A Review of Separation Technologies in Current and Future Biorefineries

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Separation and Purification Technology 62 (2008) 121
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
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Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1. Corn-to-ethanol biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2. Lignocellulosic biomass-to-ethanol biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3. Integrated lignocellulose/forest biorefinery (ILCB) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.2. Extraction of corn fiber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.3. Extraction of zein . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2. Pre-extraction of value-added chemicals in integrated forest biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.1. Pre-extraction of hemicellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.2. Pre-extraction of antioxidants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Removal of inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Recovery of ethanol and ethanol dehydration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1. Ordinary distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2. Azeotropic distillation (AD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3. Extractive distillation (ED) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.1. Extractive distillation with liquid solvent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.2. Extractive distillation with dissolved salt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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
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H.-J. Huang et al. / Separation and Purication Technology 62 (2008) 121
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4.3.3. Extractive distillation with the mixture of liquid extractant and dissolved salt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.4. Extractive distillation with ionic liquid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.5. Extractive distillation with hyperbranched polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.6. Summary of extractive distillation with different separating agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.4. Liquidliquid extraction-fermentation hybrid (extractive fermentation) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.5. Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.5.1. Vapor-phase adsorption of water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.5.2. Liquid-phase adsorption of water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.5.3. Advantages and disadvantages of adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.6. Membrane separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.6.1. Hydrophilic membrane for removal of water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.6.2. Hydrophobic membrane for removal of ethanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.6.3. Membrane pervaporation-bioreactor hybrid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.6.4. Vacuum Membrane Distillation (VMD) bioreactor hybrid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
Among the variety of possible products from the biorefinery, liquid transportation fuels in the form of ethanol (or what
is now referred to as bioethanol) is rapidly gaining significance.
Bioethanol is likely to be a prominent product for future biorefineries; hence this review will focus on separation technologies
incorporating bioethanol as a principal product.
There has been an increasing interest in biomass derived
ethanol due to the rapid increase in the price of crude oil and the
perceived strength of the global demand of petroleum. There
are many advantages in using bioresource derived ethanol as
a liquid transportation fuel. Bioethanol blended with gasoline
extends crude oil utilization, reduces reliance on oil imports and
help mitigate increasing oil prices. The higher oxygen content
of ethanol results in relatively cleaner combustion and has long
been used as an additive in gasoline to reduce urban smog and
other environmental pollution problems. Agricultural sources
such as corn or sugar cane are annual crops which sequester
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 biomassto-ethanol biorefinery and integrated lignocellulosic biomassto-ethanol and other co-products including the concept of
integrated forest biorefinery.
with enzymes, fermentation of the sugars to ethanol with yeast,

followed by distillation and dehydration processes of ethanol.
The solids from the distillation bottom are dried to obtain
distillers dried grains with protein (DDG) as an animal feedstuff [2]. Based on the conventional dry mill process, a few
modified dry-grind processes have been developed by recovering germ or both germ and fiber before fermentation. As an
example, the Quick Germ process recovers germ prior to fermentation (Fig. 1) [3]. Recently, another modified dry-grind
process, which allows separation of non-fermentable corn components such as germ and fiber for further reduction of cost,
was developed by Taylor and Singh [4]. In their process, corn
kernels are treated with anhydrous ammonia gas, so the kernel components become loose and thus germ and fiber can
be readily recovered as value-added co-products for food or
feedstuff.
In the wet mill process (Fig. 2), corn is cleaned, steeped,
de-germed to obtain germ from which corn oil is extracted,
defibered to obtain fiber, and subjected to separation of gluten
1.1. Corn-to-ethanol biorenery

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 coproducts such as fiber, germ and gluten by pre-processing prior
to fermentation to ethanol, thus it is more capital- and energyintensive [2]. The conventional dry mill consists of grinding,
cooking, liquefaction, saccharification of the starch to sugars
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Fig. 1. Modified corn dry-grind (Quick Germ) process [3].
wastewater treatment;
pre-extraction of hemicellulose and separation of hemicellulose from other components in the extract when considering
separate fermentation of pentoses and hexoses.
1.3. Integrated lignocellulose/forest biorenery (ILCB)
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, distillation 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 biorenery
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, pretreatment and conditioning/detoxification, saccharification and
co-fermentation, product separation and purification, wastewater 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;
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 encountered severe competition from overseas, leading to mergers and
significant downsizing [8]. Thus, a new conceptthe forest
biorefinery based on the existing pulp mills was proposed to produce 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 todays 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 hemicellulose 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.
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 additional 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 modified 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.
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$ 0.530.66/kg) than that of
DDG (US$ 0.130.20/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 fermentation 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 ber
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 abundant in hemicellulose (xylose and other pentose sugars). Both
hexose and pentose can be hydrolyzed by dilute acid hydrolysis 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 manufacture 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 liquid 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 510% solids loadings obtained much higher pentosan recovery than with steam
at 210220 C and >50% solids loadings. In addition, the liquid 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 hexane [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 cornethanol 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 difference, and washing the recovered fiber, etc. [15,19]. Experimental
results show that the quick fiber yields are 67%, corresponding
to 4660% of the total fiber recovered by the wet mill process
[15].
2.1.3. Extraction of zein

Zein which is prolamine (gluten)-rich, water insoluble protein 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 4550% 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$ 1040/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 settling 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 biorenery
In conventional kraft pulping processes, most of the hemicellulose 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 hemicellulose 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, preseparation 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 (3550 of dry weight), hemicellulose (2035%) and
lignin (1025%). Conversion of lignocellulosic materials to
higher value products requires fractionation of the material into
its components: lignin, cellulose, and hemicellulose. Hemicellulose 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
essential feature of pretreatment processes for biological conversion to ethanol or other products [28]. To date, a variety
of effective pretreatment methods to hydrolyze and fractionate hemicellulose components have been investigated, including
dilute acid pretreatments [2932], liquid hot water extraction
[3335], steam explosion-based extraction [3642], dilute acidsteam explosion [43] and alkaline extraction [4446]. Ammonia
fiber/freeze explosion (AFEX) is another well-known pretreatment. 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 hemicellulose, 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 [4446]. In the following, dilute acid pretreatment, liquid hot water extraction, steam explosion-based
extraction, dilute acidsteam explosion and alkaline extraction
will be discussed.
Dilute sulfuric acid pretreatment, with pH control by ammonia 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 (0.51.0% sulfuric) at moderate temperatures
(140190 C) effectively can recover most of the hemicellulose
as dissolved sugars [29].
Higher temperatures (200230 C) water extraction can completely 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 extraction temperature at 150170 C, and the extraction time with
1530 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 extraction, the aqueous process gave almost 90% recovery of xylose,
superior to steam explosion-based extraction [34].
Steam explosion is an effective pretreatment for hemicellulose hydrolysis [3942]. 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 hemicellulose and lignin, can be recovered with alkali extraction [41].
Shimizu et al. [39] performed steam-explosion of various species
of hardwood chips at 180308 C for 120 min, leading to partial hydrolysis of hemicellulose, and the resulting sugars can
then be extracted with water. The xylose yield was 1020% 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 explosion 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 different 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 investment [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 acidsteam
explosion method for biomass treatment. Corn stover was subjected to 1 wt% H2 SO4 for 70840 s in a steam explosion reactor
at 160, 180, and 190 C. The obtained yields of xylose were
6377% of theoretical at 160180 C, and more than 90% at
190 C.
NDiaye 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 fractionation system [47], allows the integration of extrusion, cooking,
liquidsolid 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].
Fig. 6. Hemicelluloses recovery process [45].
was subjected to a NaOH (1%)ethanol (70%) solution to solubilize 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 extraction with toluene-ethanol mixture (2:1, v/v), followed by partial
delignification with an acidic NaCl solution, hemicelluloses
exaction with 1.58.5% NaOH leading to 65.689.3% solubilization of the original hemicelluloses, filtration of the slurry
obtained into solid (cellulose) and filtrate (hydrolyzates), neutralization of the hydrolyzates to pH 5.5, and precipitation of
hemicelluloses in 95% EtOH, and filtration, washing and drying
of hemicelluloses.
From Figs. 57, it is found that alkali extraction with NaOH
is used in all these three processes, and this method is effective in extraction of hemicelluloses from hardwood. Since the
hemicelluloses concentration of filtered hydrolyzates is very
low, e.g., 23% depending on the solid/solvent ratio used, it
is very important to concentrate hemicelluloses in order for efficient subsequent fermentation into ethanol or xylitol, or to obtain
Fig. 7. Separation of hemicellulose and cellulose from fast-growing poplar wood

[46].
pure hemicelluloses for other use, for example, in making new

bio-based materials. It is also found that the method of precipitation 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 55.5 suitable for precipitation of hemicelluloses with
ethanol. In this process, ethanol and acid are additional chemicals required and additional equipments for recovery of ethanol
is necessary, thus leading to increase in production and capital 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 representing 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 molecular 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, producing hemicelluloses with smaller molecular weights. Thus, with
ultrafiltration for these hydrolyzates, the hemicelluloses retention 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 separating hemicelluloses from hydrolyzates by alkaline procedure.
They investigated the performance of four polymeric nanofiltration 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 cutoff (MWCO) of 200300 and 200250 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 hemicelluloses where pre-filtration units with a screen size of 400650
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 procedure 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
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 standard conditions. Results showed that with these two approaches
the pulp yield decreased 57%, 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 delignification 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 antioxidants (phenolics or polyphenolics) which could be used as a
cheap, renewable food additive, can also be produced from lignocellulosic 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 2.55% H2 SO4
at a liquid/solid ratio of 8:1 g/g and 100130 C. The resulting
slurry was vacuum-filtered into a hydrolyzates and a solid consisting 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 lignocelluloses, 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 microorganisms 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 detoxification 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 derivatives 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 compounds 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 fermentation, in addition to optimization of the pretreatment and
hydrolysis process for minimizing formation of the hydrolysis byproducts (inhibitors), it is necessary to remove inhibitors
(detoxify hydrolyzates) prior to fermentation or in situ detoxification. The detoxification can be either chemical, physical, or
biological [56]. The most commonly used methods for detoxification of hydrolyzates before fermentation are: evaporation [57],
solvent extraction [25,26,58], overliming with calcium hydroxide [54,59], activated charcoal [54,6062], ion exchange resins
[54,62], and enzymatic detoxification [63,64].
Evaporation is a simple procedure to remove acetic acid, furfural 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].
In the overliming process, the hydrolyzate is detoxified by

addition of Ca(OH)2 to adjust the pH to 910, leading to precipitation 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 experiments to observe the effect of different operating variables, i.e.,
hydrolyzate concentration, adsorbent charge (hydrolyzate: charcoal 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 elimination 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 phenoloxidase 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 detoxification procedures. For instance, Cantarella et al. [59] made
a comparison between Ca(OH)2 overliming, water rinsing,
waterethyl acetate two-phase contacting, and in situ detoxification with high level yeast inocula, for the purpose of
eliminating the inhibition problem in saccharification of cellulose from steam-exploded (SE) poplar wood to glucose by
cellulases and fermentation of glucose to ethanol by S. cerevisiae (Bakers yeast). The water-rinsing treatment removed
water-soluble inhibitors, thus enhanced the enzymatic hydrolysis 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 comparison showed that overliming with Ca(OH)2 is the most efficient
method among those investigated.
Most recently, Chandel et al. [54] investigated the detoxification of sugarcane bagasse hydrolyzate to improve ethanol
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 efficient 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 detoxification 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 guilliermondii 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 distillation (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 difficult 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
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) operation 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 usually dilute aqueous solution containing about 512 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 ethanolwater in a single distillation column. In general, for the solution containing 1085 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 separation of dilute ethanolwater 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 distillation, then the resulting ethanol is further dehydrated in order
to achieve anhydrous ethanol by employing azeotropic distillation, extractive distillation, liquidliquid 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 following.
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 closeboiling mixtures or azeotrope.
The AD system typically consists of two distillation columns
for dehydration of 92.4 wt% ethanol solution from the OD column:
(1) A dehydration column (azeotropic column) for further concentration in the presence of entrainer.
(2) An entrainer recovery column (stripping column) for separation of entrainer from the product stream.
In the dehydration column, ethanol (>99 wt%) exits from the bottoms, 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 [7073]. The process flow sheet is
shown in Fig. 10.
The commonly used entrainers for breaking binary
ethanolwater azeoptropes by heterogeneous azeoptropic distillation 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 heterogeneous azeotropic distillation for ethanol dehydration. For
many years, however, benzene has been substituted by other solvents because of its carcinogenic effect. Currently, cyclohexane
is one of the most used entrainers for this separation [77]. However, 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.
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 temperatures. The ethanolwater azeotrope can be eliminated or broken
down to produce anhydrous ethanol by only lowering the operation 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 component, called entrainer, which forms a ternary azeotrope with
the two components to be separated and thus changes their rela-
Fig. 10. Flow sheet of two-column process for ethanol dehydration [72,73].
11
4.3. Extractive distillation (ED)

Like AD, ED is a vaporliquid 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 commonly employed in chemical industry to separate close boiling
point or azeotropic mixtures. The third component added as separating agent can be liquid solvent, ionic liquid, dissolved salt,
a mixture of volatile liquid solvent and dissolved salt, or hyperbranched 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 (extractive 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 extractive distillation for ethanol dehydration is ethylene glycol, with
which anhydrous ethanol could be produced from the fermentation 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 ethanolwater 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 ethanolsolvent mixture 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).
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. ethanolwater system, a dissolved
salt can be added as a separating agent into extractive distillation where the salt dissolved into the liquid so as to enhance
considerably the relative volatility of the more volatile component 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 distillation for ethanol dehydration are potassium acetate [8082],
sodium acetate [83] and calcium chloride [68,79,84]. Cook and
Furter [81] studied the extractive distillation process with potassium acetate as separating agent in a pilot-scale bubble-cap tray
column, and found that the ethanolwater 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 extractive distillation with salts is more efficient in ethanolwater
separation. Barba et al. [84] compared the extractive distillation using CaCl2 as separating agent, in the aspect of the energy
requirement, with azeotropic distillation (using benzene, pentane and diethyl ester), extractive distillation (using ethylene
Fig. 13. Typical simplified PFD of the extractive distillation with dissolved salt
[80].
12
glycol or gasoline), solvent extraction, and membrane pervaporation. 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 consumption) 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 extractive 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 fermentation 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 potassium 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 evaporator and a spray dryer, and then recycled to the column. In the
second, dilute ethanol solution is concentrated firstly by conventional distillation, and the resulting concentrated ethanol is
then fed to the extractive distillation column followed by a single 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 process. 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 combination of both liquid extractant and dissolved salt can be used
as separating agent in extractive distillation for ethanol purification, 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 [8789] had also investigated the ED process

for ethanol dehydration with mixtures of solvent liquid and various 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 1.94.15, 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 vaporliquid equilibria of three systems including ethanolwater, ethanolwaterethylene glycol,
and ethanolwaterethylene glycolCaCl2 , at finite concentration 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 ethanolwater 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 promising separating agents for extractive distillation of ethanolwater
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 tetrafluoroborate ([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 volatility 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-
13
Seiler et al. [95] studied the phase equilibria of ternary

ethanolwaterpolymers systems, including vaporliquid,
liquidliquid and solidliquidliquid equilibria. It is found
that the commercially available hyperbranched polyesters and
hyperbranched polyesteramides can break the ethanolwater
azeotrope. The most tested hyperbranched polymer as entrainer
for extractive distillation of the ethanolwater mixture is hyperbranched 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 conventional ED process [93].
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, hyperbranched polymers have the features of remarkable selectivity
and capacity, low viscosity and thermal stability. Therefore,
they were recently suggested as entrainers in extractive distillation 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 measured show that polymeric entrainers, e.g., Poly(ethylene glycol)
at 10 wt% and poly(acrylic acid) at 0.45 wt%, can break the
ethanolwater azeotrope for ethanol dehydration.
4.3.6. Summary of extractive distillation with different

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 pollution of distillate by separating agents, thus requires less energy
consumption. In addition, the recent development of halogenfree and hydrolysis-stable IL such as [BMIM][octylsulfate]
(ECOENGTM 418) brings some promise [93]. Therefore, extractive distillation with IL and hyperbranched polymers represent
two most promising novel separations.
4.4. Liquidliquid extraction-fermentation hybrid
(extractive fermentation)
Liquidliquid 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
Less energy consumption than azeotropic distillation because of

the high boiling point of the added solvent; flexible selection of
the possible solvents.
High production capacity and low energy assumption due to its
smaller solvent ratio; does not contaminate the overhead
product due to its non-volatility; environment-friendly and no
any safety and health hazards.
Integrates the advantages of both liquid solvent (easy operation)
and dissolved salt (high separation ability).
Very high solvent/feed mass ratio, up

to 58, leading to much consumption
of energy.
Potential problems in dissolution,
transport and recycle of salt; potential
jam and erosion to equipment.
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
(1) IL cannot pollute the distillate due to their non-volatility; (2)

considerable reduction of required heat duties because of their
non-volatility, high selectivities and capacities, especially a
larger variety of feasible IL regeneration options; (3) ILs
properties (solubility, capacity, selectivity, viscosity and
thermal stability) can be tailored; (4) Only one distillation
column required, representing low energy consumption.
(1) Excellent separation efficiency and selectivity; (2) entrainers
can not contaminate the top product.
Less availability of suitable salts;

potential corrosion of salts to the
equipment; possible contaminant of
the overhead product by liquid
extractants.
IL containing halogen anions is
expensive and has insufficient
stability to hydrolysis for long-term
applications; small amounts of
corrosive and toxic substance (HF)
forms during the hydrolysis.
14
ous fermentation broth with low energy requirement [68].

Liquidliquid extraction is generally combined with fermentation, 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 separation 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 isooctyl alcohol [100], nonanoic acid [101], etc. In the continuous
fermentation of ethanol with the thermophilic, anaerobic bacterium 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 extraction is two times that of fermentations without in situ extraction
[96]. Oleyl alcohol was also utilized in a simultaneous saccharification 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 extractant 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 fermentation 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 liquidliquid extraction 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, followed 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 extractive 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 ethanolwater
separation: the liquid-phase adsorption of water from the fermentation 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 ethanolwater mixtures include inorganic 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 ethanolwater
mixture [107]. 3A zeolite molecular sieves which has a nominal
pore size of 3 Angstroms (0.30 nm) can be used for dehydration of polar liquids such as ethanol. Water molecules, with an
approximate molecular diameter of 0.28 nm, can easily penetrate the pores of the molecular sieve adsorbent, while ethanol,
with an approximate molecular diameter of 0.44 nm, is simultaneously retained [103]. Recently, Al-Asheh et al. [104] also
studied ethanolwater separation using molecular sieves (3A,
4A and 5A).
In terms of application, inorganic adsorbents such as molecular sieves, lithium chloride, and silica gel have been successfully
applied as dehydration desiccants in fermentation ethanol plants

[105].
4.5.1.2. Bio-based adsorbents. The potential bio-based adsorbents include cornmeal, cracked corn, starch, corn cobs, wheat
straw, bagasse, cellulose, hemicellulose, wood chips, other
grains, etc. [108]. Basically, bio-based adsorbents can be classified 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 selectively 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 [67,102,104,109,110,112116].
The most potential starch-based adsorbents have been investigated. The adsorption of water from ethanolwater vapor
mixture on a variety of starchy materials, such as cooked corn,
corn grits and starch, which have different mean particle diameters and different relative amounts of amylose and amylopectin,
had been experimentally measured at 90 C. The results demonstrate 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 ethanolwater azeotrope to obtain anhydrous
ethanol. It was found that the factors influencing the adsorption 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 0.140.025 g water g/g adsorbent. The desorption (regeneration) operation was improved
by employing a fluidized bed instead of the general fixedbed, 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 capacity and selectivity of cornmeal for ethanol dehydration on a
pilot-scale fixed-bed adsorber at temperatures of 82100 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 0.50.6 under the temperature of 91 C. They [109] also fit the experimental data into
the adsorption equilibrium models, including those based on
Polanyi adsorption potential theory and Sircars model, and
found that the models are in good agreement with the experimental data.
With respect to ligno-cellulosic materials as adsorbents, the
lignocellulosic adsorbents bagasse, rice straw, and microcrystalline cellulose powder had been investigated for adsorption
of water in the vapor mixture with 8090% 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 ethanolwater
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 adsorption 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
ethanolwater 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 adsorption capacity of water increases with increasing water content
in the ethanolwater solution. Compared with silica gel and
molecular sieves, these starch-based adsorbents have lower nonequilibrium adsorption capacity at water concentration below
10 wt%. At the concentrations of above 10 wt%, however, the
starch-based adsorbents have similar non-equilibrium adsorption 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 porosity and surface properties of starch resulted in materials with
enhanced water sorption properties compared to the native material [105].
More recently, a thermodynamic and kinetic study on liquid
phase adsorption of water from ethanolwater 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 distillation, 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 regeneration 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 regeneration step.
16
4.6. Membrane separation
Table 2. lists some PV separation factors for the hydrophilic

zeolite membranes.
For a few decades, membrane pervaporation (PV) has been

considered as one of the most effective and energy-saving process 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 mechanism. 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, solution 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 general, most membranes are hydrophilic or water permselective
due to waters 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 membranes have recently become commercially available in
chemical reaction engineering, because of their superior temperature stability and mechanical strength [119]. For example,
tubular zeolite and silica membranes are still stable to temperatures of above 300 C and feed pressures of above 100 bar.
The tabular Zeolite NaA membrane module, having the pervaporation flux of ca. 2.35 kg m2 h1 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 ethanolwater with a
NaA-zeolite membrane for a wide range of operation conditions. 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].
4.6.1.2. Polymeric membrane. So far, a large number of polymeric pervaporation membranes, for example cellulose acetate
butyrate membrane [126], PDMS (polydimethylsiloxane) membrane [127], PDMS-PS IPN supported membranes [128],
aromatic polyetherimide membranes [129] have been investigated. OBrien and Craig [127] utilized the commercially
available PDMS membrane module in a continuous fermentation/membrane pervaporation system to produce ethanol,
resulting in permeate of 2023 wt% while 46 wt% level was
retained in stirred tank fermentor. The selectivity ranged from
1.8 to 4.1. Ruckenstein et al. utilized polydimethylsiloxanepolystyrene 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 filmforming 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]. Schue et al. [129] investigated the sorption, diffusion and
pervaporation of ethanol solution in homogeneous and composite aromatic polyetherimide membranes. The performance of
these membranes was found dependent on the permeate diffusivity 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 polymerpolymer composite
membranes, such as polystyrenesulfonate/alumina [130], polyelectrolytes multi-layer [131], KA zeolite-incorporated crosslinked 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 Martin 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].
Table 2
PV performance of zeolite membranes for separating ethanolwater mixtures
Membrane
xw (wt% water)
T (K)
Flux (kg m2 h1 )
w/e
Ref.
Zeolite T
Zeolite T
NaA
NaA
NaX
NaY
10
10
5
10
10
10
348
348
368
348
348
348
1.25
1.10
2.35
2.15
1.91
1.59
2,200
900
5,000
10,000
170
130
[122]
[123]
[106]
[124]
[125]
[125]
Where w/e is the separator factor of water over ethanol.
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-comethyl 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 threelayer zeolite-embedded PVA composite membranes have been
successfully fabricated using different zeolites with a loading of 20 wt%, including 3A, 4A, 5A, NaX, NaY, silicalite
and beta. Results showed that the addition of zeolite resulted
in decrease in activation energies for water and ethanol, and
hence increase in separation selectivity [132]. The hydrophilic
PVA is chosen as the polymeric material because it is the
most attractive and economical polymer material for ethanol
dehydration [134].
Dong et al. prepared a hollow-fiber composite membrane,
PVA-SA blend, supported by a polysulfone (PS) hollow-fiber
ultrafiltration membrane for pervaporation ethanol dehydration.
With ethanol concentration at 90 wt% in the feed at 45 C,
the separation factors and permeation fluxes were 384 and
384 g/m2 h, respectively [118].
4.6.2. Hydrophobic membrane for removal of ethanol
So far, many researchers have investigated a number of
hydrophobic membranes, including (1) the most potential
hydrophobic polymeric membranes poly(1-trimethylsilyl-1propyne) (PTMSP) [135,136] and poly(dimethyl siloxane)[PDMS] [137139] membranes, (2) hydrophobic zeolite
membranes [140142], and (3) the potential composite membranes, i.e., silicalite-PDMS membranes which consists of
silicatlite-1 particles dispersed in PDMS [143145]. In Vanes
recent review [146], the ethanolwater separation factors of
PTMSP and PDMS membranes (polymeric), hydrophobic azeolite membranes, and composite silicate-silicone rubber (PDMS)
membranes are tabulated from a large number of published work
in the literature. Based on literature data, the ethanolwater
separation factors of PDMS, PTMSP, composite membranes,
and zeolite are reported to be in the range of 4.410.8,
926, 759, 12106, respectively. However, the ethanolwater
separation factors in some other cases might exceed these
ranges. For instance, the separation factor of ethanol over
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 general, the ethanolwater separation factors are largely ranked
in the following order: PDMS < PTMSP < composite membranes < 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
[146].
17
Fig. 16. A simplified membrane pervaporation-bioreactor hybrid process [148].
4.6.3. Membrane pervaporation-bioreactor hybrid

Fermentation broth generally contains inhibiting substances
including ethanol product, flavors (phenolics), and other chemicals. This problem can be overcome by combining fermentation
with hydrophobic membrane pervaporation for removal of the
inhibitors from the fermentation broth, as seen in Fig. 16. Hence,
the process can be carried out continuously and the recovered
organic VOCs (ethanol, acetone, butanol, 2-propanol) can be
reused within other processes.
In the real application, a microfiltration membrane is added
before pervaporation to avoid fouling of the hydrophobic membrane. Besides, the ethanol-enriched solution, i.e., the permeate
of the hydrophobic membrane, can be further dehydrated to
produce anhydrous ethanol. The complete process diagram is
illustrated in Fig. 17.
4.6.4. Vacuum Membrane Distillation (VMD) bioreactor
hybrid
Membrane distillation (MD) is an appealing process suitable
for separation of aqueous mixtures. There are four types of MD:
direct contact membrane distillation (DCMD), air gap membrane distillation (AGMD), sweeping gas membrane distillation
(SGMD) and vacuum membrane distillation (VMD). Actually,
VMD is quite similar to pervaporation, the only difference being
that the separation factor here is established by vaporliquid
equilibrium of the feed solution which is not affected by the
membrane used [149].
Similar to Membrane pervaporation-bioreactor hybrid,
VMD-bioreactor hybrid process is also suitable for separation
Fig. 17. A complete membrane pervaporation-bioreactor hybrid process for

ethanol fermentation and dehydration [146].
18
of ethanol and the other inhibitory compounds from fermentation broths. Till now, there has been much reported on this
topic [150152]. 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 todays cornethanol biorefinery
as well as the challenges and opportunities in future cellulosic
ethanol and integrated lignocellulosic biorefinery producing liquid fuels and other co-products. As shown in this review, there
are two key separation steps in the biorefinery that offers challenges and opportunities. First is the separation of fermentation
inhibitors after the pre-extraction of hemicelluloses from lignocellulosic biomass. Here the promising separation technologies
are the three in situ detoxification hybrid processes including
extractive-fermentation, membrane pervaporation-bioreactor,
and VMDbioreactor, 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 different 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 ethanolwater mixture posing challenges
to remove the last amounts of water producing fuel grade
ethanol. For ethanolwater 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 cornethanol 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 nanofiltration represents a promising separation procedure for recovery of
hemicelluloses from hydrolyzates because of its low energy consumption 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.
References
[1] W.R. Morrow, W.M. Griffin, H.S. Matthews, Modeling switchgrass
derived cellulosic ethanol distribution in the united states, Environ. Sci.
Technol. 40 (9) (2006) 28772886.
[2] R.J. Bothast, M.A. Schlicher, Biotechnological processes for conversion
of corn into ethanol, Appl. Microbiol. Biotechnol. 67 (2005) 1925.
[3] V. Singh, S.R. Eckhoff, Economics of germ preseparation for dry-grind
ethanol facilities, Cereal Chem. 74 (4) (1997) 462466.
[4] New Milling Methods Improve Corn Ethanol Production, website:
http://www.agclassroom.org/teen/ars pdf/tech/2004/07milling.pdf (Nov.
29, 2006).
[5] L.A. Kszos, Bioenergy from switchgrass: reducing production costs
by improving yield and optimizing crop management, website:
http://www.ornl.gov/webworks/cppr/y2001/pres/114121.pdf (Nov. 29,
2006).
[6] C.E. Wyman, Ethanol production from lignocellulosic biomass: overview,
in: C.E. Wyman (Ed.), Handbook on Bioethanol: Product Ion and Utilization, Taylor & Francis, Washington, DC, 1996, pp. 118.
[7] A. Aden, M. Ruth, K. Ibsen, J. Jechura, K. Neeves, J. Sheehan, et al., Lignocellulosic biomass to ethanol process design and economics utilizing
co-current dilute acid prehydrolysis and enzymatic hydrolysis for corn
stover, NREL report TP-510-32438, 2002.
[8] A.V. Heiningen, Converting a kraft pulp mill into an Integrated
Forest BioRefinery (IFBR), http://www.forestbioproducts.umaine.edu/
ForestBiorefinery.pdf (Nov. 29, 2006).
[9] D.T. Leathers, Enzymatic saccharification of defatted corn germ, Biotechnol. Lett. 26 (3) (2004) 203207.
[10] P. Blanchard, Wet milling, in: Technology of Corn Wet Milling and Associated Processes, Elsevier Science, Amsterdam, 1992, pp. 9293.
[11] V. Singh, S.R. Eckhoff, Effect of soak time, soak temperature, and lactic
acid on germ recovery, Cereal Chem. 73 (1996) 716720.
[12] B.S. Dien, R.B. Hespell, L.O. Ingram, R.J. Bothast, Conversion of corn
milling fibrous co-products into ethanol by recombinant Escherichia coli
strains KO 11 and SL 40, World J. Microbiol. Biotechnol. 13 (6) (1997)
619625.
[13] D.J. OBrien, G.E. Senske, M.J. Kurantz, J.C. Craig Jr., Ethanol recovery
from corn fiber hydrolyzate fermentations by pervaporation, Bioresour.
Technol. 92 (2004) 1519.
[14] R.A. Moreau, M.J. Powell, K.B. Hicks, Extraction and quantitative analysis of oil from commercial corn, J. Agric. Food Chem. 44 (1996)
21492154.
[15] V. Singh, R.A. Moreau, L.W. Doner, S.R. Eckhoff, K.B. Hicks, Recovery
of fiber in the corn dry-grind ethanol process: a feedstock for valuable
coproducts, Cereal Chem. 76 (6) (1999) 868872.
[16] L.W. Doner, K.B. Hicks, Isolation of hemicellulose from corn fiber by
alkaline hydrogen peroxide extraction, Cereal Chem. 74 (1997) 176181.
[17] S.G. Allen, D. Schulman, J. Lichwa, M.J. Antal, J.M. Laser, L.R. Lynd,
A Comparison between hot liquid water and steam fractionation of corn
fiber, Ind. Eng. Chem. Res. 40 (2001) 29342941.
[18] R.A. Moreau, K.B. Hicks, R.J. Nicolosi, R.A. Norton, Corn fiber oil its
preparation and use, United States Patent 5843499, 1998.
[19] J. Wahjudi, L. Xu, P. Wang, V. Singh, P. Buriak, K.D. Rausch, A.J.
McAloo, M.E. Tumbleson, S.R. Eckhoff, Quick fiber process: effect of
mash temperature, dry solids, and residual germ on fiber yield and purity,
Cereal Chem. 77 (5) (2000) 640644.
[20] R. Shukla, M. Cheryan, Zein: the industrial protein from corn, Ind. Crops
Prod. 13 (3) (2001) 171192.
[21] L.C. Dickey, N. Parris, J.C. Craig, M.J. Kurantz, Separation of maize
particles from alcohol extracts with minimal losses, Ind. Crops Prod. 16
(2002) 145154.
[22] L.C. Dickey, A. McAloon, J.C. Craig, N. Parris, Estimating the cost of
extracting cereal protein with ethanol, Ind. Crops Prod. 10 (2) (1999)
137143.
[23] M. Cheryan. Method and system for extraction of zein from corn, US
Patent 7,045,607, 2006.
[24] V. Heiningen, Hemicellulose extraction and its integration in
pulp production, in: Forest Products Industry of the Future, Quarterly
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
Status Reports, September 30, 2005, U.S. Department of Energy website:

http://www.eere.energy.gov/industry/forest/pdfs/quarterlyhighlights.pdf.
J.M. Cruz, J.M. Dominguez, H. Dominguez, J.C. Parajo, Solvent
extraction of hemicellulosic wood hydrolyzates: a procedure useful for
obtaining both detoxified fermentation media and polyphenols with
antioxidant activity, Food Chem. 67 (1999) 147153.
J. Gonzalez, J.M. Cruz, H. Dominguez, J.C. Parajo, Production of
antioxidants from Eucalyptus globulus wood by solvent extraction of
hemicellulose hydrolyzates, Food Chem. 84 (2004) 243251.
B.C. Saha, Hemicellulose bioconversion, J. Ind Microbiol. Biotechnol.
30 (2003) 279291.
N. Mosier, C. Wyman, B. Dale, R. Elander, Y.Y. Lee, M. Holtzapple, M.
Ladisch, Features of promising technologies for pretreatment of lignocellulosic biomass, Bioresour. Technol. 96 (2005) 673686.
D.R. Knappert, H.E. Grethlein, A.O. Converse, Partial acid hydrolysis
of poplar wood as a pretreatment for enzymatic hydrolysis, Biotechnol.
Bioeng. 11 (1981) 6777.
Pretreatment of biomass, in: T.-A. Hsu, C.E. Wyman (Eds.), Handbook
on Bioethanol Production and Utilization, Applied Energy Technology
Series, Taylor & Francis, Washington DC, 1996 (Chapter 10).
Y.Y. Lee, P. Iyer, R.W. Torget, Dilute-acid hydrolysis of lignocellulosic
biomass 65 (1999) 93115.
Q.A. Nguyen, M.P. Tucker, F.A. Keller, F.P. Eddy, Twostage dilute-acid
pretreatment of softwoods, Appl. Biochem. Biotechnol. 84/86 (2000)
561576.
W.S.L. Mok, M.J.J. Antal, Uncatalyzed solvolysis of whole biomass
hemicellulose by hot compressed liquid water, Ind. Eng. Chem. Res. 31
(1992) 1157.
M. Saska, E. Ozer, Aqueous extraction of sugarcane bagasse hemicellulose and production of xylose syrup, Biotechnol. Bioeng. 45 (1995)
517523.
J.R. Weil, M. Brewer, R. Hendrickson, A. Sarikaya, M.R. Ladisch,
Continuous pH monitoring during pretreatment of yellow poplar wood
sawdust by pressure cooking in water, Appl. Biochem. Biotechnol. 7072
(1998) 99111.
H.H. Brownell, J.N. Saddler, Steam pretreatment of lignocellulosic material for enhanced enzymatic hydrolysis, Biotechnol. Bioeng. 29 (1987)
228235.
M. Heitz, E. Capek-Menard, P.G. Koeberle, J. Gagne, E. Chornet, R.P.
Overend, J.D. Taylor, E. Yu, Fractionation of Populus tremuloides in the
pilot plant scale: optimization of steam pretreatment conditions using
STAKE II technology, Bioresour. Technol. 35 (1991) 2332.
J.R. Weil, A. Sarikaya, S.-L. Rau, J. Goetz, C.M. Ladisch, M. Brewer, R.
Hendrickson, M.R. Ladisch, Pretreatment of yellow poplar sawdust by
pressure cooking in water, Appl. Biochem. Biotechnol. 68 (1/2) (1997)
2140.
K. Shimizu, K. Sudo, H. Ono, M. Ishihara, T. Fujii, S. Hishiyama,
Integrated process for total utilization of wood components by steamexplosion pretreatment, Biomass Bioenergy 14 (3) (1998) 195203.
M. Ibrahim, W.G. Glasser, Steam-assisted biomass fractionation. Part III:
a quantitative evaluation of the clean fractionation concept, Bioresour.
Technol. 70 (1999) 181192.
T. Josefsson, H. Lennholm, G. Gellerstedt, Steam explosion of aspen
wood. Characterisation of reaction products, Holzforschung 56 (2002)
289297.
C. Cara, E. Ruiz, I. Ballesteros, M.J. Negro, E. Castro, Enhanced enzymatic hydrolysis of olive tree wood by steam explosion and alkaline
peroxide delignification, Process Biochem. 41 (2006) 423429.
M.P. Tucker, K.H. Kim, M.M. Newman, Q.A. Nguyen, Effects of temperature and moisture on dilute-acid steam explosion pretreatment of corn
stover and cellulase enzyme digestibility, Appl. Biochem. Biotechnol.
105 (2003) 165177.
S. NDiaye, L. Rigal, P. Larocque, P.F. Vidal, Extraction of hemicelluloses from poplar, Populus tremuloides, using an extruder-type twin-screw
reactor: a feasibility study, Bioresour. Technol. 57 (1996) 6167.
I. Gabrielii, P. Gatenholm, W.G. Glasser, R.K. Jain, L. Kenne, Separation, characterization and hydrogel-formation of hemicellulose from
aspen wood, Carbohydr. Polym. 43 (2000) 367374.
19
[46] R.C. Sun, J.M. Fang, J. Tomkinson, Z.C. Geng, J.C. Liu, Fractional isolation, physico-chemical characterization and homogeneous esterification
of hemicelluloses from fast-growing poplar wood, Carbohydr. Polym. 44
(2001) 2939.
[47] S. NDiaye, L. Rigal, Factors influencing the alkaline extraction of poplar
hemicelluloses in a twin-screw reactor: correlation with specific mechanical energy and residence time distribution of the liquid phase, Bioresour.
Technol. 75 (2000) 1318.
[48] A.J. Ragauskas, M. Nagy, D.H. Kim, C.A. Echert, J.P. Hallett, C.L.
Liotta, From wood to fuels: integrating biofuels and pulp production,
Ind. Biotechnol. 2 (2006) 5565.
[49] S. Hurlen, A. Olsen, Removal of hemicellulose from steeping lye by
ultrafiltration, in: Proc. 5th International Dissolving Pulps Conference,
1980, pp. 5458.
[50] R. Schlesinger, G. Gotzinger, H. Sixta, A. Friedl, M. Harasek, Evaluation
of alkali resistant nanofiltration membranes for the separation of hemicellulose from concentrated alkaline process liquors, Desalination 192
(2006) 303314.
[51] O.F. Ali, J.T. Cenicola, J. Li, J.D. Taylor, Process for producing alkaline
treated cellulosic fibers, United States Patent 6,896,810 (2005).
[52] M. von Sivers, G. Zacchi, L. Olsson, B. Hahn-Hagerdal, Cost analysis
of ethanol production from willow using recombinant Escherichia coli,
Biotechnol. Prog. 10 (1994) 555560.
[53] E. Palmqvist, B. Hahn-Hagerdal, Fermentation of lignocellulosic
hydrolyzates II: inhibitors and mechanisms of inhibition, Bioresour. Technol. 74 (2000) 2533.
[54] A.K. Chandel, R.K. Kapoor, A. Singh, R.C. Kuhad, Detoxification of
sugarcane bagasse hydrolyzate improves ethanol production by Candida
shehatae NCIM 3501, Bioresour. Technol. 98 (10) (2007) 19471950.
[55] C. Luo, D.L. Brink, H.W. Blanch, Identification of potential fermentation
inhibitors in conversion of hybrid poplar hydrolyzate to ethanol, Biomass
Bioenergy 22 (2002) 125138.
[56] E. Palmqvist, B. Hahn-Hagerdal, Fermentation of lignocellulosic
hydrolyzates I: inhibition and detoxification, Bioresour. Technol. 74
(2000) 1724.
[57] A. Converti, J.M. Dominguez, P. Perego, S.S. Silva, M. Zilli, Wood
hydrolysis and hydrolyzate detoxification for subsequent xylitol production, Chem. Eng. Technol. 23 (2000) 10131020.
[58] J.J. Wilson, L. Deschatelets, N.K. Nishikawa, Comparative fermentability of enzymatic and acid hydrolyzates of steam-pretreated aspenwood
hemicellulose by Pichia stipitis CBS 5776, Appl. Microbiol. Biotechnol.
31 (1989) 592596.
[59] M. Cantarella, L. Cantarella, A. Gallifuoco, A. Spera, F. Alfani, Comparison of different detoxification methods for steam-exploded poplar wood
as a substrate for the bioproduction of ethanol in SHF and SSF, Process
Biochem. 39 (2004) 15331542.
[60] J.C. Parajo, H. Dominguez &, J.M. Dominguez, Charcoal adsorption of
wood hydrolyzates for improving their fermentability: influence, Bioresour. Technol. 57 (1996) 179185.
[61] L. Canilha, J.B. de, A. e Silva, A.I.N. Solenzal, Eucalyptus hydrolyzate
detoxification with activated charcoal adsorption or ion-exchange resins
for xylitol production, Process Biochem. 39 (2004) 19091912.
[62] M.L.M. Villarreal, A.M.R. Prata, M.G.A. Felipe, J.B. Almeida E Silva,
Detoxification procedures of eucalyptus hemicellulose hydrolyzate for
xylitol production by Candida guilliermondii, Enzyme Microb. Technol.
40 (1) (2006) 1724.
[63] L.J. Jonsson, E. Palmqvist, N.-O. Nilvebrant, B. Hahn-Hagerdal, Detoxification of wood hydrolyzates with laccase and peroxidase from the
white-rot fungus Trametes versicolor, Appl. Microbiol. Biotechnol. 49
(1998) 691697.
[64] T. Gutierrez, L.O. Ingram, J.F. Preston, Purification and characterization
of a furfural reductase (FFR) from Escherichia coli strain LYO1an
enzyme important in the detoxification of furfural during ethanol production, J. Biotechnol. 121 (2006) 154164.
[65] C. van Zyi, B.A. Prior, J.C. du Preez, Acetic acid inhibition of d-xylose fermentation by Pichia stipitis, Enzyme Microb. Technol. 13 (1991) 8286.
[66] C. Martin, M. Galbe, C.F. Wahlbom, B. Hahn-Hagerdal, L.J. Jonsson,
Ethanol production from enzymatic hydrolyzates of sugarcane bagasse
20
[67]
[68]
[69]
[70]
[71]
[72]
[73]
[74]
[75]
[76]
[77]
[78]
[79]
[80]
[81]
[82]
[83]
[84]
[85]
[86]
[87]
[88]
[89]
[90]
[91]
[92]
[93]

using recombinant xylose-utilising Saccharomyces cerevisiae, Enzyme
Microb. Technol. 31 (2002) 274282.
J.P. Crawshaw, J.H. Hills, Sorption of ethanol and water by starchy materials, Ind. Eng. Chem. Res. 29 (1990) 307309.
C. Black, Distillation modeling of ethanol recovery and dehydration processes for ethanol and gasohol, Chem. Eng. Prog. 76 (1980) 7885.
C. Black, Azeotropic disitllation results from automatic computer calculations, in: R.F. Gould (Ed.), Extractive and Azeotropic Distillation,
1972.
F.-M. Lee, R.H. Pahl, Solvent screening study and conceptual extractive distillation process to produce anhydrous ethanol from fermentation
broth, Ind. Eng. Chem. Process Des. Dev. 24 (1985) 168172.
J.W. Kovach III, W.D. Seider, Heterogenous azeotropic distillaionhomotopy-continuation methods, Comput. Chem. Engng. 11 (6) (1987)
593605.
A. Chianese, F. Zinnamosca, Ethanol dehydration by azeotropic distillation with a mixed-solvent entrainer, Chem. Eng. J. 43 (1990) 5965.
W.L. Luyben, Control of a multiunit heterogeneous azeotropic distillation
process, AIChE J. 52 (2) (2006) 623637.
S.K. Wasylkiewicz, L.C. Kobylka, F.J.L. Castillo, Synthesis and design
of heterogeneous separation systems with recycle streams, Chem. Eng. J.
92 (2003) 201208.
L.R. Partin, A case study in applying pc software: Fowsheet synthesis, in:
Proceedings of Chemputers 4: Computer Tools for the Chemical Process
Industries, Houston, Texas, 1113 March, 1996.
G. Feng, L.T. Fan, F. Friedler, Synthesizing alternative sequences via a
P-graph-based approach in azeotropic distillation systems, Waste Manag.
20 (2000) 639643.
V. Gomis, A. Font, R. Pedraza, M.D. Saquete, Isobaric vaporliquid
and vaporliquidliquid equilibrium data for the system water +
ethanol + cyclohexane, Fluid Phase Equilibria 235 (2005) 710.
S. Meirelles, H. Weiss, Herfurth, Ethanol dehydration by extractive distillation, J. Chem. Tech. Biotechnol. 53 (1992) 268.
M. Llano-Restrepo, J. Aguilar-Arias, Modeling and simulation of saline
extractive distillation columns for the production of absolute ethanol,
Comput. Chem. Eng 27 (2003) 527549.
W.F. Furter, Extractive distillation by salt effect, in: R.F. Gould (Ed.),
Extractive and Azeotropic Distillation, Advances in Chemistry Series,
vol. 115, 1972, pp. 3545.
R.A. Cook, W.F. Furter, Extractive distillation employing a dissolved salt
as separating agent, Can. J. Chem. Eng. 46 (1968) 119123.
L.R. Lynd, H.E. Grethlein, IHOSR/Extractive distillation for ethanol separation, Chem. Eng. Prog. 80 (1984) 5962.
W.F. Furter, Extractive distillation by salt effect, Chem. Eng. Commun.
116 (1992) 3540.
D. Barba, V. Brandani, G. Giacomo, Hyperazeotropic ethanol salted-out
by extractive distillation, Theoretical evaluation and experimental check,
Chem. Eng. Sci. 40 (1985) 22872292.
R.T.P. Pinto, M.R. Wolf-Maciel, L. Lintomen, Saline extractive distillation process for ethanol purification, Comput. Chem. Eng. 24 (2000)
16891694.
E.L. Ligero, T.M.K. Ravagnani, Dehydration of ethanol with salt extractive distillation-a comparative analysis between processes with salt
recovery, Chem. Eng. Processing 42 (7) (2003) 543552.
Z.T. Duan, L.H. Lei, R.Q. Zhou, Study on extractive distillation with
salt(I), Petrochem. Technol. (China) 9 (1980) 350353.
L.H. Lei, Z.T. Duan, Y.F. Xu, Study on extractive distillation with salt(II),
Petrochem. Technol. (China) 11 (1982) 404409.
Q.K. Zhang, W.C. Qian, W.J. Jian, Study on extractive distillation with
salt(III), Petrochem. Technol. (China) 13 (1984) 19.
Z. Lei, H. Wang, R. Zhou, Z. Duan, Influence of salt added to solvent on
extractive distillation, Chem. Eng. J. 87 (2002) 149156.
M. Arlt, M. Seiler, C. Jork, T. Schneider, DE Patent No. 10114734 (2001).
Z. Lei, B. Chen, Z. Ding, Special Distillation Processes, first ed., Elsevier,
Amsterdam, 2005.
M. Seiler, C. Jork, A. Kavarnou, W. Arlt, R. Hirsch, Separation of
azeotropic mixtures using hyperbranched polymers or ionic liquids,
AIChE J. 50 (10) (2004) 24392454.
[94] Al-Amer Am, Investigating polymeric entrainers for azeotropic distillation of the ethanol/water and mtbe/methanol systems, Ind. Eng. Chem.
Res. 39 (10) (2000) 39013906.
[95] M. Seiler, D. Kohler, W. Arlt, Hyperbranched polymers: new selective
solvents for extractive distillation and solvent extraction, Sep. Purif.n
Technol. 29 (3) (2002) 245263.
[96] C. Weilnhammer, E. Blass, Continuous fermentation with product recovery by in-situ extraction, Chem. Eng. Technol. 17 (1994) 365373.
[97] J.W. Moritz, S.J.B. Duff, Simultaneous saccharification and extractive
fermentation of cellulosic substrates, Biotechnol. Bioeng. 49 (1996)
504511.
[98] M. Gyamerah, J. Glover, Production of ethanol by continuous fermentation and liquidliquid extraction, J. Chem. Tech. Biotechnol. 66 (1996)
145152.
[99] N. Boluda, V. Gomis, F. Ruiz, H. Bailador, The influence of
temperature on the liquidliquidsolid equilibria of the ternary system water + ethanol + 1-dodecanol, Fluid Phase Equilibria 235 (2005)
99103.
[100] D.P. Koullas, O.S. Umealu, E.G. Koukios, Solvent selection for the extraction of ethanol from aqueous solutions, Sep. Sci. Technol. 34 (11) (1999)
21532163.
[101] T.M. Boudreau, G.A. Hill, Improved ethanolwater separation using fatty
acids, Process Biochem. 41 (2006) 980983.
[102] K.E. Beery, M.R. Ladisch, Adsorption of water from liquid-phase
ethanolwater mixtures at room temperature using starch-based adsorbents, Ind. Eng. Chem. Res. 40 (2001) 21122115.
[103] M.J. Carmo, J.C. Gubulin, Ethanolwater adsorption on commercial 3a
zeolites: kinetic and thermodynamic data, Braz. J. Chem. Eng. 14 (3)
(1997) 110.
[104] S. Al-Asheh, F. Ganat, N. Al-Lagtah, Separation of ethanolwater mixtures using molecular sieves and biobased adsorbents, Chem. Eng. Res.
Des. 82 (A7) (2004) 855864.
[105] K.E. Beery, M.R. Ladisch, Chemistry and properties of starch based
desiccants, Enzyme Microb. Technol. 28 (2001) 573581.
[106] M. Kondo, M. Komori, H. Kita, K. Okamoto, Tubular type pervaporation
module with zeolite NaA membrane, J. Membr. Sci. 133 (1997) 133141.
[107] M.J. Carmo, M.G. Adeodato, A.M. Moreira, E.J.S. Parente Jr., R.S. Vieira,
Kinetic and Thermodynamic study on the liquid phase adsorption by
starchy materials in the alcoholwater system, Adsorption 10 (3) (2004)
211218.
[108] M.R. Ladisch, G.T. Tsao, Vapor phase dehydration of aqueous alcohol
mixtures, U.S. Patent 4 345 973, 1982.
[109] H. Chang, X.-G. Yuan, H.T.A.-W. Zeng, Experimental investigation
and modeling of adsorption of water and ethanol on cornmeal in an
ethanolwater binary vapor system, Chem. Eng. Technol. 29 (4) (2006)
454461.
[110] S.K. Rakshit, P. Ghosh, V.S. Bisaria, Ethanol separation by selective
adsorption of water, Bioprocess Biosyst. Eng. 8 (5/6) (1993) 279282.
[111] M.R. Ladisch, K. Dyck, Dehydration of ethanol: new approach gives
positive energy balance, Science 205 (1979) 898900.
[112] M.R. Ladisch, M. Voloch, J. Hong, P. Bienkowski, G.T. Tsao, Cornmeal
adsorber for dehydrating ethanol vapors, Ind. Eng. Chem. Process Des.
Dev. 23 (1984) 437443.
[113] X. Hu, W. Xie, Fixed-Bed adsorption and fluidized-bed regeneration for
breaking the azeotrope of ethanol and water, Sep. Sci. Technol. 36 (1)
(2001) 125136.
[114] H. Chang, X.-G. Yuan, H. Tian, A.-W. Zeng, Experimental
study on the adsorption of water and ethanol by cornmeal for
ethanol dehydration, Ind. Eng. Chem. Res. 45 (2006) 3916
3921.
[115] J. Berthold, M. Rinaudo, L. Salmen, Association of water to polar groups;
estimations by an adsorption model for ligno-cellulosic materials, Colloids Surf. A: Physicochem. Eng. Aspects 112 (2) (1996) 117129.
[116] T.J. Benson, C.E. George, Cellulose based adsorbent materials for the
dehydration of ethanol using thermal swing adsorption, Chem. Mater.
Sci. 11 (1) (2005) 697701.
[117] D.M. Ruthven, Principles of Adsorption and Adsorption Processes, John
Wiley, New York, 1984.

[118] Y.Q. Dong, L. Zhang, J.N. Shen, M.Y. Song, H.L. Chen, Preparation of
poly(vinyl alcohol)-sodium alginate hollow-fiber composite membranes
and pervaporation dehydration characterization of aqueous alcohol mixtures, Desalination 193 (2006) 202210.
[119] S. Sommer, T. Melin, Zeolite membranes in chemical industry, in: The
2000 18th Annual Membrane Technology/Separations Planning Conference, Boston, Massachusetts, USA, 2000.
[120] D. Shah, K. Kissick, A. Ghorpade, R. Hannah, D. Bhattacharyya, Pervaporation of alcoholwater and dimethylformamidewater mixtures
using hydrophilic zeolite NaA membranes: mechanisms and experimental
results, J. Membr. Sci. 179 (2000) 185205.
[121] Y. Morigami, M. Kondo, J. Abe, H. Kita, K. Okamoto, The first largescale pervaporation plant using tubular-type module with zeolite NaA
membrane, Sep. Purif. Technol. 25 (13) (2001) 251260.
[122] S. Takaki, H. Kita, K.I. Okamoto, Symp. Ser. Soc. Chem. Eng. Jpn. 66
(1998) 90.
[123] Y. Cui, H. Kita, K.-I. Okamoto, Zeolite T membrane: preparation, characterization, pervaporation of water/organic liquid mixtures and acid
stability, J. Membr. Sci. 236 (2004) 1727.
[124] K.I. Okamoto, H. Kita, K. Horii, K. Tanaka, Zeolite NaA membrane:
preparation, single-gas permeation, and pervaporation and vapor permeation of water/organic liquid mixtures, Ind. Eng. Chem. Res. 40 (2001)
163175.
[125] H. Kita, K. Fuchida, T. Horita, H. Asamura, K.I. Okamoto, Preparation of
Faujasite membranes and their permeation properties, Sep. Purif. Technol.
25 (2001) 261268.
[126] W.S Wu, et al., Pervaporation of water and ethanol using a cellulose
acetate butyrate membrane, J. Colloid Interface Sci. 160 (1993) 502504.
[127] D.J. OBrien, J.C. Craig, Ethanol production in a continuous fermentation/membrane pervaporation system, Appl. Microbiol. Biotechnol. 44
(1996) 699704.
[128] E. Ruckenstein, L. Liang, Pervaporation of ethanolwater mixtures
through polydimethylsiloxane-polysstyrene interpenetrating polymer
network supported membranes, J. Membr. Sci. 114 (1996) 227234.
[129] R. Schue, et al., Sorption, diffusion and pervaporation of water/ethanol
mixtures in polyetherimide membranes, Polym. Int. 48 (1999) 171180.
[130] C.R. Martin, P. Aranda, W.-J. Chen, Pervaporation separation of
ethanol/water mixtures by polystyrenesulfonate/alumina composite
membranes, J. Membr. Sci. 107 (1995) 199207.
[131] B. Tieke, L. Krasemann, Highly efficient composite membranes for
ethanolwater pervaporation, Chem. Eng. Technol. 23 (2000) 211213.
[132] Z. Huang, H.-M. Guan, W.L. Tan, X.-Y. Qiao, S. Kulprathipanja, Pervaporation study of aqueous ethanol solution through zeolite-incorporated
multilayer poly(vinyl alcohol) membranes: effect of zeolites, J. Membr.
Sci. 276 (2006) 260271.
[133] H.-M. Guan, T.-S. Chung, Z. Huang, M.L. Chng, S. Kulprathipanja,
Poly(vinyl alcohol) multilayer mixed matrix membranes for the
dehydration of ethanolwater mixture, J. Membr. Sci. 268 (2006)
113122.
[134] H. Ohya, K. Matsumoto, Y. Negishi, T. Hino, H.S. Choi, The separation
of wateralcohol separation by pervaporation with PVAPAN composite
membranes, J. Membr. Sci. 68 (1992) 141148.
[135] Y. Nagase, Y. Takamura, K. Matsui, Chemical modification of
poly(substituted-acetylene): V. Alkylsilylation of poly(1-trimethylsilyl-
[136]
[137]
[138]
[139]
[140]
[141]
[142]
[143]
[144]
[145]
[146]
[147]
[148]
[149]
[150]
[151]
[152]
21
1-propyne) and improved liquid separating property at pervaporation, J.

Appl. Polym. Sci. 42 (1991) 185190.
J.R. Gonzalez-Velasco, et al., Pervaporation of ethanolwater mixtures
through poly(1-trimethylsilyl-1-propyne) (PTMSP) membranes, Desalination 149 (2002) 6165.
C.S. Slater, P.J. Hickey, F.P. Juricic, Pervaporation of aqueous ethanol
mixtures through poly(dimethyl siloxane) membranes, Sep. Sci. Technol.
25 (1990) 10631077.
S. Takegami, H. Yamada, S. Tsujii, Pervaporation of ethanol/water
mixtures using novel hydrophobicmembranes containing polydimethylsiloxane, J. Membr. Sci. 75 (1992) 93105.
X. Chen, Z.H. Ping, Y.C. Long, Separation properties of alcohol-water
mixture through silicalite-I-filled silicone rubber membranes by pervaporation, J. Appl. Polym. Sci. 67 (1998) 629636.
T. Sano, H. Yanagishita, Y. Kiyozumi, F. Mizukami, K. Haraya, Separation of ethanol/water mixture by silicalite membrane on pervaporation, J.
Membr. Sci. 95 (1994) 221228.
T. Ikegami, H. Yanagishita, D. Kitamoto, K. Haraya, T. Nakane, H. Matsuda, T. Koura Nand Sano, Production of highly concentrated ethanol in a
coupled fermentation/pervaporation process using silicalite membranes,
Biotechnol. Tech. 11 (1997) 921924.
T. Ikegami, H. Yanagishita, D. Kitamoto, K. Haraya, T. Nakane, H. Matsuda, N. Koura, T. Sano, Highly concentrated aqueous ethanol solutions
by pervaporation using silicalite membraneimprovement of ethanol
selectivity by addition of sugars to ethanol solution, Biotechnol. Lett.
21 (1999) 10371041.
I.F.J. Vankelecom, D. Depre, S. De Beukelaer, J.B. Uytterhoeven, Influence of zeolites in PDMS membranes: pervaporation of water/alcohol
mixtures, J. Phys. Chem. 99 (13) (1995) 193197.
I.F.J. Vankelecom, S. De Beukelaer, J.B. Uytterhoeven, Sorption and pervaporation of aroma compounds using zeolitefilled PDMS membranes,
J. Phys. Chem B 101 (1997) 51865190.
B. Moermans, W. De Beuckelaer, I.F.J. Vankelecom, R. Ravishankar, J.A.
Martens, P.A. Jacobs, Incorporation of nano-sized zeolites in membranes,
Chem. Commun. (2000) 24672468.
M.V. Leland, A review of pervaporation for product recovery from
biomass fermentation processes, J. Chem. Technol. Biotechnol. 80 (2005)
603629.
M. Nomura, T. Bin, S.I. Nakao, Selective ethanol extraction from fermentation broth using a silicalite membrane, Sep. Purif. Technol. 27 (2002)
5966.
F. Lipnizki, S. Hausmanns, G. Laufenberg, R. Field, B. Kunz, Use of
pervaporation-bioreactor hybrid processes in biotechnology, Chem. Eng.
Technol. 23 (7) (2000) 569577.
C. Gostoli, G.C. Sarti, Separation of liquid mixtures by membrane distillation, J. Membr. Sci. 41 (1989) 211224.
J. Bausa, W. Marquardt, Shortcut design methods for hybrid membranedistillation processes for the separation of nonideal multicomponent
mixtures, Ind. Eng. Chem. Res. 39 (2000) 16581672.
M. Gryta, et al., Ethanol Production in membrane distillation bioreactor,
Catal. Today 56 (2000) 159165.
M.A. Izquierdo-Gil, G. Jonsson, Factors affecting flux and ethanol separation performance in vacuum membrane distillation (VMD), J. Membr.
Sci. 214 (2003) 113130.

A Review of Separation Technologies in Current and Future Biorefineries

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Separation and Purification Technology 62 (2008) 121

A review of separation technologies in current and future biorefineries

H.-J. Huang et al. / Separation and Purication Technology 62 (2008) 121

with enzymes, fermentation of the sugars to ethanol with yeast,

1.1. Corn-to-ethanol biorenery

Fig. 1. Modified corn dry-grind (Quick Germ) process [3].

H.-J. Huang et al. / Separation and Purication Technology 62 (2008) 121

Fig. 2. Corn wet mill process [3].

and starch. This is followed by the same steps as those of

Obviously, forests are an enormous source of lignocellulosic

H.-J. Huang et al. / Separation and Purication Technology 62 (2008) 121

2. Pre-extraction of hemicellulose and other

and arabinose using enzymes such as enzymes Aureobasidium

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

H.-J. Huang et al. / Separation and Purication Technology 62 (2008) 121

yield of 6.76% under the optimal soaking conditions of 12 hr

2.1.3. Extraction of zein

H.-J. Huang et al. / Separation and Purication Technology 62 (2008) 121

recovery of xylan and obtainment of almost hemicellulose-free

Fig. 5. Process block diagram for extracting hemicelluloses [44].

H.-J. Huang et al. / Separation and Purication Technology 62 (2008) 121

Fig. 6. Hemicelluloses recovery process [45].

Fig. 7. Separation of hemicellulose and cellulose from fast-growing poplar wood

pure hemicelluloses for other use, for example, in making new

H.-J. Huang et al. / Separation and Purication Technology 62 (2008) 121

of pre-extraction on the downstream pulping yield and paper

Fig. 8. Solvent extraction of hemicelluloses and antioxidant from wood [26].

extracts behind. The aqueous phase from extraction contains

H.-J. Huang et al. / Separation and Purication Technology 62 (2008) 121

In the overliming process, the hydrolyzate is detoxified by

production by Candida shehatae NCIM 3501. In their research

H.-J. Huang et al. / Separation and Purication Technology 62 (2008) 121

of different inhibitors from hydrolyzates, but the former leads

tive volatilities and finally alters their separation factor (activity

4.1. Ordinary distillation

H.-J. Huang et al. / Separation and Purication Technology 62 (2008) 121

4.3. Extractive distillation (ED)

Fig. 12. Simplified PFD of ethanol dehydration by extractive distillation with

4.3.2. Extractive distillation with dissolved salt

H.-J. Huang et al. / Separation and Purication Technology 62 (2008) 121

Some scholars [8789] had also investigated the ED process

H.-J. Huang et al. / Separation and Purication Technology 62 (2008) 121

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

tions, representing economically favorable agents for large-scale

4.3.6. Summary of extractive distillation with different

Extractive distillation with liquid solvent

Less energy consumption than azeotropic distillation because of

Very high solvent/feed mass ratio, up

Extractive distillation with dissolved salt

Extractive distillation with the mixture of

Extractive distillation with ionic liquid (IL)

Extractive distillation with hyperbranched

(1) IL cannot pollute the distillate due to their non-volatility; (2)

Less availability of suitable salts;

H.-J. Huang et al. / Separation and Purication Technology 62 (2008) 121

ous fermentation broth with low energy requirement [68].

Fig. 15. Continuous fermentation with in situ extraction [96].

ing water consumption results in obvious reduction of overall

H.-J. Huang et al. / Separation and Purication Technology 62 (2008) 121

applied as dehydration desiccants in fermentation ethanol plants

lignocellulosic materials is primarily dependent on the hydroxyl

H.-J. Huang et al. / Separation and Purication Technology 62 (2008) 121

4.6. Membrane separation