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Energy efficiency of acetone, butanol, and ethanol (ABE) recovery by heat-

integrated distillation

Article in Bioprocess and Biosystems Engineering · March 2018

DOI: 10.1007/s00449-017-1874-z

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 Grisales Diaz VH, Olivar Tost G. Energy efficiency of acetone, butanol, and
ethanol (ABE) recovery by heat-integrated distillation. Bioprocess and
Biosystems Engineering 2017
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Energy efficiency of acetone, butanol, and ethanol (ABE) recovery by heat-

integrated distillation

Victor Hugo Grisales Diaz1* and Gerard Olivar Tost2

1School of Chemical Engineering and Advanced Materials, Newcastle University, Newcastle

upon Tyne NE1 7RU, UK

2Faculty of Engineering and Architecture. Department of Electrical, Electronics and Computation

Engineering. Universidad Nacional de Colombia – Sede Manizales, Cra. 27 No. 64-60,

Manizales, Colombia.

Author information

Corresponding Author

*E-mail: [email protected]; [email protected].

Tel.:+ 573008720595

1
Abstract

Acetone, butanol, and ethanol (ABE) is an alternative biofuel. However, the energy requirement

of ABE recovery by distillation is considered elevated (>15.2 MJ fuel/Kg-ABE), due to the low

concentration of ABE from fermentation broths (between 15 and 30 g/l). In this work, in order to

reduce the energy requirements of ABE recovery, four processes of heat-integrated distillation

were proposed. The energy requirements and economic evaluations were performed using the

fermentation broths of several biocatalysts. Energy requirements of the processes with four

distillation columns and three distillation columns were similar (between 7.7 and 11.7 MJ

fuel/kg-ABE). Double-effect system (DED) with four columns was the most economical process

(0.12-0.16 $/kg-ABE). ABE recovery from dilute solutions by DED achieved energy

requirements between 6.1 and 8.7 MJ fuel/kg-ABE. Vapor compression distillation (VCD)

reached the lowest energy consumptions (between 4.7 and 7.3 MJ fuel/kg-ABE). Energy

requirements for ABE recovery DED and VCD were lower than that for integrated reactors. The

energy requirements of ABE production were between 1.3- and 2.0-fold higher than that for

alternative biofuels (ethanol or isobutanol). However, the energy efficiency of ABE production

was equivalent than that for ethanol and isobutanol (between 0.71 and 0.76) because of

hydrogen production in ABE fermentation.

Keywords: Biofuel; Distillation; Energy; Process Design; Economic Evaluation

2
Nomenclature

ABE, acetone, butanol, and ethanol

DE, double-effect

FABE, production flow of ABE [kg/h]

HS is the energy consumption of the separation [MJ/kg-ABE]

IRC, investment cost of recovery [$/kg-ABE]

LHV, lower heating value of solvents [MJ/kg-ABE]

M&S, Marshall and Swift equipment cost index

ORC, operational cost of recovery [$/kg-ABE]

Rs, the ABE yield [g-ABE/g-substrate]

TRC, total recovery cost [$/kg-ABE]

TIC, the total investment cost [$]

TOAC, the total operational annualized cost [$/year]

tri, payback period [year]

ta, annual operation time [h]

VC, vapor compression

VLE, vapor-liquid equilibrium

3DC, three distillation columns

3DC-VC, three distillation columns with vapor compression

4DC, three distillation columns

4DC-DE, four distillation columns with double-effect

5DC, five distillation columns

3
 Introduction

During the last years, biotechnological production of butanol has been renewed due to

its biofuel potential [1]. The biotechnological production is traditionally performed by mesophilic

solvent-producing strains [2], such as Clostridium acetobutylicum, Clostridium beijerinckii,

Clostridium saccharobutylicum or Clostridium saccharoperbutylicum. These biocatalysts

produce acetone, butanol and ethanol (ABE). In the Chinese industrial process, ABE is

produced in the average ratio of 2.5:4.8:1 (calculated from stoichiometric reaction reported by Ni

and Sun [3]). The main advantage of traditional Clostridium is the ability to consume a wide

variety of substrates, such as glucose, sucrose, lactose, xylose, starch and glycerol [4].

To achieve a high conversion avoiding product inhibition, the substrate is fed at low

concentration (55-75 g/l) into the reactor. This characteristic makes steam consuming

operations, such as mash sterilization, downstream product recovery and wastewater treatment

energy demanding [5]. In order to reduce water usage for biobutanol production [3], vinasses

from distillation in Chinese industry are recycled into the reactor in ~40%.

Integrated reactors with separation units have been proposed to reduce energy

requirements, investment cost and vinasses production [6–10]. Qureshi et al. [6] reported that

liquid-liquid extraction and adsorption processes have the lowest energy requirements with 8.9

and 8.2 MJ/kg-butanol, respectively. In another study, pervaporation (9 MJ/kg-ABE) and liquid-

liquid extraction (14 MJ/Kg-ABE) were the integrated systems with the lowest energy

requirements [11].

Final purification of integrated and conventional reactors for biobutanol production is

traditionally carried out by distillation. These distillation systems have conventionally five stages.

In the first column, ABE is concentrated at 60 wt%. Acetone and ethanol are concentrated in

two columns, while butanol and water are concentrated finally in an azeotropic distillation

system of two columns. In azeotropic distillation, decantation is used to break the azeotropic

behavior of butanol and water [12]. A separation agent for decantation is not needed because

butanol is partially miscible in water.

A great steam consumption (13-25 kg-steam/kg-ABE) have been reported in Chinese

industrial processes [3]. In academic evaluations of distillation processes, based on industrial

processes, high-energy requirements have been reported commonly (24.2 MJ/kg-butanol [6] or

4
28 MJ/kg-butanol [13]). However, Jilin Cathy Industrial Biotech recently reported a low energy

requirement of distillation system of 6-7 kg-steam/kg-butanol [14]. The reasons for the

differences in the energy requirements are undefined.

Distillation can be integrated to reduce its energy requirement. Process integration in

distillation follows various routes such as: internal heat integrated distillation columns [15, 16],

vapor compression (VC) distillation [17, 18], petlyuk or dividing wall columns [19], double-effect

(DE) distillation [20, 21] and cyclic distillation [22, 23]. Among these alternatives, Kaufman et al.

[17] proposed a sequential system of multiple VC for ABE recovery (patented process).

Additionally, low energy requirements have reported in our previous work with DE (7.2 MJ/kg-

ABE) [24].

In this paper, four heat-integrated distillation systems were evaluated energetically.

Integrated distillation systems may need an investment higher than that for conventional

distillation; therefore, an economic analysis was performed. Considering biofuel application, the

energy efficiency of ABE recovery by distillation was compared with that for the dehydration of

alternative biofuels (isobutanol, ethanol and isopropanol, butanol and ethanol (IBE) [25, 26]).

Due to its high-energy efficiency (between 0.71 and 0.76), the distillation systems studied in this

work will provide a new baseline of energy requirements.

Methods

The simulations were performed in Aspen Plus®. RadFrac was the unity used for

distillation simulation. Trays selection was sieve's type. Pressure drop in the column was

calculated with tray rating of RadFrac. The base method in simulations was UNIQUAC-RK with

CO2 and H2 as Henry’s components.

The accuracy of UNIQUAC or NRTL liquid-liquid equilibrium (experimental data [27, 28])

using the binary parameters of vapor-liquid equilibrium (VLE) is very low (Fig. 1). Therefore, the

binary parameters of the decanter units must be different to the distillation units. The binary

parameters of distillation were APV73 LLE-ASPEN (Fig. 1). The parameters for butanol-water

mixture were those reported by Fisher and Gmehling [13, 29]

In all the distillation systems studied in this work, condensation heat was not used to

preheat the feed of ABE concentration columns. Instead, the exit from these distillation columns

was used to preheat their respective feed, maximizing the heat integration [25]. The distillation

5
processes after this integration achieved a waste mash temperature of 47 ºC (fermentation

temperature of 37 °C, minimum approach temperature of 10 °C), which is a temperature

suitable for solids concentration by filtration [30].

Butanol boiling point is high (117 °C). However, the azeotrope of minimum boiling point

of butanol and water increased the relative volatility of butanol at low concentrations. Indeed,

butanol has a relative volatility at low concentrations in water 2.3-fold higher than ethanol.

Consequently, butanol in all processes is recovered from the top of C1 column. Vinasses were

partially recycled to the reactor to reduce the substrate concentration (18 wt%) and water

requirements [3].

System with four distillation columns (4DC)

ABE in the 4DC process was separated sequentially based on its boiling point (Fig. 2).

Therefore, acetone, ethanol, and butanol were obtained in the columns C2, C3, and C4,

respectively. Due to butanol-water azeotrope, the top stream of C1 is not anhydrous. In this

work, the concentration of water at the top of C1 was reduced with a decanter (Fig. 2). The

reflux of C1 was the aqueous phase from decanter (Fig. 2). The organic phase from the

decanter was the stream fed to C2. In this way, the water concentration (~37 wt%) of organic

phase of the decanter depends mainly on the temperature of the decanter. An additional reflux

was not required. Ethanol and acetone were purified at the top of C2 and C3, respectively.

While, the bottoms were fed at their respective decanter (Fig. 2). Therefore, three decanters

were used. These decanters reduced the water concentration because the polar components,

acetone and ethanol, were recovered sequentially.

The binary azeotrope of butanol-water was broken in the decanter between the columns

C3 and C4 (Fig. 2). The temperature of decanters was fixed at 40 ºC because the distribution

coefficient was high at this point (Fig. 1). Butanol was produced in the bottoms of C4. The top of

C4 is condensed and recirculated to the decanter. The feed of C4 from the decanter was at the

top stage. For this reason, an additional reflux was not required. Conventionally, ABE is purified

using five distillation columns (5DC). In 5DC, the aqueous phase from the decanter is fed to a

fifth column. However, in this work to reduce the number of columns the aqueous phase was

recycled to C1 (Fig. 2). The Fig. 3 shows the composition profiles for each distillation column of

4DC system.

6
 The condensation heat of columns at atmospheric pressure or higher may be used in

the boiler of another column if it operates at low-pressure. Low-pressure columns (C2, C3, and

C4) were proposed to use the heat of condensation of C1 column in their respective boilers. The

exchanger area of condensation and the diameter of columns increase a lower pressure of

operation. However, this effect is not necessary true in the acetone column (C2), due to the

increase of acetone volatility at low pressures [31–33] (Fig. 4). The total stage numbers of all

columns and processes are shown in Table 1. The total stage numbers of 4DC were 90. In all

cases, the total stages were chosen to avoid an excess of trays.

System with three distillation columns (3DC)

Total stages in the configuration with three distillation columns (3DC) were reduced

from 90 to 70 (Table 1). In the first column (C1), acetone and ethanol were obtained mainly at

the top stage (Fig. 5). A side stream from C1 was fed to the decanter (Fig. 5). The organic

phase, (~68 wt% of butanol and ~24% of water), was fed to butanol column (C3) and the

aqueous phase was recycled to C1. Acetone and ethanol were purified simultaneously in C2.

Butanol was purified in C3. The top of C3 was condensed and fed to the decanter to break the

butanol-water azeotrope.

Similar to 4DC, low-pressure operation were proposed for C2 and C3 columns. Butanol

was not present at the top of C1, making the condensation temperature at the top of this column

low (62 ºC). Consequently, heat integration using this heat of condensation is difficult. For this

reason, intermediate condensation in C1 (stage 15) was used to apply its heat in C2 and C3

boilers (Fig. 5).

Three distillation columns and vapor compression (3DC-VC)

3DC-VC is shown in Fig. 6. The configuration of streams in 3DC-VC was different to

3DC. In C1 column, one side stream was not used and the vapor on top of C1 column was split

into two streams. One stream was compressed and another was not. This effect was used to

reduce the compression work. The vapor compression was limited due to the high cost of

compressors. The condensation heat of compressed stream was applied in the boiler of C1

column. The condenser heat of vapor uncompressed was used in boilers of low-pressure

columns (C2 and C3).

7
 In the columns C2 and C3 vapor compression was not considered due to the high-

temperature difference between its condenser and boiler (42-45 ºC). Acetone was obtained

from the top of C2 column. Ethanol was obtained from the top, and butanol was obtained from

the bottoms of C3 column. Composition profiles for each distillation column of 3DC-VC system

are shown in Fig. 7.

Four distillation columns with double-effect (4DC-DE)

4DC-DE was proposed in our previous study [24]. The stream after fermentation is

divided into two streams, then preheated and fed to columns C1-HP and C1-LP (Fig. 8). In this

system, columns C1 (1.1 bar) and C3 (1.2 bar) operated at a pressure moderately higher than

atmospheric pressure to improve the heat integration. Due to butanol and water azeotrope, C3

has no-condenser and the steam from the top of C3 is fed directly to C1-HP to reduce their

energy requirements. The heat of a side condenser in column C1 was used to apply its

condensation heat to the boiler of low-pressure columns (C1-LP (0.3 bar) and C2 (0.5 bar)). The

split ratio of the stream after fermentation was iterated until the sum between condensation heat

of C1 (Q1A) and boiler heat of C1-LP (Q1B) and C2 (Q2) become nil (Fig. 8). The total energy

consumption of 4DC was given by the steam requirements of columns C1 and C3.

Energy and economic evaluation

In this work, the energy requirements were reported in two different units: the sizing

units of heat exchangers that does not necessarily required steam from furnace are reported in

the units “MJ/kg-ABE” (Table 2), while the units of fuel requirements of heat exchangers and

compressors are “MJ fuel/kg-ABE” [24] (Table 3). The units “MJ fuel” of the units that required

vapor and electricity are calculated assuming efficiencies of 0.9 and 0.33, respectively [24]. CO2

production is proportional to fuel combustion. Therefore, a reduction in fuel requirement is

proportional to CO2 reduction. Heat integration was performed with 10 ºC of minimum approach

temperature. Compressor efficiency was 0.75.

Configurations were evaluated using dilute solutions with the ABE yield of Chinese

industrial. Butanol concentration in the reactor was assumed as 10 g/l (base case). Additionally,

ABE recovery from dilute solution produced by three hyper-butanol mutant strain was studied.

The butanol concentration in the reactor of all cases evaluated are reported in Table 3. The ABE

and hydrogen yield of microorganism processes were calculated using the theoretical yield of

8
stoichiometric reactions and the specific conversions. In this work, biomass and other sub-

products of low yield in the fermentation, e.g. acetic acid, and high boiling point were not

included in the estimation. Glucose conversion in the stoichiometric reactor was 0.83. The

specific glucose conversions to butanol, ethanol and acetone are estimated from the A:B:E ratio

reported in Table 3. The stoichiometric reactions for butanol or isobutanol, acetone and ethanol

production are:

C6 H12O6  2CO2  H 2O  C4 H10O (1)

C6 H12O6  H 2O  3CO2  C3 H6O  4H 2 (2)

C6 H12O6  2CO2  2C2 H 6O (3)

In all simulations, the purities (mass fraction) of butanol, acetone, and ethanol were

0.997, 0.99, and 0.89, respectively. Non-condensable products were compressed and recycled

to the stripping column (10 stages). Cooling water (10000 kg/h) was used in the stripping

column to recover solvents from the non-condensable stream. The production of anhydrous

ethanol, isobutanol and IBE were not carried out in this study. The recovery cost per kg of

product (TRC) was calculated from:

TRC  ICR  OCR (4)

TIC
ICR  (5)
tri  FABE  ta

TOAC
OCR  (6)
FABE  ta

where FABE is the production flow (kg-ABE/h), tri is the payback period (three years), ta is the

annual operation time (8150 h/y), TOAC is the total operational annualized cost ($/y), TIC is

total investment cost ($), IRC is the investment cost of recovery ($/kg-ABE) and ORC is the

operational cost of recovery ($/kg-ABE). Equipment cost was calculated with functions reported

by Douglas [34]. Costs of steam, cooling water, and electricity and Marshall and Swift

equipment cost index (M&S) were assumed as 16 $/ton, 0.006 $/kg and 0.126 $/kWh and 1625

(dimensionless), respectively. The production capacity of solvents was 5000 kg-ABE/h. Process

equipment was designed using stainless steel material. Ideal energy efficiency of separation

(IES) system was calculated as proposed [25] using:

9
 RS  (LHV H S )
IES  (7)
LHVGlu cos e

Where, LHV is the lower heating value of solvents and hydrogen (MJ fuel/kg-solvent),

HS is the energy consumption of the separation (MJ fuel/kg-solvent), and LHVGLUCOSE is the

lower heating value of glucose (16.45 MJ/kg [35]). The energy efficiency was considered ideal

because was not calculated the energy requirement of pretreatment and downstream. The yield

(Rs) was the mass of ABE recovery per mass of substrate consumed.

Results

The distillation process with the lowest energy requirements, 3DC-VC, achieved a fuel

requirement of 7.3 MJ fuel/kg-ABE (ABE yield and ratio of the Chinese industry, Table 2). The

coefficient of performance of the heat-pump was 8.6 (-) (the energy savings (MJ) divided by the

compression work (MJ)). 3DC-VC process reduced the fuel requirement in comparison with

3DC by 37 %. Consequently, ORC decreased by 33%. However, the TRC of 3DC-VC was

equivalent to that of 3DC (Table 3) due to the high investment cost of the compressors.

The most economical process or with the lowest TRC, 4DC-DE, achieved a fuel

requirement of 8.7 MJ fuel/kg-ABE. 4DC-DE reduced the energy requirements of 4DC by

25.6%. Although the energy requirements of 4DC-DE were 1.2-fold higher than that of 3DC-VC,

4DC-DE was the most economical option because the IRC was not increased drastically using

this heat integration. For instance, the IRC of 4DC-DE increased only by 1.4% with respect to

3DC, instead of the high number of stages of 4DC-DE (95, Table 1) and the operating pressure

of C1-LP (0.2 atm at the top). This low increment of IRC was achieved because 4DC-DE was

the distillation system with the lowest total boiler flux (23.9 MJ/kg-ABE, Table 2). Due to the low

butanol concentration (~10 g/l), total boiler heat flux was the most important factor in the

calculation of IRC. Given that C1-LP was operated to low pressure, the preheating of 4DC-DE

was the lowest (Table 2). In the preheating was achieved the biggest heat integration due to the

low solvent concentration (20 g-ABE/l), (between 14.9 and 15.1 MJ/kg-ABE, Table 2).

The main difference between 3DC and 4DC configurations was the total boiler heat of

the purification columns (C2, C3 and C4), Table 2. The sum of boiler heat of purification

columns of 4DC was 3.2 MJ/kg-ABE (Table 2). While with 3DC process, this sum was 1.7-fold

lower due to less unnecessary condensation). 4DC-DE and 3DC have the lowest boiler heat of

10
purification (between 1.5 and 1.9 MJ/kg ABE) because a vapor stream, instead of a liquid

stream, was fed to column C2.

Due to heat integration, the fuel consumption of 3DC and 4DC only depended on the

boiler heat of column C1. Consequently, the fuel requirements of purification columns were nil

and the energy requirements of 4DC and 3DC configurations were equivalents (~11.5 MJ

fuel/kg-ABE, Table 3). For this reason, ORC (related to fuel requirements) of both process was

similar. ORC was approximately 58% of TRC. Given that the total boiler heat flux of 3DC was

6.2% lower than that of 4DC (Table 2), the IRC of 3DC was 4% lower (Table 3).

The fuel requirements of 4DC-DE with the ratio achieved by C. acetobutylicum JB200,

C. beijirinkii BA10, and C. acetobutylicum SolRH were reduced from 8.7 MJ fuel/kg-ABE to 6.3

MJ fuel/kg-ABE, 6.5 MJ fuel/kg-ABE and 6.1 MJ fuel/kg-ABE, respectively (Table 3). This was to

be expected because of the high concentration of butanol in the fermentation broth (around 20

g/l). Consequently, the TRC was reduced between 22% and 25% (Table 3). The least energy

requirement and TRC were obtained using a hyper-butanol producing C. acetobutylicum JB200

(Table 3). Due to a higher butanol titer, vinasses recycle into the reactor was reduced from 67%

to 56.3% and 34.8% using the yield of C. beijirinkii BA101 and C. acetobutylicum JB200 with

respect to the base case, respectively.

Vinasses recycle was an important contribution of the low energy requirements

achieved in this work. At similar total ABE recovery, vinasses recycle reduced the energy

requirements by ~18.8% with respect to 4DC or 3DC process without vinasses recycle (data not

shown). This reduction was mainly achieved because of ethanol has the lowest relative volatility

and ethanol concentration is increased in the reactor with vinasses recycle (results not shown).

Energy efficiency of ABE processes without hydrogen combustion for 3DC-VC and

4DC-DE were between 0.59 and 0.66. Hydrogen production (LHV of hydrogen, Table 4) was

between 9 and 15% of total energy produced. Therefore, the efficiency increased to 0.71-0.76

with hydrogen combustion. Energy efficiency of 3DC-VC was between 4.8 and 5.8% higher than

that for 4DC-DE. The highest efficiency of the distillation process was achieved using C.

acetobutylicum JB200. Although C. beijirinkii BA101 has the lowest theoretical yield of

hydrogen, the stoichiometric ABE yield is higher than that of C. acetobutylicum SolRH. Hence,

11
the energy efficiency of C. beijirinkii BA101 and C. acetobutylicum SolRH was similar (4DC-DE

(0.71) and 3DC-VC (0.74-0.75)).

Discussion

In some Chinese industrial processes have been reported high energy requirements,

13-25 kg-steam/kg-ABE [3] or 30-58 MJ fuel/kg-ABE. The minimum energy requirements

reported for these processes (30 MJ fuel/kg-ABE) were similar to that of 4DC without heat

integration (28.9 MJ/kg-ABE). Hence, in these industrial processes, heat integration probably

was not used.

Energy consumption of distillation reported by Jilin Cathy Industrial Biotech is 6-7 kg-

steam/kg-butanol [14] (butanol concentration from the fermentation broth is not reported).

Assuming an efficiency of steam production of 0.9 and using the ratio of Chinese industry

reported by Ni [3], the fuel consumption was between 8-9.4 MJ-fuel/kg-ABE. Based on the low

energy consumption reported for this industrial process, a heat-integrated distillation system

may have been used. These energy requirements were equal to the fuel consumption achieved

for 3DC or 4DC with a butanol titer between 14 and 15 g/l (data not shown).

It is important mention that comparisons between energy requirements of different

distillation systems must be done at the same butanol concentration in the feed. This was

suggested because it was found that increments of the concentration of butanol from 10 to 20

g/l reduced the energy requirements 1.7 times.

In academy studies of distillation, the energy requirements reported for ABE recovery

were 15.2 MJ-fuel/kg-ABE using C. beijirinkii BA101 and a distillation system of 5DC (135 ideal

stages [5]). The total energy requirements of 3DC-VC and 4DC-DE were respectively 67.1%

and 58.6% lower than that of 5DC (Table 2) due to heat integration, vinasses recycle and the

high efficiency of the distillation systems studied in this work. In similar way, using the yield of C.

acetobutylicum SolRH, the energy requirements of 3DC-VC and 3DC were 60% and 38% than

that of 5DC (12.6 MJ-fuel/kg-ABE, Table 2), respectively. Remarkably, using 3DC the total

number stages of 5DC was reduced from 135 (ideal stages) to 70 (non-ideal stages).

Several energy analysis of integrated reactors have been reported in the literature [6,

11, 13]. From an energy point of view, the most attractive units reported by Qureshi et al. [6]

were adsorption, liquid extraction, and pervaporation. Energy requirements of liquid extraction

12
and adsorption reported by Qureshi et al. [6] for C. beijirinkii BA101 are 7.1 and 7.7 MJ fuel/kg-

ABE (calculated in this work from C. beijirinkii BA101 ratio), respectively. Energy consumption of

pervaporation reported by Groot et al. [11] and Qureshi et al. [6] are 10 and 10.9 MJ fuel kg-1

ABE, respectively (assuming an efficiency in energy production of 0.9).

Fuel consumption of 4DC-DE and 3DC-VC achieved in this work were 29.1 and 34.8%

and 17.9 and 10.7 % lower than that reported by Qureshi et al. [6], for liquid-liquid extraction and

adsorption, respectively. However, an integrated reactor may have a higher productivity of

solvents. Hence, an economic study of reaction and purification system is necessary [24]. On

the other hand, an integrated reactor is not 100% selective and requires a final purification. For

this reason, it can be coupled with the distillation processes studied in this work.

The lowest energy requirement in the literature was achieved with a vapor compression

system (membrane assisted vapor stripping (MAVS), 4.2-MJ-fuel/kg-ABE (3/6/1) at 2 wt% of

ABE [36, 37]). In the evaluation of MAVS, CO2 and H2 were non-included, the minimum

approach temperature was 5 ºC, the ratio of ABE was 3/6/1, ABE titer was 20 g/l, ethanol

recovery was 90% and nil pressure drop was assumed. Using the same assumptions reported

by [36, 37], the energy requirement of 3DC-VC were reduced from 7.3 to 4.5 MJ-fuel/kg-ABE.

Hence, the low energy requirements of MAVS were mainly achieved through heat integration by

vapor compression. A similar result was observed in our previous study for ethanol or isobutanol

dehydration [25]. However, it is important to mention that non-condensable, pressure drop,

among others, may have a different effect in MAVS and recycle of vinasses are not performed in

MAVS.

Due to biofuel application, the IES of ABE process was compared with ethanol,

isobutanol and IBE dehydration by heat-integrated distillation (Table 4). IBE anhydrous was

achieved in a new approach of heat-integrated distillation [26]. In this simultaneous azeotropic

and extractive distillation system, without an additional entrainer, butanol is used to break the

azeotropes of isopropanol-water and ethanol-water. In this approach, VC was used. The energy

requirements of IBE dehydration are between 1.3- and 1.6-fold lower than that of 3DC-VC

(Table 4). For this reason, the energy efficiency of IBE dehydration was the highest (0.79-0.80,

Table 4). Although IBE dehydration achieved the highest IES, it is worth noting that the effect of

13
CO2, the efficiency of stages, pressure drop and the energy requirements for the end purification

of IBE were not studied in our previous work [26].

Ethanol and isobutanol anhydrous (99.7 wt%) are achieved by extractive and azeotropic

distillation, respectively [25]. Glycerol is the extractant used in ethanol dehydration system [25].

The concentration of ethanol and isobutanol from broth are 10 and 2 wt% [25], respectively. The

TRC of isobutanol purification by VC was 1.07-fold lower than that of ABE purification by 3DC-

VC (C. acetobutylicum JB200, Table 3). The energy requirements of 3DC-VC were between 1.3

and 2.0-fold higher than that for ethanol and isobutanol dehydration (Table 4). However, due to

hydrogen synthesis, the IES of ABE production by 3DC-VC was only between 1.5 and 2.8 %

lower than that for ethanol and isobutanol dehydration (Table 4).

Conclusions

Conventionally, distillation is considered an inefficient alternative method for ABE

recovery. However, with the configurations investigated in this paper, distillation was an

alternative energetically attractive. The energy requirements were between 4.7 and 7.3 MJ

fuel/kg-ABE and 6.1 and 8.7 MJ fuel/kg-product using vapor compression distillation and

double-effect, respectively. The fuel requirements were reduced between 1.4- and 1.7- fold

when the butanol concentration rises from 10 to 20 g/l. The most economical option was double

effect distillation with recovery cost between 0.12 and 0.16 $/kg-product. The lowest energy

requirement and the highest efficiency for ABE recovery was achieved with C. acetobutylicum

JB200. The energy efficiency of ABE recovery was 1.5-2.8% lower than that of isobutanol or

ethanol.

Acknowledgments The authors thank Colombian Administrative Department of

Science, Technology, and Innovation (COLCIENCIAS) for the financial support that made this

work possible.

Conflict of interest

The authors declare that no competing interests exist.

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18
Tables

Table 1 Feed inlet stages and number of

stages of the heat-integrated distillation
processes studied in this work
Feed inlet stage
Distillation system
Column
4DC 3CD 3DC-VC 4DC-DE
C1 1-3 21-23 1-3
C1-LP 1-3
C1-HP 15-21-23
C2 15 14 15 21
C3 12 1 20 1
C4 1
Number total of stagesb
Distillation system
Column
4DC 3CD 3DC-VC 4DC-DE
C1 20 40 20
C1-LP 20
C1-HP 40
C2 30 20 30 25
C3 30 10 30 10
C4 10
Total 90 70 80 95
a stages from the top, b Murphree tray

efficiency of 0.7

19
Table 2 Boiler heat flux of the ABE distillation
systems and the yield of Chinese industry
3DC 4DC-
Column 4DC 3CD
-VC DE
C1 10.6 10.3 10.5 -
C1-LP - - - 7.8
C1-HP - - - 2.7
C2 0.91 0.78 1 0.46
C3 1.5 1.1 1.7 1.04
C4 0.83 - - -
Preheating of
feed from 15.2 14.9 15.2 12
fermentation
Total purification
3.2 1.9 2.7 1.5
(C2-C4)
Total boiler heat
13.8 12.1 13.2 11.9
(C1-C4)
Total heat
28.9 27.1 28.4 23.9
exchangers

20
Table 3 Total recovery cost (TRC) and fuel requirement of ABE recovery by heat-integrated
distillation a
Fuel
Butano Solvent ABE IRC ORC TRC
requirement
Biocatalyst l titer ratio: System recover [$/kg- [$/kg- [$/kg-
[MJ fuel/kg-
[g/l] A/B/E y ABE] ABE] ABE]
ABE]
Typical 4DC 0.970 11.7 0.084 0.113 0.197
microorganisms 3DC 0.969 11.5 0.078 0.111 0.189
2.5/4.8/
in Chinese 10 3DC-
1 0.970 7.3 0.115 0.075 0.190
industrial VCD
process 4DC-DE 0.969 8.7 0.079 0.080 0.159
3DC 0.976 7.6 0.064 0.074 0.138
3DC-
C. beijirinkii 19.7 0.977 5.0 0.088 0.052 0.140
6/24.6/1 VCD
BA101 [38]
4DC-DE 0.980 6.3 0.064 0.059 0.123
5DC b - 15.2 - - -
3DC 0.977 7.8 0.062 0.076 0.138
3DC-
C. 0.981 5.0 0.087 0.053 0.140
18.5 VCD
acetobutylicum 4/8.4/1
[39] 4DC-DE 0.977 6.5 0.063 0.061 0.124
SolRH
5DC [5]
b - 12.6 - - -
3DC 0.977 7.0 0.059 0.069 0.128
C.
20.4 5/9.2/1 3DC-
acetobutylicum 0.976 4.7 0.083 0.050 0.133
[40] VCD
JB200
4DC-DE 0.978 6.1 0.062 0.057 0.119
e. coli
20 - VCD [25] 0.999 2.5 0.087 0.036 0.124
(isobutanol)
a Ethanol dehydration costs and energy recovery for anhydrous ethanol production were not

included. b Calculated from reference [5].

IRC, investment cost of recovery. ORC, operational cost of recovery.

21
Table 4 Energy efficiency of biofuels recovery by heat-integrated distillation
Yield Energy
LHV LHV
(kg- recovery
Recovery hydrogen solvents
Fermentation Biocatalyst solvent/ (MJ Efficiency
system (MJ/kg- (MJ/kg-
kg- fuel/kg-
ABE) ABE)
glucose) ABE)
3DC-VC 0.385 5.0 3.2 33.3 0.74
C. beijirinkii BA101
3DC-DE 0.385 6.3 3.2 33.3 0.71
ABE 3DC-VC C. acetobutylicum 0.373 4.7 5.6 32.4 0.76
(In this work) 3DC-DE JB200 0.373 6.1 5.6 32.4 0.72
3DC-VC C. acetobutylicum 0.374 5.0 5.3 32.5 0.75
3DC-DE SolRH 0.374 6.5 5.3 32.5 0.71
VC [25] 0.41 3.7 - 34.4 0.77
Isobutanol escherichia coli
DE [25] 0.41 5.7 - 34.4 0.72
DE [25] saccharomyces 0.51 3.4 - 27 0.73
Ethanol
VC [25] cerevisiae 0.51 2.5 - 27 0.76
C. acetobutylicum
VC [26] 0.39 2.9 3.9 32.7 0.80
PJC4BK
IBE
C. acetobutylicum
VC [26] 0.40 3.7 2.9 33.1 0.79
RH8

22
List of Figures

Fig. 1. Liquid-liquid equilibria (LLE) of butanol/water system to several temperatures.

Experimental data [27, 28]

Fig. 2. Heat-integrated configuration with four distillation columns (4DC) proposed by ABE
recovery. B1, flow from fermentation after preheating with vinasses. Q is the heat of condenser-
boiler. C is column. Unnamed exchanger units required cool water (blue) or steam (red). The
boiler-condenser units have an orange unit and the energy balance is at the bottom of the figure

Fig. 3. Composition profiles for each distillation column of system 4DC

Fig. 4. Vapor-liquid equilibria (VLE) of acetone/water system at several pressure. Continues

lines: UNIQUAC prediction (APV73 VLE-LIT Aspen Plus®). Points: experimental data [31–33].
The boiler-condenser units have an orange unit and the energy balance is at the bottom of the
figure

Fig. 5. Scheme with three distillation columns (3DC). B1, flow from fermentation after preheating
with vinasses. C is column. Q is the heat of condenser-boiler. Unnamed exchanger units
required cool water (blue) or steam (red)

Fig. 6. Configuration with three distillation columns and vapor compression (3DC-VC). B1, flow
from fermentation after preheating with vinasses. C is column. Q is the heat of condenser-boiler.
Unnamed exchanger units required cool water (blue) or steam (red). The boiler-condenser units
have an orange unit and the energy balance is at the bottom of the figure

Fig. 7. Composition profiles for each distillation column of system 3DC-VC

Fig. 8. Configuration with four distillation columns and double effect integration (4DC-DE). B1,
flow from fermentation after preheating with vinasses. C is column. HP and LP are high-
pressure and low-pressure, respectively. Q is the heat of condenser-boiler. The unnamed
exchanger units required cool water (blue) or steam (red). The boiler-condenser units have an
orange unit and the energy balance is at the bottom of the figure

23
 Fig. 1

0.8

Azeotropes at UNIQUAC-VLE-IG
Butanol (wt%)

0.6 several pressures NRTL-ELV-IG

UNIQUAC-LLE-ASPEN

0.4 UNIQUAC Ref. [32]

Experimental, Ref [34]
Experimental. Ref [35]
0.2

0
30 50 70 90
Temperature (°C)

24
 Fig. 2

Gas to
recycle Ethanol
(89%)
Q1
Acetone
(99%) 0.2
0.5 bar
Fermentation bar
0.5
Broth (B1) 1.4
bar
bar 40 ºC
40 ºC C4
C3 Q4
40 ºC Q3
Q2 C2
C1
Vinasses Butanol
(99.7%)
-Q1=Q2+Q3+Q4

25
 Fig. 3
0.24

Composition (g/g)
Column 1 Butanol
0.18 (Vapor) Acetone
0.12 Ethanol

0.06

0
0 5 10 15 20
1

Composition (g/g)
Butanol
Acetone
0.75 Ethanol
Column 2 Water
0.5 (Vapor)
0.25
0
0 10 20 30
Composition (g/g)

0.9 Butanol
Ethanol
0.6 Water

0.3 Column 3
(Vapor)
0
0 10 20 30
1
Composition (g/g)

Column 4 (Liquid)
0.75

0.5 Butanol Water

0.25

0
0 2 4 6 8 10

Stages number

26
 Fig. 4
1
101.3Kpa
kPa

Vapor acetone concentration (wt frx)

101.3
40Kpa
40 kPa
0.8

344.7 Kpa
344.7 kPa
0.6

689.5
689.5
0.4 Kpa
kPa

0.2

0
0 0.2 0.4 0.6 0.8 1
Liquid acetone concentration (wt frx)

27
 Fig. 5
Gas to recycle

Acetone
0.5 (99%)
bar
Q1 1.1 0.1
bar C2 bar
40 ºC Ethanol
Fermentation (89%) C3
Q2
broth (B1) Butanol
C1
(99.7%)
Q3
Vinasses V1
-Q1=Q2+Q3

28
 Fig. 6

-Q1A

4.2 bar Q1 Gas to recycle

Ethanol
Acetone (89%)
CM -Q0
(99%)
Q0
0.5
bar
Fermentation 1.4 40 ºC
broth (B1) bar 0.2
40 ºC bar
C2
C1 C3
-Q1A=Q2 +Q3 Q2
Butanol
Q1 (99.7%) Q3

29
 Fig. 7
1,0

Vapor composition (g/g)

0,8

0,6 Butanol Acetone

Ethanol Water
0,4

0,2 Column 1
0,0
1 6 11 16 21

Liquid composition (g/g)

1,0
Butanol Acetone
0,8
Ethanol Water
0,6

0,4 Column 2
0,2

0,0
1 6 11 16 21 26 31

1,0
Liquid composition (g/g)

Butanol Acetone
0,8 Ethanol Water
0,6
Column 3
0,4

0,2

0,0
1 6 11 16 21 26 31
Stage number

30
 Fig. 8
Gas to
Gas to recycle
recycle
Acetone
(99%)
0.5
0.2 bar
bar 40 ºC Q1A 1.1 1.2
bar bar
C2
C1- Ethanol
LP (89%) C3
Q2
Fermentation C1- 40 ºC Butanol
broth (B1) Q1B V1
HP (99.7%)

Vinasses V1 -Q1A=Q1B+Q2

31

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