Author's Accepted Manuscript

Design/optimization of energy-saving extrac-

tive distillation process by combining pre-
concentration column and extractive
distillation column
Yi An, Weisong Li, Ye Li, Shanyuan Huang, Jian
Ma, Changlin Shen, Chunjian Xu

www.elsevier.com/locate/ces

PII: S0009-2509(15)00325-5
DOI: http://dx.doi.org/10.1016/j.ces.2015.05.003
Reference: CES12336

To appear in: Chemical Engineering Science

Received date: 29 January 2015

Revised date: 25 April 2015
Accepted date: 2 May 2015

Cite this article as: Yi An, Weisong Li, Ye Li, Shanyuan Huang, Jian Ma, Changlin
Shen, Chunjian Xu, Design/optimization of energy-saving extractive distilla-
tion process by combining preconcentration column and extractive distillation
column, Chemical Engineering Science, http://dx.doi.org/10.1016/j.ces.2015.05.003

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Design/Optimization of Energy-Saving Extractive

Distillation Process by Combining Preconcentration

Column and Extractive Distillation Column

Yi An, Weisong Li, Ye Li, Shanyuan Huang, Jian Ma, Changlin Shen, Chunjian Xu*

State key laboratory of chemical engineering,

Co-innovation center of chemistry and chemical engineering

Tianjin University, Tianjin, 300072, China

cjxu@tju.edu.cn

AUTHOR INFORMATION

Corresponding Author
*
Tel: +86 022-27404440. Fax: +86 022-27404440. E-mail: cjxu@tju.edu.cn
ABSTRACT: In extractive distillation, the addition of entrainer may reverse the relative

volatility of the feed components causing the component with higher-boiling point to be removed

as the distillate from the extractive column. In this study, the enengy saving possibility of a

three-column extractive distillation system was studied when this phenomenon occurred. Based

on a three-column conventional extractive distillation system, an innovative energy-saving

extractive distillation process with lower capital investment was developed by combining

preconcentration column and extractive distillation column. Two important case studies were

investigated to verify the above-mentioned energy and economic advantages: the separation of n-

propanol-water using N-methyl-2-pyrrolidone (NMP) as entrainer and the separation of ethyl

acetate-ethanol using furfural as entrainer. In order to separate these two mixtures, first a three-

column extractive distillation sequence including a preconcentration column was applied to

diluted fresh feedstock. Then, based on this three-column conventional extractive distillation

system, an innovative energy-saving distillation process was developed. For the two separated

mixtures, based on the method of global economic optimization, a scheme with optimum design

variables was developed for both of the conventional distillation and the new proposed

distillation processes. Results revealed that the new process offered 22.76% and 17.25% energy-

savings respectively. Similar percentage of reduction in total annual costs (TAC) can also be

obtained when compared to the conventional distillation process.

Keywords: Extractive distillation, Energy-saving, Process design

1. Introduction

Distillation is by far the most important separation process in chemical engineering, and it

exploits the relative volatility difference of the components to achieve desired separation.

However, for systems with close boiling point or azeotropic systems, a separation by

conventional distillation process becomes difficult or even impossible. For these systems, several

nonconventional techniques such as heterogeneous azeotropic distillation, pressure-swing

distillation, and extractive distillation have been proposed (Doherty et al., 2001; Seader et al.,

1998). However, the pressure-swing option is not economically feasible if the azeotropic

composition is not sufficiently sensitive to pressure, and some complexities of dealing

heterogeneous azeotropic distillation, such as multiple steady states, parametric sensitivity that

were clearly illustrated by many authors which consequently make the design and control

challenging (Doherty et al., 2001; Seader et al., 1998; Widagdo et al., 1996).

Extractive distillation is the most widely used form of homogeneous azeotropic distillation due

to the low energy consumption and flexible selection of the possible entrainers (Lei et al., 2003;

Sucksmith, 1982). In extractive distillation, a heavier entrainer that has different interaction with

the azeotropic components is added to alter the relative volatility of the components, thereby

effectively “breaking” the azeotrope. Nowadays, extractive distillation with ionic liquids or the

mixture of ionic liquids and solid inorganic salt as entrainers attracted more and more attention

(Lei et al., 2014a; Lei et al., 2014b).

An important and special aspect of extractive distillation is that we are not free to pick which

of the components in the feed will be the distillate from the extractive column. For a given

entrainer, one and only one of the feed components can be recovered in the distillate from the
extractive column, and it is not always the component with the lowest boiling point. For

example, the separation of methanol and acetone using chlorobenzene causes higher-boiling

methanol to be recovered as the distillate from the extractive column, and the lower-boiling

acetone to leave in the bottom stream with chlorobenzene. Other entrainers, such as water,

dimethyl sulfoxide (DMSO) causes acetone to be recovered as the distillate from the extractive

column (Kossack et al., 2008; Luyben, 2008a; Luyben, 2008b; Kotai et al., 2007; Modla et al.,

2012; Modla et al., 2011; Langston et al., 2005; Gil et al., 2009). It is important to know which

of the feed components will appear in the distillate stream from the extractive column in order to

design the equipment. Isovolatility curve and pseudo-binary (entrainer-free) equilibrium diagram

are reliable ways. (Doherty et al., 2001; Hsu et al., 2010).

Extractive distillation is widely used in a number of processes (Lladosa et al., 2011; Pacheco-

Basulto et al., 2012; Arifin et al., 2008; Abushwireb et al., 2007; Wang et al., 2012; Gil et al.,

2012; Xu et al., 2006; Hsu et al., 2010), but it is still energy intensive, different methods to

overcome the drawback of energy intensive have been reported. Process integration is a useful

option and it has been proven that the process integration leads to a significant reduction in

energy consumption compared to conventional process with no integration. Doherty et al.

(Knapp et al., 1990) developed thermally-integrated extractive distillation sequences for the

separation of ethanol from water using ethylene glycol as entrainer and methanol from acetone

using water as entrainer, results showed that thermally-integrated extractive distillation system

greatly reduced the energy consumption. Abushwireb et al. (Abushwireb et al., 2007)

investigated the recovery of aromatics from pyrolysis gasoline using N-methylpyrolidone as

entrainer, the results presented in their report proved that the heat-integrated extractive

distillation system was the best candidate. Luyben also studied the heat-integrated extractive
distillation system for the separation of acetone-methanol using water as entrainer, 27% reboiler

duty was saved as compared to the two-column sequence without thermal integration (Luyben,

2008b). In recent years, the use of dividing wall columns has drawn considerable attention. Kiss

et al. (Kiss et al., 2012) studied bioethanol dehydration by extractive dividing-wall column (E-

DWC) system, which led to 10% energy savings. In our previous study, the E-DWC system was

used to separate methylal-methanol mixture, results showed that 8% reboiler duty could be saved

(Xia et al., 2012). Wu et al. (Wu et al., 2013) made a critical assessment of the energy-saving

potential of E-DWC, they found that the energy-saving potential of E-DWC was limited.

Although the methods mentioned above are energy efficient, they have some defects along the

way. For example, heat-integrated extractive distillation systems lead to high investment cost

(Knapp et al., 1990). E-DWC has not been widely used in industry yet due to the complexities of

design and control. As stated by Errico and coauthors (Errico et al., 2013a; Errico et al., 2013b;

Errico et al., 2013c), many studies just focus on extractive distillation column and entrainer

recovery column without considering the preconcentration column. The preconcentration column

of the process, which in fact is commonly used in extractive distillation system especially for

diluted fresh feed should also be considered since they are also energy intensive.

This paper intends to investigate the energy-saving possibility of extractive distillation system

when the adding of the high-boiling solvent reverse relative volatility of feed components. Based

on a three-column conventional extractive distillation system, an innovative extractive

distillation process will be developed. Two case studies will be used as demonstrating examples

to verify the energy and economic advantages of the new process. In the studies, based on global

economic optimization procedure, an optimum design for both conventional and innovative

process will be investigated.

2. Problem Statement and Process Synthesis Procedure

In general, for diluted two-component mixtures, the extractive distillation process is made up

of three columns: preconcentration distillation column (PDC), extractive distillation column

(EDC) and entrainer recovery column (ERC). The process flow diagram of the extractive

distillation process is presented in Fig. 1. The diluted mixture A-B is fed into the PDC to

separate a pure B (higher-boiling point) as bottom product and a near-azeotropic composition

mixture of A-B as distillate product. Then, the distillate product taken from the PDC is sent

afterward to the second column (EDC). In the EDC unit, the extractive entrainer S is added near

the top of the EDC. Due to the addition of entrainer the relative volatility of A and B is changed,

thereby causing the component having the greater volatility, not necessarily the component with

the lowest boiling point, is taken overhead as a pure distillate. The other feed component and S

are recovered in the bottom of the extractive distillation column and then fed to the ERC. The

heavy entrainer S is separated from the remaining component in ERC and then recycled to the

EDC. A small makeup stream of entrainer is added to balance tiny entrainer losses in both

distillate streams.

As shown in Fig. 1, it is worth noting that two pure B streams are obtained from the bottom of

the PDC and the top of the EDC respectively, which is an opportunity to improve the energy

efficiency. Instead of cooling the overhead vapor of the EDC to serve as the liquid reflux flow,

the vapor flow can be directly fed to the bottom of the PDC, which provides part of the vapor

required for the PDC, thereby causing the vapor flow generated by the reboiler of the PDC to be

reduced. Due to the reduction of the vapor flow provided by the reboiler of the PDC, the reboiler

heat duty and heat transfer area can then be significantly decreased. Part of liquid B stream can

be directly fed on the top of the EDC, thus serving as the liquid-phase flow.
 The process flow diagram of the new sequence is presented in Fig. 2 including two distillation

units: combined preconcentration/extractive distillation column, entrainer recovery column. The

first column in the sequence can be divided into two sections: the preconcentration section and

extractive distillation section. Its function corresponds to that of the preconcentration column and

the extractive distillation column in the conventional extractive distillation system. The

preconcentration section and extractive distillation section is in fact acting as the PDC and EDC

unit of the conventional sequence respectively.

The diluted mixture A-B is fed into the preconcentration section, and a near-azeotropic

composition mixture of A-B is removed as distillate. Then, the distillate product taken from the

preconcentration section is sent afterward to the extractive distillation section. The feed

component A and S are recovered in the bottom of the first column and then fed to the ERC. The

heavy entrainer S is separated from component A in ERC and then recycled to the first column.

As shown in Fig. 2, there is only one product B stream rather than two products B stream in Fig.

1, and it is removed as liquid side stream of the first column. It is worth noting that the

intermediate heat exchange is an option. If the vapor flow provided by the extractive distillation

section is not sufficient, a sidestream reboiler has to be installed to return the required amount of

vapor flow to the preconcentration section. Otherwise, the sidestream reboiler is not required.

Hence, a two-column extractive distillation system is generated by combining

preconcentration/extractive distillation columns which is energy efficient as well as has lower

capital investment. In this paper, two case studies are studied to testify the above-mentioned

energy and economic advantages: the separation of n-propanol/water using N-methyl-2-

pyrrolidone (NMP) as entrainer, and the separation of ethyl acetate/ethanol using furfural as

entrainer.
3. Process Design and Economical Optimization

The new process is more complicated when compared with the conventional extractive

distillation process. Also from the analysis above, the conventional extractive distillation process

can be directly retrofitted to the new process. Therefore, the steady state design begins from the

conventional extractive distillation system.

For the new process, the first column is a special column with complex configuration. From

Fig. 1 to Fig. 2 the path from conventional process to the new process, it is clear to know that

when the combined preconcentration/extractive distillation column is decomposed, it should be

exactly the PDC and EDC in the conventional extractive distillation system. Thus, after we get

the optimal design variables of the conventional extractive distillation system, the optimum

design variables of the conventional extractive distillation system can be directly applied to the

new process. Therefore, the original optimal configurations are all kept the same in the new

process (Errico et al., 2014a; Errico et al., 2014b).

3.1. Process Design

In this work, the commercial software Aspen Plus V7.1 was used in the steady state

simulations. The desired product quality requirements were achieved by the “Design Spec/Vary”

feature in Aspen Plus. In all cases, the reflux ratio and distillate rate were used as the operation

variables of each column.

The PDC and the ERC are all simple columns with one feed stream and two product streams.

It’s easy to design these two columns. The EDC with two feed streams and two product streams,

it is more complicated. There are some very simple and reliable tools can be used. Residue curve
maps that allow us to determine whether the entrainer is feasible and they can be used as simple

method to analysis and design feasible extractive distillation sequence (Doherty et al., 2001;

Doherty et al., 1985). It is important to know which of the feed components will appear in the

distillate stream from the extractive column in order to design the equipment. Isovolatility curve

is a reliable way, plot the isovolatility curve on the composition triangle. If the curve intersects

the A-S edge, then component A will be the distillate from the extractive column, otherwise

component B will appear in the distillate stream (Doherty et al., 2001; Hsu et al., 2010). A

relative volatility at various feed ratios plot is a useful tool to demonstrate the effectiveness of

the entrainer. The feed ratio is a very important design variable. In fact, there is a minimum value

of feed ratio where the minimum and maximum reflux ratios occur simultaneously. Below this

value, we are unable to get the desired purity of the product. With the sensitivity analysis tool in

Aspen Plus, it can clearly show the feasible range of feed ratio and reflux ratio. It can help us

choose the appropriate feed ratio and reflux ratio to meet the product specifications.

3.2. Economical Optimization

Once a base-case design is developed, the next step is to optimize the design variables. It is

conventional to use the total annual cost (TAC) as the objective function to be minimized to

screen process candidates, which including annualized capital costs and operating costs

(Douglas, 1988; Muńoz et al., 2006; Kraemer et al., 2009; Harwardt et al., 2012). The following

objective function was used to carry out a global economic optimization.

TAC (103$/year) = Cv + ir·FCI (1)

Where FCI is the fixed capital investment. In this paper, just major pieces of equipment were

concerned, which are the three distillation column vessels (including column internals), three
reboilers, and four condensers. The “tray sizing” function in Aspen Plus was used to calculate

the diameter of column vessels and sieve plate is selected in all columns. An overall heat

transfer coefficient and a differential temperature driving force in each heat exchange were used

to calculate the required heat transfer area. Here the overall heat transfer coefficient and

differential temperature for the condenser and reboiler were all taken from Luyben (Luyben,

2006). A cost estimation program CAPCOST of Turton was used to estimate all the major

equipment costs (Turton et al., 2009). ir is the fixed capital recovery rate, it is assumed to be 0.3.

Cv is the operating cost, which includes mostly utilities consumption (steam, cooling water). The

utilities consumption costs can be calculated from the heat duties of reboilers and condensers.

High pressure steam with pressure of 41 barg (254℃), medium pressure steam with pressure of

10 barg (184℃) and low pressure steam with pressure of 5 barg (160℃) and cooling water with

temperature of 30℃ are supposed to be available in the plant. The utility prices taken from

CAPCOST are listed in Table 1 (Turton et al., 2009).

The design variables need to be optimized in the conventional process include the total stages

of the PDC (NT1), the EDC (NT2), and the ERC (NT3), fresh stream feeding location of the PDC

(NF1), entrainer and fresh streams feeding locations (NFE and NF2) of the EDC, and the feeding

location of the ERC (NF3) and the entrainer flow rate (S). As so many design variables need to be

optimized, a calculation sequence was established to facilitate the optimization. Such sequential

iterative optimization procedure is clearly demonstrated in Fig. 3 (Liang et al., 2009).

4. Case Study: N-propanol and Water Separation

N-propanol is widely used as solvent or as important fine chemical in the chemical and

pharmaceutical production process. It is impossible to separate n-propanol from water through

conventional distillation because of the existence of a binary azeotrope. The n-propanol/water

mixture has a minimum azeotrope with composition of about 42.5 mol% n-propanol at 1 atm.

Traditional separation method for the system include heterogeneous azeotropic distillation using

cyclohexane or diisopropyl ether (DIPE) as entrainer (Lee et al., 2003; Pienaar et al., 2013).

There is little report about separating this system through extractive distillation. In this section,

conventional extractive distillation is studied for the separation of this system. The new

combined preconcentration/extractive distillation column setup is applied to investigate the

energy-saving possibility of this extractive distillation system.

4.1. Conventional Three-Column Process

4.1.1. Steady State Design Analysis

The thermal condition specifications of the feed, products, and recycle solvent streams are

listed in Table 2. In all the alternatives proposed the amount of product is always the same. The

RADFRAC distillation routine was used to design and simulate the processes. The operating

pressure was set at 1atm for each column at both the conventional and the new process. The

NRTL thermodynamic model was selected to predict the physical properties in the simulation

and built-in binary interaction parameters was used. Table 3 shows the binary interaction

parameters for the NRTL model. The tray spacing for each column in the conventional and the

new process was specified as 0.4 m. In this work, we chose N-methyl-2-pyrrolidone (NMP) as

the heavy entrainer. From Fig. 4a, it is observed that NMP is a feasible entrainer for the

separation of n-propanol-water system. That is because the entrainer NMP does not form any

azeotropes with the original components, and is completely miscible with them in all

proportions. The residue curve map has the optimal configuration-the minimum boiling n-

propanol-water azeotrope is the unstable node, the entrainer NMP is the stable node, and the two
components of n-propanol and water are both saddles. From Fig. 4a, it is observed that

isovolatility curve intercepts the water-NMP edge of the triangle. This observation determines

that the overhead product removed from the EDC should be water (the higher-boiling

component) and not n-propanol (the lower-boiling component). It is worth mentioning that, in an

extractive distillation system, the component with lower-boiling point cannot automatically be

assumed to be the distillate product removed from the EDC. From Fig. 4b, it is observed that

NMP is an effective entrainer, causing an increase in the relative volatility of the water and n-

propanol, thus effectively “breaking” the azeotrope.

Beginning the design process from the PDC, the distillate composition was specified to be 40.0

mol% n-propanol, a near-azeotropic composition mixture of n-propanol-water. The bottom

composition was specified to be 99.9 mol% water to reduce the n-propanol loss.

The EDC, it’s more complicated. The flow rate of the entrainer is an important design variable.

Without appropriate entrainer flow rate and reflux ratio, we are unable to get the desired purity of

the product. With the sensitivity analysis tool in Aspen Plus, several case studies were made to

investigate the effects of changing the flow rate of entrainer and reflux ratio on the product

compositions of the distillate stream from the EDC, which is the water product. In each case, the

number of theoretical plates (NT2), the distillate rate with different S and RR2 were fixed. Fig. 5a

shows the effects of changing the flow rate of NMP and RR2 on the water product of the EDC

with NT2=58. Fig. 5a shows that at any value of the entrainer flow rate, there is a minimum reflux

ratio and also a maximum reflux ratio, RRmin and RRmax get closer as we add less entrainer. At

small values of entrainer flow rate there will be a narrow range of RR2 over which the desired

separation is possible. For a given entrainer flow rate S, there is an optimum reflux ratio, which

gives the desired water purity. It is critical to choose the feasible range of the entrainer flow rate
and reflux ratio to meet the water purity. To achieve the desired 99.9 mol% water purity, the

entrainer flow rate must be above 290kmol/h, and the reflux ratio RR2 is about 0.75. Below this

value, the separation is not possible. Fig. 5b shows the effects of changing the flow rate of NMP

and RR2 on the impurity of n-propanol of the EDC.

Similar with the PDC, the ERC is a simple column. The bottom composition of NMP purity

was specified to be 99.999 mol%, the reason for the ultra-high purity in NMP is because the

impurity in the NMP will have a very bad influence on the water purity. A heat exchanger must

be placed between the EDC and the ERC to cool the NMP temperature. In this case, the

temperature of the entrainer NMP was cooled to be 90.0℃. This is because Knight et al. (Knight

et al., 1989). suggested that the entrainer feed temperature to the EDC should be 5-15℃ below

the boiling temperature of the distillate product from the EDC.

4.1.2. Economical Optimization

Fig. 6 shows the results of the optimization runs for the PDC with NT1 and NF1 as the design

variables. From this plot, the best NT1 is stage 9 and the best NF1 is stage 6.

Fig. 7a shows the summary of the TAC plots at each entrainer flow rate for the EDC, it can be

observed that the optimal entrainer flow rate is 330 kmol/h. Fig. 7c shows the results for varying

NT2 with the entrainer flow rate fixed at 330 kmol/h. From the Fig. 7c, the optimal NT2 is 58. Fig.

7b shows the results of the optimization runs for varying NF2 and NFE with NT2 fixed at 58 and the

entrainer flow rate fixed at 330 kmol/h. QR2 is chosen as the objective function instead of using

TAC to investigate the effect of changing NF2 and NFE. From the Fig. 7b, the optimal NFE is stage

6 and the optimal NF2 is stage 44. The final optimal design variables for the EDC are S=330

kmol/h, NT2 =58, NFE =6 and NF2 =44.

 Fig. 8 shows the summary of the TAC plots for the ERC. From the Figure, the optimal NT3 is

stage 27 and the optimal NF3 is stage 8.

4.2. New Two-column Process

After the optimal design variables of the conventional extractive distillation system are

determined, the optimal design variables of the conventional extractive distillation system can be

directly applied to the new process. Thus, the original optimal configurations are all kept the

same in the new process. The optimal design variables for the PDC and the EDC can be directly

applied to the preconcentration section and extractive section for the first column of the new

process respectively. The final optimum process flow diagrams for the conventional extractive

distillation system and the new process are shown in Fig. 9.

4.3. Process Comparison

In this section, heat duty, TAC of the above two processes will be compared. Table 4 shows

the heat duty and the minimized TAC results for the optimal conventional extractive distillation

system and the new combined preconcentration/extractive column system. It is shown that the

total reboiler duty of the new process is less than that of the conventional design by about 1575.9

kW, which is about 22.76 % saving in total reboiler energy consumption. The reason is that part

of the vapor flow required for the preconcentration section is provided by the extractive section,

thereby causing the vapor flow provided by the intermediated reboiler to be reduced. From the

economical data, it is observed that the separation using the new process leads to 15.63 %

reduction in total capital investment cost, that is because the new process saves one condenser

and the side stream reboiler is much smaller compared to that of the conventional configuraion.

There is also a significant reduction in operating cost. The total operating cost for the
conventional process is 3371.4 (103 $/year) while the new process costs 2752.4 (103 $/year). This

represents a reduction of 18.36 % of the cost of the energy, that is mainly because the new

process leads to 22.76 % saving in total reboiler energy consumption. The TAC of the new

process is 3918.0.0 (103 $/year), this can be directly compared to the TAC of the conventional

process. Thus, the separation using the optimum new two-column desgin leads to the reduction

in total annual cost as much as 17.57 %.

5. Case Study: Ethyl Acetate and Ethanol Separation

Ethyl acetate (EA) is an important environmental friendly solvent, and is industrially used in a

wide range of applications. In the synthetic processes for ethyl acetate, ethyl acetate/ethanol

mixture is commonly obtained. It is impossible to achieve the separation of ethyl acetate/ethanol

mixture by conventional distillation, because the ethyl acetate/ethanol mixture forms a minimum

azeotrope with composition of about 46.55 mol% ethanol at 1 atm. The purification techniques

for ethyl acetate have been investigated, such as azeotropic distillation, extractive distillation,

and membrane separation (Berg et al., 1999; Zhang et al., 2008; Sato et al., 2008). In this section,

conventional extractive distillation is studied for the separation of this system. The new process

is also applied to investigate the energy-saving possibility of this extractive distillation system.

5.1. Conventional Three-Column Process

5.1.1. Steady State Design Analysis

Table 5 shows the thermal condition specifications for the feed, products, and solvent recycle

stream. In all the alternatives proposed the amount of product is always the same. The

RADFRAC distillation routine was used to design and simulate the processes. The operating
pressure was set at 1atm for each column at both the conventional and the new process. The

NRTL thermodynamic model was selected to predict the physical properties in the simulation

and built-in binary interaction parameters was used. Table 6 shows the binary interaction

parameters for the NRTL model. The tray spacing for each column in the conventional and the

new process was specified as 0.4 m. In this work, we chose furfural as the heavy entrainer for its

low price. From Fig. 10a, it is observed that furfural is a feasible entrainer for the separation of

ethyl acetate/ethanol mixture. From Fig. 10a, it is observed that ethanol (the higher-boiling

component) is the distillate of the EDC. From Fig. 10b, it is observed that furfural is an effective

entrainer, causing an increase in the relative volatility of the ethyl acetate and ethanol, thus

effectively “breaking” the azeotrope.

At the beginning of the design process from the PDC, the distillate composition was specified

to be 45.0 mol% ethyl acetate, a near-azeotropic composition mixture of ethyl acetate/ethanol.

For column 2, Fig. 11a shows the effects of changing the flow rate of furfural and RR2 on the

ethanol product of the EDC with NT2=46. To achieve the desired 99.5 mol% ethanol purity, the

furfural flow rate must be set above 390kmol/h at a reflux ratio of about 1.25. The feed ratio is

about 2.36, which is much larger than the feed ratio 1.94 in case 1 indicating that furfural to the

ethyl acetate/ethanol system is less effective than NMP to the n-propanol/water system. Fig. 11b

shows the effects of changing the flow rate of furfural and RR2 on the impurity of ethyl acetate of

the EDC. The bottom composition of the ERC was set at 99.999 mol% furfural. A heat

exchanger must be placed between the ERC and the EDC. In this case, the temperature of the

entrainer furfural was cooled to be 70.0℃.

5.1.2. Economical Optimization

 Fig. 12 shows the results of the optimization runs for the PDC. From this plot, the best NT1 is

stage 27 and the best NF1 is stage 11. The result shows that the separation of ethyl acetate/ethanol

system is much more difficult than the separation of n-propanol/water system.

Fig. 13a shows the summary of the TAC plots at each entrainer flow rate for the EDC, it can

be observed that the optimal entrainer flow rate is 540 kmol/h. The result also indicates that the

entrainer furfural to the ethyl acetate-ethanol system is less effective than NMP to the n-

propanol-water system. Fig. 13c shows the results for varying NT2 with the entrainer flow rate

fixed at 540 kmol/h. From the Fig. 13c, the optimal NT2 is 46. Fig. 13b shows the results of the

optimization runs for varying NF2 and NFE with NT2 fixed at 46 and the entrainer flow rate fixed at

540 kmol/h. From the Fig. 13b, the optimal NFE is stage 8 and the optimal NF2 is stage 31. The

final optimal design variables for the EDC are S=540 kmol/h, NT2 =46, NFE =8 and NF2 =31.

Fig. 14 shows the summary of the TAC plots for the ERC. From the Fig. 14, the optimal NT3 is

stage 25 and the optimal NF3 is stage 11.

5.2. New Two-column Process

Similar to case 1, after the optimal design variables of the conventional extractive distillation

system are determined, the optimal design variables of the conventional extractive distillation

system can be directly applied to the new process. Thus, the original optimal configurations are

all kept the same in the new process. The optimal design variables for the PDC and the EDC can

be directly applied to the preconcentration section and extractive section for the first column of

the new process respectively. The final optimum process flow diagram for the conventional

extractive distillation system design and the new process design is shown in Fig. 15.
 5.3. Process Comparison

In this section, heat duty, TAC of the above two processes for the separation of ethyl

acetate/ethanol were compared. Table 7 shows the heat duty and the minimized TAC results for

the optimal conventional extractive distillation system and the new combined preconcentration/

extractive column system. It is shown that the total reboiler duty of the new process is less than

that of the conventional design by about 1495.9 kW, which is about 17.25 % saving in total

reboiler energy consumption. From the economical data, it is observed that the separation using

the new process leads to 14.10 % reduction in total capital investment cost. There is also a

significant reduction in operating cost. The total operating cost for the conventional process is

3748.7 (103 $/year) while the new process cost is 3163.2 (103 $/year). This represents a reduction

of 15.62 % of the cost of the energy, that is mainly because the new process leads to 17.25 %

saving in total reboiler energy consumption. The TAC of the new process is 4567.2 (103 $/year),

this can be directly compared with the TAC of the conventional process. Thus, the separation

using the optimum new two-column desgin leads to the reduction in total annual cost by as much

as 15.16 %.

5. Summary and Conclusion

In the extractive distillation process, the adding of high-boiling entrainer (organic solvent,

ionic liquids) may reverse the relative volatility of the feed components causing the component

with higher-boiling point be removed as the distillate from the extractive column. The energy-

saving possibility of extractive distillation system was investigated when this phenomenon

occurred. Based on a three-column conventional extractive distillation system, an innovative

process by combining preconcentration column and extractive distillation column was proposed.
The new process is energy efficient with lower capital investment. The main reason is that part

of the vapor flow required for the preconcentration section is provided by the extractive section,

thereby causing the vapor flow provided by the intermediated reboiler to be reduced. The new

process is not limited to the studied systems which can also be used to separate other azeotropic

and in systems with close boiling point as long as the bottom product removed from the

preconcentration column and the distillate product removed from the extractive distillation

column have the same composition specification. Two important systems were used to verify the

energy and economic advantages: the separation of n-propanol/water and the separation of ethyl

acetate/ethanol. Using these two systems as examples, important observations of this paper are

summarized as below:

1. The separation of n-propanol/water using N-methyl-2-pyrrolidone (NMP) as entrainer and

the separation of ethyl acetate/ethanol using furfural as entrainer causing the component with

higher-boiling point be removed as the distillate from the extractive column, which are water and

ethanol respectively in these two case studies.

2. The new process is a useful technology to save energy and lower the capital investment.

The optimal design of the conventional extractive distillation process and the new process were

presented. For the two case studies-the separation of n-propanol/water and ethyl acetate/ethanol,

the results show that the new process leads to energy savings of 22.76 % and 17.25 %

respectively and a similar reduction in capital investment and the total annual costs. In the new

process, an intermediate reboiler was used to meet the energy requirment in the preconcentration

section.

.
Nomenclature

NRTL=Non-Random Two Liquid

E-DWC=extractive dividing-wall column

PDC =preconcentration distillation column

EDC =extractive distillation column

ERC =entrainer recovery column

NF1= feeding location for the fresh feed

NFE =feeding location for the entrainer

NF2= feeding location for the feed to column EDC

NF3=feeding location for the feed to column ERC

NTn=number of theoretical plates for column n

QCn=condenser duty for column n (KW)

QRn=reboiler duty for column n (KW)

QCT = total condenser heat duty (KW)

QRT= total reboiler heat duty (KW)

NMP= N-methyl-2-pyrrolidone

EA= ethyl acetate

RRn=reflux ratio for column n

TAC=total annual costs

TIC=total investment costs

TOC=total operating costs

 Acknowledgment

The authors thank for the support by the Programme of Introducing Talents of Discipline to

Universities (No: B06006) and the assistance from the staffs in the State Key Laboratories of

Chemical Engineering (Tianjin University).

Notes

The authors declare no competing financial interest

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 Table 1. Utility prices

Utility Price ($/GJ)

High pressure steam (41 barg) 17.7

Medium pressure steam (10 barg) 14.19
Low pressure steam (5 barg) 13.28
Cooling water 0.354

Table 2. Specifications for streams

Stream Conditions

Feed Saturated liquid

n-propanol product Saturated liquid

H2O product Saturated liquid

NMP entrainer recycle 90.0℃

Table 3. The Binary Interaction Parameters for the Aspen Plus NRTL Model

n-propanol (i) n-propanol (i) H2O(i)

Binary parameters
H2O(j) NMP(j) NMP(j)

Aij 0.0 0.0 0.0

Aji 0.0 0.0 0.0

Bij/K 181.2160 -234.2208 -120.5810

Bji/K 927.9748 -205.8249 288.7615

 Cij 0.4687 0.3000 0.3055

Table 4. Comparision Between the Optimum Conventional Design and Corresponding

New Two-column Design

Conventional process New process % difference

Heat duty
QRT (kW) 6925.3 5349.4 -22.76%
QCT(kW) 6876.9 5301.0 -22.92%
Economical data
TIC (103 $) 4605.3 3885.3 -15.63%
TOC (103 $/year) 3371.4 2752.4 -18.36%
TAC (103 $/year) 4753.0 3918.0 -17.57%

Table 5. Specifications for streams

Stream Conditions

Feed Saturated liquid

Ethyl acetate product Saturated liquid

Ethanol product Saturated liquid

Furfural entrainer recycle 70.0 ℃

 Table 6. The Binary Interaction Parameters for the Aspen Plus NRTL Model

Ethanol (i) Ethanol (i) Ethyl acetate (i)

Binary parameters
Ethyl acetate (j) Furfural (j) Furfural (j)

Aij 0.0 0.0 0.0

Aji 0.0 0.0 0.0

Bij/K 216.3048 139.6013 548.0231

Bji/K 95.0457 425.8981 -257.2865

Cij 0.3000 0.30000 0.30000

Table 7. Comparision Between the Optimum Conventional Design and Corresponding New

Two-column Design

Conventional process New process % difference

Heat duty
QRT (kW) 8672.5 7176.6 -17.25%
QCT(kW) 8647.8 7151.9 -17.30%
Economical data
TIC (103 $) 5448.0 4680.0 -14.10%
TOC (103 $/year) 3748.7 3163.2 -15.62%
TAC (103 $/year) 5383.1 4567.2 -15.16%
 Figure captions

Fig. 1. Sketch of conventional extractive distillation process.

Fig. 2. Sketch of combined preconcentration/extractive distillation process.

Fig. 3. Sequential iterative optimization procedure for the conventional extractive distillation

system.

Fig. 4. (a) Residue curve map with isovolatility curves for the N-propanol-H2O-NMP system at 1atm. (b)

Relative volatility at various feed ratios.

Fig. 5. (a) Effect of RR2 and entrainer flow rate S in extractive column (NT2=58) on H2O purity. (b) Effect of

RR2 and entrainer flow rate S in extractive column (NT2=58) on impurity of n-propanol.

Fig. 6. TAC vs NT1 with the optimum NF1 plot for the PDC.

Fig. 7. (a) TAC plot at various entrainer flow rate S for the EDC. (b) QR2 vs NFE and NF2 for S=330 kmol/h,

NT2=58 plots for the EDC. (c) TAC vs NT2 for S=330 kmol/h plot for the EDC.

Fig. 8.TAC vs NT3 with the optimum NF3 plot for the ERC.

Fig. 9. (a) The optimum process flow diagram for the new combined preconcentration/ extractive

column system. (b) The optimum process flow diagram for the conventional extractive distillation

system.
Fig. 10. (a) Residue curve map with isovolatility curves for the Ethanol-Ethyl acetate-Furfural system at

1atm. (b) Relative volatility at various feed ratios.

Fig. 11. (a) Effect of RR2 and entrainer flow rate S in extractive column (NT2=46) on ethanol purity. (b)

Effect of RR2 and entrainer flow rate S in extractive column (NT2=46) on impurity of ethyl acetate.

Fig. 12. TAC vs NT1 with the optimum NF1 plot for the PDC.

Fig. 13. (a)TAC plot at various entrainer flow rate S for the EDC. (b) QR2 vs NFE and NF2 for

S=540 kmol/h, NT2=46 plots for the EDC. (c) TAC vs NT2 for S=540 kmol/h plot for the EDC.

Fig. 14.TAC vs NT3 with the optimum NF3 plot for the ERC.

Fig. 15. (a) The optimum process flow diagram for the new combined preconcentration/

extractive column system. (b) The optimum process flow diagram for the conventional extractive

distillation system.
 MAKEUP

D1 D3
D2

B A
F

A+B

B1 B2 B3

Preconcentration Extractive distillation Entrainer recovery

column column column

Fig. 1

A+B Preconcentration D1
section D2

B A

MAKEUP

S Extractive
distillation
section

B1 B2

A+S

Combined Entrainer
preconcentration/extractive recovery
column column

Fig. 2
 Fig. 3

H2O (100.02 C) Ternary Map (Mole Basis)

0.9
2.5
0.8
Relative Volatility

0.7 87.65 C
0.6 2.0
0.5
0.4
0.3 1.5
0.2
0.1
1.0
NMP C3H8O-01 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
(203.99 C) 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 (97.20 C) NMP/Azeotrope Feed Ratio

(a) (b)
 Fig. 4

XD(mole frac of n-propanol)

1.000 0.005
XD(mole frac of H2O)

0.999 0.004 S=280kmol/h

S=310kmol/h
S=290kmol/h
0.998 0.003
S=300kmol/h S=300kmol/h
0.997 0.002
S=290kmol/h S=310kmol/h
0.996 S=280kmol/h 0.001

0.995 0
0.8 1.0 1.2 1.4 1.6 1.8 2.0 0.8 1.0 1.2 1.4 1.6 1.8 2.0
RR2 RR2

(a) (b)

Fig. 5

998.0
997.5
TAC(x1000$/year)

997.0
996.5 NT1=9 with the
optimum NF1=6
996.0
995.5
995.0
994.5
7 8 9 10 11
NT1

Fig. 6
 2372.0 3340
NFE=5
TAC(x1000$/year) 2371.5 NFE=6
3335
2371.0 NFE=7

QR2/kW
2370.5 3330

2370.0
3325
2369.5

2369.0 3320
320 330 340 350 43 44 45 46
S-solvent flow rate(kmol/h) NF2

(a) (b)

2375

2374
TAC(x1000$/year)

2373

2372

2371

2370

2369
54 56 58 60
NT2

(c)

Fig. 7

1302
TAC(x1000$/year)

1301

1300 NT3=27 with the

optimum NF3=8
1299

1298

1297
25 26 27 28 29 30
NT3

Fig. 8
 F
2 1atm 2 1atm
300.000 kmol/hr
1794.4kW 1353.1kW
0.200 N-prorpanol
0.800 H2O 6
240.181kmol/hr RR2=0.957
RR1=0.0425
219.0 kW 9.803E-04N-pnol
0.999 H2O
1.972E-05NMP D2
S MAKEUP 8
0.005 kmol/hr 8 59.824 kmol/hr
1.000 NMP D1 0.999 N-prorpanol
13 149.624kmol/hr 0.00099 H2O
0.400 N-prorpanol 0.00001NMP
0.600 H2O
2153.6 kW 51 3.1164E-14 NMP

64 B2 26
B1 329.998kmol/hr
389.822kmol/hr 1E-05 N-prorpanol
0.153 N-prorpanol 3.213E-19H2O
3325.0 kW 0.000152 H2O 0.99999 NMP 1805.5 kW
0.847 NMP

Combined preconcentration/extractive Entrainer recovery

column column

(a)

1atm S 1atm 1atm

2 1784.4kW 2 2 1353.1kW
MAKEUP 1585.8 kW
6

0.005 kmol/hr
1.000 NMP RR3=0.957
RR1=0.0367 RR2=0.557
F D2
D1 D3
89.805 kmol/hr 8 59.823 kmol/hr
300.000 kmol/hr 0.000958 N-prorpanol
149.624 kmol/hr 0.999 N-prorpanol
0.200 N-prorpanol 0.999 H2O
0.400 N-prorpanol 0.00099 H2O
0.800 H2O 0.600 H2O 4.199E-05NMP
6 0.00001NMP
44

57 26
8 B2 B3
B1 389.823kmol/hr 330.000 kmol/hr
150.376 kmol/hr 0.153 N-prorpanol 1E-05 N-prorpanol 2153.6 kW
0.001 N-prorpanol 0.000152 H2O 1805.4 kW 3.2185E-19 H2O
1795.1 kW 3324.7 kW
0.999 H2O 0.847 NMP 0.99999 NMP

Extractive distillation Entrainer recovery

Preconcentration column
column
column

(b)

Fig. 9
 ETHANOL (78.31 C) Ternary Map (Mole Basis)

0.9
2.8
0.8
2.6

Relative Volatility
0.7
2.4
0.6 2.2
72.14 C
0.5 2.0
0.4 1.8
0.3 1.6
0.2 1.4
0.1 1.2
FURFURAL C4H8O-01 1.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
(161.35 C) 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 (77.20 C)
Furfural/Azeptrope Feed Ratio

(a) (b)

Fig. 10

0.998 0.010
XD(mole frac of Ethanol)

XD(mole frac of EA)

0.997 0.009
0.996 0.008 S=380kmol/h
0.995 S=410kmol/h 0.007
S=390kmol/h
0.994 S=400kmol/h 0.006
0.005 S=400kmol/h
0.993
S=390kmol/h
0.992 0.004 S=410kmol/h
S=380kmol/h 0.003
0.991
0.990 0.002
1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0
RR2 RR2

(a) (b)

Fig. 11
 1911

TAC(x1000$/year)
1910

1909
NT1=27 with the
optimum NF1=11
1908

1907

1906
25 26 27 28 29 30 31
NT1

Fig. 12

1927.0 3250
NFE=7
TAC(x1000$/year)

1926.5 3248 NFE=8

NFE=9
3246

QR2/kW
1926.0
3244
1925.5
3242
1925.0
3240
1924.5 3238
525 530 535 540 545 550 555 30 31 32 33
S-solvent flow rate(kmol/h) NF2

(a) (b)

1932
TAC(x1000$/year)

1930

1928

1926

1924
42 44 46 48
NT2

(c)

Fig. 13
 1457

TAC(x1000$/year)
1456
NT3=25 with the
optimum NF3=11

1455

1454
24 25 26 27
NT3

Fig. 14
 F
300.000 kmol/hr 2 1atm 2 1atm
0.750 Ethanol 3395.5kW 1340.9kW
0.250 EA
11
225.758kmol/hr RR2=1.012
RR1=1.068
1908.4 kW 0.995Ethanol
0.00454 EA
0.000460Furfural D2
S MAKEUP 26
0.100 kmol/hr 11 74.347 kmol/hr
1.000 Furfural D1 0.00499 Ethanol
33 165.169kmol/hr 0.995 EA
0.550Ethanol 0.00001 Furfural
0.450 EA
2415.6 kW 56 5.0696E-21Furfural

70 B2 24
B1 536.721kmol/hr
611.068kmol/hr 1.2334E-16 Ethanol
0.000607Ethanol 1E-05 EA
3239.9kW 0.121 EA 0.99999 Furfural 2028.3 kW
0.878Furfural

Combined preconcentration/extractive Entrainer recovery

column column

(a)

1atm S 2
2 2 1atm 1atm
3391.8 kW MAKEUP 1481.4kW 1344.6kW
8
0.1kmol/hr
F 1.000 Furfural RR2=0.507 RR3=1.018
RR1=1.066
300.000 kmol/hr D2 D3
0.750 Ethanol D1 90.926 kmol/hr 74.342 kmol/hr
0.250 EA 11
11 165.169 kmol/hr 0.995 Ethanol 0.00499 Ethanol
0.550 Ethanol 0.004 EA 0.995 EA
0.450 EA 0.001 Furfural 0.00001 Furfural
31

26 45 B2 24 B3
B1 614.248 kmol/hr 539.906kmol/hr
134.831kmol/hr 0.000604 Ethanol 1.226E-16 Ethanol 2429.9kW
0.995 Ethanol 0.120 EA 1E-05 EA
3399.6kW 0.005 EA 3239.2 kW 0.879 Furfural 2033.7kW 0.99999 Furfural

Preconcentration Extractive distillation Entrainer recovery

column column column

(b)

Fig. 15
 F
PDC A
A+B

B A B ERC
Higher-boiling
component
F PDC EDC ERC EDC
A+B

Path from conventional setup to energy-saving new process