Renewable and Sustainable Energy Reviews 74 (2017) 873890

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Renewable and Sustainable Energy Reviews

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

Membranes as a tool to support bioreneries: Applications in enzymatic MARK

hydrolysis, fermentation and dehydration for bioethanol production

Koel Sahaa, Uma Maheswari Ra, Jaya Sikdera, , Sudip Chakrabortyb, Silvio Silverio da Silvac,
Julio Cesar dos Santosc
a
Department of Chemical Engineering, National Institute of Technology Durgapur, West Bengal 713209, India
b
Department of Informatics, Modeling, Electronics and Systems Engineering (DIMES), University of Calabria, Via P. Bucci, Cubo 42a, 87036, Rende, CS,
Italy
c
Department of Biotechnology, School of Engineering of Lorena, University of Sao Paulo, 12-602-810, Lorena, SP, Brazil

A R T I C L E I N F O A BS T RAC T

Keywords: The consumption of fossil fuels in excess leads to chronic eect of greenhouse gas (GHG) emissions on the
Biorenery environment. These adverse environmental impacts of GHG have invoked reasonable awareness on renewable
Bioethanol energy resources. Bioethanol from lignocellulosic agricultural residue (profusely available renewable raw
Ionic liquid materials in the tropical areas) exhibits promising alternative to the petroleum based fossil fuel which reduces
Enzymatic hydrolysis
the net emission of GHGs. But due to certain technological barriers the large scale production of lignocellulosic
Membrane separation
bioethanol has not been successfully commercialized. To achieve the goal, economically viable bioethanol
production technology, which includes pretreatment, enzymatic hydrolysis, fermentation, and dehydration,
needs to be developed. Ionic liquid aided pretreatment can recover more than 80% cellulose and 42% lignin
from lignocelluloses, which generally contains 3046% cellulose and 1825% lignin. Processing of the
recovered cellulose towards bioethanol production requires enzymatic hydrolysis, which gives almost 76%
reducing sugar yield. Use of ultraltration and nanoltration in hydrolysis concentrates 27% reducing sugar as
well as recovers more than 73% enzyme with 50% catalytic activity. Ultraltration rejects 100% yeast as well as
reveals 15 g/l/h ethanol productivity, which can be subjected to membrane based dehydration by way of
pervaporation to produce 99.8 wt% ethanol. The scope of this review focuses on eco-friendly and sustainable
method for bioethanol production. A holistic and dedicated approach of this review helps to solve the various
technological concerns and realize large scale commercialization of lignocellulosic ethanol.

1. Introduction
International Energy Outlook (IEO) 2013 predicts an increase of
56% in World energy consumption over 30 years (from 2010 to 2040).
Herein 79.7% of the consumed energy is supplied by non renewable
fossil energy source (coal, natural gas, crude oil/petroleum etc.) and
nuclear source, 15.3% is supplied by hydro-power and rest 5% by other
renewable energy source. High cost, limited reservoir, depleting supply,
and random consumption hinder the dependency on petroleum as
transport fuel [1]. Over consumption of fossil fuel is a major threat to
environment as it leads to acid rain, climate change, global warming,
and harmful eect on human health and aquatic life. Global scenario
shows extensive use of conventional diesel engines throughout the
world due to exibility, reliability, high burning eciency, and low cost

Abbreviations: GHG, Green house gas; IEO, International Energy Outlook; NOx, Nitrous oxide; SCR, selective catalytic reduction; CO, Carbon monoxide; HC, Hydrocarbon; RFA,
Renewable Fuel Association; CO2, Carbon dioxide; NaOH, Sodium hydroxide; [bmim]Cl, 1-butyl-3 methylimidazolium chloride; [bmim][CH3SO3], 1-butyl-3 methylimidazolium
methylsulfonate; [EMIM]oAc, 1-ethyl-3-methylimidazolium acetate; [EMIM]Ace, 1-ethyl-3-methylimidazolium acesulfamate; [BMIM]Ace, 1-butyl-3 methylimidazolium acesulfamate;
AEL, alkaline ethanol lignin; H2SO4, Sulphuric acid; IL, Ionic liquid; EFB, empty fruit bunch; FTIR, Fourier Transform Infrared Spectrophotometer; TGA, Thermogravimetric Analysis;
NMR, Nuclear magnetic resonance; GPC, Gel permeation chromatography; DFRC, Derivatization followed by reductive cleavage; DMSO, Dimethyl sulfoxide; MWL, Milled wood lignin;
ILL, Ionic liquid lignin; APAWAO, Alkaline Peroxide Wet Air Oxidation; PEG, Polyethylene glycol; DWC, Dividing-wall columns; CA, cellulose acetate; NY, Nylon; PS, Polysulfone; PES,
Polyethersulfone; UF, Ultraltration; NF, Nanoltration; RO, Reverse osmosis; MWCO, Molecular weight cut o; MD, Membrane distillation; PTFE, Polytetrauoroethylene; PP,
Polypropylene; PVDF, Polyvinydilene uoride; DCMD, Direct Contact Membrane Distillation; EtOH, Ethanol; VMD, Vacuum membrane distillation; PDMS, Polydimethylsiloxane;
PDMS-PS IPN, polydimethylsiloxane-polystyrene interpenetrating polymer network; PS, Polystyrene; PDMS-PS, Polydimethylsiloxane-polystyrene; PVA, Poly(vinyl alcohol); MMMMs,
Multilayer mixed matrix membranes; PVA, Poly(vinyl alcohol); SA, Sodium alginate; PTMSP, 1-(trimethylsilyl)-1-propyne; PDMS, Poly[dimethylsulfoxane]; NH42SO4, Ammonium
sulfate; PTMSP, Poly(1-trimethylsilyl-1-propyne)

Corresponding author.
E-mail address: umuniqueme1@gmail.com (J. Sikder).

http://dx.doi.org/10.1016/j.rser.2017.03.015
Received 23 May 2016; Received in revised form 21 November 2016; Accepted 4 March 2017
Available online 10 March 2017
1364-0321/ 2017 Elsevier Ltd. All rights reserved.
K. Saha et al.
[2] but the most detrimental pollutants (particulate matter like carbon,
trace element, inorganic ion etc. and nitrous oxide (NOx)) are emitted
from diesel engines [3]. Application of two-cell selective catalytic
reduction (SCR) system in diesel engine can reduce pollutant emission
to a certain extent, as the rst catalyst cell minimizes NOx emission
whereas the second cell adsorbs ammonia generated from the previous
cell [4]. But the major limitation of SCR system is the chance of
contamination and blocking of the catalysts pore by ne particles,
silicon compounds etc. Contrastingly, the use of natural gas in a single
cylinder diesel engine by dual fuel mode of application decreases
carbon dioxide, particulate matter, and NOx but a drastic increase in
carbon monoxide (CO) and hydrocarbon (HC) emission occurs as
compared to the emission observed in the case of traditional diesel
engine [5]. These major drawbacks have invoked reasonable awareness
regarding investigation of alternative renewable energy sources, which
are environmentally benign, economically and technically feasible,
biodegradable, and non-toxic [6]. Water, biomass, wind, geothermal
heat can serve as renewable energy source and can potentially
substitute fossil fuel [7,8]. The developed nations are focussing on
the application of biomass based fuel, given that biofuel is a cost wise
competitor of fossil fuel, as it satises all the necessities of clean
technology, including renewability, sustainability, common availability,
reduction in green house gas emission, and biodegradability [9].
Biofuel can be classied into two groups. Primary biofuel is referred
to as natural and untreated biomass, such as wood chips and fuel wood.
These are directly combusted to supply energy for cooking, heating and
electricity production. Secondary biofuel is produced by processing or
modifying primary biofuel. These are generally solid, liquid or gases.
Secondary liquid biofuel can be further divided into three generation
fuel depending upon the raw material used [10]. First generation liquid
requires simple production process and uses sugar [11] or grain [12] as
possible raw material while second generation fuel is produced from
agricultural lignocellulosic biomass by biological or thermochemical
process and third generation biofuel is derived from microbes and
microalgae [10,13]. Main aim of biofuel research is to produce energy
products like bioethanol, biomethanol, biodiesel, biogas, biohydrogen
etc. using biological source [14].
Bioethanol and bioethanol/gasoline are most commonly used
transport fuel worldwide and can be viewed as viable alternatives to
petroleum fuel [15]. As burning of ethanol causes emission of carbon
dioxide, it can be mixed with gasoline to oxygenate the fuel mixture to
reduce carbon dioxide emission. Bioethanol is mainly produced from
biomass by hydrolysis of cellulose and fermentation of sugar, which
comes from energy crops including maize and wheat crops, sawdust,
cord grasses, sorghum plants, corn, sugarcane etc. The main advantage
of bioethanol over conventional fuel is its biodegradability, less toxicity,
reduction of green house gas emission and use of renewable and
ubiquitous biomass as primary substrate. Bioethanol-based economy is
more environmentally benecial than gasoline-based or conventional
petroleum-based economy and endorsement of the use of Bioethanol
can also inspire rural economy to cultivate the required crops. Fig. 1
Shows the graph of year wise worldwide average bioethanol produc-
Fig. 1. Year wise worldwide bioethanol production as reported in Outlook 20082013
reports.
874
Renewable and Sustainable Energy Reviews 74 (2017) 873890
tion. Brazil and United States account 87.1% of World bioethanol
production in 2011 as estimated by Renewable Fuel Association (RFA).
US produce fuel ethanol from corn stover [16] where Brazil use
sugarcane bagasse and straw as the possible raw material for ethanol
production. Sugarcane is the most plentiful agricultural crop cultivated
in this country [17]. Brazil has been producing sugarcane ethanol since
early 20th century [18] and the popularity of sugarcane ethanol
increased in 2003 with the use of ex fuel vehicle. Currently, 5%
ethanol blending policy with gasoline has been followed in India. Later,
it will move towards 20% blending by 2020. But, the currently available
feedstock in the form of sugarcane molasses is inadequate to meet the
necessity and also raises the food vs fuel debate [19]. Thus bioethanol
produced from agricultural residue especially lignocelluloses came into
scenario to overcome this debate. Huge demand of lignocelluloses
residue to support industrial production of bioethanol can be enhanced
by increasing the cultivation of potential agricultural crops which can
be successfully achieved by implementing modern agriculture and
irrigation system. Applying proper agricultural water management,
the ratio of irrigation to cultivated area can be improved day by day in
Indian Ocean Islands [20] which can inuence the agriculture strategy
of India. Among available dierent irrigation systems surface irrigation
has been used in most of the agricultural areas all over the world. Due
to the complexity of the technique three dierent models have been
investigated to simulate surface irrigation. Among these zero inertia
and full hydrodynamic models are more powerful as compared to
kinematic wave model [21]. Trickle and sprinkle irrigation system also
improves overall cultivation process but for applying these techniques
pressure loss must be appropriately adjusted to avoid the failure of the
system, which can be done by using tapered pipes [22]. Due to
requirement of large amount of water in irrigation process, world
population suers from water crisis. Therefore use of non-conventional
water resources, mostly treated wastewater, will be eective in this
aspect in developing countries like India and Brazil [23]. Water lifting
technology, which is attained by pump system, also plays a vital role in
irrigation practice. Though the use of modern pump improves water
supply for expanding irrigating agriculture, but this require high energy
which is supplied conventional electric power [24]. This may leads to
energy crisis which can be overcome by the use of biomass based
energy. Hence lignocelluloses based bioenergy, more specically
bioethanol may contribute for the generation of its own source.
Production of bioethanol from lignocellulosic biomass grabs attention
because of renewable and ever-present nature of biomass, its non-
competitiveness with food crops and reduction of threat to global
warming.
Lignocelluloses are generally composed of lignin, cellulose, hemi-
celluloses, organic extractives and some inorganic components which
turn into ash after combustion [25]. Cellulose and hemicelluloses are
strongly linked to lignin through covalent linkage and hydrogen
bonding [26]. Cellulose consists of hexose sugar monomer and hemi-
cellulose consists of dierent pentose sugar monomers which are
fermented by microorganism to produce ethanol. Thus cellulose is
the main component which is converted to bioethanol. The main
sources of lignocellulosic biomass are forest woody feedstock (includ-
ing dierent plant woody material like pine, r, hemlock spruce etc.),
forestry and industrial residue, agricultural wastes i.e dierent crops
residue such as corn stalks, rice straws, sugarcane bagasse etc [27,28].
Fig. 2 shows a chart of potential lignocellulosic residue generated per
year in million metric tons in India. The potentiality of all the resource
in bioethanol production has been studied. Maximum cellulosic
ethanol concentration of 3.20 0.36 g/l was achieved when rice husk
was used as raw material which contained 3550% cellulose [29]. Rice
straw (contains 32.70% cellulose), a potential lignocellulosic substrate,
has been well studied for bioethanol synthesis. Surfactant assisted
combined ultrasonic pretreatment and enzymatic hydrolysis of rice
straw produced maximum 0.374 g/g reducing sugar which was sub-
jected to fermentation and 1.48% ethanol yield was achieved with
K. Saha et al.
Fig. 2. Potential Lignocellulosic substrates based on Indian Scenario [36].
61.25% fermentation eciency on the basis of theoretical yield of
ethanol from glucose [30]. Maximum 512 mg reducing sugar was
produced per gram of biomass and 0.74% ethanol yield was achieved
when rice straw was processed by hydrotrope sodium cumene sulfonate
[31]. Sugarcane top is a feasible feed stock for bioethanol synthesis as
studied by Sindhu et al. 0.685 g/g reducing sugar was obtained by
hydrolysis of dilute acid pretreated sugarcane tops. Fermentation of
reducing sugar by yeast produced 11.365 g/l ethanol with 50%
eciency on the basis of theoretical yield of ethanol from glucose
[32]. 21.6 g/l ethanol concentration and 54.45 yield was attained while
wheat straw was treated by acid, subsequently hydrolysis by cellulase
isolated from Penicillium janthinellum and fermentation of hydroly-
zate by K. marxianus [33]. Sugarcane bagasse, the most popular
lignocellulosic residue is widely used for ethanol production. As it is
one of the most important crops cultivated in India, thus each year a
huge quantity of sugarcane bagasse is generated as agro-residue.
Bagasse containing 36.4% cellulose was processed for ethanol produc-
tion and 11.5% ethanol was obtained from it [34]. Ethanol concentra-
tion of 7.81 g/l was achieved from metal chloride pretreated sugarcane
bagasse hydrolyzate, which contained 16.47 0.12 g/l glucose [35].
The main technological challenge to convert lignocelullose to
bioethanol is developing a clean, eco-friendly and cost-eective pre-
treatment followed by enzymatic hydrolysis, fermentation and down-
stream separation and purication. The conversion of lignocellulosic
biomass to bioethanol can be done either by one of the following
process or by combinations i.e. chemical, mechanical, physicochemical
or biological process. This would separate lignin from lignocellulosic
material, the unique valuable byproduct, and exposes cellulose, convert
cellulose and hemicelluloses to simple sugar by enzymatic or acid
hydrolysis and undergoes hexose and pentose sugar fermentation to
ethanol by using appropriate microorganism. Downstream separation
and purication of bioethanol by suitable technique is required to
manufacture anhydrous and puried alcohol. To establish the bioetha-
nol production process as a clean technology every byproduct should be
utilized properly in an eco-friendly manner.
Bioethanol has been successfully applied as an alternate of conven-
tional fossil fuel due to its environmental benets. This study aims to
review the main production steps involved in biorenery system to
manufacture bioethanol and application of eco-friendly membrane
based process in each step. This literature review discusses green
solvent based pretreatment of lignocelluloses to recover lignin, fol-
lowed by necessary steps to produce ethanol. Application of membrane
based separation technique in enzymatic hydrolysis, fermentation and
downstream purication for dehydration and overall techno-economic-
al evaluation of ethanol production is discussed for better under-
standing, to develop a sustainable and environmental friendly and
economically viable biorenery scheme.
2. Production of bioethanol from lignocellulosic biomass
Production of bioethanol in a clean and eco friendly manner
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Renewable and Sustainable Energy Reviews 74 (2017) 873890
involves dierent steps: Separation and recovery of value added
products by green solvent based pretreatment method, enzymatic
hydrolysis of polysaccharide followed by fermentation of monosacchar-
ide and downstream purication.
2.1. Recovery of value added product by ionic liquid pretreatment
The major components of lignocellulosic biomass are lignin, hemi-
celluloses, cellulose, ash, salt, mineral, protein, pectin etc. among
which cellulose is essential necessitate for bioethanol production.
Lignin, a cross- linked three dimensional polymer consists of three
monolignols: p-coumeryl alcohol, coniferyl alcohol and sinapyl alcohol
[37]. Lignin is covalently linked to polysaccharides in lignocellulose. It
can be described as value added product as it has a wide range of
application in dierent aspects. It is used in manufacturing of
dispersants, bioplastic, nanoparticles, (nano) composites, carbon bre
and in agriculture and biofuel eld [38]. So one of the main aims is to
remove lignin from biomass successfully and use it in various elds.
Dierent chemical, physical, biological pretreatment methods have
been suggested by researcher to change the lignocellulosic biomass
structure i.e disruption of covalent linkage between lignin and cellu-
lose, to alter the structure of lignin and ecient removal of hemi-
celluloses and lignin to make the cellulose accessible to hydrolytic
enzyme that can convert it to monosaccharide [7]. The limitations of
this conventional pretreatment methods are use of irradiation, high
electricity consumption, high chemical cost etc. In contrast to this, use
of ionic liquid, a green solvent as pretreatment medium can eciently
dissolve cellulose or lignin or both in it due to its cationic and anionic
structure and remove lignin successfully as well as alter the crystalline
structure of cellulose [39]. Though ionic liquid is expensive as
compared to other chemicals, it has been given attention by researcher
as it is a low melting organic salt, non-ammable, and has a very low
vapour pressure, stable liquid range, and the potential to replace
volatile organic compound. Besides, the ionic liquid also demonstrates
selective solubility in water and organics and appreciable recyclability
[40]. The solvent property can be controlled by way of appropriate
cation and anion selection, which make it a designer solvent and
accounts for its commendable performance in the eld of green
chemistry [41]. Mai et al. [42] summarized dierent process like
distillation (distillation of ionic liquid, distillation of volatile solutes/
impurities in ionic liquid), extraction (solvent extraction, CO2 extrac-
tion), adsorption (adsorption/desorption, chromatography), induced
phase separation (salting out, introduction of CO2, changing the
temperature), membrane based processes (nanoltration, electrodia-
lysis, reverse osmosis, pervaporation), magnetic separation, and cen-
trifugation to recover and recycle ionic liquid to make the ionic liquid
based lignin recovery an industrially acceptable procedure. The main
steps involved in lignin recovery process are mixing of powder form of
biomass with ionic liquid in a particular ratio, heating and stirring at
high temperature for a particular time period followed by extraction of
lignin from ionic liquid lignin solution by precipitation with an organic
antisolvent and recycling of ionic liquid after evaporation of antisol-
vent.
Though lignin can be recovered from poplar wood biomass by only
alkaline pretreatment, treatment with ionic liquid followed by NaOH
gradually increases lignin yield [43]. Lignin was recovered from soft-
wood (Pine) as well as hardwood (Eucalyptus) dissolved in imidazo-
lium based acetate and chloride ionic liquid. Characterization of
recovered lignin showed 31% recovery of lignin [44]. Moghaddam
et al. [45] isolated and determined physico-chemical characteristics of
sugarcane bagasse lignin using IL 1-butyl-3 methylimidazolium chlor-
ide [bmim]Cl and also 1-butyl-3 methylimidazolium methylsulfonate
[bmim][CH3SO3] with HCl as catalyst, followed by extraction with
NaOH and the lignin yield was 4243%. Lignin recovery was less due
to the presence of high concentration of acid and high moisture
content. Optimization of pretreatment parameters (time, temperature
K. Saha et al.
and ionic liquid to solid ratio, H2SO4 (catalyst) concentration) was
studied for extraction of lignin from empty fruit bunch using [bmim]Cl.
Experimental data was analyzed by Central Composite Design of
Response Surface Methodology to nd out optimal condition for lignin
extraction. The usefulness of acid catalyst was to enhance lignin
dissolution in IL. The optimal condition for maximum lignin yield
was 150.5 C temperature, 151 min time period, 3:1 IL to EFB ratio,
4.73 wt% H2SO4 concentrations. At this condition the predicted value
for lignin yield was 27.9% and experimental value was 26.6%. IL was
recovered and recycled four times and lignin yield decreased not less
than 14 wt% [46]. Sun et al. [47] investigated the extraction and
separation of lignin from eucalyptus by dissolving biomass in 1-butyl-3
methylimidazolium acesulfamate [BMIM]Ace and dierent organic co-
solvent like N,N-dimethyacetamide, dioxane, ethyl acetate, tolune and
named as IL-organic solvent lignin and also recovered lignin from
residual carbohydrate rich material by NaOH treatment and named as
alkaline ethanol lignin (AEL). IL-tolune treatment recovered maximum
lignin i.e 15.4% whereas fresh IL could only recover 11.5% lignin. The
order of lignin recovery eciency was IL-tolune > IL-dioxane > IL-N,N-
dimethyacetamide > Fresh IL. The dierences in the extraction e-
ciency of organic solvents are due to the dierences in their con-
ductivity as well as dielectric constant. NaOH is used to remove lignin
from carbohydrate enriched material as alkaline can cleave the alkali
labile bond between lignin and carbohydrate. AEL yield (823%) is
more than IL-organic solvent extracted lignin (11.514.5%) but less in
case of fresh ionic liquid extracted lignin. Pretreatment of corncob with
ionic liquid 1-ethyl-3-methylimidazoleum acetate [EMIM]oAc and
water/DMSO followed by alkaline extraction demonstrated 85.04% of
lignin recovery. HSQC spectra analysis exhibited presence of cinnamyl
alcohol end group and -O-4, -, -5, -1 linkage in the corncob lignin
[48]. 1-ethyl-3-methylimidazolium acetate [EMIM]oAc was also used
for softwood (southern yellow pine) processing and yield of 31% of
original lignin as carbohydrate free and 38% as carbohydrate bond was
achieved . Pinkert et al. [49] reported the process of delignication,
isolation of Pinus radiata wood lignin and retention of crystalline
structure of cellulose in carbohydrate rich residue by treating the wood
our with imidazolium acesulfamate ionic liquids i.e [BMIM]Ace,
[EMIM]Ace which are derived from commercial sugar acesulfamate
potassium and studied the impact of dierent variable like wood
species, water content, wood particle size and type of IL cation plus
recycling of IL on lignin extraction eciency (mass of extracted lignin/
mass of initial lignin content) with [BMIM]Ace. Increasing the extrac-
tion temperature from 353 K to 416 K and extraction time from 1 h to
4 h raises the extraction eciency from 0.32 to 0.81 and 0.05 to 0.07.
Extraction eciency decreases as the water content in the atmosphere
increases from dry condition (inert gas) to normal atmosphere and
increasing the moisture content in atmosphere. It increases 13% for
[EMIM]Ace treatment than [BMIM]Ace treatment at 373 K, 2 h
pretreatment due to two reasons. First, the presence of shorter alkyl
substituent in [EMIM]Ace as compared to [BMIM]Ace, which de-
creases its viscosity and toxicity and increases mobility to enhance IL
biomass interaction and secondly, the existence of more halide
impurity in [EMIM]Ace, which has a positive impact on IL lignin
interaction. IL should be completely recycled to attain a green biomass
processing. To achieve this, researchers recycled IL six times at 373 K,
2 h operation period but no noticeable reduction in extraction e-
ciency occurred and no IL degradation could be observed in NMR
spectra after each recycling process. They have suggested the presence
of small quantity of DMSO as co-solvent can suciently increases
lignin extraction due to untying the H-bond in cellulose and reducing
the gross viscosity which boost the penetration of IL in lignocelluloses
and subsequently enhance IL lignin interaction. Kim et al. investigated
the extraction of poplar wood (Populus albaglandulosa) lignin using
[EMIM]Ace and characterization by GPC, FTIR, TGA NMR, DFRC
method and compared the yield with milled wood lignin and found out
more IL lignin by ionic liquid lignin (ILL) process (5.8 0.3%) than
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Renewable and Sustainable Energy Reviews 74 (2017) 873890
milled wood lignin (MWL) process(4.4 0.4%). Though the structural
features were same for both the processes, but the average molecular
weight of MWL is more than ILL [50]. [EMIM]oAc is an ecient
solvent for sugarcane bagasse treatment while comparing with other
imidazolium IL and conventional pretreatment [51]. All the studies
reveal the eciency of ionic liquid, a green and environment favourable
solvent to treat the lignocellulosic biomass to remove and recover
lignin adequately which is the second most plentiful biological compo-
nent in world next to cellulose and hemicellulose.
2.2. Summary
Literature review discussed lignin recovery and ionic liquid recycle
during ionic liquid mediated pretreatment of lignocellulose biomass.
Conventional physical, chemical, physicochemical and biological pro-
cesses are available to recover lignin. But these processes have some
major drawbacks. Physical treatments are either high energy consum-
ing or require high temperature, whereas physicochemical processes
need high pressure and high temperature that can give rise to
byproduct formation. Chemical pretreatment uses corrosive solvent
and forms toxic byproducts, whereas fungus assisted biological proces-
sing is time consuming. Contrastingly, ionic liquid pretreatment of
lignocellulose is eective, apropos of lignin recovery in pure form. This
process is advantageous due to recyclability, eco-friendliness, non-
volatility and high thermal stability of ionic liquid.
1. Lignin yield increases with increasing reaction temperature and
time. Supplement of catalyst (acid or alkali) or organic solvent along
with ionic liquid enhances lignin extraction. But the presence of
moisture content in the reaction atmosphere reduces extraction
eciency.
2. Among dierent available ionic liquids, imidazolium based ionic
liquid with shorter alkyl chain is the most ecient, as regards lignin
recovery during pretreatment of lignocelluloses.
3. Recycle and reuse of ionic liquid in further pretreatment stage is
necessary to make the process economical viable which can be
achieved by distillation, adsorption, extraction etc.
4. Sugarcane bagasse is a widely available lignocellulosic residue in
tropical country and [EMIM]oAc is the most ecient ionic liquid for
bagasse pretreatment with regard to lignin recovery as well as
disruption of the crystalline structure of cellulose.
Thus ionic liquid based processing develops a clean and sustainable
pretreatment technology.
2.3. Enzymatic hydrolysis of lignocellulosic biomass
Enzymatic hydrolysis is an important step in the conversion of
cellulose present in the pretreated biomass to glucose for subsequent
fermentation. The bioconversion of cellulose to glucose is carried out
by cellulase enzymes under mild conditions of temperature 4050 C
and pH 4.55.0, which negates the corrosion problems [52]. The
eciency of the hydrolysis process depends on the degree of pretreat-
ment of the biomass in terms of lignin removal and hemicelluloses
solubilisation, hydrolysis period, and enzyme loading. The initial rate
of the hydrolysis process is aected by the crystalline structure of the
cellulose. Lignin and the acetyl group present in the hemicelluloses
produce unproductive binding with cellulase and limit the hydrolysis
process [53]. The eciency of the hydrolysis process was found to be
enhanced by the addition of non-ionic surfactants, which changes the
cellulose surface properties and lowers the enzyme loading.
Surfactants, such as polyethylene glycol (PEG), were found to increase
the enzymatic convertibility of the lignocellulosic biomass from 42% to
78% in 16 h. PEG prevented the unproductive binding of lignin to the
surface of the enzyme [54]. Microwave irradiation pretreatment was
found to enhance the enzymatic saccharication of rice straw by 30.3%.
K. Saha et al.
The enzymatic saccharication was dependent on factors like irradia-
tion time, microwave intensity and substrate concentration [55].
Banerjee et al. reported the utility of the liquid fraction obtained after
Alkaline Peroxide Wet Air Oxidation (APAWAO) of rice husk during
enzymatic hydrolysis. The hydrolysis experiment was carried out with
the APAWAO pretreated solid fraction (in buer) and slurry (solid
fraction in liquid fraction). It was noted that the hydrolysis in the
APAWAO pretreated liquid fraction produced more glucose when
compared to hydrolysis of the solid fraction in buer medium. Thus
recycling of APAWAO liquid fraction was feasible during enzymatic
hydrolysis, which resulted in glucose concentration enhancement at
50C hydrolysis temperature. The enzymatic cellulose convertibility
was up to 86 wt% within 24 h and the glucose yield was 21 g glucose
per 100 g untreated rice husk. The eect of dierent dry matter
loadings on the hydrolysis yield was also investigated [56]. The
structural characteristic of biomass aects the cellulose digestibility
with respect to surface area, large pore volume, crystallinity of
cellulose, degree of polymerization and presence of lignin, hemicellu-
loses and acetyl group [57]. Ultrasound assisted pretreatment is a
promising and a novel process which increases the glucose yield after
enzymatic saccharication by removing lignin and hemicelluloses [58].
Ultrasonic pretreatment of sugarcane bagasse at a frequency of 40 kHz
increased the amount of fermentable sugars when compared to
untreated sample [59]. Bian et al. investigated the eect of ionic liquid
([Emim]Ac) pretreatment on the enzymatic hydrolysis of sugarcane
bagasse. It was observed that ionic liquid pretreatment enhanced
enzymatic convertibility of cellulose and achieved 95.2% cellulose
conversion after 96 h enzymatic hydrolysis. Lowering the degree of
polymerization and reducing cellulose crystallinity by ionic liquid
pretreatment resulted in high hydrolysis convertibility [60]. The
enzymatic digestibility of cellulose was found to be more associated
with lignin removal than hemicelluloses solubilisation [61].
The overall process economics of bioethanol production can be
improved by operating enzymatic hydrolysis at higher substrate con-
centration so that the glucose yields in the hydrolysate could be more.
The substrate concentration aects the rate and extent of the hydrolysis
process. The hydrolysis yield and substrate concentration is inversely
related [62]. It is well documented that cellulolytic enzymes suers
from end product (such as cellobiose and glucose) inhibition. Addition
of cellobiase enzyme alleviates the inhibitory eect of cellobiose as it
hydrolyzes the cellobiose to glucose. Operating hydrolysis reaction at
low substrate concentration reduces the end product inhibition. It was
observed that glucose concentration increased with increase in dry
matter loading (up to 10% of dry matter). A further increase in dry
matter concentration does not proportionately increase the glucose
yield. This may be attributed to possible mass transfer limitations due
to high substrate concentration where there is little convective mixing
due to minimum water available to facilitate the mass transfer of the
water soluble compounds. Sugars build up around the active sites of
cellulase enzyme and inhibit further hydrolysis reaction [63]. Table 1.
shows comparative chart for the work reported on hydrolysis of
lignocellulosic biomass.
2.4. Summary
1. Hydrolysis is aected by structural characteristics of cellulose and
presence of lignin and hemicellulose. Removal of lignin, solubilisa-
tion of hemicelluloses and decrystallization of cellulose by pretreat-
ment, strongly induce cellulose accessibility to enzyme.
2. Pretreatment of biomass by ionic liquid, addition of surfactant,
applying microwave irradiation or ultrasound enhances cellulose
conversion.
3. Glucose yield increases with increasing hydrolysis period but
decreases with substrate loading above a certain limit. This is caused
by end product inhibition and mass transfer limitation.
877
Renewable and Sustainable Energy Reviews 74 (2017) 873890
2.5. Traditional downstream purication
Aqueous ethanol that is produced after conventional fermentation
process is not accepted to use as fuel ethanol. As ethanol and water
forms azeotropic mixture it is dicult to get almost pure or fuel grade
ethanol. Thus advanced research directs to initiate high energy
demanding industrially acceptable distillation process to break the
azeotrope nature for achieving almost pure ethanol. Azeotropic and
extractive distillation processes are used widely for this purpose [69
74]. Distillation separates liquid mixtures based on their boiling point
by evaporation following condensation. Gill et al. designed the use of
glycerol as entrainer in extractive distillation process to dehydrate
ethanol, as glycerol has high availability, relatively low cost and
enhanced relative volatility, which impart a positive eect on azeo-
tropic mixture. The study of the impact of this entrainer on feed stage,
reux ratio, entrainer feed temperature, feed molar ratio has also been
done to get the most appropriate design for minimizing the require-
ment of energy [75]. A novel approach of extractive dividing-wall
columns (DWC), which combines solvent recovery column, extractive
distillation column and pre-concentration column in a single distilla-
tion unit, is ecient to separate 99.8 wt% bioethanol. This ethanol
dehydration conguration can be applied in large scale bioethanol
production [76]. While using ethylene glycol and n-pentane as mass
separating agent, DWC in extractive and azeotropic distillation can
separate highly pure i.e. 99.8% ethanol, and also saves 1020% of
overall energy [77]. Employing ionic liquid as mass separating agent
during extractive distillation lowers energy consumption in per kg
ethanol purication. This process can achieve 0.995 (in mass) ethanol
purity and 99.9 wt% ethanol recovery [78].
2.6. Summary
Most of the industries use distillation in downstream purication to
dehydrate ethanol. But this technique is highly energy demanding and
hence results in high power consumption. Energy consumption should
be reduced in order to attain energy ecient dehydration method.
1. Azeotropic distillation and extractive distillation are industrially
acceptable ethanol dehydration processes.
2. Use of highly available, low cost glycerol as entrainer in extractive
distillation dehydrates ethanol as well as minimizes energy con-
sumption.
3. Use of ethylene glycol, n-pentane or ionic liquid as mass separating
agent minimizes energy consumption.
3. Possibilities of application of membrane in bioethanol
production
Membrane, a thin barrier where placed between two medium and
driving force is applied on it, it allows the selectively transfer of one or
more component from one phase to another phase. Membranes that
are used in bioseparation process are generally porous and semi-
permeable in nature. . The components that pass through the mem-
brane and collected in other side is called permeate and the compo-
nents that retain is called retentate Microltration, nanoltration,
ultreltration, vacuum ltration, reverse osmosis are most useful
pressure driven membrane based separation method. Others are
pervaporation, dialysis, gas separation. Most of the membrane used
in dierent chemical process is made of organic matter generally
polymer. But nowadays, the use of inorganic and hybrid membrane is
common. The common used membrane congurations are plate-and-
frame module, spiral-wound module, and hollow-bre module. In
bioethanol industry membrane is generally used in downstream
purication to concentrate the produced ethanol. But it can be
suciently used in cellulase enzyme recycling, cell recycling and
removal of inhibitory by products.
 K. Saha et al.

Table 1
Comparative chart for previous work reported on hydrolysis of lignocellulosic biomass.

Sl. No. Pretreatment Pretreatment Conditions Biomass Lignin Enzyme loading Hydrolysis Cellulose convertibility Main findings Ref.
removal (% condition (%w/w)
w/w)

1 Alkaline Peroxide 185 C, 5 bar, 15 min Rice husk 88% 25 FPU/g dry mass 50 C, 150 rpm 86% Oxidize lignin, solubilise hemicellulose, alter biomass [56]
Assisted Wet Air (cellulase), 12 IU/g dry for 2472 h structure and 55 g/l glucose obtained after 72 h
Oxidation (APAWAO) mass (-glucosidase) hydrolysis
2 Sodium hydroxide 180 C, 20 min Sugarcane 84.3% 550 FPU/g glucan 50 C, 150 rpm 97.5% (glucan) Retains most xylan, remove maximum lignin and [61]
+Liquid Hot Water 1% NaOH Bagasse for 72 h pretreated residue shows higher enzymatic digestibility
3 Dilute sulphuric acid and 150200 C for 320 min Corn stover Not reported 40 mg/g 45 C, 130 rpm 8085% Detoxification is not necessary as enzymatic hydrolysis [63]
steam heating for 168 h is tolerant to inhibitor; 100200 g/l sugar inhibits
hydrolysis
4 Steam Explosion 205 C, 40 bar, 10 min Sugarcane 35% 25 FPU/g dry mass 50 C, 150 rpm 48.9% Wet oxidation solubilises lignin, hemicelluloses and [64]
Wet oxidation 195 C, 12 bar, 15 min bagasse 50% (cellulase), 0.46 CBU/ml for 24 h 57.4% recovers cellulose more than steam explosion. Wet

878
(-glucosidase) oxidation is more effective for pretreatment as
enzymatic digestibility is higher.
5 Wet Air Oxidation (WAO) 195 C, 12 bar, 15 min Sugarcane 50% 25 FPU/g dry mass 50 C, 150 rpm 75% Though pretreatment is effective for biomass [65]
bagasse (cellulase), 0.46 CBU/ml for 2448 h fractionation, some polysaccharides got lost due to
(-glucosidase) degradation and by-product formation
6 Sodium Hydroxide 0.75% NaOH, 15 min, Coastal 86% 76.4 FPU/ml (cellulase), 55 C, 150 rpm 90.43% Higher lignin removal enhance enzyme hydrolysis, xylan [66]
Pretreatment 121 C Bermuda Grass 283.1 CBU/ml for 72 h conversion is more than glucan conversion
(Cellobiase)
7 Hydrated Lime 10% w/w Ca(OH)2 Rice Straw 13.127% 15 FPU/g glucose 50 C, 150 rpm 48.5% Increasing alkaline loading induce glucose yield, [67]
95 C, 3 h (cellulase), 15 CBU/g for 3 days Treatment with Ca(OH)2 shows higher glucose yield
glucose (-glucosidase) than NaOH.
8 Ionic liquid ([EMIM] 20:1 ionic liquid to Energy cane 32% 15, 30 FPU/g glucan 50 C, 150 rpm 87% IL treatment exhibits better lignin removal, higher [68]
[OAc]) biomass, 120 C 30 min bagasse (cellulase), 15, 30 GBU/g for 072 h enzymatic digestibility as compare to water treatment
glucan (cellobiase)
Renewable and Sustainable Energy Reviews 74 (2017) 873890
K. Saha et al.
3.1. Membrane assisted enzymatic hydrolysis
Fermentation of lignocellulosic biomass to fuel-grade ethanol
confronts two major diculties. 1) Crystalline structure of cellulose
which resists enzymatic hydrolysis of cellulose. 2) Lignin-cellulose
association that impede enzymatic attack on cellulose [79]. Dilute acid
catalyzed hydrolysis of cellulose use high pressure and temperature
that leads to destruction of monomer glucose to hydroxymethyl
furfural, levulinic acid, formic acid and the side reaction cause
disruption of cellulose leading to formation of nonreactive materials
[80]. In contrast to this chemical process, enzymatic hydrolysis of
cellulose requires low energy as well as normal temperature and
pressure, and abolishes the formation of toxic inhibitors. Cellulolytic
enzyme containing endoglucanase, cellobiohydrolases and -glucosi-
dase obtained from dierent bacteria or fungi can suciently hydrolyze
pre-treated lignocellulosic biomass to release fermentable sugar. But
the cost of the enzyme constitutes 20% of total ethanol production cost
and 50% of total cost of whole hydrolysis process [81]. One way to
reduce the production cost of ethanol from lignocellulosic biomass is to
recover, recycle and reuse of enzyme as well as the specic activity of
enzyme should be retained. Enzyme recycling is inuenced by various
factors like nature of biomass, origin and activity of enzyme and
process parameters [82]. After hydrolysis, cellulase can either appear in
solution as free enzyme or can be adsorbed in remaining biomass [83].
Recovery and recycling of bound enzyme after initial hydrolysis require
separation and desorption method [84,85] but the catalytic activity
gradually decreases in subsequent hydrolysis steps. Recovery of lter
paper activity decreases from 91% to 22% by this method. But the use
of alkali or surfactant enhances enzyme activity. Membrane based
process adequately recover the enzyme from hydrolysis solution,
retains its catalytic activity, satisfactorily recycle and reuse the enzyme
in further hydrolysis procedure and it was established as best recover-
ing procedure [86]. Membrane ltration that are widely used in this
process mostly use organic membrane made of cellulose acetate (CA),
nylon (NY), polysulfone (PS), polyethersulfone (PES) The membrane
module that are usually adopted for this process are hollow bre , spiral
wound and at sheet/plate-and-frame membrane. Microltration can
eciently remove remaining biomass after hydrolysis whereas ultra-
ltration is used to recover soluble enzyme from hydrolysis solution.
Permeate ux for microltration is higher than ultraltration due to
large pore size of microltration membrane [87]. Sedimentation
followed by microltration and ultraltration method can recover
and recycle 75% of the enzyme used in active catalytic form, and
exhibits a cost benet of 18 cents/gal of ethanol produced from
pretreated ground yellow poplar. Microltration membranes were
made of cellulose acetate, polysulfone and nylon where ultraltration
membranes were made of polysulfone and polyethersulfone. The
permeate ux of microltration was 400 l/(m2 h) and ultraltration
was 80 l/(m2 h) [88]. In combined sedimentation and crossow ultra-
ltration method, sedimentation using inclined settler removes ligno-
cellulose particles larger than 50 m in length and ultraltration
transmits fermentable sugar, while retaining remaining biomass par-
ticle and cellulase enzyme. The permeate ux from ultraltration is 64
5 l/(m2 h) when feed consists of 0.22 w/v% cellulose and it increases
upto 130 20 l/(m2 h) when feed consists of 10 wt% lignocelluloses
and settler overow from mixture of 0.22 w/v% cellulose. As cellulase
binds to the lignocellulosic particle during enzymatic hydrolysis and
ltration, it prevents the enzyme from fouling the membrane, and thus
increases the permeate ux [89]. High conversion rate of cellulose and
low consumption of cellulase can be achieved in a continuously or semi
continuously operated attrition bioreactor conjugated with a mem-
brane lter which retains cellulase and remaining cellulose in reactor
and allow sugar to pass through it as product [90]. Hydrothermal
pretreated wheat straw for ethanol production was mixed with
Celluclast supplemented with -glucosidase at dierent loading and
subjected to hydrolysis followed by fermentation using yeast strain.
879
Renewable and Sustainable Energy Reviews 74 (2017) 873890
After fermentation cellulase was recovered by passing the liquid phase
through 0.22 m Polyethersulfone membrane (PES), followed by
concentration and NaAc buer exchange in a tangential ultraltration
system. Pellicon XL membrane with a 10 kDa cut-o PES membrane
achieves 80% recovery of soluble enzyme, 70% recovery of activity from
liquid phase providing high conversion degree. Increasing the hydro-
lysis temperature and enzyme loading drops the recovery of cellulase
from liquid phase about 40% [91]. Ultraltration with PES10 mem-
brane was investigated to recycle 73.9% cellulase present on hydro-
lyzate suspension of steam-exploded wheat straw, thereby minimizing
the hydrolysis cost. Permeate acquired from UF was concentrated by
nanoltration using NF270 membrane to concentrate glucose 3.5 times
more from UF permeate, thus improve fermentation eciency as well
as lower the cost of downstream processing of fermentative product.
Permeate ux for ultraltration was 25.6 l/m2 h at 1.27 bar transmem-
brane pressure whereas for nanoltration ux reduced to 13.3 l/m2 h
at 35 bar pressure [92]. Another investigation was the eect of
pretreatment method of lignocellosic biomass on recovery and recy-
cling of cellulase used in bioethanol production. Dilute alkali treated
wheat straw showed better recycling of substantial amount of enzyme
as it contains about 4 times less lignin than dilute acid treated wheat
straw, indicating the inimical eect of lignin on enzyme recovery and
recycling. In contrast to adsorption recycling, ultraltration using glass
microber membrane can eciently retain -glucosidase, thus keeping
away from the loading of -glucosidase in successive round of hydro-
lysis, thereby boost the economics of enzymatic hydrolysis [84].
Recover and recycle of cellulase and cellobiase used in hydrolysis of
Ammonia Fibre Explosion-treated corn stover can be eciently
attained by ultraltration using polyethersulfone 76 mm, 10 kDa,
membrane. Cellulase was recovered from 60% to 66% and cellobiase
from 76.4% to 88%. Increasing the total enzyme recovery from 70% to
90% rise the cost saving from 25% to 50% [93]. Electroultraltration,
an advancement of ultraltration caused by intensication of ultra-
ltration by electric eld, can eciently lessen concentration polariza-
tion as well as increase membrane ux using cation exchange mem-
brane and polymeric membrane. Suitable condition i.e low buer
concentration, room temperature and high current increase the ux
and suciently recover and recycle cellulase from hydrolizate of acid
treated wheat straw. Concentration polarization resistance decreased
from 7.5 to 8109 Pas/m to 33.5109 Pa s/m while increasing electric
eld strength from 0 to 144 V/m. Thus ux is proportional to electric
eld. Permeate ux decreased from 3.510-6 m/s to 2.610-6 m/s from
beginning to 3500 s hydrolysis period applying 144 V/m electric eld
strength [94]. Polymeric ultraltration membrane can hydrolyze max-
imum amount of microcrystalline cellulose pretreated with ionic liquid.
This process permits maximum recovery and recycling of cellulase
retaining its utmost activity for 9 running cycle in semi-continuous
process. Continuous process with tangential ow ceramic ultraltration
membrane shows constant permeate ux and glucose concentration at
dierent residence time proving itself as a good practice for cellulose
hydrolysis procedure [95]. Submerged vibration and stirring at mem-
brane surface reduce fouling and concentration polarization. Thus
enhances permeate ux [96,97]. All the experimental studies reveal the
importance of membranes and membrane assisted separation process
for retrieving and reuse of cellulase in an energy ecient manner as
well as reducing the cost of enzyme and enzymatic hydrolysis step in
recent fuel-grade bioethanol industry. Table 2 shows the summary of
membrane assisted cellulase recovery. The other cellulase recovery by
membrane processes were already reviewed elsewhere [87,98].
3.2. Summary
Membrane based separation process has been successfully applied
for enzyme recovery and glucose concentration. The overall perfor-
mance of membrane depends on various parameters. Certain outcomes
of the aforementioned discussion are:
 Table 2
Summary of membrane assisted enzyme recovery.

Source of cellulose Pretreatment Type of Membrane material Membrane MWCO Membrane Membrane Cellulose Glucose Rejection Enzyme Main findings References
K. Saha et al.

method cellulase based process module flux conversion production activity

(l/m2 h) (%) Recovery

Wheat straw Dilute acid Cellulase of Organic (PES) Ultrafiltration 10 kDa Dead end 17% (acid 9.8 (mg/ml) Recycling of enzyme by [84]
and dilute Trichoderma treated) (acid ultrafiltration is more
alkali reesei and - treatment) beneficial for -
glucosidase 67% (alkali 19.6 (mg/ glucosidase retention
from treated) ml) (alkali than by adsorption.
Aspergillus treatment) Alkali pretreatment
niger shows higher reducing
(Novozym sugar yield and better
188) enzymne recycling as
compare to acid
pretreatment
Wheat straw Hydrother- Celluclast, - Organic (PES) Ultrafiltration 0.22 m 93.6% 2022 g/l 33%, 31% Ultrafiltration recovers [91].
mal glucosidase (enzyme (enzyme (celluclast), soluble enzyme with
(Novozyme loading: 20 loading: 20 61% (- 80% yield, At maximum
A/S) FPU/g FPU/g glucosidase) cellulose conversion
cellulose, cellulose, (enzyme also 2030% enzyme
50 C) 50C, 48 h loading: 20 remains attached to end
incubation) FPU/g residue
cellulose,
50 C)
Wheat straw Steam Organic (PES, NF) Ultrafiltration 10,000 g/ 25.6 l/m2 h 31.484.5% 30.2 (g/l) 73.9% Application of two-stage [92]
Explosion and mol (UF) for UF and (from 3 to For UF enzyme membrane filtration
Nanofiltration 13.3 l/m2 h 48 h 110.2 (g/l) (UF), 100% scheme recover

880
150 g/mol for NF hydrolysis) For NF enzyme maximum cellulase
(NF) (NF) during 1st step i.e. UF
and concentrate glucose
during NF (2nd step)
Wheat Straw Acid Cellulase Cation exchenge Electroultrafil- DF-120 Declines with 60.5% (10% Electroultrafiltration is [94].
treatment from membrane (CEM), tration (CEM) time at all substrate an efficient technique
Trichoderma Organic (PES) 10 kDa electric field, con., 20 for cellulase retention.
longibrachia- (PES) Increase FPU/g Temperature has most
tum with enzyme significant effect on
increasing loading, permeate flux
electric 50 C, 48 h
eld incubation,
strength
Microcrystalline Ionic-liquid Cellulase Organic (PES ) Ultrafiltration 10 kDa Tubular 24.7 l/m2 h, 95% Up to 113 mM 99.8 0.2 Both 10 kDa MWCO [95]
cellulose (1-butyl-3- from inorganic 5 kDa (10 kDa PES) (at 24.7 l/m2 h 100 0.1 organic and 5 kDa
(20 m methylimida- Trichoderma (PES) Fall from permeate ow) 99.4 0.3 MWCO inorganic
powder) zolium reesei (ceramic) 5 kDa 14.2 to 98.4 0.5 membrane retains
chloride) (Celluclast 11.3 l/m2 h maximum cellulase and
1.5L), cellobiase enzyme while
And (CE) 99.4 0.4 performing hudrolysis
cellobiase 10 kDa (5 kDa) 98.1 0.3 in membrane reactor
from 5 kDa (PES) using ionic liquid
Aspergillius (PES) pretreated
niger 5kDa microcrystalline
(Novozyme (CE) cellulose
188)
Sugar beet pulp Cellulase Organic Ultrafiltration 5 kDa, 2540 l/m2 h 0.48 (PES) PES membrane shows [96].
from (Polyethersulfone, (PES) better efficiency for
Trichoderma Thin film) 2530 l/m2 h enzyme recovery.
(continued on next page)
Renewable and Sustainable Energy Reviews 74 (2017) 873890
 Table 2 (continued)

Source of cellulose Pretreatment Type of Membrane material Membrane MWCO Membrane Membrane Cellulose Glucose Rejection Enzyme Main findings References
method cellulase based process module flux conversion production activity
K. Saha et al.

(l/m2 h) (%) Recovery

reesei, (TF) Stirring at the

Cellobiase 4 kDa 3.5 bar 0.52 (TF) membrane surface
from pressure) inhibit concentration
Aspergillus polarization
niger
(Novozyme
A/S)
straw and hay 0.4 M NaOH, Novozyme Organic magnetically 10 kDa Flat-sheet 89, 49 83% 55% Submerged vibration [97]
mixture (1:1) 20 h, room Biomass-kit (Polysulfone, induced 10 kDa (l/m2 h bar) 78% 67% membrane removes
temperature, hydrophilic, membrane 10 kDa (FM, AF) 83% 30% sugar as well as end
5 g/100 g Composite uoro- vibration 1 kDa 52, 35 product and enhances
liquid polymer (MMV) (l/m2 h bar) 81% 100% filtration. Vibration
(FM, AF) enhanced filtration is
Polyethersulfone 55, 20 more efficient for
Composite uro- (l/ fouling prevention as
polymer m2 h bar) compared to
(FM, AF) hydrophilic
27, 27 modification membrane
(l/m2 h surface.
bar)
(FM, AF)
Solka Floc BW200 Celluclst Organic (Polymeric) Ultrafiltration 30 kDa Flat-sheet 5.8 48% 3.1 (g/h/ml Cellulose conversion is [99].
microcrystal- enzyme) higher for tubular
line white, module and the process

881
delignied, retains cellulase,
pure cellulose (Novozyme (NADIR Tubular 6.6 53% 5.8 (g/h/ml separate inhibitory
powder and A/S) type) enzyme) product and enhance
Mavicell productivity and
cellulose conversion
pellets
Rice straw Steam Cellulase Organic Ultrafiltration 10 kDa Hollow- 27.2 (g/l) 50% (FPA) Hydrolysis rate and [100]
explosion from (Polysulfone) fibre 70% reducing sugar yield
Trichoderma (- increased with
ressei glucosidase) continuous separation
of inhibitory product.
Corn stalk Steam Cellulase Organic (PS) Ultrafiltration 10 kDa Hollow- 79 85% (at 3035 (g/l) (at Use of membrane [101]
explosion from fibre 85 g/l 30FPU/gm reactor increased
Trichoderme substrate) enzyme hydrolysis rate and
ressei loading) reducing sugar yield, as
compared to
conventional batch
process
Knot rejects from Ammonia Novozymes Membrane 10 kDa Tubular 2025 8085 (g/l) A technology developed [102].
sulphite and DI water North filtration (Lab Scale) (Lab Scale) with enzyme recycling
pulping America 6 kDa (Pilot scale) and high-consistency
(Franklinton, (Pilot (48 h hydrolysis reduces
NC) Scale) duration, overall cost of
20% hydrolysis process
consistency,
10 FPU/g
enzyme
loading
Corncob Dilute Cellulase Microfiber Filtration 78.1% 36.5% Among the four [103].
(continued on next page)
Renewable and Sustainable Energy Reviews 74 (2017) 873890
K. Saha et al. Renewable and Sustainable Energy Reviews 74 (2017) 873890

References 1. Conventional chemical process for hydrolysis of cellulose forms toxic

byproducts due to the use of high pressure and temperature.
Enzymatic hydrolysis is advantageous as this method uses moderate
temperature and does not lead to byproduct formation.

recovery and recycling

pretreatment methods
acid-base combined 2. As the price of cellulase is too high, recovery and reuse is necessary

conversion, ethanol
in order to reduce the total cost involved. Recovery of cellulase by

yield and enzyme

processing shows
highest cellulose
adsorption-desorption method reduces the catalytic activity in the
Main findings

subsequent hydrolysis process. Membrane ltration is better in this

aspect as catalytic activity of enzyme remains same, even after
repeated usage.
3. Ultraltration, using organic polyethersulfone or polysulfone mem-
brane shows best performance in terms of higher permeate ux and
cellulase rejection, as compared to inorganic or composite mem-
Recovery
Enzyme
activity

30.4%
81.6%

brane.
4. Permeate ux increases with increasing transmembrane pressure or
applying electric eld over membrane and declines with ltration
Rejection

time, concentration polarization, and fouling.

5. Irreversible fouling at membrane surface becomes less while using
(%)

membrane with lower MWCO. Rejection is higher in this case.

Application of electric eld or stirring at membrane surface reduces
fouling and concentration polarization.
production

6. Two stage membrane ltration enhances glucose concentration in

Glucose

the fermentation process.

3.3. Membrane in fermentation process

conversion

ammonia
Cellulose

Aqueous
83.8%

41.2%

Fermentation of sugar to ethanol is the most crucial step in the

production of second and third generation bioethanol especially from
lignocellulosic material. The production process focuses on dierent
Membrane

pre-treatment of biomass. Formation of inhibitors during pretreatment

(l/m2 h)

FM Fresh membrane, AF After filtration, UF Ultrafiltration, NF Nanofiltration, PES Plyethersulfone, PS Polysulfone.

of lignocelluloses aects the growth of fermentative microorganism and

flux

reduces ethanol yield as well as productivity [55,87]. The conventional

process for detoxication and sugar concentration consumes high
Membrane

energy and require high operating cost. Pressure driven nanoltration

module

(NF) or reverse osmosis (RO), membrane distillation (MD) was success

fully applied to overcome the drawbacks with an advantage of high
rejection, lowering energy consumption and enhancing membrane ux.
Generally the separation of inhibitory compound depends on mem-
MWCO

brane type, feed ow rate, feed temperature and initial sugar concen-
tration. RO has been widely studied for separating inhibitors and
saccharification

concentrating sugar from lignocellolosic hydrolyzate. Rejection of

Silmultaneous
based process

fermentation
employed in
Membrane

acetic acid, the main inhibitory compound present in hydrolyzate is

directly proportional to pH. But sugar retention is not dependent on
and

temperature and pH. Application of membrane distillation achieved

100% rejection of sugar [104]. Applying RO, 99% glucose and 40%
Membrane material

acetic acid rejection was achieved from acetic acid-glucose model

solution [105]. Separation of furfural, phenol and carboxylic acid by
RO was studied by dierent research groups [106108]. Nanoltration
membrane

membranes with MWCO ranging from 200 to 1000 g/mol are ecient
62.4%

to separate the major compound of fermentation broth including sugar,

phenols, furan derivatives and aliphatic acid with a molecular weight
ranging from 40 to 150 g/mol [104]. Liu et al. studied sugar rejection
(Novozyme
Cellobiase

eciency of 0.993 from hot water pretreated woody biomass while

(GC220)
cellulase
Type of

84.8%

applying 100 g/mol MWCO nanoltration membrane [109]. While

188)

applying vacuum membrane distillation using solar energy, 99.5%

glucose was rejected and 8.46 l/m2 h ux was achieved with complete
Pretreatment

removal of furfural [110]. As the fermentation process use microorgan-

hydroxide,
sulphuric

Sodium
method

isms to ferment sugar to ethanol it is very essential to separate the

acid,

fermentative microbes (generally Yeast) from treated euent and

recycle back to fermentor to maintain a continuous fermentation
Table 2 (continued)

Source of cellulose

process with high cell density to achieve high productivity of ethanol.

Dilute sulphuric

For this purpose membrane bioreactor technology i.e combination of

ammonia
acid plus
aqueous

biological process with membrane separation technique has been

widely used in biorenery and bioenergy industry to increase the
concentration of product, microbial cell and lower toxic inhibition. He
et al. reviewed the performance of pervaporation, membrane distilla-

882
K. Saha et al.
tion and membrane lm bioreactor in ethanol production. Though
pervaporation membrane bioreactor and membrane distillation bior-
eactor use dierent membrane structure, driving force and separation
mechanism, but both methods are ecient to reduce product inhibi-
tion, concentrate cell and enhance ethanol yield and productivity [87].
Pervaporation membrane bioreactor successfully performed in cell
recycling, enhancing cell concentration and ethanol production. Cell
retention by microltration followed by ethanol water separation by
pervaporation, achieved 150 g/l cell concentration, 111169 g/l etha-
nol in permeate and a total ux of 1.682.5 kg/m2 h [111]. A series of
continuous fermentation with Saccharomyces cerevisiae in membrane
bioreactor using ultraltration tubuler membrane
(Polyphenylenephthalamide membrane with 25,000 MWCO) achieved
100% cell recycle with maximum 81 g/l ethanol concentration and
15 g/l/h ethanol productivity. Biomass concentration at steady state
varied from 10 to 60 g/l. To alleviate membrane fouling feed ow rate
was maintained from 600 ml/h to 800 ml/h [112]. A continuous
fermentation coupled with a hydrophobic, tubular polytetrauoroethy-
lene (PTFE) assisted membrane distillation can achieve a long time run
using ethanol stripping module in the fermentation of glucose and
molasses. Ethanol production rate increased from 0.22 to 0.38 g/gh
was attained while glucose concentration was increased from 3 to 5 g/l
10 g/l during continuous fermentation 350 g/l average ethanol con-
centration was observed in cold trap. Cell occulation, aected by salt,
occurs when molasses medium with high sugar concentration is used in
fermentation but it does not at all aect the ethanol separation.
Backwashing was not required in this method [113]. Continuous
ethanol extraction increased ethanol productivity from 0.99 to
1.85 g/lh while using membrane distillation [114]. While studying
membrane lm bioreactor employed with hollow bre polypropylene
membrane, immobilized yeast cell density on membrane surface
reached to 3.5109 cells/ml and ethanol productivity reached to
26 g/l/h [115]. Generally two membrane congurations are widely
used. External cross ow membrane module use bioreactor and
membrane module separately and reduce membrane fouling but
require higher energy to be operated in continuous mode where in
submerged or immersed membrane conguration membrane is in
direct contact with broth which is an energy ecient method, but the
major disadvantage is membrane fouling due to high cell concentration
[116]. Membrane fouling, caused by deposition of microbes and
polysaccharide on membrane surface leads to decline in permeate ux.
Increasing cross ow velocity and controlling hydrodynamic para-
meters i.e. lowering transmembrane pressure and shear-rate reduces
membrane fouling as well as cake formation. Increasing the use of
rotational speed while using rotational dynamic ltration reduced
concentration polarization which is a main cause of membrane fouling,
thus induce permeate ux [117]. Applying air scour for backwash or
increasing cross ow velocity reduces fouling [118].
3.4. Summary
Microbial fermentation is the critical step that converts monosac-
charide to bioethanol. Inhibitors formed during pretreatment of
biomass reduce ethanol production during microbial fermentation.
Thus separation of inhibitory components and recycling of fermenta-
tive microorganism are necessary in order to achieve higher ethanol
yield. Assistance of membrane is this process leads to the development
of eco-friendly fermentation process. Performance of membrane based
process depends on certain factors.
1. Nanoltration and reverse osmosis are ecient with regard to the
separation of toxic inhibitors and concentration of sugar.
2. An increase in pH enhances the rejection of acetic acid, the main
inhibitory compound present in hydrolyzate.
3. Microltration, followed by pervaporation, achieves high cell density
and high ethanol productivity.
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Renewable and Sustainable Energy Reviews 74 (2017) 873890
4. Membrane fouling can be reduced by increasing feed ow rate,
lowering transmembrane pressure, and shear-rate, backwashing,
and increasing rotational speed
3.5. Membranes in downstream processing for dehydration
The last stage in the ethanol production process is the downstream
processing section. The importance of this section cannot be over-
stressed enough, owing to the fact that the products produced in here,
are put up directly for sale, generally without any further processing.
Downstream processing may be distinguished into separation by
traditional methods and by modern methods. The modern methods
broadly signify the rise of membranes as the principal processing
media in extraction of ethanol from the end product of biomass
fermentation. The industrial production of ultrapure ethanol brings
up several diculties. In the case of bioethanol production by
fermentation of six (and ve) carbon sugars, most of the generated
by-products, if not all, inhibit the fermentation as the mass fraction of
the by-products increase in the reaction broth, which is why dynamic
removal of the by-products needs more research in addition to the
meagre number of ongoing ones. The by-products known to inhibit the
reaction in some way or the other [119121] can broadly be classied
into three groups: First, the weak acids like acetic, formic, and levulinic
acid; second, the derivatives of furan and thirdly, phenolic compounds
in the likes of vanillin, phenol and p-hydroxybenzoic acid. The most
common inhibitor is, surprisingly, produced ethanol working via the
product inhibition pathway. The largest processing load in the down-
stream processing section comes from dehydrating bioethanol, and
unless the inhibiting by-products are taken care of prior to dehydra-
tion, they can incur additional costs that could have been reduced with
a pre-emptive remedy [122,123]. In some extreme cases, even a low
concentration as 0.1 mM of inhibitors can have a negative impact on
the main reaction [124]. In the case of ethanol production using non-
biological means, the traditional methods of ethanol extraction from
the product stream, such as conventional and azeotropic distillation
and/or solvent extraction and the likes, by their very denition of being
non-biological, renders the step of by-product removal redundant.
Biologically assisted ethanol production has seen some of the
proposed ethanol purication methods fail while others have suc-
ceeded, with some to the extent that they have already been industrially
adopted. Pervaporation is one such well established process [125].
Membrane distillation is presently being researched as the next best
method with a lot of promise [126,127]. Also, some innovative
methods are surfacing, such as the use of forward osmosis to dehydrate
ethanol [128,129].
3.5.1. Membrane distillation
The major limitation of ethanol fermentation comes from the end
product inhibition when ethanol concentration reaches 12% by volume,
the specic growth rate of the yeast cells decline [130]. The aforesaid
limitation could be alleviated by employing a suitable membrane
distillation system. Membrane distillation plays an important part in
the downstream processing and recovery of fuel ethanol. The volu-
metric productivity of bioethanol can be eciently increased with the
membrane distillation process. Microporous hydrophobic membranes
which are impermeable to water are used for membrane distillation.
The membranes for the membrane distillation process are prepared
from low surface energy hydrophobic polymers such as polytetraur-
oethylene (PTFE), Polypropylene (PP) or polyvinydilene uoride
(PVDF). Good thermal stability and chemical resistance are exhibited
by these polymers as available from the literature [131]. The process
principle is based on the dierential vapour pressure at the membrane
surface which acts as a driving force for separation. Gryta et al.
reported the use of Direct Contact Membrane Distillation (DCMD)
for ethanol synthesis from lactose solution in a BIOTRON reactor.
Ethanol was continuously removed from the fermentation broth
K. Saha et al.
through porous hydrophobic polypropylene membrane along with
other volatile organic compounds which resulted in increase of ethanol
productivity. Outside and inside diameter of polypropylene capillary
membrane module was 2.6 mm and 1.8 mm respectively and eective
membrane area was 490 cm2. The permeate ux was found to be at
constant level when the studies on fermentation with membrane
distillation was carried out for 860 h. The ethanol yield was 0.40.51
(g EtOH)/(g of sugar) and the production rate was 2.54 (g EtOH)/
dm3 h when compared to 0.350.45 (gEtOH)/(g of sugar) and 0.82 (g
EtOH)/dm3 h obtained in the conventional batch fermentation. The
ethanol ux acquired in the process was in the range of 14 (kg EtOH)/
m2 per day. Thus it was found that fermentation integrated with DCMD
was eective in selective removal of ethanol from the fermentation
broth without the phenomenon of membrane wetting thereby increas-
ing the ethanol productivity [130]. Performance of DCMD was also
evaluated for ethanol production from whey. Maximum 61.16 g/dm3
ethanol concentration after 24 h of fermentation was achieved in
permeate when feed contained deprotinized whey along with sucrose
building 100 g/dm3 sugar concentration. Maximum ethanol ux ob-
tained 1.2 kg/m224 h. Ethanol ux is directly proportional to sugar
concentration in broth [132]. It was observed that membrane distilla-
tion increased the eciency of ethanol production through by selective
removal of the fermentation products. Direct contact membrane
distillation (DCMD) with cross ow membrane ltration module was
reported for brewers wort fermentation. Microporous hydrophobic
polypropylene membrane having capillary inside diameter of 1.8 mm
and an outside diameter of 2.6 mm, and 0.2 m pore size was used for
the purpose. The eected surface area of the hydrophobic membrane
was 0.1 m2 with 40 numbers of capillaries in the membrane module.
The ethanol production increased with complete fermentation of
sugars and decreasing the glycerol synthesis level. The yeast cell
number and viability were maintained during the process. During the
continuous fermentation process the conversion eciency of carbohy-
drates to ethanol was as high as 88.2% of the theoretical yield. The
conversion eciency was found to be 15.6% higher than the classical
batch fermentation process. Ethanol ux was found to be directly
proportional to the temperature and ethanol concentration in the broth
[126]. The process economics of the bioethanol production can be
improved by utilizing continuous fermentation process with membrane
integrated system. Vacuum membrane distillation (VMD) with solar
energy was reported by Zhang et al. for concentrating the lignocellu-
losic hydrolysate obtained from steam explosion pretreatment [133]. In
this study PVDF membranes with average pore diameter and porosity
of 0.18 m and 85% respectively were used. It was observed that feed
velocity and temperature had a signicant eect on VMD. The ux
increased by 24% from 4.7 l m-2 h-1 to 5.8 l m-2 h-1 at 0.6 m/s and
1.1 m/s feed velocity respectively. The membrane distillation ux
doubled to 9.5 l m-2 h-1 from 4.6 l m-2 h-1 when the temperature was
increased from 50 C to 70 C. The result indicated the rejection of
glucose to be more than 98% and the ethanol concentration in the
fermentation broth was 2.64 times as much as that of the original
hydrolysate solution.
The membrane distillation is not practiced in industrial scale at
present. Further research is needed before implementing membrane
distillation from lab scale to industrial scale. Other membrane cong-
urations apart from DCMD need to be explored and investigated
further.
3.5.2. Summary
1. Ethanol productivity increases during fermentation which is coupled
with membrane distillation due to selective removal of the fermen-
ted products.
2. Fermentation integrated with DCMD was eective in selective
removal of ethanol from the fermentation broth without wetting.
3. Flux increases with temperature, but does not decline rapidly with
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Renewable and Sustainable Energy Reviews 74 (2017) 873890
respect to time.
3.5.3. Pervaporation
Pervaporation, as the name delineates, incorporates permeation of
a component into the involved membrane matrix and the successive
evaporation of the permeated component into the vapour phase inside
the membrane matrix. The vapour-liquid interface is extent inside the
membrane. The component from the liquid feed that permeates into
the membrane vaporizes into its corresponding vapour state in situ and
gets selectively permeated to the other side which depends on the
dierence between the transport rates of the components in the liquid
feed. Generally, the feed or the upstream side is at atmospheric
pressure, while permeate or the downstream side is kept under vacuum
so as to allow the selective evaporation of the target component after
permeation through the membrane [134]. The driving force is the
dierences in partial pressures of the components on either side of the
membrane. The volatility dierence between the feed components does
not play any role whatsoever in determining the selectivity of the
components [135]. The mechanism involved in pervaporation is the
solution-diusion. Pervaporation membranes can be classied depend-
ing on the material used for their construction i.e organic, inorganic
and hybrid membrane and on their selectivity towards water which
further categorize pervaporation membranes in hydrophobic and
hydrophilic. By using pervaporation it is possible to dehydrate ethanol
to 99.8% [87].
Hydrophilic membranes, used to remove water from the feed, have
been categorized into three depending on the material and method of
synthesis of the membrane. Those membranes may be inorganic,
polymeric and composite [135]. Inorganic membranes have recently
gained a lot of commercial attention due to its superior temperature
and mechanical stability and are generally made from zeolites [136
139]. A large number of polymeric membranes for pervaporation have
been studied in detail, for example cellulose acetate butyrate mem-
brane [140], PDMS (polydimethylsiloxane) membrane [141], polydi-
methylsiloxane-polystyrene interpenetrating polymer network (PDMS-
PS IPN) supported membranes [142], aromatic polyetherimide mem-
branes [143]. A few of these studies churned out quite interesting
results. In a particular case, it was found that as polystyrene (PS) is
more hydrophobic than PDMS and also has a property of higher tensile
strength, the mechanical and lm forming a dual layer polydimethylsi-
loxane-polystyrene (PDMS-PS) membrane was found to be better than
PDMS itself. The study also pointed out that for high ethanol
concentrations in the feed, the membrane was selective for water,
while for low ethanol feed concentrations, the membrane was selective
for ethanol [142] . The sorption, diusion and pervaporation of
aqueous ethanol in homogenous/composite aromatic polyetherimide
membranes were explored by [143]. Recently, various inorganic-
polymer and polymer-polymer combinations for composite membranes
have been developed and tested, in order to combine the advantages of
inorganic and polymeric membranes to get superior performance with
low cost. Some of these include polystyrenesulfonate/alumina [144],
polyelectrolytes multi-layer [145], zeolite KA-incorporated cross-linked
poly (vinyl alcohol) (PVA) multilayer mixed matrix membranes
(MMMMs) [146] and poly(vinyl alcohol) (PVA)-sodium alginate (SA)
blend membranes [147]. Chen et al. [148] found out that lithiation of
polysulphone membrane improves the pervaporation performance. In
addition to indicating that the ethanol concentration in feed strongly
aected the separation performance; the study also found out that
permeation ux was strongly inuenced by the operating temperature
while the separation factor went down as the operating temperature
went up. Chen et al. [144] pointed out that for polystyrenesulphonate/
alumina membranes, the separation factor could be as high as 400.
Hydrophobic membranes can be categorized into three sub cate-
gories: 1) the polymeric membranes include poly[1-(trimethylsilyl)-1-
propyne] (PTMSP) [149,150] and poly[dimethylsulfoxane] (PDMS)
[151153], 2) Zeolite membranes including zeolite A [154] and multi
K. Saha et al.
channel MFI [155] membranes, with occasional use of silicalite based
membranes [156158], the very recent composite membranes, which
hold a lot of promise which is a relatively newer branch and needs a lot
of research. Examples of hydrophobic composite membranes include
silicalite particles dispersed in PDMS [159,160] and crosslinked PDMS
membrane incorporated with HF acid etched ZSM-5 [161]. Chovau
et al. investigated the impact of fermentation byproducts like imperme-
able components and carboxylic acid on hydrophobic pervaporative
separation of ethanol from aqueous solution containing 5 wt% ethanol
using at sheet PDMS membrane separately. Addition of 5 wt%
glucose, 5 wt% xylose, 1 wt% (NH4)2SO4 separately increase ethanol
permeate concentration due to enhanced ethanol ux with addition of
these components respectively. Addition of 1 wt% glycerol causes the
reduction of vapour pressure of both ethanol and water, thus do not
aect ethanol ux and permeate ethanol concentration. 0.1 wt% 2,3-
butanediol decrease ethanol ux due to the strong sorption to PDMS
membrane. Carboxylic acid interacts with silanol group of Si-based
lter of the membrane causing membrane fouling, therefore decrease
hydrophobicity degree and separation performance of PDMS mem-
brane as well as rises the water ux [123]. Moermans et al. explored the
eect of additional glucose and xylose in feed on the selectivity and
total ux in pervaporation of a 2% w/w ethanol-water solution at
varying feed temperature and permeate side pressure. Total ux and
ethanol selectivity decreases moderately for all varying glucose level as
permeate side pressure increases from 1 to 20 mm Hg and more
apparently at 40 mm Hg and increases as feed temperature rises.
Xylose has less eect than glucose on polydimethylsiloxane membrane
selectivity [160]. Fermentation operation time and temperature aect
the permeate ux as well as ethanol separation factor of at sheet
cellulose acetate membrane for sweet sorghum juice fermentation.
Increasing the fermentation operating time from 15 to 60 min
decreases total permeate ux from 2.7 to 1.5 kg/m2 h and separation
factor from 6.6 to 2.3 and a rise in temperature reduce the total ux
and separation factor which indicates the demerits of cellulose acetate
membrane in pervaporation system for sweet sorghum juice fermenta-
tion [162]. Some researcher investigated the ethanol recovery from
lignocellulosic fermentation broth which is mentioned in Table 3.
From existing literature [167], it can be seen that each membrane
has a separation factor which determines how well it performs. The
Polydimethylsiloxanediol (PDMS), poly(1-trimethylsilyl-1-propyne
(PTMSP), zeolite and composite membranes have been reported to
have separation factors of 4.410.8, 926, 759, 12106, respectively.
However, in some cases, the separation factor gets way higher than
expected, such as a separation factor of 218 during the separation of
ethanol (98.2% permeate) over water-ethanol solution (20% by weight
ethanol), using a silicate zeolite membrane [168]. In general the
ranking of separation factors are in order: PDMS < PTMSP < composite
membranes < zeolite membranes.
3.5.4. Summary
1. Pervaporation process can concentrate ethanol to 99.8 wt%.
2. Hydrophilic membranes are classied as organic, inorganic and
polymeric membranes. Inorganic membrane has more temperature
resistance and mechanical stability as compared to organic and
composite membrane.
3. Permeate ux increases with feed temperature but separation factor
is inversely proportional to operating temperature.
4. An increase in ethanol concentration in feed enhances the permeate
ux.
3.6. Techno economic evaluation
Bioethanol from lignocellulosic biomass is one of the most promis-
ing fuels which can be used to replace gasoline in modern vehicles. It is
an oxygenated fuel and burns cleaner than fossil fuel. Production of
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Renewable and Sustainable Energy Reviews 74 (2017) 873890
bioethanol by fermentation of lignocellulosic or other feed stock
comprises of dierent steps like pretreatment, recovery of value added
products, enzymatic hydrolysis, cell and enzyme recycle, removal of
inhibitory byproduct formed during fermentation, recovery and dehy-
dration of ethanol from fermentation broth either by conventional
downstream process or by advanced membrane based separation
process. Furthermore during pretreatment with acidic or basic process,
dierent inhibitory product like weak acids, furan derivatives and
phenolic compounds are formed which are used in dierent chemical
and pharmaceutical industries. Thus complete utilization of the
byproducts increases overall process economy. Due to rising price of
petroleum fuel, bioethanol is grabbing attention now a days as eco-
friendly and economically viable transportation fuel. Gnansounou et al.
reviewed techno economic evaluation of lignocellulosic bioethanol
production by conventional process. In simultaneous saccharication
and co fermentation of lignocellulose, bioethanol and electricity are
produced as per the conguration of ethanol plant. The main produc-
tion cost depends on investment cost and cost of feedstock. Fixed
operation cost that includes tax, overhead, maintenance and insurance,
whereas variable operation cost which includes the price of consum-
able, sales of electricity are less signicant. Various transportation costs
for feedstock includes loading and unloading and xed and variable
cost. Availability of biomass is an important factor. Among the four
dierent feedstock (eucalyptus, poplar, switchgrass and straw) exam-
ined, eucalyptus is cheaper and poplar is the most costly one. Ethanol
yield is lower for straw and higher for poplar. Except eucalyptus, 50
55% production cost comprises of feedstock. Higher ethanol yield
reduces electricity output and production cost including feedstock
expenses and xed operating cost [169]. Quintero et al. gave an
economic analysis of bioethanol production from four dierent ligno-
cellulosic wastes (Sugarcane bagasse (SCB), Coee cut-stems (CCS),
Rice Husk (RH), and Empty Fruit Bunches EFB)) in Colombia and
found out the highest production cost for SCB due to high cost of raw
material and utilities. On dry basis ethanol production is 313.83 l/t,
305.11 l/t, 298.21 l/t, 250.56 l/t of EFB, CCS, SCB, RH. On dry basis
EFB produce higher amount of ethanol due to its high hemicelluloses
content. For SCB, utilities cost share 37% of total cost. Raw material
cost is 15 US$/t and ethanol price is 0.3472 US $/l, which share
45.32% of total production cost due to higher price of SCB and the
requirement of high ow rate to produce ethanol 100,000 l/day. The
other residues require utility cost more than 45% of total cost due to
high energy cost in dierent steps. Though the price of CCS is higher
relative to others, but the low moisture content is low leading to high
ethanol production in wet basis, this residue require only 35.06% of
production cost. The use of lignin of lignocellulosic biomass as primary
source of power and heat can reduce the utility cost and focus on other
required parameter administrative, maintenance, labor, capital depre-
ciation cost etc. So the authors have suggested a energy cogeneration
scheme coupled with ethanol production process for this purpose
which can reduce the production cost of 10.67% for SCB, 15.74% for
EFB, 16.91% for RH and 13.95% for CCS. Selling of electricity surplus
reduce production cost [170,171]. Luccioa et al. investigated the
economic feasibility of ethanol production and dehydration by fermen-
tation coupled to pervaporation system and the formation of fructose
as byproduct of fermentation. The ethanol plant was designed to
operate 330 days/yr to produce 6000 m3/yr ethanol and 10,000 t/yr
fructose as byproduct which gave the project economic viability.
Maximum membrane cost was about 500 US $/m3. Raw material i.e.
inverted sugar cost was 0.035 US$/L and the price of ethanol was 0.37
US$/l in a fermentor, costs 450,000 US$. Yield of fructose is 90% and
95% is recovered using fructose extraction column costs 410,000 US
$/l. Internal return rate (IRR) was adopted for analysing economic
viability. The higher IRR could make the project viable, although the
membrane cost is high [171]. According to Sassner et al., raw material,
pretreatment, steam generator and fermentor are contributor of
maximum investment cost, while bioethanol is produced by simulta-
 K. Saha et al.

Table 3
Overview of ethanol dehydration by pervaporation from lignocellulosic hydrolysate.

Lignocellulosic raw Microorganism Membrane type Membrane Pervaporation Total/Ethanol flux Separation Pervaporation Main findings References
material used configuration operating condition factor/selectivity index
(kg/m2 h) (kg/m2 h)

Sweet sorghum juice Saccharomyces Organic (cellulose acetate Flat sheet FT: 5070 C, EF 4.2 (FT 70 C) 2.2 9.2 Increase in temperature and [162].
cerevisiae membrane) PSP: 50.8 mm Hg, (maximum ux) ethanol concentration rise flux but
time: 1560 min reduce selectivity whereas
operating time does not have
significant effect
Forages and Organic FT: 3060 C, EF 0.036 (FT- 1.66 FT and PSP have significant effect [163].
agricultural (polytetrafluoroethylene PSP: 120 mm Hg, 30 C, PSP-20 mm 2.25 on total flux but selectivity does
residues membrane) time: around 2 h Hg) not change with FT, PSP and
0.465 (FT-60 C, 2.85 Reynolds number
PSP-20 mm Hg)
86 (FT-30 C,
PSP-10 mm Hg)

886
Banana pulp waste Organic (polydimethylsiloxane Hollow fibre FT: 22 C, 30 C, PSP: TF-0.0058 (feed 0.062 By-product formation during [164]
membrane) 5, 20, 45 mm Hg flow rate 20 l/h fermentation influence separation
TF-0.0036 (feed at lower feed flow rate
ow rate 80 l/h)
Barley traw Saccharomyces Organic Flat-sheet FT: 30 C TF-0.567, EF-0.065 4.2 0.1 [165]
sWillow wood chips cerevisiae (polydimethylsiloxane) TF-0.533, EF-0.069 4.8
TF-0.498, EF- 4.8 0.1
0.064
Rejected banana fruit Saccharomyces Organic (polydimethylsiloxane Hollow fibre FT: 295 K, PSP < TF-0.0058 10.63 0.062 Fermentation broth shows better [166]
(Musa cerevisiae membrane) 667 Pa EF-0.001 3.97 0.014 separation efficiency as compare
cavendishii) (feed ow rate to model ethanol water mixture
5.510-6 m3/s)
TF-0.0036
EF-0.0003
(feed ow rate
22.210-6 m3/s)

FT Feed temperature, PSP Permeate side pressure, EF Ethanol flux, TF Total flux.
Renewable and Sustainable Energy Reviews 74 (2017) 873890
K. Saha et al.
neous saccharication and fermentation using softwood, corn stover
and hardwood as feedstock. Raw material comprises of maximum
production cost. Lignin, the co-product of bioethanol production, has
an important eect on the whole process economy. Insurance, main-
tenance and labor have been subjected as Other cost. Capability of
yeast to utilize both pentose and hexose sugar resulted in 90% of
conversion of pentose sugar to ethanol and an 42% and 32% increase in
ethanol yield for corn stover and hardwood respectively. This phenom-
enon improves process economy. 50% decrease in enzyme loading
would be economically feasible if the residence time is increased by
30% and the yield of ethanol should not decrease more than 67%
[172]. Capital comprises of 40% of total bioethanol production cost
from lignocelluloses. Power usage is the major constituent of capital
cost. Production part contributes half of the capital investment.
Implementation of simultaneous fermentation and saccharication
instead of separate hydrolysis and fermentation reduce the cost [173].
3.7. Summary
Above discussed techno-economic evaluation of bioethanol produc-
tion from lignocelluloses reveals that overall production cost incorpo-
rates investment cost and cost of feedstock, xed operation cost that
includes tax, overhead, maintenance and insurance and variable
operation cost which include the price of consumable, sales etc. The
overall cost can be reduced by considering following point.
1. Locating ethanol plant near cultivating area reduces the transporta-
tion cost of biomass.
2. Feedstock or raw material holds maximum cost. Thus, using cheaper
feedstock and plentiful available raw material can reduce overall
cost.
3. During pervaporation assisted continuous fermentation of ethanol,
recovery of fructose as byproduct enhances economic viability.
4. Reducing enzyme loading and elongating the residence time reduces
process cost
5. Fermentation of pentose along with hexose improves process
economy.
6. Implementation of simultaneous fermentation and saccharication
instead of separate hydrolysis and fermentation reduces the cost.
4. Conclusion
Lignocelluloses are one of the most abundantly available renewable
resources on earth which could be exploited for bioethanol production.
To meet the demand of bioethanol as an alternative to fossil fuel,
extensive research is going on for bioethanol production using cheap,
abundantly available lignocellulosic residue. To upgrade lignocellulosic
ethanol production, an eco-friendly, energy ecient and economically
viable scheme needs to be developed. The scheme usually includes a
pretreatment strategy addressing eective lignin separation and re-
covery, cost eective enzymatic hydrolysis by recycling enzyme,
fermentation equipped with microorganism recycle system as well as
aqueous ethanol separation, and nally eco-friendly ethanol dehydra-
tion. Separation of ethanol from fermentation broth was successfully
performed by membrane based ultraltration, pervaporation and
membrane distillation. But to attain all the desired criteria for
commercial bioethanol production, integration of membrane in only
a specic stage is not sucient. Development of a well organised
production scheme, which comprises of cost eective pretreatment of
lignocelluloses using a green solvent that recovers lignin and recycles
the solvent, is, as such, necessary. Flat sheet cross ow ultraltration,
followed by nanoltration based enzymatic hydrolysis of pretreated
lignocelluloses recovers and recycles enzyme as well as concentrate
sugar respectively. Applying microltration, followed by nanoltration
in fermentation method, recycles microorganism and retains uncon-
verted sugar respectively. Finally vacuum membrane distillation attains
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Renewable and Sustainable Energy Reviews 74 (2017) 873890
dehydrated ethanol with high productivity in an environmentally
feasible manner. Research on such scheme needs to be investigated
for commercialization and scaling up.
Acknowledgement
The authors would like to acknowledge Department of
Biotechnology, Government of India (Grant no. DBT/In-Bz/2013-16/
06) and MCTI-CNPq-Brazil (vide Grant no. DBT/In-Bz/2013-16/06
and CNPq process no: 401361/2013-6) for the bilateral collaboration
to carry out the review work. The authors thank Jhilly Dasgupta,
Research Scholar, for her help to improve the manuscript.
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