These are not the final page numbers!

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Research Article 1

Amit K. Chandra1
Eco-efficient Separation of Mono- and
Iulian Patras˛cu2
Costin Sorin Bı̂ldea2 Dichloroacetic Acid by Thermally Coupled
Anton A. Kiss1,*
Extractive Distillation
Due to its high reactivity, monochloroacetic acid (MCA) is an essential intermedi-
ate used in the manufacturing of a wide variety of chemicals. Its industrial pro-
duction process is highly energy- and capital-intensive, requiring costly purifica-
tion steps to remove dichloroacetic acid (DCA) impurities. Here, an innovative
eco-efficient process for MCA-DCA separation is proposed based on extractive
distillation in a fully thermally coupled system (a dividing-wall column (DWC) or
an equivalent side-rectifier configuration) using a new effective solvent: diethylene
glycol dipentylether. The design was optimized by performing sensitivity analyses
and varying key operating and design parameters. The study proves that separat-
ing MCA-DCA by an extractive DWC (or thermally coupled) is feasible, efficient,
controllable, economic, and sustainable.

Keywords: Chloroacetic acids, Extractive dividing-wall columns, Industrial separation,

This is an open access article under
the terms of the Creative Commons Process control, Process design
Attribution License, which permits
use, distribution and reproduction Received: May 16, 2020; revised: August 18, 2020; accepted: September 21, 2020
in any medium, provided the
original work is properly cited. DOI: 10.1002/ceat.202000232

1 Introduction chloride to dichloroacetyl chloride, which undergoes chlorine

In the quest for a more sustainable future, the chemical process
industry has embarked on making major changes to improve
the energy efficiency and to reduce its carbon footprint, while
remaining competitive and cost-effective in producing a range
of essential chemicals.
Monochloroacetic acid (MCA) is an essential intermediate
that is used for the manufacturing of a wide range of chemical
compounds. The ease of substitution of the chlorine atom and
the reactivity of the carboxylic group make MCA an excellent
chemical intermediate. Around 30–40 % of the MCA produced
is used for manufacturing carboxymethyl cellulose (CMC; used
in the paper, oil and gas, food and beverages industries) and
pharmaceuticals [1]. MCA is used in the agrochemical industry
to manufacture herbicides, and it also finds many applications
in the cosmetic and textile industry [2]. The MCA market is
expected to increase to around 1000 kt a–1 by 2020.
The high reactivity of MCA is the main reason that MCA is
not found naturally and has to be synthesized. The most popu-
lar industrial route to MCA manufacturing is by chlorination
of acetic acid using acetyl chloride as homogeneous catalyst
[1, 3]. Green acetic acid could be used as raw material, such as
obtained in biorefineries (by fermentation or via the syngas
platform) using intensified processes [4–6].
A simplified flow sheet for the industrial production of
MCA is presented in Fig. 1. The drawback of this production
method is that it forms 3–5 wt % of undesired by-product –
dichloroacetic acid (DCA) – by overchlorination of acetic acid.
DCA is actually formed mainly via the chlorination of acetyl
exchange with MCA [7]. Due to the carcinogenicity of DCA
and its inhibiting effects in CMC production, the maximum
allowable limit of DCA in the MCA product is only 50 ppm
[8, 9]. For this reason, the chlorinator effluent stream has to be
further processed by hydrogenation of DCA to MCA, where
some of the MCA is also converted to acetic acid. The final
MCA purification is achieved by crystallization, where addi-
tional MCA is lost with the mother liquor containing 30 wt %
MCA [8, 9]. Therefore, the selection and design of a superior
fluid separation process is of utmost importance [10].
Due to the rather low relative volatility (about 1.05–1.3,
depending on the mixture composition), the separation of
MCA-DCA by conventional distillation is highly energy-inten-
sive and, hence, not economically feasible [11]. However,
extractive distillation (ED) is a promising alternative and it is
often applied industrially to separate close-boiling components
[12–16]. In case of the MCA-DCA separation, complexation
agents, such as ethers, ketones, and phosphine oxides (along
with the benchmark extractant, sulfolane), are the only extract-
ants that proved to be thermally and chemically stable in a
–
1
Amit K. Chandra, Prof. Anton A. Kiss
tonykiss@gmail.com, tony.kiss@manchester.ac.uk
Department of Chemical Engineering and Analytical Science, The
University of Manchester, Sackville Street, Manchester M13 9PL, UK.
2
Dr. Iulian Patras˛cu, Prof. Costin Sorin Bı̂ldea
University ‘‘Politehnica’’ of Bucharest, Polizu 1–7, 011061 Bucharest,
Romania.

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 These are not the final page numbers! ((
Research Article 2

HCl HCl

MCA 95 wt. % Acec Acid MCA

(recycled back to feed)
DCA 5 wt. % (DCA conc. < 50 ppm)

Chlorinaon
Reactor
Mother Liquor
(containing 30 wt. % of MCA)
Chlorine Centrifuge
Hydrogen
MCA + DCA
Hydrogenaon (DCA conc. < 1000 ppm)
Acec Acid Reactor
Disllaon Column

Crystallizer
Figure 1. Simplified process flow diagram of an industrial process for MCA manufacturing.

strongly acidic environment (Tab. 1) [17]. Jongmans et al. [18]
concluded that glymes, e.g., diethylene glycol dipentyl ether
(DGDP), are actually the most promising extractants when
considering their relative volatility, regeneration ability, and
stability. Using glymes as extractants can significantly increase
the relative volatility of MCA-DCA up to 2.1–2.4 at a DCA/
extractant molar ratio of 1. A conventional ED process was
suggested (as illustrated in Fig. 2a), but actually no follow-up
research paper has been published after the study on the
extractants [18]. In addition to ED, even better alternatives
should be possible based on thermally coupled distillation [19]
(shown in Fig. 2b), which could be implemented in practice
using dividing-wall column (DWC) technology [19–23] which
proved effective in bioethanol dehydration [24–26] or bio-
butanol separation [27].
The novelty of this paper consists in a novel integrated pro-
cess (including the techno-economic and environmental analy-
sis as well as the process dynamics and control) for MCA-DCA
separation based on ED in a DWC or thermally coupled col-
umns (an equivalent configuration of DWC using a column

Table 1. Various solvents and their effect on the relative volatility at a solvent/DCA molar ratio of 1.a)

No. Solvent Abbreviation Normal boiling point [K] Relative volatility [–] Classification

1 Tri-n-hexylamine THA 534.7 2.47 Strong complexing agents

2 Tri-n-octylphosphine oxide TOPO 474 2.79

3 18-Crown-6 18C6 711 2.47

4 Dibenzylether DBE 571 1.65 Weak complexing agents

5 Diphenylether DPE 531 1.44

6 Sulfolane SF 560.3 1.59

7 Succinonitrile SN 539 1.39

8 Tetraethyleneglycol dimethylether TGDE 548.3 2.44 Moderate complexing agents

9 Diethylene glycol dipentylether DGDP 555.3 2.34

10 Diethylene glycol dibutylether DGDB 529 2.29

11 n,n-Diethyl-m-toluamide DEET 433 2.28

12 Dihexylether DHE 499 1.96

13 Dihexylketone DHK 534 1.85

14 Tri-n-butylphosphate TBP 562 2.23

a)
Based on data from [11].

Chem. Eng. Technol. 2020, 43, No. 00, 1–16 ª 2020 The Authors. Published by Wiley-VCH GmbH www.cet-journal.com
 These are not the final page numbers! ((
Research Article 3

a) b)

MCA
SOLVENT DCA
SOLVENT MCA
DCA
DCA/ Thermally
Solvent Coupled Side
Solvent Recfier
FEED Recovery
Extracve
MCA/DCA Column
Disllaon Main
Column FEED Column
MCA/DCA P-41

Solvent (recycle) Solvent (recycle)

Figure 2. (a) Conventional two-column ED system and (b) thermally coupled configuration implementable as an E-DWC for MCA-DCA
separation.

coupled with a side-rectifier) employing DGDP as solvent. The
results included here cover the process design, dynamics and
control, sensitivity analysis as well as process economics and
carbon footprint calculations. The novel separation process
was rigorously simulated in Aspen Plus and Dynamics, for a
processing capacity of 8750 kg h–1 (70 kt a–1) MCA.
2 Problem Statement
In industrial processes for MCA production, the concentra-
tion of undesired DCA by-product is usually reduced by re-
converting it into MCA by a hydrogenation process, such
that a DCA impurity level of ~300–1000 ppm is obtained
[18]. However, the hydrogenator also converts some of the
MCA back into acetic acid, thus requiring an additional step
to separate the acetic acid from MCA. Melt crystallization is
currently applied as a final polishing step to obtain a DCA
impurity level lower than 50 ppm [1]. The disadvantage of
melt crystallization is the high MCA loss via the mother
liquor [8, 9]. Instead of feeding the MCA-DCA mixture from
the chlorination reactor to a hydrogenation process, it would
be much more efficient to perform first a sharp DCA-MCA
separation. This would avoid converting MCA into acetic
acid during hydrogenation and would allow obtaining high-
purity MCA without using melt crystallization. Also, if only
DCA is fed to the hydrogenator, the required reactor volume
can be much smaller. A major efficiency improvement is pos-
sible by avoiding one distillation and the melt crystallization
steps, and by reducing the hydrogenator size. Thus, there is
a clear incentive for an alternative method to effectively sepa-
rate DCA from MCA.
To solve this important industrial problem, this study pro-
poses a novel ED process for the separation of MCA-DCA
(highly acidic and corrosive mixture), using DGDP as one of
the most suitable experimentally proven solvents [18]. A sin-
gle-step separation should be feasible by using either a DWC
or a column with a side-rectifier.
3 Process Simulation Approach
This section provides information about the physical property
model used as well as the simulation approach used for the
process design, dynamics and control, process improvement,
economics, and carbon footprint calculations. The present
work includes the following steps:
– Implementation of a suitable thermodynamic model, vali-
dated by experimental data
– Conceptual design of two processes employing conventional
ED-solvent recovery columns (EDC (extractive distillation
column)-SRC (solvent recovery column)) and an extractive
DWC (E-DWC)
– Sensitivity analysis of the simulated designs (base case and
improvement)
– Process comparison in terms of key performance parameters
(economics and sustainability)
– Dynamics and control of the E-DWC process.
3.1 Physical Properties
To develop the conceptual design and perform rigorous simula-
tions, it is essential to have the right physical properties of the
pure components (MCA, DCA, DGDP) as well as the vapor-
liquid equilibrium (VLE) data of the binary systems of MCA-
DCA, MCA-DGDP, and DCA-DGDP. The experimental vapor
pressure data for the pure components and VLE data for each
binary system were obtained from the literature [28, 29]. The
extended Antoine equation parameters are available in the
Aspen Properties Pure32 databank (v8.8). The non-random
two-liquid (NRTL) activity coefficient model can be used to

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Research Article 4

describe the properties of non-ideal systems, such as MCA- Table 3. Properties of pure components used for the Hayden-
DCA-DGDP, as reported previously [28]. The VLE can be O’Connell model and Wagner equation [11].
modeled by using the chemical association theory for the vapor
phase (namely, the Hayden-O’Connell (HOC) model) com- Property MCA DCA DGDP
bined with activity description for the liquid phase (NRTL- MW [kg kmol ] –1
94.5 128.9 246.39
HOC), in order to account for the dimerization of carboxylic
acids in the vapor phase. The Hayden-O’Connell, the Nothna- Tb [K] 189.4 194 293.25
gel, or the Marek-Standart correction should be used as appro- Tc [K] 686 686 719.1
priate, to account for the non-ideality of the vapor phase [30].
The chemical bonding term in the NRTL-HOC model depends Pc [kPa] 5780 5170 1408.4
on the association parameter, set to 4.5 for acid dimerization 3
Vc [m kmol ] –1
0.221 0.265 0.866
[28]. The solvent DGDP is an ether that does not form hetero-
Zc 0.224 0.240 0.204
or homodimers with carboxylic acids in the vapor phase;
hence, the parameter for ether-ether or ether-acid association w 0.546 0.555 0.640
was set to zero.
R [Å] 3.157 3.780 6.449
Tabs. 2 and 3 provide detailed information about the physi-
cal properties of the components used in the simulations, and m [Debye] 2.308 1.090 1.550
the binary interaction parameters that were obtained by regres-
sion of experimental VLE data for the binary systems MCA-
DCA, MCA-DGDP, and DCA-DGDP [11, 28]. Fig. 3 illustrates 3.2 Setting up the Process Simulations
the vapor pressure data for MCA, DCA, and DGDP. Note that
the mixtures are not very sensitive to changes in pressure, The conventional ED system using two columns (extractive
except for MCA-DCA which has closer boiling points at lower column and SRC) was developed using Aspen Plus v8.8. The
pressures. Reducing the pressure is a requirement to avoid configuration of the two columns (ED + SRC) is shown in
thermal degradation in a boiling system, but this makes the Fig. 5. Both the reflux and distillate streams are subcooled.
separation even more challenging due to the reduced relative Fig. 7 shows an alternative ED process taking place in a fully
volatility between MCA-DCA. thermally coupled column with a side-rectifier, which is the
equivalent configuration of an E-DWC. Being thermodynami-
120000 cally equivalent to fully thermally coupled columns, a DWC
Experimental
Simulaon can be considered as a single-shell realization of fully thermally
100000 coupled columns (such as Petlyuk systems) [19, 22, 23]. In this
Vapour pressure [Pa]

case, only the reflux is subcooled, leading to a small difference

80000
in the condenser duty (0.2 MW). The initial estimates of the
60000
design and operating parameters for the conventional ED pro-
cess are based on a report where the basics of a conventional
MCA ED system were described [11]. Note that MCA and DCA
40000
components tend to decompose at temperatures higher than
DCA DGDP
20000 453 K [1]. Hence, the maximum operating temperature is re-
stricted to below 448 K and, correspondingly, the operating
0 pressure is fixed at 4.5 kPa. Note that using packed columns
370 390 410 430 450 470 490 510 530 ensures a small pressure drop between the bottom (reboiler)
Temperature [K] and the top (condenser) of the distillation columns.
Figure 3. Vapor pressure data for MCA, DCA, and DGDP (experi- Sensitivity analysis was performed, and the process condi-
mental data from [28]). tions were optimized by minimizing the total annual cost
(TAC) as the objective function (according to standard indus-
Fig. 4 shows the residue curve map of the ternary mixture trial practices):
MCA-DCA-DGDP and the T-xy diagram for the binary mix- CAPEX
ture DCA-DGDP (both of them at 5 kPa). No azeotropes are TAC ¼ OPEX þ (1)
Payback period
present in the system.

Table 2. Binary NRTL interaction parameters for the system MCA + DCA + DGDP [28].

System a12 a21 b12 b21 a12

MCA(1) + DCA(2) –1.536 1.188 623.668 –396.683 0.3

MCA(1) + DGDP(2) 0.316 5.677 –571.568 –2005.537 0.614

DCA(1) + DGDP(2) 6.441 1.652 –3146.591 –1304.112 0.473

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Research Article 5

a) DCA 1593.7 (value at the end of 2017). The cost of the heat exchang-
ers is given by:
0.1 0.9


0.2 0.8 CHEX ðUS $Þ ¼ ðM&S=280Þ 474:7A0:65


0.3 0.7 · 2:29 þ Fm Fd þ Fp (2)
0.4 0.6

0.5 0.5
where A is the area (m2), Fm = 3.75 is the material factor (glass-
lined steel (GLS)), Fd = 1 (fixed tube), Fp = 0 (less than 20 bar).
0.6 0.4
The heat transfer coefficient used to calculate the heat
0.7 0.3 transfer area was U = 0.85 kW m–2K–1 for the reboiler and
0.8 0.2 U = 0.57 kW m–2K–1 for other heat exchangers. The design fac-
0.9 0.1
tor was taken as Fd = 1.35 for the reboilers and heat exchang-
ers. The cost of the column shells is calculated as follows:
DGDP 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 MCA

Cshell ðUS $Þ ¼ ðM&S=280Þ 957:9D1:066 H 0:82 ð2:18 þ Fc Þ (3)

b) 460
Exp. data where the following correction factor is considered:
Regression NRTL
450 Pressure = 5 kPa
Fc ¼ Fm Fp (4)
440
Temperature [K]

430 where the material factor is Fm = 3.67 (glass-lined steel), and

420 the pressure (vacuum) factor is:
410
Fp ¼ 1 þ 0:0074ðP  3:48Þ þ 0:00023ðP  3:48Þ2 (5)
400
390 The diameters (D) of the distillation columns were obtained
by the packing sizing utility from Aspen Plus and the column
380
0 0.2 0.4 0.6 0.8 1 height was calculated using the height equivalent to a theoreti-
cal plate (HETP) from the vendor data. The corresponding
Mole fracon DCA - DGDP
HETP value for the MellaCarbon 250Y packing was calculated
Figure 4. (a) Residue curve map for the ternary mixture MCA- using the flooding velocity, to which additional heights were
DCA-DGDP and (b) T-xy diagram for the DCA-DGDP binary mix- added (vapor disengagement 1 m, feed distribution 0.5 m, side
ture. draw and liquid return 0.5 m, liquid holdup 1 m):

Several design parameters (MCA-DCA feed location, DGDP H ðin mÞ ¼ NTS · HETP þ 3 (6)
solvent feed location, number of stages in the main column,
side-draw stage, number of stages in the side-rectifier, number The cost of the Sulzer MellaCarbon structured packing was
of stages in the stripping section of the main column) and estimated to be 7000 $ m–3. The heating and cooling costs con-
operating parameters (reflux ratio in the main column and sidered here are: steam (11 bar, 457 K, 11.03 $ GJ–1), cooling
side-rectifier, side-draw rate, DCA impurity specification in the water (293 K, 0.89 $ GJ–1), and chilled water (278 K, 1.92 $ GJ–1).
solvent recovered, flow rate of the solvent, solvent temperature, Note that a vacuum pump was also considered in the process
feed temperature) were varied. evaluation. For the extractive section, the cost of the vacuum
was estimated at 15 536 $, and for the side-rectifier section, the
cost of the vacuum pump was estimated at 22 393 $.
3.3 Economic Evaluation

MCA is highly corrosive, and most metals cannot be used for 3.4 Carbon Footprint Calculation
MCA service. Ceramic, glass-lined, or lead-coated vessels or
pipelines are generally preferred, and graphite reboilers must For a quantitative estimate of potential reduction, the green-
be used, with a maximum operability limit in the range of house gas (GHG) emission of all processes was evaluated using
453–473 K [1]. Glass-lined carbon steel for distillation the carbon footprinting tool, CCaLC2, developed at the Univer-
columns, graphite exchangers, and corrosion-resistant Sulzer sity of Manchester [32], which proved to be a powerful tool for
MellaCarbon 250Y structured packing were chosen as suitable managing and reducing the carbon footprints of products, pro-
material for construction. cesses, or supply chains. CCaLC2 enables quick and easy estima-
The total investment costs (CAPEX) include the heat tions of the life cycle GHG emissions along the whole supply
exchangers and distillation columns. A payback period of chains, as it comes with comprehensive databases, including the
3 years is used, with 8400 h a–1 operating time. The cost of the ecoinvent database (www.ecoinvent.org). The methodological
equipment can be estimated using cost correlations [21] and approach follows the internationally accepted life cycle method-
considering a Marshall & Swift equipment cost index (M&S) of ology as defined by the standards ISO 14044 and PAS 2050.

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Research Article 6

QC = 2.78 MW Reflux Drum QC = 1.24 MW

Height = 1.99 m
Diam = 0.99 m
1 MCA 1
MCA-DCA DCA
8312.6 kg/h
(from chlorinaon) 388 K, 4.5 kPa 378.3 K, 4.5 kPa
437.4 kg/h
8750 kg/h 5 sub-cooled: 323 K DCA-DGDP 381.3 K, 4.5 kPa
DGDP 5 sub-cooled: 298 K
373 K, 4.5 kPa MCA: 99.99 %wt 6932.3 kg/h
MCA: 95.0 %wt EDC DCA: 41 ppm 445.4 K, 4.5 kPa MCA: 576 ppm
DCA: 5.0 %wt MCA: 0.05 %wt DCA: 99.99 %wt
378.5 K, 4.5 kPa
HEX 18 DCA: 6.27 %wt Reflux Drum
MCA-DCA DGDP: 93.68 %wt Height = 1.22 m
DGDP QHEX = 0.25 MW Diam = 0.614 m
0.1 kg/h A = 12.2 m2 SRC
298 K, 4.5 kPa 32
LMTD = 31.9 K EDC
DGDP: 100 %wt SRC
RR= 0.75 RR= 18
Purge QR = 2.55 MW Diam = 2.42 m
Mixer Reboiler / sump: Height = 24.26 m
Height = 1.93 m Pack vol. = 20.62 m3
Diam = 0.965 m QR = 1.28 MW
447.6 K, 4.5 kPa Secon 1 (NT = 2…17)
Diam = 2.16 m 70
Height = 6.62 m
Pack vol. = 3.86 m3 DGDP
Secon 2 (NT = 18…31) 6494.9 kg/h
Diam = 3.01 m 447.6 K, 4.5 kPa
DCA: 106 ppm
Height = 5.48 m
DGDP: 99.99 %wt
Pack vol. = 6.58 m3

Figure 5. Process flow sheet and key design and operating parameters for a conventional ED system for MCA-DCA separation (both the
reflux and distillate streams are sub-cooled). HEX, heat exchanger.

The materials considered were chloroacetic acid for the
MCA separation, while for the GLS equipment, an equivalent
of stainless steel was considered (which does not suffer degra-
dation over time, can be recycled and reused and also helps to
prolong the lifetimes of applications). The solvent (DGDP)
used in this work is not defined in the available databank of
CCaLC2; hence, a similar component (ethylene glycol diethyl
ether (EGDE)) was used instead. Note that DGDP is structural-
ly similar to EGDE, both belonging to the family of glycol
ethers and having very similar physical properties. As practi-
cally all the solvent used is recovered and then recycled, this
approximation does not affect the accuracy of the calculations.
Steam generated from combustion of natural gas was chosen as
the heating utility to meet the energy demand.
4 Results and Discussion
This section provides results related to a classic extractive pro-
cess and the new thermally coupled ED alternative (equivalent
to an E-DWC), with a focus on the latter and covering key
aspects such as: process design, dynamics and process control,
sensitivity analysis, and process comparison in terms of eco-
nomics and carbon footprint indicators.
The simulations consider a feed flow rate of 8750 kg h–1
(equivalent to 70 kt a–1), with a composition of 95 wt % MCA
and 5 wt % DCA. The best solvent-to-feed ratio was found to
be 0.75; hence, the flow rate of DGDP is 6562.5 kg h–1. The
specifications related to the product purities include: < 50 ppm
DCA and < 1 ppm DGDP in the main MCA product stream;
< 1000 ppm MCA and < 1 ppm DGDP in the DCA by-product
stream; and < 30 ppm DCA in the DGDP solvent that is re-
cycled in the ED process.
4.1 Extractive Distillation Process
The conventional ED system uses a sequence of two columns:
an ED column (EDC; where MCA is separated as distillate and
a mixture of DCA-DGDP as bottom product) and an SRC
(where DCA is removed as distillate and the DGDP solvent is
recovered as bottom product and recycled). Fig. 5 illustrates the
process flow sheet, the mass and energy balance, and the key
design and operating parameters for the conventional ED pro-
cess. The hot solvent recycle stream is used to preheat the feed
to 378.5 K. The log mean temperature difference (LMTD) of
the heat exchanger is 31.89 K. The feed could be heated to a
higher temperature, but (for the same reflux) the concentration
of DCA in the distillate increases, thereby risking an excess of
the 50-ppm limit specification. The total heating requirement
for this process was calculated to be 3.83 MW.
Fig. 6 provides the results of the sensitivity analysis, focusing
on the effects of various parameters, e.g., the number of stages
and the feed stage, on the composition of the product streams.
To not contaminate the bottom product of the SRC with DCA,
as shown Fig. 6a, the total number of stages required in the

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Research Article 7

a) 800 The data available from the conventional ED process was used
DCA in booms as initial estimates for the proposed side-rectifier column, and
700
DGDP in disllate the values of the operating and design parameters, i.e., side
Impurity (ppm)

600 draw rate, number of stages, and reflux ratio, were found by
500 performing sensitivity studies. After initially setting the side
draw rate (vapor flow rate from the extractive distillation col-
400
umn (EDC) to the solvent recovery system (SRS); Fig. 7) equal
300 to the vapor flow rate of the conventional SRC (Fig. 5), the
200 effect of changing this parameter was investigated. Thus, it was
found that increasing the side-draw rate removes the DCA
100
impurity from the main column, but at the cost of increased
0 reboiler duty. As a result, the side-draw flow rate was fixed to
60 65 70 75 80 27 kmol h–1, a value that is sufficient to achieve the product
NT in the convenonal SRC specifications and beyond which no significant improvement
in DCA distillate purity was obtained.
b) 750 0.99862
Likewise, the number of stages (NTS) and the reflux ratio

DCA mass fracon in disllate

650 0.9986 (RR) were initially set at the same values as in the SRC from
the conventional process. Sensitivity studies showed that more
Impurity (ppm)

550
450
350
DGDP in disllate (ppm)
250 DCA in booms (ppm)
DCA mass fracon in disllate
150
50
3 4 5 6 7 8
NF of convenonal SRC
Figure 6. Sensitivity analysis results: (a) effects of the number of
stages and (b) the solvent feed stage on the composition of the
product streams. NT, number of trays; NF, feed stage number.
SRC is 70. Increasing the number of stages in the SRC lowers
the DCA and DGDP impurity levels in the bottom and distil-
late streams, respectively, but against an increased capital
expenditure. The number of stages was fixed at 70 as the
impurity concentration in both the streams follows a flat pro-
file beyond that and was sufficient to maintain the product
specifications. Fig. 6b shows that, when changing the feed stage
of the SRC above or below stage 6, the distillate (DCA) may be
contaminated with DGDP. However, the relative volatility of
DCA-DGDP is high at high molar concentrations of DCA in
the liquid phase. Consequently, a feed stage near the reflux is
preferable. However, too high a feed stage compromises the
number of stages available for rectification and increases the
DGDP impurity level in the distillate. Hence, the optimum feed
stage (number 5) was chosen. Other results and performance
data are given in a subsequent section on process comparison.
4.2 Thermally Coupled Distillation Column with
Side-Rectifier
The thermally coupled distillation column with a side-rectifier
is the thermodynamic equivalent to an E-DWC configuration.
Fig. 7 provides the complete process flow sheet, the mass and
energy balance, and the key design and operating parameters
for the simulated E-DWC process for MCA-DCA separation.
0.99858
stages and a higher reflux ratio improve the distillate quality,
0.99856 with simultaneous increases in capital and operating costs. To
0.99854
achieve a given distillate purity, a lower reflux ratio is required
when more stages are used. Thus, these parameters were
0.99852 chosen as NTS = 10 and RR = 6.75, values that minimize the
0.9985
NTS ·(RR + 1) factor, which is an indirect estimate of the total
annual cost.
0.99848 Fig. 8 provides the main results of the sensitivity analysis,
9 10 namely the effect of various parameters (e.g., number of stages,
feed stage, solvent stage position, side-draw product stage) on
the composition of the product streams, while keeping other
parameters constant. These results provide early insights into
the effects of various parameters in order to allow informed
decisions regarding the E-DWC design.
The rectification section in the EDC must have sufficient
stages to avoid contamination of the MCA product with DCA.
However, if the MCA-DCA feed location is too close to the
reboiler, the DCA might vaporize and reach the MCA product.
The optimum feed stage for the MCA-DCA mixture was found
at stage 18, while the optimum feed stage for the solvent is on
stage 5. A minimum of 4 stages at the top is required to avoid
contamination of the MCA product with DGDP. The side-draw
product stage and the number of stripping stages can influence
the distillate quality. If DCA reaches the solvent recycle stream,
it can contaminate the MCA product. The trade-off side-draw
stage was found at stage 29 and the number of stripping stages
was found as 30 stages. To satisfy the composition required for
the DCA product for a minimal total annual cost, 10 stages
were found to be necessary for the side-rectification section.
Fig. 9 shows the composition and temperature profiles in the
main ED column and the side-rectifier. The MCA product con-
tains just 43 ppm of DCA traces and the DCA product contains
just 712 ppm of MCA traces. The DGDP is recycled with high
purity. The operating temperature is below 448 K, thanks to the
low pressure used (4.5 kPa), thereby avoiding the decomposi-
tion of the compounds (MCA/DCA). The energy requirement
for purification of MCA and DCA in the E-DWC design is just
2.77 MW.

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QC = 2.24 MW QC = 0.49 MW

1 DCA
1 437.5 kg/h
MCA-DCA MCA 381.3 K, 4.5 kPa
(from chlorinaon) 388 K, 4.5 kPa 8312.5 kg/h SRS MCA: 712 ppm
8750 kg/h 5 378.3 K, 4.5 kPa DCA: 99.99 %wt
373 K, 4.5 kPa
DGDP MCA: 99.99 %wt
MCA: 95.0 %wt EDC DCA: 43 ppm
DCA: 5.0 %wt 10 SRS
378.5 K, 4.5 kPa Reflux Drum DCA-DGDP (vap)
HEX 18 RR= 6.75
MCA-DCA Height = 1.99 m 5893.1 kg/h
Diam = 0.99 m 444.9 K, 4.5 kPa Diam = 1.32 m
DGDP QHEX = 0.25 MW DCA: 15.0 %wt Height = 4.06 m
0.1 kg/h A = 12.1 m2 DGDP: 85.0 %wt Pack vol. = 0.72 m3
298 K, 4.5 kPa LMTD = 31.9 K Reflux Drum
DGDP: 100 %wt 29
DCA-DGDP (liq) Height = 1.22 m
Purge EDC-SRC 5455.5 kg/h Diam = 0.614 m
Mixer 444.9 K, 4.5 kPa
RR= 0.55 SRC DCA: 7.25 %wt
QR = 2.77 MW DGDP: 92.75 %wt
Secon 1 (NT = 2…17)
Diam = 2.52 m
60
Height = 9.82 m
Pack vol. = 8.53 m3
Secon 2 (NT = 18…59) DGDP
Diam = 3.53 m Reboiler/Sump 6476.1 kg/h
Height = 11.74 m Height = 1.94 m 447.6 K, 4.5 kPa
Pack vol. = 20.67 m3 Diam = 0.965 m DCA: 43 ppm
DGDP: 99.99 %wt

Figure 7. Process flow sheet and key design and operating parameters for a column with side-rectifier (equivalent to an
E-DWC configuration) for MCA-DCA separation (only the reflux is sub-cooled).

a) 400 b) 90
DCA in disllate
350
DCA in booms 80 DCA in disllate
300
Impurity (ppm)
Impurity (ppm)

70
250
200 60
150
50
100
50 40

0 30
49 51 53 55 57 59 61 63 65 15 16 17 18 19 20
NT in main column Feed stage locaon in main column

c) 2000 d) 80
DCA in disllate DCA in disllate
70
1600 DCA in booms
DGDP in disllate
Impurity (ppm)
Impurity (ppm)

60
1200
50
800
40

400 30

0 20
3 4 5 6 7 27 28 29 30 31 32
Solvent feed stage locaon Side-draw stage in main column

Figure 8. Sensitivity analysis results: effect of the number of stages (a), the feed stage (b), the solvent feed stage (c), and the
side draw product stage (d) on the composition of the product streams.

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Research Article 9

a) 1 470 Table 5. Comparison of the process parameters and key perfor-

0.9 460
mance indicators.
0.8 450
Process parameter/ Conventional E-DWC Difference

Temperature [K]
0.7 440
Mass fracon

Liquid mass fracon MCA performance indicator ED [%]

Liquid mass fracon DCA
0.6 Liquid mass fracon DGDP 430
0.5
Temperature (K)
420 Feed flow rate 8750 8750 –
[kg h–1]
0.4 410
0.3 400 Solvent flow rate 6495 6475 –0.30
0.2 390 [kg h–1]a)
0.1 380 MCA product yield 8312 8312 –
0 370 [kg h–1]
0 10 20 30 40 50 60
Total heating requirements 3.83 2.77 –27.67
Stage
[MW]
b) 1 470
Specific energy use 1.658 1.199 –27.67
0.9 460 [MJ kgMCA–1]
0.8 450
GHG emissions 0.120 0.086 –28.33

Temperature [K]
0.7 440
Mass fracon

Liquid mass fracon MCA

Liquid mass fracon DCA
[kg kgMCA–1]
0.6 Liquid mass fracon DGDP 430
0.5
Temperature (K)
420 Total operating cost 1428.4 1023.5 –28.35
[103 $ a–1]
0.4 410
0.3 400 Total capital cost 3662.9 2932.3 –19.94
0.2 390 [103 $]
0.1 380 Total annual cost 2649.4 2000.9 –24.50
0 370 [103 $ a–1]
0 2 4 6 8 10
Stage Fresh solvent flow rate is only 0.1 kg h–1.

Figure 9. Composition and temperature profiles in the main ED

column and the side-rectifier.
the systems use the same raw materials and around 95 % of the
contribution towards carbon emission is from raw materials
(mainly chloroacetic acid).
Table 4. Comparison of the carbon footprints of the E-DWC
Tab. 5 provides a comparison of the process parameters and
and conventional ED systems. Functional unit (f.u.) = 1 kg of
MCA. key performance indicators. We emphasize that both configu-
rations (conventional ED and the new column with side-recti-
Conventional ED E-DWC Reduction fier) are designed to achieve the same product specifications;
[kgCO2 eq/f.u.] [kgCO2 eq/f.u.] [%] thus, the comparison is correct from this perspective. The E-
DWC process allows 10 % savings in the construction material
Raw materials 2.63 2.60 1.14 and 28 % reduction in energy usage, with a total annual cost
Stainless steel 0.373 0.336 9.92 that is 24.5 % lower than for the classic ED. Moreover, there
are no changes in terms of raw materials (MCA and DGDP) as
Chloroacetic acid 2.26 2.26
there are no losses in both ED processes.
–8
Solvent 1.95 ·10 1.95 ·10–8

Energy 0.120 0.086 28.33

4.4 Process Dynamics and Control
Production stage 1 0.08 0.086
The steady-state simulation of the E-DWC process was built in
Production stage 2 0.04 0.0
Aspen Plus and then exported for dynamics using a flow-driv-
en dynamic model. The control structure is shown in Fig. 10,
4.3 Economics and Carbon Footprint with the tuning parameters of the controllers listed in Tab. 6.
The Aspen Dynamics software provides a basic control struc-
Tab. 4 shows a direct comparison of the carbon footprint of the ture based on the sizing made in the steady state, e.g., pressure
E-DWC and the conventional ED system. The E-DWC system and level controllers. Then, temperature controllers were
reduces the energy use by 27 % and, consequently, the associ- added. The stages for the temperature control were chosen on
ated carbon emissions are also reduced by 28.33 %. The CO2 the basis of sensitivity at different feed flow rate and concentra-
equivalent against stainless-steel consumption is curtailed by tion disturbances. For the temperature control loops, the stabil-
9.92 % as the E-DWC system uses less equipment. However, ity limit was found using the auto tuning variation (ATV)
the reduction in the total carbon footprint is 2.18 %, as both method implemented in Aspen Plus Dynamics. Then, the

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Research Article 10

PC
PC
LC

LC 1 DCA
1 RR
MCA
2 TC
FC DGDP RR SRS
5
MCA EDC
DCA 10
HEX 18
FC LC
x
FC
24

DGDP 29

LC/SR
SRC TC

Mixer

60

LC

DGDP

Figure 10. Improved process control structure for the ED. FC, flow control; LC, level control; PC, pressure control; TC, temperature
control.

Table 6. Controller tuning parameters.

Controller PV, value and range OP, value and range Kc Ti

[% %–1] [min]

FC MCA-DCA Flow rate = 8750 kg h–1

LC solvent/split range Level = 1.52 m Flow rate DGDP = 0.0503 kg h–1

0–1.52 m/1.52–3 m 0–10 000 kg h–1/purge split 0–1

Ratio control Flow rate MCA-DCA = 8750 kg h–1 Flow rate DGDP = 6478.27 kg h–1 0.74
–1
PC EDC Column pressure = 0.045 bar Condenser duty = –1.84 MMkcal h 20 12
–1
0–0.09 bar –3.67–0 MMkcal h

LC reflux drum EDC Level = 1.24 m (reflux drum EDC: H = 1.99 m, D = 0.99 m) Flow rate distillate = 8312.6 kg h–1 10 60
–1
0–2.48 m 0–16 625.2 kg h

LC sump EDC Level = 1.2 m (sump EDC: H = 1.93 m, D = 0.965 m) Bottom flow rate = 6478.2 kg h–1 10 60
–1
0–2.4 m 0–12 956.4 kg h

TC stage 24 EDC Temperature = 391.5 K Reboiler duty = 2.39 MMkcal h–1 21.12 2.76

381–401 K 0–4.78 MMkcal h–1

PC SRS Column pressure = 0.045 bar Condenser duty = –0.356 MMkcal h–1 20 12

0–0.09 bar –0.71–0 MMkcal h–1

Chem. Eng. Technol. 2020, 43, No. 00, 1–16 ª 2020 The Authors. Published by Wiley-VCH GmbH www.cet-journal.com

Research Article
Table 6. Continued.
Controller PV, value and range
LC reflux drum SRS Level = 0.768 m (reflux drum SRS: H = 1.22 m, D = 0.614 m)
0–1.53 m
LC sump SRS Level = 1.13 m
0–2.26 m
TC stage 2 SRS Temperature = 382.23 K
373–392 K
parameters of the proportional-integral (PI) controllers were
set, following the Tyreus-Luyben rule [31, 33]. The temperature
control loops include 2 min of dead time to account for sam-
pling and reading.
The control structure includes the following:
– The liquid level in the solvent mixer is controlled by using a
split range controller. This controller works as follows:
When the production is increased, more solvent is necessary
to keep the solvent-to-feed ratio; thus, the controller
increases the fresh-solvent flow rate to bring the level back
to the set point. When the production is decreased, less
solvent is necessary; the controller purges the excess of the
solvent out of the process
– Ratio controller for MCA-DCA/DGDP, by manipulating the
flow rate of the mixer output
– Main column: fixed reflux ratio; temperature of stage 24, by
manipulating the reboiler duty (this stage was chosen such
that the feed disturbances are seen quickly when they occur);
pressure, by manipulating the condenser cooling duty; liquid
level of the reflux drum, by manipulating the distillate mass
flow rate (MCA); liquid level of the sump, by manipulating
the mass flow rate of the bottom stream; the rate of vapor
mass flow going to the side-rectifying section is fixed
– Side-rectifier: temperature of sensitive stage 2 (382 K), by
manipulating the reflux ratio to avoid product contamina-
tion with DGDP; pressure, by manipulating the condenser
cooling duty; liquid level of the reflux drum, by manipulat-
ing the distillate mass flow rate; liquid level in the bottom,
by manipulating the liquid mass flow rate that returns to the
main column.
Fig. 11 shows the dynamic results for +10 % (Figs. 11a, c, and
e) and –10 % (Figs. 11b, d, and f) changes in the feed flow rate
of MCA-DCA. The process runs in steady state for 2 h. Then,
the feed flow rate is increased and decreased by 10 % within
1 h. The ratio controller acts quickly and changes the flow rate
of the solvent according to the specified ratio. The temperature
controller immediately sees the change of temperature that
occurs near the feed location and acts on the reboiler duty. The
purity of the MCA produced and of the solvent recycled is
practically unchanged. Meanwhile, the purity of DCA pro-
duced remains within the desired parameters.
Fig. 12 shows the dynamic results for +2 wt % (Figs. 12a, c,
and e) and –2 wt % (Figs. 12b, d, and f) changes of DCA in the
feed, the disturbance being introduced after 2 h of steady-state
Chem. Eng. Technol. 2020, 43, No. 00, 1–16 ª 2020 The Authors. Published by Wiley-VCH GmbH
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11
OP, value and range Kc Ti
[% %–1] [min]
Distillate flow rate = 437.45 kg h–1 10 60
–1
0–874.90 kg h
Bottom flow rate = 5456.27 kg h–1 10 60
–1
0–10 912.64 kg h
Reflux ratio = 6.75 23.58 7.92
0–13.5
operation. The product flow rates change according to the
amounts of MCA and DCA present in the feed. When the
DCA is decreased by –2 % in the feed, the system stabilizes
after 40 h. The quality of the MCA product is practically
unchanged, while the DCA concentration is changed but
remains within the desired parameters (< 1000 ppm MCA
impurity).
5 Conclusions
This work proves the feasibility of a novel ED process using a
DWC (or thermally coupled distillation) for the separation of
the close-boiling mixture of MCA and DCA. This intensified
solution provides a sustainable and eco-efficient alternative to
the current energy- and capital-intensive hydrogenation and
crystallization steps used in the industrial process for the
removal of DCA impurities from MCA. This original study is
the first to employ a fully thermally coupled column with a
side-rectifier (equivalent to an E-DWC configuration), for the
separation of corrosive mixtures of close-boiling components
at low pressure. The substantial savings achievable are expected
to inspire similar academic works for separating close-boiling
mixtures of industrial importance.
The results reveal that savings of 28 % in operating cost and
19 % in capital cost and a reduction of 24.5 % in total annual
cost are possible as compared to a conventional ED system.
The reduced energy requirements (with specific energy use of
1.2 MJ kg–1 MCA) are accompanied by 28 % reduction in GHG
emissions generated from energy use.
Acknowledgment
A. A. Kiss gratefully acknowledges the Royal Society Wolfson
Research Merit Award (No. WM170003). The financial support
of the European Commission through the European Regional
Development Fund and of the Romanian state budget, under
the grant agreement POC P-37-449 (acronym ASPiRE), is
gratefully acknowledged.
The authors have declared no conflict of interest.
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Research Article 12

10000 1000 9000 1000

FEED
9500 900 8500 FEED 900
MCA prod.
9000 800 8000 800
Flow rate [kg/h]

Flow rate [kg/h]

8500 700 7500 MCA prod. 700
8000 600 7000 600
7500 DCA prod. 500 6500 DGDP 500
DGDP DCA prod.
7000 400 6000 400
6500 300 5500 300
6000 200 5000 200
0 2 4 6 8 10 12 14 16 18 20 22 0 2 4 6 8 10 12 14 16 18 20 22
Time [h] Time [h]

1 DGDP 1000 1 DGDP 1000

MCA MCA
0.9998 800 0.9998 800
MCA in DCA

Impuries [ppm]

Impuries [ppm]
MCA in DCA
Mass fracon

Mass fracon
0.9996 600 0.9996 600

0.9994 400 0.9994 400

DCA DCA

0.9992 200 0.9992 200

DCA in MCA DCA in MCA
0.999 0 0.999 0
0 2 4 6 8 10 12 14 16 18 20 22 0 2 4 6 8 10 12 14 16 18 20 22
Time [h] Time [h]

3200 0 3200 0

3100 DCA cond. -400 3100 DCA cond. -400

Condenser duty [kW]

Condenser duty [kW]
Reboiler duty [kW]

Reboiler duty [kW]

3000 -800 3000 -800

2900 -1200 2900 -1200

Reb. Reb.
2800 -1600 2800 -1600
MCA cond.
2700 -2000 2700 -2000
MCA cond.
2600 -2400 2600 -2400

2500 -2800 2500 -2800

0 2 4 6 8 10 12 14 16 18 20 22 0 2 4 6 8 10 12 14 16 18 20 22
Time [h] Time [h]

Figure 11. Dynamic results for changes in the feed flow rate: (a, c, e) +10 %, (b, d, f) –10 %.

Symbols used LMTD [K] log mean temperature difference

M&S [–] Marshall & Swift equipment cost
A [m2] area index
CHEX [$] cost of heat exchangers MW [g mol–1] molecular weight
Cshell [$] cost of column shell NF [–] feed stage number
CAPEX [$] capital expenditures NT [–] number of trays
D [m] diameter NTS [–] number of theoretical stages
Fc [–] correction factor OPEX [$ a–1] operational expenditures
Fd [–] design factor P [Pa] pressure
Fm [–] material factor Pc [Pa] critical pressure
Fp [–] pressure factor QC [MW] condenser duty
H [m] height QHEX [MW] heat exchanger duty
HETP [m] height equivalent to a theoretical QR [MW] reboiler duty
plate R [Å] radius of gyration

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Research Article 13

9000 800 9000 800

FEED FEED
8500 700 8500 MCA prod. 700
MCA prod.
Flow rate [kg/h]

Flow rate [kg/h]

8000 DCA prod. 600 8000 600

7500 500 7500 500

7000 400 7000 400

6500 DGDP 300 6500 DGDP 300

DCA prod.
6000 200 6000 200
0 2 4 6 8 10 12 14 16 18 20 22 0 2 4 6 8 10 12 14 16 18 20 22
Time [h] Time [h]

1 DGDP 1000 1 DGDP 1000

MCA MCA
MCA in DCA
0.9998 800 0.9998 800

Impuries [ppm]

Impuries [ppm]
MCA in DCA
Mass fracon

Mass fracon
0.9996 600 0.9996 600

0.9994 400 0.9994 400

DCA DCA

0.9992 200 0.9992 200

DCA in MCA DCA in MCA

0.999 0 0.999 0
0 2 4 6 8 10 12 14 16 18 20 22 0 2 4 6 8 10 12 14 16 18 20 22
Time [h] Time [h]

3100 0 3100 0
DCA cond. DCA cond.
3000 -400 3000 -400

Condenser duty [kW]

Condenser duty [kW]

Reboiler duty [kW]

Reboiler duty [kW]

2900 -800 2900 -800

2800 Reb. -1200 2800 Reb. -1200

2700 -1600 2700 -1600

2600 MCA cond. -2000 2600 -2000

MCA cond.
2500 -2400 2500 -2400
0 2 4 6 8 10 12 14 16 18 20 22 0 2 4 6 8 10 12 14 16 18 20 22
Time [h] Time [h]

Figure 12. Dynamic results for DCA changes in the feed: (a, c, e) +2 %, (b, d, f) –2 %.

RR [–] reflux ratio Abbreviations

Tb [K] boiling point temperature
ATV auto tuning variation
Tc [K] critical temperature
CMC carboxymethyl cellulose
TAC [$ a–1] total annual cost
DCA dichloroacetic acid
U [kW m–2K–1] heat transfer coefficient
DGDP diethylene glycol dipentyl ether
Vc [m3mol–1] critical volume
DWC dividing-wall column
Zc [–] critical compressibility factor
ED extractive distillation
EDC extractive distillation column
Greek letters
E-DWC extractive dividing-wall column
m [C m] dipole moment EGDE ethylene glycol diethyl ether
w [–] acentric factor GHG greenhouse gas
GLS glass-lined steel

Chem. Eng. Technol. 2020, 43, No. 00, 1–16 ª 2020 The Authors. Published by Wiley-VCH GmbH www.cet-journal.com

Research Article
HOC Hayden-O’Connell
MCA monochloroacetic acid
NRTL non-random two-liquid
PI proportional-integral
SRC solvent recovery column
SRS solvent recovery system
VLE vapor-liquid equilibrium
References
[1] G. Koenig, E. Lohmar, N. Rupprich, Chloroacetic Acids, in
Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH,
Weinheim 2010, 473–488. DOI: https://doi.org/10.1002/
14356007.a06_537.pub3
[2] Monochloroacetic Acid, Nouryon Industrial Chemicals,
Amsterdam 2019. https://industrialchemicals.nouryon.com/
chlorine-derivatives/derivatives/mca-smca/
[3] P. Martikainen, T. Salmi, E. Paatero, L. Hummelstedt,
P. Klein, H. Damén, T. Lindroos, Kinetics of Homogeneous
Catalytic Chlorination of Acetic Acid, J. Chem. Technol.
Biotechnol. 1987, 40, 259–274. DOI: https://doi.org/10.1002/
jctb.280400405
[4] P. Pal, J. Nayak, Acetic Acid Production and Purification:
Critical Review Towards Process Intensification, Sep. Purif.
Rev. 2017, 46, 44–61. DOI: https://doi.org/10.1080/
15422119.2016.1185017
[5] A. A. Kiss, J. P. Lange, B. Schuur, D. W. F. Brilman, A. G. J.
van der Ham, S. R. A. Kersten, Separation Technology –
Making a Difference in Biorefineries, Biomass Bioenergy
2016, 95, 296–309. DOI: https://doi.org/10.1016/
j.biombioe.2016.05.021
[6] A. Vidra, A. Németh, Bio-produced Acetic Acid: A Review,
Period. Polytech., Chem. Eng. 2018, 62, 245–256. DOI:
https://doi.org/10.3311/PPch.11004
[7] P. Mäki-Arvela, E. Paatero, T. Salmi, The Role of Acetyl
Chloride in the Chlorination of Acetic Acid, J. Chem. Tech-
nol. Biotechnol. 1994, 61, 1–10. DOI: https://doi.org/
10.1002/jctb.280610102
[8] J. Crouzen, J. J. Gorissen, C. J. G. van Strien, Process for
Preparation of Monochloroacetic Acid, US Patent 7,135,597
B2, 2009.
[9] J. Crouzen, J. J. Gorissen, C. J. G. van Strien, Process for
Separating Monochloroacetic Acid and Dichloroacetic Acid
via Extractive Distillation, Patent WO2012175229, 2012.
[10] M. Blahusiak, A. A. Kiss, K. Babic, S. R. A. Kersten,
G. Bargeman, B. Schuur, Insights into the Selection and De-
sign of Fluid Separation Processes, Sep. Purif. Technol. 2018,
194, 301–318. DOI: https://doi.org/10.1016/
j.seppur.2017.10.026
[11] M. T. G. Jongmans, Energy Efficient Trace Removal by
Extractive Distillation, Ph.D. Thesis, Eindhoven University
of Technology 2012.
[12] V. Gerbaud, I. Rodrı́guez-Donis, L. Hegely, P. Lang, F. Denes,
X. You, Review of Extractive Distillation. Process Design,
Operation, Optimization and Control, Chem. Eng. Res. Des.
2019, 141, 229–271. DOI: https://doi.org/10.1016/
j.cherd.2018.09.020
Chem. Eng. Technol. 2020, 43, No. 00, 1–16 ª 2020 The Authors. Published by Wiley-VCH GmbH
These are not the final page numbers! ((
14
[13] A. A. Kiss, in Reference Module in Chemistry, Molecular
Sciences and Chemical Engineering, Elsevier, Waltham, MA
2013. DOI: https://doi.org/10.1016/
B978-0-12-409547-2.05949-7
[14] Z. Lei, C. Li, B. Chen, Extractive Distillation: A Review, Sep.
Purif. Rev. 2003, 32, 121–213. DOI: https://doi.org/10.1081/
SPM-120026627
[15] Z. Lei, C. Li, Y. Li, B. Chen, Separation of Acetic Acid and
Water by Complex Extractive Distillation, Sep. Purif.
Technol. 2004, 36, 131–138. DOI: https://doi.org/10.1016/
S1383-5866(03)00208-9
[16] P. Lek-Utaiwan, B. Suphanit, P. L. Douglas, N. Mongkolsiri,
Design of Extractive Distillation for the Separation of Close-
Boiling Mixtures: Solvent Selection and Column Optimiza-
tion, Comput. Chem. Eng. 2011, 35, 1088–1100. DOI: https://
doi.org/10.1016/j.compchemeng.2010.12.005
[17] M. T. G. Jongmans, J. J. Pragt, G. Bargeman, B. Schuur, K. T.
J. Aaldering, A. B. de Haan, M. R. Nieuwhof, P. Verwer,
A. A. Kiss, A. J. B. ten Kate, C. J. G. van Strien, Process for
Separating Monochloroacetic Acid and Dichloroacetic Acid
via Extractive Distillation, Patent WO/2012/175229, 2011.
[18] M. T. G. Jongmans, A. Londono, S. B. Mamilla, H. J. Pragt,
K. T. J. Aaldering, G. Bargeman, M. R. Nieuwhof, A. J. B. ten
Kate, P. Verwer, A. A. Kiss, C. J. G. van Strien, B. Schuur,
A. B. de Haan, Extractant Screening for the Separation of
Dichloroacetic Acid from Monochloroacetic Acid by Extrac-
tive Distillation, Sep. Purif. Technol. 2012, 98, 290–297. DOI:
https://doi.org/10.1016/j.seppur.2012.06.040
[19] R. Smith, in Encyclopedia of Separation Science, Vol. 9,
Academic Press, London 2000, 4363–4371.
[20] C. Bravo-Bravo, J. G. Segovia-Hernandez, C. Gutierrez-
Antonio, A. L. Duran, A. Bonilla-Petriciolet, A. Briones-
Ramirez, Extractive Dividing Wall Column: Design and
Optimization, Ind. Eng. Chem. Res. 2010, 49, 3672–3688.
DOI: https://doi.org/10.1021/ie9006936
[21] D. Staak, T. Grützner, Process Integration by Application of
an Extractive Dividing-Wall Column: An Industrial Case
Study, Chem. Eng. Res. Des. 2017, 123, 120–129. DOI:
https://doi.org/10.1016/j.cherd.2017.04.003
[22] A. A. Kiss, Advanced Distillation Technologies: Design, Con-
trol and Applications, John Wiley & Sons, Chichester 2013.
[23] Ö. Yildirim, A. A. Kiss, E. Y. Kenig, Dividing Wall Columns
in Chemical Process Industry: A Review on Current Activ-
ities, Sep. Purif. Technol. 2011, 80, 403–417. DOI: https://
doi.org/10.1016/j.seppur.2011.05.009
[24] A. A. Kiss, D. J.-P. C. Suszwalak, Enhanced Bioethanol De-
hydration by Extractive and Azeotropic Distillation in Di-
viding-Wall Columns, Sep. Purif. Technol. 2012, 86, 70–78.
DOI: https://doi.org/10.1016/B978-0-444-59519-5.50134-9
[25] A. A. Kiss, R. M. Ignat, Innovative Single Step Bioethanol
Dehydration in an Extractive Dividing-Wall Column, Sep.
Purif. Technol. 2012, 19, 290–297. DOI: https://doi.org/
10.1016/j.seppur.2012.06.029
[26] I. Patrascu, C. S. Bildea, A. A. Kiss, Dynamics and Control
of a Heat Pump Assisted Extractive Dividing-Wall Column
for Bioethanol Dehydration, Chem. Eng. Res. Des. 2017, 119,
66–74. DOI: https://doi.org/10.1016/j.cherd.2016.12.021
[27] I. Patrascu, C. S. Bildea, A. A. Kiss, Eco-efficient Butanol
Separation in the ABE Fermentation Process, Sep. Purif.
www.cet-journal.com

Research Article
Technol. 2017, 177, 49–61. DOI: https://doi.org/10.1016/
j.seppur.2016.12.008
[28] M. T. G. Jongmans, A. Londono, B. Schuur, A. B. de Haan,
Isobaric Low-Pressure Vapour-Liquid Equilibrium Data of
the System Monochloroacetic Acid plus Dichloroacetic Acid
plus Diethylene Glycol Dipentyl Ether and the Constituent
Binary Systems, Fluid Phase Equilib. 2012, 334, 15–21. DOI:
https://doi.org/10.1016/j.fluid.2012.07.027
[29] A. Londoño, M. T. G. Jongmans, B. Schuur, A. B. de Haan,
Isobaric Low Pressure Vapor-Liquid Equilibrium Data for
the Binary System Monochloroacetic Acid + Dichloroacetic
Acid, Fluid Phase Equilib. 2012, 313, 97–101. DOI: https://
doi.org/10.1016/j.fluid.2011.09.020
Chem. Eng. Technol. 2020, 43, No. 00, 1–16 ª 2020 The Authors. Published by Wiley-VCH GmbH
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15
[30] A. C. Dimian, C. S. Bildea, A. A. Kiss, Applications in Design
and Simulation of Sustainable Chemical Processes, Elsevier,
Amsterdam 2019.
[31] A. C. Dimian, C. S. Bildea, A. A. Kiss, Integrated Design and
Simulation of Chemical Processes, 2nd ed., Elsevier, Amster-
dam 2014.
[32] Carbon Calculation over Life Cycle of Industrial Activities,
University of Manchester, Manchester 2016. www.ccalc.or-
g.uk/ccalc2.php
[33] W. L. Luyben, M. L. Luyben, Essentials of Process Control,
McGraw-Hill, New York 1997.
www.cet-journal.com
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Research Article 16

PC

Research Article: The feasibility of a Eco-efficient Separation of Mono- and PC

LC

LC 1 DCA
novel extractive distillation process Dichloroacetic Acid by Thermally 1
MCA
2
RR
TC
FC DGDP RR SRS

using a divided-wall column for the Coupled Extractive Distillation MCA

5

EDC
DCA 10
separation of the close-boiling mixture x
HEX 18
FC LC

of mono- and dichloroacetic acid is A. K. Chandra, I. Patras˛cu, C. S. Bı̂ldea, DGDP

FC
24

29

demonstrated as a sustainable and eco- A. A. Kiss* LC/SR

SRC TC

efficient alternative to the current Mixer

60

energy- and capital-intensive Chem. Eng. Technol. 2020, 43 (XX),

hydrogenation and crystallization steps. XXX K XXX LC

DGDP

Optimization was done by sensitivity

analyses and variation of key operating DOI: 10.1002/ceat.202000232
and design parameters.

Chem. Eng. Technol. 2020, 43, No. 00, 1–16 ª 2020 The Authors. Published by Wiley-VCH GmbH www.cet-journal.com