2+, and Na+ which react
with carbonate, nitrogen, and sulfate ions. This work designed and integrated NOx, SO2, and CO2 capture and
utilization processes using desalination wastewater for cleaner production. To design and integrate the NOx, SO2,
and CO2 capture and utilization process, a process model is developed based on validated experimental data. The
proposed process model comprises the following three steps: (1) electrolysis and metal ion separation of desa­
lination wastewater to produce NaOH, Mg(OH)2, and Ca(OH)2; (2) NOx and SO2 capture and utilization via Ca
(OH)2; (3) CO2 capture and utilization using NaOH, Mg(OH)2 and Ca(OH)2. Then the economic feasibility of the
suggested process is demonstrated compared to conventional process by economic assessment. As a result, the
NOx and SO2 are captured and utilized at about 90% and 99% respectively. In addition, the CO2 is captured at
about 91% and the conversion yields of each carbonate are 99% and 63% respectively. To demonstrate the
economic feasibility of the proposed process, two cases are set. Case 1 is the case that employs selective catalytic
reduction (SCR), wet flue gas desulfurization (WFGD), and a CO2 capture process that uses amine as a CO2
absorbent with an electrodialysis reclaiming unit. Case 2 is the case that employs SCR, WFGD, and the CO2
capture process that uses amines with an ion-exchange resin reclaiming unit. As a result, the total annualized cost
of the proposed process was ~7.9% and 14% lower than those of Case 1 and Case 2, respectively.

just discarded rather than used, causing serious environmental pollution

like the destruction of the ecosystem and economic losses.
1. Introduction
In recent years, the reusing metal ions in desalination wastewater is
being investigated rather than discarding it and a few previous studies
Numerous industries such as thermal power plants and chemical
addressed the utilization of these useful metal ions. Na et al addressed
plants consume large amounts of fossil fuels [1–3]. As fossil fuels are
the utilization of seawater bittern as a source of Mg production and as an
combusted, large amounts of NOx, SO2, and CO2 are discharged, which
absorbent for CO2 capture [8]. The results indicated the use of seawater
cause serious environmental problems, such as global warming and acid
bittern can reduce economic losses. F. Vidal B. et al. proposed the use of
rain [4,5]. Under these circumstances, the world is facing serious envi­
high-efficiency structured packing at pilot plant scale catalytic seawater
ronmental contamination, and it is becoming more important to reduce
flue gas desulfurization [9]. As a result, a 47% reduction in seawater
gaseous emissions [6,7]. To reduce pollution caused by gaseous emis­
flow is possible to be obtained and the operation costs are reduced by
sions, desalination wastewater is possible to be used. Desalination has
33%. Hongwei Li et al. used seawater as a CO2 absorbent with CaO [10].
been employed as a feasible water supply alternative in many countries;
The results show that CO2 solubility in seawater increased by 79.25% in
thus, a lot of desalination wastewater is emitted. In addition, highly
seawater with 0.4% CaO.
concentrated mineral ions, such as Ca2+, Mg2+, and Na+, are present in
Among them, a previous study investigated the utilization of desa­
wastewater, these useful mineral ions react with carbonate, nitrogen,
lination wastewater for CO2 utilization to reduce greenhouse gas
and sulfate ions. However, a great part of the desalination wastewater is

* Corresponding author.
E-mail address: kjh31@kitech.re.kr (J. Kim).

https://doi.org/10.1016/j.fuel.2022.124986
Received 25 April 2022; Received in revised form 16 June 2022; Accepted 20 June 2022
Available online 2 July 2022
0016-2361/© 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
J. Lim and J. Kim Fuel 327 (2022) 124986

Nomenclature CA-IZ Alkaline slurry tank

SLURRY Alkaline slurry stream
Abbreviation Definition DE-SOX Top of the scrubber
DSRB Desalination reject brine stream DESUL2 Flue gas stream containing CO2
NAOH NaOH stream DE-SOX2 Bottom of the scrubber
NAOH2 NaOH stream GYPSLURY Gypsum slurry stream
LEANIN NaOH stream GYP-SEP Gypsum separator
PH-SW-1 pH swing process to separate Mg2+ W-SEP Waste water separator
DR-MGOH2 Desalination reject brine with Mg(OH)2 stream W-WATER Waste water
MGOH2-SP Mg(OH)2 separator D-GYPSUM Desulfurization gypsum stream
CA-ION Desalination reject brine containing Ca2+ DS-GAS Flue gas stream containing CO2
PH-SW-2 pH swing process to separate Ca2+ ABSORBER Absorber for CO2 capture
CAOH2-SP Ca(OH)2 separator CLEANGAS Clean gas stream
REJECT Reject brine RICHOUT Rich solution stream
CAOH-S Separated Ca(OH)2 SPLIT-1 Splitter
SPLIT-2 Splitter RICH-1 Rich solution stream
CAOH2-1 Ca(OH)2 stream RICH-2 Rich solution stream
CAOH2-2 Ca(OH)2 stream MGOH2 Mg(OH)2 stream
CAOH2-3 Ca(OH)2 stream HCL HCl stream
FLUEGAS Flue gas stream containing NOx, SO2 and CO2 MG-IZ Acidification process
DN-GAS Flue gas stream containing SO2 and CO2 MG-ION Ionized Mg(OH)2 stream
DE-NOX Absorber for NOx capture and utilization MG-CARBO Carbonation process
CN-SP Ca(NO3)2 separator CA-CARBO Carbonation process
CAL-NIT Ca(NO3)2 CACO3 CaCO3 stream
DN-GAS2 Flue gas stream containing SO2 and CO2 MGCO3 MgCO3 stream
WATER Water stream

emissions and air pollutants [11]. And the effectiveness of the use of
desalination wastewater is demonstrated for CO2 capture and utiliza­
tion. The presented process is composed of the following three proced­
ures: (1) electrolysis of the desalination wastewater; (2) metal ion
separation (i.e. pH swing process); (3) CO2 capture and utilization. First,
in the electrolysis process, the NaOH is generated from the desalination
wastewater and the generated NaOH is used for metal ion separation as a
buffer solution. Second, the Ca2+ and Mg2+ are separated as a form of Ca
(OH)2 and Mg(OH)2 respectively, in metal ion separation based on the
difference in the pH level. Finally, the CO2 is captured using the
generated NaOH and the captured CO2 is carbonated using the formed
Ca(OH)2 and Mg(OH)2. As a result of carbonation, CaCO3 and MgCO3
are also produced, and they are commercialized.
Despite the substantial contribution of the previous study to utilize
the desalination wastewater for CO2 capture and utilization, there are
still remain several major limitations and they are elaborated as follows.
First, the previous study did not consider the SO2 capture and utilization
procedure. The conventional desulfurization technology uses CaCO3 as a
SO2 absorbent and during desulfurization, the SO2 is captured as contact
SO2-containing flue gas with an alkaline aqueous slurry. In general,
limestone is used as a CaCO3 source; however, the resource depletion of
limestone is significant. In addition, in the process of desulfurization
with CaCO3, CO2 is inevitably emitted in the process of SO2 removal;
thus, the increased greenhouse gas emissions become problematic.
Second, the previous study also did not consider the denitrification
procedure and assumed the NOx is already treated. The conventional
denitrification technologies use NH3 or urea as reactants and NOx is
reduced to N2 which is not harmful to the environment and is emitted
into the atmosphere [12]. Representative denitrification methods using
NH3 or urea are selective catalytic reduction (SCR), non-selective cata­
lytic reduction (SNCR), and absorption methods [13,14]. However, the
use of NH3 and urea not only increases the operating cost but is also
difficult to apply in densely populated areas owing to the generation of
odors [15]. In addition, if the NH3 or urea is used to capture the NOx, the
NOx is just emitted into the atmosphere as N2 and thus the utilization of
NOx is impossible. NOx can be utilized if a calcium-containing substance
such as CaCO3 and CaO is used as a reactant, but there are problems such
as resource depletion of calcium-containing substances [11]. Further­
more, because high-temperature conditions and catalysts are required
for the proper reduction of NOx, the operating cost is significantly
increased [16].
To overcome these challenges, this work designed and integrated
NOx, SO2, and CO2 capture and utilization processes using desalination
wastewater. The aim of this work is to overcome conventional chal­
lenges by efficiently using desalination wastewater and integrating the
capture and utilization of not only SO2 and CO2 but also NOx for cost-
effective and environmental protection. The novelty of our study can
be summarized as follows: 1) this study is the first attempt to capture
and utilize the NOx, SO2, and CO2 by using the desalination wastewater
which is the unlimited feedstock to overcome the challenges of the
conventional methods; 2) the suggested process is possible to integrate
capture and utilization of NOx, SO2 and CO2 with a high removal effi­
ciency of these pollutants by using the one-site feedstock which
conventionally just discharged; 3) the use of desalination wastewater
enables the complete replacement of other absorbent or reactants, and
thus the economic problem posed by the use of costly absorbent or re­
actants is possible to be solved; 4) the environmental problem caused by
desalination wastewater and NOx, SO2 and CO2 in flue gas is possible to
be solved simultaneously and thus it is the efficient and environmental-
friendly way.
2. Methodology
In this section, the procedure for capturing and utilizing NOx, SO2,
and CO2 using the suggested process and model are described. Section
2.1 describes the procedure for the capture and utilization of NOx, SO2,
and CO2 by the suggested process, and Section 2.2 shows a model of the
suggested novel process considering the overall procedure of NOx, SO2,
and CO2 capture and utilization.

2
J. Lim and J. Kim
2.1. Procedure of capture and utilization of NOx, SO2 and CO2 by the
suggested process
This section describes the overall procedure for the simultaneous
capture and utilization of NOx, SO2, and CO2 using the proposed process.
Fig. 1 shows a simplified illustration of the NOx, SO2, and CO2 capture
and utilization procedures employed.
Step 1. Electrolysis and metal ion separation of desalination
wastewater
First, in the chlor-alkali electrolysis, NaOH is produced using desa­
lination wastewater. The generated NaOH was used to capture CO2 at
the absorber and split into pH swing processes to separate Mg2+ and
Ca2+. Since nucleate and crystallization of the MgCO3 is slow compared
with CaCO3, the conversion rate is also significantly low and thus the
Mg2+ and Ca2+ ions in desalination wastewater should be separated.
Thus, Mg(OH)2 is first separated during the pH swing process when
NaOH reacts with Mg2+ ions in the desalination wastewater. Finally, Ca
(OH)2 was separated by reacting with NaOH and the remaining Ca2+.
Step 2. NOx and SOx capture and utilization
The separated and filtered Ca(OH)2 was then used to capture NOx
and SO2. First, under dry conditions of the absorber, NOx in the flue gas
reacts with Ca(OH)2, and as a result, Ca(NO3)2 and Ca(NO2)2 are
generated and commercialized. Then, the denitrated flue gas enters the
scrubber for desulfurization. The SO2 in denitrated flue gas is captured
when the alkaline slurry reacts at the top of the scrubber, and an alkaline
Fig. 1. Illustration of the procedure employed to capture and utilize NOx, SOx and CO2 using desalination wastewater.
3
Fuel 327 (2022) 124986
slurry is generated by mixing Ca(OH)2 and water in an alkaline slurry
tank. As a result of desulfurization, CaSO4 (i.e., desulfurized gypsum) is
produced for utilization at the bottom of the scrubber which is liquid
phase, and denitrated and desulfurized flue gas is emitted.
Step 3. CO2 capture and utilization
Finally, the CO2 in the denitrated and desulfurized flue gas is
captured at the absorber using the NaOH generated in step 1. Subse­
quently, the rich solution containing ionic CO2 enters the carbonation
process of MgCO3 and CaCO3. Because Mg(OH)2 is insoluble in pure
water which indicates that difficult to convert it to MgCO3, acidification
is performed, and Mg(OH)2 is dissolved by treatment with HCl. The
dissolved Mg(OH)2 then reacts with the rich solution, generating
MgCO3. Finally, CaCO3 is generated by reacting with Ca(OH)2, which is
generated in the pH swing process, thus separating Ca2+ from the
desalination wastewater and the rich solution.
2.2. Process model
Fig. 2 shows a model of the suggested process for capturing and
utilizing NOx, SO2, and CO2 from desalination wastewater. To model the
electrolysis process, MATLAB® version R2020b was used, and the uti­
lization process of NOx, SO2, and CO2 via desalination wastewater was
simulated using Aspen Plus V10.0. The definition of abbreviation in the
process model is presented in supplementary materials.
The ELECNRTL thermodynamic equation model, was used to
J. Lim and J. Kim Fuel 327 (2022) 124986

Fig. 2. Model of the suggested process to capture and utilize NOx, SOx, and CO2 using desalination wastewater.

consider the vapor–liquid equilibrium and liquid–liquid equilibrium

while supplementing the interaction between ions. The equations for 2Cl− → Cl2 + 2e− (5)
ELECNRTL are as follows (Eq. (1)) [17].
∑n ∑n
−
2H2O + 2e → H2 + 2OH −
(6)
j=1 τji xj Gji
∑n
xG m=1 τmi xm Gmi
lnγi = ∑n + ∑n j ij (τji − ∑ n ) (1) + −
Na + OH → NaOH (7)
k=1 xk Gki j=1 k=1 x k G ki k=1 xk Gki

A detailed description of the ion balance model of the electrolysis

where, γ denotes activity coefficient,τ denotes temperature dependent
parameter and x denotes mole fraction.
G is determined from the binary NRTL parameters at a given tem­
perature (α and τ) (Eq. (2)):
Gxy = exp(− αyx • τxy )
During process simulation and modeling, ELECNRTL method is used
to treat a non-ideal aqueous electrolyte solution and to consider the gas
phase the Redlich-Kwong equation is used (Eq. (3))[18].
R•T a pH swing process, which applies the difference of solubility between
p= − √̅̅̅̅
Vm − b T • Vm • (Vm + b)
where, p denotes the gas pressure, R denotes the gas constant, T denotes
temperature, Vm denotes the molar volume, a denotes a constant that
corrects for attractive potential of molecules and b denotes a constant
that corrects for volume.
The following assumptions were considered to model the suggested
process.
• The process is steady state.
• The Ca/S molar ratio is set to 1.05 [19].
• The Ca/N and Ca/C molar ratio is set to 1.00.
• The composition of flue gas is CO2 (15.5%), N2 (65.0 vol%), O2 (16.5
vol%), H2O (3.00 vol%), SO2 (700 ppm), NO (320 ppm) and NO2 (51
ppm) [20].
• The metal cation concentrations in the desalination wastewater
considered in the model are Ca2+ (21,285 ppm), Mg2+ (20,968 ppm),
Na2+ (22,631 ppm) and Ba2+ (0.709 ppm) [21].
• Since the scrubber is simulated in equilibrium, the oxidation air is
not considered.
2.2.1. Electrolysis and metal ion separation
As a result of chlor-alkali electrolysis procedure, the NaOH is
generated by the NaCl in desalination wastewater. To simulate elec­
trolysis, MATLAB® version R2020b was used and the ionic behavior and
water molecules were considered to derive results of the electrolysis
process. The reactions of electrolysis of NaCl to produce NaOH are as
follows (Eqs (4)–(7)) [22]:
2Na+ + 2Cl− → Cl2 + 2Na+ + 2e−
process is presented in the supplementary material. The generated H2
and Cl2 were separated to form NaOH for collection, and the generated
NaOH (LEAN-IN) was used to capture the CO2 in the denitrated and
desulfurized flue gas at the absorber. In addition, in the pH swing pro­
(2) cess, NaOH is used for metal ion separation as a buffer solution. The
Ca2+ and Mg2+ in desalination wastewater are precipitated in the pro­
cess and it decreases the efficiency of electrodialysis and increases en­
ergy consumption. However, in this work, the effect of the Ca2+ and
Mg2+ is assumed to be ignored. NaOH(NAOH-1, NAOH-2) is split in each
(3) Mg2+ and Ca2+ under various pH conditions to separate Mg2+ and Ca2+
by converting Mg(OH)2 and Ca(OH)2, respectively (Equation 7,8).
Ca2+ + 2OH− ↔ Ca(OH)2 (7)
Mg 2+ −
+ 2OH ↔ Mg(OH)2 (8)
The metal ions Mg2+ and Ca2+ should be separated. Since the Gibbs
free energy of formation for CaCO3 is − 1,129 kJ/kmol and the MgCO3 is
− 1,095 kJ/mol and thus if the both Ca2+ and Mg2+ ions are abundant
when carbonation is performed, the nucleation and crystallization of
MgCO3 are slower than those of CaCO3, and the production rate of
MgCO3 is significantly low[4,23]. Thus, Mg(OH)2 is first separated
during the pH swing process (PH-SW-1) to separate Mg2+ by allowing
the generated NaOH to react with Mg2+ ions in the desalination
wastewater. Finally, Ca(OH)2 is separated by allowing the generated
NaOH to react with the remaining Ca2+ in PH-SW-2. The RCSTR model
was used to model PH-SW-1 and PH-SW-2, and the generated Mg(OH)2
and Ca(OH)2 were separated and it is modeled using the Sep model
(MGOH2-SP, CAOH2-SP). The RCSTR model is a rigorous model and it
can model maximum three-phase reactors as well as kinetic and equi­
librium reactions[24]. Then the Sep model combines streams and sep­
arates the results into two or more streams according to splits specified
for each component[24].
2.2.2. Nox and SO2 capture and utilization
NOx and SO2 were captured using the Ca(OH)2 separated and filtered
during metal-ion separation. First, the NOx in flue gas (FLUEGAS) was
captured under dry conditions of the absorber by reacting with Ca(OH)2,
Ca(NO3)2, and Ca(NO2)2. NOx is first captured before SO2 because if the
SO2 capture occurs first, the temperature of the flue gas significantly
(4) decreases because of the vapor–liquid contact with the alkaline slurry in

4
J. Lim and J. Kim Fuel 327 (2022) 124986

the desulfurization procedure, which reduces the effectiveness of NOx
reduction. Then, Ca(NO3)2 and Ca(NO2)2 are utilized, which are mainly
used as components of fertilizers, wastewater treatment, and admixtures
that accelerate concrete. The reactions for NOx capture and utilization
are as follows[25,26]:
2NO2 → N2O4
generated Ca(NO3)2 was separated using the Sep model (CN-SP). Then,
CA-IZ was modeled using the RSTOIC model, and DE-SOX and DE-SOX2
were simulated using the RCSTR model. In the RCSTR model, the
equilibrium constant of each reaction was considered based on Gibbs
free energy minimization. The detailed specifications are presented in
the supplementary material.
(9)

NO + NO2 → N2O3 (10) 2.2.3. CO2 capture and utilization

Finally, CO2 in denitrated and desulfurized flue gas (DS-GAS) is
N2O3 + H2O → 2HNO2 (11) captured at the absorber (CO2-CAP) using the generated NaOH in step 1,
and the clean gas (CLEANGAS) is released. To maximize the reaction
N2O4 + H2O → HNO2 + HNO3 (12)
surface area between the vapor and liquid phases, denitrated and
NO + O2 + H2O → HNO3 (13) desulfurized flue gas was introduced at the bottom of the absorber, and
NaOH was introduced at the top. In addition, CO2 is nonreactive; it is
Ca(OH)2 + 4NO2 → Ca(NO3)2 + Ca(NO2)2 + 2H2O (14) important to convert it into ionic CO2 substance and the reactions are as
3Ca(NO2)2 + 2H2O → Ca(NO3)2 + 4NO + 2Ca(OH)2 (15) follows (Eqs. (22)–(26)) [30]:

Then, the denitrated flue gas (DN-GAS2) enters the scrubber for CO2(g) → CO2 (aq) (22)
desulfurization. The scrubber is modeled in two stages according to the 2NaOH → 2Na + 2OH− (23)
phase. The SO2 in the denitrated flue gas is captured when the alkaline
slurry (CA-SL) reacts with the vapor–liquid contact at the top of the CO2 + OH− ↔ HCO3 (24)
scrubber (DE-SOX), and the alkaline slurry is generated by mixing Ca
HCO−3 −
+ OH ↔ H2O + CO2− (25)
(OH)2 and water in the alkaline slurry tank (CA-IZ). First, in the alkaline 3

slurry tank, Ca(OH)2 is continuously dissolved by stirring the slurry +

2Na + CO2−
3 → Na2CO3 (26)
using an agitator installed at the bottom of the tank. The conversion rate
of Ca(OH)2 was set to 0.99 because this process was assumed to be in a Subsequently, the rich solution containing ionic CO2 enters the
steady-state. The dissolution reaction of Ca(OH)2 in an alkaline slurry carbonation process of MgCO3 and CaCO3. First, because Mg(OH)2 is
tank is given as follows (Equation 16): insoluble in pure water, acidification is performed, and Mg(OH)2 is
dissolved by treatment with HCl (Eq. 27) [4].
Ca(OH)2 → Ca2+ + 2OH− (16)
Mg(OH)2 + 2HCl → MgCl2(aq) + 2H2O (27)
Second, the alkaline slurry was sprayed on top of the scrubber, and
the SOx is captured through liquid–gas contact with the flue gas. The Then, the dissolved solution (MG-ION) containing MgCl2 is subjected
desulfurization reaction at the top of the scrubber is as follows (Eqs. to the magnesium carbonation process (MG-CARBO) and reacts with a
(17)–(19)) [27]: rich solution containing ionic CO2, generating nesquehonite
(MgCO3⋅3H2O) (Eq. (28)–(32)) [4].
SO2 + H2O → H2SO3 (17)
Mg2++ CO2−
3 → MgCO3 (28)
H2SO3 → H + +
HSO−3 (18)
2+
Mg + HCO−3 → MgCO3 + H +
(29)
HSO−3 + 0.5O2 → H+ + SO2−
4 (19)
MgCO3 → Mg 2+
+CO2−
3 (30)
Then, at the bottom of the scrubber (DE-SOX2), CaSO4 (i.e., desul­
furization gypsum) (F-GYPSUM) is produced by centrifugation (W-SEP) MgCO3 + H+ → Mg2++HCO−3 (31)
for utilization, and the denitrated and desulfurized flue gas (DS-GAS) is
Mg2++CO2−
3 + 3H2O → MgCO3 3H2O (32)
emitted for CO2 capture and utilization. The CaSO4 crystallization re­
action is as follows (Eqs. (20)–(21)) [28]: Finally, the ionic CO2 in the rich solution also reacts with Ca(OH)2,
which leads to metal ion separation in step1. Because Ca2+ ions easily
Ca 2+
+ SO2−
4 + 2H2O → CaSO4⋅2H2O (20) react with ionic CO2, additional acidification procedures are not
Ca 2+
+ HSO−3 + 0⋅.5H2O → CaSO3⋅0⋅.5H2O + H+
(21) required. Thus, CO2 precipitates as CaCO3, based on the following
equations (Eqs. (33)–(36)) [4].
The Mg(OH)2 is also useful for SO2 capture and utilization and it can
prevent the problem caused by scales in the scrubber. The SO2 is Ca2+ + CO2−
3 → CaCO3 (33)
captured by Mg(OH)2 and is converted to MgSO3 and MgSO4, which are 2+
Ca + HCO−3 → CaCO3 + H +
(34)
soluble in pure water and do not cause scales in the scrubber. In addi­
tion, the molar mass of Mg(OH)2 is less than that of Ca(OH)2. Thus, the CaCO3 → Ca 2+
+ CO2−
3 (35)
capacity of the scrubber can be reduced, which indicates a decrease in +
CaCO3 + H → Ca 2+
+ HCO−3 (36)
the capital cost. However, since the Mg(OH)2 is insoluble in pure water,
there is a limitation to adopt the SO2 capture and utilization. The To model the CO2-CAP, the rate-based Radfrac model was used, MG-
additional HCl is required to dissolve the Mg(OH)2 and thus the oper­ CARBO and CA-CARBO were modeled using the RCSTR model, and the
ating cost is significantly increased. In addition, when the Mg(OH)2 is equilibrium constant was calculated based on Gibbs free energy mini­
used, it is difficult to recover at a high concentration and utilize, so it is mization. The Radfrac model is rigorous model for simulating all types
recovered as sulfuric acid. And thus this work uses the Ca(OH)2 as a SO2 of multistage vapor–liquid fractionation operations such as ordinary
absorbent. To model DE-NOX, the RSTOIC model was used, and the distillation, absorption, stripping, etc. It can model columns in which
removal efficiency of NOx was set to 90%, based on Horjnies et al. chemical reactions are occurring and the reaction is possible to be
(2012) [29]. When the reaction kinetics are unknown but stoichiometry considered equilibrium, rate-based, and electrolytic [31]. The detailed
is known, the RSTIC model is generally employed, and the conversion specifications of the CO2 capture and utilization process are presented in
rate of reactant or product should be specified in the model [24]. The the supplementary material.

5
J. Lim and J. Kim Fuel 327 (2022) 124986

3. Results and discussion Table 2

Simulation results of Ca2+ ion separation.
This section explains the simulation results of the proposed novel Components CA-ION [mol/h] NAOH2 [mol/h] DR-CAOH2 [mol/h]
process for capturing and utilizing NOx, SO2, and CO2 from desalination
H2O 42,800 5,000 47,800
wastewater. In addition, to address the economic feasibility, we Na+ 132 1,200 5,130
compared the total annual cost (TAC) of the suggested and conventional OH− 0 1,200 4,940
processes. Ca2+ 28 0 0
Mg2+ 5 0 0
NaOH 0 3,800 0
3.1. Simulation results Mg(OH)2 0 0 5
Ca(OH)2 0 0 28
3.1.1. Metal ion separation results Total flow 42,960 11,200 57,900
The metal ions Mg2+ and Ca2+ were separated using a pH swing
process, and NaOH was used as the buffer solution. The simulation re­
sults for electrolysis are presented in the supplementary material. Table 3
Table 1 shows the simulation results for Mg2+ ion separation. Simulation results of NOx capture and utilization.
The table shows that approximately 45 mol/h of Mg2+ in DSRB and Components CaOH2-1 [mol/ FLUEGAS [mol/ CAL- DN-GAS2 [mol/
81 mol/h of OH− in NAOH1 reacted; thus, 40 mol/h of Mg(OH)2 is h] h] NIT h]
generated and separated for the carbonation procedure, resulting in the [mol/
conversion efficiency of approximately 89%. Table 2 shows the simu­ h]
lation results of Ca2+ ion separation. Ca(OH)2 0.214 – – –
The table shows that approximately 28 mol/h of Mg2+ in DSRB and NO – 0.185 – 0.021
1,200 mol/h of OH− in NAOH reacted, and thus, 28 mol/h of Ca(OH)2 is NO2 – 0.029 – –
Ca(NO3)2 – – 0.079 –
generated and separated for the carbonation procedure, which resulted Ca(NO2)2 – – 0.002 –
in the conversion efficiency of approximately 99%. With the separation N2O3 – – 0.010 –
of MgOH2 and CaOH2 by the metal ion separation process, the carbon­ N2O4 – – 0.005 –
ation rate of MgOH2 can be increased. H2O – 17.28 – 17.36
SO2 – 0.403 – 0.403
CO2 – 89.28 – 89.28
3.1.2. Nox capture and utilization results O2 – 95.04 – 94.93
The Ca(OH)2 generated by the metal-ion separation process is split N2 – 374.4 – 374.4
into NOx capture and utilization processes, and Ca(OH)2 is split by the Total flow 0.081 576.6 0.097 576.4
number of moles of NOx. Then, under the dry conditions of the absorber,
the NOx in the flue gas reacts with Ca(OH)2, and as a result of the re­
3.1.3. SO2 capture and utilization results
action, Ca(NO3)2 is generated, which is utilized by the product. Table 3
The Ca(OH)2 produced in the metal ion separation process was also
shows the simulation results for NOx capture and utilization.
split into SO2 capture and utilization processes as an alkaline slurry, and
As shown in Table 3, approximately 0.214 mol/h of Ca(OH)2 in
the split ratio was set to consider the number of moles of SO2, which
CaOH2-1 reacts with 0.184 mol/h of NO and 0.029 mol/h of NO2. Thus,
indicated a Ca/S ratio of 1.05. Then, at the top of the scrubber, the SO2 in
approximately 90% of NOx is captured and utilized, and 0.079 mol/h
the de-nitrified flue gas is absorbed in the alkaline slurry, and CaSO4 (i.
and 0.002 mol/h of Ca(NO3)2 and Ca(NO2)2 are generated, respectively,
e., desulfurization gypsum) is generated at the bottom of the scrubber.
without any odor generation, which is mainly caused by NH3 that is
Table 4 presents the simulation results for the SO2 capture and
conventional NOx absorbent. Furthermore, the molar utilization ratio of
utilization.
NOx to Ca(NO3)2 and Ca(NO2)2 is approximately 38%; thus, significantly
As shown in the table, approximately 0.004 mol/h of Ca(OH)2 in
higher utilization of NOx is possible compared with conventional deni­
SLURRY reacted with 0.403 mol/h of SOx. As a result of desulfurization,
trification methods that use NH3 or urea as reactants. The generated Ca
approximately 99% of SO2 was captured and utilized, and 0.403 mol/h
(NO3)2 is a useful by-product that is used as a component of fertilizers,
of CaSO4⋅2H2O was generated. CaSO3⋅0.5H2O, which is an intermediate
wastewater treatment, and admixture of concrete. Also, Ca(NO2)2 is
substance as an impurity, was only produced at 0.0004 mol/h. The re­
possible to be utilized as an antifreeze and metal corrosion inhibitor. In
sults showed that the amount of CaSO3⋅0.5H2O was significantly small.
addition, because the proper reduction of NOx does not require any high-
The results show that the molar utilization ratio of SO2 to CaSO4 is
temperature conditions or catalysts, the increase in operating cost can
approximately 99%; thus, significantly high utilization of SO2 is
also be decreased. In this work, we referred to the reduction efficiency of
NOx; however, in further studies, the main parameters that determine
the reduction efficiency of NOx, such as the presence or absence of
Table 4
activated charcoal, mean residence time of flue gas, and surface area of
Simulation results of SO2 capture and utilization.
the absorbent, would be determined optimally.
Components SLURRY DN-GAS2 [mol/h] D-GYPSUM DS-GAS
[mol/h] [mol/h] [mol/h]

CaOH2 0.004 – – –
Ca2+ 0.420 – – –
Table 1 OH− 0.841 – – –
Simulation results of Mg2+ ion separation. SO2 – 0.403 – –
CaSO4⋅2H2O – – 0.403 –
Components DSRB [mol/h] NAOH1 [mol/h] DR-MGOH2 [mol/h]
CaSO3⋅0.5H2O – – 0.0004 –
H2O 2,880 39,920 42,800 H+ – – – –
Na+ 51 81 132 H2O 42.64 17.36 – 17.28
OH− 0 81 0 CO2 – 89.28 – 89.28
Ca2+ 28 0 28 O2 – 94.93 – 94.72
Mg2+ 45 0 5 N2 – 374.4 – 374.4
Mg(OH)2 0 0 40 NO – 0.021 – 0.021
Total flow 3,000 40,080 43,000 Total flow 43.91 576.4 0.403 575.7

6
J. Lim and J. Kim Fuel 327 (2022) 124986

possible. In addition, as the proposed process uses Ca(OH)2 to capture 3.2. Comparison of NOx, SO2 and CO2 removal efficiency
the SO2 that is generated using Ca2+ in desalination wastewater, 99.55
wt% high-purity desulfurization gypsum can be produced. In general, To demonstrate the NOx, SO2, and CO2 removal efficiency, twelve
the quality standard for the desulfurization gypsum must be above 93% conventional cases are set and the simulation results of the developed
for commercialization, but if low-grade limestone (<94 wt% CaCO3) is process are compared with the reduction efficiency of each conventional
used, the quality standard of desulfurization gypsum may not be satis­ case. Table 6 shows the conventional cases to demonstrate NOx, SO2,
fied. However, only 20% of the high-grade limestone (≥94 wt% CaCO3) and CO2 capture efficiency.
of conventional SO2 absorbent reserves remains; thus, the proposed Fig. 3 shows the NOx removal efficiency of the proposed and con­
process is the appropriate solution to solve the problem of feedstock ventional processes. To capture the NOx, in general, selective non-
limitation with high-purity desulfurization gypsum production by uti­ catalyst reduction (SNCR) and selective catalyst reduction (SCR) are
lizing metal ions as an SO2 absorbent. In addition, in the process of employed. In Fig. 3, the NOx removal efficiency of Case N1 and N2
desulfurization using CaCO3, CO2 is inevitably emitted in pursuit of SO2 which are SNCR are 56% and 59% respectively. The NOx capture effi­
removal; thus, the problem of increased greenhouse gas emissions arises. ciency of Case N3 and Case N4, which are SCR by 96% and 94%,
However, in this work, we used Ca(OH)2 without sintering CaCO3 under respectively. The SCR has an advantage of higher NOx removal effi­
high-temperature conditions, which causes additional combustion of ciency but the gas disadvantage of the high capital and operating cost
fossil fuels and increases the cost of the SO2 absorbent, thus preventing compared to SNCR. Thus, SNCR is still employed in many industries
additional CO2 emissions and ensuring economic feasibility. because of its economic feasibility. However, the NOx removal effi­
ciency of the proposed process which uses Ca(OH)2 as a NOx absorbent,
3.1.4. CO2 capture and utilization results is determined by 90%. In addition, the Ca(NO3)2 and Ca(NO2)2 are
Finally, the CO2 in the denitrated and desulfurized flue gas was generated, respectively, without any odor generation, which is mainly
captured using the NaOH generated in step1 at the absorber. Then, the caused by NH3 which is a conventional NOx absorbent. Thus, signifi­
rich solution containing ionic CO2 enters the carbonation process, in cantly higher utilization of NOx is possible compared with conventional
which the separated Mg2+ and Ca2+ ions react with Na2CO3 and are denitrification methods that use NH3 or urea as reactants. The generated
converted to MgCO3 and CaCO3, respectively. Table 5 presents the Ca(NO3)2 is a useful by-product that is used as a component of fertilizers,
simulation results for CO2 capture and utilization. wastewater treatment, and admixture of concrete. Also, Ca(NO2)2 is
The table shows that 91% of CO2 is absorbed and is converted to possible to be utilized as an antifreeze and metal corrosion inhibitor. In
ionic CO2 in the form of CO2− 3 and HCO3 . Furthermore, CO2 mainly
−
addition, because the proper reduction of NOx does not require any high-
exists in the CO2−3 form because of the acid-base equilibrium of the so­ temperature conditions or catalysts, the increase in operating cost can
lution. Then, CO2 dissolves in water to form carbonic acid, which reacts also be decreased. Then, Fig. 4 shows the SO2 removal efficiency of the
to produce CO2− 3 or HCO3 depending on the pH of the solution. In acidic
−
proposed and conventional processes.
solutions, aqueous CO2 is predominantly present, whereas the CO2− 3 In Fig. 4, the SO2 removal efficiency of the Case S1 and S2 which are
structure is dominant at higher pH levels when NaOH is present. In the WFGD are 94% and 97%, respectively. The Case S3 and S4 which are
results of the carbonation process, 27.05 mol/h Ca(OH)2 and 25.37 mol/ DFGD removed SO2 of about 85% and 65%, respectively. The DFGD and
h MgCO3 are generated. The conversion yields of each metal hydroxide, WFGD are classified according to the moisture content of the SO2
Ca(OH)2 and Mg(OH)2, to each carbonate are 99% and 63%, respec­ absorbent. The results indicate that the WFGD has a high SO2 removal
tively. This result indicates a high carbonation rate of Ca(OH)2 as well as efficiency compared to that of the DFGD. This is because the reaction
Mg(OH)2 because of the metal ion separation process. The Gibbs energy time of the WFGD is longer than that of the DFGD. Finally, in the pro­
of formation for CaCO3 is − 1,129 kJ/mol, while that for MgCO3 is posed process, which is WFGD, the SO2 removal efficiency is determined
− 1,095 kJ/mol. Thus, the metal ion separation process adopted in this by 99%. In conventional WFGD uses CaCO3 as a SO2 absorbent and it is
study can increase the carbonation rate efficiency by increasing the generally obtained in limestone. Since other impurities, such as SiO2 and
production of the final product. Furthermore, the proposed process Al2O3, decrease the desulfurization gypsum purity, the limestone should
utilizes NaOH without any feedstock limitation, which makes it possible
to solve the problem of the conventional CCS process caused by irre­
versible heat-stable salt, such as the requirement of replenishment of the Table 6
absorbent, which is very expensive, but also reduces the stability of the Conventional cases to demonstrate NOx, SO2 and CO2 capture efficiency.
overall process, making it possible to obtain economic feasibility with Classification Case Process type Process features
high stability of the overall process. NOx capture N1 *SNCR No catalyst, NH3/NO2 ratio
efficiency = 1.5
N2 SNCR No catalyst, NH3/NO2 ratio
= 2.0
**
Table 5 N3 SCR NiFe-500 catalyst,
Simulation results of CO2 capture and utilization. NH3/NO2 ratio = 1.0
N4 SCR TiO2/CeO2 catalyst,
Components LEAN-IN [mol/ DS-GAS RICHOUT CLEANGAS NH3/NO2 ratio = 1.0
h] [mol/h] [mol/h] [mol/h] SOx capture S1 ***
WFGD Ca/S ratio = 1.04, pH = 5.9
Na+ 160.6 – 160.6 – efficiency S2 WFGD Ca/S ratio = 1.04, pH = 4.8
****
CO2 – 89.28 0.0001 7.853 S3 DFGD Ca/S ratio = 3
HCO−3 – – 4.574 – S4 DFGD Ca/S ratio = 1.5
*****
CO2− – – 76.85 – CO2 capture C1 CCS using CO2 loaded/ NaOH ratio =
3
OH− 160.6 – 2.306 – efficiency NaOH 0.23
H2O 73,23 17.28 73,31 12.14 C2 CCS using NaOH CO2 loaded/ NaOH ratio =
O2 – 94.72 0.295 94.43 0.56
N2 – 374.4 0.592 373.8 C3 CCS using MEA CO2 loaded/ MEA ratio =
NO – 0.021 – 0.021 0.18
Total flow 73,55 575.7 73,55 488.3 C4 CCS using MEA CO2 loaded/ MEA ratio =
Generated CaCO3 [mol/ 27.05 0.50
h] *
SNCR = Selective non-catalytic reduction, **SCR = Selective catalytic
Generated MgCO3 25.37
reduction, ***WFGD = Wet flue gas desulfurization, ****DFGD = Dry flue gas
[mol/h]
desulfurization, *****CCS = Carbon capture and storage.

7
J. Lim and J. Kim Fuel 327 (2022) 124986

Fig. 3. NOx removal efficiency of the proposed and conventional processes.

Fig. 4. SO2 removal efficiency of the suggested and conventional processes.

have a CaCO3 purity of more than 94 wt% which is called high-grade
limestone. However, the reserves of high-grade limestone are only
20% of the total reserves; thus, the need for a substitute for high-grade
limestone is inevitable. In addition, the use of CaCO3 inevitably emitted
CO2 in the removal of SO2 and thus greenhouse gas emissions increased.
To address the problem of the conventional process, the Ca(OH)2 from
the desalination wastewater is a suitable solution. As desalination
wastewater is a substitute for high-grade limestone, resource depletion
is possible to be avoided. In addition, the use of Ca(OH)2 is not generated
any additional CO2 and thus it is a carbon–neutral desulfurization
method. Finally, Fig. 5 shows the CO2 removal efficiency of the sug­
gested and conventional processes.
In Fig. 5, the CO2 removal efficiency of the Case C1 and C2 which
used the NaOH for CO2 capture, is about 90% and 91% respectively. In
Case C3 and C4 which use amine for CO2 capture, 85% and 92% of CO2
is removed. Finally, the proposed process removed 91% of CO2 by using
NaOH. In general, CO2 is removed by using chemical absorption which
uses the amine solution and alkaline solution (e.g. NaOH and KOH). The
amine solution has the advantage of high reactivity with low cost but
when it reacts with other acid components which are more acidic than
CO2, the heat-stable salt is produced. It causes loss of the absorbent
during CO2 capture, resulting in low CO2 capture efficiency [32]. In
addition, to regenerate the rich amine, the steam energy consumption in
the regenerator is significant and thus the operating cost is high. To solve
these problems, the NaOH is possible to be used but since the NaOH is
not regenerated, there is a problem of an increase in the raw material
cost and feedstock availability. However, the proposed process uses
NaOH from the desalination waste water the problem of the increase in
the raw material cost and feedstock availability is possible to be solved.

8
J. Lim and J. Kim
Fig. 5. CO2 capture efficiencies of proposed and conventional processes.
3.3. Economic assessment
This section presents an economic assessment of the proposed novel
process to address the economic feasibility. Two cases were set to prove
the economic feasibility of the suggested process and two cases have
different amine reclaiming unit which used to separate the heat-stable
salt. The descriptions are as follows: 1) the case that employs selective
catalytic reduction (SCR) for NOx reduction, wet flue gas desulfurization
(WFGD) for SO2 capture and utilization, and a CO2 capture process that
uses amine as a CO2 absorbent with an electrodialysis reclaiming unit. 2)
The case that employs SCR for NOx reduction, WFGD for SO2 capture
and utilization, and CO2 capture process that uses amines with an ion-
exchange resin reclaiming unit. Then, the total annualized cost (TAC)
of the suggested process and each case were calculated as evaluation
criteria for economic feasibility. To calculate the TAC of each case, we
referred to the parameters for cost calculation based on Lim et al. (2021)
and Lim and Kim (2020). TAC is the annual overall cost, and the TAC
equation is as follows (Eq. (37)) [3]:
TAC = EAC + TPC − Revenue. (37)
where EAC denotes the equivalent annual cost, TPC denotes the total
product cost, and Revenue denotes revenue from selling by-products
[18].
3.3.1. Equivalent annual cost (EAC)
First, for the TAC calculation, the EAC is the annualized cost that is
generated over the entire lifespan of the overall process and is calculated
by dividing the total capital investment (TCI) of a project by the current
annuity factor (AF) (Eq. (38)) [33]:
TCI
EAC = (38)
AF
where TCI is determined by summing the fixed capital cost (FCI),
start-up cost (SUC), and working capital investment (WCI)[34] (Eq.
(39)).
TCI = FCI + SUC + WCI. (39)
In TCI, FCI denotes the cost of building a process facility and
generally contains the equipment cost, installation cost of equipment
and land, etc. In this study, the FCI was calculated from the equipment
9
Fuel 327 (2022) 124986
cost of the overall process (Cequipment) as follows (Eq. (40)):
FCI = 3.33 × Cequipment (40)
Here, Cequipment of the proposed process is estimated using the Aspen
plus Economic Analyzer, and Cequipment of each case was obtained from
Lim et al. (2021) and John et al. (2019) [35,36]. The Aspen plus Eco­
nomic Analyzer is cost estimating software that provides capital and
operating cost estimates and it must be mapped the Aspen plus unit
operation model into equipment models. Then it estimates the equip­
ment cost considering the capacity of each unit operation. However,
since the electrolysis process is modeled using MATLAB® version
R2020b, and thus the equipment cost of it is referred to based on the
Herz et al. [37]. The detailed equipment cost of suggested process and
each case is presented in supplementary materials. Second, SUC is the
cost generated when starting a new business, and it generally includes
research, technology, and loans [38]. The SUC was determined as 10%
of the FCI and is given as follows (Eq. (41):
SUC = 0.1 × FCI (41)
Finally, the WCI indicates the capital cost required to maintain stocks
of feedstocks, products, etc. The WCI was calculated as 10% of FCI, and
the equation is as follows (Eq. (42)):
WCI = 0.1 × FCI (41)
AF is then used to calculate the present value of a series of future
annuities, and it is defined as follows (Eq. (42)):
[
1
]
1 − (1+RP)
AF =
NP
(42)
RP
where RP is the rate per period and NP is the number of periods [39].
Detailed descriptions of the parameters, equations, and variables
regarding the EAC calculation are described in the supplementary
materials.
3.3.2. Total product cost (TPC)
Second, TPC is the annual operating cost that is generated during
production and represents the ongoing cost of process operation, which
is generally composed of labor, raw material, and energy costs. To
calculate TPC, the annual operating time was set to 365 d, and TPC was
J. Lim and J. Kim Fuel 327 (2022) 124986

determined from fixed charges (FC), direct production cost (DPC), plant
overhead cost (OVHD), and general expenses (GE) (Equation 43) [40].
TPC = FC + DPC + OVHD + GE
First, the FC is the local tax and cost of insurance and is calculated as
4% of the FCI (Eq. (44)). It can be calculated as the sum of local tax
(Clocal tax) and insurance (Cinsurance) costs (Eq. (44)) [40].
FC = 0.04 × FCI
Second, the DPC is the cost of direct production, which is determined
by summing the costs of raw materials (rawmaterials), water (Cwater),
electricity (Celectricity), maintenance (Cmaintenance), labor (Clabor), super­
vision (Csupervision), operating supplies (Coperating supplies), and laboratory
(Claboratory) (Eq. (45)) [40].
DPC = Craw materials + Cwater + Celectricity + Cmaintenance + Clabor + Csupervision
+ Coperating supplies + Claboratory .
In cases 1 and 2, the raw material cost includes limestone for SOx
capture and utilization, NH3 for NOx capture, and additional input of
amine in the CO2 capture process. Then, Cwater and Celectricity of the
proposed process are calculated using the Aspen Economic Analyzer,
and Cwater and Celectricity of each case are based on Lim et al. (2021) and
John L et al. (2019).
Third, OVHD is the cost that includes factory rental, advertising,
insurance, etc., and it is determined as 60% of the sum of maintenance,
labor, and supervision costs (Eq. (46)) [24].
( )
OVHD = 0.6 × Cmaintenance + Clabor + Csupervision . (46)
Finally, general expenses (GE) are the costs incurred in organizing
and controlling general activities and are incurred as part of the day-to-
day operation. It is calculated by summing the administrative cost
(Cadministrative), marketing cost (Cmarketing), and research and develop­
ment cost (CR&D) (Eq. (47)) [40].
GE = Cadministrative + Cmarketing + CR&D ,
Detailed descriptions, such as parameters, equations, and variables
regarding TPC calculation, are also described in the Electronic Supple­
mentary Information (ESI).
3.3.3. Revenue
Finally, the revenue is generated when the produced carbonate and
desulfurization gypsum is sold. The revenue is determined from the
profit of each carbonate and desulfurization gypsum (Eq. (48)):
Revenue = Rcaco3 + Rmgco3 + Rca(no2)2 + Rca(no3)2 + Rgypsum
where, Rcaco3 denotes profit of CaCO3, Rmgco3 denotes profit of MgCO3,
Rca(no2)2 denotes profit of Ca(NO2)2, Rca(no3)2 denotes profit of Ca(NO3)2
and Rgypsum denotes profit of desulfurization gypsum. In general, the
selling price of desulfurization gypsum can changed according to the
purity of impurities, but this work ignored the change in selling price of
desulfurization gypsum.
3.3.4. Economic assessment results
Subsequently, the TAC of the proposed process and each case are
calculated by summing the EAC and TPC. First, Table 7 presents the
(43)
economic assessment results for the EAC.
From the table, all the variables of the proposed process cost
decreased compared to other cases; in particular, Cequipment of the pro­
posed process is 674,000 US$/y. The results indicate that the proposed
process has a higher equipment cost than Case 1 because additional
(44)
installation of electrodialysis and equipment for metal ion separation.
Cequipment of Case 2 is higher than that of Case 1 because the ion ex­
change resin reclaiming unit is more expensive than the electrodialysis
reclaiming unit. The TCI of the proposed process, Case 1, and Case 2
were determined to be 2,695,000 US$/y, 2,359,000 US$/y, and
2,767,000 US$/y, respectively. Finally, the EAC of the proposed process
was determined using the TCI, and the results show that the EAC of the
proposed process was higher than Case 1 by 12% and lower than Case 2
by 2.7%. Second, Table 8 shows the economic assessment results for TPC
(45) and revenue.
The table shows that all costs of the proposed process are the lowest.
Especially, the DPC of the proposed process is 337,000 US$/y, and it is
possible to decrease the cost by ~26% and 6.4% compared to the costs of
Case 1 and Case 2, respectively. This is because the proposed process
does not require any raw material apart from HCl for acidification to
dissolve Mg(OH)2, but only uses desalination wastewater. Thus, as the
additional CaCO3, which is the conventional SO2 absorbent, NH3, the
conventional NOx absorbent, and the additional requirement of amine
are replaced by desalination wastewater, the cost of raw material of the
proposed process is significantly decreased, and thus, the DPC is the
lowest compared to those of the other cases. In addition, the revenue of
the proposed process is 20,000 USD/y, which is significantly higher than
that of the other cases. The reason for this result is that the proposed
process can utilize gypsum as well as CaCO3, MgCO3, Ca(NO2)2, and Ca
(NO3)2, but other processes only utilize gypsum. In addition, while
calculating the revenue, the selling price of gypsum was specified to be
the same as that of the proposed process and other cases, but the gypsum
(47) generated in the proposed process has high-purity CaSO4, and thus, the
selling price will be higher.
Furthermore, the TPC of the proposed process was determined to be
~580,677 US$/y, which indicated a reduction of 19% and 5.7%
compared to those of Case 1 and Case 2, respectively. Finally, Fig. 6
shows the TAC of the proposed process and those of each case calculated
from the derived EAC, TPC, and revenue.
The TACs of the proposed process, Case 1, and Case 2 were
approximately 736,000 US$/y, 842,000 US$/y, and 794,000 US$/y,
respectively. Thus, the TAC of the proposed process was ~7.9% and 14%
lower than those of Case 1 and Case 2, respectively. This is because the
(48)
capture and utilization of NOx, SO2, and CO2 using the desalination
wastewater does not require any high-temperature conditions or
expensive raw materials; thus, the economic benefit is also high in spite
of additional installation of equipment for metal ion separation and
electrodiaylsis. In addition, using desalination wastewater, all pollutants
are not only captured but also utilized, such as gypsum, CaCO3, MgCO3,
Ca(NO2)2, and Ca(NO3)2. Therefore, the process has a competitive
advantage in terms of economy and availability compared to the con­
ventional process. Furthermore, the proposed process utilizes the metal

Table 7 Table 8
Economic assessment results for the EAC. Economic assessment results about TPC and revenue.
Variables Proposed process [US$] Case 1 [US$] Case2 [US$] Variables Proposed process [US$/y] Case 1 [US$/y] Case2 [US$/y]

Cequipment 674,000 590,000 692,000 FC 22,000 20,000 23,000

FCI 2,246,000 1,966,000 2,306,000 DPC 337,000 423,000 358,000
SUC 225,000 197,000 231,000 OVHD 122,000 128,000 127,000
WCI 225,000 197,000 231,000 GE 99,000 118,000 105,000
TCI 2,695,000 2,359,000 2,767,000 TPC 581,000 689,000 614,000
EAC 175,000 153,000 180,000 Revenue 20,000 72 72

10
J. Lim and J. Kim
Fig. 6. Calculated TAC of the proposed process and the two cases.
ion source of desalination wastewater, which is an infinite resource; it is
possible to capture and utilize NOx, SO2, and CO2 without any feedstock
limitations. Moreover, although the currently proposed process is a
small capacity process, if it is designed as a large capacity process, raw
material cost savings and revenue from CaCO3 and desulfurization
gypsum increase linearly. However, as the increase in the equipment
cost through the installation of additional equipment gradually de­
creases as the capacity increases, the economic feasibility is expected to
be superior.
Remark. The suggested approach can be further extended to the field of
shale gas wastewater (SGWW) treatment [41,42]. To produce shale gas and
oil, substantial amounts of wastewater are inventively generated [43,44]. In
the SGWW treatment, the precipitation process is employed to improve the
quality of the wastewater for reuse. To precipitate the SGWW, the lime
softening which adds Ca(OH)2 for the precipitation of Mg(OH)2 and Na2CO3
addition for the precipitation of CaCO3 is employed. However, the require­
ment of Ca(OH)2 and Na2CO3 increases the operating cost of the overall
process, and also the feedstock availability problem occurs. To solve these
problems, the Ca(OH)2 and Na2CO3 from the desalination wastewater can
efficiently be used. A combination of the pre-treatment techniques of SGWW
and the novel desalination wastewater recovery approach will be expected to
address minimizing the environmental impact of SGWW with economic
feasibility.
4. Conclusion
This work designed and integrated NOx, SO2, and CO2 capture and
utilization processes using desalination wastewater. This study makes
two major contributions to the existing literature. First, because the
suggested process enables the integration of capture and utilization of
NOx, SO2, and CO2 using one-site feedstock and wastewater that is
conventionally discharged, it is efficient and environmentally friendly.
Second, the results enable the complete substitution of other absorbents
or reactants with desalination wastewater, and thus, contribute to the
alleviation of the environmental problems posed by such wastewater
and the economic problems posed by the use of costly absorbents or
reactants. Approximately 90% NOx was captured and utilized, and the
desulfurization efficiency was 99% with high-purity gypsum produc­
tion. In addition, ~91% CO2 was captured, and the conversion yields of
each metal hydroxide to each carbonate were 99% and 63%, respec­
tively. In addition, the total annual cost of the proposed process is
approximately 735,618 US$/y, and it is possible to decrease it by a
11
Fuel 327 (2022) 124986
maximum of 14%; thus, it is profitable and suitable for large-capacity
processes, compared with other conventional processes. Thus, we
believe that this work provides valuable insights for the efficient use of
desalination wastewater and the capture and utilization of NOx, SO2,
and CO2 for cost-effective and environmentally friendly processes by
overcoming the challenges of conventional denitrification, desulfuriza­
tion, and CCS technology.
In this work, the conceptual design for the NOx, SO2, and CO2 capture
and utilization processes using desalination wastewater is addressed.
However, in further studies, the main parameters that determine the
reduction efficiency of NOx, SO2, and CO2 such as the presence or
absence of activated charcoal, mean residence time of flue gas, and
surface area of the absorbent and liquid–gas ratio would be determined
optimally. In addition, in general, the concentrations of metal cations
are not generally sensitive to changes, but if they change, the results of
NOx, SO2, and CO2 capture and utilization can change. Therefore, it is
necessary to split Ca(OH)2 and Mg(OH)2 at an appropriate ratio in
consideration of major parameters such as the Ca/S ratio that must be
satisfied.
CRediT authorship contribution statement
Jonghun Lim: Conceptualization, Investigation, Methodology,
Formal analysis, Writing – original draft. Junghwan Kim: Supervision,
Validation, Funding acquisition, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was supported by the Korean Institute of Industrial
Technology within the framework of the following projects: “Develop­
ment of Global Optimization System for Energy Process [grant number
IR-22-0040, IZ-22-0049 and UR-22-0031]”, “Development and Appli­
cation of Industry 4.0 Technology for Process Intensification [grant
number IR-22-0041, IZ-22-0051 and UR-22-0030]”, and “Development
of AI Platform for Continuous Manufacturing of Chemical Process [grant
number JH-22-0004]”.
J. Lim and J. Kim
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.fuel.2022.124986.
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