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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 renewable energy source. High cost, limited reservoir, depleting supply,
and random consumption hinder the dependency on petroleum as
International Energy Outlook (IEO) 2013 predicts an increase of transport fuel [1]. Over consumption of fossil fuel is a major threat to
56% in World energy consumption over 30 years (from 2010 to 2040). environment as it leads to acid rain, climate change, global warming,
Herein 79.7% of the consumed energy is supplied by non renewable and harmful eect on human health and aquatic life. Global scenario
fossil energy source (coal, natural gas, crude oil/petroleum etc.) and shows extensive use of conventional diesel engines throughout the
nuclear source, 15.3% is supplied by hydro-power and rest 5% by other 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. Renewable and Sustainable Energy Reviews 74 (2017) 873890

[2] but the most detrimental pollutants (particulate matter like carbon, tion. Brazil and United States account 87.1% of World bioethanol
trace element, inorganic ion etc. and nitrous oxide (NOx)) are emitted production in 2011 as estimated by Renewable Fuel Association (RFA).
from diesel engines [3]. Application of two-cell selective catalytic US produce fuel ethanol from corn stover [16] where Brazil use
reduction (SCR) system in diesel engine can reduce pollutant emission sugarcane bagasse and straw as the possible raw material for ethanol
to a certain extent, as the rst catalyst cell minimizes NOx emission production. Sugarcane is the most plentiful agricultural crop cultivated
whereas the second cell adsorbs ammonia generated from the previous in this country [17]. Brazil has been producing sugarcane ethanol since
cell [4]. But the major limitation of SCR system is the chance of early 20th century [18] and the popularity of sugarcane ethanol
contamination and blocking of the catalysts pore by ne particles, increased in 2003 with the use of ex fuel vehicle. Currently, 5%
silicon compounds etc. Contrastingly, the use of natural gas in a single ethanol blending policy with gasoline has been followed in India. Later,
cylinder diesel engine by dual fuel mode of application decreases it will move towards 20% blending by 2020. But, the currently available
carbon dioxide, particulate matter, and NOx but a drastic increase in feedstock in the form of sugarcane molasses is inadequate to meet the
carbon monoxide (CO) and hydrocarbon (HC) emission occurs as necessity and also raises the food vs fuel debate [19]. Thus bioethanol
compared to the emission observed in the case of traditional diesel produced from agricultural residue especially lignocelluloses came into
engine [5]. These major drawbacks have invoked reasonable awareness scenario to overcome this debate. Huge demand of lignocelluloses
regarding investigation of alternative renewable energy sources, which residue to support industrial production of bioethanol can be enhanced
are environmentally benign, economically and technically feasible, by increasing the cultivation of potential agricultural crops which can
biodegradable, and non-toxic [6]. Water, biomass, wind, geothermal be successfully achieved by implementing modern agriculture and
heat can serve as renewable energy source and can potentially irrigation system. Applying proper agricultural water management,
substitute fossil fuel [7,8]. The developed nations are focussing on the ratio of irrigation to cultivated area can be improved day by day in
the application of biomass based fuel, given that biofuel is a cost wise Indian Ocean Islands [20] which can inuence the agriculture strategy
competitor of fossil fuel, as it satises all the necessities of clean of India. Among available dierent irrigation systems surface irrigation
technology, including renewability, sustainability, common availability, has been used in most of the agricultural areas all over the world. Due
reduction in green house gas emission, and biodegradability [9]. to the complexity of the technique three dierent models have been
Biofuel can be classied into two groups. Primary biofuel is referred investigated to simulate surface irrigation. Among these zero inertia
to as natural and untreated biomass, such as wood chips and fuel wood. and full hydrodynamic models are more powerful as compared to
These are directly combusted to supply energy for cooking, heating and kinematic wave model [21]. Trickle and sprinkle irrigation system also
electricity production. Secondary biofuel is produced by processing or improves overall cultivation process but for applying these techniques
modifying primary biofuel. These are generally solid, liquid or gases. pressure loss must be appropriately adjusted to avoid the failure of the
Secondary liquid biofuel can be further divided into three generation system, which can be done by using tapered pipes [22]. Due to
fuel depending upon the raw material used [10]. First generation liquid requirement of large amount of water in irrigation process, world
requires simple production process and uses sugar [11] or grain [12] as population suers from water crisis. Therefore use of non-conventional
possible raw material while second generation fuel is produced from water resources, mostly treated wastewater, will be eective in this
agricultural lignocellulosic biomass by biological or thermochemical aspect in developing countries like India and Brazil [23]. Water lifting
process and third generation biofuel is derived from microbes and technology, which is attained by pump system, also plays a vital role in
microalgae [10,13]. Main aim of biofuel research is to produce energy irrigation practice. Though the use of modern pump improves water
products like bioethanol, biomethanol, biodiesel, biogas, biohydrogen supply for expanding irrigating agriculture, but this require high energy
etc. using biological source [14]. which is supplied conventional electric power [24]. This may leads to
Bioethanol and bioethanol/gasoline are most commonly used energy crisis which can be overcome by the use of biomass based
transport fuel worldwide and can be viewed as viable alternatives to energy. Hence lignocelluloses based bioenergy, more specically
petroleum fuel [15]. As burning of ethanol causes emission of carbon bioethanol may contribute for the generation of its own source.
dioxide, it can be mixed with gasoline to oxygenate the fuel mixture to Production of bioethanol from lignocellulosic biomass grabs attention
reduce carbon dioxide emission. Bioethanol is mainly produced from because of renewable and ever-present nature of biomass, its non-
biomass by hydrolysis of cellulose and fermentation of sugar, which competitiveness with food crops and reduction of threat to global
comes from energy crops including maize and wheat crops, sawdust, warming.
cord grasses, sorghum plants, corn, sugarcane etc. The main advantage Lignocelluloses are generally composed of lignin, cellulose, hemi-
of bioethanol over conventional fuel is its biodegradability, less toxicity, celluloses, organic extractives and some inorganic components which
reduction of green house gas emission and use of renewable and turn into ash after combustion [25]. Cellulose and hemicelluloses are
ubiquitous biomass as primary substrate. Bioethanol-based economy is strongly linked to lignin through covalent linkage and hydrogen
more environmentally benecial than gasoline-based or conventional bonding [26]. Cellulose consists of hexose sugar monomer and hemi-
petroleum-based economy and endorsement of the use of Bioethanol cellulose consists of dierent pentose sugar monomers which are
can also inspire rural economy to cultivate the required crops. Fig. 1 fermented by microorganism to produce ethanol. Thus cellulose is
Shows the graph of year wise worldwide average bioethanol produc- 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
Fig. 1. Year wise worldwide bioethanol production as reported in Outlook 20082013 straw produced maximum 0.374 g/g reducing sugar which was sub-
reports. jected to fermentation and 1.48% ethanol yield was achieved with

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K. Saha et al. 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
Fig. 2. Potential Lignocellulosic substrates based on Indian Scenario [36]. can be described as value added product as it has a wide range of
application in dierent aspects. It is used in manufacturing of
61.25% fermentation eciency on the basis of theoretical yield of dispersants, bioplastic, nanoparticles, (nano) composites, carbon bre
ethanol from glucose [30]. Maximum 512 mg reducing sugar was and in agriculture and biofuel eld [38]. So one of the main aims is to
produced per gram of biomass and 0.74% ethanol yield was achieved remove lignin from biomass successfully and use it in various elds.
when rice straw was processed by hydrotrope sodium cumene sulfonate Dierent chemical, physical, biological pretreatment methods have
[31]. Sugarcane top is a feasible feed stock for bioethanol synthesis as been suggested by researcher to change the lignocellulosic biomass
studied by Sindhu et al. 0.685 g/g reducing sugar was obtained by structure i.e disruption of covalent linkage between lignin and cellu-
hydrolysis of dilute acid pretreated sugarcane tops. Fermentation of lose, to alter the structure of lignin and ecient removal of hemi-
reducing sugar by yeast produced 11.365 g/l ethanol with 50% celluloses and lignin to make the cellulose accessible to hydrolytic
eciency on the basis of theoretical yield of ethanol from glucose enzyme that can convert it to monosaccharide [7]. The limitations of
[32]. 21.6 g/l ethanol concentration and 54.45 yield was attained while this conventional pretreatment methods are use of irradiation, high
wheat straw was treated by acid, subsequently hydrolysis by cellulase electricity consumption, high chemical cost etc. In contrast to this, use
isolated from Penicillium janthinellum and fermentation of hydroly- of ionic liquid, a green solvent as pretreatment medium can eciently
zate by K. marxianus [33]. Sugarcane bagasse, the most popular dissolve cellulose or lignin or both in it due to its cationic and anionic
lignocellulosic residue is widely used for ethanol production. As it is structure and remove lignin successfully as well as alter the crystalline
one of the most important crops cultivated in India, thus each year a structure of cellulose [39]. Though ionic liquid is expensive as
huge quantity of sugarcane bagasse is generated as agro-residue. compared to other chemicals, it has been given attention by researcher
Bagasse containing 36.4% cellulose was processed for ethanol produc- as it is a low melting organic salt, non-ammable, and has a very low
tion and 11.5% ethanol was obtained from it [34]. Ethanol concentra- vapour pressure, stable liquid range, and the potential to replace
tion of 7.81 g/l was achieved from metal chloride pretreated sugarcane volatile organic compound. Besides, the ionic liquid also demonstrates
bagasse hydrolyzate, which contained 16.47 0.12 g/l glucose [35]. selective solubility in water and organics and appreciable recyclability
The main technological challenge to convert lignocelullose to [40]. The solvent property can be controlled by way of appropriate
bioethanol is developing a clean, eco-friendly and cost-eective pre- cation and anion selection, which make it a designer solvent and
treatment followed by enzymatic hydrolysis, fermentation and down- accounts for its commendable performance in the eld of green
stream separation and purication. The conversion of lignocellulosic chemistry [41]. Mai et al. [42] summarized dierent process like
biomass to bioethanol can be done either by one of the following distillation (distillation of ionic liquid, distillation of volatile solutes/
process or by combinations i.e. chemical, mechanical, physicochemical impurities in ionic liquid), extraction (solvent extraction, CO2 extrac-
or biological process. This would separate lignin from lignocellulosic tion), adsorption (adsorption/desorption, chromatography), induced
material, the unique valuable byproduct, and exposes cellulose, convert phase separation (salting out, introduction of CO2, changing the
cellulose and hemicelluloses to simple sugar by enzymatic or acid temperature), membrane based processes (nanoltration, electrodia-
hydrolysis and undergoes hexose and pentose sugar fermentation to lysis, reverse osmosis, pervaporation), magnetic separation, and cen-
ethanol by using appropriate microorganism. Downstream separation trifugation to recover and recycle ionic liquid to make the ionic liquid
and purication of bioethanol by suitable technique is required to based lignin recovery an industrially acceptable procedure. The main
manufacture anhydrous and puried alcohol. To establish the bioetha- steps involved in lignin recovery process are mixing of powder form of
nol production process as a clean technology every byproduct should be biomass with ionic liquid in a particular ratio, heating and stirring at
utilized properly in an eco-friendly manner. high temperature for a particular time period followed by extraction of
Bioethanol has been successfully applied as an alternate of conven- lignin from ionic liquid lignin solution by precipitation with an organic
tional fossil fuel due to its environmental benets. This study aims to antisolvent and recycling of ionic liquid after evaporation of antisol-
review the main production steps involved in biorenery system to vent.
manufacture bioethanol and application of eco-friendly membrane Though lignin can be recovered from poplar wood biomass by only
based process in each step. This literature review discusses green alkaline pretreatment, treatment with ionic liquid followed by NaOH
solvent based pretreatment of lignocelluloses to recover lignin, fol- gradually increases lignin yield [43]. Lignin was recovered from soft-
lowed by necessary steps to produce ethanol. Application of membrane wood (Pine) as well as hardwood (Eucalyptus) dissolved in imidazo-
based separation technique in enzymatic hydrolysis, fermentation and lium based acetate and chloride ionic liquid. Characterization of
downstream purication for dehydration and overall techno-economic- recovered lignin showed 31% recovery of lignin [44]. Moghaddam
al evaluation of ethanol production is discussed for better under- et al. [45] isolated and determined physico-chemical characteristics of
standing, to develop a sustainable and environmental friendly and sugarcane bagasse lignin using IL 1-butyl-3 methylimidazolium chlor-
economically viable biorenery scheme. ide [bmim]Cl and also 1-butyl-3 methylimidazolium methylsulfonate
[bmim][CH3SO3] with HCl as catalyst, followed by extraction with
2. Production of bioethanol from lignocellulosic biomass NaOH and the lignin yield was 4243%. Lignin recovery was less due
to the presence of high concentration of acid and high moisture
Production of bioethanol in a clean and eco friendly manner content. Optimization of pretreatment parameters (time, temperature

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and ionic liquid to solid ratio, H2SO4 (catalyst) concentration) was milled wood lignin (MWL) process(4.4 0.4%). Though the structural
studied for extraction of lignin from empty fruit bunch using [bmim]Cl. features were same for both the processes, but the average molecular
Experimental data was analyzed by Central Composite Design of weight of MWL is more than ILL [50]. [EMIM]oAc is an ecient
Response Surface Methodology to nd out optimal condition for lignin solvent for sugarcane bagasse treatment while comparing with other
extraction. The usefulness of acid catalyst was to enhance lignin imidazolium IL and conventional pretreatment [51]. All the studies
dissolution in IL. The optimal condition for maximum lignin yield reveal the eciency of ionic liquid, a green and environment favourable
was 150.5 C temperature, 151 min time period, 3:1 IL to EFB ratio, solvent to treat the lignocellulosic biomass to remove and recover
4.73 wt% H2SO4 concentrations. At this condition the predicted value lignin adequately which is the second most plentiful biological compo-
for lignin yield was 27.9% and experimental value was 26.6%. IL was nent in world next to cellulose and hemicellulose.
recovered and recycled four times and lignin yield decreased not less
than 14 wt% [46]. Sun et al. [47] investigated the extraction and 2.2. Summary
separation of lignin from eucalyptus by dissolving biomass in 1-butyl-3
methylimidazolium acesulfamate [BMIM]Ace and dierent organic co- Literature review discussed lignin recovery and ionic liquid recycle
solvent like N,N-dimethyacetamide, dioxane, ethyl acetate, tolune and during ionic liquid mediated pretreatment of lignocellulose biomass.
named as IL-organic solvent lignin and also recovered lignin from Conventional physical, chemical, physicochemical and biological pro-
residual carbohydrate rich material by NaOH treatment and named as cesses are available to recover lignin. But these processes have some
alkaline ethanol lignin (AEL). IL-tolune treatment recovered maximum major drawbacks. Physical treatments are either high energy consum-
lignin i.e 15.4% whereas fresh IL could only recover 11.5% lignin. The ing or require high temperature, whereas physicochemical processes
order of lignin recovery eciency was IL-tolune > IL-dioxane > IL-N,N- need high pressure and high temperature that can give rise to
dimethyacetamide > Fresh IL. The dierences in the extraction e- byproduct formation. Chemical pretreatment uses corrosive solvent
ciency of organic solvents are due to the dierences in their con- and forms toxic byproducts, whereas fungus assisted biological proces-
ductivity as well as dielectric constant. NaOH is used to remove lignin sing is time consuming. Contrastingly, ionic liquid pretreatment of
from carbohydrate enriched material as alkaline can cleave the alkali lignocellulose is eective, apropos of lignin recovery in pure form. This
labile bond between lignin and carbohydrate. AEL yield (823%) is process is advantageous due to recyclability, eco-friendliness, non-
more than IL-organic solvent extracted lignin (11.514.5%) but less in volatility and high thermal stability of ionic liquid.
case of fresh ionic liquid extracted lignin. Pretreatment of corncob with
ionic liquid 1-ethyl-3-methylimidazoleum acetate [EMIM]oAc and 1. Lignin yield increases with increasing reaction temperature and
water/DMSO followed by alkaline extraction demonstrated 85.04% of time. Supplement of catalyst (acid or alkali) or organic solvent along
lignin recovery. HSQC spectra analysis exhibited presence of cinnamyl with ionic liquid enhances lignin extraction. But the presence of
alcohol end group and -O-4, -, -5, -1 linkage in the corncob lignin moisture content in the reaction atmosphere reduces extraction
[48]. 1-ethyl-3-methylimidazolium acetate [EMIM]oAc was also used eciency.
for softwood (southern yellow pine) processing and yield of 31% of 2. Among dierent available ionic liquids, imidazolium based ionic
original lignin as carbohydrate free and 38% as carbohydrate bond was liquid with shorter alkyl chain is the most ecient, as regards lignin
achieved . Pinkert et al. [49] reported the process of delignication, recovery during pretreatment of lignocelluloses.
isolation of Pinus radiata wood lignin and retention of crystalline 3. Recycle and reuse of ionic liquid in further pretreatment stage is
structure of cellulose in carbohydrate rich residue by treating the wood necessary to make the process economical viable which can be
our with imidazolium acesulfamate ionic liquids i.e [BMIM]Ace, achieved by distillation, adsorption, extraction etc.
[EMIM]Ace which are derived from commercial sugar acesulfamate 4. Sugarcane bagasse is a widely available lignocellulosic residue in
potassium and studied the impact of dierent variable like wood tropical country and [EMIM]oAc is the most ecient ionic liquid for
species, water content, wood particle size and type of IL cation plus bagasse pretreatment with regard to lignin recovery as well as
recycling of IL on lignin extraction eciency (mass of extracted lignin/ disruption of the crystalline structure of cellulose.
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 Thus ionic liquid based processing develops a clean and sustainable
4 h raises the extraction eciency from 0.32 to 0.81 and 0.05 to 0.07. pretreatment technology.
Extraction eciency decreases as the water content in the atmosphere
increases from dry condition (inert gas) to normal atmosphere and 2.3. Enzymatic hydrolysis of lignocellulosic biomass
increasing the moisture content in atmosphere. It increases 13% for
[EMIM]Ace treatment than [BMIM]Ace treatment at 373 K, 2 h Enzymatic hydrolysis is an important step in the conversion of
pretreatment due to two reasons. First, the presence of shorter alkyl cellulose present in the pretreated biomass to glucose for subsequent
substituent in [EMIM]Ace as compared to [BMIM]Ace, which de- fermentation. The bioconversion of cellulose to glucose is carried out
creases its viscosity and toxicity and increases mobility to enhance IL by cellulase enzymes under mild conditions of temperature 4050 C
biomass interaction and secondly, the existence of more halide and pH 4.55.0, which negates the corrosion problems [52]. The
impurity in [EMIM]Ace, which has a positive impact on IL lignin eciency of the hydrolysis process depends on the degree of pretreat-
interaction. IL should be completely recycled to attain a green biomass ment of the biomass in terms of lignin removal and hemicelluloses
processing. To achieve this, researchers recycled IL six times at 373 K, solubilisation, hydrolysis period, and enzyme loading. The initial rate
2 h operation period but no noticeable reduction in extraction e- of the hydrolysis process is aected by the crystalline structure of the
ciency occurred and no IL degradation could be observed in NMR cellulose. Lignin and the acetyl group present in the hemicelluloses
spectra after each recycling process. They have suggested the presence produce unproductive binding with cellulase and limit the hydrolysis
of small quantity of DMSO as co-solvent can suciently increases process [53]. The eciency of the hydrolysis process was found to be
lignin extraction due to untying the H-bond in cellulose and reducing enhanced by the addition of non-ionic surfactants, which changes the
the gross viscosity which boost the penetration of IL in lignocelluloses cellulose surface properties and lowers the enzyme loading.
and subsequently enhance IL lignin interaction. Kim et al. investigated Surfactants, such as polyethylene glycol (PEG), were found to increase
the extraction of poplar wood (Populus albaglandulosa) lignin using the enzymatic convertibility of the lignocellulosic biomass from 42% to
[EMIM]Ace and characterization by GPC, FTIR, TGA NMR, DFRC 78% in 16 h. PEG prevented the unproductive binding of lignin to the
method and compared the yield with milled wood lignin and found out surface of the enzyme [54]. Microwave irradiation pretreatment was
more IL lignin by ionic liquid lignin (ILL) process (5.8 0.3%) than found to enhance the enzymatic saccharication of rice straw by 30.3%.

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The enzymatic saccharication was dependent on factors like irradia- 2.5. Traditional downstream purication
tion time, microwave intensity and substrate concentration [55].
Banerjee et al. reported the utility of the liquid fraction obtained after Aqueous ethanol that is produced after conventional fermentation
Alkaline Peroxide Wet Air Oxidation (APAWAO) of rice husk during process is not accepted to use as fuel ethanol. As ethanol and water
enzymatic hydrolysis. The hydrolysis experiment was carried out with forms azeotropic mixture it is dicult to get almost pure or fuel grade
the APAWAO pretreated solid fraction (in buer) and slurry (solid ethanol. Thus advanced research directs to initiate high energy
fraction in liquid fraction). It was noted that the hydrolysis in the demanding industrially acceptable distillation process to break the
APAWAO pretreated liquid fraction produced more glucose when azeotrope nature for achieving almost pure ethanol. Azeotropic and
compared to hydrolysis of the solid fraction in buer medium. Thus extractive distillation processes are used widely for this purpose [69
recycling of APAWAO liquid fraction was feasible during enzymatic 74]. Distillation separates liquid mixtures based on their boiling point
hydrolysis, which resulted in glucose concentration enhancement at by evaporation following condensation. Gill et al. designed the use of
50C hydrolysis temperature. The enzymatic cellulose convertibility glycerol as entrainer in extractive distillation process to dehydrate
was up to 86 wt% within 24 h and the glucose yield was 21 g glucose ethanol, as glycerol has high availability, relatively low cost and
per 100 g untreated rice husk. The eect of dierent dry matter enhanced relative volatility, which impart a positive eect on azeo-
loadings on the hydrolysis yield was also investigated [56]. The tropic mixture. The study of the impact of this entrainer on feed stage,
structural characteristic of biomass aects the cellulose digestibility reux ratio, entrainer feed temperature, feed molar ratio has also been
with respect to surface area, large pore volume, crystallinity of done to get the most appropriate design for minimizing the require-
cellulose, degree of polymerization and presence of lignin, hemicellu- ment of energy [75]. A novel approach of extractive dividing-wall
loses and acetyl group [57]. Ultrasound assisted pretreatment is a columns (DWC), which combines solvent recovery column, extractive
promising and a novel process which increases the glucose yield after distillation column and pre-concentration column in a single distilla-
enzymatic saccharication by removing lignin and hemicelluloses [58]. tion unit, is ecient to separate 99.8 wt% bioethanol. This ethanol
Ultrasonic pretreatment of sugarcane bagasse at a frequency of 40 kHz dehydration conguration can be applied in large scale bioethanol
increased the amount of fermentable sugars when compared to production [76]. While using ethylene glycol and n-pentane as mass
untreated sample [59]. Bian et al. investigated the eect of ionic liquid separating agent, DWC in extractive and azeotropic distillation can
([Emim]Ac) pretreatment on the enzymatic hydrolysis of sugarcane separate highly pure i.e. 99.8% ethanol, and also saves 1020% of
bagasse. It was observed that ionic liquid pretreatment enhanced overall energy [77]. Employing ionic liquid as mass separating agent
enzymatic convertibility of cellulose and achieved 95.2% cellulose during extractive distillation lowers energy consumption in per kg
conversion after 96 h enzymatic hydrolysis. Lowering the degree of ethanol purication. This process can achieve 0.995 (in mass) ethanol
polymerization and reducing cellulose crystallinity by ionic liquid purity and 99.9 wt% ethanol recovery [78].
pretreatment resulted in high hydrolysis convertibility [60]. The
enzymatic digestibility of cellulose was found to be more associated 2.6. Summary
with lignin removal than hemicelluloses solubilisation [61].
The overall process economics of bioethanol production can be Most of the industries use distillation in downstream purication to
improved by operating enzymatic hydrolysis at higher substrate con- dehydrate ethanol. But this technique is highly energy demanding and
centration so that the glucose yields in the hydrolysate could be more. hence results in high power consumption. Energy consumption should
The substrate concentration aects the rate and extent of the hydrolysis be reduced in order to attain energy ecient dehydration method.
process. The hydrolysis yield and substrate concentration is inversely
related [62]. It is well documented that cellulolytic enzymes suers 1. Azeotropic distillation and extractive distillation are industrially
from end product (such as cellobiose and glucose) inhibition. Addition acceptable ethanol dehydration processes.
of cellobiase enzyme alleviates the inhibitory eect of cellobiose as it 2. Use of highly available, low cost glycerol as entrainer in extractive
hydrolyzes the cellobiose to glucose. Operating hydrolysis reaction at distillation dehydrates ethanol as well as minimizes energy con-
low substrate concentration reduces the end product inhibition. It was sumption.
observed that glucose concentration increased with increase in dry 3. Use of ethylene glycol, n-pentane or ionic liquid as mass separating
matter loading (up to 10% of dry matter). A further increase in dry agent minimizes energy consumption.
matter concentration does not proportionately increase the glucose
yield. This may be attributed to possible mass transfer limitations due 3. Possibilities of application of membrane in bioethanol
to high substrate concentration where there is little convective mixing production
due to minimum water available to facilitate the mass transfer of the
water soluble compounds. Sugars build up around the active sites of Membrane, a thin barrier where placed between two medium and
cellulase enzyme and inhibit further hydrolysis reaction [63]. Table 1. driving force is applied on it, it allows the selectively transfer of one or
shows comparative chart for the work reported on hydrolysis of more component from one phase to another phase. Membranes that
lignocellulosic biomass. are used in bioseparation process are generally porous and semi-
permeable in nature. . The components that pass through the mem-
2.4. Summary brane and collected in other side is called permeate and the compo-
nents that retain is called retentate Microltration, nanoltration,
1. Hydrolysis is aected by structural characteristics of cellulose and ultreltration, vacuum ltration, reverse osmosis are most useful
presence of lignin and hemicellulose. Removal of lignin, solubilisa- pressure driven membrane based separation method. Others are
tion of hemicelluloses and decrystallization of cellulose by pretreat- pervaporation, dialysis, gas separation. Most of the membrane used
ment, strongly induce cellulose accessibility to enzyme. in dierent chemical process is made of organic matter generally
2. Pretreatment of biomass by ionic liquid, addition of surfactant, polymer. But nowadays, the use of inorganic and hybrid membrane is
applying microwave irradiation or ultrasound enhances cellulose common. The common used membrane congurations are plate-and-
conversion. frame module, spiral-wound module, and hollow-bre module. In
3. Glucose yield increases with increasing hydrolysis period but bioethanol industry membrane is generally used in downstream
decreases with substrate loading above a certain limit. This is caused purication to concentrate the produced ethanol. But it can be
by end product inhibition and mass transfer limitation. suciently used in cellulase enzyme recycling, cell recycling and
removal of inhibitory by products.

877
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. Renewable and Sustainable Energy Reviews 74 (2017) 873890

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

879
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. Renewable and Sustainable Energy Reviews 74 (2017) 873890

tion and membrane lm bioreactor in ethanol production. Though 4. Membrane fouling can be reduced by increasing feed ow rate,
pervaporation membrane bioreactor and membrane distillation bior- lowering transmembrane pressure, and shear-rate, backwashing,
eactor use dierent membrane structure, driving force and separation and increasing rotational speed
mechanism, but both methods are ecient to reduce product inhibi-
tion, concentrate cell and enhance ethanol yield and productivity [87]. 3.5. Membranes in downstream processing for dehydration
Pervaporation membrane bioreactor successfully performed in cell
recycling, enhancing cell concentration and ethanol production. Cell The last stage in the ethanol production process is the downstream
retention by microltration followed by ethanol water separation by processing section. The importance of this section cannot be over-
pervaporation, achieved 150 g/l cell concentration, 111169 g/l etha- stressed enough, owing to the fact that the products produced in here,
nol in permeate and a total ux of 1.682.5 kg/m2 h [111]. A series of are put up directly for sale, generally without any further processing.
continuous fermentation with Saccharomyces cerevisiae in membrane Downstream processing may be distinguished into separation by
bioreactor using ultraltration tubuler membrane traditional methods and by modern methods. The modern methods
(Polyphenylenephthalamide membrane with 25,000 MWCO) achieved broadly signify the rise of membranes as the principal processing
100% cell recycle with maximum 81 g/l ethanol concentration and media in extraction of ethanol from the end product of biomass
15 g/l/h ethanol productivity. Biomass concentration at steady state fermentation. The industrial production of ultrapure ethanol brings
varied from 10 to 60 g/l. To alleviate membrane fouling feed ow rate up several diculties. In the case of bioethanol production by
was maintained from 600 ml/h to 800 ml/h [112]. A continuous fermentation of six (and ve) carbon sugars, most of the generated
fermentation coupled with a hydrophobic, tubular polytetrauoroethy- by-products, if not all, inhibit the fermentation as the mass fraction of
lene (PTFE) assisted membrane distillation can achieve a long time run the by-products increase in the reaction broth, which is why dynamic
using ethanol stripping module in the fermentation of glucose and removal of the by-products needs more research in addition to the
molasses. Ethanol production rate increased from 0.22 to 0.38 g/gh meagre number of ongoing ones. The by-products known to inhibit the
was attained while glucose concentration was increased from 3 to 5 g/l reaction in some way or the other [119121] can broadly be classied
10 g/l during continuous fermentation 350 g/l average ethanol con- into three groups: First, the weak acids like acetic, formic, and levulinic
centration was observed in cold trap. Cell occulation, aected by salt, acid; second, the derivatives of furan and thirdly, phenolic compounds
occurs when molasses medium with high sugar concentration is used in in the likes of vanillin, phenol and p-hydroxybenzoic acid. The most
fermentation but it does not at all aect the ethanol separation. common inhibitor is, surprisingly, produced ethanol working via the
Backwashing was not required in this method [113]. Continuous product inhibition pathway. The largest processing load in the down-
ethanol extraction increased ethanol productivity from 0.99 to stream processing section comes from dehydrating bioethanol, and
1.85 g/lh while using membrane distillation [114]. While studying unless the inhibiting by-products are taken care of prior to dehydra-
membrane lm bioreactor employed with hollow bre polypropylene tion, they can incur additional costs that could have been reduced with
membrane, immobilized yeast cell density on membrane surface a pre-emptive remedy [122,123]. In some extreme cases, even a low
reached to 3.5109 cells/ml and ethanol productivity reached to concentration as 0.1 mM of inhibitors can have a negative impact on
26 g/l/h [115]. Generally two membrane congurations are widely the main reaction [124]. In the case of ethanol production using non-
used. External cross ow membrane module use bioreactor and biological means, the traditional methods of ethanol extraction from
membrane module separately and reduce membrane fouling but the product stream, such as conventional and azeotropic distillation
require higher energy to be operated in continuous mode where in and/or solvent extraction and the likes, by their very denition of being
submerged or immersed membrane conguration membrane is in non-biological, renders the step of by-product removal redundant.
direct contact with broth which is an energy ecient method, but the Biologically assisted ethanol production has seen some of the
major disadvantage is membrane fouling due to high cell concentration proposed ethanol purication methods fail while others have suc-
[116]. Membrane fouling, caused by deposition of microbes and ceeded, with some to the extent that they have already been industrially
polysaccharide on membrane surface leads to decline in permeate ux. adopted. Pervaporation is one such well established process [125].
Increasing cross ow velocity and controlling hydrodynamic para- Membrane distillation is presently being researched as the next best
meters i.e. lowering transmembrane pressure and shear-rate reduces method with a lot of promise [126,127]. Also, some innovative
membrane fouling as well as cake formation. Increasing the use of methods are surfacing, such as the use of forward osmosis to dehydrate
rotational speed while using rotational dynamic ltration reduced ethanol [128,129].
concentration polarization which is a main cause of membrane fouling,
thus induce permeate ux [117]. Applying air scour for backwash or 3.5.1. Membrane distillation
increasing cross ow velocity reduces fouling [118]. The major limitation of ethanol fermentation comes from the end
product inhibition when ethanol concentration reaches 12% by volume,
3.4. Summary the specic growth rate of the yeast cells decline [130]. The aforesaid
limitation could be alleviated by employing a suitable membrane
Microbial fermentation is the critical step that converts monosac- distillation system. Membrane distillation plays an important part in
charide to bioethanol. Inhibitors formed during pretreatment of the downstream processing and recovery of fuel ethanol. The volu-
biomass reduce ethanol production during microbial fermentation. metric productivity of bioethanol can be eciently increased with the
Thus separation of inhibitory components and recycling of fermenta- membrane distillation process. Microporous hydrophobic membranes
tive microorganism are necessary in order to achieve higher ethanol which are impermeable to water are used for membrane distillation.
yield. Assistance of membrane is this process leads to the development The membranes for the membrane distillation process are prepared
of eco-friendly fermentation process. Performance of membrane based from low surface energy hydrophobic polymers such as polytetraur-
process depends on certain factors. oethylene (PTFE), Polypropylene (PP) or polyvinydilene uoride
(PVDF). Good thermal stability and chemical resistance are exhibited
1. Nanoltration and reverse osmosis are ecient with regard to the by these polymers as available from the literature [131]. The process
separation of toxic inhibitors and concentration of sugar. principle is based on the dierential vapour pressure at the membrane
2. An increase in pH enhances the rejection of acetic acid, the main surface which acts as a driving force for separation. Gryta et al.
inhibitory compound present in hydrolyzate. reported the use of Direct Contact Membrane Distillation (DCMD)
3. Microltration, followed by pervaporation, achieves high cell density for ethanol synthesis from lactose solution in a BIOTRON reactor.
and high ethanol productivity. Ethanol was continuously removed from the fermentation broth

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K. Saha et al. Renewable and Sustainable Energy Reviews 74 (2017) 873890

through porous hydrophobic polypropylene membrane along with respect to time.


other volatile organic compounds which resulted in increase of ethanol
productivity. Outside and inside diameter of polypropylene capillary 3.5.3. Pervaporation
membrane module was 2.6 mm and 1.8 mm respectively and eective Pervaporation, as the name delineates, incorporates permeation of
membrane area was 490 cm2. The permeate ux was found to be at a component into the involved membrane matrix and the successive
constant level when the studies on fermentation with membrane evaporation of the permeated component into the vapour phase inside
distillation was carried out for 860 h. The ethanol yield was 0.40.51 the membrane matrix. The vapour-liquid interface is extent inside the
(g EtOH)/(g of sugar) and the production rate was 2.54 (g EtOH)/ membrane. The component from the liquid feed that permeates into
dm3 h when compared to 0.350.45 (gEtOH)/(g of sugar) and 0.82 (g the membrane vaporizes into its corresponding vapour state in situ and
EtOH)/dm3 h obtained in the conventional batch fermentation. The gets selectively permeated to the other side which depends on the
ethanol ux acquired in the process was in the range of 14 (kg EtOH)/ dierence between the transport rates of the components in the liquid
m2 per day. Thus it was found that fermentation integrated with DCMD feed. Generally, the feed or the upstream side is at atmospheric
was eective in selective removal of ethanol from the fermentation pressure, while permeate or the downstream side is kept under vacuum
broth without the phenomenon of membrane wetting thereby increas- so as to allow the selective evaporation of the target component after
ing the ethanol productivity [130]. Performance of DCMD was also permeation through the membrane [134]. The driving force is the
evaluated for ethanol production from whey. Maximum 61.16 g/dm3 dierences in partial pressures of the components on either side of the
ethanol concentration after 24 h of fermentation was achieved in membrane. The volatility dierence between the feed components does
permeate when feed contained deprotinized whey along with sucrose not play any role whatsoever in determining the selectivity of the
building 100 g/dm3 sugar concentration. Maximum ethanol ux ob- components [135]. The mechanism involved in pervaporation is the
tained 1.2 kg/m224 h. Ethanol ux is directly proportional to sugar solution-diusion. Pervaporation membranes can be classied depend-
concentration in broth [132]. It was observed that membrane distilla- ing on the material used for their construction i.e organic, inorganic
tion increased the eciency of ethanol production through by selective and hybrid membrane and on their selectivity towards water which
removal of the fermentation products. Direct contact membrane further categorize pervaporation membranes in hydrophobic and
distillation (DCMD) with cross ow membrane ltration module was hydrophilic. By using pervaporation it is possible to dehydrate ethanol
reported for brewers wort fermentation. Microporous hydrophobic to 99.8% [87].
polypropylene membrane having capillary inside diameter of 1.8 mm Hydrophilic membranes, used to remove water from the feed, have
and an outside diameter of 2.6 mm, and 0.2 m pore size was used for been categorized into three depending on the material and method of
the purpose. The eected surface area of the hydrophobic membrane synthesis of the membrane. Those membranes may be inorganic,
was 0.1 m2 with 40 numbers of capillaries in the membrane module. polymeric and composite [135]. Inorganic membranes have recently
The ethanol production increased with complete fermentation of gained a lot of commercial attention due to its superior temperature
sugars and decreasing the glycerol synthesis level. The yeast cell and mechanical stability and are generally made from zeolites [136
number and viability were maintained during the process. During the 139]. A large number of polymeric membranes for pervaporation have
continuous fermentation process the conversion eciency of carbohy- been studied in detail, for example cellulose acetate butyrate mem-
drates to ethanol was as high as 88.2% of the theoretical yield. The brane [140], PDMS (polydimethylsiloxane) membrane [141], polydi-
conversion eciency was found to be 15.6% higher than the classical methylsiloxane-polystyrene interpenetrating polymer network (PDMS-
batch fermentation process. Ethanol ux was found to be directly PS IPN) supported membranes [142], aromatic polyetherimide mem-
proportional to the temperature and ethanol concentration in the broth branes [143]. A few of these studies churned out quite interesting
[126]. The process economics of the bioethanol production can be results. In a particular case, it was found that as polystyrene (PS) is
improved by utilizing continuous fermentation process with membrane more hydrophobic than PDMS and also has a property of higher tensile
integrated system. Vacuum membrane distillation (VMD) with solar strength, the mechanical and lm forming a dual layer polydimethylsi-
energy was reported by Zhang et al. for concentrating the lignocellu- loxane-polystyrene (PDMS-PS) membrane was found to be better than
losic hydrolysate obtained from steam explosion pretreatment [133]. In PDMS itself. The study also pointed out that for high ethanol
this study PVDF membranes with average pore diameter and porosity concentrations in the feed, the membrane was selective for water,
of 0.18 m and 85% respectively were used. It was observed that feed while for low ethanol feed concentrations, the membrane was selective
velocity and temperature had a signicant eect on VMD. The ux for ethanol [142] . The sorption, diusion and pervaporation of
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 aqueous ethanol in homogenous/composite aromatic polyetherimide
1.1 m/s feed velocity respectively. The membrane distillation ux membranes were explored by [143]. Recently, various inorganic-
doubled to 9.5 l m-2 h-1 from 4.6 l m-2 h-1 when the temperature was polymer and polymer-polymer combinations for composite membranes
increased from 50 C to 70 C. The result indicated the rejection of have been developed and tested, in order to combine the advantages of
glucose to be more than 98% and the ethanol concentration in the inorganic and polymeric membranes to get superior performance with
fermentation broth was 2.64 times as much as that of the original low cost. Some of these include polystyrenesulfonate/alumina [144],
hydrolysate solution. polyelectrolytes multi-layer [145], zeolite KA-incorporated cross-linked
The membrane distillation is not practiced in industrial scale at poly (vinyl alcohol) (PVA) multilayer mixed matrix membranes
present. Further research is needed before implementing membrane (MMMMs) [146] and poly(vinyl alcohol) (PVA)-sodium alginate (SA)
distillation from lab scale to industrial scale. Other membrane cong- blend membranes [147]. Chen et al. [148] found out that lithiation of
urations apart from DCMD need to be explored and investigated polysulphone membrane improves the pervaporation performance. In
further. addition to indicating that the ethanol concentration in feed strongly
aected the separation performance; the study also found out that
3.5.2. Summary permeation ux was strongly inuenced by the operating temperature
while the separation factor went down as the operating temperature
1. Ethanol productivity increases during fermentation which is coupled went up. Chen et al. [144] pointed out that for polystyrenesulphonate/
with membrane distillation due to selective removal of the fermen- alumina membranes, the separation factor could be as high as 400.
ted products. Hydrophobic membranes can be categorized into three sub cate-
2. Fermentation integrated with DCMD was eective in selective gories: 1) the polymeric membranes include poly[1-(trimethylsilyl)-1-
removal of ethanol from the fermentation broth without wetting. propyne] (PTMSP) [149,150] and poly[dimethylsulfoxane] (PDMS)
3. Flux increases with temperature, but does not decline rapidly with [151153], 2) Zeolite membranes including zeolite A [154] and multi

884
K. Saha et al. Renewable and Sustainable Energy Reviews 74 (2017) 873890

channel MFI [155] membranes, with occasional use of silicalite based bioethanol by fermentation of lignocellulosic or other feed stock
membranes [156158], the very recent composite membranes, which comprises of dierent steps like pretreatment, recovery of value added
hold a lot of promise which is a relatively newer branch and needs a lot products, enzymatic hydrolysis, cell and enzyme recycle, removal of
of research. Examples of hydrophobic composite membranes include inhibitory byproduct formed during fermentation, recovery and dehy-
silicalite particles dispersed in PDMS [159,160] and crosslinked PDMS dration of ethanol from fermentation broth either by conventional
membrane incorporated with HF acid etched ZSM-5 [161]. Chovau downstream process or by advanced membrane based separation
et al. investigated the impact of fermentation byproducts like imperme- process. Furthermore during pretreatment with acidic or basic process,
able components and carboxylic acid on hydrophobic pervaporative dierent inhibitory product like weak acids, furan derivatives and
separation of ethanol from aqueous solution containing 5 wt% ethanol phenolic compounds are formed which are used in dierent chemical
using at sheet PDMS membrane separately. Addition of 5 wt% and pharmaceutical industries. Thus complete utilization of the
glucose, 5 wt% xylose, 1 wt% (NH4)2SO4 separately increase ethanol byproducts increases overall process economy. Due to rising price of
permeate concentration due to enhanced ethanol ux with addition of petroleum fuel, bioethanol is grabbing attention now a days as eco-
these components respectively. Addition of 1 wt% glycerol causes the friendly and economically viable transportation fuel. Gnansounou et al.
reduction of vapour pressure of both ethanol and water, thus do not reviewed techno economic evaluation of lignocellulosic bioethanol
aect ethanol ux and permeate ethanol concentration. 0.1 wt% 2,3- production by conventional process. In simultaneous saccharication
butanediol decrease ethanol ux due to the strong sorption to PDMS and co fermentation of lignocellulose, bioethanol and electricity are
membrane. Carboxylic acid interacts with silanol group of Si-based produced as per the conguration of ethanol plant. The main produc-
lter of the membrane causing membrane fouling, therefore decrease tion cost depends on investment cost and cost of feedstock. Fixed
hydrophobicity degree and separation performance of PDMS mem- operation cost that includes tax, overhead, maintenance and insurance,
brane as well as rises the water ux [123]. Moermans et al. explored the whereas variable operation cost which includes the price of consum-
eect of additional glucose and xylose in feed on the selectivity and able, sales of electricity are less signicant. Various transportation costs
total ux in pervaporation of a 2% w/w ethanol-water solution at for feedstock includes loading and unloading and xed and variable
varying feed temperature and permeate side pressure. Total ux and cost. Availability of biomass is an important factor. Among the four
ethanol selectivity decreases moderately for all varying glucose level as dierent feedstock (eucalyptus, poplar, switchgrass and straw) exam-
permeate side pressure increases from 1 to 20 mm Hg and more ined, eucalyptus is cheaper and poplar is the most costly one. Ethanol
apparently at 40 mm Hg and increases as feed temperature rises. yield is lower for straw and higher for poplar. Except eucalyptus, 50
Xylose has less eect than glucose on polydimethylsiloxane membrane 55% production cost comprises of feedstock. Higher ethanol yield
selectivity [160]. Fermentation operation time and temperature aect reduces electricity output and production cost including feedstock
the permeate ux as well as ethanol separation factor of at sheet expenses and xed operating cost [169]. Quintero et al. gave an
cellulose acetate membrane for sweet sorghum juice fermentation. economic analysis of bioethanol production from four dierent ligno-
Increasing the fermentation operating time from 15 to 60 min cellulosic wastes (Sugarcane bagasse (SCB), Coee cut-stems (CCS),
decreases total permeate ux from 2.7 to 1.5 kg/m2 h and separation Rice Husk (RH), and Empty Fruit Bunches EFB)) in Colombia and
factor from 6.6 to 2.3 and a rise in temperature reduce the total ux found out the highest production cost for SCB due to high cost of raw
and separation factor which indicates the demerits of cellulose acetate material and utilities. On dry basis ethanol production is 313.83 l/t,
membrane in pervaporation system for sweet sorghum juice fermenta- 305.11 l/t, 298.21 l/t, 250.56 l/t of EFB, CCS, SCB, RH. On dry basis
tion [162]. Some researcher investigated the ethanol recovery from EFB produce higher amount of ethanol due to its high hemicelluloses
lignocellulosic fermentation broth which is mentioned in Table 3. content. For SCB, utilities cost share 37% of total cost. Raw material
From existing literature [167], it can be seen that each membrane cost is 15 US$/t and ethanol price is 0.3472 US $/l, which share
has a separation factor which determines how well it performs. The 45.32% of total production cost due to higher price of SCB and the
Polydimethylsiloxanediol (PDMS), poly(1-trimethylsilyl-1-propyne requirement of high ow rate to produce ethanol 100,000 l/day. The
(PTMSP), zeolite and composite membranes have been reported to other residues require utility cost more than 45% of total cost due to
have separation factors of 4.410.8, 926, 759, 12106, respectively. high energy cost in dierent steps. Though the price of CCS is higher
However, in some cases, the separation factor gets way higher than relative to others, but the low moisture content is low leading to high
expected, such as a separation factor of 218 during the separation of ethanol production in wet basis, this residue require only 35.06% of
ethanol (98.2% permeate) over water-ethanol solution (20% by weight production cost. The use of lignin of lignocellulosic biomass as primary
ethanol), using a silicate zeolite membrane [168]. In general the source of power and heat can reduce the utility cost and focus on other
ranking of separation factors are in order: PDMS < PTMSP < composite required parameter administrative, maintenance, labor, capital depre-
membranes < zeolite membranes. ciation cost etc. So the authors have suggested a energy cogeneration
scheme coupled with ethanol production process for this purpose
3.5.4. Summary 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
1. Pervaporation process can concentrate ethanol to 99.8 wt%. reduce production cost [170,171]. Luccioa et al. investigated the
2. Hydrophilic membranes are classied as organic, inorganic and economic feasibility of ethanol production and dehydration by fermen-
polymeric membranes. Inorganic membrane has more temperature tation coupled to pervaporation system and the formation of fructose
resistance and mechanical stability as compared to organic and as byproduct of fermentation. The ethanol plant was designed to
composite membrane. operate 330 days/yr to produce 6000 m3/yr ethanol and 10,000 t/yr
3. Permeate ux increases with feed temperature but separation factor fructose as byproduct which gave the project economic viability.
is inversely proportional to operating temperature. Maximum membrane cost was about 500 US $/m3. Raw material i.e.
4. An increase in ethanol concentration in feed enhances the permeate inverted sugar cost was 0.035 US$/L and the price of ethanol was 0.37
ux. 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
3.6. Techno economic evaluation $/l. Internal return rate (IRR) was adopted for analysing economic
viability. The higher IRR could make the project viable, although the
Bioethanol from lignocellulosic biomass is one of the most promis- membrane cost is high [171]. According to Sassner et al., raw material,
ing fuels which can be used to replace gasoline in modern vehicles. It is pretreatment, steam generator and fermentor are contributor of
an oxygenated fuel and burns cleaner than fossil fuel. Production of maximum investment cost, while bioethanol is produced by simulta-

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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. Renewable and Sustainable Energy Reviews 74 (2017) 873890

neous saccharication and fermentation using softwood, corn stover dehydrated ethanol with high productivity in an environmentally
and hardwood as feedstock. Raw material comprises of maximum feasible manner. Research on such scheme needs to be investigated
production cost. Lignin, the co-product of bioethanol production, has for commercialization and scaling up.
an important eect on the whole process economy. Insurance, main-
tenance and labor have been subjected as Other cost. Capability of Acknowledgement
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 The authors would like to acknowledge Department of
ethanol yield for corn stover and hardwood respectively. This phenom- Biotechnology, Government of India (Grant no. DBT/In-Bz/2013-16/
enon improves process economy. 50% decrease in enzyme loading 06) and MCTI-CNPq-Brazil (vide Grant no. DBT/In-Bz/2013-16/06
would be economically feasible if the residence time is increased by and CNPq process no: 401361/2013-6) for the bilateral collaboration
30% and the yield of ethanol should not decrease more than 67% to carry out the review work. The authors thank Jhilly Dasgupta,
[172]. Capital comprises of 40% of total bioethanol production cost Research Scholar, for her help to improve the manuscript.
from lignocelluloses. Power usage is the major constituent of capital
cost. Production part contributes half of the capital investment. References
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