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Separation and Purification Technology 62 (2008) 1–21

Review

A review of separation technologies in current and future biorefineries

Hua-Jiang Huang a , Shri Ramaswamy a,∗ , U.W. Tschirner a , B.V. Ramarao b
a Department of Bioproducts and Biosystems Engineering, Kaufert Lab, University of Minnesota, Saint Paul, MN 55108, USA
b Department of Paper and Bioprocess Engineering, SUNY-CESF, Syracuse, NY 13210, USA

Received 5 December 2007; accepted 14 December 2007

Abstract
Biorefineries process bioresources such as agriculture or forest biomass to produce energy and a wide variety of precursor chemicals and
bio-based materials, similar to the modern petroleum refineries. Industrial platform chemicals such as acetic acid, liquid fuels such as bioethanol
and biodegradable plastics such as polyhydroxyalkanoates can be produced from wood and other lignocellulosic biomass. Biorefineries use a
variety of separation methods often to produce high value co-products from the various feed streams. In this paper, a critical review of separation
methods and technologies related to biorefining including pre-extraction of hemicellulose and other value-added chemicals, detoxification of
fermentation hydrolyzates, and ethanol product separation and dehydration is presented. For future biorefineries, extractive distillation with ionic
liquids and hyperbranched polymers, adsorption with molecular sieve and bio-based adsorbents, nanofiltration, extractive-fermentation, membrane
pervaporation in bioreactors, and vacuum membrane distillation (VMD) hold significant potential and great promise for further investigation,
development and application.
© 2008 Elsevier B.V. All rights reserved.

Keywords: Biorefinery; Separation technologies; Ethanol; Biofuels; Bioprocess engineering; Detoxification

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1. Corn-to-ethanol biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2. Lignocellulosic biomass-to-ethanol biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3. Integrated lignocellulose/forest biorefinery (ILCB) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2. Pre-extraction of hemicellulose and other value-added chemicals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1. Extraction of value-added co-products from corn-to-ethanol process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1.1. Extraction of corn germ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1.2. Extraction of corn fiber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.1.3. Extraction of zein . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2. Pre-extraction of value-added chemicals in integrated forest biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2.1. Pre-extraction of hemicellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2.2. Pre-extraction of antioxidants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3. Removal of inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4. Recovery of ethanol and ethanol dehydration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.1. Ordinary distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.2. Azeotropic distillation (AD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.3. Extractive distillation (ED) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.3.1. Extractive distillation with liquid solvent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.3.2. Extractive distillation with dissolved salt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

∗ Corresponding author. Tel.: +1 612 624 8797; fax: +1 612 625 6286.
E-mail address: shri@umn.edu (S. Ramaswamy).

1383-5866/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2007.12.011
2 H.-J. Huang et al. / Separation and Purification Technology 62 (2008) 1–21

4.3.3. Extractive distillation with the mixture of liquid extractant and dissolved salt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.3.4. Extractive distillation with ionic liquid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.3.5. Extractive distillation with hyperbranched polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.3.6. Summary of extractive distillation with different separating agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.4. Liquid–liquid extraction-fermentation hybrid (extractive fermentation) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.5. Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.5.1. Vapor-phase adsorption of water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.5.2. Liquid-phase adsorption of water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.5.3. Advantages and disadvantages of adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.6. Membrane separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.6.1. Hydrophilic membrane for removal of water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
4.6.2. Hydrophobic membrane for removal of ethanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.6.3. Membrane pervaporation-bioreactor hybrid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.6.4. Vacuum Membrane Distillation (VMD) – bioreactor hybrid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

1. Introduction with enzymes, fermentation of the sugars to ethanol with yeast,

followed by distillation and dehydration processes of ethanol.
Among the variety of possible products from the biorefin- The solids from the distillation bottom are dried to obtain
ery, liquid transportation fuels in the form of ethanol (or what distillers’ dried grains with protein (DDG) as an animal feed-
is now referred to as bioethanol) is rapidly gaining significance. stuff [2]. Based on the conventional dry mill process, a few
Bioethanol is likely to be a prominent product for future biore- modified dry-grind processes have been developed by recov-
fineries; hence this review will focus on separation technologies ering germ or both germ and fiber before fermentation. As an
incorporating bioethanol as a principal product. example, the “Quick Germ” process recovers germ prior to fer-
There has been an increasing interest in biomass derived mentation (Fig. 1) [3]. Recently, another modified dry-grind
ethanol due to the rapid increase in the price of crude oil and the process, which allows separation of non-fermentable corn com-
perceived strength of the global demand of petroleum. There ponents such as germ and fiber for further reduction of cost,
are many advantages in using bioresource derived ethanol as was developed by Taylor and Singh [4]. In their process, corn
a liquid transportation fuel. Bioethanol blended with gasoline kernels are treated with anhydrous ammonia gas, so the ker-
extends crude oil utilization, reduces reliance on oil imports and nel components become loose and thus germ and fiber can
help mitigate increasing oil prices. The higher oxygen content be readily recovered as value-added co-products for food or
of ethanol results in relatively cleaner combustion and has long feedstuff.
been used as an additive in gasoline to reduce urban smog and In the wet mill process (Fig. 2), corn is cleaned, steeped,
other environmental pollution problems. Agricultural sources de-germed to obtain germ from which corn oil is extracted,
such as corn or sugar cane are annual crops which sequester defibered to obtain fiber, and subjected to separation of gluten
carbon from the atmosphere in annual cycles. Forest resources
such as woody biomass capture and release atmospheric carbon
over a few decades. Fossil fuels release ancient carbon and other
greenhouse gases into the atmosphere significantly contributing
to global climate change processes whereas bioresource based
transportation fuels can be carbon neutral [1].
Basically, there are three kinds of biomass-to-ethanol
biorefineries: corn-to-ethanol, basic lignocellulosic biomass-
to-ethanol biorefinery and integrated lignocellulosic biomass-
to-ethanol and other co-products including the concept of
integrated forest biorefinery.

1.1. Corn-to-ethanol biorefinery

At present, there are two major processes to produce fuel

ethanol from corn: the dry-grind (67%) and the wet mill (33%).
In general, the wet milling process produces high-value co-
products such as fiber, germ and gluten by pre-processing prior
to fermentation to ethanol, thus it is more capital- and energy-
intensive [2]. The conventional dry mill consists of grinding,
cooking, liquefaction, saccharification of the starch to sugars Fig. 1. Modified corn dry-grind (“Quick Germ”) process [3].
 H.-J. Huang et al. / Separation and Purification Technology 62 (2008) 1–21
Fig. 2. Corn wet mill process [3].
and starch. This is followed by the same steps as those of
corn-grind process including saccharification, fermentation, dis-
tillation and dehydration of ethanol, etc. [3].
Therefore, in general, the common separation steps in the
corn-to-ethanol biorefinery are as follows:
• pre-separation of non-fermentable germ and fiber, for the
modified dry-grind process;
• pre-separation of starch and other high-value co-products
such as fiber, germ and gluten, for the wet mill process;
• separation of ethanol from dilute beer liquors and dehydration
of ethanol.
1.2. Lignocellulosic biomass-to-ethanol biorefinery
While significant progress has been made in the conversion of
lignocellulosic or cellulosic biomass to fuel ethanol, it has not yet
been commercialized due to existing technical, economic, and
commercial barriers. However, cellulosic ethanol can be more
effective and promising as an alternative renewable bio-fuel than
corn ethanol in the long run because it could greatly reduce the
net greenhouse gas (GHG) emissions as well as higher net fossil
fuel displacement potential [5].
The largest potential feedstock for ethanol is lignocellulosic
biomass such as agricultural residues (e.g., corn stover, crop
straws, sugar cane bagasse), herbaceous crops (e.g., alfalfa,
switchgrass), forestry wastes, wood (hardwoods, softwoods),
wastepaper, and other wastes such as municipal waste [6].
The basic process for conversion of cellulosic biomass to fuel
ethanol mainly consists of eight steps: feedstock handling, pre-
treatment and conditioning/detoxification, saccharification and
co-fermentation, product separation and purification, wastewa-
ter treatment, product storage, lignin combustion for production
of electricity and steam, and all other utilities (Fig. 3) [7]. This
overall process involves the following separation steps:
• removal of inhibitors in fermentor;
• ethanol recovery from beer and its dehydration;
3
• wastewater treatment;
• pre-extraction of hemicellulose and separation of hemicellu-
lose from other components in the extract when considering
separate fermentation of pentoses and hexoses.
1.3. Integrated lignocellulose/forest biorefinery (ILCB)
Obviously, forests are an enormous source of lignocellulosic
material. At present, pulp mills represent an excellent existing
platform for retrofitting in forest products industry. In recent
years, however, the U.S. forest products industry has encoun-
tered severe competition from overseas, leading to mergers and
significant downsizing [8]. Thus, a new concept—the forest
biorefinery based on the existing pulp mills was proposed to pro-
duce added fuel and chemicals, together with pulp and paper, in
order to increase the overall revenue streams and profitability.
Fig. 4 below is the general process block diagram of integrated
forest biorefinery. This process involves careful pre-extraction
of hemicellulosic sugars prior to pulping and isolation of long
and short fiber after pulping, hemicellulose conversion to ethanol
in a bioreactor; the short fiber (cellulose) can be converted into
ethanol in another bioreactor, and the long fiber (cellulose) used
for the production of paper and other fiber based materials such
as bio-composites. Besides, lignin dissolved into black liquor
after pulping can be further gasified to produce syngas. The
resulting syngas can be further synthesized to produce fuels and
chemicals, and electricity and process steam.
In brief, therefore, the integrated forest biorefinery can make
full use of all the feedstock components to produce value-added
multiple co-products including energy (electricity and steam),
and various chemicals, along with the major products such as
paper and fuel grade ethanol. This scenario of optimized system
of multiple co-products similar to today’s petroleum refinery
offers enormous opportunity for the future renewable resources
based integrated biorefinery.
In addition to the same separation tasks as those of the basic
lignocellulosic biomass-to-ethanol biorefinery, the integrated
forest biorefinery includes the following additional separation
tasks:
• pre-extraction of hemicellulose, and separation of hemicellu-
lose from other components in the extract;
• separation of short fiber and long fiber;
• syngas cleaning and conversion.
The purpose of the present paper is to explore a large variety
of potential separation approaches and technologies which might
help reduce the overall ethanol production cost, and improve the
overall techno-economic feasibility of the biorefinery based on
a large number of published separation technology literature.
Thus, the following sections will focus on variety of separation
technologies in the pre-extraction of hemicellulose and other
value-added chemicals, removal of fermentation inhibitors for
increasing product yield, and recovery of ethanol and ethanol
dehydration.
4 H.-J. Huang et al. / Separation and Purification Technology 62 (2008) 1–21

Fig. 3. Overall process block diagram for a basic lignocellulose to ethanol biorefinery [7].

2. Pre-extraction of hemicellulose and other
value-added chemicals
2.1. Extraction of value-added co-products from
corn-to-ethanol process
2.1.1. Extraction of corn germ
It is important to extract corn germ since it can bring addi-
tional value. The defatted germ from dry-grind or wet mill
processes can be saccharified efficiently into glucose, xylose
and arabinose using enzymes such as enzymes Aureobasidium
sp. [9]. These sugars can later be fermented to ethanol. The
value-added co-products represent a potentially considerable
profit from germ extraction.
In the conventional wet-milling degermination (refer to
Fig. 2), after soaking of corn, the germ is recovered by means
of hydrocyclones [10]. Singh and Eckhoff proposed a modi-
fied dry-grind, called “Quick Germ” ethanol process (Fig. 1),
involving soaking whole corn in water and then recovering
germ by conventional wet-milling degermination, with the germ

Fig. 4. Process block diagram of an integrated forest biorefinery.

 H.-J. Huang et al. / Separation and Purification Technology 62 (2008) 1–21
yield of 6.76% under the optimal soaking conditions of 12 hr
and 59 ◦ C [11]. They also performed the economic assessment
of the “Quick Germ” process, and showed it to be profitable.
The corn oil and the germ meal recovered from the germ
have a much higher price (US$ 0.53–0.66/kg) than that of
DDG (US$ 0.13–0.20/kg) [3]. This means that the “Quick
Germ” modified process produces more value from co-products
than the conventional dry-grind process with only DDG as the
co-product. In addition, the removal of non-fermentables can
enhance the subsequent fermentation. The combination of the
germ recovery as a co-product and the increase in the fer-
mentation capacity leads to ethanol cost reduction by 2.69 ¢/L
(10.19 ¢/gal), compared with the conventional dry-grind ethanol
process [3].
2.1.2. Extraction of corn fiber
At present, most corn fiber is not recovered, and it finally
mixed into low-value animal feeds, which will have a narrow
market in the future due to the growing ethanol production [2].
Corn fiber can be used to produce ethanol [12,13] and higher
value co-products such as corn fiber oil [14,15] and corn fiber
gum [15,16]. Corn fiber, i.e. bran from the corn hull, is abun-
dant in hemicellulose (xylose and other pentose sugars). Both
hexose and pentose can be hydrolyzed by dilute acid hydroly-
sis of corn fiber, which can then be fermented to ethanol with
E. coli strain [12,13]. The additional fermentation of the fiber
fraction of corn kernel could increase the ethanol yield more
than 10% through appropriate pretreatment of the corn fiber
[17]. In addition, corn fiber can also be utilized to manufac-
ture corn fiber oil by extraction, which has low cholesterol
due to its ferulate esters content, particularly sitostanyl ester.
Thus, it is a healthy dietary additive. Therefore, corn fiber and
corn fiber oil have potential added values in the corn-to-ethanol
process.
Dried, milled corn fiber can be separated by either hot liq-
uid water or steam. Allen made an experimental comparison
between hot liquid water and steam fractionation of corn fiber
by using the same equipment [17]. The results show that the
treatment with hot liquid water at 215 ◦ C and 5–10% solids load-
ings obtained much higher pentosan recovery than with steam
at 210–220 ◦ C and >50% solids loadings. In addition, the liq-
uid product from the former method did not have inhibition to
the final glucose fermentation by S. cerivisiae while the later
method did [17].
The fiber oil can be extracted by a novel process which
includes a pre-grinding step followed by extraction with hex-
ane [18]. The so-called “Quick Fiber” process was developed to
recover corn fiber from the mash after degermination and before
fermentation in the dry-grind corn–ethanol process. This process
mainly consists of the following steps: soaking corn in water,
germ recovery, fiber separation where dry starch is added to the
remaining slurry after degermination to increase its density so
that the fiber is floated and separated due to the density differ-
ence, and washing the recovered fiber, etc. [15,19]. Experimental
results show that the quick fiber yields are 6–7%, corresponding
to 46–60% of the total fiber recovered by the wet mill process
[15].
5
2.1.3. Extraction of zein
Zein which is prolamine (gluten)-rich, water insoluble pro-
tein is a value-added co-product for a dry-grind ethanol plant.
Zein or its resins have many potential uses, for instances, in fiber,
adhesive, coating, cosmetic, textile, and biodegradable plastics
[20]. Zein takes up 45–50% protein in corn. At present, only
about 500 tons/year of zein was produced from corn gluten
meal, with price in the range of US$ 10–40/kg, depending on
purity [20]. Thus, to minimize the overall cost of ethanol plant,
it is necessary to extract zein from milled maize [21]. Recent
studies showed that extractive separation of zein from maize
could be commercially feasible in an ethanol plant [22]. In 2002,
Dickey et al. [21] investigated the low-cost extraction of zein in
a dry-grind ethanol plant. They explored three different methods
for displacing extracted liquid from the extracted corn particle.
Results show that centrifugation with ethanol rinsing, was more
efficient and feasible in recovering zein (protein) in the extract,
and settling the extracted corn in water, compared to the other
two methods (packed bed displacement and gravitational set-
tling into water). Most recently in 2006, Cheryan [23] received
a patent for extracting zein and/or oil from dry-milled corn with
ethanol, separating the liquid phase containing ethanol, oil and
zein and the solid phase containing corn solids. Then, the liquid
phase is ultra-filtered with a membrane to retain zein and pass
the oil and ethanol mixture.
2.2. Pre-extraction of value-added chemicals in integrated
forest biorefinery
In conventional kraft pulping processes, most of the hemicel-
lulose from wood is degraded into oligomers or mono sugars,
etc., which are dissolved in black liquor along with dissolved
lignin and the pulping chemicals (inorganic substance). The
black liquor is usually combusted for steam and electricity
generation. However, since hemicellulose has a considerably
lower heating value than lignin, the combustion of hemicel-
lulose represents uneconomical use of the feedstock resource.
In an integrated lignocellulose biorefinery (ILCB), therefore,
pre-extraction of hemicelluloses followed by the production of
value-added products such as ethanol, sugar-based polyesters or
other chemicals offers a tremendous valued-added opportunity
[24].
In addition to the pre-extraction of hemicellulose, pre-
separation of naturally occurring food antioxidants (phenolics)
prior to pulping can also be considered, in order to make full
use of feedstock to get added value and thus reduce the overall
production cost and improve the overall profitability [25,26].
2.2.1. Pre-extraction of hemicellulose
Lignocellulosic biomass consists of three major fractions:
cellulose (35–50 of dry weight), hemicellulose (20–35%) and
lignin (10–25%). Conversion of lignocellulosic materials to
higher value products requires fractionation of the material into
its components: lignin, cellulose, and hemicellulose. Hemicellu-
lose is a heterogeneous polymer comprising of pentoses (xylose,
arabinose), hexoses (mannose, glucose, galactose), and sugar
acids [27]. The removal and recovery of hemicellulose is an
6 H.-J. Huang et al. / Separation and Purification Technology 62 (2008) 1–21
essential feature of pretreatment processes for biological con-
version to ethanol or other products [28]. To date, a variety
of effective pretreatment methods to hydrolyze and fraction-
ate hemicellulose components have been investigated, including
dilute acid pretreatments [29–32], liquid hot water extraction
[33–35], steam explosion-based extraction [36–42], dilute acid-
steam explosion [43] and alkaline extraction [44–46]. Ammonia
fiber/freeze explosion (AFEX) is another well-known pretreat-
ment. However, it is hard to remove hemicellulose by AFEX,
even though it has been shown to remove lignin very well [28].
Mosier et al. also pointed out that dilute acid pretreatment,
liquid hot water extraction, steam explosion-based extraction,
dilute acid-steam explosion are effective in removing hemicel-
lulose, though they considered alkaline extraction to have only
minor effect for removal of hemicellulose [28]. On the other
hand, alkaline extraction has been shown to very effective for
hemicellulose removal [44–46]. In the following, dilute acid pre-
treatment, liquid hot water extraction, steam explosion-based
extraction, dilute acid–steam explosion and alkaline extraction
will be discussed.
Dilute sulfuric acid pretreatment, with pH control by ammo-
nia or/and lime is one of the most promising approaches, because
of its lower costs and higher hemicellulose yields (up to 90%)
[30]. Dilute-acid (0.5–1.0% sulfuric) at moderate temperatures
(140–190 C) effectively can recover most of the hemicellulose
as dissolved sugars [29].
Higher temperatures (200–230 ◦ C) water extraction can com-
pletely recover hemicellulose from hardwoods and herbaceous
materials, without significant degradation [33]. Saska and Ozer
[34] showed that hemicellulose from sugar cane bagasse can be
successfully extracted with water as the extractant. Under the
operating conditions of the solid/liquid ratio at 1:5, the extrac-
tion temperature at 150–170 ◦ C, and the extraction time with
15–30 min, 89% the original amount of xylose was recovered.
The major advantages of the water extraction method over the
dilute acid pretreatment are: lower corrosion to equipment, less
xylose degradation and thus less byproducts including inhibitory
compounds in the extracts, and more easier recovery of acid from
the hydrolyzate. With particle size reduction prior to extrac-
tion, the aqueous process gave almost 90% recovery of xylose,
superior to steam explosion-based extraction [34].
Steam explosion is an effective pretreatment for hemicellu-
lose hydrolysis [39–42]. In this process, biomass is pretreated
by pressurized steam followed by rapid relieving of pressure,
which breaks down the lignocellulosic structure so that the
lignin is readily depolymerized and thus the hemicellulose is
easily hydrolyzed [42]. The steam explosion process can result
in around 50% insoluble residue of the wood, consisting mainly
of cellulose. The remainder which chiefly contains hemicellu-
lose and lignin, can be recovered with alkali extraction [41].
Shimizu et al. [39] performed steam-explosion of various species
of hardwood chips at 180–308 ◦ C for 1–20 min, leading to par-
tial hydrolysis of hemicellulose, and the resulting sugars can
then be extracted with water. The xylose yield was 10–20% of
the starting materials [39]. Ibrahim and Glasser [40] used steam
treatment to break down and separate the red oak wood chips
into fibers and polymer products, resulting in nearly complete
recovery of xylan and obtainment of almost hemicellulose-free
pulps. Recently, Josefsson et al. [41] utilized the steam explo-
sion process to fractionate the aspen wood components, for the
purpose of obtaining a high cellulose yield and an appropriate
MW distribution, while recovering hemicelluloses. Pulps with
different xylan contents ranging from less than 1% to 7% and dif-
ferent MW of cellulose ranging from less than 40,000 to 900,000
were prepared at varying time and temperature conditions [41].
In comparison with alternative methods, the steam explosion is
more environmental friendly and it requires lower capital invest-
ment [42]. The process, however, has a disadvantage in that it is
difficult to restrain fibers from fragmentation [41].
Tucker et al. [43] investigated the combined dilute acid–steam
explosion method for biomass treatment. Corn stover was sub-
jected to 1 wt% H2 SO4 for 70–840 s in a steam explosion reactor
at 160, 180, and 190 ◦ C. The obtained yields of xylose were
63–77% of theoretical at 160–180 ◦ C, and more than 90% at
190 ◦ C.
N’Diaye et al. [44] extracted hemicelluloses from poplar
(Populus tremuloides) using a modified twin-screw extruder
with a 5% NaOH solution as extracting solvent. This extruder or
extrusion reactor, called a thermo-mechanico-chemical fraction-
ation system [47], allows the integration of extrusion, cooking,
liquid–solid extraction, and liquid/solid separation (filtration) in
a single step, and operates in a continuous mode. With such a
reactor, alkaline extraction can be operated at a lower L/S ratio
(six times less than a batch reactor) and lower residence time, and
90% of the initial hemicelluloses (pentosans) can be recovered.
The whole process for extracting the hemicelluloses is shown in
Fig. 5.
Recently, as illustrated in Fig. 6., hemicellulose was separated
from aspen (Populus tremula) by alkali extraction combined
with hydrogen peroxide treatment, ultrafiltration and recovery
by spray drying [45]. Specifically, aspen wood were first cut and
refined. The resulting fiber suspension was treated with a dilute
HCl solution to make the fibers swollen, then cooled, added
ammonium hydroxide to dissolve the pectins, stirred overnight
and centrifuged to remove pectins, starch and fat. The residue
Fig. 5. Process block diagram for extracting hemicelluloses [44].
 H.-J. Huang et al. / Separation and Purification Technology 62 (2008) 1–21
Fig. 6. Hemicelluloses recovery process [45].
was subjected to a NaOH (1%)–ethanol (70%) solution to solu-
bilize lignin. After centrifugation, hemicellulose was extracted
with 4% NaOH. The combined two filtrates were bleached with
peroxide to minimize the residual lignin content. The suspension
was finally ultrafiltered and spray-dried to obtain hemicellulose.
Sun et al. [46] investigated the extraction of hemicelluloses
from fast-growing poplar wood. In their process shown in Fig. 7,
poplar wood chips were firstly dried, and dewaxed by extrac-
tion with toluene-ethanol mixture (2:1, v/v), followed by partial
delignification with an acidic NaCl solution, hemicelluloses
exaction with 1.5–8.5% NaOH leading to 65.6–89.3% solubi-
lization of the original hemicelluloses, filtration of the slurry
obtained into solid (cellulose) and filtrate (hydrolyzates), neu-
tralization of the hydrolyzates to pH 5.5, and precipitation of
hemicelluloses in 95% EtOH, and filtration, washing and drying
of hemicelluloses.
From Figs. 5–7, it is found that alkali extraction with NaOH
is used in all these three processes, and this method is effec-
tive in extraction of hemicelluloses from hardwood. Since the
hemicelluloses concentration of filtered hydrolyzates is very
low, e.g., 2–3% depending on the solid/solvent ratio used, it
is very important to concentrate hemicelluloses in order for effi-
cient subsequent fermentation into ethanol or xylitol, or to obtain
Fig. 7. Separation of hemicellulose and cellulose from fast-growing poplar wood
[46].
7
pure hemicelluloses for other use, for example, in making new
bio-based materials. It is also found that the method of pre-
cipitation with ethanol is used for separation of hemicelluloses
in the two processes of Figs. 5 and 7, while the ultrafiltration
is used in the process of Fig. 6. First two methods mentioned
above involve acidification or neutralization with acid to adjust
pH to 5–5.5 suitable for precipitation of hemicelluloses with
ethanol. In this process, ethanol and acid are additional chemi-
cals required and additional equipments for recovery of ethanol
is necessary, thus leading to increase in production and capi-
tal cost. In addition, some ethanol is probably included in the
precipitated solid phase representing ethanol loss or additional
separation cost. The latter process is simplified by employing
ultrafiltration, leading to possible reduction in operation cost
and capital cost. As to reactors, a twin-screw extruder repre-
senting a highly efficient continuous operation is used in the
process of Fig. 5. Though the types of reactors are not shown in
the other two processes, they are likely to be the batch reactors
on the lab-scale. Basically, the water extraction method, which
represents a mild pretreatment, brings about a higher molecu-
lar weight hemicellulose [48]. Taking this into comprehensive
consideration, twin-screw extruder combined with ultrafiltration
might be a good choice for isolation of hemicelluloses by water
extraction.
Most extraction procedures, other than water extraction, are
often operated in more severe pretreatment conditions, produc-
ing hemicelluloses with smaller molecular weights. Thus, with
ultrafiltration for these hydrolyzates, the hemicelluloses reten-
tion was not high enough to obtain efficient isolation [49,50].
In these cases, however, nanofiltration can be used instead of
ultrafiltration. Most recently, Schlesinger et al. [50] proved that
nanofiltration, which has been commercially used in industry for
around fifteen years, is much better than ultrafiltration for sepa-
rating hemicelluloses from hydrolyzates by alkaline procedure.
They investigated the performance of four polymeric nanofil-
tration and one tight ultrafiltration membranes for isolating
hemicelluloses from alkaline process liquors containing 200 g/l
NaOH. The experimental results showed that the hemicelluloses
of molar mass over 1000 g/mol are almost retained. In addition,
two of the membranes with the nominal molecular weight cut-
off (MWCO) of 200–300 and 200–250 g/mol, respectively, are
most efficient in retention of up to 90% of hemicelluloses, while
the tight ultrafiltration membrane with MWCO of 2000 g/mol
exhibited less than 70% retention of hemicelluloses. Ali et al.
patented an alkaline treatment system for recovering hemicel-
luloses where pre-filtration units with a screen size of 400–650
mesh, followed by one nanofiltration membrane was able to
retain compounds with a molecular weight of about 200 and
higher [51].
Therefore, nanofiltration is an excellent separation proce-
dure for recovery of hemicelluloses from hydrolyzates, and the
combination of a twin-screw extruder and nanofiltration can be
considered to be the best selection for extracting hemicelluloses
from hardwood chips.
The above referenced research can be directly related to the
basic lignocellulosic biomass-to-biorefinery without the pulping
process. However, these researches did not evaluate the effect
8 H.-J. Huang et al. / Separation and Purification Technology 62 (2008) 1–21
of pre-extraction on the downstream pulping yield and paper
quality, which is very important for ILCB. Taking this into
consideration, more recently, van Heiningen [24] pre-extracted
hemicellulose from mixed hardwood chips with two methods
of different extractants: pure water and 10% alkaline solutions.
The extracted chips were then subjected to Kraft cooking at stan-
dard conditions. Results showed that with these two approaches
the pulp yield decreased 5–7%, though 10% organics could be
extracted. To avoid this problem, they employed a new method
which can increase the pulp yield to the same level or even 1%
higher than that of a Kraft cook control (no extraction). This
method, which is still in the process of a patent application, was
shown to result in other benefits: (1) a 3% reduction of effective
alkali (EA) charge in the digester, (2) a 40% increase in deligni-
fication rate, (3) rejects reduction at higher kappa numbers, and
(4) an 8% decrease in organic load to the recovery boiler, based
on o.d. (oven-dried) wood.
2.2.2. Pre-extraction of antioxidants
In addition to hemicelluloses, naturally occurring antioxi-
dants (phenolics or polyphenolics) which could be used as a
cheap, renewable food additive, can also be produced from lig-
nocellulosic wood materials [25,26]. The process for production
of both hemicelluloses and antioxidants by mild acid hydrolysis
is seen in Fig. 8. [26]. In this process, Eucalyptus globules wood
chips were subjected to acid hydrolysis with 2.5–5% H2 SO4
at a liquid/solid ratio of 8:1 g/g and 100–130 ◦ C. The resulting
slurry was vacuum-filtered into a hydrolyzates and a solid con-
sisting of cellulose and lignin. Then antioxidants were extracted
from hydrolyzate with ethyl acetate as solvent. The resulting
organic phase was vacuum-evaporated to remove and recycle
ethyl acetate to the extractor, leaving the antioxidants-containing
Fig. 8. Solvent extraction of hemicelluloses and antioxidant from wood [26].
extracts behind. The aqueous phase from extraction contains
xylose (representing hemicellulose) which can be fermented to
yield ethanol and/or xylitol with different yeasts.
3. Removal of inhibitors
It is well-known that thermo-chemical pretreatment of lig-
nocelluloses, e.g. dilute acid hydrolysis and steam explosion,
can release not only the fermentable pentose and hexose sugars,
but also various compounds which are inhibitory to microorgan-
isms and lead to apparent reduction in fermentation yield and
productivity. Since the detoxification process can be expensive
and take a large portion of the whole ethanol production cost,
detoxification is a key step and selection of the proper detoxifi-
cation method becomes very important. For example, one study
showed that detoxification process comprised 22% of the ethanol
production cost with Willow as feedstock [52].
In general, there are three major groups of inhibitors:
aliphatic acids (acetic, formic and levulinic acid), furan deriva-
tives furfural and 5-hydroxymethylfurfural (HMF), and phenolic
compounds (phenol, vanillin, p-hydroxybenzoic acid) [53,54].
The mechanisms of inhibition for these three groups of inhibitors
was reviewed by Palmqvist and Hahn-Hagerdal [53]. In addition,
use of different biomass as feedstock, pretreatment methods,
and fermentation organisms results in different inhibitory com-
pounds and different concentration of inhibitors. As an example,
more than 35 potential inhibitors to S. cerevisiae fermentation in
dilute nitric acid hydrolyzates of hybrid poplar were identified
[55].
In order to enhance the efficiency of hydrolyzate fermen-
tation, in addition to optimization of the pretreatment and
hydrolysis process for minimizing formation of the hydroly-
sis byproducts (inhibitors), it is necessary to remove inhibitors
(detoxify hydrolyzates) prior to fermentation or in situ detoxi-
fication. The detoxification can be either chemical, physical, or
biological [56]. The most commonly used methods for detoxifi-
cation of hydrolyzates before fermentation are: evaporation [57],
solvent extraction [25,26,58], overliming with calcium hydrox-
ide [54,59], activated charcoal [54,60–62], ion exchange resins
[54,62], and enzymatic detoxification [63,64].
Evaporation is a simple procedure to remove acetic acid, fur-
fural and other volatile components in the hydrolyzates. For
instance, Converti et al. [57] hydrolyzed the E. globules wood
by steam explosion and dilute acid treatment at 100 ◦ C, followed
by boiling or evaporating the obtained hydrolyzate for 160 min
to decrease the concentration of acetic acid and furfural from
31.2 to 1.0 g/l and from 1.2 to 0.5 g/l, respectively. These are
below their inhibitory levels for the fermentation of xylose to
xylitol by Pachysolen tannophilus strain, showing that in this
case the simple evaporation method is sufficient to eliminate the
inhibition of acetic acid and furfural.
Solvent extraction with ethyl acetate is effective to remove all
of the inhibitory compounds except for the residual acetic acid
[58], e.g. ethyl acetate extraction can be used to remove 56%
acetic acid and all of furfural, vanillin, and 4-hydroxybenzoic
acid [56].
 H.-J. Huang et al. / Separation and Purification Technology 62 (2008) 1–21
In the overliming process, the hydrolyzate is detoxified by
addition of Ca(OH)2 to adjust the pH to 9–10, leading to pre-
cipitation of inhibitory compounds. After filtration, the resulting
hydrolyzate is then readjusted to 5.5 with dilute H2 SO4 ready
for fermentation [56,57]. This is a very effective process, but it
produces a large amount of gypsum [7].
In the activated charcoal adsorption process, lignin-derived
inhibitory compounds (phenolics) are adsorbed on activated
charcoal, and after its adsorption saturation, the charcoal is
reactivated or regenerated by heating, e.g., by boiling it in
distilled water for 3 h [57]. Parajo et al. [60] performed experi-
ments to observe the effect of different operating variables, i.e.,
hydrolyzate concentration, adsorbent charge (hydrolyzate: char-
coal ratio) and adsorption time, on the subsequent fermentation
of xylose to xylitol by the yeast Debaryomyces hansenii. Results
show that a hydrolyzate:charcoal ratio of 205 g/g was sufficient
for improving subsequent fermentation.
Ion exchange resin (IER) is a well-known detoxification
method. For illustration, Van Zyi et al. [65] studied the elimina-
tion of acetic acid inhibition of d-xylose fermentation by Pichia
stipitis with ion exchange resin. The inhibition degree was found
to be dependent on the acetic acid concentration, the oxygen
availability, and the pH value. A comparison was done between
the fermentation of an untreated acid hydrolyzate of sugar cane
bagasse and the fermentation of the hydrolyzate treated by an
anion exchange resin with the removal of 84% of the acetic acid.
The results show that the former ethanol yield is 0.27 g/g sugar,
while the latter ethanol yield increased by 0.36 g/g sugar.
Enzymatic treatment is usually effective to remove phenolic
compounds, e.g. removal of phenolics from Willow hydrolyzates
treated with steam and SO2 by applying laccase [63]. Basically,
laccase treatment can remove most of the phenolics, but not
acetic acid, furfural and HMF. For example, around 80% of
the phenolic compounds was removed from sugarcane bagasse
hydrolyzates obtained by steam explosion with the phenoloxi-
dase laccase [66]. In addition, reductive detoxification of furfural
to less toxic furfuryl alcohol can be performed by using the
ethanologenic bacterium Escherichia coli strain LYO1 [64].
In order to select an efficient detoxification approach, some
researchers have made comparisons between different detoxi-
fication procedures. For instance, Cantarella et al. [59] made
a comparison between Ca(OH)2 overliming, water rinsing,
water–ethyl acetate two-phase contacting, and in situ detox-
ification with high level yeast inocula, for the purpose of
eliminating the inhibition problem in saccharification of cel-
lulose from steam-exploded (SE) poplar wood to glucose by
cellulases and fermentation of glucose to ethanol by S. cere-
visiae (Baker’s yeast). The water-rinsing treatment removed
water-soluble inhibitors, thus enhanced the enzymatic hydroly-
sis of SE-substrate. Obviously, however, this method is suitable
for washing away the inhibitors in cellulose hydrolyzates, but
not for removal of inhibitors in hemicellulosic pre-hydrolyzates
since most pentose sugars are also water-soluble. This compar-
ison showed that overliming with Ca(OH)2 is the most efficient
method among those investigated.
Most recently, Chandel et al. [54] investigated the detoxi-
fication of sugarcane bagasse hydrolyzate to improve ethanol
9
Fig. 9. Block diagram of the hydrolyzate detoxification with IER [62]: (1) cation
exchanger in H+ form; (2) anion exchanger in Cl− form; (3) cation exchanger
in H+ form; (4) anion exchanger in OH− form.
production by Candida shehatae NCIM 3501. In their research
work, five detoxification methods were compared, including
neutralization, overliming, activated charcoal, ion exchange
resins (IER), and enzymatic detoxification using laccase. It
was demonstrated that ion exchange treatment was most effi-
cient in removing furans (63.4%), total phenolics (75.8%)
and acetic acid (85.2%). Activated charcoal could remove
38.7, 57 and 46.8% of furans, phenolics and acetic acid,
respectively. Laccase treatment could remove 77.5% of total
phenolics, but it could not reduce the furans and acetic
acid contents in its hydrolyzates. Overliming could reduce
45.8% furans and 35.8% phenolics in its treated hydrolyzate,
but not acetic acid. Fermentation of hydrolyzates detoxified
by different methods with Candida shehatae NCIM 3501
showed that the ethanol yields obtained by different detox-
ification treatments are in the following decreasing order:
ion exchange (0.48 g/g) > activated charcoal (0.42 g/g) > laccase
(0.37 g/g) > overliming (0.30 g/g) > neutralization (0.22 g/g).
Villarreal et al. [62] studied on detoxification of Eucalyptus
hemicellulose hydrolyzate, i.e., removal of acetic acid, furfural,
HMF, and phenolics, for xylitol production by Candida guil-
liermondii with active charcoal and a series of IER columns
(Fig. 9) composed of four different resins (alternate cationic and
anionic) in sequence. Their results showed that IER can remove
all inhibitory components (aliphatic acids, furan derivatives and
phenols) without significant loss of sugar, superior to activated
charcoal.
As will be discussed in Sections 4.4, 4.6.3 and 4.6.4, in
situ detoxification by using extractive-fermentation, membrane
pervaporation-bioreactor hybrid, and vacuum membrane dis-
tillation (VMD)-bioreactor hybrid processes can effectively
separate product ethanol and remove inhibitors simultaneously.
Briefly, in summary, evaporation is a simple way to remove
acetic acid, furfural and other volatile components, but it is dif-
ficult to remove the heavier components with higher boiling
points. Extraction with solvent (e.g., ethyl acetate) is efficient
in removing all the inhibitors, but it needs additional solvent
(ethyl acetate) and solvent recovery for recycle use. Activated
charcoal adsorption can remove the phenolic compounds, but
it is not so efficient in removal of acetic acid and furfural.
Overliming and IER are more efficient procedures for removal
10 H.-J. Huang et al. / Separation and Purification Technology 62 (2008) 1–21
of different inhibitors from hydrolyzates, but the former leads
to a large amount of gypsum. It could be concluded that IER
method is the current best choice for detoxification because
of its high detoxification efficiency, easy (continuous) oper-
ation and flexible combination of different anion and cation
exchangers, while the enzymatic treatment can possibly be the
future choice. In addition, extractive-fermentation, membrane
pervaporation-bioreactor hybrid, and VMD-bioreactor hybrid
are very promising processes to remove inhibitory compounds
in addition to increasing ethanol yield.
4. Recovery of ethanol and ethanol dehydration
Downstream from the fermentor, the so-called beer, is usu-
ally dilute aqueous solution containing about 5–12 wt% ethanol.
Separation of ethanol from beer is an energy-intensive process.
It usually takes up a large fraction of the total energy requirement
for the whole biorefinery.
There is a common problem in the dehydration of ethanol,
because ethanol forms a minimum boiling mixture, so called
azeotropic mixture or azeotrope, at 95.6% by weight (97.2% by
volume) with water at a temperature of 78.15 ◦ C, which makes it
impossible to separate ethanol–water in a single distillation col-
umn. In general, for the solution containing 10–85 wt% ethanol,
distillation is effective, while for the mixture containing more
than 85 wt% ethanol, distillation becomes expensive because the
feed ethanol concentration is near the azeotropic point (95.6%),
requiring high reflux ratios and additional equipment, especially
when anhydrous ethanol is required [67]. Recently, the separa-
tion of dilute ethanol–water mixture is usually divided into two
large steps: approximately 92.4 wt% ethanol is firstly obtained
from the dilute aqueous solution by using the ordinary distil-
lation, then the resulting ethanol is further dehydrated in order
to achieve anhydrous ethanol by employing azeotropic distilla-
tion, extractive distillation, liquid–liquid extraction, adsorption,
or some complex hybrid separation methods. To help select the
best or suitable separation method from these alternatives, the
detailed description of all these methods is given in the follow-
ing.
4.1. Ordinary distillation
Ordinary distillation (OD) is a commonly used process for
separation of two or more components in a solution based on
their relative volatilities or the difference in their boiling temper-
atures. The ethanol–water azeotrope can be eliminated or broken
down to produce anhydrous ethanol by only lowering the opera-
tion pressure to a vacuum condition like 0.11 atm, but this is not
economical [68]. In a biorefinery, therefore, an OD column, also
called beer column or pre-concentrator column, is often used to
concentrate dilute ethanol to 92.4 wt%, as mentioned above.
4.2. Azeotropic distillation (AD)
Azeotropic distillation involves adding a third volatile com-
ponent, called entrainer, which forms a ternary azeotrope with
the two components to be separated and thus changes their rela-
tive volatilities and finally alters their separation factor (activity
coefficients) in the distillation system. The two components
to be separated are generally close boiling components or an
azeotropic mixture [69]. So, AD can be used to separate close-
boiling mixtures or azeotrope.
The AD system typically consists of two distillation columns
for dehydration of 92.4 wt% ethanol solution from the OD col-
umn:
(1) A dehydration column (azeotropic column) for further con-
centration in the presence of entrainer.
(2) An entrainer recovery column (stripping column) for sepa-
ration of entrainer from the product stream.
In the dehydration column, ethanol (>99 wt%) exits from the bot-
toms, while water vapor, solvent, and small amounts of ethanol
exit from the tops. The top stream enters a separator, called
decanter, and splits into ethanol-entrainer (organic phase) and
water-entrainer (aqueous phase) streams. The former is refluxed
back into the first column, while the latter is processed in the
entrainer recovery column [70–73]. The process flow sheet is
shown in Fig. 10.
The commonly used entrainers for breaking binary
ethanol–water azeoptropes by heterogeneous azeoptropic dis-
tillation are benzene [72,74], toluene [75,76] and cyclohexane
[77]. A mixed solvent, e.g., a mixture of benzene and n-octane
can also be used [72]. Benzene is a traditional entrainer in het-
erogeneous azeotropic distillation for ethanol dehydration. For
many years, however, benzene has been substituted by other sol-
vents because of its carcinogenic effect. Currently, cyclohexane
is one of the most used entrainers for this separation [77]. How-
ever, cyclohexane also has the disadvantage of flammability.
The two-columns azeotropic system mentioned above has the
disadvantage of high energy requirement, large capital cost, and
health and safety concerns with the storage of either carcinogenic
(benzene) or highly flammable (cyclohexane) solvent. For this
reasons, AD method is less applied in the ethanol production.
Fig. 10. Flow sheet of two-column process for ethanol dehydration [72,73].
 H.-J. Huang et al. / Separation and Purification Technology 62 (2008) 1–21
4.3. Extractive distillation (ED)
Like AD, ED is a vapor–liquid separation process with the
addition of a third component to increase the relative volatility
of the components to be separated. In the ED process, a selective
high boiling solvent is utilized to alter the activity coefficients
and hence increase the separation factor. This method is com-
monly employed in chemical industry to separate close boiling
point or azeotropic mixtures. The third component added as sep-
arating agent can be liquid solvent, ionic liquid, dissolved salt,
a mixture of volatile liquid solvent and dissolved salt, or hyper-
branched polymer, leading to corresponding five categories of
extractive distillations, which will be discussed in the following.
4.3.1. Extractive distillation with liquid solvent
The conventional liquid solvents used as extractants (extrac-
tive agents) in extractive distillation are usually of high boiling
points. The typical extractive distillation for ethanol dehydration
is illustrated in Fig. 11 where a suitable amount of high-boiling
non-ideal solvent is introduced in the upper part above the feed.
One of the most commonly used extractive solvents in extrac-
tive distillation for ethanol dehydration is ethylene glycol, with
which anhydrous ethanol could be produced from the fermen-
tation broth in a column with only 18 theoretical stages, a low
reflux ratio of 1.5 and a low solvent/feed ratio of 0.27 [70].
Meirelles et al. (1992) had verified that this process could be
competitive with azeotropic distillation, under specific operating
conditions [78].
Gasoline is a good solvent for extractive distillation of beer
solution to produce motor fuel ethanol, i.e., gasohol. Fig. 12
shows the simplified process flow diagram (PFD) for gasohol
production where the ethanol–water volatility is reversed by the
addition of gasoline consisting of high percent of C7 and C8
fractions, causing water to be withdrawn overhead with residual
ethanol and lighter hydrocarbons, and the ethanol–solvent mix-
ture to exit at the bottom. The bottom stream is then mixed with
the organic phase of the decanter to provide the final gasohol
product [72].
Fig. 11. Extractive distillation (C1: extractive distillation column, C2: solvent
recovery column).
11
Fig. 12. Simplified PFD of ethanol dehydration by extractive distillation with
gasoline [72]. (HH: heavier hydrocarbon; LH: lighter hydrocarbon).
4.3.2. Extractive distillation with dissolved salt
For some systems, e.g. ethanol–water system, a dissolved
salt can be added as a separating agent into extractive distilla-
tion where the salt dissolved into the liquid so as to enhance
considerably the relative volatility of the more volatile compo-
nent of the mixture to be separated, due to the so-called “salt
effect” [79]. Fig. 13 is a typical simplified PFD of this process.
The most commonly tested dissolved salts in extractive dis-
tillation for ethanol dehydration are potassium acetate [80–82],
sodium acetate [83] and calcium chloride [68,79,84]. Cook and
Furter [81] studied the extractive distillation process with potas-
sium acetate as separating agent in a pilot-scale bubble-cap tray
column, and found that the ethanol–water azeotrope could be
eliminated with relatively small amount of salt. They also made a
comparison of advantages and disadvantages between dissolved
salts and conventional liquid extractants, and found that extrac-
tive distillation with salts is more efficient in ethanol–water
separation. Barba et al. [84] compared the extractive distilla-
tion using CaCl2 as separating agent, in the aspect of the energy
requirement, with azeotropic distillation (using benzene, pen-
tane and diethyl ester), extractive distillation (using ethylene
Fig. 13. Typical simplified PFD of the extractive distillation with dissolved salt
[80].
12 H.-J. Huang et al. / Separation and Purification Technology 62 (2008) 1–21
glycol or gasoline), solvent extraction, and membrane pervapo-
ration. It was found that the extractive distillation with CaCl2
consumes almost the same energy as membrane pervaporation,
and these two methods are superior to the other mentioned
in energy-saving. In addition, a mixture of two or more salts
can also be employed in extractive distillation. For instance, a
70/30 mixture of potassium and sodium acetate was utilized
in the HIAG (Holz Industrie Acetien Geselleschaft) extractive
distillation process, which could produce more than 99.8 wt%
ethanol, with lower capital and operating costs (energy con-
sumption) compared to conventional azeotropic distillation with
benzene or extractive distillation with ethylene glycol [79,83].
Recently, Pinto et al. [85] simulated both conventional (using
ethylene glycol) and saline extractive distillation with different
salts such as NaCl, KCl, KI and CaCl2 for ethanol dehydration
by use of Aspen Plus, and made comparison between them. It
was shown that CaCl2 provides the largest salting out effect on
ethanol among the four salts mentioned, and that saline extrac-
tive distillation with CaCl2 has the lower energy consumption as
compared with conventional extractive distillation with ethylene
glycol. It was demonstrated that the saline extractive distillation
is a better process to obtain anhydrous ethanol from the fermen-
tation broth, due to the use of only one column, which requires
the lowest energy consumption, and uses non-toxic solvent.
Recently, Ligero et al. [86] proposed and compared two
different process flowsheets of extractive distillation with potas-
sium acetate as separating agent by simulation. In the first flow
sheet, dilute ethanol solution is fed to the extractive distillation
column, followed by salt recovery in a multiple effect evapora-
tor and a spray dryer, and then recycled to the column. In the
second, dilute ethanol solution is concentrated firstly by con-
ventional distillation, and the resulting concentrated ethanol is
then fed to the extractive distillation column followed by a sin-
gle spray dryer for recovery of salt, which is also recycled in the
column. It is shown that the second flowsheet has less energy
consumption than the first.
In order to reduce energy consumption, heat integration is
often considered and included in the ethanol separation pro-
cess. For example, Lynd and Grethlein [82] optimized a process
flowsheet by heat integration for anhydrous ethanol production
from beer liquors. The process consists of a pre-concentration
column with intermediate heat pumps and optimal side-stream
return, a saline extractive distillation column with potassium
acetate as an agent, a salt-concentrating evaporator, and a spray
dryer. It was shown that the process proposed requires lower
capital costs and much less energy consumption in comparison
with conventional separation procedures for making anhydrous
ethanol.
4.3.3. Extractive distillation with the mixture of liquid
extractant and dissolved salt
Similar to the liquid extractant or dissolved salt, the combi-
nation of both liquid extractant and dissolved salt can be used
as separating agent in extractive distillation for ethanol purifi-
cation, with the same process flowsheet. In general, only a little
amount of salt was required in the mixture of liquid extractant
and dissolved salt.
Some scholars [87–89] had also investigated the ED process
for ethanol dehydration with mixtures of solvent liquid and vari-
ous dissolved salts (NaCl, CaCl2 , SrCl2 , AlCl3 , KNO3 , Cu(NO3 )
2 , Al(CO3 )3 , CH3 COOK and K2 CO3 ). The relative volatilities
with mixtures of ethylene glycol and different salts are found
in the range of 1.9–4.15, with the following order of salt effect:
AlCl3 > CaCl2 > NaCl; Al(CO3 )3 > Cu(NO3 )2 > KNO3 , and the
order of the effect of acidic roots: Ac− > Cl− > NO3 − , where
the ethanol solution : separating agent ratio (v/v) is 1.0, and the
salt concentration is 0.2 g salt per ml of solvent. More recently,
Lei et al. [90] measured the vapor–liquid equilibria of three sys-
tems including ethanol–water, ethanol–water–ethylene glycol,
and ethanol–water–ethylene glycol–CaCl2 , at finite concentra-
tion and normal pressure. The results proved that the extractive
distillation with combined ethylene glycol and dissolved salt
was more efficient in separating ethanol and water than with
ethylene glycol only.
4.3.4. Extractive distillation with ionic liquid
Extractive distillation with ionic liquids (IL) as separating
agent is a novel method for separation of ethanol–water mixture
[91]. This process has the advantages of high separation ability,
easy operation, and no problem of entrainment of the solvent
into the top product of the column as compared to extractive
distillation with the mixture of liquid solvent and solid salt [92].
Ionic liquid as separating agent can greatly enhance the relative
volatility of ethanol over water, due to the similar salt effect to
the solid salt.
Ionic liquids (IL), or room-temperature ionic liquids (usually
a mixture of organic cation and an inorganic anion), are promis-
ing separating agents for extractive distillation of ethanol–water
mixture, due to their favorable properties such as low viscosity,
thermal stability, good solubility and lower corrosiveness than
ordinary high melting salts. The commercially available ionic
liquids suitable for use as separating agent for the extractive
distillation, are 1-butyl-3-methylimidazolium tetrafluoroborate
([BMIM]+ [BF4]− ), 1-ethyl-3-methylimidazolium tetrafluorob-
orate ([EMIM]+ [BF4]− ) and 1-butyl-3-methylimidazolium
chloride ([BMIM]+ [Cl]− ). Seiler et al. [93] investigated the
possibility of using these ionic liquids as separating agent in
the extractive distillation for ethanol dehydration, the process
diagram of which is illustrated in Fig. 14. It was shown that
these ionic liquids remarkably increase the relative volatil-
ity of ethanol to water, in the following order: [BMIM]
+ [Cl]− > [EMIM]+ [BF ]− > [BMIM]+ [BF ]− . It was also found
4 4
that the influence of [BMIM] + [Cl]− and [EMIM]+ [BF4 ]− on
the relative volatility is greater than that of the conventional
separating agent 1,2-ethanediol. In addition, it was shown by
process simulation that the overall heat duty can be saved up
to 24% for the [EMIM]+ [BF4 ]− process as compared with the
conventional ED process.
4.3.5. Extractive distillation with hyperbranched polymers
Like ionic liquids, hyperbranched polymers are also novel
separating agents used in extractive distillation for dehydration
of ethanol from aqueous solutions. Hyperbranched polymers,
the highly branched macromolecules with a large number of
functional groups, can be readily manufactured by one-step reac-
 H.-J. Huang et al. / Separation and Purification Technology 62 (2008) 1–21 13

Seiler et al. [95] studied the phase equilibria of ternary

ethanol–water–polymers systems, including vapor–liquid,
liquid–liquid and solid–liquid–liquid equilibria. It is found
that the commercially available hyperbranched polyesters and
hyperbranched polyesteramides can break the ethanol–water
azeotrope. The most tested hyperbranched polymer as entrainer
for extractive distillation of the ethanol–water mixture is hyper-
branched polyglycerol (PG). It was found that the effect of PG
on the relative volatility of ethanol to water was the same order
as that of the conventional entrainer 1,2-ethanediol. It was also
found by process simulation that the overall heat duty can be
saved up to 19% for the PG process, compared to the conven-
tional ED process [93].

4.3.6. Summary of extractive distillation with different

Fig. 14. Extractive distillation using ionic liquid as non-volatile entrainer (A:
main column, B: flash drum, C: stripping column) [93].
tions, representing economically favorable agents for large-scale
industrial applications [93]. Unlike linear polymers, hyper-
branched polymers have the features of remarkable selectivity
and capacity, low viscosity and thermal stability. Therefore,
they were recently suggested as entrainers in extractive dis-
tillation for separating azeotropic mixtures [91]. For instance,
Am [94] employed non-volatile polymeric entrainers such as
poly(ethylene glycol) and poly(acrylic acid) for dehydrating
ethanol. In his research, the experimental test of solubility and
group contribution model calculations were used to guide in
the initial selection of possible polymers. The VLE data mea-
sured show that polymeric entrainers, e.g., Poly(ethylene glycol)
at 10 wt% and poly(acrylic acid) at 0.45 wt%, can break the
ethanol–water azeotrope for ethanol dehydration.
separating agents
The advantages and disadvantages of extractive distillation
with different separating agents are summarized in Table 1.
Briefly, compared to extractive distillation with liquid solvent,
dissolved salt or the mixture of liquid solvent and dissolved
salt, extractive distillation with IL or hyperbranched polymers
has excellent separation efficiency and selectivity without pollu-
tion of distillate by separating agents, thus requires less energy
consumption. In addition, the recent development of halogen-
free and hydrolysis-stable IL such as [BMIM][octylsulfate]
(ECOENGTM 418) brings some promise [93]. Therefore, extrac-
tive distillation with IL and hyperbranched polymers represent
two most promising novel separations.
4.4. Liquid–liquid extraction-fermentation hybrid
(extractive fermentation)
Liquid–liquid extraction is a particularly promising approach
for the recovery of anhydrous ethanol from the aque-

Table 1
Summary of dehydration technologies of extractive distillation with different agents
Technologies Advantages Disadvantages

Extractive distillation with liquid solvent
Extractive distillation with dissolved salt
Extractive distillation with the mixture of
liquid extractant and dissolved salt
Extractive distillation with ionic liquid (IL)
Extractive distillation with hyperbranched
polymers
Less energy consumption than azeotropic distillation because of Very high solvent/feed mass ratio, up
the high boiling point of the added solvent; flexible selection of to 5–8, leading to much consumption
the possible solvents. of energy.
High production capacity and low energy assumption due to its Potential problems in dissolution,
smaller solvent ratio; does not contaminate the overhead transport and recycle of salt; potential
product due to its non-volatility; environment-friendly and no jam and erosion to equipment.
any safety and health hazards.
Integrates the advantages of both liquid solvent (easy operation) Less availability of suitable salts;
and dissolved salt (high separation ability). potential corrosion of salts to the
equipment; possible contaminant of
the overhead product by liquid
extractants.
(1) IL cannot pollute the distillate due to their non-volatility; (2) IL containing halogen anions is
considerable reduction of required heat duties because of their expensive and has insufficient
non-volatility, high selectivities and capacities, especially a stability to hydrolysis for long-term
larger variety of feasible IL regeneration options; (3) IL’s applications; small amounts of
properties (solubility, capacity, selectivity, viscosity and corrosive and toxic substance (HF)
thermal stability) can be tailored; (4) Only one distillation forms during the hydrolysis.
column required, representing low energy consumption.
(1) Excellent separation efficiency and selectivity; (2) entrainers
can not contaminate the top product.
14 H.-J. Huang et al. / Separation and Purification Technology 62 (2008) 1–21
ous fermentation broth with low energy requirement [68].
Liquid–liquid extraction is generally combined with fermen-
tation, called extractive-fermentation, where in situ extraction
is carried out to remove product ethanol and other inhibitory
compounds, hence inhibitions caused by ethanol and other
inhibitors is eliminated, causing an increase in the ethanol
yield.
It is very important to select a high efficient solvent for
extracting ethanol from beer liquors. The criteria of solvent
selection are [96]:
• non-toxic to microorganism,
• high distribution coefficient,
• high selectivity with respect to the product,
• low solubility in the aqueous phase,
• density different from that of the broth to ensure phase sepa-
ration by gravity,
• low viscosity, large interfacial tension and low tendency to
emulsify in the broth,
• high stability,
• not expensive.
Some potential biocompatible solvents for extraction of ethanol
from beer liquor reported by several investigators include oleyl
alcohol [96,97], n-dodecanol [98,99], isoamyl acetate and iso-
octyl alcohol [100], nonanoic acid [101], etc. In the continuous
fermentation of ethanol with the thermophilic, anaerobic bac-
terium Clostridium thermohydrosulfuricum, as shown in Fig. 15,
oleyl alcohol was used as extractant for simultaneously in situ
extraction of ethanol in order to eliminate the ethanol product
inhibition. Results showed that the ethanol yield of in situ extrac-
tion is two times that of fermentations without in situ extraction
[96]. Oleyl alcohol was also utilized in a simultaneous sac-
charification and extractive fermentation (SSEF) process where
cellulose hydrolyzate was fermented to ethanol, and the ethanol
product was removed by extraction with oleyl alcohol. With
SSEF, ethanol productivity increased by 65% and the amount of
water required was greatly reduced, compared to non-extractive
fed batch simultaneous saccharification and fermentation (SSF)
[97]. The combination of increasing ethanol yield and decreas-
Fig. 15. Continuous fermentation with in situ extraction [96].
ing water consumption results in obvious reduction of overall
ethanol production cost.
Gyamerah and Glover [98] developed a pilot-scale extractive
fermentation for producing ethanol with n-dodecanol as extrac-
tant to remove the product and with recycle of the fermented
broth raffinate. It was found that the fresh water consumption
reduced by 78%, due to the successful recycle of the fermen-
tation water. Koullas et al. [100] experimentally screened and
examined several organic solvents such as isoamyl acetate,
iso-octyl alcohol, n-butyl acetate, dibutyl ether and dibutyl
oxalate as potential extractants for the liquid–liquid extrac-
tion of ethanol from aqueous solutions. Both isoamyl acetate
and iso-octyl alcohol were found to be very good agents with
ethanol distribution coefficients of above 1, and separation
factors in Bancroft coordinates of the order of 70 and 2000,
respectively. Most recently, Boudreau and Hill [101] extracted
ethanol from fermentation broth by use of three fatty acids
(valeric acid, oleic acid and nonanoic acid) as solvents, fol-
lowed by a flash process. It was found that the combined
nonanoic acid extraction with the flash process consumed 38%
less thermal energy, compared with the conventional distillation
process.
In short, extractive fermentation, which combines solvent
extraction and fermentation together, results increase in ethanol
yield and decrease in fresh water consumption. Coupling extrac-
tive fermentation with flash separation can also bring about
significant reduction in energy consumption. However, this
process requires careful selection of biocompatible extracting
agents.
4.5. Adsorption
There are two categories of adsorption in the ethanol–water
separation: the liquid-phase adsorption of water from the fer-
mentation broth and the vapor-phase adsorption of water from
the process stream out of distillation column [102].
4.5.1. Vapor-phase adsorption of water
The most potential adsorbents applied for vapor-phase
adsorption of water from ethanol–water mixtures include inor-
ganic adsorbents such as molecular sieves [103,104], lithium
chloride [105], silica gel [105], and activated alumina [106],
and bio-based adsorbents such as corn grits [67,102,105].
4.5.1.1. Inorganic adsorbents. Zeolites molecular sieve (type
3A and 4A) are widely employed in separating ethanol–water
mixture [107]. 3A zeolite molecular sieves which has a nominal
pore size of 3 Angstroms (0.30 nm) can be used for dehydra-
tion of polar liquids such as ethanol. Water molecules, with an
approximate molecular diameter of 0.28 nm, can easily pene-
trate the pores of the molecular sieve adsorbent, while ethanol,
with an approximate molecular diameter of 0.44 nm, is simul-
taneously retained [103]. Recently, Al-Asheh et al. [104] also
studied ethanol–water separation using molecular sieves (3A,
4A and 5A).
In terms of application, inorganic adsorbents such as molecu-
lar sieves, lithium chloride, and silica gel have been successfully
 H.-J. Huang et al. / Separation and Purification Technology 62 (2008) 1–21
applied as dehydration desiccants in fermentation ethanol plants
[105].
4.5.1.2. Bio-based adsorbents. The potential bio-based adsor-
bents include cornmeal, cracked corn, starch, corn cobs, wheat
straw, bagasse, cellulose, hemicellulose, wood chips, other
grains, etc. [108]. Basically, bio-based adsorbents can be clas-
sified into starch-based (e.g., cornmeal, corn crite) [109], and
lignocellulosic adsorbents (e.g., rice straw, bagasse [110]).
Ladisch and Dyck first investigated the biomass adsorption
of water for ethanol dehydration and demonstrated that starchy
and cellulosic biomass can be employed as an adsorbent to selec-
tively adsorb water in the vapor mixture to obtain more than
99.5 wt% ethanol [111]. Since then, much attention has been
paid on this field and a number of related papers have been
published [67,102,104,109,110,112–116].
The most potential starch-based adsorbents have been inves-
tigated. The adsorption of water from ethanol–water vapor
mixture on a variety of starchy materials, such as cooked corn,
corn grits and starch, which have different mean particle diame-
ters and different relative amounts of amylose and amylopectin,
had been experimentally measured at 90 ◦ C. The results demon-
strate that water selectivity over ethanol can be increased with
the amylopectin/amylose ratio in starches [67]. Recently, the
vapors of 92.4 wt% ethanol from distillation were passed over
a fixed bed of corn grits, after which almost all the water
is adsorbed on corn grits and anhydrous ethanol is obtained
[102]. This approach of water vapor adsorption had already
been applied in many fermentation ethanol plants [112]. Hu and
Xie [113] experimentally studied on fixed-bed adsorption with
Chinese cornmeal as adsorbent and fluidized-bed regeneration
for breaking the ethanol–water azeotrope to obtain anhydrous
ethanol. It was found that the factors influencing the adsorp-
tion capacity of water include the vapor superficial velocity
flowing through the fixed bed, the bed temperature, and the
particle size distribution of cornmeal. The adsorption capacity
of water was determined to be 0.14–0.025 g water g/g adsor-
bent. The desorption (regeneration) operation was improved
by employing a fluidized bed instead of the general fixed-
bed, in order to efficiently control the bed channel and faster
the operation. The regeneration temperature was 105 ◦ C. Most
recently, Chang et al. [114] investigated the adsorption capac-
ity and selectivity of cornmeal for ethanol dehydration on a
pilot-scale fixed-bed adsorber at temperatures of 82–100 ◦ C.
Results show that for the vapor containing 93.8 wt% ethanol,
the water selectivity over ethanol on the adsorbent for at
the breakthrough point is about 0.5–0.6 under the tempera-
ture of 91 ◦ C. They [109] also fit the experimental data into
the adsorption equilibrium models, including those based on
Polanyi adsorption potential theory and Sircar’s model, and
found that the models are in good agreement with the exper-
imental data.
With respect to ligno-cellulosic materials as adsorbents, the
lignocellulosic adsorbents – bagasse, rice straw, and microcrys-
talline cellulose powder had been investigated for adsorption
of water in the vapor mixture with 80–90% ethanol to produce
anhydrous ethanol [110]. It is reported that the adsorption on
15
lignocellulosic materials is primarily dependent on the hydroxyl
groups of the carbohydrates and the lignin [115]. Most recently,
Al-Asheh et al. [104] studied the separation of ethanol–water
mixtures using natural corncobs, natural and activated palm
stone and oak. The other three lignocellulose-based adsorbents
(bleached wood pulp, oak sawdust, and kenaf core) have also
been explored for dehydrating the concentrated ethanol solution
containing 90, 95, and 97 wt% ethanol in a thermal swing adsorp-
tion column. It was shown that water is selectively adsorbed and
anhydrous ethanol was obtained [116].
4.5.2. Liquid-phase adsorption of water
Nearly twenty years ago, A-type zeolites were shown to
have a high capacity and selectivity in separating water from
ethanol–water mixtures [117]. Recently, several combinations of
starch-based and cellulosic materials, including white corn grits,
␣-amylase-modified yellow corn grits, polysaccharide-based
synthesized adsorbent, and slightly gelled polysaccharide-based
synthesized adsorbent, have also been tested and screened for
liquid-phase adsorption of water. It was shown that starch-based
adsorbents can remove liquid-phase water between 1 and 20 wt%
from ethanol without the adsorbent being dissolved. The adsorp-
tion capacity of water increases with increasing water content
in the ethanol–water solution. Compared with silica gel and
molecular sieves, these starch-based adsorbents have lower non-
equilibrium adsorption capacity at water concentration below
10 wt%. At the concentrations of above 10 wt%, however, the
starch-based adsorbents have similar non-equilibrium adsorp-
tion capacity to that of the inorganic adsorbents, under the
same adsorption and regeneration conditions. The starch-based
adsorbents adsorb water by forming hydrogen bonds between
the hydroxyl groups on the surface of the adsorbent and the
water molecules [102]. The use of ␣-amylase to modify poros-
ity and surface properties of starch resulted in materials with
enhanced water sorption properties compared to the native mate-
rial [105].
More recently, a thermodynamic and kinetic study on liquid
phase adsorption of water from ethanol–water mixtures using
starch as the adsorbent has also been published [107]. Among
a variety of bio-based adsorbents, corn grits are reported as the
only bio-based adsorbents which have been successfully applied
in industry, though the other bio-based material such as cellulose
and hemicellulose also have adsorptive properties [105].
4.5.3. Advantages and disadvantages of adsorption
The vapor phase adsorption consumes lower energy than dis-
tillation, because of only one-time vaporization required [113].
Zeolite molecular sieves are highly selective, but water is very
strongly adsorbed and high temperatures and/or low pressures
are required to regenerate them [67]. Bio-based adsorbents have
lower separation capacity than molecular sieves, but their regen-
eration temperature is much lower than molecular sieves. In
addition, molecular sieves are more expensive than bio-based
adsorbents. In some cases of using bio-based adsorbents for
removal of water, the saturated adsorbents can be used directly as
feedstock, and simply fresh adsorbents are used without regen-
eration step.
16 H.-J. Huang et al. / Separation and Purification Technology 62 (2008) 1–21
4.6. Membrane separation
For a few decades, membrane pervaporation (PV) has been
considered as one of the most effective and energy-saving pro-
cess for separation of azeotropic mixtures. So far, over 100 plants
in the world use PV technique for alcohol dehydration [118]. In
principle, pervaporation is based on the solution-diffusion mech-
anism. Its driving force is the gradient of the chemical potential
between the feed and the permeate sides of the membrane. In
general, there are two different pervaporation processes: vacuum
and sweep gas pervaporation. In the vacuum PV process, solu-
tion to be separated contacts the membrane at the feed side, i.e.
retentate or upstream side, where the retained retentate leaves
the unit. On the permeate (downstream) side, the partial pressure
of pervaporated permeate is lowered by using a vacuum pump.
The sweep gas pervaporation uses an inert sweep gas such as N2
on the permeate side to reduce the permeate partial pressure.
Membranes can be either hydrophilic or hydrophobic. In gen-
eral, most membranes are hydrophilic or water permselective
due to water’s smaller molecular size, while few membranes
are hydrophobic or ethanol permselective. Based on materials
used for membrane production, there are three categories of
membranes: inorganic, polymeric and composite membrane.
4.6.1. Hydrophilic membrane for removal of water
4.6.1.1. Inorganic membrane. Inorganic pervaporation mem-
branes have recently become commercially available in
chemical reaction engineering, because of their superior tem-
perature stability and mechanical strength [119]. For example,
tubular zeolite and silica membranes are still stable to temper-
atures of above 300 ◦ C and feed pressures of above 100 bar.
The tabular Zeolite NaA membrane module, having the perva-
poration flux of ca. 2.35 kg m−2 h−1 and the separation factor
of above 5000 for the solution of 95 wt% ethanol at 95 ◦ C,
can be available at a low price [106]. Shah et al. [120] also
studied the pervaporation separation of ethanol–water with a
NaA-zeolite membrane for a wide range of operation condi-
tions. It was demonstrated that the ionic Na+ sites in the zeolite
matrix play an important role in the water transport through the
membrane.
The first commercial large-scale PV plant, composed of
16 membrane modules, with each containing 125 NaA-zeolite
membrane tubes, could produce 530 L/h of more than 99.8 wt%
ethanol from 90 wt% solvent at 120 ◦ C. The NaA-zeolite
membrane showed high water-selective permeation and high
permeation flux [121].
Table 2
PV performance of zeolite membranes for separating ethanol–water mixtures
Membrane xw (wt% water) T (K)
Zeolite T 10 348
Zeolite T 10 348
NaA 5 368
NaA 10 348
NaX 10 348
NaY 10 348
Where αw/e is the separator factor of water over ethanol.
Table 2. lists some PV separation factors for the hydrophilic
zeolite membranes.
4.6.1.2. Polymeric membrane. So far, a large number of poly-
meric pervaporation membranes, for example cellulose acetate
butyrate membrane [126], PDMS (polydimethylsiloxane) mem-
brane [127], PDMS-PS IPN supported membranes [128],
aromatic polyetherimide membranes [129] have been inves-
tigated. O’Brien and Craig [127] utilized the commercially
available PDMS membrane module in a continuous fermen-
tation/membrane pervaporation system to produce ethanol,
resulting in permeate of 20–23 wt% while 4–6 wt% level was
retained in stirred tank fermentor. The selectivity ranged from
1.8 to 4.1. Ruckenstein et al. utilized polydimethylsiloxane-
polystyrene interpenetrating polymer network (PDMS-PS IPN)
supported membranes for pervaporation separation of ethanol
from aqueous solutions. As PS is more hydrophobic and has
higher tensile strength than PDMS, the mechanical and film-
forming properties of PDMS-PS are better than those of PDMS.
The selectivity of these PDMS-PS membranes varied with the
feed composition. For the feed having low ethanol concentration,
the membrane was more selective for ethanol, while for the feed
with high ethanol concentration it was more selective for water
[128]. Schué et al. [129] investigated the sorption, diffusion and
pervaporation of ethanol solution in homogeneous and compos-
ite aromatic polyetherimide membranes. The performance of
these membranes was found dependent on the permeate diffu-
sivity rather than its solubility.
4.6.1.3. Composite or mixed membrane. To combine the
advantages of inorganic membrane and polymeric membrane for
obtaining high ratio of membrane performance/cost, recently,
various inorganic-polymer or polymer–polymer composite
membranes, such as polystyrenesulfonate/alumina [130], poly-
electrolytes multi-layer [131], KA zeolite-incorporated cross-
linked PVA multilayer mixed matrix membranes (MMMMs)
[132], and poly(vinyl alcohol) (PVA)-sodium alginate (SA)
blend membranes [118], have been studied for pervaporation
separation of ethanol/water mixtures. It is demonstrated by Mar-
tin that the separation factor of polystyrenesulfonate/alumina
composite membranes was up to 400 [130]. Tieke et al. prepared
multi-layer membranes by alternate adsorption of cationic and
anionic polyelectrolytes onto porous support membranes, and
achieved highest separation capability when polyelectrolytes
with high charge density such as polyetherimide (PEI) and
polyvinylsulfate (PVS) are used [131].
Flux (kg m−2 h−1 ) αw/e Ref.
1.25 2,200 [122]
1.10 900 [123]
2.35 5,000 [106]
2.15 10,000 [124]
1.91 170 [125]
1.59 130 [125]
 H.-J. Huang et al. / Separation and Purification Technology 62 (2008) 1–21 17

In 2006, Guan et al. fabricated MMMMs (multilayer mixed

matrix membranes) consisting of a selective mixed matrix
membrane (MMM) top layer, a porous poly(acrylonitrile-co-
methyl acrylate) [poly(AN-co-MA)] intermediate layer and a
polyphenylene sulfide (PPS) nonwoven fabrics substrate. It
is found that the separation performance of the MMMM is
superior to that of multi-ply homogenous membranes (MHM)
containing no zeolite [133]. In addition, a series of three-
layer zeolite-embedded PVA composite membranes have been
successfully fabricated using different zeolites with a load-
ing of 20 wt%, including 3A, 4A, 5A, NaX, NaY, silicalite
and beta. Results showed that the addition of zeolite resulted Fig. 16. A simplified membrane pervaporation-bioreactor hybrid process [148].
in decrease in activation energies for water and ethanol, and
hence increase in separation selectivity [132]. The hydrophilic 4.6.3. Membrane pervaporation-bioreactor hybrid
PVA is chosen as the polymeric material because it is the Fermentation broth generally contains inhibiting substances
most attractive and economical polymer material for ethanol including ethanol product, flavors (phenolics), and other chemi-
dehydration [134]. cals. This problem can be overcome by combining fermentation
Dong et al. prepared a hollow-fiber composite membrane, with hydrophobic membrane pervaporation for removal of the
PVA-SA blend, supported by a polysulfone (PS) hollow-fiber inhibitors from the fermentation broth, as seen in Fig. 16. Hence,
ultrafiltration membrane for pervaporation ethanol dehydration. the process can be carried out continuously and the recovered
With ethanol concentration at 90 wt% in the feed at 45 ◦ C, organic VOCs (ethanol, acetone, butanol, 2-propanol) can be
the separation factors and permeation fluxes were 384 and reused within other processes.
384 g/m2 h, respectively [118]. In the real application, a microfiltration membrane is added
before pervaporation to avoid fouling of the hydrophobic mem-
4.6.2. Hydrophobic membrane for removal of ethanol brane. Besides, the ethanol-enriched solution, i.e., the permeate
So far, many researchers have investigated a number of
of the hydrophobic membrane, can be further dehydrated to
hydrophobic membranes, including (1) the most potential
produce anhydrous ethanol. The complete process diagram is
hydrophobic polymeric membranes poly(1-trimethylsilyl-1-
illustrated in Fig. 17.
propyne) (PTMSP) [135,136] and poly(dimethyl silox-
ane)[PDMS] [137–139] membranes, (2) hydrophobic zeolite
membranes [140–142], and (3) the potential composite mem- 4.6.4. Vacuum Membrane Distillation (VMD) – bioreactor
branes, i.e., silicalite-PDMS membranes which consists of hybrid
silicatlite-1 particles dispersed in PDMS [143–145]. In Vane’s Membrane distillation (MD) is an appealing process suitable
recent review [146], the ethanol–water separation factors of for separation of aqueous mixtures. There are four types of MD:
PTMSP and PDMS membranes (polymeric), hydrophobic azeo- direct contact membrane distillation (DCMD), air gap mem-
lite membranes, and composite silicate-silicone rubber (PDMS) brane distillation (AGMD), sweeping gas membrane distillation
membranes are tabulated from a large number of published work (SGMD) and vacuum membrane distillation (VMD). Actually,
in the literature. Based on literature data, the ethanol–water VMD is quite similar to pervaporation, the only difference being
separation factors of PDMS, PTMSP, composite membranes, that the separation factor here is established by vapor–liquid
and zeolite are reported to be in the range of 4.4–10.8, equilibrium of the feed solution which is not affected by the
9–26, 7–59, 12–106, respectively. However, the ethanol–water membrane used [149].
separation factors in some other cases might exceed these Similar to Membrane pervaporation-bioreactor hybrid,
ranges. For instance, the separation factor of ethanol over VMD-bioreactor hybrid process is also suitable for separation
water was 218, when using a silicate zeolite membrane where
ethanol (98.2 wt%) at permeate was continuously obtained
from the fermentation broth of 20 wt% ethanol [147]. In gen-
eral, the ethanol–water separation factors are largely ranked
in the following order: PDMS < PTMSP < composite mem-
branes < zeolite membranes.
To date, hydrophobic zeolite membranes are commercially
available, while polymeric membranes (PDMS, PTMSP) and
composite membranes are still under investigation. Zeolite
membranes are more expensive than polymer membranes,
but zeolite membranes have higher separation factors and
flux than polymer membranes. Therefore, zeolite membranes
may be more cost effective on per unit ethanol basis Fig. 17. A complete membrane pervaporation-bioreactor hybrid process for
[146]. ethanol fermentation and dehydration [146].
18 H.-J. Huang et al. / Separation and Purification Technology 62 (2008) 1–21
of ethanol and the other inhibitory compounds from fermen-
tation broths. Till now, there has been much reported on this
topic [150–152]. As an example, Gryta et al. produced ethanol
in a membrane distillation bioreactor where porous capillary
polypropylene membranes were applied for separating volatile
compounds, including ethanol and other inhibitors, from the
feed (broth), leading to increase in the productivity and the
sugar-to-ethanol conversion rate [151]. VMD is commercially
competitive because of its high selectivity of ethanol over water,
large flux, high thermal efficiency and low energy cost [92].
5. Conclusions
This paper attempts to provide a critical review of the various
separation technologies used in today’s corn–ethanol biorefinery
as well as the challenges and opportunities in future cellulosic
ethanol and integrated lignocellulosic biorefinery producing liq-
uid fuels and other co-products. As shown in this review, there
are two key separation steps in the biorefinery that offers chal-
lenges and opportunities. First is the separation of fermentation
inhibitors after the pre-extraction of hemicelluloses from ligno-
cellulosic biomass. Here the promising separation technologies
are the three in situ detoxification hybrid processes including
extractive-fermentation, membrane pervaporation-bioreactor,
and VMD–bioreactor, which can eliminate the inhibition of
products and inhibitory compounds, increase the fermentation
yield and productivity, and reduce (fresh) water consumption
due to recycle. Currently, ion exchange resin (IER) method is
the preferred choice for detoxification and will be still used in the
future biorefinery because of its high detoxification efficiency,
easy (continuous) operation and flexible combination of differ-
ent anion and cation exchangers, while the enzymatic treatment
will grow in the future.
The second key separation challenge in biorefinery is the
azeotropic nature of ethanol–water mixture posing challenges
to remove the last amounts of water producing fuel grade
ethanol. For ethanol–water azeotropic separation, promising
technologies are the extractive distillation with ionic liquid and
hyperbranched polymers, adsorption with molecular sieve and
bio-based adsorbents, representing low energy consumption.
In addition to the above key steps, other separation steps in
biorefining are pre-extraction of hemicellulose (for ILCB) and
other value-added chemicals (corn germ, fiber, zein or gluten
from corn–ethanol plants). Key separation technologies for these
steps include “Quick Germ” process for corn germ recovery,
“Quick Fiber” process for corn fiber recovery, extraction of
zein from corn with ethanol followed by ultrafiltration, and
the effective pretreatments for hemicellulose extraction such
as dilute acid pretreatments, liquid hot water extraction, steam
explosion-based extraction, dilute acid-steam explosion and
alkaline extraction. Membrane separation, especially nanofiltra-
tion represents a promising separation procedure for recovery of
hemicelluloses from hydrolyzates because of its low energy con-
sumption and excellent separation efficiency. In addition, the
combination of a twin-screw extruder and nanofiltration may
become the preferred choice for extracting hemicelluloses from
hardwood chips in the future.
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