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Separation and Purication Technology 132 (2014) 513540

Contents lists available at ScienceDirect

Separation and Purication Technology


journal homepage: www.elsevier.com/locate/seppur

Review

Separation and purication of biobutanol during bioconversion


of biomass
Hua-Jiang Huang a,, Shri Ramaswamy a,, Youyan Liu b
a
b

Department of Bioproducts and Biosystems Engineering, University of Minnesota, St. Paul, USA
School of Chemistry & Chemical Engineering, Guangxi University, Nanning, Guangxi, PR China

a r t i c l e

i n f o

Article history:
Received 27 January 2014
Received in revised form 5 June 2014
Accepted 7 June 2014
Available online 17 June 2014
Keywords:
Butanol separation
Gas stripping
Vacuum ash
Solvent extraction
Membrane separation
Adsorption

a b s t r a c t
Biofuels from biomass are becoming increasingly more important, due to the need for reduction in greenhouse gas (GHG) emissions, energy independence, and limited global availability and increasing demand
and costs of fossil fuels. Butanol has several advantages over ethanol as a drop-in biofuel such as higher
energy content, potential for higher blending percentage with gasoline, lower vapor pressure, and lower
hygroscopy. It can be used in existing transportation fuel distribution infrastructure. Butanol can be produced by fermentation of carbohydrates derived from biomass using Clostridium acetobutylicum or C. beijerinckii under anaerobic conditions. There are still many unsolved challenges for making biobutanol
technically, and economically viable. The unsolved challenges lie in severe product (especially butanol)
inhibition during bioprocessing, which leads to low butanol yield and productivity, and very low nal
product concentration (<3 wt%), causing expensive downstream processing (product separation) costs.
There are two ways for solving these problems. One is the modication of microorganisms for ABE (Acetone, Butanol and Ethanol) fermentation by genetic engineering, which could keep the microorganisms
alive and active under higher concentration of products in the broth. This could signicantly increase
the product yield, productivity, and concentration and hence reduce the production costs. However, this
is still an unrealized long term goal. Another approach is the development of efcient separation and
purication processes for product recovery. And, even if the modication of microorganisms becomes
a reality, product separation and purication will still remain a major critical challenge. In this study,
an extensive review of separation and purication of butanol from fermentation broth is provided,
including gas stripping, vacuum ash, liquidliquid extraction, membrane solvent extraction or perstraction, membrane pervaporation, membrane distillation, thermopervaporation, reverse osmosis, adsorption, and integrated bioprocessing with various separation methods. It is concluded that membrane
pervaporation, solvent extraction, and adsorption are the most energy-efcient approaches for removal
of butanol from the ABE fermentation broths. It should be noted that this is not a strict comparison
and it is suggested that each separation process should be optimized before comparison. Integration of
bioreactors with these energy-efcient separation methods could signicantly increase the product yield,
productivity and concentration and hence lower the production cost. Butanol dehydration is also discussed. This review could be helpful in the research and development and commercialization of biobutanol as renewable drop-in biofuels and biochemicals.
2014 Elsevier B.V. All rights reserved.

Abbreviations: [BMIM]+, 1-butyl-3-methylimidazolium; BTESE, 1,2-bis(triethoxysilyl)ethane; [DCA], dicyanamide; [DHSS], dihexylsulfosuccinate; [DMIM]+, 1-decyl-3methylimidazolium; [FAP], tris(pentauoroethyl)triuorophosphate; ETES, ethyl triethoxysilane; [Hmim]+, 1-hexyl-3-methylimidazolium; [HOhmim], 1-(6-hydroxyhexyl)-3methylimidazolium; IPA, isopropanol; [N1,8,8,8], methyltrioctylammonium; [NTf2], bis(triuoromethylsulfonyl)imide; OA, oleyl alcohol; [OMIM]+, 1-octyl-3-methylimidazolium;
[P6,6,6,14], trihexyltetradecylphosphonium; PDMS, poly(dimethyl siloxane); PE, polyethylene; PEBA, poly(ether-block-amide); PES-DVB, poly(4-ethylstyrene-co-DVB); [PF6],
hexauorophosphate; [Phosph], bis(2,4,4-trimethylpentyl) phosphinate; PS-DVB, poly(styrene-co-divinylbenzene); PTMSP, poly(1-trimethylsilyl-1-propyne), membranes; TBP, tributyl phosphate; [TCB], tetracyanoborate; [THA]+, tetrahexylammonium; [TOA MNaph], tetraoctylammonium 2-methyl-1-naphthoate; b-CD, b-cyclodextrin.
Corresponding authors. Address: Department of Bioproducts and Biosystems Engineering, University of Minnesota, 2004 Folwell Ave, St. Paul, MN 55108, USA. Tel.: +1
6126248797.
E-mail addresses: huang159@umn.edu (H.-J. Huang), shri@umn.edu (S. Ramaswamy).
http://dx.doi.org/10.1016/j.seppur.2014.06.013
1383-5866/ 2014 Elsevier B.V. All rights reserved.

514

H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540

Nomenclature
concentration (g L1 or mol L1)
pervaporation permeate ux (kg m2 h1)
distribution coefcient
distribution coefcient
distribution coefcient
mass (g) or mole numbers (mol)
pressure (Pa)
selectivity of an extracting agent (extractant) for the
solute (butanol/isobutanol) over water
temperature
weight percent (wt%) or mass fraction (g g1)
mole fraction

C
J
K
K0
K00
m
P
S
T
w
x

l
c

viscosity (mPa s)
solventair interfacial tension (i.e., surface tension) or
solventwater interfacial tension (mN m1)
separation factor of butanol/isobutanol (over water) for
membrane pervaporation
thickness of membrane (lm)

Subscript
AP
D
i
OP
Perm

aqueous phase
distribution
component
organic phase
permeate side

Greek letters
q
density (kg m3)

Contents
1.
2.

3.
4.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Separation of butanol from dilute solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Gas stripping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.1.
Batch fermentationgas stripping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.2.
Fed-batch fermentationgas stripping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.3.
Continuous fermentationgas stripping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.4.
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Vacuum flash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.
Liquidliquid extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.1.
Extractive fermentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.2.
External solvent extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.3.
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4.
Membrane-assisted solvent extraction (perstraction). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5.
Membrane pervaporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5.1.
Pervaporation with hydrophobic polymeric membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5.2.
Pervaporation with polymeric composite membranes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5.3.
Pervaporation with supported liquid membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5.4.
Integrated fermentationmembrane pervaporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5.5.
Energy requirement for membrane pervaporation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.5.6.
Advantages and disadvantages of membrane pervaporation, and summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.6.
Other membrane technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.6.1.
Membrane distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.6.2.
Thermopervaporation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.6.3.
Reverse osmosis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.7.
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.8.
Comparison of separation methods for product removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Further separation and purification/dehydration of butanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1. Introduction
Biofuels from biomass are becoming increasingly more important, due to the need for reduction in GHG emissions, energy independence, and limited global availability and increasing demand
and costs of fossil. Biobutanol as biofuel has several advantages
over bioethanol such as higher energy content, lower vapor pressure, higher ash point (37 C vs. 15 C), lower hygroscopy, and
better miscibility with gasoline [14]. Specically, butanol contains 30% more energy content on a unit volume basis than ethanol
(27.83 MJ (L butanol)1 vs. 21.27 MJ (L ethanol)1 [5]. Life-cycle
assessments by Swana et al. [4] show that the net energy return

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associated with corn-to-biobutanol conversion is greater than that


of the corn-derived bioethanol (6.53 MJ L1 vs. 0.40 MJ L1). Butanols lower vapor pressure and higher ash point represents that
it is safer than ethanol, and being less hygroscopic means less corrosion to the fuel pipelines and equipments. Besides, butanol can
be blended with gasoline at a higher percentage than ethanol. Current US regulations allow biobutanol to be blended at up to 16% by
volume vs. 10% for ethanol (butamax.com). In addition, butanol is
compatible with the current automobile engine design and can be
used as a drop-in fuel and used in existing transportation fuel distribution infrastructure, making it an ideal candidate to replace
gasoline [6,7]. In addition to being used as biofuel, butanol can

H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540

be used as solvent in food and pharmaceutical industries, a building block for producing a variety of chemical products, such as
paints, coatings, bio-based polymers and plastics, and other chemicals. Butanol is even more valuable than ethanol as a chemical [8].
Butanol has four isomers: n-butanol (1-butanol), sec-butanol
(2-butanol), isobutanol (2-methyl-1-propanol), and tert-butanol
(2-methyl-2-propanol). They have different physicochemical properties due to their different structures. Among these four isomers,
tert-butanol is miscible with water and it has a low melting point
of about 2526 C. Sec-butanol has a high solubility in water (29 g/
100 ml at 25 C). Thus, both tert-butanol and sec-butanol are not
suitable for use as gasoline alternatives, though tert-butanol can
be used as gasoline octane booster and oxygenate. The other two
isomers n-butanol and isobutanol have limited solubility in water,
and they are potential gasoline alternatives. In this review, n-butanol and isobutanol will be mainly discussed.
Currently, n-butanol is mainly produced from petroleum, with a
global capacity of 2.8 million tons of petro-butanol, equivalent to
$5 billion. Using low-cost biomass feedstock and pretreatment
technology, advanced biocatalyst, faster fermentation system and
energy-efcient product separation process, production cost of
bio-based n-butanol can be 3060% less than the cost of petroleum
based butanol (cobalttech.com). Also, butanol has the potential to
substitute both bioethanol and biodiesel in the biofuels market
estimated to be worth $247 billion by 2020 [9].
Recently, due to the signicant advantages of biobutanol over
bioethanol as alternative fuels as described above, and its higher
protability than ethanol in the chemicals market, there have been
increasing interests in butanol bioconversion and signicant
efforts have been made in commercial production of biobutanol
or retrotting some existing bioethanol plants for butanol production. In China, for instance, the total ABE solvent production capacity was about 0.21 million TPA (tons per annum) in 2008 and
expected to be expanded to 1 million TPA [10]. In USA, for example,
Gevo, a Denver-based company, and Butamax, a joint venture
between BP and DuPont, vigorously conducted research on isobutanol and n-butanol bioconversion, respectively, aiming at the
commercialization of the solvent production, with current ongoing retrot of existing bioethanol plants for isobutanol/n-butanol production. Other companies around the world such as Cobalt
Biofuels, Cathay Industrial Biotech, and Green Biologics are also
dedicated to the research and development of butanol bioconversion [11].
Biochemically, n-butanol can be produced by ABE fermentation
of biomass carbohydrates. Current commercial biobutanol processes are based on fermentation of starch or sugar-based feedstocks such as corn [12], molasses [13], whey permeate [13], and
dried distillers grains and solubles [14]. Most existing biobutanol
plants use corn, which competes with food and animal feed. The
relatively high cost of corn leads to higher butanol production cost.
For this reason, there has been a growing research interest in
developing technologies for producing drop-in biofuels such as
butanol from non-food cellulosic biomass including corn ber
[13,15], corn stover [16], corn stalk [13], rice bran [17], rice straw
[18], barley straw [19], wheat straw [2022], wheat bran [23],
switchgrass [16], and cassava bagasse [24] as well as other nonfood, renewable biomass such as starch-containing microalgae;
for example, Chlorella, which contains up to 3065% starch on
dry basis, making it a good substrate for butanol fermentation
[2527]. In addition to starch, sugar, and cellulosic biomass as
carbohydrate sources, stillage [28] and glycerol [2832], a major
by-product of biodiesel plants, can also be applied for butanol
production by fermentation.
There are four species of ABE producing clostridia for ABE
fermentation of various carbohydrates (glucose, xylose, etc.):

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C. Acetobutylicum, C. beijerinckii, saccharobutylicum, and C.


Saccharoperbutylacetonicum [33], which are based on the Clostridia
butanol metabolic pathway [34]. Among these, the most commonly researched clostridia are C. acetobutylicum [10,18,24,35
42] and C. beijerinckii [12,2023,4349]. Due to the toxicity or inhibition of butanol to the cell, the obtained ABE fermentation broth is
very dilute, usually with total ABE concentration of less than
20 g L1 (the common weight ratio A:B:E = 3:6:1, dependent on
the substrate and the type of bacteria used), or the butanol concentration of less than 12 g L1. Based on the best solventogenic clostridia strains in the literature summarized by Green [9], the best
total ABE solvent titer and butanol titer are about 28 g L1 and
20 g L1, respectively. Such low concentrations of butanol make
the product separation highly costly. Furthermore, the butanol
yield and productivity are also low. Thus, the overall biobutanol
production cost is relatively high. Recent reviews on biobutanol
production have been published [11,34,5055].
The ABE fermentation could be switched to the isopropanol,
butanol and ethanol (IBE) fermentation with engineered C. acetobutylicum through introducing a single secondary alcohol dehydrogenase, where acetone is converted to isopropanol [56,57]. As
isopropanol can be used as a fuel additive for increasing highoctane value of gasoline, the IBE mixture produced can be directly
used as biofuel. Also, isopropanol can be used as an industrial solvent. The IBE fermentation is equivalent to the ABE fermentation
plus further conversion of acetone to isopropanol. Thus, IBE concentration is also dilute, similar to ABE.
Isobutanol, which has similar energy content to that of n-butanol, can also be produced biochemically from glucose and cellulosic biomass, using the recombinant organisms such as
Escherichia coli, Saccharomyces cerevisiae, Bascillus subtilis, Corynebacterium glutamicum, and Clostridium cellulolyticum, based on
the valine pathway. The metabolic pathways for producing higher
alcohols from various resources are reviewed [53,55]. Among these
organisms, E. coli was engineered to produce 22 g L1 isobutanol at
a yield of 0.35 g isobutanol (g glucose)1, corresponding to 86% of
the theoretical maximum yield of isobutanol [53]. In addition,
the integration of fermenters with in situ product removal (ISPR)
by gas stripping could increase isobutanol titer to 50 g L1 [54],
which represents the highest concentration among the literature
reviewed.
In this review, separation of n-butanol and isobutanol from
their dilute fermentation broths will be mainly discussed. While
most references reported are related to separation of n-butanol
from ABE fermentation broth, usually, the separation technologies
are also suitable for the separation of isobutanol from its fermentation broth.
In general, challenges for biobutanol production from biomass
[9] include high feedstock cost, low butanol titers (ABE < 20 g L1),
increasing separation costs, low butanol yield, low volumetric productivity increasing capital and operating costs, and high water
usage [9]. In order to make biomass-based butanol economically
and commercially viable, two major challenges need to be solved:
(i) severe product (especially butanol) inhibition, i.e., solvent toxicity to the microorganisms used for fermentation, which leads to
low butanol yield and productivity, and (ii) expensive downstream
processing (product separation and purication) [6,58]. Though
genetic modication of the microorganisms for ABE production
could increase their tolerance to the toxicity of products, leading
to increase in butanol yield, broth concentration, and productivity
as described previously, a high toxicity-tolerant microorganism for
ABE that can tolerate ABE titer of well over 3% is still years away. A
more near term plausible solution is to eliminate or reduce the
product inhibition through continuous product removal from the
broth during fermentation, i.e., integration of in situ product sepa-

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ration with ABE fermentation so that the ABE titer remains below
the inhibition concentration (usually <2 wt% butanol).
Recent review on separation technologies for biofuels with
more focus on separation of bioethanol from fermentation broth
includes Huang et al. [59], and Vane [60]. There are similarities
between separation of bioethanol from fermentation broth and
biobutanol from ABE fermentation broth. For example, both broths
are very dilute and hence their separation from dilute solutions are
energy intensive and costly; both have larger molecular size than
water, so a small fraction of water can be removed from alcoholrich mixture by using molecular sieve for alcohol dehydration;
both have a OH group, so they can be extracted from aqueous
solutions using some similar type of extraction solvents, for example, oleyl alcohol, n-dodecanol, butyl acetate, and [P6,6,6,14][DCA],
just to name a few. However, there exists signicant differences
between them. Specically, the concentration of ethanol fermentation broth is signicantly higher than that of ABE fermentation
broth (512 wt% ethanol vs. <2 wt% butanol). Also, at atmospheric
pressure, the ethanol forms azeotropes with water at 95.5% ethanol
at 78.2 C that is signicantly lower than the waters boiling point
(100 C), while butanol forms azeotropes with water at 55.5 wt%
butanol at 93 C that is only slightly lower than that of water. Thus,
separation or pre-concentration of butanol from initial ABE broths
by using ordinary distillation directly should consume much more
energy compared to the case for ethanol separation from ethanol
fermentation broth. In fact, the separation of butanol from ABE
broths by using direct ordinary distillation is infeasible as it
requires more energy than the energy content in the recovered
butanol. Thus it is necessary to explore some other separation
methods for pre-concentration of butanol from ABE broths. On
the other hand, ethanol is completely miscible with water and
the azeotropes formed by ethanol with water are homogeneous.
In contrast, at 20 C butanol has a lower solubility limit in water
(7.7 wt% butanol) and an upper solubility limit in water
(79.9 wt% butanol) [61], i.e., the water solubility in butanol being
20.1 wt% water. Thus, the azeotropes formed by butanol with
water are heterogeneous. This is favorable for butanolwater system for further separation of butanol from pre-concentrated solutions containing more than 7.7 wt% butanol through phase
separation. The pre-concentrated solutions having butanol concentrations between 7.7% and 79.9% will be separated into two phases:
one aqueous phase containing 7.7wt% butanol, and another organic
phase containing butanol of more than 7.7wt% at 20 C and
101.325 kPa. This suggests that special separation approaches such
as gas stripping, vacuum ash, and membrane pervaporation can
be rst used for in situ product removal and/or pre-concentrate
ABE solutions to signicantly higher than 7.7 wt% of butanol concentration. After phase separation of the pre-concentrated solutions, a solution of higher concentration of signicantly over 7.7%
butanol will be achieved, along with another (aqueous) solution
of 7.7%.
In order to enhance substrate utilization and butanol productivity, many researchers investigated in situ simultaneous removal
of butanol from fermentation broth to reduce product inhibition
using different separation techniques. To explore butanol recovery technologies for reducing its overall production cost, in this
study, an extensive review of separation and purication of butanol from fermentation broth is provided, including gas stripping,
vacuum ash, liquidliquid extraction, membrane solvent extraction or perstraction, membrane pervaporation, other membrane
technologies such as membrane distillation, thermopervaporation
and reverse osmosis, adsorption, as well as different integrated
fermentationseparation processes. The comparison between different separation methods in terms of energy consumption and
the further separation and purication of butanol are also discussed. This could be helpful in the research and development

and commercialization of renewable butanol biofuels and


biochemicals.
2. Separation of butanol from dilute solutions
2.1. Gas stripping
Gas stripping is a simple approach for removal of product inhibition from ABE fermentation [8]. The fermentation off-gas (CO2
and H2) or another inert gas can be used as the carrier gas. A number of researchers have studied the use of gas stripping for butanol
removal from fermentation [12,21,22,4648,62]. Gas stripping can
be integrated into the ABE fermentation system for in situ recovery
of ABE product. The gas stripping mechanism is based on one-stage
gasliquid equilibrium [60]. Batch, fed-batch, or continuous fermentation can be integrated with gas stripping for in situ product
removal. Fig. 1 shows an integrated fed-batch fermentation
(FBF)gas stripping product recovery system where the fermentation gas are used as the carrier gases. In this system, substrate inhibition and product inhibition are reduced by fed-batch operation
and gas stripping, respectively. At the fermentation temperature,
ABE is stripped off by the fermentation gas, and condensed into
liquid. After separation from the liquid products, the uncondensed
inert gas is recycled back to the fermenter.
2.1.1. Batch fermentationgas stripping
The combination of gas stripping and simultaneous saccharication (enzymatic hydrolysis) and fermentation (SSF) for ABE production from wheat straw also signicantly increases the ABE
productivity. For example, the solvent productivity of the integrated SSFgas stripping process in a batch bioreactor using C. beijerinckii P260 for butanol production from wheat straw is up to
0.31 g L1 h1, 15% higher than the SSF only, while having similar
yield (0.41 g g1 of SSFgas stripping vs. 0.42 g g1 of SSF only)
[21]. It is also found that the yield of the SSFgas stripping system
using wheat straw hydrolyzate is comparable to the batch fermentation control using expensive glucose substrate. Xue et al. [63]
investigated the integration of the batch ABE fermentation in a
brous bed bioreactor with two-stage gas stripping for butanol
recovery. The rst-stage gas stripping was used for in situ product
removal. Its condensate contained 175.6 g L1 butanol (227.0 g L1
ABE), which was subjected to phase separation resulting in an
organic phase containing 612.3 g L1 butanol (660.7 g L1 ABE)
and an aqueous phase containing 101.3 g L1 butanol (153.2 g L1
ABE). The second-stage gas stripping was then used to strip off
the product from the aqueous phase, leading to a highly concentrated product containing 420.3 g L1 butanol (532.3 g L1 ABE).
The high product concentration implies the signicant energy-saving in the subsequent product separation and purication process.
Similarly, gas-stripping can be used in the IBE fermentation for

Fig. 1. Simplied block diagram of the integrated FBFgas stripping system [60].

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in situ removal of IBE mixture. The recovery of IPA and butanol


from model solutions (17 g L1 IBE mixture with I:P:A weight ratio
of 6:10:1) by gas stripping at 37 C are 77.2% and 82.3% respectively. For the IBE batch fermentation, the use of gas-stripping
could increase the IBE productivity to 0.29 from 0.16 g L1 h1 of
the control (without gas-stripping) [64]. The comparisons between
some batch fermentation (BF)gas stripping ISPR processes and
batch fermentation controls are given in Table 1.
2.1.2. Fed-batch fermentationgas stripping
Ezeji et al. [47] studied the ABE production from the glucose
substrate using C. beijerinckii BA101 as biocatalyst in the fed-batch
fermentation (FBF) integrated with gas stripping. Results showed
that the product yield and the productivity were signicantly
improved to 0.47 g g1 and 1.16 g L1 h1 respectively, compared
to 0.39 g g1 and 0.29 g L1 h1 of the batch control [47]. Fermentation of wheat straw hydrolysate using C. beijerinckii P260 for
butanol production in a fed-batch reactor where a sugar solution
consisting of glucose, xylose, arabinose, mannose, and galactose
was added as supplement showed signicant improvement in
ABE productivity of 0.36 g L1 h1 and ABE yield of 0.44 compared
to the SSFgas stripping in batch fermentation as described above
[22]. The gas stripping method not only continuously separates
ABE products from the broth and hence removes the product inhibition but also brings agitation, which causes more hydrolysis in
the SSF process and hence increases the ABE productivity [21].
Most recently, gas stripping was also integrated with fed-batch fermentation for producing butanol from concentrated cassava
bagasse hydrolysate (584.4 g L1) with C. acetobutylicum [24]. With
continuous ABE removal by gas stripping, an ABE concentration of
108.5 g L1 (butanol 76.4 g L1, acetone 27.0 g L1, and ethanol
5.1 g L1) was obtained, with the ABE yield of 0.32 g g1 and butanol yield of 0.23 g g1. The butanol concentration could be
increased to about 64% (w/v) after phase separation [24], which
could result in signicant cost reduction in the post separation
and purication of the product. Also, high concentration of n-butanol was produced from glucose by C. acetobutylicum JB200 in a fedbatch fermentation coupled with intermittent gas stripping [65].
Setlhaku et al. [67] investigated a two-stage ABE fermentation process using C. acetobutylicum ATCC 824 strain, with the 1st stage
operated in a continuous mode and the 2nd stage as a fed-batch.
With gas stripping integrated with the 2nd stage and operated
intermittently, additional glucose feeding was allowed and the
broth concentration of up to 59 g L1 of butanol and 73 g L1 of
total ABE was obtained. The comparisons between some fed-batch

fermentation (FBF)gas stripping ISPR processes and batch fermentation controls are also given in Table 1.
2.1.3. Continuous fermentationgas stripping
Ezeji et al. [66] integrated the continuous one-stage ABE fermentation using C. beijerinckii BA101 with gas stripping for
in situ product recovery. With semi-continuous removal of inhibitory chemicals and products, the integrated system produced
461.3 g L1 ABE from 1125.0 g L1 sugar as compared to a control
batch process in which 18.4 g L1 ABE was produced from 47.3 g
sugar. These results demonstrate that ABE fermentation can be
operated in an integrated continuous one-stage fermentation and
product recovery. The comparisons between the continuous fermentationgas stripping system (CFGS) and the BF control (without gas stripping) are also given in Table 1.
2.1.4. Summary
In summary, gas stripping has many advantages: simple technology and operation, selective removal of volatile compounds
without loss of nutrients, use of fermentation off-gas, without
requirement of chemicals or membrane, and no toxicity to cells,
efcient removal of product inhibition. This also has additional
advantages of improvement of hydrolysis for SSF process by introducing agitation, signicant increase in reactor productivity and
product yield, higher product concentration after condensation
and phase separation, and hence potential cost reduction.
2.2. Vacuum ash
Flash is a separation process based on a one-stage VL equilibrium. The continuous vacuum ashing process can be combined
with the ABE fermentation for in situ product removal from the
microbial culture, as seen in Fig. 2. In this process, a side stream
of the fermentation broth liquor is heated by heat exchanger to a
ash temperature. The heated stream then enters the ash tank
and is ashed into a vapor phase and a liquid phase. The obtained
liquid phase, mainly containing water, is pumped back to the fermenter for reuse, while the vapor phase, after combined with the
fermentation off-gas, enters the condenser where the volatile solvents (ABE) and chemicals are condensed into liquid mixture that
is later fed into the liquidliquid phase separator connected to a
vacuum system. The butanol-rich (organic phase) and the waterrich (aqueous phase) solutions are obtained from the phase separator, and the non-condensable gas is pulled out of the system by a
vacuum pump.

Table 1
Comparisons of BFgas stripping, FBFgas stripping, and continuous fermentationgas stripping with batch controls without gas stripping.
BFgas stripping vs. batch control
Butanol conc. (g L1)
Total ABE titer (g L1)
Cond. conc. (g L1)
Org. phase conc. (g L1)
BuOH yield (g g1)
ABE yield (g g1)
BuOH prod. (g L1 h1)
ABE prod. (g L1 h1)
Cells conc. (g L1)
Initial glucose (g L1)
Glucose used (g L1)
Glucose utiliz. rate (g L1 h1)
Gas ow rate (L min1)
Condenser temp. (C)
Refs.

75.9(17.7)a

0.47(0.40)
0.60(0.29)
11.0(3.2)
161.7(59.2)

1.53(0.76)

[46]

19.8(16.2)
31.8(25.5)
175.6/227.0b
612.3/660.7
0.25(0.20)
0.40(0.32)
0.41(0.30)
0.66(0.48)
80(80)

1.5
2
[63]

FBFgas stripping vs. batch control


21.42(11.93)

151.7
232.8(17.6)

0.41(0.42)

0.47(0.39)

0.31(0.27)

26.1(25.6)

1.16(0.29)
15.0
100.0(59.9)
500.1(45.4)
2.49(0.76)

[21]

[47]

GS = Gas Stripping; CF = Continuous Fermentation.


a
Data between parentheses is the data of the control without gas-stripping.
b
The data over the slash / is the data for butanol while the data after / is the data for ABE.

113.3(19.1)
172
150.5/195.9
610/660
0.24(0.21)
0.36
0.35(0.24)
0.53
600(100)
474.9(86.4)
1.46(1.11)
1.5
2
[65]

CFGS vs. BF
76.44(9.71)
108.50(15.41)

461.3(18.4)

640
0.23(0.22)
0.32(0.34)
0.29(0.24)
0.41(0.39)

0.41(0.39)

584.4
336.6(44.8)
1.28(1.12)

1125(47.3)
0.92(0.28)

[24]

[66]

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Fig. 2. Continuous vacuum ash fermentation process for removal of butanol.

A few of studies on the ABE fermentationvacuum ash systems, simply called vacuum ash fermentations, have been conducted [6872]. For instance, Mariano et al. [6970] studied an
ABE fermentation using C. beijerinckii P260 under continuous or
intermittent vacuum at normal fermentation temperature. The solvents were boiled and ashed out, reducing the butanol inhibition.
Evanko et al. [71] used the combined fermentation and continuous
vacuum ashing process for butanol recovery. The fermentation is
operated under simultaneous saccharication and fermentation
(SSF) mode at 32 C. A side stream containing 4 wt% butanol is continuously removed from the fermenter and a heat exchanger is
used to control the temperature of a ash tank feed at 34 C. The
vacuum pressure is about 6.7 kPa (50 mmHg). The ashed butanolwater azeotrope vapor containing 54 wt% butanol and
46 wt% water is condensed into a butanol rich phase having a butanol concentration of about 680 g L1 and a water rich phase having
a butanol concentration of about 86 g L1. It has been veried by
Aspen Hysys process simulation that a binary aqueous solution
containing 4 wt% isobutanol (rather than n-butanol) under the
absolute (rather than vacuum) pressure of 6.7 kPa could be ashed
to obtain a vapor containing 52.36 wt% isobutanol and 47.64 wt%
water, i.e., 21.08 mol% isobutanol and 78.92 mol% water. This is
in agreement with the Txy diagram as shown in Fig. 3.
Abdehagh et al. [68] simulated the vacuum ash fermentation
to determine the nal concentration of butanol recovered. For

the vacuum fermentation conducted at 37 C with a composition


of 7 g ABE L1 with a ratio of A:B:E of 3:6:1, the boiling of the quaternary mixture at this temperature would occur at an absolute
pressure of around 7.1 kPa as calculated using UniSim Design
R400 (Honeywell). The vapor exiting the fermenter at equilibrium
with the model fermentation broth was predicted to have mass
fractions of 0.144, 0.164, 0.008 and 0.684 for butanol, acetone, ethanol and water, respectively. These corresponds to the enrichments of 34, 78, and 11 times for butanol, acetone, and ethanol,
respectively. In terms of this, vacuum fermentation appears to be
a promising alternative for biobutanol production.
Vacuum ash fermentation has many advantages including
no requirement of additional equipment such as membrane,
sparger or agitator, no damage to the microorganism, and
signicant increase in butanol concentration in the product
vapor stream [68]. Its major disadvantage is that it requires a
vacuum system.

2.3. Liquidliquid extraction


Liquidliquid (LL) extraction, or solvent extraction, is a conventional separation process used to extract desirable solutes from
dilute solution with one or more mixed extractants that is immiscible with the solvent of the solution. LL extraction has been commercially used in chemical and pharmaceutical industries. It also
has great potential in separation of butanol from dilute fermentation broth. Liquidliquid extraction is even more favorable for
butanol separation from ABE fermentation broth than cellulosic
ethanol separation from carbohydrates-to-ethanol fermentation.
This is because butanol is more hydrophobic hence less miscible
with water than ethanol due to its longer carbon chain, and at
the same time, the concentration of butanol from ABE fermentation is much less than that of ethanol obtained from carbohydrates-to-ethanol fermentation.
In general, there are two basic categories in separating butanol
from the ABE fermentation broth with solvent extraction: one is
integration of solvent extraction into the bioreactor, also called
extractive fermentation, where butanol can be recovered in situ
during fermentation so that product (especially butanol) inhibition
is signicantly reduced and hence the butanol yield and productivity signicantly increased. The other one is external solvent extraction of butanol from the broth after the fermentation step.

Fig. 3. Txy for water/isobutanol at 6.7 kPa (plotted by Aspen Hysys 8.0).

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H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540

To our knowledge, few of the literatures cited dened the distribution coefcient of component i by the ratio of the amount (mol
or g) of the component i in the organic phase to the amount of the
component i in the aqueous phase at extraction equilibrium:

K 00Di

mi;OP
mi;AP

1c

where mi is the mass (g) or mole numbers (mol) of component i in


organic phase (OP) or aqueous phase (AP).
Eq. (1c) is less commonly used.
In this paper, the extraction of butanol or isobutanol will be
mostly discussed, so the distribution coefcient of butanol or isobutanol will be simply expressed by KD, K 0D , or K 00D , depending on
the unit basis used.
The relationship between KD and K 0D can be derived as follows:
Fig. 4. Extractive fermentation.

K Di

2.3.1. Extractive fermentation


Extractive fermentation, an integration of fermentation and
in situ solvent extraction for butanol removal, has been widely
studied. The simplied diagram of integrated fermentation LL
extraction process is shown in Fig. 4 assuming that no water is
extracted [59,73]. The distillation column in the process is usually
a multi-stage distillation column where the extractant is recovered
and recycled to the fermenter, while the product ABE is isolated
out for further separation. However, if a nonvolatile extractant,
e.g., ionic liquid that is discussed later in this article, is applied,
an evaporator, the simplest distillation with only one-stage phase
equilibrium, can be used instead of the distillation column.
For efcient in situ isolation of butanol from ABE fermentation,
suitable solvents should be selected based on the following criteria
[59,60]:

Nontoxic to microorganism and environment.


High distribution coefcient.
High selectivity (separation factor).
Low solubility in aqueous solution.
Density signicantly different from that of the broth for easy
phase separation.
Low viscosity for less energy consumption in extraction.
Large interfacial tension for easy coalescence of emulsions and
phase separation.
High stability.
Suitable volatility or boiling point.
Commercial availability at low cost.

Distribution coefcient and selectivity are the two major


parameters for determining an extractant. The distribution coefcient of the component i between organic and aqueous phases is
dened as the ratio of the concentration of the component i in
the organic phase to the concentration of the component i in the
aqueous phase at extraction equilibrium. That is,

K Di

C i;OP
C i;AP

1a

where the subscript OP is used to represent the organic phase and


AP the aqueous phase. i can be butanol, acetone, ethanol, or water,
for example, in the ABE broth. The concentration C in g L1 or
mol L1 (both have the same value of KD).
The distribution coefcient of component i can also be
expressed by

K 0Di

wi;OP
wi;AP

where w is weight percent (wt%) or mass fraction (g g1).

1b

qOP 0
K
qAP Di

where q is density of organic phase (OP) or aqueous phase (AP).


Assuming the density of organic phase being close to the density of extractant and the density of aqueous phase being close to
the density of water, Eq. (2) can be simplied to:

K Di 

qExtractant 0
K Di
qH2 O

Thus, if the density of extractant is not very different from that of


water, then KD andK 0D should be the same for a given extraction
system.
The selectivity (Si) for the solute i (to be extracted, e.g., butanol)
over water, is dened by the ratio of the distribution coefcient of
the component i to the distribution coefcient of water:

Si

C i;OP =C H2 O;OP
K Di

K D;H2 O C i;AP =C H2 O;AP

4
K0

K 00

Apparently, whether Si is dened as (2), or Si K 0 Di , or Si K 00 Di ,


D;H2 O
D;H2 O
the Si value should be the same.
The potential extractants for butanol recovery include oleyl
alcohol [35], glyceryl tributyrate [74,75], methylated crude palm
oil [76] and other chemically modied plant oils such as hydroxylated corn oil [77], biodiesel [76,78], surfactants [79], and ionic liquids [8083]. These extractants have signicantly higher boiling
points than butanol, thus from an energy consumption standpoint,
favoring the subsequent separation of the extractants and butanol
by distillation.
2.3.1.1. Conventional extractants for recovery of butanol. Oleyl alcohol is a nontoxic, most widely researched benchmark extractant
for separating butanol from dilute ABE broth with a butanol distribution coefcient (KD) of 3.4 and a selectivity of 208 for initial concentration of 1 wt% butanol in aqueous solution [84]. The
distribution coefcients (KD) of butanol, acetone, and ethanol are
4.1, 0.45, and 0.22, respectively, using oleyl alcohol as extractant
for the cell-free broth containing 5.2 kg m3 butanol, 2.9 kg m3
acetone and 0.07 kg m3 ethanol at 37 C and a ratio of organic
phase: aqueous phase = 2:5 (v/v) [85]. Davison and Thompson
[35] used oleyl alcohol to remove butanol in a uidized-bed bioreactor with immobilized C. acetobutylicum, and direct simultaneous
extraction and fermentation. Their results showed a 5090%
increase in product yield and butanol productivity as organic-toaqueous ratio increased from 1 to 4, compared to the non-extractive case. The maximum productivity obtained was 1.8 g butanol
L1 h1, and the extractant had a distribution coefcient (KD) of
around 3 for butanol at an aqueous concentration of 1 g L1 (no
selectivity was given). The density of oleyl alcohol is 845
855 kg m3, signicantly different from that of water, which is

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H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540

Table 2
Extraction equilibrium compositions for selected solvents at 25 C [71].
Solvent

Organic phase

Butyl acetate
Butyl acetate
TBP
TBP
Decanol
Decanol
2-Heptanone
2-Heptanone

Aqueous phase

i-BuOH (wt%)

H2O (wt%)

i-BuOH (wt%)

H2O (wt%)

0.83
3.1
1.2
5.6
1.11
7.5
1.15
5.4

1.3
1.9
7.1
6.5
3.8
4.4
1.7
2.5

0.34
1.5
0.22
1.2
0.30
1.4
0.44
1.7

99.7
98.4
99.8
98.8
99.7
98.6
99.2
98.0

K 0D

Selectivity for i-BuOHa

2.5
2.0
5.4
4.9
3.8
5.2
2.6
3.3

187
105
76
74
99
116
155
125

a
The original term used for this column was enrichment factor, which expressed as the ratio of alcohol/water in the condensed vapor divided by the ratio of alcohol/
water in the aqueous dilute solution [71]. This is actually equivalent to the term Selectivity as described by Eq. (4). The conventional term enrichment factor or
concentration factor of a phase (e.g., organic phase) is usually dened as the solute concentration in this phase divided by the solute concentration in the initial feed
solution.

favorable for phase separation after extraction. In addition, a continuous two-stage ABE fermentation using immobilized cells integrated with liquidliquid extraction was reported for removal of
product inhibitions and improvement of the fermentation performance [86]. With a mixture of oleyl alcohol and decanol as extractant, high solvent (ABE) productivity of 2.5 g L1 h1 and solvent
yield of 0.35 g g1 were obtained.
Glyceryl tributyrate is a water-immiscible solvent capable of
extracting both n-butanol and acetone from aqueous solution
[75]. Recently, glyceryl tributyrate was studied for the in situ selective extraction of both alcohols and acetone to enable the simple
integration of ABE fermentation and chemical catalysis, for the
purpose of reducing the overall process energy consumption [74].
Compared to oleyl alcohol, the benchmark solvent, glyceryl tributyrate has much lower boiling point (287288 C vs. 330360 C
at 1 atm). Thus, the subsequent separation of glyceryl tributyrate
and butanol could have less energy demand than the separation
of oleyl alcohol and butanol. However, the specic gravity of glyceryl tributyrate is very close to 1.0 (1.03401.0370 at 25.00 C),
leading to more difculty in phase separation between the organic
and aqueous phases, especially in commercial practice.
Non-ionic surfactants were also investigated as butanol extractants. For example, ve non-ionic surfactants (Triton X 114, L64,
L62, L62LF, and L61) were examined as extractants for butanol
recovery from the fermentation broth in extractive acetonebutanol (AB) fermentation using Clostridium pasteurianum. Biocompatibility tests using 3% (vol) surfactants showed that L62, L62LF, and
L61 did not show inhibition to AB production in 72-h fermentation
using C. pasteurianum, while L64 reduced the AB yield and Triton X
114 inhibited the AB production. The results showed that L62 is a
good extractant for isolating butanol from the fermentation broth,
with the distribution coefcient (KD) of 34 for butanol, and it signicantly enhanced the butanol production with a butanol yield of
225% higher than the control using 6% (vol) L62 [79].
In addition to the above solvents, butyl acetate, TBP, decanol,
and 2-Heptanone, etc. were also tested for extracting isobutanol
(i-BuOH) from dilute aqueous solution. The related compositions
of two liquid phases under equilibrium, distribution coefcients,

and selectivities, obtained at 25 C, are summarized in Table 2.


The extraction performances of these solvents at 25 C for specic
conditions (initial isobutanol concentration and solvent to aq. sol.
vol. ratio) are shown in Table 3 [71]. Furthermore, Groot et al.
[87] examined thirty-six conventional extractants for the distribution coefcient for butanol, the selectivity of butanol over water,
and the toxicity towards Clostridia.
2.3.1.2. Biodiesel and oil-derived extractants. Oil derived from biomass, or plant oil can be chemically modied into an extractant
for in situ butanol removal from a fermentation broth. Ishizaki
et al. [76] studied the removal of product inhibition and
enhancement of butanol productivity in ABE fermentation using
methylated crude palm oil (MCPO) as extractant. With this
extractant, 47% of the total butanol generated was recovered,
with butanol concentration up to 20.9 g L1. Results also showed
that MCPO did not inuence the fermentation performance of the
organism used. The glycerides in the oil can be chemically converted into a product of C7 to C22 carbons, such as fatty acids,
fatty alcohols, fatty amides, fatty acid methyl esters, fatty acid
glycol esters, and hydroxylated triglycerides, and mixtures
thereof, which is water-immiscible and can be utilized as
extractant having a greater distribution coefcient for a product
alcohol than the biomass oil [77]. The distribution coefcient
(KD), one of the most important parameters for the extraction
performance, of representative corn oil derived extractants for
the isobutanol fermentation broth are summarized in Table 4
as compared with conventional commercial solvents of oleyl
alcohol and 2-butyl-1-octanol [77]. It has been shown that corn
oil derived extractants have the distribution coefcients of 2.1
3.2 for isobutanol, representing good candidates as extractant,
though the coefcients are lower than those of oleyl alcohol
and 2-butyl-1-octanol. The selectivities of these extractants for
butanol, though not shown, should be very high due to the
immiscibility between oil and water.
Being non-toxic to species of clostridia [76,88], biodiesel was
studied as a biocompatible extractant for in situ separation of
butanol from fermentation [76,78,88]. It has lower distribution

Table 3
Extraction performance of selected solvents at 25 C [71].

Solvent

Initial wt% i-BuOH

Extractant/aq. sol. (w/w)

i-BuOH wt% in org. phase

i-BuOH wt% in aq. phase

K 0D

Extraction yield (%)a

Butyl acetate
Decanol
2-Heptanone
TBP

0.7
0.8
1.0
1.4

0.5
0.5
0.5
1.0

0.8
1.1
1.1
1.2

0.3
0.3
0.4
0.2

2.67
3.67
2.75
6.0

60
60
60
85

The extraction yield was calculated by dividing the alcohol amount in the organic phase by the initial alcohol amount in the aqueous solution.

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H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540

coefcient for butanol compared to oleyl alcohol (KD = 0.91 vs. 2.8
at the biodiesel/aq. sol. vol. ratio of 1:1), but it is much less costly
than oleyl alcohol. The major advantage of biodiesel as extractant
is its capability of good blending with butanol as fuel, thus subsequent separation of biodieselbutanol could be avoided resulting
in cost savings. With biodiesel as solvent in a single-stage extraction, butanol recovery of 4551% was obtained at a biodiesel/aqueous phase volume ratio of 1:1 and an initial butanol concentration
of 11.1 g L1 and 16.7 g L1 [78]. Biodiesel has a density of about
880 kg m3, making the phase separation relatively easy. Gasoline
can also be used for in situ extraction
of butanol from fermentation.
 
The distribution coefcient K 0D of gasoline for butanol is 0.62
0.66 at 24 C [71], which is much lower than that of oleyl alcohol.
However, gasoline has a very high selectivity for n-butanol (>600)
[71]. Yen and Wang [88] studied the fed-batch ABE fermentation
using C. acetobutylicum and the glucose substrate coupled with
in situ butanol removal using biodiesel extraction for improvement
of productivity. The butanol productivity of 0.295 g L1 h1 and the
maximum total butanol concentration of 31.44 g L1 were
obtained at an extractant/broth volume ratio of 1:1, as compared
to the productivity of 0.185 g L1 h1 and the butanol concentration of 9.85 g L1 obtained in the control batch (without the addition of biodiesel).
2.3.1.3. Ionic liquids for butanol extraction. Room temperature ionic
liquids (RTILs), the organic salts in the liquid state at or below
room temperature, are the novel extractants having potential for
use in recovering butanol from dilute solution [80,81]. For instance,
Simoni et al. [81] studied the LLE of n-butanol from water using
ionic liquids (ILs) as solvents. Experimental results show that some
ILs have high distribution coefcients and selectivities of 25300.
[Hmim][FAP] shows especially good extraction capability with
 
the distribution coefcient K 00D of 5 and the selectivity of 300
for 5 wt% n-butanol aqueous mixture. Ha et al. [83] investigated
the extraction behavior of 11 different imidazolium-based ionic
liquids for butanol extraction. The butanol distribution coefcients
of ILs are highly dependent on the hydrophobicity of anions of ILs
followed by the hydrophobicity of cations of ILs. The hydrophobicity of anions studied is in the increasing order of [TfO]
< [BF4] < [PF6] < [NTf2]. Considering extraction efciency and
selectivity, [NTf2]-based ILs among the tested ILs showed to be
the best extractants for recovery of butanol from aqueous solution.
Among them, [OMIM][NTf2] showed the highest selectivity (132),

with high butanol distribution coefcient (KD = 1.939) and extraction efciency (74%) at 50 C, respectively, for aqueous solution
having initial butanol concentration of 6 wt%.
Other ILs including 1-decyl-3-methylimidazolium tetracyanoborate ([DMIM][TCB]) [89,90], 1-decyl 3-methylimidazolium
tris(pentauoroethyl)triuorophosphate ([DMIM][FAP]) [89], trihexyltetradecylphosphonium tetracyanoborate ([P6,6,6,14][TCB])
[84,90], and 1-hexyl-3-methylimidazolium tetracyanoborate
[HMIM][TCB] [90] were also studied as extractants for extracting
butanol from dilute aqueous solution. For instance, Domanska
and Krlikowski [90] determined the LL equilibrium data for the
three ternary systems [HMIM][TCB], or [DMIM[TCB], or
[P6,6,6,14][TCB] + n-butanol + water at 35 C and ambient pressure.
The NRTL model was well in agreement with the experimental
LLE data. In addition, the RTIL with the longer alkyl chain on the
cation showed higher selectivity and distribution coefcient. The
distribution coefcient and the selectivity of these three ionic
liquids are in the same order: [P6,6,6,14][TCB] > [DMIM[TCB] >
[HMIM][TCB]. The phosphonium cation shows higher distribution
coefcient and selectivity as compared to imidazolium cation.
Davis and Morton [91] studied the ternary liquidliquid equilibrium data for two ionic liquid + water + butanol systems. The RTILs
used are 1-butyl-3-methylimidazolium bis(triuoromethylsulfonyl)imide ([BMIM][NTf2]) and 1-hexyl-3-methylimidazolium
bis(triuoromethylsulfonyl)imide ([HMIM][NTf2]). The LLE data
show that [BMIM][NTf2] and [HMIM][NTf2] exhibit high selectivity
for butanol for solutions of low initial (feed) butanol concentrations. However, the IL-rich phases contain some water as the hydrophobic properties of [BMIM][NTf2] and [HMIM][NTf2] are not strong
enough. The liquidliquid equilibrium data for the ternary system
butanol + water + ionic liquid such as 1-ethyl-3-methylimidazolium bis(triuoromethylsulfonyl)imide ([EMIM][NTf2]) at temperature ranging from 281 K to 340 K were also published [92].
The liquidliquid equilibriums in the binary systems have also
been investigated. For instance, n-butanol + ionic liquid such as
1-alkyl-3-methylimidazolium hexauorophosphate ([RnMIM]
[PF6], where Rn = butyl, pentyl, hexyl, heptyl, and octyl) [93], 1ethyl-3-methylimidazolium hexauorophosphate ([EMIM][PF6])
at 55116.5 C [94], 1-ethyl-3-methyl-imidazolium bis(triuoromethylsulfonyl)imide ([C2MIM][NTf2]) at 275345 K and ambient
pressure [95], 1-n-butyl-3-methylimidazolium hexauorophosphate ([BMIM][PF6]) [96], and 1-butyl-3-methylimidazolium
hexauorophosphate ([BMIM][PF6]) [97].

Table 4
Distribution coefcients for isobutanol at initial aqueous solution of 3wt% i-BuOH [77].
Extractant

i-BuOH conc. in organic phase (g L1)

i-BuOH conc. in aqueous phase (g L1)

KD for i-BuOH

2-Butyl-1-octanol
2-Butyl-1-octanol
Oleyl alcohol
Oleyl alcohol
Oleic acid
Oleic acid
Corn oil fatty acid
Corn oil fatty acid
Corn oil ethylene glycol ester
Corn oil ethylene glycol ester
Corn oil fatty alcohols
Corn oil fatty alcohols
Corn oil fatty amides/acid
67% hydroxylated corn oil
28% hydroxylated corn oil
Corn oil fatty acid (COFA)
Corn oil fatty acid methyl esters (FAME)

20.1
20.0
21.5
13.6
12
3
16.3
9.8
13.4
12.2
18.0
14.5
12.0

4.8
5.0
6.4
3.6
4.6
1.2
5.9
3.9
5
4
6.3
5.0
4.3

4.22
4.05
3.38
3.77
2.61
2.51
2.76
2.52
2.68
3.07
2.87
2.88
2.81
3.2
2.1
2.8
1.06

Note: Values in the 4th column (directly from the literature [77]) deviate a bit from the ratio of the values in the 3rd and the 2nd columns (e.g., 4.19 instead of 4.22 in the rst
row). The difference might be the fact that the values of the 3rd and the 2nd columns are data retaining only one precision, while KD values of the 4th column might be
calculated using the original data having two or more precisions of the 3rd and the 2nd columns.

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H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540

Table 5
Extraction performance of representative ILs.
IL
[HMIM][FAP]
[BMIM][PF6]
[HMIM][PF6]
[OMIM][PF6]
[BMIM][NTf2]
[HMIM][NTf2]
[HMIM][NTf2]
[HOHIMI][NTf2]
[OMIM][NTf2]
[P6,6,6,14][NTf2]
[N1,8,8,8][NTf2]
[P6,6,6,14][DCA]
[THA][DHSS]
[DMIM][FAP]
[DMIM][TCB]
[DMIM][TCB]
[OMIM][TCB]
[P6,6,6,14][TCB]
[P6,6,6,14][Phosph]
[TOA MNaph]
Oleyl alcohol
Oleyl alcohol
Eq.
a

Initial/eq. BuOH conc. of aq. sol. (wt%)


5
6
6
6
6
2
6
5
6
2
2
2
2
1
1
2
1
1
0.66Eq.
1.09Eq.
0.05Eq.
1
1

Temp (C)
22
25
25
25
25
22
25
22
25
25
25
25
25
25
25
25
25
25
25
25
25
25
25

KD (or K 0D ; K 00D )
(K 00D )
a

5
0.74
0.97
1.11
1.03
6 (K 00D )
1.25
1.5 (K 00D )
1.37
1.10
1.44
7.49
7.99
0.8
3.2
3.27
3.7
2.0
41.8
46.11
21 (K 0D )
3.42 (K 0D )
3.4

Refs.

300
21
37
49
39
90
66
40
79

420
100
104
97
500
266
219
274
194
208

[81]
[83]
[83]
[83]
[83]
[81]
[83]
[81]
[83]
[102]
[102]
[102]
[102]
[89]
[89]
[84]
[84]
[84]
[103]
[101]
[101]
[84]

Equilibrium mole percent of aqueous phase.


Data without stated as K 0D or K 00D between parentheses are the values of KD.

Table 5 shows the extraction performance of representative


ionic liquids in terms of distribution coefcient and selectivity.
Density, viscosity and interfacial tension are also important data
for choosing a suitable extractant. The density, viscosity and interfacial tension for ILs (only those with available data) in Table 5 are
tabulated in Table 6. Viscosities and surface tensions of
[BMIM][PF6], [HMIM][PF6], [OMIM][PF6], and [BMIM][NTf2] were
also reported elsewhere [98]. The surface tension of ionic liquids
and ionic liquid solutions were recently reviewed [99].
Extractants with good distribution coefcient (KD,BuOH > 2) and
good selectivity (ideally >100), immiscibility with water, and
non-toxicity to the microorganism are considered good candidates
for butanol recovery [84]. From Table 5 it can be seen that
[DMIM][TCB], [OMIM][TCB], [P6,6,6,14][TCB], [P6,6,6,14][Phosph], and
[TOA MNaph] have good distribution coefcient (KD,BuOH > 2) and
good selectivity (100 or >100). Note that given K 0D 21 for
[TOA MNaph], its KD,BuOH is estimated to be larger than 2 based
on Eq. (3). [HMIM][FAP] is not included in the good list as its
KD cannot be derived from its K 0D (=5), thus it is not sure whether
its KD is larger or smaller than 2. From Table 6, it is found that
the interfacial tension of ILs are large enough for coalescence of
emulsions and phase separation; The densities of ILs are often signicantly different from that of water, for example, the densities of
[BMIM][PF6] and [OMIM][PF6] are 1369 kg m3 and 1235 kg m3,
respectively [83]. This makes the aqueous and organic phases easily separated after extraction. However, most ILs except those containing the anion [TCB] have very high viscosity compared to
conventional extractants (e.g., OA), which results in low mass
transfer and requires high energy consumption for mixing and agitation for extraction. Note that the presence of water in ILs significantly changes their viscosities, especially for the less
hydrophobic ILs where the water content is signicantly higher
[100]. However, even the water-saturated ILs are still much more
viscous than the conventional solvents. To improve the mass transfer and extraction performance through decreasing the viscosity of
ILs, extraction temperature can be increased and/or appropriate
diluents can be added with the extractants. For the extractants
with good distribution coefcient and selectivity as just mentioned, [DMIM][TCB], [OMIM][TCB] and [P6,6,6,14][TCB] should have

much lower viscosity than those ILs that do not consist of the
[TCB] anion. This can be seen by comparing the viscosity between
[HMIM][TCB] and [HMIM][PF6]. The ILs containing the [TCB]
anion are often called low-viscosity family of ILs. Hence,
[DMIM][TCB], [OMIM][TCB] and [P6,6,6,14][TCB] favor mass transfer
and requires low energy consumption. The densities of them were
not found yet. [P6,6,6,14][Phosph] has a density of slightly more than
10% lower than that of water. This is still signicantly far away
from the good density of extractants that should be 20% higher
or lower than that of aqueous phase. It is worth noting that
[P6,6,6,14][Phosph] and [TOA MNaph] have very high selectivity
and the best distribution coefcients (from a few to 20 times
higher than the other ILs listed in Table 5). The conceptual design
and simulation showed that the butanol extraction with [TOAMNaph] requires 73% less energy in comparison with conventional
distillation (5.65 MJ (kg BuOH)1 vs. 21.3 MJ kg1) [101].
Ionic liquids have many advantages as extractants for butanol
separation, including: non-volatility or negligible vapor pressure,
which can translate into less energy demand, extremely low solvent loss, and much less capital cost in the subsequent ILs-butanol
separation process. Their physicalchemical properties can be
tailored or tuned for better separation performance [59,81].
Especially, its non-volatility makes it easily separated from butanol
after extraction by simply using evaporation or a one-stage VL
equilibrium operation (ash distillation), resulting in less energy
consumption, compared to ordinary multi-stage distillation.
The binary mixtures of butanol and ILs are non-ideal solutions.
The activity coefcients and the VLE of organic solvents in the
(organic solvent + IL) binary mixtures can be predicted by
COSMO-RS model. The energy consumptions of the IL recovery
via evaporation mainly consist of the energy required for the uid
heating and vaporization. In addition, the operating conditions for
the binary mixtures of organic solvents and ILs were determined
[121].
With a butanolwater model solution (2.0 wt% butanol, 0.5 wt%
ethanol, 0.7 wt% acetone, 0.5 wt% acetic acid and 0.2 wt% butyric
acid), the KD values measured at 25 C were found in the order
[110]: [THA][DHSS] (7.99) > [P6,6,6,14][DCA] (7.39) > OA (3.32) >
[N1,8,8,8][NTf2] (1.44) > [P6,6,6,14][NTf2] (1.10). No selectivity data

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H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540
Table 6
Density, viscosity and interfacial tension of representative ILs.
IL

q (kg m3) at 25 C

l (mPa s) at 25 C

c (mN m1), 25 C

[BMIM][PF6]
[HMIM][PF6]
[OMIM][PF6]
[BMIM][NTf2]
[HMIM][NTf2]
[OMIM][NTf2]
[P6,6,6,14][NTf2]
[N1,8,8,8][NTf2]
[P6,6,6,14][DCA]
[THA][DHSS]
[OMIM][TCB]
[P6,6,6,14][Phosph]
Oleyl alcohol

1369 [83]
1301 [83]
1235 [83]
1436 [83]
1372 [83]
1325 [83]
1.070 [110]
1.105 [110]
0.898 [110]
0.975 [110]

207.2 [82]; 204@30a [104]


363@30 [104]
477.4 [82], 452@30 [104]
52 [106]

43.52@30 [105]
38.35@30 [105]
34.60@30 [105]
33.09@30 [105]
35.92@30 [107]; 14.49*@30 [108]
22.81*@30 [109];16.47*@30 [108]
33.08 [111]
27.93 [113]
35.04 [111]

895 [103]
0.855 [110]

785.77/97.03@35 [100]
28.32 [119]; 26@30 [120]

91/46b@45 [102]
83/42@45 [102]
123/37@45 [102]

Mutual solubilities (wt%) of IL and water at 25 C


ILs in H2O

H2O in ILs

1.70 [83]
0.60 [83]
0.15 [83]
0.51 [83]
0.23 [83]
0.09 [83]
0.087 [112]

2.69
2.25
1.75
1.75
1.47
1.19

0.510 [112]
8.60  105 mol L [115]

3.31  102 [114]


5 [116]

0.0019

1.14

[83]
[83]
[83]
[83]
[83]
[83]

38.6@30 [118]

q = density, l = viscosity, c = ionic liquidair interfacial tension (i.e., surface tension), or ionic liquidwater interfacial tension (labeled with ).
a

The data right after @ represent the temperature in C at which the physical properties were measured. Properties without following @ were all measured at 25 C.
The data right after slash / for the l column are the viscosities of the water-saturated ILs; otherwise, they represent the viscosities of the pure (dry) ILs.
Data with star () in c column are ionic liquidwater interfacial tension; otherwise, data without are ionic liquidair interfacial tension (i.e., surface tension).

b
*

were reported. OA can be used as a possible RTIL diluent [110] as it


has good distribution coefcient and much lower viscosity than the
ILs discussed here. The biocompatibility tests shows that among
these extractants only [P6,6,6,14][NTf2] and OA are both completely
biocompatible with C. beijerinckii at saturation levels but inhibitory
with C. acetobutylicum [110]. In addition, [P6,6,6,14][NTf2] [122],
[N1,8,8,8][NTf2] [122] are biocompatible with E. coli.
Stoffers and Grak [123] conducted an experimental and modeling study on continuous multi-stage extraction of n-butanol from
dilute aqueous mixtures using [HMIM][TCB] in a mixer-settler unit
at 35 C. The NRTL model was found suitable for description of the L
L equilibrium of the ternary system [HMIM][TCB]/n-butanol/water.
The continuous separation of n-butanol was conrmed feasible.
2.3.1.4. Biocompatibility or toxicity. It is worth noting that biocompatibility between extractants and the microorganisms used for
ABE fermentation must be strictly tested before use in extractive
fermentation. Though the extractants discussed above have good
extraction capabilities and have large potentials to use in ABE
extractive fermentation for in situ product removal, all of their biocompatibilities have not been tested yet. Most recently, the toxicity
of solvents towards C. beijerinckii was discussed by Yang and Lu
[124].
The anions [BF4] and [PF6] hydrolyze in aqueous media and
the resulting hydrolytic products are toxic to microorganisms
[125]. Thus, ILs consisting of these anions might not be suitable
for in situ extraction of butanol from fermentation broth [83]. In
addition, [OMIM][PF6] suppresses biological activity in the ABE

fermenter if present at saturation level [82]; its concentration level


in the broth must be well controlled under the limit if it is used as
extractant. These ILs, though discussed under this section of
Extractive Fermentation, should be considered for external
extraction or ex situ product removal.
2.3.2. External solvent extraction
Extractive fermentation with in situ product removal, as
described above, may not be suitable for large-scale production
due to slow mass transfer into organic phase, formation of emulsions through agitation, cell inhibition by solvent (interface toxicity) and loss of cells at interface, and difcult process control, etc.
[126]. In addition, as described above, extractants for in situ separation in extractive fermentation must be biocompatible with the
organisms used. This greatly limits the range of suitable solvents
and till now only limited biocompatible solvents have been identied. For this reason, fermentation integrated with external product
removal in an extraction column with a recycle of product-lean
broth (Fig. 5) was proposed [126].
Kraemer et al. [126] used the computer-aided molecular design
to screen potential solvents for butanol, and identied mesitylene
(i.e., 1,3,5-trimethybenzene) as novel solvent with excellent properties for ABE extraction from the fermentation broth. The comparisons between mesitylene (measured data) and oleyl alcohol are
shown in Table 7 [126]. Specically, mesitylene has much lower distribution coefcient for butanol than oleyl alcohol at lower temperatures (2530 C), but it has relatively large distribution coefcient
for butanol at higher temperatures (80 C). Simulation results

Fig. 5. Simplied block diagram of hybrid fermentation-external LLE process [126].

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H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540

showed that, the energy demand of the hybrid extraction-distillation process with mesitylene as extractant is much lower than the
extraction with oleyl alcohol (4.8 vs. 13.3 MJ kg1 butanol).
The major advantages of mesitylene over oleyl alcohol are:
much higher selectivity (6 times), much lower (40 times) viscosity, and much lower (2 times) boiling point. The major disadvantage of fermentation followed by external solvent extraction is
the requirement of a very large volume external extractor, which
would greatly increase the capital cost.
2.3.3. Summary
LL extraction is a potentially energy-efcient approach for
removal of butanol from the ABE fermentation broths. Novel solvents ILs are especially promising extractants due to their properties such as nonvolatility, tunability of properties such as
hydrophobility or afnity to butanol, viscosity, and density. Novel
extractants are still needed to be developed with the aid of molecular modeling technique and chemically modifying its afnity to
butanol or hydrophobicity. The disadvantages of extraction in situ
continuous recovery of butanol are: potential emulsions, high viscosity of ILs, and possible toxicity to the biocatalysts,
2.4. Membrane-assisted solvent extraction (perstraction)
Membrane-assisted solvent extraction, also referred as membrane solvent extraction, or perstraction, is a special solvent
extraction for recovery of butanol from the fermentation broth. It
is the combination of membrane separation and LL extraction in
one unit operation. In the perstraction process, the extractant
and the fermentation broth are isolated by a membrane where
butanol diffuses through the membrane and then extracted by
the extractant, while the other components are retained.
Perstraction can be utilized for recovery and separation of butanol from ABE fermentation broth [75,127]. Membrane-assisted
extractive (MAE) fermentation of ABE by C. saccharoperbutylacetonicum N1-4 using a polytetrauoroethylene (PTFE) membrane and
1-dodecanol was studied. The membrane separates the aqueous
Table 7
Comparisons between mesitylene and oley alcohol as solvents for butanol extraction.
1,3,5-Trimethybenzene [126]

Oleyl alcohol [120]

25 C

80 C

30 C

K 0D;BuOH
K 0D;Acetone
K 0D;EtOH

0.76

2.2

3.8

0.43

0.83

0.34

0.03

0.1

0.28

Selectivity
Viscosity (mPa s)
Boiling point (C)

1650
0.66
165

1970

330
26
330360

phase from the organic phase allowing the use of the toxic extractant 1-dodecanol with high distribution coefcients in extraction of
butanol without direct contact and toxifying the microorganism.
Compared to conventional batch fermentation, MAEABE batch
fermentation with 1-dodecanol as an extractant decreased butanol
inhibition and increased glucose consumption from 59.4 to
86.0 g L1, and the total butanol production increased from 16.0
to 20.1 g L1. The maximum butanol production rate increased
from 0.817 to 0.979 g L1 h1. The butanol productivity was
remarkably high with this system, i.e., 78.6 g L1 h1 m2 [128].
Qureshi and Maddox [38] studied the ABE fermentation with whey
permeate as substrate and lactose as supplement in a batch reactor
using C. acetobutylicum P262, coupled with the ABE removal by
perstraction using oleyl alcohol as extractant. ABE of 98.97 g L1
was produced from lactose of 227 g L1 at a yield of 0.44 and productivity of 0.21 g L1 h1. Results show that the coupled fermentationperstraction process is superior to the control batch
fermentation where ABE concentration is only 9.34 g L1.
The major advantages of perstraction are that the extractants
toxic to cells having good extraction performance (high distribution coefcient and selectivity) can be chosen for in situ product
extraction as the organic phase and the aqueous phase do not contact directly. In situ product removal by perstraction could reduce
product inhibition, enhance cell growth, increase productivity,
and save energy in recovering butanol. However, perstraction also
has the obvious disadvantage in that the membrane barrier limits
the extraction rate [38], which results in low butanol productivity.
2.5. Membrane pervaporation
Pervaporation is a separation process where a liquid mixture
(feed) is in contact with one side of a membrane and permeate is
removed as a low-pressure vapor from the other side connected
to a vacuum system. Membrane pervaporation is highly selective,
efcient, and safe. It is the most promising technology in the
molecular-scale liquid/liquid separations existing in biorenery,
petrochemical, pharmaceutical industries [129], and has been
widely studied for removal of inhibitory products from fermentation broth [59]. Fermentation incorporated with membrane pervaporation has been regarded as an efcient way to remove or
reduce the butanol inhibition in ABE fermentation. A typical fermentationpervaporation system for product removal is shown
in Fig. 6. In the fermentationpervaporation system, ultraltration
(UF) is used to retain and recycle the microorganisms or cells used
back to the fermenter. The permeates without microorganisms
then enter the hydrophobic pervaporation (PV) unit where the
ABE solvents pass through the pores of the hydrophobic membrane, and then evaporated under the vacuum. The recovered
solvents are then condensed into liquid for further product

Fig. 6. ABE fermenter integrated with pervaporation.

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H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540

separation. The aqueous retentate is recycled to the fermenter.


Hydrophobic membranes are chosen in separating butanol from
dilute broth by pervaporation as butanol is hydrophobic. In general, there are three categories of hydrophobic membranes: polymeric, inorganic, and composite membranes.

rethaneurea (HTPB-PU) [149], PDMSPAN [150], PDMS/polyimide


[41], and PDMS/PTFE [151] were studied. Li et al. [143] studied a
novel composite membrane consisting of three active layers of
PDMS (Sylgard 184) and dual support layers of high porosity
polyethylene (PE) and high mechanical stiffness perforated metal
for separation of butanol from dilute aqueous solution by pervaporation. Experiments showed that both total ux and separation
factor increased when placing a layer of hydrophobic PE between
the PDMS and the metal support. With the PDMS/PE/Brass support
composite membrane, a total ux of 132 g h1 m2 and a separation factor of 32 were obtained at 37 C for the feed solution of
2% butanol. Tong et al. [149] prepared hydroxyterminated polybutadiene-based polyurethaneurea (HTPB-PU) pervaporation membranes for recovering n-butanol and acetone from dilute aqueous
solutions. The results demonstrated that the pervaporation performance for the ternary mixture was superior to that for the binary
mixture because of the permeantpermeant and permeantmembrane interactions. High selectivity towards n-butanol and acetone
was obtained. Butanol and acetone were concentrated from 3.0 to
43.5 wt% and 1.5 to 11.9 wt% at 40 C for the simulated ternary
mixtures, respectively. For fermentation broth at 45 C, the separation factors of butanol and acetone were 17.6 and 18.9, respectively, with concentration of butanol and acetone increased from
1.1 to 16.4 wt% and 0.5 to 8.7 wt%, respectively. However, the total
ux was only 9.7 g m2h1. Relatively low permeate ux is the
common weakness of heterogeneous polymeric membranes. This
is because this category of membrane made of only polymers usually has to be relatively thicker to achieve the necessary strength
and the ability to endure long time operation. This leads to low
permeate ux, though the increase in thickness could increase
the butanol separation factor.
Overall, unlike composite membranes described later, heterogeneous polymeric membranes have not shown signicant improvement of pervaporation performance over single polymeric
membranes. Hence, there is an increasing interest towards the
study of composite membranes.

2.5.1. Pervaporation with hydrophobic polymeric membranes


The commonly investigated hydrophobic polymeric membranes for separating n-butanol from ABE fermentation broth
include polyether block amide (PEBA) [40,130133], polyvinylidene uoride (PVDF) [134], polytetrauoroethylene (PTFE) [135],
polypropylene (PP) [43], poly(1-trimethylsilyl-1-propyne) (PTMSP)
[136,137], and polydimethylsiloxane (PDMS) [67,133,138140].
Most of single-polymer membranes have either low separation factors or low permeate uxes. PTFE and PP membranes allow a large
amount of water pass through the membrane [141], leading to low
selectivity. PTMSP shows best performance based on the permeate
ux and separation factor. This is similar to the case of ethanol
recovery from ethanol fermentation broth by pervaporation where
pervaporation using PTMSP membranes shows a distinct advantage over PDMS membranes in ethanol removal [142]. PDMS was
also reported to have good performance and promising potential
due to its highly hydrophobic properties, good thermal, chemical
and mechanical stability, relatively low price, as well as its ability
to be easily fabricated [143]. A thin PDMS membrane has high ux
but low selectivity for butanol, while a thick PDMS membrane
offers high selectivity but low ux [141]. Thus, its thickness must
be appropriate in order to achieve appropriate ux and selectivity.
The performance of membrane pervaporation is basically
expressed by solute (butanol) permeate ux, total permeate ux,
and separation factor. The separation factor of butanol (over water)
for membrane pervaporation is dened as:

wBuOH =wH2 O P
wBuOH =wH2 O F

where wBuOH and wH2 O are concentrations of butanol and water


(in wt%) in permeate (P) and feed (F), respectively.
The pervaporation performances of representative hydrophobic
polymeric membranes for butanol removal are shown in Table 8.
To improve the overall pervaporation performance, heterogeneous polymeric membranes consisting of different polymers, such
as PDMS/PE [143], hydroxyterminated polybutadiene-based polyu-

2.5.2. Pervaporation with polymeric composite membranes


The performance of polymeric membranes is often limited by
the trade-off between permeability and selectivity [40]. For this
reason, the composite membranes consisting of polymers and
inorganic llers such as ceramic, zeolites (especially silicalite),

Table 8
Pervaporation performance of polymeric membranes for butanol recovery.
Membrane
PDMS
PDMS
PDMS
PDMS (GFT 1060)
PDMS (Pervap 4060)
PDMS (Pervap 4060)
Thin PDMS on polyimide (Pervatech)
PTMSP
PTMSP
PTMSP
PEBA
PDMS/b-CD
Polysiloxane (CMX-GF-010-D)
PDMS copolymers (PERTHESE@ 5001)
PEBA

Thickness
(lm)

Butanol in feed
(wt% or g L1)

50
170
190

1.0
1
1.0
(58.9)a
5
0.581.8
0.31.5
0.31.5
2
0.81.2F
1.0
0.2
0.2
2.34

50
10

T (C)
35
50/70
78
37
37
50
37
25
70
53
37
40
40
40
37

PPerm (Pa)

67400
267667
107
1000
4
1230

53336666
307
1000

Total permeate
ux (kg m2 h1)

Sep. factor, BuOH/


acetone/EtOH

0.0250.035
0.145/0.350
0.084
0.129
>0.4
3.4
0.5610.621
0.060.124
0.7621.03
1.75
0.161
0.800
0.330
0.033
0.297(BuOH)

8.818.8
49.6/48.7
44.9
27
26.4
39
1620/2033/610
5178
4770
115
14
40
38
52
11.57

CMX-GF-010-D: commercial hydrophobic membrane by CELFA AG, Switzerland.


GFT 1060: membrane of PDMS only, by Deutsche Carbone AG, Germany.
PERTHESE@ 500-1: dimethyl and methyl vinyl siloxane copolymers by Perouse Plastie, France.
PERVAP 4060: Sulzer Chemtech, Switzerland.
Pervatech thin PDMS: product of Pervatech, The Netherlands.
F
Fermentation broth; others are simulated solutions.
a
Concentration of butanol in feed and permeate shown in () are in the unit g L1; others are in wt%.

Butanol in permeate
(wt% or g L1)

(167.1)
(60.4131.6)
13.245.6
12.351.6

27.08

Refs.
[44]
[144]
[138]
[145]
[67]
[146]
[41]
[136]
[136]
[137]
[40]
[147]
[148]
[148]
[133]

526

H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540

and silica are gaining more interests and have been widely tested
[143,144,148,152156]. Both polymers and inorganic llers are
hydrophobic, favoring separation of butanol. Polymers are easy to
use to fabricate membranes. They are relatively cheap, but they
lack sufcient strength, and are subject to aging over a long period
of time, especially at a given temperature. The hydrophobic inorganic materials possess strong afnity to butanol and have high
strength and long-term stability under high temperature, but the
materials and the production cost for inorganic membrane are
expensive. With incorporating the advantages of both polymers
and inorganic materials, the composite membranes can usually
be prepared to have high permeate ux and separation factor at
a moderate cost. The incorporation of hydrophobic inorganic llers
into polymer could increase the permeate ux without losing the
separation selectivity.
The polymeric composite membranes commonly studied for
pervaporation of butanol from aqueous solutions include PEBAinorganic composite membranes [40,157,168], PDMS-based composite membranes such as PDMS/ceramic [154156,158], PDMS/
zeolites [147,159,160], PDMS/silica [143], PDMS/silicalite-1
[138,161,162], and PDMS/PE/perforated alloy metal (i.e., PDMS
composite with the dual support consisting of the porous polyethylene sheet and perforated alloy metal) [163], PTMSP/silica
[146,164], and PVA/ceramic [165,166]. Marszaek and Kaminski
[167] used commercial at-sheet membrane PERVAP 4060 for pervaporative separation of butanol from dilute solution. Pervaporation allows to concentrate butanol over 10 times. The permeate
uxes were 523, 1494, and 1063 g m2h1 for butanol, ethanol
and acetone, respectively. The separation factor for butanol is
within the range of 4.1219.48.
Some researchers investigated pervaporation using PEBA-inorganic composite membranes for butanol separation [40,157,168].
Tan et al. [157] prepared and characterized the composite membranes incorporating ZSM-5 zeolite into PEBA. Characterization
by TGA, XRD, and SEM showed that the zeolite could distribute
well in the polymer matrix. Using the 5% ZSM-5-PEBA membrane
for separation of butanol from aqueous solution, the separation
factor of 2230 and the permeate ux of 250550 were obtained
for 2.5 wt% butanol feed at the ow rate of 50 L h1 and the feed
temperature of 3045 C. The PEBA carbon nanotubes (CNTs)
pervaporation membrane, a special kind of composite membranes
using the novel inorganic material carbon nanotubes, has great
potential when integrated in the ABE fermentation [40]. The combination of a 5-L fermenter with the pervaporation membrane of
PEBA + CNTs (10%) resulted in a 26% increase in butanol productivity and a 18% increase in its yield compared to using PEBA only.
Also, the addition of CNTs to PEBA could greatly enhance the solvent permeate ux without decreasing the separation factor, and
the mechanical strength of the membrane, which can be used for
a longer operation. Most recently, Paradis et al. [169] developed
and characterized the hydrophobic hybrid silica membranes consisting of different R-triethoxysilanes (R = C1 to C10 alkyl) and
1,2-bis(triethoxysilyl)ethane (BTESE). The afnity of these membranes could be tailored from hydrophilic to hydrophobic, specically, their hydrophobicity increases with increasing the length of
the ending R-group, on which their separation properties are
strongly dependent. Using the membrane of this type with C10
alkyl ending group for pervaporative separation of n-butanol from
aqueous solution containing 6.8% butanol, permeate of more than
40 wt% butanol was obtained. In addition, being stable and nonswelling, the membrane separation factor remained constant at
around 15 over a wide range of temperatures (3090 C) and butanol feed concentrations (0.56.8 wt%). The butanol uxes obtained
are 0.50.6 kg m2 h1 at 60 C and 1.21.5 kg m2 h1 at 90 C.
Butanol forms azeotropes with water at 55.5 wt% butanol.
When butanol concentration of permeate is between about 7.7

and 79.9 wt%, it separates into two layers of liquid phases: a butanol-rich solution and a butanol-thin solution. To recover all the
butanol in the permeate, butanol needs to be separated from these
two layers of liquid. The butanol-rich solution can be further separated by distillation, and the butanol-thin solution can be recycled
to the membrane system. Another option is to develop membranes
having very high separator factors that can produce high butanol
concentrations of over 80% in the permeate through pervaporation
of dilute solution containing less than 1% butanol. The solution of
high butanol concentration can be directly separated further by
distillation. Without the need of recycling butanol-thin solution,
the burden of membrane process can be relieved. For example,
Negishi et al. [170] developed silicalite membranes coated with
0.3% silicone-rubber on a porous support tube for pervaporative
separation of butanol from 1 wt% butanol solution. Using this
membrane, permeates with high butanol concentration of
81.8 wt% were obtained, which could simplify the butanol concentration process.
The pervaporation performances of representative hydrophobic
composite membranes for butanol removal are shown in Table 9.
Membrane fouling is a critical issue and should be paid attention to. It was reported that the silicalitesilicone composite membrane exposed to fermentation broth for 120 h was not fouled by
fermentation broths [37]. Based on another literature [158], the
PV membrane exposed to the fermentation broth for 200 h was
fouled by the active fermentation broth, nevertheless the separation performances were partially recovered by ofine membrane
cleaning, and the solvent productivity was increased to
0.252 g L1 h1, corresponding to 19% higher compared with that
in situ recovery process without membrane cleaning. To avoid fouling of PV membrane, UF is often considered to be used prior to the
PV module as seen in Fig. 6.
2.5.3. Pervaporation with supported liquid membranes
Polymeric membranes for pervaporative separation of butanol
are usually difcult to offer high values in both permeate ux
and butanol selectivity. As described above, composite membranes
consisting of polymers lled with inorganic llers such as sillicalite
and ceramic are designed for enhancing the permeability and separation factor [144,152,154]. Supported liquid membranes (SLMs)
provide another approach for improving the pervaportion performance (permeability and separation factor) [172]. Generally, there
are several types of SLMs in terms of different methods for immobilizing the hydrophobic organic solvent liquid on the membrane
support [173]: covalent binding of ILs, ion exchange membranes,
gelation of ILs, inclusion in polymer matrix, and inclusion by silicone coating. An immobilized liquid membrane is the membrane
system in which the immobilized liquid (called the membrane
phase) is held by capillary forces in the pores of microporous polymeric or inorganic lm (the support for the membrane). Usually a
hydrophobic organic solvent is immobilized in a polymeric membrane through impregnation to form a SLM used for pervaporative
separation of butanol [174]. In principle, in a SLM system the
immobilized extractant as membrane phase separates two aqueous solutions: the feed (donor) and the strip (receiving, acceptor)
phase. The compounds are separated from the aqueous feed phase
into the immobilized extractant in a support diffusing through the
membrane phase, and then they are continuously stripped to the
other side of the membrane into the strip phase [174].
Supported liquid membranes for separating butanol from dilute
fermentation broths have been studied using conventional solvents
such as oleyl alcohol [120,175177] and recently ionic liquids
[102,172,178,179] as extractants. Thongsukmak and Sirkar [177]
studied SLM using trioctylamine (TOA) as liquid membrane for separating butanol from aqueous solution. High selectivities of 275, 220
and 80 for butanol, acetone and ethanol, respectively, were obtained

527

H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540
Table 9
Pervaporation performance of representative composite membranes for butanol recovery.
Membrane

Thickness (lm)

Butanol in
feed (wt%)

T (C)

PPerm (Pa)

Total ux a
(kg m2 h1)

Sep. factor
for BuOH

PEBA + CNTs
PEBA/ZIF-71 (20 wt%)
PDMS/ceramic
PDMS/ceramic
PDMS/ceramic
PDMS/ceramic
PDMS/ZSM-5 zeolite
PDMS/silicalite-1
PDMS/silicalite-1
PDMS/silicalite (Pervap 1070)
PDMS/silicalite
PDMS-PE/silica (Sylgard 184)
Thin-lm silicalite-lled silicone
Thin-lm silicalite-lled silicone
PERVAP-1070
HybSi@ membrane
Hydrophobic HybSi@
Hydrophobic HybSi@
PTMSP/silica (Vito 1)
Silicone-rubber-coated silicalite
ETES/silicalite-1

50
1020

0.81.2F
1
1.26
1
12
0.5F
1.0
1
1
0.35
0.23
2
1.52.0F
1.0
1.0
5
2
2
5
1.04
2

37
37
37
40
30
37
40
78
78
35/65
80
37
70
50/70
50/70
60
60
90
50
45
60

53336666
<400
<400

0.147
0.520
0.951
0.457
0.360.47
0.3380.847
1.500
0.235
0.090
0.170/0.55
5.011.2
0.132
0.907
0.191/0.607
0.137/0.344
0.4501.40
0.50.6BuOH
1.21.5BuOH
9.5
0.038
0.100

18
18.8
16
26.1
1114
527
45
50
97
16/10
2542
32
49/14/4
111/93
50/48
11
15
15
104
465
150

30

96
306
29
0.3
1315
19
29
0.5 silica

2.4

<300
<400
267667
267667
667
<133
67400
67400
67400

Butanol in permeate
(wt% or g L1)
18.6
17.1
2630
(96.2)b

5.5/3

45.7
46.242.9
42

82.9

Refs.
[40]
[168]
[154]
[155]
[156]
[158]
[147]
[138]
[138]
[152]
[161]
[143]
[144]
[144]
[144]
[169]
[169]
[169]
[146]
[170]
[171]

HybSi@ membrane: hybrid organic (BTESE-based)inorganic (silica) membranes.


PERVAP-1070: silicate-lled composite PDMS membrane, by Sulzer Chemtech, Germany.
F
Fermentation broth; others are simulated solutions.
a
For the Total Permeate Flux column, all data are total permeate uxes except those data with BuOH representing butanol permeate ux.
b
Concentration of butanol in feed and permeate shown in () are in the unit g L1; others are in wt%.

at 54 C for a feed mixture containing 1.5 wt% butanol, 0.8 wt% acetone, and 0.5 wt% ethanol, with the permeate mass uxes of 11, 5
and 1.2 g m2 h1 for butanol, acetone and ethanol, respectively.
Results also showed that selectivities and uxes increased considerably as the temperature of the feed solution was increased from
25 C. The permeate uxes could be increased by a factor of 5 by
reducing the thickness of the TOA layer in the porous wall of the
coated bers. For instance, with 50 lm of thin TOA-LM containing
20 vol% TOA and hexane (80 vol%) as diluent, the butanol ux of
53 g m2 h1 and the selectivity of 240 were achieved for a feed
solution of 1.5 wt% butanol. More recently, hydrophobic ILs were
selected for SLMs as ILs are novel and mostly green solvents with
high extraction performance as in the extraction section described
above. With proper selection of IL components, PM-ILs can offer high
uxes and faster separation [178]. Izk et al. [172] prepared a supported ionic liquid membrane (SILM) and integrated it into an ABE
fermentation system using C. acetobutylicum at 37 C. The SILM
was impregnated with 15 wt% of the ionic liquid, tetrapropylammonium tetracyanoborate, and 85 wt% of PDMS. The product was continuously removed at 2.34 g L1 h1 by in situ pervaporation using
SILM when aqueous feed concentration was 0.9 wt% butanol. Cascon
and Choudhari [102] studied the SILMs using hydrophobic ammoniumand
phosphonium-based
RTILs:
[P6,6,6,14][NTf2],
[N1,8,8,8][NTf2], [P6,6,6,14][DCA], and the mixture of [P6,6,6,14][NTf2]
and [P6,6,6,14][DCA] for pervaporative recovery of n-butanol from
aqueous solutions containing 0.52.5 wt% butanol at temperature
varying from 35 to 70 C. Among these four SLMs, [P6,6,6,14][DCA]
shows the best evaporation performance. Some of their results are
shown in Table 10.
The immobilized SLMs could not offer long-term stability, i.e.,
leaking of the impregnated or immobilized ILs from the support
membrane because of the large pressure difference in the pervaporation process [180]. For this reason, polymer inclusion membranes (PIMs) and gelled liquid membranes have been studied to
improve SLM stability. PIMs are formed by casting the solution
containing a liquid extractant and a base polymer, usually cellulose
triacetate (CTA) or poly (vinyl chloride) (PVC), and plasticizer to
form a thin, exible and stable lm (self-supporting PIM), while

gelled liquid membranes are form by liquid-phase gelation in the


PVC pores of an SLM. Separation by SLMs combines the solvent
extraction and stripping processes in a single step, with great
potential for energy saving, low capital and operating cost [174].
Recently, Matsumoto and co-workers [180] investigated the separation of n-butanol from a ternary mixture (butanol/IPA/water) by
pervaporation using polymer inclusion membranes containing
ionic liquids: Cyphos IL-101, 102, 104, and 109, Aliquat 336 and
[Bmim][PF6]. PVDF membranes were used as the support membrane. The highest n-butanol ux, total ux, and separation factor
obtained by the membrane (30 lm in thickness) with the ratio of
Aliquat 336/PVC = 70/30 (w/w) were 26.08 g m2 h, 1193 g m2 h
and 4.5 respectively, for initial butanol concentration of 5 g L1 in
the feed. Obviously, the separation factor (4.5) obtained is much
lower compared to the other pervaporation membranes. Plaza
et al. [181] prepared a SLM by gellation of the ionic liquid,
[bmim][PF6], into the pores of PTFE hollow bers and used the
SLM for separating ABE from its fermentation broth by sweep gas
pervaporation. The butanol/ethanol selectivity was improved compared to the membrane pervaporation process using the same hollow ber support with IL. Heitmann et al. [173] studied SILMs
using [DMIM][TCB], [P6,6,6,14][TCB], and [DMIM][FAP] as liquid
membrane and PEBA as host polymer for pervaporation of butanol
from aqueous solutions. Two types of SILMs were tested: one with
IL immobilized by inclusion between silicone layers, and the other
with IL immobilized by dissolution in PEBA. Results showed that
the maximum permeate ux was 560 g m2 h1 for the initial
butanol concentration of 5 wt% at pervaporation temperature of
37 C. It was also found that the permeate ux increased with
increasing IL content in the membrane.
2.5.4. Integrated fermentationmembrane pervaporation
Membrane pervaporation were widely integrated into batch
fermentation [44,182], fed-batch fermentation [37,152,154,182],
and continuous fermentation [39,41,42,182] of carbohydrates to
ABE, for product removal so as to eliminate or reduce the product
inhibition and hence increase the product yield, the ABE concentration, and the productivity. In a fed-batch fermentationpervapora-

528

H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540

Table 10
Pervaporation performance of representative supported liquid membranes for butanol recovery.
Solvents as
liquid membrane

d (lm)

T (C) PPerm (Pa) Total permeate


BuOH permeate Sep. factor
ux (kg m2 h1) ux (kg m2 h1) for B/A/E

Butanol in permeate Refs.


(wt% or g L1)

TOA
(Full thickness) 1.5/0.8/0.5
TOA (20 vol%) + Hexane (diluent) 50
1.5/0.8/0.5

54
54

426.6
426.6

11.0/5.0/1.2
53

67

[177]
[177]

TOA (30 vol%) + Hexane (diluent) 50

54

426.6

31/9/4

275/220/80
240/220/
100
197/111/54

[177]

45
45
45
45
37

<310
<310
<310
<310

77
82
298
117
0.560

29
22
126
72

63
37
77
57

37
26
42
38
55

[102]
[102]
[102]
[102]
[173]

[P6,6,6,14][NTf2]
[N1,8,8,8][NTf2]
[P6,6,6,14][DCA]
[P6,6,6,14][NTf2]/[DCA]
[DMIM][TCB]

25
25
25
25

B/A/E in
feed (wt%)

1.7/0.8/
0.7F
1.0
1.0
1.0
1.0
5

tion system, ultraltration membrane with 500,000 molecular


weight cut-off was used to retain and recycle the cell culture to
the fermenter while allowing its cell-free permeate enter the pervaporation membrane for product recovery and concentration, as
similar in Fig. 6 but with additional buffering tank placed between
the UF membrane unit and the hydrophobic PV membrane unit.
Using the glucose substrate and C. acetobutylicum biocatalyst, and
the hydrophobic silicalitesilicone composite membrane for product recovery and concentration, the ABE concentration is up to
154.97 g L1 while the ABE yield is in the range of 0.310.35. The
average selectivity of butanol and acetone were about 40 and
95200, and the average ux was about 86 g m2 h1. Table 11
summarizes the performance of the integrated FBF-pervaporation
(PV) vs. the performance of the control batch fermentation (BF)
[37].
Most recently, continuous fermentation systems integrated
with membrane pervaporation have been studied. Fig. 7 shows
the general continuous fermentation coupled with membrane pervaporation. For instance, a continuous two-stage ABE fermentation
using C. acetobutylicum ATCC 824 was coupled with pervaporation
separation using hydrophobic thin PDMS composite membranes
with 1 lm PDMS separating layer on 200 lm porous polyimide
support for product (butanol) removal, leading to signicant
decrease in the product inhibition in the fermenter. Hence, the glucose concentration increased from 60 to 126 g L1, the productivity
increased from 0.13 to 0.30 g L1 h1, and the permeate was
enriched to 57195 g L1 total solvents depending on the solvent
concentrations in the fermenter [39]. Hecke et al. [41] integrated
a continuous two-stage ABE fermentation using C. acetobutylicum
ATCC 824 with pervaporation where PDMS composite pervaporation membranes were directly coupled to the second fermenter
resulting in decreased solvent titers. With increasing the initial
carbohydrate concentration in the feed from 60 g L1 to
150 g L1, the overall productivity was increased from 0.45 g L1 h1 to 1.13 g L1 h1, even though productivity decreased signicantly in the rst fermenter due to substrate inhibition. In the

last phase that lasted 200 h, the average ux of 0.621 kg m2 h1,
the separation factor for butanol of 19.8, and the total solvent concentration in the permeate of 202 g L1 were achieved.
Chen et al. [42] integrated an ABE fermentation using C. Acetobutylicum with PDMS composite membrane pervaporation for
in situ butanol recovery into a continuous and closed-circulating
fermentation (CCCF) system. Two cycles of experiment were conducted for 274 h and 300 h, respectively. At their respective broth
concentrations of 7.6 and 7.0 g L1, the total permeate uxes of the
two cycles were 784 and 566 g m2 h1, respectively, the separation factors are 10 and 7, respectively, and the corresponding permeate butanol concentrations are 71 and 47 g L1, respectively.
The average cell concentration, the glucose consumption rate, the
butanol productivity, and the butanol production of the second
cycle were 1.68 g L1, 1.12 g L1 h1, 0.205 g L1 h1 and
61.43 g L1, respectively.
2.5.5. Energy requirement for membrane pervaporation
The evaporation energy requirement for the PV separation of
butanol from dilute aqueous solutions varies with the concentration of butanol in the feed and the membrane separation factor
was estimated by Vane [60] and is shown in Fig. 8. It can be seen
from this gure that evaporation energy consumption decreases
with increasing feed butanol concentration. It also decreases with
increasing butanol separation factor. At the feed butanol concentration of 2 wt% the evaporation energy required is about 8.8, 4.9,
and 2.8 MJ/kg BuOH (data read from gure) for separation factor
of 30, 60, and 120, respectively. These energy consumptions correspond, respectively, to 24.4, 13.6, and 7.8 wt% of the butanol
energy content. At this 2wt% feed concentration level, it is suggested that the membrane butanol separation factor of PV should
be at least 30, and 50 or above would be considered as good butanol separation factor. At a higher feed butanol concentration, the
evaporation energy required drops signicantly, especially for the
low separation factor cases. At 4 wt% feed butanol concentration,
for example, the evaporation energy required by PV with a

Fig. 7. Two-stage ABE fermentation integrated with a pervaporation unit [39].

529

H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540

separation factor of 30 is about the same as the energy required by


the PV with a separation factor of 60 at the feed concentration of
2 wt% butanol. This suggests that if the ABE fermentation can be
improved via advanced biotechnologies such as genetic engineering and higher broth concentration, e.g., 4 wt% butanol, is achieved,
the hydrophobic membrane with high permeate ux but low separation factor (e.g., 30) could still be energy-efcient in the PV
process. This also gives a hint that improvement of microorganisms is also important for enhancing the separation efciency
and reducing the separation cost.
Matsumura et al. [175] estimated the energy requirement of a
combined OA-LM plus distillation system based on the assumptions: Fermentation broth with a butanol mass fraction of 0.005
at 30 C is fed to the membrane module at a mass ow rate of
24 kg/h. The outlet butanol mass fraction: xB,out = 0.004. Membrane
pervaporation operates at T = 25 and P = 0.133 kPa. The average
butanol composition of the permeate was 0.439. The condensation
temperature is 13.0 C. Assuming that 98% vapor permeate was
condensed. The condensed permeate was then fed to a distillation
column for purication to the product purity of 99.9%. The sum of
the energies supplied to the cold trap and vacuum pump, and the
specic energy requirement was 4.67 MJ/kg of butanol, while the
energy requirement for butanol purication was 2.75 MJ/kg of
butanol. Thus, the overall energy requirement in the combined
OA-LM + distillation system was 7.42 MJ/kg of butanol.
Most recently, Qureshi et al. [183] carried out an economic evaluation of biological conversion of wheat straw to butanol. The
results showed that the use of a membrane recovery process
including membrane pervaporation for butanol removal from
ABE fermentation broth signicantly reduced the butanol production cost compared to the distillative recovery process. Negishi
et al. [170] estimated the energy requirement for pure butanol production from 1 wt% butanol solution using silicone-rubber coated
silicalite membranes. The resulting permeates contained a very
high butanol concentration of 81.8 wt%. The energy requirement
estimated was 4.3 MJ kg1 n-butanol, mainly consisting of the
energy required for concentrating from 1 wt% butanol to
81.8 wt% butanol by pervaporation using the silicone-rubber
coated silicalite membrane and the energy required for the subse-

quent product dehydration using a hydrophilic PV membrane. This


is only about 13% of the energy content of butanol.
2.5.6. Advantages and disadvantages of membrane pervaporation, and
summary
Membrane pervaporation have many advantages [129]:
(1) high separation efciency in terms of both permeate ux
and separation factor, since separation mechanism is based
on the differential transport/diffusion of permeates through
the pores of membrane, instead of the vaporliquid
equilibrium;
(2) high energy-efciency due to the fact that only the permeates need to be evaporated and consume the latent heat.
Energy efciency is dened as the ratio of energy gained to
energy consumed, i.e., the ratio of energy content in per unit
weight of butanol to energy consumption for producing unit
weight of butanol;
(3) no harmful effects on the microorganisms used because
there is no need for adding any other components;
(4) good exibility, simplicity in scaling-up, operation, and
control.
The major issues of membrane pervaporation are associated
with the potential membrane fouling especially when dealing with
real fermentation broths, the long-term stability for polymeric and
composite membranes, as well as the membrane preparation cost.
Thus, it is required to study the long-term fouling characteristics of
fermentation broth on PV membranes. In addition, there are many
factors inuencing the pervaporation separation performance: (1)
factors of membrane itself such as thickness of active layer, membrane structure, membrane pore size, llers adsorption capacity
for butanol, particles of lled inorganic materials of composite
membranes, and membrane surface modication (2) operation factors such as feed temperature and concentration, and pressure on
permeate side. Therefore, further work on optimization of membrane preparation and pervaporation operating conditions are still
needed.
Earlier critical reviews provide additional discussions on membrane pervaporation [184,185].
In summary, even though hydrophobic PV membrane has not
yet been utilized in industry as hydrophilic PV membrane, it has
great potential in efcient separation of butanol from ABE fermentation broth and is a very promising technology in bioreneries.
2.6. Other membrane technologies
2.6.1. Membrane distillation
Membrane distillation (MD) is a separation process involving
evaporation and transportation of volatile components (vapor)
through a porous hydrophobic membrane based on a temperature-induced vapor pressure difference [186188]. As the volatile
compounds evaporate through the pores of MD membrane, the
separation mechanism of MD is based on the VLE of the liquid mixture. There are four types of MD: direct contact membrane distillation (DCMD), air gap membrane distillation (AGMD), sweeping gas
membrane distillation (SGMD), and vacuum membrane distillation

Table 11
Performance of integrated fermentationpervaporation and the control BF [37].

Fig. 8. Evaporation energy requirement as a function of separation factor and


butanol feed concentration for PV separation of butanol from water for a xed
butanol recovery of 80% (permission from John Wiley and Sons Ltd.) [60].

Total ABE conc. (g L1)


ABE yield
Glucose conc. in feed (g L1)

Control BF

Integrated FBF-PV

19.2
0.29
70.30

155.0
0.310.35
700.0

H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540

2.6.2. Thermopervaporation
Thermopervaporation (TPV) is a novel concept of pervaporation
with internal heat recovery [191]. TPV uses similar nonporous
membrane to that of conventional PV, but the former operates
under the atmospheric pressure while the latter usually under
the vacuum condition. On the other hand, the TPV system is similar
to the MD system in that both operates under atmospheric pressure and donot require the vacuum system, with difference in that
a nonporous membrane is used for the former while a porous
membrane is use for the latter. In the TPV process shown in
Fig. 9, the feed enters the condenser of the module at a temperature TF1, where it is heated by the heat of condensation of pervaporated vapors to a temperature TF2 (heat recovery from
condensation heat). The feed is further heated to TF3 in an external
heat exchanger using additional heat, and then enters the feed side
of the membrane module where a fraction of feed permeates the
membrane as a vapor and condenses on the condenser plate while
the remaining feed leave as retentate at a temperature TR. As the
condensation occurs inside the membrane module with a small
distance from the membrane surface on the permeate side to the
condensing sheet and the heat resistance in the condenser could
be neglected, the internal heat recovery is maximized. As a proof
of principle, heat recovery was up to 30% for ethanol separation
using TPV based on the literature [191]. Till now, heat recovery
for butanol separation, which is equally important, has not yet
been reported. In addition, low grade heat (80100 C) can be used
for further heating the feed in the heat exchanger shown in Fig. 9 to
the required pervaporation temperature.
Borisov et al. [192] experimentally and theoretically studied the
selective TPV of butanol from dilute aqueous solution through a
hydrophobic PTMSP membrane in a plate-and-frame module with
an air gap, as seen in Fig. 10. In the TPV process, feed of initial fermentation broth at 3040 C was heated to 4075 C in a heat
exchanger using low grade heat, and then entered the membrane
module. A fraction of liquid permeated and pervaporated through
the membrane. The resulting vapor on the membrane permeate
side (airgap channel) was condensed on the condensing sheet
(cooling wall) by the cooling liquid (15 C) on the other side into

Feed, TF1

Retentate , TR

Condensing
Sheet

Membrane

TF2

Permeate

Liquid feed

Saturated vapor

(VMD) [59,186]. Among these types, AGMD and VMD are suitable
for removal of volatile components from an aqueous solution. Separation of ethanol using MD (mainly VMD) from dilute ethanol
aqueous solutions were previously reviewed elsewhere [59,60].
Besides, a general comprehensive review on membrane distillation
was recently presented [189]. Literature on recovery of butanol
from aqueous solution by VMD is rare. Banat and Al-Shannag
[187] studied the separation of butanol from ABE aqueous solutions using AGMD by mathematical simulation based on the multicomponent StefanMaxwell model. The effects on the AGMD
performances (permeate ux and concentration factor) by the
operating conditions such as coolant temperature, ABE concentrations, and airgap width were predicted. MD was claimed to be a
cost and energy efcient process for separation of aqueous mixtures, which could use low-grade energy such as industrial residual
heat and waste heat, and alternative energy sources such as solar
and geothermal energy [186,190]. However, this simulation has
not yet been veried by experimental studies. Also, since MD is
based on VLE and butanol is less volatile (or has low partial pressure), the MD technique is not applicable in separating butanol
from water. It also has several limitations including MD membrane
and module design, membrane pore wetting, low permeate ow
rate and ux decay, as well as uncertain energetic and economic
costs [190]. In addition, the porous membrane of VMD cannot offer
signicant selectivity advantages over what is offered by a single
stage of VLE. Thus, VMD is not a very attractive process compared
to pervaporation [60].

Liquid permeate

530

TF3
Heat
Exchanger

Fig. 9. TPV concept [191].

liquid permeate. Note that there exists a liquid lm (not shown in


Figs. 9 and 10) between the liquid phase on the condensing sheet
and the vapor phase.
The effects of feed temperature, coolant temperature, initial
feed concentration, and membrane thickness on the permeate ux
and the permeate composition were observed. Results showed that
the permeate ux of the TPV is not inferior to that of vacuum pervaporation at condensation temperatures of 0.515.0 C [192].
With the TPV membrane of 19 lm in thickness operated at the feed
temperature (or PV temperature) of 65 C, coolant temperature of
15 C, and under atmospheric pressure inside the membrane space,
increasing the butanol feed concentration from 2 wt% to 5.5 wt%,
the separation factor increased from 25 to 75, the total permeate
ux increased from 0.18 to 0.55 kg m2 h1, and the concentration
of butanol in permeate from 33 to 60 wt% [192]. This means that
higher concentration of feed broths resulted from the future successful modication of microorganism could signicantly improve
the separation performance of TPV. This also means the modication of microorganism is equally important.
In brief, TPV can operate with low grade heat, e.g., at 80100 C
for separation of butanol from ABE fermentation. TPV congured
with internal condenser can efciently recover the condensation
heat of pervaporated vapors for increasing the feed temperature
to the pervaporation temperature. In addition, it has a great potential for commercial uses [191], and as it is a novel technology, more
research work are required for further study of the TPV process.
2.6.3. Reverse osmosis
Reverse osmosis (RO), a relatively mature technology, is widely
used for desalination and water purication [193]. RO can also be
used to concentrate aqueous butanol solutions. For instance, Ito
et al. [194] recently invented a patented butanol separation and
purication process using RO technology to concentrate the fermentation broth. The process consists of three steps: nanoltration
(NF) of aqueous butanol solution by a butanolpermeable membrane to remove impurities and get a butanol-containing solution
from the permeate side; concentration of the butanol permeate
using RO, followed by phase separation of the concentrated butanol solution into a butanol phase and aqueous phase; separation
of butanol from the butanol phase with distillation. The NF membrane used is a composite membrane with a polyamide functional

H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540

Retentate, TR

Condensing
Sheet

Cooling
fluid

Permeate

Liquid feed

Saturated vapor

Liquid permeate

Membrane

Feed
Heat Exchanger

Fig. 10. The plate-and-frame ow-through TPV membrane module.

layer placed on a support made of a porous membrane or nonwoven fabric. It has high pressure resistance, high permeability
to water and high solute removal performance. In the RO step
the butanol concentration in the concentrated solution is not less
than the butanol saturation solubility of 8 wt%. As the RO process
operates at high pressure, it should cost more energy than the
hydrophobic pervaporation process. However, the former is a
mature technology while the latter has not yet been commercially
applied. It would be interesting and important to estimate the efciency and the cost for the RO process to see if the RO process is
feasible for concentrating the butanol solution.

2.7. Adsorption
Adsorption technology, specically molecular sieve adsorption,
has been widely used in dehydration of bioethanol for production
of anhydrous fuel-grade ethanol in corn-to-ethanol plants. Adsorption also has the potential to be used for removal of butanol from
ABE fermentation broth. The fundamentals of adsorption can refer
to the recent work of Venkatesan [195]. A typical integrated fermentationadsorption process is shown in Fig. 11. In this process,
broth liquor enters ultraltration (UF) membrane unit where cells
are retained and recycled to the fermenter. The cell-free permeates
then enter the adsorption column containing adsorbents to adsorb
ABE. The ABE lean liquid is recycled to the fermenter. The use of UF
membrane for cells retaining and recycling prior to the adsorption
columns can not only avoid the possible fouling of adsorbent by
cells, but also reduce cells loss and retain high cell concentration
in the fermenter.
As butanol is hydrophobic, based on the similarity rule hydrophobic adsorbents are utilized for separation of butanol from dilute
solution by adsorption. Compared to ethanol, butanol is more
hydrophobic due to its longer carbon chain. Hence, butanol is a
better suited solute for product recovery using hydrophobic resins.
Three types of hydrophobic adsorbents have been explored for
butanol recovery, including activated carbon [197199], zeolites
or molecular sieve [198203], composite such as calixarene-based
adsorbents [204], and polymer resins such as XAD-4, XAD-16
[205], polyvinylpyridine [36,206], poly(styrene-co-divinylbenzene)
(PS-DVB)-derived resins Dowex Optipore L-493 and SD-2, Dowex M43, and Diaion HP-20 [207], polystyrene diethylbenzene-

531

derived polymeric resins H-511 and KA-I [208210], and polyamide-derived resin XD-41 [208].
Hydrophobic polymeric resins have been studied for adsorption
of butanol by a number of researchers [36,71,197,204213]. Polymeric resins including XAD-2, XAD-4, XAD-7, XAD-8, XAD-16,
and Bonopore, the copolymer of divinylbenzene and styrene are
hydrophobic, non-ionic, and cross-linked polymeric adsorbents.
Experimental studies on adsorption of butanol in dilute model
solutions show that the butanol adsorption capacity of resins
XAD-2, XAD-7, XAD-8, and Bonopore are far below 100 mg butanol
(g adsorbent)1 [197,205,214], while the maximum equilibrium
adsorption capacities of XAD-4 is 0.1 g butanol g1 adsorbent
[197]. Recently, Evanko et al. used Amberlite XAD-16 to extract
butanol from an aqueous solution. The adsorption capacity of
Amberlite, XAD16 is dependent on its macromolecular structure,
high surface area and the aromatic nature of its surface. The experiments demonstrated high efciency of butanol enrichment with
distribution coefcients ranging from 10 to 35 at 25 C. The distribution coefcient for butanol adsorption is dened as the ratio of
concentration of butanol adsorbed in the resin to the concentration
of butanol in the aqueous solution [71]. Nielsen and Prather [207]
compared and screened 20 commercially available polymeric resins derived from poly(styrene-co-DVB), poly(ester), poly(acrylates), poly(amide), polyurethane, poly(styrene-butadiene), and
poly(ethylene-co-vinyl acetate) at initial n-butanol concentration
of 20 g L1 in the aqueous solution. Three different PS-DVB-derived
resins Dowex Optipore L-493 and SD-2, and Diaion HP-20, as
well as poly(ethylene-co-vinyl acetate) possess high n-butanol
afnity and have high adsorption capacity for n-butanol. Their
adsorption capacities were strongly limited or controlled by their
specic surface area. The recovery of n-butanol from these resins
by heating is efcient and economical [207]. About 95% of the
adsorbates on the adsorbent Dowex Optipore L-493 can be recovered using 140 C steam at the steam-to-adsorbent mass ratio of 1
[215]. The other resins tested have low adsorption capacity (well
below 100 mg butanol (g adsorbent)1) [207].
For adsorption of butanol from fermentation broth, XAD-16
showed the highest adsorption capacity of 75 mg g1 among tested
XAD resins [205,211]. Yang et al. [36] used polyvinylpyridine as
adsorbent for in situ removal of products from the acetone-butanol
batch fermentation. With the integration of fermentation-in situ
adsorption, the total nal product concentration increased by
54% and the productivity by 130%, compared to batch fermentation
control without in situ adsorption.
In general, those resins with non-polar monomeric structure
and high specic surface area provide the highest loading of butanol [212]. For instance, PS-DVB derived resins that are comprised
of non-polar monomeric units, exhibit the highest butanol afnity.
Those resins with the highest surface area, such as Dowex
Optipore L-493 and SD-2, provided the greatest equilibrium

Fig. 11. Integrated fermentationadsorption process [196].

532

H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540

distribution coefcients for n-butanol between resin-aqueous


solution as the total number of sites available for interaction with
solute molecules increases with increasing the specic surface area
of the resin [207].
Activated carbons (Norit-Row 0.8, AC F600 and AC F400) were
tested and found to have very high adsorption capacity in the
range of 150280 mg g1 for butanol from dilute solution
[197,198,216]. However, the recovery of butanol from the adsorbent by desorption is incomplete [214]. In general, the stronger
the adsorption, the more difcult the desorption. Thus, activated
carbons are the most difcult to be regenerated.
Zeolites also possess high adsorption capacity for butanol
adsorption from dilute solutions [138,198,202,217219]. It was
found that ZSM-5 and NaY had the butanol adsorption capacities
of 155 and 116 mg g1, respectively, at the same concentration
equilibrium [198]. Saravanan et al. [202] examined two commercial zeolites ZSM-5 with high Si/Al ratio, CBV28014, and CBV901
(faujasite), as adsorbents for recovering butanol from ABE fermentation broth. Results showed that these two zeolites adsorbed nbutanol quickly and almost completely from aqueous solutions
with around 1% butanol. Their adsorption capacities were about
0.12 g butanol g1 zeolite, and remained constant until the equilibrium butanol concentration as low as 0.04 wt% in aqueous solution.
Desorption was conducted by carefully choosing the temperature
program, i.e., initial stage of desorption was conducted at lower
temperature to rstly remove the more volatile components
including water, acetone, and ethanol, followed by butanol desorption at higher temperature to obtain a high concentration of butanol up to 84.3%, which corresponds to a concentration factor of 65.
The major disadvantage of this adsorbent is that only 80% butanol
recovery was obtained at 150 C. At higher temperature butanol
could only be desorbed as butene. More recently, Oudshoorn
et al. [220] studied the desorption of water and butanol from
CBV28014 and CBV901. The results show that the desorption heat
required for CBV901 are 2440 J g1 of water and 1080 J g1 of butanol, while the desorption heat required for CBV28014 are
2730 J g1 (water) and 1160 J g1 (butanol); CBV28014 showed
less water adsorption than CBV901; the desorption rate of butanol
from CBV28014 was signicantly slower than from CBV901, and a
catalytic reaction, most probably butanol dehydration, occurs at
the desorption temperature of 200 C for CBV28014.
Metalorganic framework ZIF-8 is a promising adsorbent for
butanol recovery from the fermentation broth [199,221]. Remi
et al. [199] compared the butanol adsorption performances of the
metalorganic framework ZIF-8, silicalite zeolite, and active carbon
for recovery of butanol from dilute mixtures by experiments. It was
found that ZIF-8 has a high adsorption capacity for n-butanol in an
aqueous solution, a high selectivity of n-butanol over the by-products, and easy desorption ability. In addition, SAPO-34 was tested
to remove water and ethanol from n-butanol for purication of
biobutanol by adsorption. SAPO-34 showed a high afnity and
adsorption capacity for water and ethanol, while butanol was
excluded from the pores of SAPO-34. Thus, the combination of
ZIF-8 and SAPO-34 is very attractive for the recovery and purication of biobutanol by adsorption. Ikegami et al. studied the adsorption properties of butanol on silicalite powder under various
conditions. It was found that the adsorbed amounts of ABE at equilibrium per gram of silicalite from aqueous solutions of binary mixtures at 30 C increased in the order: ethanol (95 mg) < acetone
(100 mg) < n-butanol (120 mg) [219]. The same order of adsorption capacity of silicalite-1 for ethanol, acetone and butanol was
found elsewhere [144]. The desorption of butanol from silicalite
occurred efciently at 78 C and 13 Torr [138]. As the hydrophobicity of zeolites increases with increasing the ratio of SiO2/Al2O3,
sililcalite-1, the special zeolites having no aluminum, is the most
hydrophobic zeolite. Therefore, sililcalite shows good adsorption

for butanol, with the butanol adsorption capacity of 85125 mg


L1 for dilute aqueous solution [138,217,218]. With silicalite as
adsorbent, high butanol concentration of up to 98% (by weight)
was achieved from dilute aqueous solutions (0.52% by weight)
after desorption [222]. This could save signicant energy consumption in the further separation and purication costs. The desorption
for ABE recovery and silicalite regeneration was conducted by
sequential heating, i.e., heating to 40 C to rstly desorb and
remove most of water from silicalite, followed by heating to
150 C to recover butanol [214,217]. In addition, desorption at
78 C could recover 100%, 95.5%, and 80% of butanol, acetone,
and ethanol, respectively, of the absorbed amount [223]. Thus, heat
treatment at 150 C for silicalite regeneration was suggested [214].
The column dynamics of an adsorptiondryingdesorption (ADD)
process for butanol recovery from aqueous solutions using silicalite pellets as adsorbent was experimentally studied at the drying
temperature of 5070 C and the desorption temperature of 130
150 C. Also, the models of adsorption, drying, and desorption were
established to simulate the ADD process with heat integration with
the butanol fermentation process for heat recovery from the efuent of the desorption process (to pretreat the feed streams to the
fermenter, and to dry the solid residues of fermentation [222]. Simulation showed that the proposed process can be an energy-efcient alternative, with high butanol recovery (95%) and low
energy requirement (3.4 MJ kg1).
Unlike materials for membrane pervaporation, composites as
adsorbents were rarely studied. Thompson et al. [204] synthesized
grafted calixarenes as adsorbents, characterized them, and investigated their adsorption performances for butanol isolation from
dilute solutions. The adsorbents are composed of hydrophobic,
cavity-containing calixarenes covalently bound directly to porous,
hydrophilic silica supports through a Si linker atom rather than a
exible organic linker. The butanol adsorption capacity of 0.119 g
butanol g1 adsorbent was obtained at equilibrium concentration
below 8.9 g L1. As a representative adsorbent of this type, tertbutylcalix(4)arene was explored. Butanol could be desorbed as
gas phase from tert-butylcalix(4)arene at 150 C, which is well
below the stability temperature of calixarenes (<300 C).
Table 12 below summarizes the major properties (surface area
and butanol adsorption capacity) of typical adsorbents for butanol
removal by adsorption (usually at room temperature). Additional
properties see the earlier review by Qureshi et al. [214].
Integration of adsorption with ABE batch, or fed-batch fermentation can signicantly improve the sugar substrate concentration,
ABE yield and productivity. Yang and Tsao [196] made comparisons between the integrated fermentationadsorption for product
recovery system, or simply called in situ adsorptive fermentation,
with the batch fermentation control without in situ product recovery, as shown in Table 13. Compared with the batch fermentation
(BF) control without the simultaneous product removal, the in situ
adsorptive batch process has 130% and 54% higher productivity
and solvent concentration, respectively, while the in situ adsorptive
fed-batch (FBF) process has 323% and 145% higher productivity and
solvent concentration, respectively.
Comparison of different types of adsorbents in terms of butanol
adsorption property Abdehagh et al. [198] compared two activated
carbons (AC F600 and AC F400) and two zeolites (ZSM-5 and NaY)
for butanol adsorption from dilute solutions. It was found that AC
F600 and AC F400 showed at least two times faster adsorption
kinetics than zeolites. From Table 12, by rough comparison it is
found that among four categories of adsorbents (activated carbons,
zeolites, composites, and polymeric resins), activated carbons in
general have the highest butanol adsorption capacity. Zeolites have
the second highest butanol adsorption capacity, which are usually
above 100 mg g1. Polymeric resins have a wide range of butanol
adsorption capacities between different resins. PS-DVB, PES-DVB,

533

H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540
Table 12
Major properties of typical adsorbents for butanol.

Activated
carbon

Adsorbent

Matrix

Norit-ROW 0.8
AC 400
AC 400
AC F600
AC F600

Activated
Activated
Activated
Activated
Activated

Zeolites
CBV28014
CBV901

Composite
Polymeric
resins

carbon
carbon
carbon
carbon
carbon

ZSM-5
ZSM-5
ZSM-5 (MFI)
Y (FAU)
MFI
NaY
NaY
Silicalite
Silicalite
Silicalite
Silicalite

Surface area
(m2 g1)

BuOH adsorp. capacity


(mg g1)

Butanol conc. in aq. sol


(g L1)

1090
1090
710
710

252
283
258
150
149

15EBS
10IBS
15EBS
10IBS

400

155
139
120
120
120
116
107
120
8597
6485
103

1100

175

425
400
700

Calixarenesilica
Dowex Optipore
L-493
Dowex Optipore
L-493
Dowex Optipore
SD-2
Diaion HP-20
KA-I resin
H-511
XD-41
Amberlite XAD-16
Amberlite XAD-4

15EBS
10IBS
10IQS
10IQS
20IQS
15EBS
10IBS

11.716.8BF
10IBS

119

PS-DVB

Refs.
[197]
[198]
[216]
[198]
[216]
[198]
[216]
[202]
[202]
[224]
[198]
[216]
[219]
[217]
[225]
[216]
[204]

20IBS
EBS

[207]

PS-DVB

1100

50100

28

[215]

PS-DVB

800

152

20IBS

[207]

PES-DVB
PS-DVB
Polystyrene diethylbenzene
Polystyrene diethylbenzene
Cross-linked polyamide
Macroreticular aliphatic cross-linked
polymer
Macroreticular cross-linked aromatic
polymer

650
500
850900
10001100
549620
900a

110
118
100304
100140
6090
75

20IBS
20IBS
410EBS
410EBS
410EBS
9.2BF

[207]
[207]
[208,209]
[208]
[208]
[211]

725a

27

11.716.8BF

[205]

EBS: equilibrium butanol concentration for binary solutions of butanolwater.


IBS: initial butanol concentration for binary solutions of butanolwater.
IQS: initial (not equilibrium) butanol concentration in quaternary (ABE and H2O) model solution.
BF: batch fermentation broth.
a
As available and reported by the supplier.

Table 13
Comparison of performances between integrated batch/fed-batch fermentationadsorption processes and the control batch
fermentation (BF) [196].

Total glucose used (g)


Total ABE produced (g)
Productivity (g L1 h1)
ABE yield (g g1)
ABE concentration (g L1)

BF control

Integrated BFadsorption

Integrated FBFadsorption

43.8
13.5
0.40
0.31
19.3

73.3
23.2
0.92
0.32
29.8

1198.5
387.3
1.69
0.32
47.2

and polystyrene diethylbenzene derived resins have comparable or


similar butanol adsorption capacities to those of the zeolites. Most
of other resins including those not shown in Table 12, for examples, XAD-2, XAD-7, and XAD-8 have low butanol adsorption
capacities of far below 100 mg g1. It should be noted that more
stricter comparison of the adsorption capacities should be based
on comparison of the adsorption isotherms.
By comparing the adsorption performance in terms of adsorption
capacity, kinetics and selectivity, among the adsorbents F-400, F600, ZSM-5, silicalite and NaY, it was found that F-400 is mostly suitable for butanol adsorption with a highest adsorption capacity and
the fastest kinetics for butanol adsorption. In addition, the adsorption capacity of F-400 for other broth components was very low, thus
it has high selectivity for butanol [216]. The effect of the presence of
other components in the broths on butanol adsorption was also
studied, and results showed that the presence of ethanol, glucose,
and xylose did not affect the butanol adsorption of F-400; the pres-

ence of acetone slightly decreased the adsorption capacity at low


BuOH concentrations, while acids, especially butyric acid, affected
the adsorbent capacity signicantly [216].
In summary, activated carbons are the most strong adsorbents
and have the highest adsorption capacities for butanol, but they
have disadvantages such as incomplete desorption and difculty
in regeneration. PS-DVB, PES-DVB, and polystyrene diethylbenzene
derived resins have good butanol adsorption capacities as zeolites,
but they have less long-term stability as zeolites, e.g., aging problems. Zeolites, especially, silicalite-1 is the most promising adsorbent for butanol recovery, having many advantages such as high
adsorption capacity (100 mg g1), high selectivity, complete
desorption by heating (200 C), high stability (<1000 C), and high
butanol concentration obtained (810 g L1).
Adsorption is one of the most energy-efcient approaches for
removal of butanol from the ABE fermentation broths. Modication
of current high performing adsorbents, study on adsorbent fouling

534

H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540

problems and stability of adsorbents, methods for efcient desorption or adsorbent regeneration with high concentration of butanol
are also worthy of further exploration.
2.8. Comparison of separation methods for product removal
Comparisons of different separation methods for butanol recovery from dilute ABE fermentation broths in terms of energy consumption have been carried out [200,214,226]. Groot et al. [226]
compared gas stripping, pervaporation, LL extraction, perstraction, and adsorption for separating butanol from dilute solution
containing 0.78 wt% butanol in terms of energy consumption.
Among them, pervaporation, LL extraction, and perstraction were
found the best. However, this was published many years ago in
1992, and the comparison needs to be updated due to the signicant advances in the research and development of novel pervaporation membranes, extracting solvents, and adsorbents with high
separation performance. For example, the adsorbent used for comparison by Groot et al. [226] has low specic surface area and low
butanol adsorption ability thus leading to high energy consumption of up to 33 MJ kg1 of n-butanol. By contrast, the current
adsorption technology using high adsorption capacity of adsorbent
could be an energy-efcient process. For instance, comparative
study for separation and concentration from 5 to 810 g L1 by
Qureshi et al. [214] showed that the adsorption with silicalite is
the most energy efcient method for n-butanol recovery from
the ABE dilute solution, with 8.2 MJ kg1 of n-butanol. LL extraction and pervaporation are the second and the third best methods
in terms of energy consumption [214]. However, this work did not
consider the product purication. In addition, similar comparisons
between gas stripping, pervaporation, LL extraction and adsorption were made, and pervaporation, LL extraction and adsorption
were also found the most energy-efcient. However, only the product recovery/pre-concentration step and a simple quantitative
approach were considered, rather than a detailed process modeling
and simulation. In this work, an updated comparison is presented
in Fig. 12 using the energy consumption data from the most recent
literature except in the case of gas stripping distillation where
data from old literature was used. The energy consumption of
the gas stripping plus distillation as downstream separation process under the same conditions did not change over time as it is
based on one stage vaporliquid equilibrium. From this gure, it
can be seen that pervaporation, LL extraction and adsorption
are the most energy-efcient for butanol recovery and purication
from dilute solution.
For the gas-stripping process, a large fraction of water will be
stripped off with butanol, leading to low separation factor. A typical
range of the gas-stripping separation factor for butanol is 419
[200]. Similar to gas stripping, one stage distillation or evaporation
is based on vaporliquid equilibrium. Distillation of dilute solutions
also has low separation factor for butanol. Therefore, the energy consumptions of the gas-stripping and distillation for recovery of butanol from fermentation broth are larger than the other methods.
Some membranes (Table 9 and Table 10) and extractants (Table 2
and Table 5) have high separation factors of over 100. Novel adsorbents such as zeolites [198,216] and PS-DVB [207] also have high
separation factors for butanol due to their high adsorption capacity.
Therefore, these three processes are more energy-efcient for recovery of butanol from the fermentation broth.
Strictly speaking, data from different literature are not comparable as they were not based on the same feed concentration and
product purity, and their downstream separation processes or their
operating conditions were different. Thus, Fig. 2 only shows the
very simple (not strict) comparison, though to some extent the
trend is reasonable as the feed concentration and product purity
for different cases are very close.

3. Further separation and purication/dehydration of butanol


The above reviews are focused on separation of butanol from
ABE fermentation broths, including integration of fermentation
with different separation processes. In the whole separation process, ABE is isolated and pre-concentrated from the fermentation
broth by one of the separation approaches described above. The
resulting ABE solution usually has a butanol concentration of above
7.7 wt% butanol. This pre-concentrated ABE mixture is then further
separated and puried. Acetone (A) can be rstly separated out of
the ABE mixture by a simple distillation column as it is the most
volatile among acetone, butanol, ethanol, and water. Ethanol is
then separated from the remaining butanolethanol (BE) aqueous
solution in the another distillation column where ethanolwater
homogeneous azeotrope comes out of the top of the column while
the butanolwater heterogeneous azeotrope exits at the bottom.
The resulting ethanolwater azeotrope can be dehydrated to
obtain high purity ethanol by using one of the methods such as
hydrophilic membrane pervaporation and adsorption with hydrophilic adsorbents [59,60,129]. The butanolwater heterogeneous
azeotrope can be carried out in the two-column-and-decanter system proposed by Doherty and Malone [227]. Luyben [228] used
this owsheet (Fig. 13) for the steady-state simulation, dynamic
simulation and control study.
In the steady-state simulation [228], the feed enters the decanter at a ow rate of 1000 kmol h1 with mole fraction compositions
of 0.40 (butanol) and 0.60 (water). Phase separation occurs in the
decanter at 0.5 atm and 343 K, with aqueous liquid phase containing 97 mol% water and the organic phase containing 58 mol% nbutanol. The butanol product purity was specied as 99.9 mol%.
Other operation conditions and the calculated energy consumptions by two boilers of two distillation columns and the condensers
were also shown in the gure. By simple calculation, the total
energy consumptions was 1.792 MJ kg1 butanol, which is 5.0%
of the energy content in recovered butanol. The calculation
omitted the energy consumed by the four pumps (note that two
other pumps for transporting two bottoms streams are not shown
in the gure) as this part of energy is very small compared to the

Fig. 12. Simple comparison of energy consumption between different separation


approaches (percent data on the top of bars, e.g., 199.9% represents recovery,
concentration and purication from 1 wt% of dilute butanol solutions to 99.9 wt%
purity of butanol product; 0.78%-pure means recovery, concentration and
purication from 0.78 wt% of dilute butanol solutions to pure butanol, without
detailed purity data; Literature numbers are shown as x label ticks. For the gure
legend, the separation method placed after the dash represents the downstream
separation process, e.g., gas stripping distillation means gas stripping for
butanol recovery from dilute butanol solutions while distillation is used as the
major downstream separation processes).

H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540

535

Fig. 13. Butanolwater separation [228].

energy required by the boilers and the condenser. Simulation for


two other feeds of different compositions, i.e., 2 mol% (7.75 wt%)
butanol and 10 mol% (31.39 wt%) butanol, at the same mole ow
rate of 1000 kmol h1 were also performed. The energy required
by the boilers and condenser were 9.566 and 2.279 MJ kg1 butanol for these two cases, respectively. These corresponds to 26.6%
and 6.3% of the energy content in recovered butanol, respectively.
By comparison, it can be seen that the feed butanol concentration
signicantly inuences the energy consumption required for the
further separation and purication with distillation. The higher
the feed butanol concentration, the lower amount of energy
required per kg butanol, and also lower capital cost of distillation
columns required for the same butanol production capacity.
LL extraction with solvents such as RTILs could also be used for
dehydration of butanol. For example, Hu et al. [229] presented the
ternary LL equilibrium of 1-(2-hydroxyethyl)-3-methylimidazolium tetrauoroborate ([C2OHmim]BF4) or 1-(2-hydroxyethyl)2,3-dimethylimidazolium tetrauoroborate ([C2OHdmim]BF4) +
water + 1-butanol at 20 C. The experimental results show that
the two ionic liquids are potential candidates to extract water from
n-butanol by liquidliquid extraction. The experimental tie lines
were correlated with the NTRL equation.
Purication and dehydration of butanol-rich solution for high
purity butanol product is quite similar to that of ethanol in that
both processes are to remove minor amount of water from the concentrated solution to get higher purity products. Methods for ethanol dehydration discussed previously [59,60,129] can usually be
used for butanol dehydration. For example, hydrophilic membrane
pervaporation was used for butanol dehydration in the economic
evaluation performed by Qureshi et al. [183].
Furthermore, TPV with water selective membranes is also suitable for dehydration of butanol [191]. Especially, adsorption using
molecular sieves that has been widely and commercially used for
the nal ethanol purication and dehydration can also be effective
in butanol purication and dehydration.
4. Conclusions
Biobutanol can be widely used as fuel superior to bioethanol,
solvent in food and pharmaceutical industrials, and important
building block for producing a variety of chemicals and materials

such as paints, coatings, biopolymers, bioplastics, and other


chemicals. Butanol can be produced through ABE fermentation,
but the production cost are still relatively high due to its very
dilute concentration. Separation of butanol from ABE fermentation broth is very challenging and critical for successful
commercialization.
Integration of ABE fermentation with a product recovery process such as gas stripping, vacuum ash, solvent extraction, perstraction, membrane pervaporation, thermopervaporation, and
adsorption, as process intensication, can efciently eliminate
product inhibition, enhance cell growth, increase productivity
and yield, and hence could reduce energy consumption and downstream separation cost and make the overall system more viable.
Based on comprehensive review of the literature and comparison of the various separation and purication technologies, it is
concluded that membrane pervaporation, LL extraction, and
adsorption are the most energy-efcient approaches for removal
of butanol from the ABE fermentation products. Improvement of
membrane technologies, especially development of thin membranes with higher ux, higher separation factor, increased
strength and high stability, as well as anti-fouling characteristics
or better cleaning technologies, etc. still need to be explored. For
LL extraction, novel extractants are still needed to be developed
with the aid of molecular modeling technique and chemically
modifying its afnity to butanol or hydrophobicity. For adsorption
method, modication of current high performing adsorbents, study
on adsorbent fouling problems and stability of adsorbents, methods for efcient desorption or adsorbent regeneration with high
concentration of butanol are also worthy of further exploration.
In addition, these three hybrid separation processes incorporated
with fermentation as a whole system need to be optimized, and
rigorous comparison based on modeling and analysis of the whole
bioreneries are important and need to be considered. It is also
critical to understand the effects of different separation processes
integrated with fermentation on the overall production costs and
the capital costs. Process synthesis and modeling of the whole
hybrid reactionseparation system integrated with the whole biorenery with heat integration, combined with experimental study
and pilot scale analysis would enable us to gain a deeper insight
and aid in the successful commercial implementation of the butanol biorenery.

536

H.-J. Huang et al. / Separation and Purication Technology 132 (2014) 513540

TPV can operate with low grade heat, e.g., at 80100 C for
butanol separation from ABE broths. TPV with internal condenser
can efciently recover the condensation heat of pervaporated
vapors for increasing the feed temperature to the required PV
operation temperature. In addition, it has a great potential for
commercial success. As TPV is a novel promising technology,
more research work is needed further exploring its capabilities
and potentials.

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