Journal of Cleaner Production 349 (2022) 131419

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Journal of Cleaner Production

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

Multi-criteria assessment of sodium bicarbonate optimized production

through CO2 utilization strategies
Henryck Cesar Massao Hungaro Yoshi a, *, André Batista Silva a, Marcos de Souza a, Sérgio
Henrique Bernardo de Faria a, André Bernardo b, Lucas Bonfim-Rocha c
a
Department of Chemical Engineering, State University of Maringá, 5790 Colombo Avenue, Maringá, 87020-900, Brazil
b
Department of Chemical Engineering, Federal University of São Carlos, km 235 Washington Luiz Road, São Carlos, 13565-905, Brazil
c
Department of Chemical Engineering, Technological Federal University of Paraná, 3131 dos Pioneiros Avenue, Londrina, 86036-370, Brazil

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

Handling Editor: Kathleen Aviso The use of CO2 as a feedstock for generating industrial products has been one of the most promising efforts for
mitigating the impacts of human society on the environment. Among the options, sodium bicarbonate stands out
Keywords: as a versatile and highly demanded compound. This work aims to further expand studies in this subject, assessing
Baking soda alternative production routes while drawing multiple criteria comparisons with the conventional processes. All
Soda ash
processes are simulated in Aspen Plus® at different operating conditions, and, then, rigorous optimization
Carbon dioxide utilization
techniques based on metaheuristics are carried out. Results indicate that soda ash carbonation shows the best
Solvay process
Sustainable processes overall results at 35 ◦ C, with a gross profit of US$ 0.23/kg of sodium bicarbonate, while the Solvay process and
sodium sulfate carbonation showed a potential gross profit of 0.14 and 0.12 US$/kg at the same temperature,
respectively. Availability of raw materials and demand for secondary products are, therefore, key aspects in
evaluating the competitiveness of each route. Furthermore, the captured CO2 for each of these routes was of 0.32,
0.70 and 1.04 kg CO2/kg of product, respectively, and the secondary products of sodium sulfate carbonation
indicate that it is an interesting approach to reduce waste, beign aligned to circular economy principles. Thus, the
integration of such processes to industries with high CO2 emissions stands out as a promising strategy to further
address society’s growing concern regarding sustainable development. Lastly, the applied method was efficient
in optimizing the models, enabling further studies not only regarding the entire sodium bicarbonate supply chain
but also for comparing production routes for other products.

1. Introduction
Government authorities worldwide are increasingly discussing and
proposing new politics regarding the minimization of greenhouse gas
(GHG) emissions aligned to the use of renewable sources of energy and
sustainable products. Among these gases, CO2 emissions stands out,
being mainly attributed to the burning and consumption of fossil fuels
for industrial use and energy production, but general activities such as
agriculture, forest exploitation, trade and services are also important
factors (Sesso et al., 2020).
The global surface temperature change is forecasted to likely exceed
1.5 ◦ C in the end of the 21st century (2081–2100, relative to
1850–1900), except if a scenario of stringent mitigation of emissions
occurs (IPCC, 2014). Studies have applied different models to forecast
CO2 emissions, indicating that emissions of most countries are expected
to grow due to aspects such as deforestation, industrialization, and de­
pendency on fast depleting fossil fuels for power generation (Qiao et al.,
2020; Wu et al., 2015, 2020). Developing countries have demands and
concerns to be addressed before a GHG emissions balance is achieved
(UNFCCC, 2015). Therefore, the usage of cleaner energy and the
adoption of conservation policies to reduce energy waste and CO2
emissions are mandatory in order to achieve environmental goals, and
the challenge is to do so without compromising economic gains.
With this reasoning, the concept of circular economy (CE) has risen –
an economic system that aims to eliminate the generation of waste and
pollution throughout the materials lifecycle. Such an approach gener­
ates value not only in terms of sustainability, but also in the economic
sphere, since the use of resources and raw materials is optimized. This

* Corresponding author.
E-mail addresses: pg402278@uem.br (H.C.M. Hungaro Yoshi), batista.eq@gmail.com (A.B. Silva), msouza2@uem.br (M. de Souza), shbfaria@uem.br
(S.H. Bernardo de Faria), abernardo@ufscar.br (A. Bernardo), lucasrocha@utfpr.edu.br (L. Bonfim-Rocha).

https://doi.org/10.1016/j.jclepro.2022.131419
Received 13 October 2021; Received in revised form 4 March 2022; Accepted 16 March 2022
Available online 21 March 2022
0959-6526/© 2022 Elsevier Ltd. All rights reserved.
H.C.M. Hungaro Yoshi et al.
idea recently became a global trend, both among companies in the
private sector and within the scientific community – in fact, in the period
of 2004–2020, 75% of all the CE publications were published in the last
three years (Nobre and Tavares, 2021). CE can be described based on its
so-called “principles”, which can be summed up as: reduce, reuse,
recycle, recover, remanufacturing and redesign, indicating that the
systemic transition to a CE requires the adoption of a holistic perspective
on the actions taken in each sector (Stumpf et al., 2021).
As a possible sink of GHG, the idea of carbon capture, use and storage
(CCUS) has gained attention, as emissions reductions by energy
enhancement and process efficiency by themselves are insufficient for
limiting global warming (IPCC, 2018). This acronym also includes the
concept of carbon dioxide utilization (CDU) technologies, which
consume CO2 to provide services or to manufacture products, resulting
in economic benefits while also reducing emissions, thus being aligned
with CE. Examples of industrial products obtainable reusing CO2 as a
feedstock are chemicals such as methanol, formic acid, and dimethyl
ether, and fuels such as methane and kerosene (Pacheco et al., 2019; Roh
et al., 2016).
Another promising class of products are carbonates, which can be
obtained through mineral carbonation of metal oxides (such as mag­
nesium or calcium), and stand out due to being capable of storing CO2
for long periods (Styring et al., 2011). Furthermore, mineral carbonation
does not demand high purity CO2 sinks, since the presence of most im­
purities (such as nitrogen oxides) from flue gas do not interfere with the
reactions (IPCC, 2005). Additionally, products with longer lifetimes are
of special interest, as the storage time of CO2 is a significant issue to be
addressed in order to achieve a positive economic and environmental
balance in CDU technologies (Cuéllar-Franca and Azapagic, 2015).
Each source of emission is distinct in terms of CO2 flow rate,
composition and moisture content of the flue gas, and the high cost of
CO2 capture, purification, compression and transportation may be cost-
prohibitive (Hasan et al., 2015). Considering this, recent studies have
also focused on identifying opportunities for CDU based on CO2 avail­
ability, mainly in scenarios where it is emitted as a consequence of a
process such as power generation, thermal and cement industries, and
bioethanol distilleries.
For example, in Brazil, the 20 natural gas-based thermoelectric
power plants with the highest installed capacity have been assessed
regarding their CO2 emissions and geographical location, indicating that
Brazilian southeast region is the country’s most promising region in
terms of CO2 availability, accounting for 17.2 Mton/year from the 4
highest installed capacity power plants alone (Pacheco et al., 2019).
Additionally, countries with bioethanol distilleries, such as Brazil and
USA, have advantages in implementing such reuse strategies, where CO2
is a by-product of the fermentation stage being commonly vented to the
atmosphere. Macowski et al. (2020) analyzed the Brazilian supply chain
of bioethanol distilleries, identifying a potential of approximately 21.1
Mton/year of CO2 in the country.
In this scenario, Bonfim-Rocha et al. (2018) pointed out the
techno-economic feasibility of biomethanol production using CO2
captured from distilleries, producing on average 1562 tonnes of meth­
anol per year with a negative CO2 balance. Furthermore, CO2 reuse
complements the biorefinery concept already addressed by other
byproducts derived from the process wastes, such as vinasse bio­
digestion for synthesis gas production, which may be converted into
other valuable products (e.g., biogas, dimethyl ether, methanol) (de
França Lopes et al., 2020; Orgeda et al., 2021; Silva et al., 2017). Food
waste is also a possible raw material for biorefineries, stimulating local
sustainable development and thus contributing to the transition to a CE,
where collaborative decision-making is not only socio-environmentally
correct, but also economically beneficial (Weber et al., 2020). Howev­
er, less than 1% of bioethanol plants are concerned about reusing CO2
and the possibility of developing CDU technologies for carbon mitiga­
tion in Brazil (Bonfim-Rocha et al., 2020).
Among the possible products that can be obtained by reusing CO2
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Journal of Cleaner Production 349 (2022) 131419
captured from bioethanol distilleries, sodium bicarbonate stands out, as
it is an inorganic salt with high global demand due to its many appli­
cations, such as surface cleaning, neutralizer of acids in exhaust flue gas
of several industries, food additive, animal feeds, paper sizing, plastic
foams, soft water treatment, smoke scrubbing and fire extinguisher
powders (Aresta et al., 2016; Goharrizi and Abolpour, 2012), with a
market estimated to surpass USD 2 billion by 2024 (Pulidindi and Pra­
kash, 2019). Although promising, this production strategy still needs to
be further studied in order to achieve optimum process design, consid­
ering aspects such as possible raw materials, their availability, second­
ary products, transportation and importing costs. The possible
production routes need to be firstly assessed in order to evaluate their
techno-economical feasibility, encouraging investors and supporting
economic policies.
In view of elucidating the main difficulties and the best alternatives
of this scenario, our work aims to assess the reactional stages of three
possible routes for the production of sodium bicarbonate as a CDU
technology integrated to a bioethanol distillery. Rigorous simulation
and optimization using a metaheuristics based supplement for global
optimization are implemented, in order to demonstrate and maximize
the processes profitability. The decision variables are the main operating
conditions and are evaluated in order to appraise their effect on the
productivity of the processes. After optimization, a multi-criteria anal­
ysis is performed, considering the potential profitability of secondary
products, conversion, CO2 capture, energy requirements, and costs,
enabling comparisons between the routes and providing insights regard
them as cleaner production processes, which may be used as a starting
point for further studies regarding the entire sodium bicarbonate supply
chain.
2. Methodology
Initially, a brief review of the use of CO2 as a reactant for the pro­
duction of sodium bicarbonate is provided, focusing on the relevant
aspects of more conventional and well known routes (i.e., Solvay process
and soda ash carbonation) in front of a non-traditional route based on
previous patents (i.e., sodium sulfate carbonation). Such review is
crucial and plays a key role for achieving data and understanding per­
formance characteristics of each route. Then, the entire methodology
employed is presented, through which the three routes are assessed as
carbon dioxide utilization scenarios. The modelling, simulation and
optimization procedures are throughly described in the context of a
systematic methodology for the design of sustainable CO2 utilization
processes.
2.1. Sodium bicarbonate production routes
Soda ash carbonation and the Solvay process are conventional and
well known-routes for the production of sodium bicarbonate. The re­
actions involved in each of these routes are presented in Sections 2.1.1
and 2.1.2. More recently, patents (most notably Bichel and Schaaf,
2008) have suggested alternative raw materials such as sodium sulfate,
enabling the production of secondary products (i.e., ammonium sulfate
and/or calcium sulfate), which are considered to be of higher interest
than the secondary products of the Solvay process (i.e., calcium chlo­
ride), reducing waste and thus being in line with CE. The reactions
involved in sodium sulfate carbonation are presented in Section 2.1.3.
2.1.1. Solvay process
The Solvay process has been historically the most conventional
process for sodium bicarbonate production, where soda ash (Na2CO3) is
produced from sodium chloride (NaCl) and limestone (CaCO3) (Lee
et al., 2018; Solvay, 1887). In this route, the first step consists in the
carbonation of ammoniated brine (Eq. (1)), in which sodium bicarbon­
ate (NaHCO3) is precipitated. The remaining solution of ammonium
chloride (NH4Cl) is treated with slaked lime (Ca(OH)2) obtained from
H.C.M. Hungaro Yoshi et al.
the hydration and slaking of the limestone (Eq. (2)), thus recovering the
utilized ammonia and producing calcium chloride (CaCl) as a secondary
product (Eq. (3)). Traditionally, Eq. (2) also produces the reactant CO2,
so the Solvay process may not be the best suited when considering CDU
technologies. Depending on the process purpose, NaHCO3 is then
calcined to Na2CO3 through Eq. (4). Summarizing, the global reactions
are represented in Eqs. (5) and (6) (Bonfim-Rocha et al., 2020; Stein­
hauser, 2008).
NaCl + NH3 + CO2 + H2 O→NaHCO3 + NH4 Cl (1)
CaCO3 + H2 O→Ca(OH)2 + CO2 (2)
2 ​ NH4 Cl + Ca(OH)2 →2 ​ NH3 + CaCl2 + 2 ​ H2 O (3)
2 ​ NaHCO3 → Na2 CO3 + CO2 + H2 O (4)
2 ​ NaCl + Ca(OH)2 + 2 ​ CO2 →2 ​ NaHCO3 + CaCl2 (5)
2 ​ NaCl + CaCO3 →Na2 CO3 + CaCl2 (6)
However, for achieving the purity requisites, Na2CO3 itself may be
reconverted to NaHCO3 through solution and carbonation, which is
essentially a reversed Eq. (4), as shown in Eq. (7):
2 ​ Na2 CO3 + CO2 + H2 O ​ →2 ​ NaHCO3 (7)
2.1.2. Soda ash carbonation
A simplified route is often commercially used to produce NaHCO3
using Na2CO3 obtained from trona, a naturally occurring mineral of the
formula described in Eq. (8), through a CO2 capture process. Such route
is also referred to as soda ash carbonation, which also consists of Eq. (7),
being present in the dry carbonate process, where Na2CO3 is used as a
sorbent to separate CO2 from other flue gases producing NaHCO3
(Bonaventura et al., 2017).
Na2 CO3 ⋅ NaHCO3 ⋅2 ​ H2 O (8)
2.1.3. Sodium sulfate carbonation
Other raw materials have been more recently studied as alternatives
to these conventional processes. The most proeminent example is
probably sodium sulfate (Na2SO4), initially proposed as an improvement
to the Solvay process in which no calcareous material is required,
instead, removing the chlorine from sodium chloride in the form of
gaseous hydrochloric acid (HCl) (Stiers, 1970). The process consists of
essentially using the sulfate anion to transportate the sodium cations
from sodium chloride to the bicarbonating process. Ammonium sulfate
((NH4)2SO4) is precipitated as an intermediary. The reactions involved
are demonstrated in Eqs. (9)–(11). The overall reaction of this route
remains being reacting carbon dioxide with sodium chloride to yield
crystallized sodium bicarbonate, as demonstrated in Eq. (12).
Na2 SO4 + 2 ​ NH3 + 2 ​ H2 O + 2 ​ CO2 →(NH4 )2 SO4 + 2 ​ NaHCO3 (9)
(NH4 )2 SO4 + Na2 SO4 →2 ​ NaHSO4 + 2 ​ NH3 (10)
2 ​ NaHSO4 + 2 ​ NaCl→2 ​ Na2 SO4 + 2 ​ HCl (11)
NaCl + H2 O + CO2 →NaHCO3 + ​ HCl (12)
Later, Kresnyak et al. (1998) reviewed this process, criticizing it for
being a co-precipitation method which could not provide for selective
precipitation of desired products, since if ammonium sulfate reaches a
saturation point in the bicarbonating stage (due to continuous recycling
of the mother liquor) it would co-precipitate with sodium sulfate in the
form of a double salt compound, thus being lesser desirable from a
commercial point of view. Instead, the authors propose a method in
which commercial grade baking soda is obtainable with ammonium
sulfate as a secondary product in purity levels that it could be
3
Journal of Cleaner Production 349 (2022) 131419
commercialized as a fertilizer. The method is essentially based on Eq.
(9), with a series of evaporation, cooling and precipitation steps, making
possible to recycle the unreacted sodium sulfate. For temperatures
above 35 ◦ C, the solubility of ammonium sulfate increases with the
temperature, while the solubility of sodium sulfate decreases, making
possible to selectively precipitate one or another.
A possible natural source of sodium sulfate are the vast reserves of
Glauber’s salt (sodium sulfate decahydrate, Na2SO4. 10 H2O). This hy­
drate, however, is one of the main difficulties in this process: for tem­
peratures below 32 ◦ C, saturated solutions of sodium sulfate will
precipitate the decahydrate, causing tremendous operating difficulties.
Above this temperature, sodium bicarbonate formation is not affected,
as the formation of ammonium bicarbonate ((NH4)HCO3) is also avoi­
ded. In order to maximize the bicarbonate yield, the final temperature of
the reactor’s solution may be reduced to about 21 ◦ C, but it would be on
the edge of possible contamination with sodium sulfate (Kresnyak and
Halldorson, 1999). On the other hand, high temperatures may result in
the calcination of the sodium bicarbonate, returning it to sodium car­
bonate (as in Eq. (4)).
Finally, Bichel and Schaaf (2008) further addressed this route,
identifying that previous works were not concerned with energy con­
sumption and conversion efficiency, requiring significant input of en­
ergy to the evaporators and subsequent cooling. The researchers then
suggested improvements to the process, achieving higher yields and
purities while using commercially viable and energy efficient unit op­
erations in proper sequence, with the utilization of strategies such as
acidification in order to remove residual bicarbonate in the solution
before precipitating ammonium sulfate. However, it is important to note
that this route requires low cooling temperatures (5 ◦ C). Since then, the
process has been further reviewed, identifying that the price of the raw
materials could compromise the economical competitiveness of the
process, even though the required capital investments are lower than the
conventional processes, with most of it being due to the crystallizers
(Kumar et al., 2013).
However, there is a lack of scientific literature regarding studies
evaluating NaHCO3 crystallization and purification in parallel with
(NH4)2SO4 production in a cost effective and technical detailed
approach when using Na2SO4, NH3 and CO2 as raw materials (Bon­
fim-Rocha et al., 2020). Recently, this production route has been
assessed regarding the production of soda ash, utilizing the commercial
process simulation software Aspen Plus®, corroborating some known or
expected technical aspects: a saturated feed of Na2SO4 is beneficial to
the process, and the amount of NH3 used, while increasing productivity,
may require higher amounts of water during the purification steps,
which might be problematic as the energy and electricity consumption
increase with the recycle ratio (Pak et al., 2021).
Based on available literature regarding sodium bicarbonate pro­
duction from different routes, quantitative results are provided in ways
that are difficult to draw proper comparisons between the traditional
and the innovative processes, not only regarding their profitability but
also aspects such as energy demand, capital and operating costs, and the
susceptibility to market conditions such as product prices and raw ma­
terials availability. All of these are fundamental points that industry
decision-makers and policymakers need to be aware of in order to pro­
mote smart CO2 mitigation strategies that best suit their region’s needs
and are clarified hereafter.
2.2. Process synthesis and design
Process synthesis and design literatures have shown that the reaction
step is often where performance limitations occur or even their cause,
which includes sodium bicarbonate crystallizers (Lutze et al., 2013;
Turton et al., 2018). Under CE considerations, Baratsas et al. (2021)
developed a framework for the analysis of food supply chains, which is
based on mathematical modeling and multicriteria optimization. The
authors pointed that such strategy should be improved by academic
H.C.M. Hungaro Yoshi et al.
Fig. 1. Overview of the 3-stage approach to sustainable process design (Garg et al., 2019).
Fig. 2. Soda ash carbonation process model flowsheet.
efforts that focus on the improvement of existing tasks, or expanding it
into other classes of problems (e.g., by the incorporation of sensitivity
analysis, and stochastic optimization) (Avraamidou et al., 2020).
In the context of CDU technologies, previous works have presented
and improved a systematic methodology for the design of sustainable
CO2 utilization processes while also guaranteeing profitability (Babi
et al., 2015; Garg et al., 2019; Roh et al., 2016). This methodology is
adopted for this work and consists of three stages: (1) process synthesis
(Section 2.2.1), (2) process design (Section 2.2.2), and (3) innovative
and sustainable design (Section 2.2.3), as illustrated in Fig. 1. Section
2.2.4 presents a detailed description of the optimization problem’s
mathematical modelling.
2.2.1. Stage 1: synthesis
Starting from process synthesis, a superstructure is constructed to
link the raw material (CO2) to possible products via processing paths,
listing all of the thermodynamically feasible reactions. Once that the
desired products are known, reaction path synthesis is performed,
determining the reactions that satisfy the atomic balance and stoichio­
metric coefficients with the possible reactants and products involved.
4
Journal of Cleaner Production 349 (2022) 131419
In this work, this assessment is performed through modeling of these
processes utilizing Aspen Plus® V12.0. For simulation purposes, Elec­
trolyte Wizard, an Aspen Plus® supplement tool, is used to detect and
generate the possible reactions and components of each system and their
intermediate components, while also evaluating their equilibrium con­
stants and the equilibrium properties. For electrolyte systems with
inorganic components such as sodium bicarbonate, it is also necessary to
consider ionic components and reactions (Aspen Technology Inc.,
2000).
For the simulation, the thermodynamic property method ELECNRTL-
RK may be used for aqueous and mixed solvent applications, being
capable of properly estimating properties and thermodynamic equilib­
rium data for electrolyte systems (e.g. sodium bicarbonate precipitation)
based on an electrolyte Non-Random Two-Liquid (NRTL) model for the
aqueous phase and the Redlich-Kwong equation of state for vapor phase
calculation, as in some of the evaluated routes equilibria between
gaseous H2O, NH3 and CO2 in low to moderate pressures is possible
(Aspen Technology Inc., 2000; Magdeldin and Järvinen, 2020).
Then, the optimal processing path must be obtained, formulating the
process design model as a mixed-integer nonlinear programming
H.C.M. Hungaro Yoshi et al.
Fig. 3. Solvay process model flowsheet.
Fig. 4. Sodium sulfate carbonation process model flowsheet.
problem (MINLP) to be solved with an appropriate software containing
optimization solvers (such as GAMS and MATLAB). Since the desired
product of this work is already defined (sodium bicarbonate), as well as
the processing paths (soda ash carbonation, Solvay process and sodium
sulfate carbonation), these steps are preestablished. The sets of com­
ponents and reactions considered in each of these processes are pre­
sented in the supplementary material (Tables S.1, S.2 and S.3), as
defined by Aspen Plus®.
2.2.2. Stage 2: design & analysis
In the next stage, the flowsheet alternatives defined in stage 1 are
designed in detail in order to set up a base case design using the com­
ercial process simulator, solving detailed mass and energy balances data,
which are analyzed regarding energetic, economical, and environmental
aspects.
For all scenarios, each of the feed streams consists of dissolved so­
dium salts, at a temperature of 30 ◦ C and pressure is kept fixed at 1.471
bar throughout the flowsheet. The reactor is defined as a crystallizer
where the carbon dioxide stream (CO2) is injected, with saturation
calculation method set as “Chemistry” (i.e. the precipitation is based on
the components’s solubilities) and operating at a designated tempera­
ture through the removal of reaction heat (Q-RX). The temperatures
evaluated are 5, 35 or 65 ◦ C, except for sodium sulfate carbonation,
which is unfeasible at 5 ◦ C due to the formation and precipitation of
Glauber’s salt (Kresnyak and Halldorson, 1999).
In the soda ash carbonation scenario (Fig. 2), soda ash is initially
mixed with water forming a solution (RX-IN) into a tank (T1), which is
5
Journal of Cleaner Production 349 (2022) 131419
then fed into the crystallizer (REACTOR) where carbon dioxide (CO2) is
injected. The crystallizer has a gaseous and a solid-liquid outlet (RX-
VENT and RX-OUT, respectively), with the latter being directed to the
centrifuge (CFUGE), from which the product stream (NAHCO3) is
separated from the remaining mother liquor (MTH-LIQ). The centrifuge
is configurated as a solids separator, where all of the solids are removed
in the solid outlet and a small fraction (6%) of the mother liquor is
carried by the solids as moisture.
Similarly, in the Solvay process model (Fig. 3), sodium chloride
(NACL) is initially dissolved with water (H2O-1) into a tank (T2) and
mixed with an ammonia solution (AM-SOL) which is kept at 30 ◦ C at a
previous concentration step (mixing the streams NH3 and H2O-2 at the
tank T1) with the removal of heat (Q-NH) with a cooler (C1). The
resulting mixture (RX-IN) is then fed alongside a carbon dioxide stream
(CO2) into the crystallizer (REACTOR) whose outlet streams (and the
subsequent centrifuge and product streams) are similar to the soda ash
carbonation model previously described.
In the last route, the sodium sulfate carbonation process model
(Fig. 4), sodium sulfate (NA2SO4) is initially dissolved with water (H2O-
1) to an aqueous solution (NA-RX-IN). It is then fed into the crystallizer
(REACTOR) alongside an ammonia solution (NH-RX-IN, obtained from a
previous concentration step similarly to the Solvay process) and a car­
bon dioxide stream (CO2). The subsequent process is similar to the
previously described in Figs. 2 and 3. Alternatively, the flowsheet could
be defined sequentially prior to feeding into the reactor – that is, NH3
could be directly fed into the Na2SO4 solution. However, this would lead
to temperature variations and possible gaseous NH3 release, since it
H.C.M. Hungaro Yoshi et al. Journal of Cleaner Production 349 (2022) 131419

Table 1
Material streams data for initial process evaluation of soda ash carbonation.
Reaction Temperature: 5 ◦ C

Parameters SODA-ASH WATER CO2 RX-VENT NAHCO3 MTH-LIQ

Temperature (K) 303.15 303.15 303.15 278.15 278.15 278.15

Pressure (bar) 1.47 1.47 1.47 1.47 1.47 1.47
Mole flow (kmol/h) 7.55 194.28 22.72 14.76 15.14 190.27
Mass flow (kg/h) 800.00 3500.00 1000.00 647.05 1063.71 3589.23
Mass frac Na2CO3 1.0000 – – 0.0000 0.0000 0.0000
Mass frac H2O – 1.0000 – 0.0026 0.0522 0.9214
Mass frac CO2 – – 1.0000 0.9974 0.0004 0.0063
Mass frac NaHCO3 – – – 0.0000 0.9434 0.0000
Mass frac Na+ – – – 0.0000 0.0011 0.0198
Mass frac HCO3- – – – 0.0000 0.0030 0.0522
Mass frac CO32- – – – 0.0000 0.0000 0.0002

Reaction Temperature: 35 ◦ C
Parameters SODA-ASH WATER CO2 RX-VENT NAHCO3 MTH-LIQ

Temperature (K) 303.15 303.15 303.15 308.15 308.15 308.15

Pressure (bar) 1.47 1.47 1.47 1.47 1.47 1.47
Mole flow (kmol/h) 9.43 277.54 22.72 13.38 14.64 279.65
Mass flow (kg/h) 1000.00 5000.00 1000.00 575.99 1033.13 5390.88
Mass frac Na2CO3 1.0000 – – 0.0000 0.0000 0.0000
Mass frac H2O – 1.0000 – 0.0157 0.0501 0.8851
Mass frac CO2 – – 1.0000 0.9843 0.0002 0.0044
Mass frac NaHCO3 – – – 0.0000 0.9434 0.0000
Mass frac Na+ – – – 0.0000 0.0017 0.0307
Mass frac HCO3- – – – 0.0000 0.0044 0.0783
Mass frac CO32- – – – 0.0000 0.0001 0.0015

Reaction Temperature: 65 ◦ C
Parameters SODA-ASH WATER CO2 RX-VENT NAHCO3 MTH-LIQ

Temperature (K) 303.15 303.15 303.15 338.16 338.16 338.16

Pressure (bar) 1.47 1.47 1.47 1.47 1.47 1.47
Mole flow (kmol/h) 11.56 277.54 22.72 13.66 14.85 283.88
Mass flow (kg/h) 1225.00 5000.00 1000.00 544.26 1054.35 5626.39
Mass frac Na2CO3 1.0000 – – 0.0000 0.0000 0.0000
Mass frac H2O – 1.0000 – 0.0724 0.0475 0.8385
Mass frac CO2 – – 1.0000 0.9276 0.0002 0.0042
Mass frac NaHCO3 – – – 0.0000 0.9434 0.0000
Mass frac Na+ – – – 0.0000 0.0026 0.0456
Mass frac HCO3- – – – 0.0000 0.0058 0.1026
Mass frac CO32- – – – 0.0000 0.0005 0.0090

Initial inputs were defined by the authors based on previous knowledge of the processes. Results are obtained from Aspen Plus®.

suffers salting-out effects at high concentrations and the potential pre­
cipitation of Na2SO4 (Rumpf and Maurer, 1993). Certainly, this would
be a more rigorous analysis, however, considering that the temperatures
and concentrations evaluated are considerably low, it was decided to
feed the two solutions and the CO2 directly into the reactor, for conve­
nience and valuing the safety of the process.
2.2.3. Stage 3: Innovation
At this stage, the whole process is available as a base case flowsheet,
so information such as stream data, equipment operating and design
parameters, economic and sustainability indicators are known. This is
hereafter called the “initial process evaluation” of each route.
Then, sensitivity analysis, ranging the input variables within the
search space is performed to evaluate how they affect the process out­
puts. For reactional systems as sodium bicarbonate production, the re­
actants proportions are critical for the process performance. Hence, a
reasonable range for analysis can be drawn based on the initial evalu­
ation of the base case flowsheet and the solubility curves of the involved
salts, i.e., the reactants need to be fed into the systems in quantities
capable of producing the desired amounts of sodium bicarbonate
(around 1000 kg/h) in accordance to the stoichiometry of the reactions.
Due to the high dependency on the temperature in crystallization sys­
tems, this procedure is done for the forementioned temperatures (5, 35
and 65 ◦ C) to assess its effects, resulting into preliminary optimums for
each of the 8 scenarios (as the temperature of 5 ◦ C is not evaluated for
the sodium sulfate process).
Lastly, each one of the 8 scenarios is optimized ranging the variables
around the preliminary optimums. Due to the significant mathematical
complexity of chemical processes, potentially many local minima are
possible, and a suitable global optimization method is desired. Nor­
mally, using a deterministic approach (i.e. one that guarantees conver­
gence to global optimality) for highly nonlinear systems such as
equilibrium-based reactional systems, usually requires a prohibitive
computational effort. In these cases, stochastic methods show up as a
more feasible alternative, with metaheuristics being efficient methods
for most of applications (Segovia-Hernández and Gómez-Castro, 2017).
However, there is a limited availability of metaheuristic tools for
process optimization aligned to process simulators – to address this
issue, Egea et al. (2014) developed MEIGO, an open-source software
suite that provides state-of-the-art metaheuristics (Enhanced Scatter
Search – eSS, and Variable Neighbourhood Search – VNS) as a toolbox
for MATLAB®, covering both nonlinear programming problems (NLPs)
and MINLPs. One particularly interesting feature of MEIGO is that it is
capable of optimizing defined objective functions with subjective con­
straints that are handled as black-boxes, therefore being applicable to
optimize systems that involve solving inner problems (e.g. simulations)
to obtain explicit values for the objective functions and the possible
constraints (Bonfim-Rocha et al., 2018; Luna et al., 2021). Thus, being a
MATLAB® toolbox, MEIGO allows to integrate it to Aspen Plus®,
through MATLAB® application, combining both metaheuristic global
optimization and rigorous simulation of thermodynamic properties,
chemical equilibria and unit operations. Such procedure may greatly

6
H.C.M. Hungaro Yoshi et al. Journal of Cleaner Production 349 (2022) 131419

Table 2
Material streams data for initial process evaluation of the Solvay process.
Reaction Temperature: 5 ◦ C

Parameters NACL H2O-1 NH3 H2O-2 CO2 RX-VENT NAHCO3 MTH-LIQ

Temperature (K) 303.15 303.15 303.15 303.15 303.15 278.15 278.15 278.15
Pressure (bar) 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47
Mole flow (kmol/h) 29.09 263.67 14.09 97.42 36.36 19.69 14.78 409.41
Mass flow (kg/h) 1700.00 4750.00 240.00 1755.00 1600.00 863.90 1049.51 8131.57
Mass frac NaCl 1.0000 – – – – 0.0000 0.0000 0.0000
Mass frac H2O – 1.0000 – 1.0000 – 0.0022 0.0432 0.7631
Mass frac NH3 – – 1.0000 – – 0.0000 0.0000 0.0000
Mass frac CO2 – – – – 1.0000 0.9978 0.0008 0.0146
Mass frac NaHCO3 – – – – – 0.0000 0.9434 0.0000
Mass frac Na+ – – – – – 0.0000 0.0027 0.0486
Mass frac NH4+ – – – – – 0.0000 0.0018 0.0309
Mass frac Cl− – – – – – 0.0000 0.0071 0.1259
Mass frac HCO3- – – – – – 0.0000 0.0009 0.0166
Mass frac NH2COO− – – – – – 0.0000 0.0000 0.0002
Mass frac CO32- – – – – – 0.0000 0.0000 0.0000

Reaction Temperature: 35 ◦ C
Parameters NACL H2O-1 NH3 H2O-2 CO2 RX-VENT NAHCO3 MTH-LIQ

Temperature (K) 303.15 303.15 303.15 303.15 303.15 – 308.16 308.16

Pressure (bar) 1.47 1.47 1.47 1.47 1.47 – 1.47 1.47
Mole flow (kmol/h) 21.39 263.67 34.35 97.42 22.72 – 15.07 411.19
Mass flow (kg/h) 1250.00 4750.00 585.00 1755.00 1000.00 – 1073.02 8266.98
Mass frac NaCl 1.0000 – – – – – 0.0000 0.0000
Mass frac H2O – 1.0000 – 1.0000 – – 0.0420 0.7422
Mass frac NH3 – – 1.0000 – – – 0.0008 0.0136
Mass frac CO2 – – – – 1.0000 – 0.0000 0.0005
Mass frac NaHCO3 – – – – – – 0.9434 0.0000
Mass frac Na+ – – – – – – 0.0015 0.0258
Mass frac NH4+ – – – – – – 0.0028 0.0499
Mass frac Cl− – – – – – – 0.0052 0.0911
Mass frac HCO3- – – – – – – 0.0023 0.0404
Mass frac NH2COO− – – – – – – 0.0019 0.0335
Mass frac CO32- – – – – – – 0.0002 0.0029

Reaction Temperature: 65 ◦ C
Parameters NACL H2O-1 NH3 H2O-2 CO2 RX-VENT NAHCO3 MTH-LIQ

Temperature (K) 303.15 303.15 303.15 303.15 303.15 338.16 338.16 338.16
Pressure (bar) 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47
Mole flow (kmol/h) 29.09 263.67 34.35 97.42 68.17 56.95 14.69 418.38
Mass flow (kg/h) 1700.00 4750.00 585.00 1755.00 3000.00 2250.11 1047.91 8491.97
Mass frac NaCl 1.0000 – – – – 0.0000 0.0000 0.0000
Mass frac H2O – 1.0000 – 1.0000 – 0.0600 0.0402 0.7098
Mass frac NH3 – – 1.0000 – – 0.0172 0.0010 0.0172
Mass frac CO2 – – – – 1.0000 0.9228 0.0003 0.0052
Mass frac NaHCO3 – – – – – 0.0000 0.9434 0.0000
Mass frac Na+ – – – – – 0.0000 0.0026 0.0466
Mass frac NH4+ – – – – – 0.0000 0.0024 0.0424
Mass frac Cl− – – – – – 0.0000 0.0068 0.1206
Mass frac HCO3- – – – – – 0.0000 0.0019 0.0340
Mass frac NH2COO- – – – – – 0.0000 0.0013 0.0233
Mass frac CO32- – – – – – 0.0000 0.0001 0.0009

Initial inputs were defined by the authors based on previous knowledge of the processes. Results are obtained from Aspen Plus®.

increase the range of possibilities for optimization using process simu­ ( ) ( ) ∑

lation softwares and makes possible to detect the best process design s.t.: G x, u, xR = Cw . W x, u, xR − Cr .xrR
conditions, which, in our study, maximize the profitability per mass of
r
∑ ( )
product. The optimal scenarios are then assessed regarding − Cu .Qu x, u, xR − Ce . Qe
multiple-criteria, in order to provide more depth and complexity to
u
( )
comparisons between the processes. HM x, u, xR = 0
( )
HE x, u, xR = 0
2.2.4. Optimization problem ( )
Ls x, u, xR − 1 = 0
The scenarios are all optimized within a search space around the ( )
preliminary optimal solution found in the sensitivity analysis as an P x, u, xR ≥ 0.995
( )
initial estimate. The constrained global optimization model (M) is 970 ≤ W x, u, xR ≤ 1030
expressed next according to Eq. (13):
In model M, L is the objective function that evaluates the gross profit
− G(x, u, xR ) (G, in US$/h) per mass of sodium bicarbonate produced (W, in kg/h),
M: min L = (13)
xR ∈R+ W(x, u, xR ) being negative in order to maximize it when in a minimization algo­
rithm. The vector x denotes process variables calculated by the simu­
lator, whereas u represents fixed parameters not modified during the

7
H.C.M. Hungaro Yoshi et al. Journal of Cleaner Production 349 (2022) 131419

Table 3
Material streams data for initial process evaluation of sodium sulfate carbonation.
Reaction Temperature: 35 ◦ C

Parameters NA2SO4 H2O-1 NH3 H2O-2 CO2 RX-VENT NAHCO3 MTH-LIQ

Temperature (K) 303.15 303.15 303.15 303.15 303.15 – 309.28 309.28

Pressure (bar) 1.47 1.47 1.47 1.47 1.47 – 1.47 1.47
Mole flow (kmol/h) 12.67 213.71 23.49 49.96 22.72 – 14.18 300.61
Mass flow (kg/h) 1800.00 3850.00 400.00 900.00 1000.00 – 1036.02 6913.98
Mass frac Na2SO4 1.0000 – – – – – 0.0000 0.0000
Mass frac H2O – 1.0000 – 1.0000 – – 0.0356 0.6281
Mass frac NH3 – – 1.0000 – – – 0.0001 0.0023
Mass frac CO2 – – – – 1.0000 – 0.0005 0.0080
Mass frac NaHCO3 – – – – – – 0.9434 0.0000
Mass frac Na+ – – – – – – 0.0026 0.0452
Mass frac NH4+ – – – – – – 0.0032 0.0560
Mass frac HCO3- – – – – – – 0.0043 0.0764
Mass frac NH2COO− – – – – – – 0.0004 0.0077
Mass frac CO32- – – – – – – 0.0001 0.0017
Mass frac SO42- – – – – – – 0.0099 0.1746

Reaction Temperature: 65 ◦ C
Parameters NA2SO4 H2O-1 NH3 H2O-2 CO2 RX-VENT NAHCO3 MTH-LIQ

Temperature (K) 303.15 303.15 303.15 303.15 303.15 338.17 338.17 338.17
Pressure (bar) 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47
Mole flow (kmol/h) 21.58 368.78 65.19 164.52 60.59 24.64 14.54 633.78
Mass flow (kg/h) 3065.61 6643.65 1110.18 2963.84 2666.44 966.92 1060.00 14422.80
Mass frac Na2SO4 1.0000 – – – – 0.0000 0.0000 0.0000
Mass frac H2O – 1.0000 – 1.0000 – 0.0641 0.0352 0.6220
Mass frac NH3 – – 1.0000 – – 0.0182 0.0010 0.0174
Mass frac CO2 – – – – 1.0000 0.9176 0.0003 0.0045
Mass frac NaHCO3 – – – – – 0.0000 0.9434 0.0000
Mass frac Na+ – – – – – 0.0000 0.0028 0.0496
Mass frac NH4+ – – – – – 0.0000 0.0028 0.0501
Mass frac HCO3- – – – – – 0.0000 0.0040 0.0702
Mass frac NH2COO− – – – – – 0.0000 0.0021 0.0379
Mass frac CO32- – – – – – 0.0000 0.0003 0.0052
Mass frac SO42- – – – – – 0.0000 0.0081 0.1432

Initial inputs were defined by the authors based on previous knowledge of the processes. Results are obtained from Aspen Plus®.

Eqs. (1) and (5) for the Solvay process, when either considering the
Table 4 intermediary ammonium chloride as a secondary product or executing
Energy stream data for initial process evaluation of each sodium bicarbonate the complete process, further processing it into calcium chloride. As the
production route.
model does not account for further processing costs required to obtain
Processes Reaction Temperature (◦ C) the secondary products, function G in Eq. (14) is considered as a “po­
Soda Ash Carbonation 5 35 65 tential” gross profit, where the index w indicates each of the products.
Q-RX
( ) ∑ ( ) ∑ ∑ ( )
G x, u, xR = Cw .Ww x, u, xR − Cr .xRr − Cu .Qu x, u, xR
Reaction Cooling (kW) 282.950 161.633 − 17.505 w r u
Electricity (kW) 70.97 58.72 82.16
Solvay Process 5 35 65 − Ce . Q e (14)
Q-NH
Ammonia Concentration (kW) 126.197 279.577 126.195
Parameters Cw, Ce, Cr and Cu are the costs of products, electricity,
Q-RX reactants and heating/cooling utilities, respectively. For Cw and Cr, the
Reaction Cooling (kW) 524.143 489.840 524.104 unit is US$/kg, while Cu is in US$/cal. For convenience, Ce is provided in
Electricity (kW) 126.92 126.92 126.92 US$/kWh. The cost parameters of the products and the reactants are
Sodium Sulfate Carbonation 5 35 65
defined based on their market prices and are reported in the supple­
Q-NH
Ammonia Concentration (kW) – 183.050 521.637 mentary material (Table S.4), while the costs of electricity and utilities
Q-RX are estimated from Aspen Plus® database (Table S.5). The function Qu
Reaction Cooling (kW) – 448.504 386.293 represents the heat demand (in cal/h) of the utility indicated by the
Electricity (kW) – 126.92 164.22 index u, while Qe (in kW) corresponds to the electricity demand.
Initial inputs were defined by the authors based on previous knowledge of the As equality constraints, functions HM and HE are implicit equations
processes. Results are obtained from Aspen Plus®. solved by the process simulator to evaluate mass balance and energy
balance, respectively, while the function L is the liquid molar fraction of
calculations, such as streams temperature, pressure, and other design the reactor inlet solution streams, each of them being indicated by the
variables. The reactants mass flows are given by xR (in kg/h), while the index s, remembering that no precipitate is present in the inlets. Lastly,
index r represents each reactant individually. two inequality constraints are defined: the product sodium bicarbonate
Initially, G is evaluated only regarding sodium bicarbonate produc­ purity evaluated as function P is of at least 99.5% (w/w) to meet market
tion, thus not accounting for secondary products. Then, its definition can requirements, while the total product outlet is within the estipulated
be further expanded as demonstrated in Eq. (14), admitting stoichio­ range of 970–1030 kg/h of pure NaHCO3. It should be noted that, when
metric production in relation to the sodium bicarbonate outlet, where it considering practical industrial execution, analytical methods are
is evaluated regarding the overall reactions of each process, that is: Eq. required in order to evaluate the purity of the product (e.g. titration).
(7) for soda ash carbonation, Eq. (9) for sodium sulfate carbonation, and Finally, multiple indicators other than the gross profit are obtainable

8
H.C.M. Hungaro Yoshi et al. Journal of Cleaner Production 349 (2022) 131419

Fig. 5. Gross profit per kilogram of product for every feasible solution in each scenario of sodium bicarbonate production (in $/kg NaHCO3).

from the optimized simulation, such as yield, conversion, CO2 capture
and heating/cooling requirements. Furthermore, economic results such
as capital, operating and utility costs are estimated using Aspen Process
Economic Analyzer® (APEA) directly in the resulting flowsheets. All
results may be then used as criteria to draw better comparisons between
each of the evaluated scenarios. The procedure is executed on a com­
puter with an Intel® Core™ i7-4510U CPU (2.00 GHz), 8 GB of RAM and
a NVIDIA GeForce 710M GPU.
3. Results and discussion
3.1. Process evaluation
Based on previous works and patents presented in Section 2.1 (Bichel
and Schaaf, 2008; Bonfim-Rocha et al., 2020; Kresnyak et al., 1998;
Kumar et al., 2013; Lee et al., 2018; Pak et al., 2021; Solvay, 1887;
Stiers, 1970), and considering the solubility curves and properties of the
involved compounds, initial simulations are used as base cases for the
optimization process (sensitivity analysis), with a target of sodium bi­
carbonate production in the range of 970–1030 kg/h (dry basis), and
ensuring complete dissolution of the reactor inlet streams. The resulting
inputs and the outputs for evaluation of mass and energy balances of the
three processes obtained from Aspen Plus® (i.e., compositions, pressure,
temperature, mass and mole flows, and heat duties) are shown in
Tables 1–4, for each of the evaluated temperatures in each scenario.
From a mass balance perspective, a point that draws attention is the
mass flow of the mother liquor in each scenario. Soda ash carbonation
shows the lowest results for this flowrate, being as low as 3589.23 kg/h
(at 5 ◦ C) and as high as 5626.39 kg/h (at 65 ◦ C). On the other hand, the
Solvay process presents values from 8131.57 (at 5 ◦ C) to 8491.97 (at
65 ◦ C), while sodium sulfate carbonation ranges from 6913.98 kg/h (at
35 ◦ C) to 14422.80 kg/h (at 65 ◦ C).
Even though the aforementioned scenarios are only the initial esti­
mates, these are considerable differences, and majorly due to the
amount of water in the process – in general, these values suggest that
soda ash carbonation has a lower demand of water, i.e., requires less
water for the proper solution and mixture of the reactants, while in the
other routes the precipitation of contaminating salts must be avoided.
The optimization procedure may properly adjust the amounts of water
fed to the processes, evidencing this trend more accurately.
The heat values of the energy balances indicate that soda ash
carbonation is a lesser energy demanding process, both from lower re­
action cooling requirements and the absence of an ammonia concen­
tration step. It is important to note that even though the feed streams are
at the temperature of 30 ◦ C, the temperature of the inlet streams (as well
as the initial temperature of the reactional mixture) may be higher in the
equilibrium due to the heat of mixing. For this reason, soda ash
carbonation at 65 ◦ C happened to be the only condition where the
reactor has to be heated rather than cooled, but such observation is not
expected in practical scenarios.
3.2. Sensitivity analysis
In Fig. 5, each of the scenarios presenting feasible solutions evalu­
ated in the sensitivity analysis are plotted as pairs of the gross profit per
mass of NaHCO3 ($/kg) and the ratio between the masses of the CO2 feed
and the sodium source feed (w/w) (i.e., Na2CO3, NaCl, Na2SO4 for soda
ash carbonation, Solvay process and sodium sulfate carbonation,
respectively). The same restrictions of the model M are applied for the
definition of the preliminary optimum, however, in order to provide a
more insightful analysis, scenarios not achieving the required sodium
bicarbonate production range are also screened and plotted (hence the
points above the indicated preliminary optimum, which do not meet the
production requirements).
Soda ash carbonation has its best result apparently limited to a
maximum gross profit margin at around $0.22/kg of NaHCO3. This
value is achieved at the temperature of 5 ◦ C, using 1.31 kg CO2/kg
Na2CO3, and at 35 ◦ C, using 0.76 kg CO2/kg Na2CO3.
The Solvay process has its best solution that meets the sodium bi­
carbonate production range at 35 ◦ C, achieving $0.08/kg of NaHCO3
from 1.17 kg CO2/kg NaCl. In contrast, at 5 ◦ C, feasible results achieve
values above $0.10/kg of NaHCO3, but the production requirement is

9
H.C.M. Hungaro Yoshi et al. Journal of Cleaner Production 349 (2022) 131419

Table 5
Material streams data for optimal once-through reaction of soda ash carbonation.
Reaction Temperature: 5 ◦ C

Parameters SODA-ASH WATER CO2 RX-VENT NAHCO3 MTH-LIQ

Temperature (K) 303.15 303.15 303.15 278.14 278.14 278.14

Pressure (bar) 1.47 1.47 1.47 1.47 1.47 1.47
Mole flow (kmol/h) 6.94 102.86 11.90 4.73 15.53 96.12
Mass flow (kg/h) 735.38 1853.09 523.80 207.46 1091.55 1813.26
Mass frac Na2CO3 1.0000 – – 0.0000 0.0000 0.0000
Mass frac H2O – 1.0000 – 0.0026 0.0522 0.9214
Mass frac CO2 – – 1.0000 0.9974 0.0004 0.0063
Mass frac NaHCO3 – – – 0.0000 0.9434 0.0000
Mass frac Na+ – – – 0.0000 0.0011 0.0198
Mass frac HCO3- – – – 0.0000 0.0030 0.0522
Mass frac CO32- – – – 0.0000 0.0000 0.0002

Reaction Temperature: 35 ◦ C
Parameters SODA-ASH WATER CO2 RX-VENT NAHCO3 MTH-LIQ

Temperature (K) 303.15 303.15 303.15 308.15 308.15 308.15

Pressure (bar) 1.47 1.47 1.47 1.47 1.47 1.47
Mole flow (kmol/h) 7.28 92.28 14.05 6.90 15.46 86.32
Mass flow (kg/h) 771.40 1662.48 618.43 297.14 1091.25 1663.92
Mass frac Na2CO3 1.0000 – – 0.0000 0.0000 0.0000
Mass frac H2O – 1.0000 – 0.0157 0.0501 0.8851
Mass frac CO2 – – 1.0000 0.9843 0.0002 0.0044
Mass frac NaHCO3 – – – 0.0000 0.9434 0.0000
Mass frac Na+ – – – 0.0000 0.0017 0.0307
Mass frac HCO3- – – – 0.0000 0.0044 0.0783
Mass frac CO32- – – – 0.0000 0.0001 0.0015

Reaction Temperature: 65 ◦ C
Parameters SODA-ASH WATER CO2 RX-VENT NAHCO3 MTH-LIQ

Temperature (K) 303.15 303.15 303.15 338.13 338.13 338.13

Pressure (bar) 1.47 1.47 1.47 1.47 1.47 1.47
Mole flow (kmol/h) 8.14 104.03 16.45 10.02 15.37 99.42
Mass flow (kg/h) 862.78 1874.06 723.96 399.40 1091.05 1970.35
Mass frac Na2CO3 1.0000 – – 0.0000 0.0000 0.0000
Mass frac H2O – 1.0000 – 0.0723 0.0475 0.8385
Mass frac CO2 – – 1.0000 0.9277 0.0002 0.0042
Mass frac NaHCO3 – – – 0.0000 0.9434 0.0000
Mass frac Na+ – – – 0.0000 0.0026 0.0456
Mass frac HCO3- – – – 0.0000 0.0058 0.1026
Mass frac CO32- – – – 0.0000 0.0005 0.0090

only met with values of $0.06/kg of NaHCO3 at best. This indicates,
preliminarily, that the best result for this process within the desired
production range may be found at 5 ◦ C during the optimization.
For the sodium sulfate carbonation process, the best condition is
identified at 0.87 kg CO2/kg Na2SO4 and 35 ◦ C, achieving at this point a
value of -$0.18/kg of NaHCO3. This negative result suggests that the
profitability of secondary products and proper recycling of the remain­
ing mother liquor is mandatory for this route to be economically
feasible.
Therefore, without evaluation of the possible secondary products,
the Solvay process and sodium sulfate carbonation show great disad­
vantage when compared to soda ash carbonation. The three processes
benefit from lower temperatures, which is in accordance to the behavior
of NaHCO3 solubility in that range.
3.3. Process optimization
After running MEIGO routines of optimization, the inputs (i.e., the
resulting decision vectors of the optimization) and the outputs for the
optimal conditions of the three processes are shown in Tables 5–8, for
each of the evaluated temperatures, as obtained from the mass and en­
ergy balances of the flowsheets from Aspen Plus®.
As previously discussed in Section 3.1, for most scenarios, the
resulting mass flow of the mother liquor is significantly reduced. At 5, 35
and 65 ◦ C, respectively, the reductions for soda ash carbonation are of
49.48%, 69.13% and 64.98%, while for the Solvay process the re­
ductions are of 40.60%, 37.30% and 17.10%. These reductions are good
indicators that the optimization process was effective, minimizing
amounts in the streams that require further processing. In a smaller
proportion, the mother liquor of sodium sulfate carbonation at 65 ◦ C
decreased by 3.18%. However, a different behavior is observed for so­
dium sulfate at 35 ◦ C, where the mother liquor actually increased by
22.55%, but with increment at the product mass flow output.
In order to expand the analysis regarding the optimization step, the
processes are organized in the form of boxplots, in which each one’s data
is the sweeping of every feasible scenario evaluated. Fig. 6 display the
boxes segregated by process and the number of data points for each
scenario is indicated in the figures by the letter “n”. For the Solvay
process and sodium sulfate carbonation, the results are further analyzed
regarding the potential production of secondary products (Eq. (14)),
accounting for the gross profit gain obtainable from them being pro­
duced stoichiometrically in relation to the NaHCO3 produced according
to Eqs. (1), (5) and (9). Then, the secondary products are ammonium
chloride and calcium chloride (for the Solvay process) and ammonium
sulfate (for the sodium sulfate carbonation). It is important to note that
while this approach makes the results more suitable for direct compar­
isons between the processes, they are not perfectly accurate, as they do
not consider the operating and capital costs of further separation and
purification steps of these secondary products, besides the economic
evaluation being affected by market fluctuations of raw materials. Under
this approach, Fig. 7 compares the boxes of the processes at each tem­
perature (i.e., with potential calcium chloride production for the Solvay
process and ammonium sulfate production for the sodium sulfate
carbonation).

10
H.C.M. Hungaro Yoshi et al. Journal of Cleaner Production 349 (2022) 131419

Table 6
Material streams data for optimal once-through reaction of the Solvay process.
Reaction Temperature: 5 ◦ C

Parameters NACL H2O-1 NH3 H2O-2 CO2 RX-VENT NAHCO3 MTH-LIQ

Temperature (K) 303.15 303.15 303.15 303.15 303.15 278.15 278.15 278.15
Pressure (bar) 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47
Mole flow (kmol/h) 20.83 162.78 13.89 46.64 27.05 11.77 15.03 239.36
Mass flow (kg/h) 1217.35 2932.59 236.55 840.18 1190.39 516.49 1070.64 4829.94
Mass frac NaCl 1.0000 – – – – 0.0000 0.0000 0.0000
Mass frac H2O – 1.0000 – 1.0000 – 0.0021 0.0408 0.7203
Mass frac NH3 – – 1.0000 – – 0.0000 0.0000 0.0001
Mass frac CO2 – – – – 1.0000 0.9979 0.0008 0.0134
Mass frac NaHCO3 – – – – – 0.0000 0.9434 0.0000
Mass frac Na+ – – – – – 0.0000 0.0023 0.0414
Mass frac NH4+ – – – – – 0.0000 0.0029 0.0511
Mass frac Cl− – – – – – 0.0000 0.0085 0.1510
Mass frac HCO3- – – – – – 0.0000 0.0013 0.0224
Mass frac NH2COO− – – – – – 0.0000 0.0000 0.0003
Mass frac CO32- – – – – – 0.0000 0.0000 0.0000

Reaction Temperature: 35 ◦ C
Parameters NACL H2O-1 NH3 H2O-2 CO2 RX-VENT NAHCO3 MTH-LIQ

Temperature (K) 303.15 303.15 303.15 303.15 303.15 308.15 308.15 308.15
Pressure (bar) 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47
Mole flow (kmol/h) 23.77 139.41 15.92 77.32 32.91 17.10 15.26 253.52
Mass flow (kg/h) 1389.03 2511.43 271.11 1392.88 1448.52 739.27 1090.07 5183.63
Mass frac NaCl 1.0000 – – – – 0.0000 0.0000 0.0000
Mass frac H2O – 1.0000 – 1.0000 – 0.0122 0.0392 0.6923
Mass frac NH3 – – 1.0000 – – 0.0004 0.0001 0.0020
Mass frac CO2 – – – – 1.0000 0.9874 0.0006 0.0115
Mass frac NaHCO3 – – – – – 0.0000 0.9434 0.0000
Mass frac Na+ – – – – – 0.0000 0.0029 0.0505
Mass frac NH4+ – – – – – 0.0000 0.0029 0.0515
Mass frac Cl− – – – – – 0.0000 0.0091 0.1606
Mass frac HCO3- – – – – – 0.0000 0.0016 0.0279
Mass frac NH2COO− – – – – – 0.0000 0.0002 0.0035
Mass frac CO32- – – – – – 0.0000 0.0000 0.0002

Reaction Temperature: 65 ◦ C
Parameters NACL H2O-1 NH3 H2O-2 CO2 RX-VENT NAHCO3 MTH-LIQ

Temperature (K) 303.15 303.15 303.15 303.15 303.15 338.17 338.17 338.17
Pressure (bar) 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47
Mole flow (kmol/h) 28.24 151.95 28.66 135.07 25.53 7.71 15.22 344.39
Mass flow (kg/h) 1650.17 2737.36 488.18 2433.25 1123.37 305.27 1086.94 7040.14
Mass frac NaCl 1.0000 – – – – 0.0000 0.0000 0.0000
Mass frac H2O – 1.0000 – 1.0000 – 0.0574 0.0388 0.6860
Mass frac NH3 – – 1.0000 – – 0.0180 0.0010 0.0182
Mass frac CO2 – – – – 1.0000 0.9246 0.0003 0.0059
Mass frac NaHCO3 – – – – – 0.0000 0.9434 0.0000
Mass frac Na+ – – – – – 0.0000 0.0029 0.0519
Mass frac NH4+ – – – – – 0.0000 0.0026 0.0463
Mass frac Cl− – – – – – 0.0000 0.0080 0.1410
Mass frac HCO3- – – – – – 0.0000 0.0016 0.0287
Mass frac NH2COO- – – – – – 0.0000 0.0012 0.0214
Mass frac CO32- – – – – – 0.0000 0.0000 0.0006

Once again, soda ash carbonation achieves the overall best results,
with relatively low variation in the evaluated range. Also, the Solvay
process performed better at 5 ◦ C than at 35 ◦ C, as was expected from the
sensitivity analysis discussion. More interestingly, both the Solvay pro­
cess and sodium sulfate carbonation demonstrate a noticeable
improvement in performance (20.13% and 28.00%, respectively),
especially when accounting for potential secondary products. However,
at 65 ◦ C, both processes showed unpromising and not economically
feasible implementation.
Another important result is demonstrated in Fig. 6b, where for the
Solvay process, producing ammonium chloride seems to be as good as or
even better than completing the traditional route with further process­
ing to precipitate calcium chloride. This is in accordance with the
modified Solvay process, also known as the Hou process, utilized by
many producers in the world to co-produce ammonium chloride, which
is then commonly utilized as a fertilizer in rice cultivation in countries
such as China (Alonso-Moreno and García-Yuste, 2016; European Soda
Ash Producers Association, 2004). Thus, the decision making regarding
the production of one or other seems to be also dependent on market
conditions (e.g., prices, competitors, demand of products, availability of
raw materials) besides technical conditions – however, the evaluated
optimal conditions for the production of NaHCO3 should remain un­
changed, with the subsequent process pointing to the most profitable
process in each scenario.
3.4. Multi-criteria comparison
In addition to an economic perspective, the multi-criteria assessment
performed and illustrated in Table 9 compares other indicators for the
optimal scenarios. For proper comparison, these results are normalized
and then compiled in six radar charts – one for each process, and one for
each temperature, as shown in Fig. 8.
According to Fig. 8, for soda ash carbonation, gross profit values are
best at 5 ◦ C, however, with a relatively small difference when compared

11
H.C.M. Hungaro Yoshi et al. Journal of Cleaner Production 349 (2022) 131419

Table 7
Material streams data for optimal once-through reaction of sodium sulfate carbonation.
Reaction Temperature: 35 ◦ C

Parameters NA2SO4 H2O-1 NH3 H2O-2 CO2 RX-VENT NAHCO3 MTH-LIQ

Temperature (K) 303.15 303.15 303.15 303.15 303.15 308.15 308.15 308.15
Pressure (bar) 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47
Mole flow (kmol/h) 15.11 278.12 24.28 52.01 50.94 27.98 14.68 373.68
Mass flow (kg/h) 2146.06 5010.33 413.47 936.91 2241.77 1206.36 1069.37 8472.82
Mass frac Na2SO4 1.0000 – – – – 0.0000 0.0000 0.0000
Mass frac H2O – 1.0000 – 1.0000 – 0.0141 0.0368 0.6497
Mass frac NH3 – – 1.0000 – – 0.0003 0.0001 0.0017
Mass frac CO2 – – – – 1.0000 0.9856 0.0005 0.0083
Mass frac NaHCO3 – – – – – 0.0000 0.9434 0.0000
Mass frac Na+ – – – – – 0.0000 0.0028 0.0491
Mass frac NH4+ – – – – – 0.0000 0.0027 0.0476
Mass frac HCO3- – – – – – 0.0000 0.0037 0.0661
Mass frac NH2COO− – – – – – 0.0000 0.0003 0.0061
Mass frac CO32- – – – – – 0.0000 0.0001 0.0014
Mass frac SO42- – – – – – 0.0000 0.0096 0.1701

Reaction Temperature: 65 ◦ C
Parameters NA2SO4 H2O-1 NH3 H2O-2 CO2 RX-VENT NAHCO3 MTH-LIQ

Temperature (K) 303.15 303.15 303.15 303.15 303.15 338.18 338.18 338.18
Pressure (bar) 1.47 1.47 1.47 1.47 1.47 1.47 1.47 1.47
Mole flow (kmol/h) 21.07 362.41 64.96 151.22 59.05 22.86 14.96 611.84
Mass flow (kg/h) 2992.73 6528.94 1106.33 2724.34 2598.96 896.61 1090.97 13963.72
Mass frac Na2SO4 1.0000 – – – – 0.0000 0.0000 0.0000
Mass frac H2O – 1.0000 – 1.0000 – 0.0639 0.0349 0.6173
Mass frac NH3 – – 1.0000 – – 0.0190 0.0010 0.0179
Mass frac CO2 – – – – 1.0000 0.9171 0.0003 0.0045
Mass frac NaHCO3 – – – – – 0.0000 0.9434 0.0000
Mass frac Na+ – – – – – 0.0000 0.0028 0.0490
Mass frac NH4+ – – – – – 0.0000 0.0029 0.0517
Mass frac HCO3- – – – – – 0.0000 0.0040 0.0714
Mass frac NH2COO− – – – – – 0.0000 0.0022 0.0387
Mass frac CO32- – – – – – 0.0000 0.0003 0.0053
Mass frac SO42- – – – – – 0.0000 0.0082 0.1443

being on a similar level to sodium sulfate carbonation. Both also pre­

Table 8 sented considerably lower conversions with higher CO2 capture, which
Energy stream data for optimal process evaluation of each sodium bicarbonate based on the optimal reactant proportions is most likely related to the
production route.
high requirement of water for these processes, in a way that much of CO2
Processes Reaction Temperature (◦ C) fed is held in the substantially higher mass flow of the remaining mother
Soda Ash Carbonation 5 35 65 liquor. Normally, low conversions also imply higher recycle streams,
Q-RX
which results in higher operating costs. Therefore, the results highlight
Reaction Cooling (kW) 224.384 155.014 74.387 that it may be cost effective to prioritize gains in once through conver­
Electricity (kW) 62.45 59.84 66.18 sion instead of absolute profit.
Solvay Process 5 35 65 This aspect leads to another important observation: since secondary
Q-NH
products are required for the proper competitiveness of each route, the
Ammonia Concentration (kW) 115.664 138.285 248.246
Q-RX further processing of the mother liquor should also take into account the
Reaction Cooling (kW) 452.104 325.087 185.193 technical requirements for obtaining recycle streams. For example, the
Electricity (kW) 74.70 74.70 74.70 use of evaporation leads to possible recovery of low pressure CO2, NH3
Sodium Sulfate Carbonation 5 35 65 and steam in the gaseous stream, possibiliting precipitation of a mix
Q-NH
Ammonia Concentration (kW) – 189.432 513.493
between products and feed salts. On the other hand, further crystalli­
Q-RX zation of the sodium sulfate carbonation mother liquor through tem­
Reaction Cooling (kW) – 74.70 74.70 perature reduction could lead to the precipitation of Na2SO4 in the form
Electricity (kW) – 74.70 74.70 of Glauber’s salt, which could bring practical disadvantages to the
process. From an environmental perspective, residual sulfate may result
in higher potential impacts, such as eutrophication, so the usage of CaO
to 35 ◦ C, temperature in which the optimal conditions indicate lower
in order to produce CaSO4 is an interesting approach for further evalu­
capital, operational and utility costs, while also achieving approxi­
ation. While the Solvay process is relatively well known, sodium sulfate
mately the same production and higher CO2 capture. Considering these
carbonation could still benefit greatly from innovative strategies for
aspects, soda ash carbonation at 35 ◦ C is arguably the most promising
proper utilization of the mother liquor in the production of secondary
condition among the evaluated scenarios. It should be noted, however,
products and recovery of recycle streams, thus improving the overall
that temperature also has an effect on crystal growth, becoming more
conversion of the process and the competitiveness of this route.
diffusion controlled at higher temperatures rather than integration
controlled, and different crystal sizes may be required to address
different markets (Mullin, 2001). 3.5. Performance analysis
In an intermediary position, the Solvay process benefits greatly from
lower temperatures, being a potentially competitive route. Regardless of For reference, Table 10 presents the variable ranges searched during
it, in the three scenarios, costs were higher than soda ash carbonation, the optimization step for each of the routes at the optimal temperature of

12
H.C.M. Hungaro Yoshi et al. Journal of Cleaner Production 349 (2022) 131419

Fig. 6. Boxplot of the feasible solutions evaluated in the optimization of a) soda ash carbonation process; b) the Solvay process; c) sodium sulfate carbonation process
(in $/kg NaHCO3).

Fig. 7. Boxplot of the feasible solutions evaluated in the optimization of each scenario of sodium bicarbonate production, considering potential calcium chloride
production for the Solvay process and ammonium sulfate production for sodium sulfate carbonation (in $/kg NaHCO3).

Table 9
Multiple criteria results evaluated for the optimal solutions obtained for each scenario of sodium bicarbonate production.
Process Soda Ash Carbonation Solvay Process Sodium Sulfate Carbonation

Temperature (◦ C) 5 35 65 5 35 65 35 65

NaHCO3 Gross Profit ($/kg NaHCO3) 0.2278 0.2190 0.2029 0.1252 0.0961 − 0.0256 − 0.1296 − 0.5401
Potential Gross Profit ($/kg NaHCO3) 0.2278 0.2190 0.2029 0.1715 0.1424 0.0207 0.1166 − 0.2939
Yield (kg NaHCO3/kg Na source) 1.400 1.335 1.193 0.830 0.740 0.621 0.470 0.344
Conversion (% molar basis) 88.35 84.21 75.27 57.72 51.51 43.23 39.73 29.78
Captured CO2 (kg CO2/kg NaHCO3) 0.3077 0.3166 0.3434 0.6683 0.6988 0.8203 1.0436 1.7262
Heating/Cooling Requirement (kW) 224.384 155.014 74.387 567.769 463.372 433.439 647.326 924.472
Capital Cost ($) 2,120,700.00 1,981,240.00 2,244,580.00 2,919,440.00 2,925,500.00 2,943,260.00 2,934,050.00 2,965,030.00
Operational Cost ($/year) 998,051.00 990,455.00 1,006,820.00 1,035,640.00 1,036,520.00 1,039,080.00 1,037,360.00 1,045,600.00
Utility Cost ($/year) 42,426.30 40,652.50 44,960.40 53,237.40 53,724.40 56,091.30 54,825.80 61,800.00

35 ◦ C, in which comparisons can also be better drawn due to the results
of the Solvay process and sodium sulfate carbonation previously pre­
sented. In Table 10, “H2O (1)” refers to the water used to dissolve the
sodium source, while “H2O (2)” is the water used for the ammonia
solution.
At last, the effectiveness of the applied optimization method is
assessed comparing the improvement of the objective function (gross
profit per kg of NaHCO3) between the initial and optimal solutions, as
shown in Fig. 9.
This comparison demonstrates that the applied method is effective in
optimizing all of the eight models. It must be noted that the degree of
improvement is highly dependent on good initial estimates, and may
require proper setup and computational time to evaluate large ranges for
the variables due to the nonlinearity of these problems. For example,
soda ash carbonation at 5 ◦ C and sodium sulfate carbonation at 65 ◦ C
had the smallest improvements (10,84% and 6,77%, respectively),
indicating that the initial estimates for these two cases were relatively
closer to the optimal condition than the other scenarios, thus requiring
less computational time.
Such methodology may be further applied to other inorganic salt
crystallization systems, evaluating the optimal proportions of raw ma­
terials and operating conditions. Moreover, possibly the most intriguing
aspect of applying MEIGO for the optimization of chemical processes is
its ability to work with objective functions that are handled as black-
boxes, which proves useful for integration with commercial chemical
process simulators. Being integrated in MATLAB, it facilitates the record
and analysis of each evaluation, further confirming the usefulness of this
method. In this work, a total of 8755 simulations were evaluated
through this methodology.

13
H.C.M. Hungaro Yoshi et al. Journal of Cleaner Production 349 (2022) 131419

Fig. 8. Radar charts comparing multiple criteria between the optimal scenarios evaluated for each a) sodium bicarbonate production route; b) temperature.

Table 10
Optimization parameters set for each sodium bicarbonate production route for the temperature of 35 ◦ C.
Process Parameter Na2CO3 H2O CO2

Soda Ash Carbonation Lower Bound 630.95 1421.63 523.80

Initial Solution 767.93 1657.33 583.77
Upper Bound 904.90 1893.03 643.74
Optimal Solution 771.40 1662.48 618.43

Process Parameter NaCl NH3 H2O (1) CO2 H2O (2)

Solvay Process Lower Bound 1262.75 232.77 2126.73 1052.31 695.31

Initial Solution 1325.63 280.95 2755.94 1555.94 1649.20
Upper Bound 1642.76 343.34 4668.91 4004.69 2799.94
Optimal Solution 1389.03 271.11 2511.43 1448.52 1392.88

Process Parameter Na2SO4 NH3 H2O (1) CO2 H2O (2)

Sodium Sulfate Carbonation Lower Bound 1828.10 380.55 5007.08 1597.19 837.14
Initial Solution 2285.12 475.69 6258.85 1996.49 1046.42
Upper Bound 2742.14 570.83 7510.62 2395.79 1255.70
Optimal Solution 2146.06 413.47 5010.33 2241.77 936.91

4. Conclusion

Conclusive appointments of the investigated scenarios showed that

Fig. 9. Comparison between the performance of initial solutions (Section 3.1)
and optimal solutions (Section 3.3).
with the optimal operating conditions at 35 ◦ C, soda ash carbonation
achieved the highest gross profit of US$ 0.22/kg of sodium bicarbonate,
while the Solvay process and sodium sulfate carbonation showed a po­
tential gross profit of 0.14 and 0.12 US$/kg of sodium bicarbonate,
respectively, as these two routes also require the commercialization of
secondary products, in such way that they may show up as competitive
routes if market conditions are favorable, rather than being limited by
technical conditions. Furthermore, the employment of these processes
prove beneficial for cleaner production, capturing 0.32, 0.70 and 1.04
kg CO2/kg NaHCO3, respectively. As an innovative process, sodium
sulfate carbonation shows up as a promising way to address sodium
bicarbonate production in line with CE principles, and may be inte­
grated to high CO2 emissions industries as a CDU strategy, favoring

14
H.C.M. Hungaro Yoshi et al.
cleaner production.
Finally, the applied method proves efficient in optimizing the
models, making possible to draw the best comparisons between each
scenario, which were lacking in previous works regarding sodium bi­
carbonate production. The modeling of these processes utilizing Aspen
Plus® enabled the evaluation of multiple criteria and process perfor­
mance parameters, providing insightful concepts within each of the
considered routes. Therefore, this same approach could be applied for
comparing production routes for other products. Further studies
regarding the entire sodium bicarbonate supply chain would also be
valuable, identifying integration opportunities to employ it as a carbon
mitigation process.
CRediT authorship contribution statement
Henryck Cesar Massao Hungaro Yoshi: Investigation, Methodol­
ogy, Software, Writing – original draft. André Batista Silva: Concep­
tualization, Validation, Resources. Marcos de Souza: Supervision,
Writing – review & editing. Sérgio Henrique Bernardo de Faria:
Conceptualization, Supervision, Writing – review & editing. André
Bernardo: Validation, Writing – review & editing. Lucas Bonfim-
Rocha: Methodology, Software, Writing – original draft.
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.
Acknowledgements
The authors gratefully acknowledge the financial support from the
Brazilian National Council for Scientific and Technological Develop­
ment – Process 133539/2019-09 – CNPq to develop this research.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jclepro.2022.131419.
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