Journal Pre-proof

Energy-saving quaternary extractive distillation processes with single- or

double-dividing-wall column for separation of
acetone/methanol/butanone/tert-butyl alcohol

Xiaojing Shi (Methodology)

(Software)<ce:contributor-role>Writing-original draft), Xiaoxiao
Zhao (Software) (Data curation), Zhishan Zhang (Supervision)
(Conceptualization) (Writing - review and editing), Min Li
(Supervision), Jun Gao (Project administration) (Funding
acquisition)

PII: S0255-2701(20)30456-6
DOI: https://doi.org/10.1016/j.cep.2020.107999
Reference: CEP 107999

To appear in: Chemical Engineering and Processing - Process Intensification

Received Date: 17 March 2020

Revised Date: 4 June 2020
Accepted Date: 8 June 2020

Please cite this article as: Shi X, Zhao X, Zhang Z, Li M, Gao J, Energy-saving quaternary
extractive distillation processes with single- or double-dividing-wall column for separation of
acetone/methanol/butanone/tert-butyl alcohol, Chemical Engineering and Processing -
Process Intensification (2020), doi: https://doi.org/10.1016/j.cep.2020.107999
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Energy-saving quaternary extractive distillation processes

with single- or double-dividing-wall column for separation of

acetone/methanol/butanone/tert-butyl alcohol
Xiaojing Shi, Xiaoxiao Zhao, Zhishan Zhang*, Min Li*, Jun Gao
College of Chemical and Biological Engineering, Shandong University of Science and Technology,

Qingdao, China

∗ Corresponding to: Zhishan Zhang, Min Li

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E-mail: tjzza@163.com (Zhishan Zhang), lemingirl@163.com (Min Li)

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Graphical abstract

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Highlights

1. Separation of quaternary azeotropic mixtures in PO/TBA coproduction is studied.

2. Extractive distillation configurations with chlorobenzene as solvent are proposed.

3. Single- or double-dividing-wall columns achieves great energy and cost savings.

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ABSTRACT

This article proposes two energy-saving extractive distillation configurations with single- or

double-dividing-wall column, based on a conventional four-column extractive distillation process

—CFC-ED, to efficiently separate a quaternary compound of acetone/methanol/butanone/

tert-butyl alcohol (TBA) with chlorobenzene as a solvent. One is composed of two

single-dividing-wall extractive distillation columns—SDWCs-ED; the other consists of an

extractive distillation column and double-dividing-wall extractive distillation

column—DDWC-ED. The parametric optimization is carried out with the minimum total annual

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cost (TAC) as a goal and adopts a sequential iterative procedure. The comparison with the

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CFC-ED process shows that the SDWCs-ED process can reduce the TAC by 12.50% and CO2

emission by 24.23% while the DDWC-ED process can save the TAC by 11.97% and CO2

emission by 14.43%. -p
Keywords: Extractive distillation; Dividing-wall column; Energy-saving; Multi-azeotropic
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compound

Nomenclature
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AC Heat transfer area of condenser [m2]

AR Heat transfer area of reboiler [m2]
B Bottom flow rate [kg/h]
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CDC Conventional distillation column

CFC-ED Conventional four-column extractive distillation
CSCinst Installed cost of column shell [$]
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D Distillate flow rate [kg/h]

DDWC-ED Double-dividing-wall extractive distillation process
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DDWC Double-dividing-wall column

EDC Extractive distillation column
F Feed flow rate [kg/h]
H Column height [m]
ID Inner diameter [m]
LP Low pressure
MC Main column

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M&S Marshall & Swift Equipment Cost Index
NF Feed location
NS Solvent location
NT Number of stages
NV Side vapor location
QC Condenser duty [kW]
QR Reboiler duty [kW]
RR Reflux ratio
S Solvent flow rate [kg/h]
SC Side column
SDWC Single-dividing-wall column

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SDWCs-ED Single-dividing-wall extractive distillation process
SRC Solvent recovery column

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S: F Solvent to feed ratio
TCinst Installed cost of trays [$]
TAC
UC
Total annual cost [$/y] -p
Heat transfer coefficient of condenser [kW/(K·m2)]
UR Heat transfer coefficient of reboiler [kW/(K·m2)]
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V Side vapor flowrate
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1. Introduction

Propylene oxide (PO) and tert-butanol (TBA) can be coproduced by the Halcon cooxidation of

isobutane and propylene with the advantages of low product cost and less environmental pollution,

and also TBA can react with methanol to form methyl tert-butyl ether for use in gasoline. During

this process, a quaternary compound of acetone/methanol/butanone/TBA is often encountered and

requires efficient treatment to recover these chemicals in high purity. It not only contains multiple

components but also forms multiple azeotropes between them. Clearly, special distillation must be

considered for separating this complex system effectively, including extractive distillation[1-8],

pressure-swing distillation[9-14], azeotropic distillation[15-18], or hybrid distillation[19-23].

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Currently, many researches have been reported for the separation of binary or ternary azeotropic

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systems by extractive distillation. For example, Kossack et al.[24] studied the choice of entrainers

through computer-aided molecular design and evaluated an extractive distillation process of

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acetone-methanol using different solvents. Luyben[25] explored a better extractive distillation

process with water as solvent than pressure-swing distillation to separate the acetone/methanol
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mixture. Wang et al.[26] investigated diverse extractive distillation sequences with chlorobenzene

(CB) as solvent to separate the acetonitrile/methanol/benzene mixture and then determined the
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best sequence. Yang et al.[27] investigated the design and control of triple-column extractive

distillation for separating the ethyl acetate/ethanol/water system using dimethylsulfoxide (DMSO)
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as solvent, achieving economic and enviomental benifis.

Simultaneously, many extractive distillation processes intensified by single-dividing-wall

column (SDWC) or double-dividing-wall column (DDWC) were developed because of cost- and
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energy-saving advantages. Kiss et al.[28] proposed the application of SDWC to extractive

distillation and azeotropic distillation using ethanol dehydration as a case study. Zhao et al.[29]
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presented an extractive distillation process with the SDWC to separate the

tetrahydrofuran/ethanol/water with the mixture of ethylene glycol (EG) and DMSO as solvent. Ma

et al.[30] applied ionic liquids as entrainer to a ternary extractive distillation intensified process

with SDWC for the ethyl acetate/ethanol/water separation. Timoshenko et al.[31] studied various

types of dividing-wall column models for extractive distillation and proposed the concept of

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double-thermally coupled extractive distillation. Aurangzeb et al.[32] enhanced a conventional

three-column extractive distillation process by the DDWC in the separation of

tetrahydrofuran/methanol/water with EG as solvent. Yang et al.[33] studied the optimization of

DDWC using genetic algorithm in the extractive distillation separation of

benzene/toluene/cyclohexane using dimethyl formamide as solvent and claimed DDWC has the

better performance in cost and energy savings than SDWC. So far, there are few reports about the

application of SDWC and DDWC in the quaternary extractive distillation process.

In this study, two energy-saving extractive distillation configurations with CB as solvent, known

as SDWCs-ED and DDWC-ED, are presented based on a conventional four-column extractive

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distillation process (CFC-ED) to separate the acetone/methanol/butanone/TBA quaternary

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compound containing multiple binary azeotropes. The first consists of two SDWCs while the other

is composed of extractive distillation column (EDC) and DDWC. The optimization is carried out

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with the minimum total annual cost (TAC) as target. On this basis, a thorough comparison

between the three processes is accomplished.

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2. Methodology

2.1. Problem statement

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In the industrial coproduction of PO/TBA, there is a TBA product stream containing a small

amount of acetone, methanol and butanone. Generally, most of pure TBA can be obtained by
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common distillation, but the remaining is a difficult-to-separate quaternary mixture. In this study,

this mixture is treated as a fresh feed, assuming the flowrate of 5000 kg/h and the composition of

43.73 wt% acetone, 24.04 wt% methanol, 23.85 wt% butanone, and 8.38 wt% TBA, and the purity
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of all products is specified as 99.5 wt%.

2.2. Analysis of vapor-liquid equilibrium (VLE)

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The non-random two liquid (NRTL) model is selected for the simulation work in this study.

Table 1 gives the binary interaction parameters between the systematic components from Aspen

database. All these data are built-in and not estimated by UNIFAC. As shown in Fig. 1, this choice

is very qualified because the model calculated values are in good agreement with the isobaric VLE

experimental data [34-36]. In terms of the temperature and composition of azeotropes, the

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calculated values are very close to the experimental results as well, as given in Table 2.

Table 1

The NRTL model parameters of the acetone/methanol/butanone/TBA system.

Fig. 1 – The predicted and experimental binary VLEs in the studied system at 1 atm. (a)

acetone-methanol, (b) methanol-butanone, (c) butanone-TBA.

Table 2

Boiling point and composition of azeotropes and pure component in the studied system

2.3 Selection of additional solvent

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For selecting the most appropriate solvent, several commonly used solvents including DMSO,

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CB, EG and methylpyrrolidone (NMP) are screening [24,26,37-39]. Table S1 lists their boiling

points and binary interaction parameters with the system’s components in Supplementary Material.

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These solvents are evaluated in terms of effects on the relative volatilities between components in

the research system. As shown in Fig. 2, each solvent can make the system’s azeotropes disappear,
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but CB has the best effect on the relative volatility increase than the other three solvents at the

same ratio of solvent to feed. Moreover, CB has the lowest boiling point of the four heavy-boiling
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solvents. As a result, the use of CB as solvent results in a lower temperature at the base of the

recovery column, which means avoiding the use of high-pressure steam and then makes solvent
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recovery more economical.

Fig. 2 – Effects of each solvent on relative volatilities between acetone-methanol (a),

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methanol-butanone (b), butanone-TBA (c) and VLE of CB-all system components (d).

2.4 Conceptual design

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The three kinds of conceptual designs based on conventional and dividing-wall extraction

distillation are illustrated in Fig.3, as described in detail below.

The CFC-ED process consists of two extractive distillation columns (EDC1 and EDC2), one

conventional distillation column (CDC), and one solvent recovery column (SRC), as shown in Fig.

3(a). The fresh feed and one solvent stream are respectively fed into the lower and upper trays of

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the EDC1. Methanol is first removed as the top product from the EDC1. Next, the bottom stream

of the EDC1 flows into the upper part of the CDC. The acetone product is obtained at the top of

the CDC. Further, the bottom stream of the CDC and the other solvent stream enter the middle and

upper trays of the EDC2 respectively. TBA is received as the top product from the EDC2. Finally,

the bottom stream of the EDC2 gets into the upper trays of the SRC. Butanone is extracted as the

top product from the SRC. The high purity solvent at the bottom of the SRC is cooled along with

make-up solvents and then flows back into the EDC1 and the EDC2.

The SDWCs-ED process is designed based on the CDC-ED process, as shown in Fig. 3(b),

including two SDWCs: one integrates the EDC1 with the CDC, and the other combines the EDC2

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with the SRC. The fresh feed and one solvent stream are fed into the middle and upper trays of the

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first main column (MC1). Methanol and acetone are obtained as the overhead products from the

MC1 and the first side column (SC1) respectively. The bottom mixture of the MC1 and the other

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solvent stream go into the upper trays of the second main column (MC2). TBA and butanone are

received as the top products from the MC2 and the second side column (SC2). The high purity
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solvent at the bottom of the MC2 is cooled with make-up solvents and then returned the MC1 and

the MC2.
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The DDWC-ED process is composed of an EDC and a DDWC, as shown in Fig. 3(c), which is

developed from the CDC-ED process by merging the three columns of CDC, EDC2 and SRC into
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one unit. This DDWC is simulated with a three-column equivalent model, i.e., one main column

(MC) and two side columns (SC1 and SC2). The fresh feed and one solvent stream enter the upper

and lower trays of the EDC. The methanol product is extracted at the top of the EDC. The bottom
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mixture of the EDC flows into the MC of the DDWC. The other solvent stream is introduced from

the SC1 of the DDWC. Acetone, TBA and butanone are obtained as overhead products from the
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MC, the SC1 and the SC2 respectively. The high purity solvent is recovered at the bottom of the

MC, after cooling with make-up solvents, and returns the EDC and the SC1 of the DDWC.

Fig. 3 – Conceptual design of different extractive distillation processes. (a) CFC-ED, (b)

SDWCs-ED and (c) DDWC-ED.

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2.5 Evaluation index

In this paper, two simplified indexes of TAC and CO2 emission are used to evaluate the

economic performance and environmental impact of the proposed processes. In this work, the

TAC only includes major capital and operating costs. The capital costs are the charges of columns

(shells and trays), condensers and reboilers without the costs of pumps, pipes and valves. The

operating costs are the expenditure of low-pressure steam and cooling water without other utilities

costs. It is assumed that the payback period of the fixed equipment is 3 years and the operating

time is 8,000h per year. The calculation of TAC is shown in Table S2 of Supplementary

materials[40-42]. The equivalent area method is used for calculating diameters of SDWC and

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DDWC and then capital costs [43]. The specific formulas are as follows:

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2 2 2
Equivalent 𝐼𝐷𝑆𝐷𝑊𝐶 = (𝐼𝐷𝑀𝐶 + 𝐼𝐷𝑆𝐶 ) (1)

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2 2 2
Equivalent 𝐼𝐷𝐷𝐷𝑊𝐶 = (𝐼𝐷𝑀𝐶 + 𝐼𝐷𝑆𝐶1 + 𝐼𝐷𝑆𝐶2 )2 (2)
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A simplified calculation model of CO2 emission is adopted from Gadalla et al.[44], as shown in S1
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of Supplementary materials.

3. The optimization of processes

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In this study, the operating pressures of all columns are set to 1 atm for guaranteeing the use of

cooling water in the condenser and low-pressure steam in the reboiler. The pressure drop of the

tray is set to 0.0068 atm. The temperature of solvent is set as 320K. All parameters to change
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during the optimization of three processes are summarized in Table 3. In this study, some

continuous parameters, namely design (dependent) variables, are used to meet the purity of
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recovery of products, including reflux ratios (RR), distillate flowrates (D) and side-vapor

flowrates (V). Other discrete parameters such as the number of theoretical stages (NT), feed stages
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(NF), solvent stages (NS), and the flowrates of recycling solvent (S), namely design (dependent)

variables are optimized for acquiring the lowest TAC.

The point regarding optimization deserve attention is that the range of these optimized variables

need to be determined through the function of sensitivity analysis in Aspen Plus for implementing

the sequential iterative optimization procedure used in this work.

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Table 3

Design and optimization variables of the proposed four processes.

Another point is that some convergence difficulties are bound to occur when such a complex

system is continuously simulated. The following attempts can be made to achieve convergence.

The number of iterations for convergence increases to the maximum. The good convergence

method is used for the highly-coupling process with multiple design constraints. The convergence

is facilitated by assigning correct initial values to some variables. When implementing design

constraints with the Design Spec function of Aspen Plus, the objectives such as the purity or

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recovery of a component should match with the design (dependent) variables.

3.1 The CFC-ED process

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3.1.1 Optimization procedure

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Fig.4 gives a sequential iterative optimization procedure of the CFC-ED process. According to

this optimization process, the optimization variables are manually changed to obtain the minimum
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TAC. Fig.5 provides the effects of optimization variables on the TAC. The optimized parameters

are seen from Fig.5, NT1=96, NT2=61, NT3=60, NT4=35, S1=13500kg/h, S2=5900kg/h, and the
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minimum TAC=26.57×105$/y.

Fig. 4 – The sequential iterative optimization procedure of the CFC-ED process.

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Fig. 5 – The effect of variables on the TAC of the CFC-ED: (a) NT1, (b) NT2, (c) NT3 (d) NT4 (e)
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S1 and (f) S2.

3.1.2 Optimization results and discussion

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The detailed optimization results of each column in the CFC-ED process are given in Table 4,

being obtained by a sequential iterative optimization procedure with TAC as a target. The first two

columns account for a large proportion of both capital and operating costs, which has a lot to do

with the feed composition. Besides, Fig.6 shows the optimal CFC-ED flowsheet with detailed

information.

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 The optimal liquid composition profiles in each column are shown in Fig. 7, demonstrating

that this process has been designed properly. As seen in Fig.7(a), there is a sharp increase in

methanol concentration and a rapid drop in CB concentration from the 30th stage and above. This

section in the EDC1 is mainly used for the separation of solvent and methanol. As seen In Fig.7(b),

there is almost no methanol in the CDC, so the lowest-boiling acetone is readily obtained as

overhead product. As seen in Fig.7(c), there is a sharp increase in TBA concentration and a rapid

drop in CB concentration from the 17th stage and above, similar with that in the EDC1. As seen in

Fig.7(d), the remaining butanone and solvent are fully separated in the SRC.

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Fig. 6 – The CFC-ED flowsheet with detailed optimal information

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Table 4

Main parameters, economic costs and CO2 emission of the CFC-ED optimal process.

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Fig.7 – The liquid composition profiles in EDC1 (a), CDC (b), EDC2 (c) and SRC (d).
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3.2 The SDWCs-ED process

3.2.1 Optimization procedure

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Fig.8 gives a sequential iterative optimization procedure of the SDWCs-ED process. According

to this optimization process, the optimization variables are manually changed to obtain the
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minimum TAC. The effects of optimization variables on the TAC are given in Fig.9. The

optimized parameters are seen from Fig.9, NT1=137, NT2=43, NT3=81, NT4=57, S1=14600kg/h,

S2=4800kg/h, and the minimum TAC=23.25×105 $/y.

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Fig. 8 – The sequential iterative optimization procedure of the SDWCs-ED process

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Fig. 9 – The effect of variables on the TAC of the SDWCs-ED: (a) NT1, (b) NT2, (c) NT3 (d)

NT4 (e) S1 and (f) S2.

3.2.2 Optimization results and discussion

The detailed optimization results of each column in the SDWCs-ED process are given in Table

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5, being obtained by a sequential iterative optimization procedure with TAC as a target. Compared

with the CFC-ED process, capital costs are saved due to the reduction of column vessels and

reboiler. Energy consumption is also dropped greatly becuause of the reduction of backmixing

degree in the dividing wall column, then leading to less energy costs and CO2 emissions. Also, the

optimal SDWCs-ED flowsheet with detailed information is shown in Fig.10.

Fig.11 illustrates the liquid composition profiles of each column under the optimal conditions to

show the proper design of the SDWCs-ED process. From Fig.11(a), the methanol composition is

rapidly raised from the 26th stage and above, thereby obtaining the specified methanol product at

the top. A side vapor is withdrawn from the 81st stage with the highest concentration of acetone

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and flows into the bottom of the SC1. From Fig.11(b), acetone gradually separates from other

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heavy components and reaches a required purity. From Fig.11(c), TBA separates fully from a little

CB from the 14th stage and above in the MC2. A side vapor is withdrawn from the 58th stage with

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a high concentration of CB and butanone and enters the bottom of the SC2. From Fig.11(d), the

qualified butanone product is obtained at the top of the SC2.

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Fig. 10 – The SDWCs-ED flowsheet with detailed optimal information.
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Table 5

Main parameters, economic costs and CO2 emission of the SDWCs-ED optimized process.
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Fig.11 – The liquid composition profiles in MC1 (a), SC1 (b), MC2 (c) and SC2 (d).
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3.3 The DDWC-ED process

It is very difficult to optimize the DDWC-ED configuration in strict accordance with the
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sequential iterative method as it is a high-coupled complex system. For the sake of simplicity, the

DDWC-ED process is optimized based on the CFC-ED optimal process above. The optimal

DDWC-ED design flowsheet with detailed information is shown in Fig.12. The optimal

conditions of the EDC including the solvent flow are the same as that of the EDC1. Besides, some

variables of the DDWC are fixed while only three variables are changed to obtain the better design,

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as shown in Table 6. The values of these fixed variables are consistent with the optimization

results of the CFC-ED process. The three changed variables require further optimization due to

their greater impacts on TAC and energy consumption. The final detailed optimization results are

determined in Table 7. Clearly, both capital costs and energy consumption are reduced in

comparison with the CFC-ED process due to the use of DDWC. When compared to the three

columns that are combined (i.e., CDC, EDC2 and SRC), DDWC can achieve obvious TAC

savings, up to 18%, but the potential operational and control problems in the industrial practice are

still on the way.

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Fig. 12 – The DDWC-ED flowsheet with detailed optimal information.

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Table 6

The optimization of the DDWC-ED process.

Table 7
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Main parameters, economic costs and CO2 emission of the DDWC-ED optimal process.
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The liquid composition profiles in the DDWC are shown in Fig.13. From Fig.13(a), the acetone

composition increases rapidly from the 13th stage and above, and achieves the purity requirement

at the top. The first side vapor flowing into the bottom of the SC1 is withdrawn from the 44th
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stage with a high concentration of TBA. The second side vapor going into the bottom of the SC2

is withdrawn at the 64th stage with a high concentration of butanone. From Fig.13(b), TBA is
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separated from butanone under the action of CB. From Fig.13(c), the butanone product is obtained

at the top of the SC2.

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Fig.13 – The liquid composition profiles in MC (a), SC1(b) and SC2 (c).

3.4 Comparing schemes

The economic costs and CO2 emission of the three schemes are compared in Fig.14. On one

hand, the CFC-ED process has the highest consumption of cooling water and steam, leading to the
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most operating costs and CO2 emission. Besides, it has higher capital costs due to the use of more

columns and reboilers. By contrast, the SDWCs-ED process can reduce 24.53% energy

consumption, 12.50% TAC and 24.23% CO2 emission, while the DDWC-ED process can

save14.50% energy, 11.97% TAC and 14.43% CO2 emission. On the other hand, although two

intensified schemes have almost no difference in the TAC, the DDWC-ED process has higher

energy consumption and lower capital costs than the SDWCs-ED process. The reason for this is

that one EDC accounts for as much as 40% TAC in the DDWC process. It has to be noted here

that the above interpretation of the results needs to be taken conservatively for the limitation of the

optimization methods used in this article. In future research, more rigorous deterministic or

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stochastic optimization methods should be developed and used to obtain more accurate solutions.

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Fig. 14 –Economic costs and CO2 emission comparison of three processes.

4. Conclusions
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In this paper, different extractive distillation processes including CFC-ED, SDWCS-ED and

DDWC-ED were presented for separating the acetone/methanol/butanone/TBA four-component

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compound into high-purity chemicals. During this, CB was selected as the solvent and the optimal

parameters were obtained with the minimum TAC as the goal. In comparison with the CFC-ED

process, the SDWCs-ED process and the DDWC-ED process can decrease the TAC by 12.50%
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and 11.97% and save energy by 24.53% and 14.23%. In addition, the DDWC-ED process has a

little more energy consumption than the SDWCs-ED process because of no energy-savings for the
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EDC, but this process still has the least capital cost. As a means of process intensification, DDWC

needs less equipment cost and energy consumption than SDWC. A more rigid optimization for the
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proposed complex configurations in this works needs to be explored in future research.

Author Statement
Xiaojing Shi: Methodology, Software, Writing-original draft preparation.

Xiaoxiao Zhao: Software, Data Curation.

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Zhishan Zhang: Supervision, Conceptualization, Writing-review & editing.

Min Li: Supervision.

Jun Gao: Project administration, Funding acquisition

Conflict of Interest statement:

The authors declare no conflicts of interest to this work.

Acknowledgement

This work was supported by the National Natural Science Foundation of China (No. 21878178).

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2409-2417. -p
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Fig. 1 – The predicted and experimental binary VLEs in the studied system at 1 atm. (a)

acetone-methanol, (b) methanol-butanone, (c) butanone-TBA.

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Fig. 2 – Effects of each solvent on relative volatilities between acetone-methanol (a),

methanol-butanone (b), butanone-TBA (c) and VLE of CB-all system components (d).
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Fig. 3 – Conceptual design of different extractive distillation processes. (a) CFC-ED, (b)

SDWCs-ED and (c) DDWC-ED.

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Fig. 4 – The sequential iterative optimization procedure of the CFC-ED process.

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Fig. 5 – The effect of variables on the TAC of the CFC-ED: (a) NT1, (b) NT2, (c) NT3 (d) NT4 (e)
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S1 and (f) S2.

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Fig. 6 – The CFC-ED flowsheet with detailed optimal information

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Fig.7 – The liquid composition profiles in EDC1 (a), CDC (b), EDC2 (c) and SRC (d).

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Fig. 8 – The sequential iterative optimization procedure of the SDWCs-ED process.

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Fig. 9 – The effect of variables on the TAC of the SDWCs-ED: (a) NT1, (b) NT2, (c) NT3 (d)

NT4 (e) S1 and (f) S2.

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Fig. 10 – The SDWCs-ED flowsheet with detailed optimal information.

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Fig.11 – The liquid composition profiles in MC1 (a), SC1 (b), MC2 (c) and SC2 (d).

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Fig. 12 – The DDWC-ED flowsheet with detailed optimal information.

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Fig.13 – The liquid composition profiles in MC (a), SC1(b) and SC2 (c).

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Fig. 14 –Economic costs and CO2 emission comparison of three processes.
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Table 1

The NRTL model parameters of the acetone/methanol/butanone/TBA system.

Component i Component j Aij Aji Bij Bji Cij

Acetone Methanol 0 0 101.886 114.135 0.3
Acetone Butanone -8.0985 5.1025 2364.93 -1083.5 0.3
Acetone TBA 0 0 354.643 -179.848 0.3
Methanol Butanone 0 0 175.347 89.4658 0.3
Methanol TBA 0 0 -160.352 44.0798 0.3
Butanone TBA 3.0218 -3.8956 -907.085 1321.78 0.3

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Table 2

Boiling point and composition of azeotropes and pure component in the studied system

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Azeotrope or pure component Boiling point (℃) Composition (mass fraction)
Acetone-methanol 55.30 (55.24) 0.8673:0.1327 (0.8637:0.1363)
Methanol-butanone
Butanone-TBA
63.64 (63.97)
78.82 (78.68)
-p0.7:0.3 (0.6901:0.3099)
0.7296:0.2704 (0.7395:0.2605)
Acetone 56.14 1
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Methanol 64.53 1
Butanone 79.34 1
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TBA 82.47 1

* The calculated data are shown in brackets.

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Table 3
Design and optimization variables of the proposed four processes.
Design (Dependent) Optimization (Independent) Degree of
Process
variables variables freedom
EDC1 D1, RR1 NT1, NF1, NS1, S1 6
CDC D2, RR2 NT2, NF2, 4
CFC-ED EDC2 D3, RR3 NT3, NF3, NS2, S2 6
SRC D4, RR4 NT4, NF4 4
Total 8 12 20
MC1 D1, RR1, V1 NT1, NF1, NS1, S1, NV1 8
SC1 D 2, NT2 2

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SDWCs-ED MC2 D3, RR3, V2 NT3, NF3, NS2, S2, NV2 8
SC2 D 4, NT4 2

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Total 8 12 20
EDC D1, RR1 NT1, NF1, NS1, S1 6

DDWC-ED
MC
SC1
D2, RR2, V1, V2
D3,
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NT2, NF2, NV1, NV2
NT3, NS2, S2
8
4
SC2 D4 NT4 2
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Total 8 12 20
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Table 4

Main parameters, economic costs and CO2 emission of the CFC-ED optimal process.

EDC1 CDC EDC2 SRC

NT 96 61 60 35
NF 74 13 37 9
NS 30 - 17 -
ID (m) 0.98 0.99 0.65 0.82
RR 1.51 4.31 2.92 4.39
S (kg/h) 13500 - 5900 -
QC (kW) -925.35 -1653.64 -237.72 -785.88

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QR (kW) 1527.25 1540.84 509.65 785.28
Capital cost (105$) 17.29 15.70 7.54 8.99

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Operating cost (105$/y) 3.49 3.59 1.16 1.83
TAC of column (105$/y) 9.25 8.82 3.67 4.83
TAC of process (105$/y) 26.57
CO2 emission (kg/h)
Total CO2 emission (kg/h)
1227.88
3507.79
1238.81
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409.75 631.35
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Table 5

Main parameters, economic costs and CO2 emission of the SDWCs-ED optimized process.

MC1 SC1 MC2 SC2

NT 137 43 81 57
NF 60 44 38 58
NS 26 - 14 -
NV 81 - 58 -
ID (m) 1.14 0.65 0.91 0.58
Equivalent ID (m) 1.31 1.08
RR 1.62 - 5.47 -

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S (kg/h) 14600 - 4800 -
QC (kW) -966.00 -669.02 -388.14 -436.09

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QR (kW) 2264.34 0 1041.48 0
Capital cost (105$) 27.38 2.81 14.63 2.13
Operating cost (105$/y) 5.13 0.07 2.36 0.04
TAC of column (105$/y)
TAC of process (105$/y)
15.26
23.25
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CO2 emission (kg/h) 1820.49 0 837.33 0
Total CO2 emission (kg/h) 2657.83
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Table 6

The optimization of the DDWC-ED process.

Fixed Changed

variable Data variable Data

NT3 37 NT2 60 70 75 80 85 90 100

NT4 10 NV1 40 41 42 44 44 46 51

NF2 13 NV2 54 56 59 64 64 65 71

NS2 17 TAC (105$/y) 33.53 24.28 23.60 23.40 23.73 23.82 23.83

S2 (kg/h) 5900

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Table 7

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Main parameters, economic costs and CO2 emission of the DDWC-ED optimal process.

EDC MC1 SC1 SC2

NT
NF
96
74
80
13
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38
10
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NS 30 - 17 -
NV - 44, 64 - -
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ID (m) 0.98 1.40 0.46 0.43

Equivalent ID (m) - 1.54
RR 1.51 4.48 - -
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S (kg/h) 13500 - 5900 -

QC (kW) -925.35 -1703.56 -214.24 -244.30
QR (kW) 1527.25 2206.22 0 0
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Capital cost (105$) 17.29 24.26 1.34 1.46

Operating cost (105$/y) 3.49 5.08 0.02 0.02
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TAC of column (105$/y) 9.25 14.14

TAC of process (105$/y) 23.39
CO2 emission (kg/h) 1227.88 1773.76 0 0
Total CO2 emission (kg/h) 3001.64

35