pubs.acs.

org/IECR Article

Innovative Reactive Distillation Process for the Sustainable

Purification of Lactic Acid
Cristina González-Navarrete, Eduardo Sánchez-Ramírez, César Ramírez-Márquez, Salvador Hernández,
Enrique Cossío-Vargas, and Juan Gabriel Segovia-Hernández*
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ABSTRACT: Lactic acid is commonly used in a wide range of fields, such as

cosmetics, pharmaceutical products, chemistry, and food. During recent years, its use
for new applications, such as the production of biodegradable and biocompatible
polymers, green solvents, and oxygenated chemicals, have received considerable
attention. However, the relatively high production cost of lactic acid hinders many
large-scale applications. It is necessary to develop more efficient methods of separation
and purification to cheapen lactic acid production processes. The main objective of this
study is to investigate the use of process intensification, particularly the reactive
distillation process, for a sustainable purification of lactic acid. To do so, there have
been proposed, on the one hand, four intensified alternatives in which synthesis and
design are based on thermal couplings and, on the other hand, three alternatives
looking for water mass integration. Design and optimization of those modified
configurations are carried out employing a stochastic optimization method, using as
objective functions some metrics associated with the concept of sustainability
(economics, environmental, and inherent safety indexes). A study on the dynamic performance of the configurations through the
use of singular value decomposition is carried out in a complementary way. The results in the first redesign stage show improvements
in all performance indexes. However, a great difference between the implementation of a thermal coupling that substitutes a
condenser instead of a reboiler has been identified. The best scheme, based on a sustainability framework, resulted in a modified
process, including a dividing wall column-based scheme.

1. INTRODUCTION acrylic acid, acetaldehyde, pyruvic acid, 1,2 propanediol, and

Biomass carbohydrates are the most abundant renewable propanoic acid. It is also used in the cosmetic industry as a
resources available, and they are currently viewed as a feedstock humectant in the preparation of creams and soaps. Moreover,
for green chemistry.1 Two types of sugars are present in biomass: lactic acid consumption has increased considerably because of
hexoses, of which glucose is the most representative, and its use as a basic input in the production of polylactates and
pentoses, of which xylose is most common. Fermentation of polylactic acid for the manufacture of biodegradable plastics.4,5
sugars represents an important route to produce new bio- Lactic acid exists in two optically active isomeric forms, L(+)
and D(−). Compared to the biological route, chemical synthesis
products. Five important bioproducts can be obtained from the
is at a disadvantage because the lactic acid produced is a mixture
fermentation of glucose: lactic acid, succinic acid, itaconic acid,
of optically inactive D(−) and L(+) lactic acid. Because of this,
glutamic acid, and 3-hydroxypropionic acid.2
Lactic acid (2-hydroxypropionic acid) can be produced by about 90% of all lactic acid in the world is produced by the
chemical synthesis or by fermentation of different carbohy- biotechnological route.2 An important step in the lactic acid
drates, such as glucose (from starch), maltose (produced by bioproduction is the recovery from fermentation broth. The
conventional process for the recovery of lactic acid is still far
specific enzymatic starch conversion), sucrose (from syrups,
from ideal since it involves the precipitation of calcium lactate
juices, and molasses), lactose (from whey), among others.1
after the separation of microorganisms and the conversion of the
However, lactic acid is commercially produced today mainly
through the fermentation of glucose. Lactic acid is a compound
with high global demand. The estimated global demand for Received: October 11, 2021
lactic acid is 200,000 to 350,000 t per year with annual growth Revised: December 16, 2021
rates between 12% and 15% (see Figure 1).3 Accepted: December 21, 2021
Demand for lactic acid is high in the food, pharmaceutical, Published: December 30, 2021
textile, and chemical feedstock industries where it is used to
produce lactate esters, propylene glycol, 2,3-pentanedione,

© 2021 American Chemical Society https://doi.org/10.1021/acs.iecr.1c04050

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Figure 1. Global and regional demand of lactic acid (USD billion).

salt into lactic acid by the addition of sulfuric acid. The dilute phase reactions, which conventionally require a large excess of
lactic acid produced is then subjected to purification. The one of the reactants.11 The technological benefits of reactive
separation and purification stages account for up to 50% of the distillation can be summarized as follows: (a) increased
production cost. One point to highlight is that the biological conversion; (b) increased selectivity; (c) reduced energy
production of lactic acid has significant advantages over the consumption; (d) overcoming of azeotropes; (e) simplified
chemical production. Advantages include the high specificity of separation of close-boiling components, and (f) capital savings.
the product, i.e., production of the optically pure isomeric form Recently, intensified process with reactive membranes12 or
by selecting the appropriate microorganisms used in the reactive distillation has been proposed to alleviate these
fermentation. limitations.13 The recovery of nonvolatile lactic acid from the
However, the concentration of lactic acid produced in the fermentation broth is difficult due to the similarity of the boiling
fermentation broth is very dilute and impurities that are points. The purification of lactic acid using reactive distillation
generally present (unconverted acids, alcohol, side esters, can be described as follows: the lactic acid is reacted with
sulfates, heavy metals, proteins, residual sugars, and nutrients) methanol, and methyl lactate is produced. Methyl lactate can be
need to be separated. In addition, lactic acid has a strong affinity more easily purified by distillation. Then, methyl lactate is sent
for water, is a high-boiling component, and tends to oligomerize to a hydrolysis column and recovered by the hydrolysis reaction.
at high temperatures. Therefore, these factors make lactic acid The advantages of this purification method are the ability to
purification energy an intensive task. Various methods of handle large capacities of raw materials and to achieve high lactic
purification have been investigated. Numerous separation and acid recovery. This is the most promising solution to the lactic
purification techniques have been proposed for lactic acid acid purification problem. This method was first described in a
production, such as precipitation,6 solvent extraction,7 adsorp- U.S. patent by Cockrem and Johnson.14 The application of
tion,7 short-path evaporator,8 and membrane separation intensified distillation systems, such as conventional reactive
processes, such as reverse osmosis, electrodialysis, and ultra- distillation or thermally coupled reactive distillation systems
filtration.9 However, these processes result in low lactic acid (thermally coupled arrangements are realized by setting up two-
recovery and have the following limitations: in solvent way vapor/liquid flows between different columns of the simple
extraction, a relatively large amount of solvent is required; column configurations15,16), shows great benefits to achieving
high-purity lactic acid is difficult to obtain; ultrafiltration and an economic process. A highlight is that sustainable design
osmosis are not suitable for a large amount of raw material; considers economic, environmental, and societal outcomes with
efficiency declines in parallel with a drop in membrane equal measures and ensures that the consumption of resources
performance; and adsorption presents several problems, does not exceed nature’s capacity to provide the needed
including particle selectivity, capacity, and regeneration. ecosystem goods and services. PI is a design concept that offers
Process intensification (PI) is an effective strategy to achieve innovative solutions for making a substantial improvement in
increased energy efficiency. PI aims at reducing the mass and terms of cost, energy efficiency, emission, environmental
heat transfer resistances while overcoming thermodynamic footprint, processing volume, and safety of a chemical process.
limitations through integrated design and operation. In recent Incorporation of PI principles at the conceptual design stage can
years, PI has attracted considerable academic interest as a pave the way for more sustainable solutions.17 Also, according to
potential means for process improvement to meet the increasing Schöggl et al.,18 sustainability contributes to the circular
demands for sustainable production.10 economy environment through the measurement of both
One of the most common examples of the process economic and green chemistry indicators. In summary, PI is a
intensification field is the reactive distillation, where the strategy that can generate sustainable designs and is therefore
integration of reaction and separation is performed in a single framed within the concept of circular economy. In this sense, the
unit, allowing the simultaneous production and removal of use of intensified systems in the lactic acid purification process is
products, thus improving the productivity and selectivity, generating sustainable alternatives to this industrial problem, in
reducing the energy use, eliminating the need for solvents, and a circular economy environment.
leading to intensified, high-efficiency systems with green In this study, we extended the lactic acid recovery process
attributes. Reactive distillation has attracted considerable based on conventional reactive distillation to a modified process
attention, especially for chemical equilibrium-limited, liquid- using thermally coupled reactive configurations. In addition,
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three alternatives for integrating a water stream will be explored the control method employed) will be inconvenient.29 The
to reduce the overall water consumption in the whole process. calculation of each of the metrics is detailed in the Supporting
As far as the authors are aware, these types of intensified Information.
processes have not been optimized, from the point of view of The optimal design of sustainable reactive distillation systems
sustainability indicators (framed within the concept of circular to purify lactic acid is a nonlinear and multivariable problem, and
economy), for lactic acid purification. The main contribution of the objective functions used as optimization criteria are
this work is to explore the possibility of using these complex, generally nonconvex with several local optimums. However,
intensified configurations at an industry level, in a framework of the task is complicated and is likely to fail to achieve
sustainability. These systems provide choices of special interest convergence. To solve this case study, a metaheuristic
for the separation of multicomponent mixtures because of their optimization method based on the theory of natural selection
potential energy savings and reduction in total annual costs.19 was applied. This evolutionary method employs the classical
Also, in this study, the advantages of those intensified differential evolution steps. However, its actions are improved
configurations are analyzed using economics, environmental, through the Tabu List (TL) concept. Initially, this hybrid
and inherent safety indexes as indicators of sustainability using a optimization algorithm was proposed because it30 improves the
stochastic optimization strategy and complementing the study computational efficiency of DE employing testing challenging
by analyzing the dynamic properties of the configurations to phase equilibrium calculations followed by parameter estimation
establish the ease of its operation at an industrial level. problems in dynamic systems known to have multiple minima.
Operationally, the hybrid algorithm is coded in Visual Basic.
2. OPTIMAL SUSTAINABLE PROCESS Through dynamic data exchange (DDE), the numerical method
Over the last five decades, with the development of process generates input vectors that are evaluated in the process model
systems engineering, chemical engineers have developed many (Aspen Plus). Then, the model evaluates the input vector and
methods and tools for reducing the environmental impact of generates output vectors. After that, the hybrid method analyzes
chemical processes. Today, the goal of such approaches is to not the input and output data and, according to the evolutionary
just reduce emissions from an individual manufacturing process nature of the algorithm, the process begins to iterate. The
but also ensure reduction in energy consumption, operating operational parameters for the stochastic method were 120
costs, maximize process safety, and generate operable processes. individuals, 900 generations, 50% of the number of individuals as
This goal of sustainable process systems engineering presents tabu list, 0.6 for the crossover, and a Taboo radius of 1 × 10−6.
formidable challenges due to the complex nature of the These parameters were obtained from a tuning process in
interacting factors, and sustainable process design solves large previous calculations.
multiobjective optimization problems due to the nonlinear The optimization of the sustainable schemes for the
nature and the presence of degrees of freedom in the purification of lactic acid will be restricted to purities (yi)
mathematical models that represent the processes to be required in the market for each product. The indexes described
designed.20 Furthermore, modification in the topology for the above are used as the objective function, subject to
same process can also modify sustainability indexes.21 Despite min(TAC, IR, Eco99)
the many definitions of the term sustainable, it is possible to
identify some basic requirements that need to be satisfied before subject to: yi ≥ xi (1)
making claims about sustainability. In particular, Jiménez-
González et al.22 propose clear mathematical strategies to In general, it might be difficult to determine which sequence is
evaluate those sustainability metrics. In this sense, sustainability optimal, in the overall notion of sustainability and green
can be viewed as a framework with targets to achieve economic, chemistry, when using a multiobjective optimization strategy. As
environmental, inherent safety indexes, and dynamic behavior, a result, the goal of this research is to give a more comprehensive
among others.21−27 This work tries to analyze different picture of the selection of the optimal design using a normalizing
topologies based on a modification of the conventional technique. The normalization of the goal functions (TAC, IR,
intensified design, for the reactive distillation process for lactic and CN) allows the optimal sequence for the ideas of
acid purification, and select the most promising ones according sustainability to be identified. In accordance with Koski,31 the
to sustainability metrics as proposed in the paper of Jiménez- goal functions should be normalized as follows:
González et al.22 Fi(x) − min Fi(x)
For this case study, the economic metric was measured fi (x) =
through the total annual cost (TAC) as suggested by Turton et max Fi(x) − min Fi(x)
al.23 In the case of environmental metrics, Eco-Indicator 99 i = objective functions, X ∈ NP (2)
(Eco-99) was used, which is based on the life cycle assessment
and the approach was proposed by Goedkoop and Spriensma.25 Details of the optimization technique and determination of
The security metric was calculated through the concept of the optimal solution can be found in the Supporting
individual risk (IR) index. The IR can be defined as the risk of Information.
injury or decease to a person in the vicinity of a hazard.28 The
main objective of this index is the estimation of likelihood 3. CASE STUDY
affectation caused by the specific incident that occurs with a Esterification and hydrolysis with methanol and oligomerization
certain frequency. Finally, controllability characteristics are reaction of the lactic acid can be performed using intensified
evaluated using the condition number as an index. Singular value alternatives, such as reactive distillation columns.
decomposition of the relative gain matrix of the assessed design The capabilities of using such technology were preliminarily
at a nominal point was used to get the condition number. In elucidated by Kim et al.13 Moreover, this case study fulfills all the
terms of controllability, a high condition number suggests that preliminary requirements to claim the complete feasibility of the
satisfying the complete set of control objectives (regardless of RD technology to purify lactic acid. For example, according to
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Shah et al.,32 before any synthesis or design task, it is necessary to are described in the following paragraph. Additionally, Table S3
determine the feasibility of any reactive distillation scheme. shows the binary interaction parameters for all chemical
Following their guidelines, the fulfillment of those requirements compounds.
in this case study must be highlighted: (1) the presence of more Using a separation scheme based solely on conventional
than one product, (2) there is a match between temperatures distillation columns is considered a base case. It is important to
required for reaction and separation (from a quite simple point note that the feed flow and the compositions were taken from
of view, this case study proposes the reaction near 50 °C and the Kim et al.13 to have a comparison with previously reported
boiling point for both reactants, CH3OH and C3H6O3, is 64 and results. Observe that the fermentation broth fed into the first
122 °C respectively), and (3) for none of the components, column (Table 1) is preconcentrated in column A (see Figure
neither the operating pressure nor the temperature are close to 2). Once the largest amount of water has been removed, before
the critical region. the azeotropic point, it is fed to a second column where an
The fulfillment of these three requirements in the industrial esterification reaction assisted by methanol is carried out (eq 3).
feasibility of reactive distillation for the purification of lactic acid Additionally, through the lower part of the column, high-purity
is demonstrated in the U.S. patent by Michael and Madison.14 succinic acid is obtained. The distillate flow feeds the third
The reaction performed in both columns can be represented column, where a hydrolysis process is carried out to form lactic
by the following reaction sequence: acid again (eqs 4 and 5). Finally, in the last distillation column,
the alcohol used in the esterification is purified to be recirculated
CH3CH(OH)COOH + CH3OH to the second column; the same happens with water.
lactic acid methanol
3.1. Synthesis of Intensified Alternatives. The method-
k f ,1
←
→ CH3CH(OH)COOCH3 + H 2O ology shown by Errico et al. is follows.34 The methodology
kr ,1 metillactate water (3) consists of four steps and assists in the determination of stripping
and rectification zones, thermal couplings, intensified sequences,
CH3CH(OH)COOH + CH3CH(OH)COOH and the location of side-streams.
lactic acid lactic acid
• Step 1. Identification of the reference configuration: The
k f ,2
←
→ C6H10O5 + H 2O first step is to define a reference configuration (as shown
kr ,2 dilactate water (4) in the middlebox of Figure 2).
k f ,3 • Step 2. Generation of modified thermally coupled
C6H10O5 + CH3CH(OH)COOH ←
→ C9H14O7 + H 2O configurations: The crucial part of the present stage is
kr ,3
dilactate lactic acid trilactate water to generate the modification of the reference config-
(5) uration by replacing the auxiliary equipment (reboiler/
Kinetic equations are represented in pseudohomogeneous condenser) with interconnection streams (liquid−vapor).
form and kinetic parameters are shown in Table S2. As shown in the first stage (Figure 2), such equipment is
From an operational point of view, a determining factor is the replaced by interconnection streams, leaving room for
dome temperature. If lactic acid is subjected to temperatures multiple options.
above 80 °C,13 there is a high probability that it will oligomerize. • Step 3. Identification of thermodynamically equivalent
In that sense, the operating pressure plays a fundamental role to configurations: It is important to consider ideal mixtures
avoid such a reaction and to carry out a successful separation. In as this will help generate thermodynamically equivalent
this work, it is assumed that the solid catalyst occupies 50% of configurations with the movement of column sections.
the tray holdup volume and that the density of the catalyst is 770 However, since it is an azeotropic mixture, it is not so
kg/m3, which was used to calculate the holdup volume. For simple. Figure 2 (third stage) shows such recombination
chemical systems with nonidealities and strong interactions of sections regarding the second stage. Several possible
between acids in the vapor phase, the UNIQUAC-HOC and configurations can be obtained by moving the individual
NRTL-HOC property models are sufficient. The UNIQUAC- sections simultaneously or independently.
HOC model was used to avoid introducing additional factors • Step 4. Construction of side-stream configurations: Now,
that might affect the comparison with previously published from the thermodynamically equivalent configurations, it
benchmark studies.13,33 For a representative broth obtained is possible to generate the new subspace of systems with
from a bioprocess producing lactic acid, the feeding conditions less than N − 1 columns. The methodology is
to the reactive distillation are displayed in Table 1. It is straightforward and consists of the elimination of side
columns, leaving only one column section. By eliminating
Table 1. Characterization Feed from Fermenter13 the single rectifying section employing a side-stream
% mol
(third stage), there are then produced the systems with
less than N − 1 columns. The connection between the
flow rate pressure temperature lactic succinic subspace with less than N − 1 columns and the
(kmol/h) (atm) (°C) acid water acid
corresponding single column sequences is demonstrated.
50 2 35 8.4 90.5 1.1
For a given thermodynamically equivalent structure, the
location of the side-stream will depend on the section
important to mention that this is a simplified case study to test removed and the final position of each zone.
the feasibility of these structures. In complex columns, it is In this specific case, the initial stage of the synthesis of this
possible to assemble new topologies and to know if it is possible intensified process was carried out by sequentially applying
to perform the esterification process in these columns. Note that, thermal couplings. Observe in Figure 2 that, from conventional
from the bioprocess, the mixture includes succinic acid and distillation columns, different intensified alternatives are
water. The retrofitted reactive distillation configurations studied obtained. In the first modification stage, a single thermal
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Figure 2. Intensification methodology applied to the base case.

coupling could be applied in the nonproduct stream (TC-C, (DWC-R). An important point to clarify is that although the
TC-R). Whereas in the second modification stage, the scheme base columns that are integrated to generate the DWC may have
TC-C is fully thermally coupled using a second thermal coupling different pressures, according to Ling and Luyben35 and Van
(DWC). Finally, based on the DWC scheme, a thermal coupling Duc Lon and Lee,15 pressure is chosen to be greater (between
is introduced again between the first and second columns the columns to be integrated) to guarantee that the system is
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Figure 3. Intensified alternative with mass water integration (TC-IM).

Figure 4. Generation of intensified alternatives with mass water integration DWC-A (A), DWC-B (B), and DWC-(C). All figures are presented in both
expanded and DWC form.

designed at the pressure that the most volatile component is water flows. As will be seen in the results section, these
distilled, and in this way, it is possible to maintain the energy configurations required different operating conditions, but,
savings in the DWC. thanks to processing synthesis work, it is possible to generate the
Several thermal couplings can be applied sequentially to alternatives presented in Figures 3−4. It is important to
generate a highly intensified separation scheme. On the other highlight that in the cases where the columns operate at
hand, enough water is probably produced in the esterification different pressures, the thermal coupling (recycles between the
reaction to avoid an additional stream, feeding water into the columns) can be carried out using pumps and/or compressors
third column. For example, note that in eqs 3−5, as a product of appropriately. According to Van Duc Long and Lee,15 carrying
the reactions themselves, a certain amount of water is generated. out this type of retrofit in the configurations, by using equipment
In other words, water is generated by the esterification reaction. to adapt the pressure differences in the columns, does not
This water can be sent immediately to the next hydrolysis substantially impact energy consumption and, therefore, the
reaction, and thus, it is possible to avoid consuming fresh water energy savings that characterize these configurations are not
through an external water stream. In this sense, it is possible to substantially affected.
generate additional alternatives that avoid the entry of an extra Note in Figure 3 the possibility of generating intensified
stream of water into the process. Note that the amount of water alternatives and eliminating a freshwater stream for the third
to be added in the conventional scheme is a degree of freedom to column for lactic acid generation. Furthermore, it is possible to
be considered in the optimization process to obtain the best generate more intensified alternatives by integrating the
results. On the other hand, the water generated from the rectification or depletion sections in the main body of the
esterification reaction and fed into the hydrolysis reaction is distillation column, as shown in the lower part of Figure 4. This
generated from the internal chemical reaction and equipment type of synthesis work has proven to be effective in separating
operating variables, so there may be a variation between the two alternatives with relatively good energy savings, according to the
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Figure 5. Pareto front valuating the TAC and the inherent safety.

work presented by Rong36 and many others.37,38 Environmental same way when a thermal coupling eliminates a condenser, as
pollution is a major concern nowadays because of the adverse when the reboiler is eliminated. Particularly in TAC calculation,
impacts it has raised in several aspects, such as human health, the thermal coupling between the first two columns generates a
weather, regional identity, food, security, biodiversity, and reduction of 11% compared to the conventional scheme. On the
economics. Research efforts using process integration strategies other hand, replacing the condenser between the last two
have addressed this concern. For instance, the rational use of columns generates a reduction of 17% (see Tables 2, 3, 4, and 5).
water in the process industry has been the subject of several The reduction in TAC is largely due to the percentage of energy
papers, in which the minimization of fresh water and wastewater saved. Although the reboiler duty of the first column was
in single process industries has been considered.39−41 For this eliminated in the TC-R scheme, there was a 76% increase in the
reason, the idea of minimizing the use of fresh water in the lactic reboiler duty of the second column compared to the
acid purification process by reusing water through mass conventional scheme. This increase took place since a single
integration is a challenge that is addressed through these reboiler heated both columns. On the other hand, in the TC-C
intensified novel designs. scheme, there was no substantial increase in the energy
requirements of the third column. In contrast, there was a
4. RESULTS 14% reduction in the reboiler duty of the last column. These
This section presents the main results obtained, as well as results speak of the high energy demand that is involved in
various trends that were observed in the optimization process. concentration (removal of water) in the first column.
The purity constraints were set as 90 wt % for lactic acid, 99.9 wt The behavior when the environmental impact is calculated is
% for succinic acid, and 99.9 wt % for both methanol and water relatively similar. With regard to inherent safety, the reboiler
for recycling. The relative low purity for lactic acid was set that duty in the first two columns appears to harm the probability of
way since it is commercially required in different qualities, for an accident, whereas in the TC-C scheme, it does not. With
the food industry (80%) and the pharmaceutical and plastic accordance to the model for individual risk calculation, the high
industry (90%).42−44 With regard to methanol, a minimum dependence on the amount of matter associated with each piece
purity of 99.7% was established to be considered as a recycle of equipment is clear. In this sense, the presence of thermal
stream to the esterification column. coupling in the first columns generates a large and continuous
Figures 5−7 show the results obtained after the optimization exchange of matter between columns. Consequently, there is a
process. At this stage, no substantial improvement was observed, slight increase in the inherent risk of the TC-R scheme with
so we assume that the optimal zone for the objective functions respect to the conventional scheme of around 1%.
evaluated was found. All results were obtained after 108,000 In the next stage of intensification, interesting things were
evaluations (120 individuals, 200 generations). Although three observed. Like in the first modification stage, the thermal
objective functions were considered simultaneously, the results coupling that replaces a reboiler to generate the DWC scheme
are presented in two-dimensional graphs for a better under- did not generate great economic savings. On the contrary, there
standing. was a slight increase in energy consumption and in the TAC
With regard to the first five alternatives, it is easy to see that values. Although due to the elimination of the reboiler a savings
the DWC-R possesses the lowest TAC and the lowest in capital cost was generated, it was not enough to generate
environmental load and is the second one in the inherent risk. savings in the TAC. In the same sense, the environmental load
On the other hand, a trend in the objective functions, according had a slight increase (3%) compared to the TC-C scheme. The
to the retrofit stages, can also be observed. It is evident that, in fact that there is an inlet and outlet stream of vapor/liquid in the
general, with thermal coupling as the first modification stage, it prefractionator reduces the net balance of matter present in the
generates a substantial improvement in almost all the indicators, prefractionator. Consequently, the individual risk decreases by
except IR. However, the improvement is not generated in the about 10%.
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 Table 2. Design Parameters of the Conventional TC-C and TC-R Schemes
conventional TC-C TC-R
columns C1 C2 C3 C4 C1 C2 C3 C4 C1 C2 C3 C4
stages 43 8 60 32 42 8 59 31 46 8 60 31
feed stage 23 4, 4 42, 42 14 24 5, 4 41, 46 17 15 4, 4 40, 34 23
side stage 16 46
reflux ratio 0.1 0.05 0.12 1.82 0.04 0.026 − 1.77 0.29 0.05 0.9
distillate flow (kmol/h) 40.4153 25.734 34.673 16.64 40.41 25.73 16.73 40.4 25.7 34.7 16.6
bottoms flow (kmol/h) 9.58 0.53 5.05 18.03 9.58 0.53 5.05 18.03 − 0.53 5.05 9.58
interconnection flow (kmol/h) 5.899 14.5858
diameter (m) 1.03 1 0.86 1.02 1.03 1 0.86 1.02 1.03 1 0.86 1.02
reactive stages 3 to 7 28 to 47 3 to 7 27 to 56 2 to 7 27 to 48
holdup (l) 29.14 97.062 28.9034124 91.6844112 30.5 96.6
pressure (atm) 0.1902 0.4599 0.211 0.37 0.12 0.37
reboiler duty (cal/s) 448115 338868 417337
succinic acid (% wt) 0.999 0.999 0.99
Industrial & Engineering Chemistry Research

lactic acid (% wt) 0.94 0.914 0.95

methanol (% wt) 0.999 0.995 0.99
TAC ($/y) 1274559 1062454 1134718
EI99 (Eco-points/y) 405025 302771 376834
IR (probability/y) 0.000818084 0.000818023 0.000823006

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Table 3. Design Parameters of the DWC and DWC-R Schemes

DWC DWC-R
columns C1 C2 C3 C4 C1 C2 C3 C4
stages 43 9 60 32 44 9 60 32
feed stage 20 5, 7 28, 52 7, 25 15 4, 4 40, 34 23
vapor interconnection flow (kg) 36.75 14.5858
input stage (vapor) 76 46
side stream (vapor) 25 5, 25 21
side stream (liquid) 6 6 6
side stream (water) 21 21 17
reflux ratio 0.1 0.05 1.8518 0.1 0.29 0.05 0.9
distillate flow (kmol/h) 40.4 25.7 16.65 40.4 25.7 34.7 16.6
bottoms flow (kmol/h) 9.58 0.53 − 5.04 − 0.53 − 5.08
diametro (m) 1.03 1 0.86 1.02 1.03 1 0.86 1.02
reactive stages 4 to 7 26 to 56 2 to 7 27 to 44
holdup (l) 42.37 90.07 30.5 96.6
pressure (atm) 0.194 0.569 1 1 0.12 0.37 1 1
reboiler duty (cal/s) 349927 338292
succinic acid (% wt) 0.999 0.99
lactic acid (% wt) 0.958 0.95
methanol (% wt) 0.999 0.99
TAC ($/y) 1086548 1062449
EI99 (Eco-points/y) 313189 303062
IR (probability/y) 0.000734825 0.000736675

Table 4. Design Parameters of the Thermally Coupled for the particular case of lactic acid purification, the thermal
Sequence with Water Integration couplings that replace reboilers do not generate a considerable
improvement compared to the thermal couplings that replace a
TC-IM
condenser. Additionally, replacing a reboiler with a thermal
columns C1 C2 C3 C4 coupling increases the risk associated with the separation
stages 43 9 76 26 process. It is also clear that any thermal coupling generates
feed stage 20 4, 4 − 7, 25 improvements compared to the conventional process, but not
vapor interconnection flow 36.75 between one stage and another in the modification process.
(kg) On the other hand, when looking at the values resulting from
input stage (vapor) 53 the optimization of the alternatives with water integration, only
interconnection flow 28.53 25 one alternative proved to be promising. The DWC-A alternative
(vapor kmol/h)
interconnection flow 2.8 6 presented better values in all the objective functions than the
(liquid kmol/h) alternatives designed only with thermal couplings.
side stream (water) 21 Then, the alternatives were based on a dividing wall. The
reflux ratio 0.1 − 2.095 DWC topology allows the integration of several walls in a single
distillate flow (kmol/h) 40.41 − 16.682 unit that reduces the capital cost and more competitive
bottoms flow (kmol/h) 9.58 0.53 − 4.873 alternatives can be generated, from the economic point of
diameter (m) 1.03 1 0.86 1.02 view. However, it should be considered that, in this work, the
reactive stages 4 to 7 26 to TAC is being evaluated as an economic indicator, which is
66 composed of the capital cost and the cost of services. It can be
holdup (l) 42.37 90.07 seen why the other alternatives presented in the form of a
pressure (atm) 0.19004 0.5331 1 1 dividing wall are not economically viable. That is, the costs
reboiler duty (cal/s) 387370 associated with utilities increase considerably, making these
succinic acid (% wt) 0.999
alternatives unfeasible.
lactic acid (% wt) 0.958
The increase in energy consumption of the alternatives could
methanol (% wt) 0.999
have been caused by some issues, for example, the topological
TAC ($/y) 1111585
complexity of the alternatives based on DWCs that simulta-
EI99 (Eco-points/y) 365591
neously perform a chemical reaction. Additionally, the
IR (probability/y) 0.000818369
elimination of the water stream made the reaction-separation
conditions more energetically strenuous for most of the
Finally, in the third modification stage, starting from the alternatives.
DWC scheme, the reboiler of the first two columns is eliminated As a result of the higher demand for energy requirements, the
through a thermal coupling to generate the DWC-R scheme. total annual cost and eco-indicator 99 markedly increased for
With observance of the performance indexes, there was no most of the dividing wall schemes.
economic savings or decrease in the environmental impact However, the inherent safety results showed a substantial
compared to the DWC scheme. On the contrary, there was an improvement. In accordance with the model presented in this
increased risk inherent in the separation scheme. It is clear that, work for the calculation of inherent safety and the cited
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Ind. Eng. Chem. Res. 2022, 61, 621−637
 Table 5. Design Parameters of the DWC Sequence with Water Integration
DWC-A DWC-B DWC-C
columns C1 wall A wall B main C1 wall A wall B main C1 wall A wall B main
stages 43 9 60 32 42 9 59 31 42 9 60 31
feed stage 23 4, 4 1, 52 20 24 4, 4 1, 52 16, 18 15 4, 4 1, 52, 60 20, 31
side stage 15 14
reflux ratio 0.085 − − 1.88 0.0805 − 1.596 1.872 − − 10.06
distillate flow (kmol/h) 40.4106 − − 16.66 40.4143 − 16.496 40.41 − − 16.506
bottoms flow (kmol/h) 9.5893 0.531 6.09 2.985 9.587 0.5319 − 4.239 − 0.528 − 4.22
interconnection flow (kmol/h) 28.637 2.899/59.654 40.008 28.535 2.89/23.61 14.5858 28.462 2.71/59.86/27.67 42.19/19.59
diameter (m) 1.017 1.16 1.008 1.02 1.017 1.07 1.0183 1.03 1.017 1.1088 1.014 1.08
reactive stages 3 to 7 28 to 47 3 to 7 27 to 47 2 to 7 27 to 48
holdup (l) 29.14 97.062 28.903 91.684 30.5 96.6
pressure (atm) 0.189 0.4599 1 1 0.181 0.37 1 1 0.18 0.37 1 1
reboiler duty (cal/s) 391938 536473 1447227
succinic acid (% wt) 0.999 0.999 0.99
Industrial & Engineering Chemistry Research

lactic acid (% wt) 0.939 0.914 0.95

methanol (% wt) 0.999 0.995 0.99
TAC ($/y) 1044799 1498392 2871129
EI99 (Eco-points/y) 356249 500695 963497
IR (probability/y) 0.000652447 0.000652398 0.000652398

630
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Article

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Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

Figure 6. Pareto front valuating the TAC and the eco indicator 99.

references, the number of equipment evaluated is a relevant the low reduction in energy requirements. Tables 2−5 show the
aspect, so that by reducing the number of equipment, there is a main design parameter for all purification alternatives. There is a
substantial improvement in this aspect. In general, the designs slight variation in the stages of each column by design. The
based on dividing wall columns showed an improvement in this explanation is due to the intimate relationship that the design
indicator. variables have. When generating thermal couplings, there is a
An overall comparison indicates that the DWC-A alternative notable change in the energy requirements. Consequently, the
showed an improvement in two indicators. It showed an lower energy consumption allows moving design variables,
improvement of approximately 4% in the economic indicator reflux ratio, or stages, for example, to minimize target functions.
and an improvement of approximately 13% in the safety index, In addition, the mass integration of a water flow generates more
compared to the best first-stage synthesis design. A considerable sustainable production alternatives for water consumption, a
penalty is observed in eco-indicator 99 due to the increase in highly precious commodity with vital functions.
energy requirements, however, this increase did not affect the The principle of selecting the operating pressure of any
economic indicator with the same magnitude due to the savings distillation column is one of the most important design
in capital cost. decisions. In the particular case of the conventional sequence,
In addition, all the alternatives based on the dividing wall the pressure has a great impact, since, as mentioned above, a
present a water savings of 252 kg/h, which represents an annual determining factor is the temperature in the column dome,
consumption of 2,143,819 kg of water. In accordance with the because if the lactic acid is subjected to temperatures above 80
World Health Organization (WHO), an average person needs °C, there is a high probability that it will oligomerize.13 The
approximately 36,000 kg of water per year to meet basic above-mentioned case is avoided by achieving vacuum
consumption and hygiene needs.45 Thus, making a direct pressures, which can be seen in Table 2 (lactic acid, water,
generalization with the mass integration of water in this process, and succinic acid have boiling points of 82 °C, 50 °C, and close
water savings can be generated so that 60 people can have their to 110 °C, respectively). As mentioned by Luyben,46 many
basic water consumption. separations benefit from allowing low temperatures; the
From a circular economy point of view, it is evident that a pressures in most columns are set by the desire to use cheap
single thermal coupling increases sustainability. Considering, for cooling water as a heat sink in the condenser. For components
example, TC-R and TC-C schemes, in comparison with the with low vapor pressures, this criterion results in pressures below
conventional scheme, the economic, environmental, and safety atmospheric. However, there seems to be some hesitation in
issues are improved. Although the flow of steam and liquid in the using vacuum distillation columns, especially in azeotropic
thermal couplings would seem to affect the esterification or separations. Luyben46 illustrates that there are operational and
hydrolysis reactions, the optimization process allows one to economic advantages to using vacuum distillation in some
know the appropriate placement and flows to avoid a decrease in systems. With regard to the behavior of the objective functions,
the performance and productivity of the reactive columns. note in Figure 5 the antagonistic relationship between TAC and
However, due to the nature of the mixture, there is a notable inherent safety. In other words, the lower the risk of accidents,
difference in the coupling. As mentioned before, the substitution the higher the TAC increase. This trend is largely due to
of a condenser by a thermal coupling decreases the energy operating variables and the nature of the mixture to be separated.
requirements and, as a consequence, the economic and For example, a decrease in the risk of the process has been
environmental impact. Otherwise, the substitution of a reboiler observed with an increase in the reflux ratio. As a consequence,
by a thermal coupling does not contribute to those circular there is a direct increase in energy requirements and, obviously,
economy indexes. Contrarily, due to the intensive energy in the TAC.
requirements, inherent safety is compromised. Regarding TAC In the same way, an antagonistic behavior is observed in
and EI99, the reduction in capital cost tries to compensate for Figure 6 in the TAC and EI99. Remember that the EI99
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Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

Figure 7. Pareto front evaluating the inherent safety and the eco indicator 99.

evaluation considered the impact of the heating steam, the steel Finally, the control study resulted in very interesting trends.
to build the column, and the electricity for pumping, with the The minimized condition number is connected to stability
main weight of the heating steam. In this sense, the Pareto front aspects. Therefore, it is possible to qualitatively interpret the
indicates that the optimum zone can be found where the values of the condition number, beyond its numerical value. In
contribution of the three categories can remain relatively stable. such a way that lower values is connected to stability aspects and
However, if you leave that area, either due to energy, steel, or in that sense to a good dynamic behavior.48 Preliminarily, the
electricity consumption, the TAC increases considerably. dynamic properties of the conventional alternatives are relatively
Finally, Figure 7 shows the relationship between the poor, compared to the schemes with a higher degree of
environmental impact (EI99) and the individual risk of the intensification. That is, the alternatives with higher topological
process (IR). In a similar situation to Figure 6, one way to reduce simplicity would have more problems to be controlled under
the environmental impact is by reducing the energy require- closed-loop analysis.
ment. This change is largely associated with designing Within the alternatives where the freshwater stream is not
equipment with low reflux ratios. In the particular case of omitted, there is a very clear trend in the presence of thermal
organic compounds diluted in water, designing with low reflux couplings. It is clear that the higher the number of couplings, the
ratios results in higher internal concentrations of the organic better the control properties. However, it should be noted that
compounds. On the other hand, high reflux ratios are an not all thermal couplings improve this indicator in general.
indication of a greater amount of water that can return to the
Observing the topological differences between the different
interior of the column, generating lower concentrations of the
alternatives without mass integration, it should be noted that the
organic compounds. This type of relationship between design
thermal coupling between the first two columns has the greatest
variables and objective functions generates antagonistic
impact on the dynamic properties of the alternatives.
behavior. One point to highlight in the optimized designs is
On the other hand, a comparison between the alternatives
that the water separated in the first column can be used in the
hydrolysis column, and the recovered methanol can be recycled with and without integration of the water current indicates that,
to the esterification column. This is a very important point since for the great majority of alternatives, this movement has a
water has to be removed and its removal is energy intensive. penalty on the dynamic properties. However, as in the case of the
Additionally, the reuse of methanol and water, recovered during alternatives without mass integration, the DWC-C scheme with
the process, allows generating an environment of sustainability the highest degree of energy integration resulted in the best
and economic profitability, which makes intensified designs very control properties. Even better than the alternatives with the
attractive to be applied at an industrial level. This is due to the presence of the freshwater current.
reduction in the use of fresh water and raw material (methanol) In this sense, although the DWC-A alternative turned out to
for the process. This class of mass integrations between be the most economically and environmentally viable of all the
recovered flow streams generates important economic and alternatives presented in that work, its typological structure
energy savings in the intensified processes.47 Finally, considering would hinder the controllability of this alternative. On the other
the DWC and DWC-A schemes as a good alternative, Figures 8, hand, the least viable alternative, in terms of economic and
9, 10, and 11 show the composition and temperature profiles, as environmental impact, turned out to be the one that would be
well as the complete balance for the reference case and the the least difficult to control in a closed-loop test. Table 6 shows a
DWC-A scheme, and additionally, Table S4 shows data about summary of the objective functions of the separation alternatives
composition, temperature, and pressure in DWC-A. analyzed.
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Figure 8. Composition and temperature profiles for the conventional scheme, columns A−D.

5. CONCLUSIONS contrary, a slight increase in the risk of the schemes with this
An analysis of various lactic acid separation and purification topology was observed. On the other hand, the coupling that
schemes was performed in this work. It was observed that the replaced a condenser did cause a general improvement in the
substitution of reboilers for thermal couplings does not reduce performance indicators. The same indexes are slightly
the environmental or economic impact significantly; on the compromised when a reboiler is substituted by a thermal
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Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

Figure 9. Composition and temperature profiles for the DWC-A scheme, columns A−D.

coupling. Once all the separation schemes had been evaluated, directly in capital cost and the impact of steel index in EI99.
the scheme that showed the best performance was the DWC-A. However, note that the IR values depend greatly on the amount
This scheme represented an approximate saving of 4% and 12%
in the TAC and IR, respectively. An interesting trend was of matter inside the equipment, which is related to column size;
observed regarding equipment sizing; bigger equipment impacts as long as the inner matter increases, the IR increases.
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Figure 10. Mass balance for the conventional scheme, columns A−D.

Figure 11. Mass balance for the DWC-A, columns A−D.

Table 6. Objective Functions of All the Alternatives Evaluated

reboiler duty (cal/s) TAC ($/y) EI99 (Eco-points/y) IR (probability/y) condition number
conventional 448115 1274559 405025 0.000818084 8.24 × 1024
TC-C 338868 1062454 302771 0.000818023
TC-R 417337 1134718 376834 0.000823006 9039.28
DWC 349927 1086548 313189 0.000734825 13654.40
DWC-R 338292 1062449 303062 0.000736675 7887.27
TC-IM 387370 1111585 365591 0.000818369 8.21E24
DWC-A 391938 1044799 356249 0.000652447 3.2 × 1018
DWC-B 536473 1498392 500695 0.000652398 2800423.9
DWC-C 1447227 2871129 963497 0.000652398 54.186

The comparison between alternatives with and without mass alternatives with greater topological simplicity do not have the
integration was favorable, from an economic and environmental best control properties, and it is possible to generate better
point of view, for the alternatives with integration. The DWC-A controllability in schemes with mass integration, but this
scheme had less impact in these areas. However, a basic controllability is associated with a higher cost and environmental
controllability study indicated some important points: the impact.
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As a product of the esterification reaction, water is inevitably Enrique Cossío-Vargas − Cuerpo Académico de Ingeniería en
produced in the esterification reaction. On the other hand, this Agrotecnología, Universidad Politécnica del Bicentenario,
water can be used directly in the next column section where the 36283 Guanajuato, México
hydrolysis reaction is developed. In that sense, the proposals Complete contact information is available at:
generated in this work demonstrate that it is possible to couple https://pubs.acs.org/10.1021/acs.iecr.1c04050
the direct production of water in this pair of columns. Evidently,
there is a stream where water is produced in a considerable Notes
amount in the last column section. It is likely that the stream The authors declare no competing financial interest.

■
arising at the bottom of the fourth column can be redirected to
direct use for the hydrolysis reaction. However, there is no
ACKNOWLEDGMENTS
evidence at this time on the impact that this recirculation of
water could have. The operation seems feasible; however, there The authors acknowledge CONACyT (Mexico).
are quite a few unknowns that arise from this possible
implementation, such as how would it affect the controllability
of the process, would there be a significant improvement in
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