Renewable and Sustainable Energy Reviews 105 (2019) 427–443

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

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

Membrane separation processes for dehydration of bioethanol from T

fermentation broths: Recent developments, challenges, and prospects
Azqa Khalida,1, Muhammad Aslamb,1, Muhammad Abdul Qyyumc, Abrar Faisala,
Asim Laeeq Khanb, Faisal Ahmedd, Moonyong Leec, Jeonghwan Kime, Nulee Jangf,
⁎ ⁎ ⁎
In Seop Changf, , Aqeel Ahmed Bazmid, , Muhammad Yasinb,
a
Department of Chemical Engineering, COMSATS University Islamabad (CUI), Lahore Campus, Defense Road, Off Raiwind Road, Lahore, Pakistan
b
Bioenergy & Environmental Sustainable Membrane Technology (BEST) Research Group, Department of Chemical Engineering, COMSATS University Islamabad (CUI),
Lahore Campus, Defense Road, Off Raiwind Road, Lahore, Pakistan
c
School of Chemical Engineering, Yeungnam University, Gyeongsan 712-749, Republic of Korea
d
Process and Energy Systems Engineering Center-PRESTIGE, Department of Chemical Engineering, Department of Chemical Engineering, COMSATS University Islamabad
(CUI), Lahore Campus, Defense Road, Off Raiwind Road, Lahore, Pakistan
e
Department of Environmental Engineering, Inha University, Namgu, Incheon, Republic of Korea
f
School of Earth Sciences and Environmental Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju 61005, Republic of Korea

A R T I C LE I N FO A B S T R A C T

Keywords: Bioethanol has garnered a great interest as a potential energy source, mainly due to its sustainable and green
Syngas fermentation nature. Generally, bioethanol is produced through the microbial conversion of biomass and biomass derived
Bioethanol syngas. However, the dehydration and purification steps for achieving fuel-grade ethanol from the microbial
Distillation production process consume tremendous amounts of energy. This high energy consumption limits the feasibility
Membrane separation
of microbial ethanol production on the commercial scale. In this context, selection of an optimal technology for
Pervaporation
product separation is essential for successful commercialization of microbially produced bioethanol. This article
presents the recent developments in dehydration and purification technologies for bioethanol production using
distillation and membrane based separation. Distillation and pervaporation are analyzed on the basis of the
overall energy requirement, consumption, and economics. Pervaporation-assisted distillation approaches are
also examined from the perspective of process systems engineering, including factors affecting the system per-
formance. Furthermore, the role of simulation in technological development along with available mathematical
models is discussed, and commercial status of pervaporation based separation is presented. Finally, the current
status of the existing technology, challenges, and future research directions are identified from the perspective of
achieving process sustainability on the industrial scale. Economic comparison between distillation and different
hybrid schemes revealed that integrating distillation with membrane based separation techniques reduce the
bioethanol production cost. Moreover, hybrid schemes that combine distillation with pervaporation, and steam
stripping with vapor permeation are proved to be the best combinations for the cheapest bioethanol production.

1. Introduction world highly dependent on oil- and gas-producing countries [3], poli-
tical instability in the organization of Oil Producing Countries (OPEC)
Global energy demand has continued to escalate as a result of im- [4], expected depletion of fossil fuel [5], and CO2 emissions from fossil
proved standards of living and population growth. The global energy fuel combustion. In order to reduce the dependence on petroleum,
requirement is anticipated to rise by as much as 48% between 2012 and bioethanol produced from fermentation of first-generation feedstock
2040 [1,2]. The primary energy source to fulfill these requirements is e.g., watermelon, corn, wheat, barley, and sorghum has been in-
fossil fuel reserves. In recent years, research focus has shifted to finding troduced as an alternative to gasoline [6]. In 2015, the bioethanol
alternate renewable energy resources. This search is mainly driven by: produced from these feedstocks in the US alone accounted for 58% of
the uneven distribution of regional fossil fuel reserves, which makes the global production, followed by production in Brazil, Canada, and China

⁎
Corresponding authors.
E-mail addresses: [email protected] (I.S. Chang), [email protected] (A.A. Bazmi), [email protected] (M. Yasin).
1
First co-authors.

https://doi.org/10.1016/j.rser.2019.02.002
Received 16 September 2018; Received in revised form 9 January 2019; Accepted 3 February 2019
1364-0321/ © 2019 Elsevier Ltd. All rights reserved.
A. Khalid, et al. Renewable and Sustainable Energy Reviews 105 (2019) 427–443

Nomenclature and Abbreviations Q Total heat content

QMod All heat losses in module
E Activation energy H Enthalpy
R Universal gas constant Δhvap Latent heat of vaporization
T Temperature Cp Heat capacity
J Flux through membrane Qvap Heat of vaporization of permeate
Qo Pre-exponential factor ƴm Experimental activity coefficient parameter in membrane
D Transport coefficient β Proportional constant
D* Relative transport coefficient φ Free volume fraction in ternary system
ƴ Activity coefficient v Volume fraction in binary mixture
y Mole fraction of component in permeate l Length of membrane
x Mole fraction of component in feed ∅ Component volume fraction
Psat Vapor pressure of pure component θ Overlap factor for free volume
B Constant ω1 Solvent weight fraction
a Free volume parameter K12,K22 Polymer free volume parameters
E1 Free volume parameter Tg Solvent glass transition temperature
c Distance along which diffusion takes place
€ Normalized permeance experimental factor Subscripts
ε Ratio of critical molar volume of solvent jumping unit to
that of polymer jumping unit ret Retentate
σ Component interaction parameter perm Permeate
ω2 Polymer weight fraction F Feed
K11, K21 Solvent free volume parameters Z Zeolite film
V Specific critical hole free volumes of component Wat Water
F Flow rate i Component in mixture
Amem Area of membrane Ref Reference
p Pressure Eth Ethanol
ρ Density SL Support Layer
α Separation factor

[7]. However, the production of bioethanol from edible feedstock is Moreover, waste streams from sugar production and first-generation
questioned by policy makers due to the potential threat to food security. bioethanol sources should also be integrated as feedstocks for bioe-
These issues can be addressed by implementing short-term and long- thanol production.
term strategies. For instance, biomass derived syngas can be one of the Bioethanol is the most desirable product of syngas-based microbial
promising feedstocks to produce energy-rich biofuels (e.g., bioethanol biorefinery. Syngas biorefinery integrates microbial conversion of
and butanol) through microbial conversion [8]. Moreover, renewable syngas to liquid products that are treated in a downstream separation
and sustainable feedstocks that do not pose a threat to world food se- unit to obtain the product with the desired concentration. To date,
curity should be exploited for syngas production for long-term usage. microbial pathways and microbial chemistry related to syngas fer-
Such feedstocks include lignocellulosic biomass, agricultural residues, mentation, i.e., the metabolism adopted by microbes to obtain nutrients
waste streams (mainly lignocellulosic components) from other in- and energy, have been extensively studied [8]. Syngas fermentation has
dustries, and waste gases from the iron and steel industries [9]. many advantages such as: a) biocatalysts are specific to the product, b)

Fig. 1. Map of the technological advances for dehydration and recovery of bioethanol from fermentation broth.

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ability to handle wide H2:CO ratios, c) operation under ambient con- liquid extraction, and vapor permeation, for product separation from
ditions, and d) operation with less costly enzymes [8]. Despite having microbial conversion processes. A comprehensive statistical economic
many advantages, the scale-up of microbial syngas conversion is still and energy analysis of distillation, pervaporation, and a combination of
hindered by many technical issues. Low microbial productivity, sub- both is presented. Pervaporation-based syngas bio-refinery with in-
strate and product inhibition, poor gas-liquid mass transfer, and low herent major issues and the current application status is discussed.
product concentrations are the major issues to be resolved (Fig. 1) [8]. Furthermore, the challenges of bio-refinery design and future research
The relatively low productivity of microbes results in low ethanol directions are identified to achieve process scale-up and sustainability.
concentrations in the fermentation media, making downstream pro- The economic comparison between distillation and different hybrid
cessing an energy-intensive step [10], mainly due to the minimum- schemes combining distillation with other conventional and membrane-
boiling homogeneous binary azeotrope between water and ethanol based technologies is made. The results revealed that integrating dis-
mixture, as shown in Fig. 2. tillation with pervaporation significantly lowers the cost to produce fuel
Distillation is the most widely employed separation technique for grade bioethanol. Moreover, distillation followed by pervaporation
bioethanol recovery (Table 1). Although the separation and recovery of proved to be the most economical hybrid scheme. The information
bioethanol from first-generation feedstocks has been achieved through presented in this review will help the research community to better
distillation, the recovery of bioethanol from syngas-based microbial align their research directions and goals according to the requirements
bio-refinery is not economical owing to low ethanol concentrations of bio-refinery (especially to produce fuel grade bioethanol).
[11]. Hence, it is desired to develop alternate separation techniques. To
make bioethanol competitive with fossil fuels, the production costs 2. Distillation in biorefinery
associated with fermentation and product separation must be reduced.
Pervaporation is one potential technique for separating mixtures based Distillation is a primary separation technique used in industry for
on differences in the diffusivity and solubility of the components for bioethanol separation [11]. Generally, the residue curve map gives
separation. Unlike the distillation process, pervaporation is not limited sufficient information to evaluate the feasibility of the separation pro-
by differences in the relative volatility of the mixture components. cess adopting distillation [21]. Distillation exploits the difference in the
Hence, this technique has the potential to be utilized for azeotrope relative volatility of the mixture components, where the liquid and
separation, which is not possible through ordinary distillation [12]. vapor phase are enriched in one component through the principles of
Additionally, the accumulation of ethanol in the fermentation broth mass transfer. Table 1 shows the major fermentation-based industries
results in inhibition of the microbial activity, known as end-product worldwide and their respective separation technologies. Although a
inhibition, which ultimately results in a lower final ethanol con- number of conventional and non-conventional techniques exist for
centration. Pervaporation during fermentation can be implemented to component separation in biorefinery (Fig. 3), distillation is the domi-
continuously remove the inhibitory products from the broth, which nant commercially approved technique because of its well-established
increases the conversion rate and ultimately improves the economics of principles, ease of operation, and readily available expertise.
the process [13]. Therefore, pervaporation has recently emerged as a To date, distillation is widely applied in the industrial sector, e.g.,
potential membrane-based technique for product separation [14]. for gasoline and hydrocarbon separation in the petroleum industry,
Major advancements have been made in membrane-based opera- phthalic anhydride and xylene separation in the petrochemical in-
tions and the process design equipment to design energy–and-cost ef- dustry, and water purification [22,23]. In biorefinery, due to the ab-
ficient schemes to produce fuel grade bioethanol. These advancements sence of alternatives, distillation has remained the dominant tech-
are still away from the commercial perspective, primarily due to the nology for product separation for decades [11]. However, the higher
communication gap between the bio-refinery design engineers and the energy consumption and higher cost associated with azeotropic dis-
research community. Therefore, from a practical and research view- tillation has triggered the search to replace distillation with more effi-
point a detailed review with respect to process design engineering and cient technology. Furthermore, in biofuel production, a higher ethanol
operational factors affecting pervaporation membrane performance is concentration inhibits the activity of the microorganisms in the fer-
required. To the best of our knowledge, this is the first review study that mentation media, hence limiting the maximum allowable ethanol
is specifically intended to give an overview of the potential of distilla- concentration. Fernandez-Naveira et al. [24] reported that the cell
tion and membrane-based technologies, including pervaporation, re- growth rate starts to decrease when the ethanol concentration increases
verse osmosis, membrane dephlegmation, membrane-based liquid- to 1 g/L in the fermentation media for Clostridium carboxidivorans. The

102

100 x 1.0133 bar

y 1.0133 bar
98

96

94
Temperature, C

92

90

88

86

84

82

80

78
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00
Liquid/vapor mass fraction, ETHANOL

Fig. 2. Vapor-liquid equilibrium (VLE) diagram for water-ethanol mixture.

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Table 1
Fermentation-based worldwide industries with their employed separation techniques.
Industry name Feed stock Separation techniques Ethanol grade Production (Ml/year) Reference

Anchor Ethanol Limited, New Zealand Whey serum Distillation Fuel 18.9 [15]
Bioagra S.A. Poland Corn Distillation Fuel 130 [16]
Impress Ethanol Co. Limited, Thailand Cassava root and molasses Distillation Fuel 72 [17]
Blue Fire Renewables, CA, USA (Izumi Wood waste, agricultural residue, Distillation 95.5% 0.036 [18]
Biorefinery, Japan) municipal waste.
Alltech, CA, USA Brewery waste Distillation/dehyd. Fuel 3.6 [19]
Synata Bio, Hugoton, Kansas, USA Cellulosic biomass Distillation/dehyd. Fuel 94.6 [19]
Almagest, Bulgaira Wheat and corn Distillation/evaporation Extra neutral 28.8 [19]
Promaíz, Argentenia Corn Distillation/dehyd./ Fuel additive 151.2 [19]
evaporation/drying
Green Plains Inc., IL, USA Corn Distillation/dehyd. Fuel 342 [19]
Lantmännen Reppe, Lidköping, Sweden Grains (wheat) Distillation Food grade 18 [19]
Tharaldson Ethanol, ND, USA Corn Distillation/dehyd. Fuel 468 [19]
Vogelbusch, Beinheim, France Corn Distillation/dehyd. Fuel 144 [19]
Ingredeon (Penford), IA, USA Corn Distillation/dehyd. Fuel 162 [19]
Chief Ethanol, NE, USA Corn/maize Distillation/dehyd. Fuel 299.52 [19]
CropEnergies, Zeitz, Germany Grains Distillation/ dehyd./ Fuel 288 [19]
evaporation/drying
Jilin Fuel Alchol Company, China Maize Distillation/ dehyd./ Fuel 380.22 [19]
evaporation/drying
Harbin Winery, China Corn Distillation/dehyd. Fuel 50.4 [19]
Inbicon demonstration plant, Denmark Wheat straw Distillation/ dehyd./evaporation Fuel 6.12 [19]
Parallel Products, USA waste consumer goods Distillation N/A 24.60 [20]

resulting low ethanol concentration leads to a large processing volume microbubble distillation required a lower number of ideal stages than
for distillation, making distillation an energy-intensive step. Nakao simple distillation to achieve the same separation factor. However, the
et al. [25] concluded that distillation accounts for more than half of the microbubble generation process must be improved to make this process
total energy consumed in the bioethanol production process. Efforts an economical alternative. Furthermore, the utility of microbubble
have been made to save energy in this conventional process. For ex- distillation for azeotropic separation makes it an attractive approach for
ample, Vander Griend patented an energy integrated approach that uses biorefinery application. Because ethanol forms an azeotrope with water
a series of evaporators prior to the column to reduce the energy load for at 96.5% mass concentration, simple distillation is ineffective for pro-
distillation [26]. In another study, Grethlein and Lynd patented another ducing fuel-grade ethanol (> 99%). Abdul razzaq et al. [30] in-
scheme utilizing a heat pump to conserve energy [27]. vestigated methods of enhancing the efficiency of breaking the water-
Microbubble distillation has also emerged as a novel technique with ethanol azeotrope using air microbubbles generated by fluidic oscilla-
potential application in the separation of fermentation broth compo- tion. A total of 98.7% volume concentration of ethanol was achieved,
nents. The concept involves heating the vapor phase rather than the which was higher than that achieved under equilibrium conditions for
liquid phase to achieve the desired separation. Microbubbles having the same liquid mole fractions.
diameters smaller than one millimeter are introduced into the mixture Another novel approach is ohmic-assisted hydro distillation
at high temperature. The microsize bubbles result in a high contact area (OAHD), which utilizes the volumetric heating benefits to overcome the
between the two distinct phases to enhance the separation efficiency shortcomings of traditional distillation. This technique proffers benefits
[28]. Al-Yaqoobi et al. [29] compared simple distillation with micro- such as high thermal efficiency, short processing time, and reduced
bubble distillation for ethanol dehydration. They reported that operation cost. This process was first applied in essential oil separation

Fig. 3. Research trends in bioethanol dehydration based on the publication numbers for each technique (keyword: bioethanol dehydration, ISI Web of Science, 11/7/
2018). The research output has increased over the past decade, particularly from 2010 to 2017.

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[31]. In this technique, an electrical current is passed through a mixture

[29,30]

[12,40]

[41,42]

[43,44]

[32,33]
[40]
for separation to generate heat due to the inherent electrical resistance

Ref.
of the medium. Ohmic processing results in rapid heating of mixture as
the process is independent of the temperature gradient. Ohmic heating

polarization on feed side

consumption in desorption step

• Temperature reduction along module
is free of surface area constraints and is less prone to environmental

dependence on feed pressure

of formation of stagnant

continuous regeneration
energy losses compared with conventional heating, and hence is con-

micro bubble dynamics

of electrolyte to less
sidered an energy saving alternative [32]. Gavahian et al. [33] in-

and scale-up concerns

condensate film on feed side
• Under developed literature

fouling by cells
vestigated the use of OAHD for bioethanol separation; the OAHD pro-

• High capital investment

complexity
cess required 33% less energy and 30% less time than the conventional

up difficulty
dehydration process. Another study evaluated OAHD for corn beer so-

conductive feed
lution and concluded that OAHD was less time consuming and more

• Concentration

recovery

recovery
• Operational
economical with better process control than conventional processing

Disadvantages

• Possibility

• Adsorbent
• Complex

• Addition
• Requires
[34]. However, there are still several challenges for scale-up and

• Energy
• Strong

• Safety
• Scale
• Low

• Low
commercialization of OAHD, including improvement in cleaning and
preventing corrosion of the electrodes, safety concerns, and the re-
luctance of industries to adopt an emerging technique [33].

at temperature lower than boiling point of

All types of distillation techniques mentioned above are able to

with respect to load and feed conditions.

dehydrate bioethanol up to 95.6 mass%; nevertheless, an advanced
technique capable of breaking the azeotrope is required. Extractive
distillation is a well-developed technique for producing anhydrous

• Less chance of concentration polarization

for heat sensitive components
ethanol. In this process, a miscible external agent having a high boiling

efficient process
chance of product contamination

phase change during permeation

point is added to the mixture to separate the components without
forming an azeotrope. The external agent must be “less hazardous and

liquid elimination of azeotrope

system can be used

toxic.” The commonly used separating agents are solid salts, liquid

energy requirement

of azeotrope

extraction times
• Simplicity of equipment
solvents, combinations of liquid salts and liquid solvents, and ionic li-

thermal efficiency
operation cost
• Environmental friendly
data
quids [35]. Deep eutectic solvents have recently been recognized as

• Thermodynamically
footprint
capable of enhancing the relative volatility of water/ethanol from 1.00

• Well-developed
to 4.70. In addition, these solvents are less expensive and en-

• Elimination
• Separation

• Multistage
• Flexibility
vironmentally friendly alternatives to conventional agents [36]. Ex-

• Reduced
• Suitable
Advantages

• Smaller

• Shorter
• Lower
tractive distillation requires an additional column for recovery of the

• High
• No
• No
separating agent from the unwanted mixture components, hence re-
quiring additional energy and capital cost. Recently, a new heat pump-
assisted approach was proposed, which integrates columns into a single

Combination of distillation and pervaporation in single unitVapor feed is entered in

Involves separation through vapor permeation followed by distillation to further
unit, resulting in reduced capital cost [37]. The integration of the heat

Involves adsorption of selected component on adsorbent material followed by

Hot air micro bubbles are introduced which causes the water to vaporize and

vertically oriented membrane, condensed vapors moves downward producing

Involves separation through pervaporation followed by distillation to further

pump resulted in 40% energy saving. However, the integrated approach

Ohmic heating through electrodes is provided to heat up the solution for

requires rigorous control of the process parameters to ensure con-
tinuous safe operation. Furthermore, Errico et al. [38] attempted to
intensify the classical extractive distillation approach for ethanol se-
paration from fermentation broth. The coupling of the energy streams
of the main column and solvent recovery column intensified the se-
quence, with an energy index of 7.93 MJ/kg compared to the reference
sequence with an energy index of 8.08 MJ/kg. Another study was
Comparison of hybrid technologies for syngas fermentation broth separations.

conducted to explore the economic aspects of this technique for se-

paration of the components of fermentation broth, and it was found that
desorption to obtain concentrated solution

thermally coupled configurations provided insignificant capital cost

saving. Hence, the trade-off between the solvent cost and capital cost
should be evaluated to successfully commercialize this technology [38].
Recently, Novita et al. [39] proposed a hybrid extractive distillation
countercurrent contacting

process employing high-selectivity pervaporation with a cellophane

enrich the feed stream

enrich the feed stream

membrane. They showed that the hybrid configuration can provide up

concentrate the feed

to 41% energy cost saving compared to conventional extractive dis-

tillation in alcohol dehydration. Table 2 shows the combination of
distillation

technologies used to produce anhydrous ethanol from syngas fermen-

Principle

tation broths.

3. Membrane-based separation
Pervaporation-distillation Hybrid

Ohmic-assisted hydrodistillation
Vapor permeation -distillation

3.1. Reverse osmosis

Membrane dephlegmation
Microbubble distillation

Adsorption/desorption

Reverse osmosis can be employed to enrich the broth at the end of

fermentation. In this process, a pressure higher than osmotic pressure is
applied to the side of the semi-permeable membrane with the fermen-
tation broth. Consequently, water molecules move through the mem-
hybrid
Technique

brane against the natural gradient, leaving behind a stream enriched in

Table 2

ethanol. This technique is used to enhance the ethanol concentration

before entry to the distillation column. The subsequent distillation may

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be more efficient as a smaller volume with a high concentration is dephlegmation. In this configuration, the pervaporation membrane
treated. This technology is widely used for water purification, whereas module was installed vertically. The vapor phase was introduced from
for water ethanol separation, this approach is not widely explored by the bottom, whereas vapors leaving the top were partially condensed
researchers [45]. Choudhury et al. [46] investigated the use of a reverse and refluxed from top to bottom. The counter-contact between the re-
osmosis process with modified cellulose acetate to purify ethanol in the fluxed condensate flowing from the top and vapors coming from the
feed concentration range of 5–20% (v/v). At a high pressure of bottom was responsible for the major part of the separation. The final
800–1400 psig, a maximum concentration of 95% (v/v) was achieved. enrichment was achieved through the pervaporation membrane, for
However, the high pressure required for the separation is the major which a vacuum was applied to the shell side. In that study, a com-
drawback of this process. Lee et al. [47] attempted to tackle this issue mercial zeolite membrane was used, and it was concluded that this
by manipulating the osmotic pressure gradient. The permeate side of scheme was capable of breaking the water-ethanol azeotrope and pro-
the membrane was supplied with less concentrated solution than the duced a concentrated stream with greater than 99 mass% ethanol.
feed, but more concentrated than the passing permeate, which lowered However, these membranes were unstable when higher water con-
the osmotic pressure difference between both sides of the membrane. It centrations were present on the feed side; hence, more stable membrane
was reported that this scheme could provide seven-fold more energy materials having better separation factors need to be explored [42].
saving than the conventional distillation process in enriching the stream
from 10 to 50 wt%. Although ethanol separation can be achieved with 3.3. Membrane-based liquid-liquid extraction
reverse osmosis, the impracticality of this technology hinders research.
The practicality is mainly limited by the higher pressure requirement, Membrane-based liquid-liquid separation is a hybrid that combines
higher fouling rates, incapability of handling higher concentrated conventional liquid-liquid extraction and membrane technology in a
ethanol solutions due to less water/ethanol selectivity, and membrane single unit, and has been used for years. In this process, two relatively
degradation [48]. The innovative development of thin film composite immiscible phases, i.e., feed and solvent, are parted through a micro-
RO membranes have enables researchers to control higher biofouling porous membrane, where the component to be separated has different
rates in the fermentation broth based ethanol separation. The surface solubility in both phases. One phase then enters into the membrane
modification using reduced graphene oxide – titanium dioxide and pores through capillary action where phase interfacing, and ultimately,
graphene oxide – silver nano particles have shown improved water extraction occur [56]. As this process does not require feed distribution
desalination performance [49,50]. However, for commercialized ap- into the solvent, which is the major advantage over the conventional
plication in bioethanol separation, this technique should be further scheme, it prevents emulsion formation and omits phase separation
explored to address the above-mentioned shortcomings. after extraction. Groot et al. [57] first used this concept of coupling
liquid-liquid extraction with membrane technology for biorefinery in
3.2. Membrane coupled with dephlegmation 1990. That study investigated 36 solvents for extraction and coupled
this technique with batch, fed batch, and continuous fermentation. An
A dephlegmator is a device used to partially condense a multi- overall three-fold increase in the substrate consumption by product
component vapor stream. The vapor stream moves upward while the removal was reported for the batch and fed batch schemes, whereas for
condensed stream moves downward under the influence of gravity; continuous fermentation, a 30% increase was observed; which shows
thus, heat transfer and mass transfer both take place between two the potential to overcome the most basic fermentation problem, i.e.,
distinctive phases [42]. This process cannot be used for fuel grade en- product inhibition. However, this hybrid approach has not yet been
richment; nevertheless, it can be applied to the reflux stream sent to the widely explored for bioethanol separation. Snochowska et al. [58] in-
fractionation and rectifying columns [41]. It assists in hydrocarbon vestigated the use of membrane-supported liquid-liquid extraction to
separation and cryogenic gas separation [51]. For alcohol concentra- separate ethanol from dilute mixtures using a novel ionic liquid as the
tion, dephlegmation can be used to improve the efficiency of perva- extracting solvent. A hollow fiber membrane module having the feed on
poration [52]. the tube side and the ionic liquid (1-butyl-3-methylimidazolium methyl
Recently, a membrane-based technique was explored in combina- sulfate) on the shell side was used. The highest extraction efficiency of
tion with dephlegmation. Vane et al. [53] patented a hybrid scheme in 20.2% was achieved with a feed concentration as low as 1 wt%. It was
which pervaporation was employed in conjunction with dephlegmation concluded that the extraction efficiency was improved by applying a
to separate water-alcohol mixtures. First, the mixture was passed higher feed flow rate and lower feed concentration. Moreover, coupling
through a pervaporation membrane that produced an organic-enriched with an ionic liquid in this process further enhanced the process effi-
permeate stream, which then entered the dephlegmator unit. Through ciency. However, membrane fouling [59], insufficient understanding of
partial condensation using the dephlegmator, the top product enriched models of the extraction and mass transfer processes, and the com-
with a volatile component and the bottom product enriched with a less plexity of the design are the major factors inhibiting the successful
volatile component were produced. In another study, Vane et al. [54] application of this technique [56]. Little information regarding this
reported an increase in the separation factor of the pervaporation technique is available in the literature and more comprehensive re-
membrane from 11- to 108- fold by utilizing a dephlegmator. Conse- search needs to be conducted.
quently, the alcohol-rich permeate stream from pervaporation was in
the vapor phase, and required additional energy for condensation. 3.4. Vapor permeation
However, by replacing the traditional condenser with a fractionating
condenser, the dephlegmator enhanced the overall efficiency of the Vapor permeation is the transfer of matter through a porous or non-
process. Recently, a pervaporation and dephlegmation-based process porous membrane from a feed in the vapor phase to a vapor permeate
called BioSep was developed, which was commercialized on a small product. In the case of porous membranes, vapor permeation is closely
scale in American rural areas to recover bioethanol [55]. In this related to gas permeation, with the only difference being the presence
scheme, pervaporation is first used to increase the ethanol concentra- of at least one condensable component in the feed of the former. In the
tion from 10 to 40 wt%, and the dephlegmation unit is then employed case of a non-porous membrane, vapor permeation is related to per-
to enrich the ethanol concentration until an azeotrope is formed. In the vaporation, where the difference is in the feed phase. Because vapor has
last step, pervaporation is again used to break the azeotrope to achieve higher permeability than gases, this technique has potential application
a final > 99 wt% stream. in the removal of pollutants from air as well [40].
Haelssig et al. [41] proposed a novel system incorporating perva- However, for separation of water-ethanol mixtures, this technique
poration and distillation in a single unit, called membrane has not been as intensively studied as other techniques. The major

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reason is because the mixture must be heated above the boiling point, pressure-driven mechanism that makes use of both asymmetric and
which increases the utility cost and energy requirement. In one study, composite non-porous structures [63]. Separation is dependent on the
integration of the vapor permeation unit after distillation was proposed affinity of the component for the membrane material and the diffusion
to further enrich the top product from the column [60]. Integration at rate; therefore, a low concentration component can be enriched in this
this point resulted in elimination of the feed evaporator. However, to process. The membrane can be directly submerged in the bioreactor or
achieve a higher separation factor, further superheating of the vapor linked to the reactor in an external configuration in a separate unit
permeation feed was required. Vane et al. [61] further investigated this requiring an intermediate pumping step (as shown in Fig. 4). The
concept through enrichment simulation of 5 wt% ethanol feed. Cou- membranes may be hydrophilic or hydrophobic. Hydrophilic mem-
pling with vapor permeation to treat the overhead column product branes will allow the permeation of water from the water/organic
resulted in 63% fuel equivalent energy saving. Another comparative mixture and the feed will be dehydrated. Hydrophobic membranes
simulation study performed by Vane et al. [62] reported a 43% energy allow the permeation of organics and retain water, leaving behind a
reduction in the production of azeotropic ethanol in membrane-assisted permeate enriched in organic components. This process is primarily
vapor stripping compared with conventional distillation. used for breaking azeotropes and dehydration of organic components,
such as for the enrichment of ethanol from a water/ethanol mixture.
The performance of a pervaporation membrane is judged by two fac-
3.5. Pervaporation
tors, the flux and selectivity. Generally, the flux increases as the se-
lectivity decreases; thus, there is always a trade-off between these two
The word pervaporation is a combination of two terms, i.e.,
parameters to obtain optimum performance [64].
permeate and evaporation, where the processes are used for separation
The first systematic study on pervaporation was done by Binning
of miscible feed components by interaction with non-porous mem-
and Lee from the American Oil Company in 1960 [40]. Separation of
branes. During the process, a vacuum is provided on one side. The
the azeotropic mixture was carried out by using a non-porous plastic
components in the liquid feed are sorbed into the non-porous mem-
membrane [65]. This process has many advantages over its competi-
brane, and the permeate components are selectively vaporized because
tors, such as low energy consumption, low module cost, high separation
of the vacuum pressure on the other side. The vapors are collected and
factors, and effective handling of temperature-sensitive components
liquefied using a condenser trap. A schematic diagram of the process
[11,12]. The advantages of integrating pervaporation with distillation
and mechanism of pervaporation is shown in Fig. 4. Pervaporation is a

Fig. 4. (a) External configuration of pervaporation unit, (b) internal configuration of pervaporation unit, (c) schematic of pervaporation process and mechanism, (d)
solution diffusion mechanism, (PV: pervaporation membrane).

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A. Khalid, et al. Renewable and Sustainable Energy Reviews 105 (2019) 427–443

for fermentation broth separation are listed in Table 2. Advantages, higher separation factor of 85 was achieved by improving the micro-
such as the lower labor and space requirement, make pervaporation a structure of the zeolite membrane through manipulation of synthesis
promising technique for integration with the fermenter [12]. Further to conditions.
make the process economical, it is vital to operate the pervaporation On the other hand, separation factor has not shown any defined
module under the optimum conditions. There are numbers of factors trend with respect to feed temperature condition (Fig. 6(b)). This is due
that can be manipulated to improve the pervaporation efficacy, as re- to the fact that separation factor is the property of membrane char-
presented in Fig. 5. acteristics. The PVA (polyvinyl alcohol) and MFI zeolite membranes
produced minimum fluxes of 0.182 and 0.47 respectively. However, the
3.5.1. Effect of temperature separation factor was comparatively higher under the same conditions
Temperature affects the transport as well as sorption of components of temperature. In order to get an optimal performance, pervaporation
in the liquid feed and in the membrane, respectively [66]. Kang et al. membrane should have high separation factor and flux. The data re-
[63] demonstrated the effect of the feed temperature on the perva- vealed a significant of research in improving the pervaporation mem-
poration performance. The study was conducted using a feed solution brane performance through material modification to achieve a tradeoff
containing 9.6 wt% ethanol at temperatures of 37, 44, 53, 60, and between separation efficiency and flux.
67 °C. It was revealed that increasing the temperature significantly
enhanced the permeate flux, while the selectivity remained nearly 3.5.2. Effect of feed concentration
constant. The temperature-induced flux enhancement is due to the so- Effect of feed concentration on pervaporation membrane perfor-
lution-diffusion action of the membrane, facilitated by higher molecule mance depends on type of the module used, either hydrophilic or hy-
mobility at higher temperatures. Moreover, free volume of polymeric drophobic, the effect is prominent in case of hydrophobic membranes.
membranes increases with an increase in temperature, resulting in Fu et al. [67] investigated the effect of the feed concentration on the
higher polymeric chain mobility and more penetration of molecules. pervaporation performance. The ethanol concentration of a model
The small increase in the selectivity is probably due to decreased hy- broth solution was changed from 3% to 15% (w/v) while maintaining
drogen-bonding between water and the alcohol, resulting in less water the operational temperature at 30 °C. The ethanol flux increased while
in the permeate [14]. the water flux showed a slightly decreasing trend with increasing feed
Fu et al. [67] studied the effect of temperature on a 9% (w/v) concentrations. As a whole, the co-influence of the water and ethanol
ethanol-containing broth solution. The temperature was varied from 20 flux caused the total flux to grow steadily with increasing feed con-
to 40 °C. The results showed that both the water and ethanol flux in- centrations. Increasing the feed concentration favors ethanol permea-
creased with increasing temperature. The increase in the ethanol flux tion as the swelling degree, and ultimately the permeation resistance,
was likely due to an increase in the partial pressure on the feed side decreases with increasing feed concentration. Moreover, the perva-
with increasing temperature. On the other hand, a minor decrease in poration separation index (PSI) showed a nonlinear trend with in-
the ethanol concentration was observed with increasing temperature. creasing feed concentration. In another study, Bello and Souza et al.
The higher water vapor pressure at higher temperature influenced the [90] discussed the effect of the feed concentration on the pervaporation
ethanol concentration in the permeate. Due to the increase in the free performance by using broth model solutions with 3 and 30 wt%
volume of the polydimethylsiloxane (PDMS) layer and varying partial ethanol. The results revealed that the enrichment factor decreased with
pressures, the separation factor also dropped slightly. an increase in the feed concentration from 8.88 to 2.06. The mass flux
Fig. 6 shows the effect of temperature on the two major membrane of the permeate also decreased from 5.85 to 4.20, whereas the permeate
characteristics (mass flux (a) and separation factor (b) from reports over concentration increased drastically from 18.18 to 66.31 when the broth
the last ten years for different membrane materials. As expected, a concentration was changed from 3 to 30 wt%. This behavior indicated
linear trend is observed between temperature and mass flux irrespective that by-products of fermentation, such as carboxylic acids, alcohols,
of the membrane material used. MFI zeolite membranes showed both and aldehydes, influence the separation process, especially at lower
maximum and minimum fluxes (in 1000 g m2 h-1) of 9.8 and 1.36 re- feed concentrations.
spectively at the same temperature value of 60 oC. The separation fac-
tors under the same conditions were 46 and 85 respectively. The higher 3.5.3. Effect of feed flow rate
flux value for the same membrane material was attributed to the use of Liang et al. [91] investigated the effect of the feed flow rate on the
hollow fiber base which provided additional surface area. Whereas, a pervaporation performance by applying a resistance in a series model

Fig. 5. Key bottlenecks affecting pervaporation membrane performance.

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A. Khalid, et al. Renewable and Sustainable Energy Reviews 105 (2019) 427–443

Fig. 6. Effect of temperature on mass flux and separation factor [68–89].

and semi-empirical Sherwood model. It was reported that the feed 3.5.5. Effect of stage cut
permeate flow rate remained unaffected, whereas the separation factor The stage cut of a membrane is defined as the ratio of the permeate
improved when the feed flow rate was increased. This is because an flow rate to the feed flow rate. The stage cut is an important parameter
increase in the feed flow rate effectively reduced the boundary layer in the design of pervaporation modules. This factor directly affects the
thickness, which is the rate determining factor for pervaporation se- membrane area and temperature drop across the membrane. A higher
paration. Similarly, Bello et al. [90] studied the effect of the feed flow stage cut results in a lower feed flow rate compared to the permeate
rate on the performance of water-ethanol separation through perva- flow, resulting in a higher temperature drop. Similarly, the membrane
poration. The evaluation was conducted using a 15% alcoholic solution area also increases when the stage cut value increases [97]. The stage
at feed flow rates of 20 and 80 L/h, where the results revealed re- cut range was reported to be 0.1–1.1%. One important limitation of
spective increases of 12.5% and 17.7% in the membrane selectivity and ethanol commercialization is the reduced stage cut of vacuum-based
permeate concentration. Consequently, the PSI and mass flux were systems [98]. By manipulating the operating parameters (Fig. 5), the
lower at higher flow rates, mainly because of negative diffusion effects. stage cut, and ultimately the ethanol recovery, can be improved. The
In contrast, Jiraratananon et al. [92] conducted experiments using feed concentration, permeate pressure, feed flow rate, and membrane
chitosan/hydroxyethylcellulose composite membranes and concluded thickness are the main parameters that can be adjusted to enhance the
that the water and ethanol flux both increased linearly with the feed stage cut [99].
flow rate due to a decrease in the concentration polarization. This re-
search showed an increase in the pervaporation separation index with 3.5.6. Effect of membrane material
an increase in the feed flow rate; hence, it was concluded that higher The membrane material is another vital factor determining the
flow rates could result in better pervaporation performance. pervaporation performance. Although a number of materials have been
studied for recovering ethanol from fermentation broth through per-
3.5.4. Effect of permeate pressure vaporation, there are very few materials with ethanol-selective prop-
The permeate pressure is an important factor as it defines the erties that meet industrial demands. Polymeric and inorganic materials
driving force for both mass and energy transfer across the membrane. are mainly used in this regard. In the polymeric class, the representative
Lower permeate pressure results in improved performance by enhan- membrane material most widely used for ethanol removal at lower
cing both the flux and separation factor due to an increase in the driving concentrations is polydimethylsiloxane (PDMS) because of its hydro-
force for transport of the components, as reported by many researchers phobic nature [14]. The free rotation of the Si-O bond due to higher
[90,92]. Theoretically, the maximum ethanol flux is achieved at zero ethanol diffusivity contributes to the excellent selectivity [100]. There
permeate pressure. However, high vacuum or the minimum operating are a number of companies that manufacture PDMS-based pervapora-
permeate pressure is directly linked to the energy cost. Hence, there is a tion membranes worldwide, including Pervatech (Netherlands), Cela-
trade-off between the vacuum pump energy cost and ethanol flux to nese Corporation (USA), Suzler (Germany), and SoISep (The Nether-
gain maximum efficiency. lands). Despite of its wide acceptance, PDMS still suffers from many
Lazarova et al. [93] studied the effect of the permeate pressure on limitations as it has lower film forming ability due to higher swelling
the transport of ethanol in a pervaporation-based system. It was con- and poor mechanical properties [101].
cluded that increasing the permeate pressure leads to lower ethanol flux To overcome these limitations, mixed matrix membranes consisting
on the account of better selectivity. In another study by Ye et al. [94], of inorganic filler dispersed in a polymer were studied. In this way, the
the authors claimed that the Knudsen coefficient parameter is a crucial mechanical properties were enhanced and better separation char-
parameter in water/ethanol pervaporation. Upon increasing the acteristics were achieved. Such membranes were first prepared and
permeate pressure, the Knudsen parameter for water decreases, while reported in 1987 [102]. Since then, modification of PDMS membranes
that for ethanol increases, which in turn results in higher water and using inorganic fillers has gained massive attention [95,103–108].
lower ethanol flux. Recent studies reported that increasing the Some novel fillers such as bio-char core-shell particles, metal organic
permeate pressure caused both parameters to decline, leading to a de- frameworks (MOF), vinyltrimethoxysilane (VTMS)‐modified silicalite‐1
crease in the membrane performance due to reduced driving force zeolite nanoparticles, and many other nano-sized particles have also
[86,95,96]. been investigated for ethanol recovery. However, there is still great

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A. Khalid, et al. Renewable and Sustainable Energy Reviews 105 (2019) 427–443

room for improvement in terms of the separation factor and relative

Reference
flux. These MMMs combine the advantages of both polymeric and in-

[111]
[110]
[112]
[113]
[114]
[115]
[116]
[117]

[118]
[119]

[120]
[121]
[12]

[10]
organic materials and are prospectively one of the best ethanol recovery
solutions because of their strong hydrophobic nature.

has 56.5% utility cost saving and 10.8% fixed operating cost saving as compared to D/AzD hybrid

has 21% greater energy consumption and 3.6% less capital cost as compared to D/AzD hybrid
4. Economic comparison of pervaporation with azeotropic

(pervaporation of 25% of the fermenter broth) has 20%savings, as compared to D/MS hybrid
distillation

Ethanol extraction from fermentation broth consists of two steps:

first, enrichment of ethanol from the fermenter outlet up to the azeo-
tropic concentration, and second, ethanol enrichment from the azeo-
tropic concentration to fuel-grade concentration. In recent years, the
potential of using pervaporation to replace azeotropic distillation has

has 12% saving in total annual cost as compared to D/AzD hybrid

has 52.4% less energy consumption as compared to D/AzD hybrid

has 5.3% less energy consumption as compared to D/AzD hybrid
been extensively explored. A number of membrane materials for fab-

has 36% less energy consumption as compared to D/AzD hybrid

has 50% less energy consumption as compared to D/AzD hybrid

has 18% less energy consumption as compared to D/AzD hybrid
ricating modules of better quality have been investigated [64]. The
energy consumption and economics of conventional distillation-based
processes were also compared with those of pervaporation-based

has 49% cost saving as compared to D/AzD hybrid

has 32% cost saving as compared to D/ExD hybrid

schemes using simulation software to highlight the clear difference
(Table 3). Azeotropic distillation carries an added raw material cost for

economic gain over conventional distillation

the solvent and cost for subsequent solvent recovery. Thus, replacing

economic gain over conventional D/AzD

economic gain over conventional D/AzD

azeotropic distillation with pervaporation can reduce both the solvent
cost and solvent recovery cost [109,110].
Table 3 shows a comparison of pervaporation/distillation with
conventional azeotropic distillation/distillation technology. In early
publications, less or no economic benefit of the pervaporation hybrid
was reported in relation to conventional distillation-based configura-
tions. The performance, and thus the economics of the system, depends
on the characteristics of the pervaporation membrane. A membrane
having a better flux and separation factor results in a lower membrane
area requirement, and ultimately, the cost is reduced. With develop-
ments in the membrane materials and characteristics, the economics of
has no

has no

has no
hybrid
hybrid

hybrid

hybrid
hybrid

hybrid
hybrid
hybrid
hybrid
hybrid
hybrid
the pervaporation/distillation hybrid have been improved, as clearly
Findings

shown in Table 3. A maximum energy saving of 52.4% is reported for

D/PV
D/PV
D/PV
D/PV
D/PV
D/PV
D/PV
D/PV
D/PV
D/PV
D/PV
D/PV
D/PV
D/PV
the ethanol production process, which clearly shows the potential of
this technique for breaking the azeotrope.
Anhydrous ethanol
Fuel grade ethanol
Fuel grade ethanol
Fuel grade ethanol

99.7 wt% ethanol

99.5 wt% ethanol
4.1. Pervaporation integration to produce azeotropic ethanol stream
Isopropanol
Isopropanol

Isopropanol
Acetic acid

The potential of pervaporation to replace distillation at the up-

Product

Butanol
Ethanol

Ethanol

ETBE
stream of the process (enrichment to the azeotropic concentration) has
not been fully explored. O’Brien et al. [13] performed a preliminary
Existing simulation-based case studies comparing distillation and pervaporation.

economic analysis of integrating pervaporation with continuous fer-

Lignocellulosic biomass produced fermentation broth

mentation at the upstream of the distillation column. This research

stated that the integration of pervaporation with continuous distillation
provided many advantages over conventional distillation-based sys-
Brown algae-derived fermentation broth

tems, including: 1) pervaporation integration at the upstream end aids

in preventing product inhibition inside the fermenter by continuously
Cassava-derived fermentation broth
Isopropanol water acetone mixture

Corn-derived fermentation broth

removing the product from the unit. Product inhibition arises when the
ethanol concentration in the fermentation broth exceeds the threshold
Isopropanol water mixture

Isopropanol water mixture

Acetic acid water mixture

value, thus decreasing the microbial activity. Fernández-Naveira,

Butanol water mixture
Ethanol water mixture

Ethanol water mixture

Ethanol water mixture

Ethanol water mixture

ETBE ethanol mixture

Abubackar et al. [122] reported 1 g/L of ethanol to be the maximum

concentration that did not decrease the growth rate of Clostridium car-
boxidivorans, thereby maintaining an ethanol concentration of 40 g/L,
highlighting the need for minimal product inhibition. 2) continuous
Feedstock

ethanol recovery results in higher fermenter volumetric productivity,

ultimately reducing the required fermenter capacity. 3) Enrichment of
the stream entering distillation results in less energy consumption and
RWTH Aachen and Aspen Plus

Visual Basic Simulation (VBS)

reduced capacity (size and utilities requirement) of the column.

A similar idea was proposed by Kang and Van der Bruggen et al.
[63]. They stated that to reduce the risk of product inhibition in fer-
mentation by ethanol, at least 20–30% of the total stream flow rate
should be treated by pervaporation. By directing this minimum amount
of mass to pervaporation in parallel with distillation, product inhibition
Aspen Plus
Aspen Plus
Aspen Plus

Aspen Plus
Aspen Plus
Aspen Plus

Aspen Plus
Aspen Plus
Software

in the fermenter can be reduced, resulting in a decrease in the energy

Table 3

MINLP

Pro II

consumption for subsequent distillation. However, due to the unavail-

–

ability of quantifiable data, the above-mentioned hypothesis has not yet

436
 A. Khalid, et al.

Table 4
Fundamentals and novel equations for pervaporation modeling [66,125,127,128].
Mass Balance Equations Energy Balance Equations

Fluxi = Conc.i *Mobilityi *Driving forcei Overall heat balance equation is

Flowrate of permeatei = Ji *Amem QF − Qret − Qperm − QMod = 0
Flowrate of retentatei = Fi − Flowrate of permeatei For insulated membrane modules, heat losses are neglected.
QF − Qret − Qperm = 0
n Energy content of feed stream is
Fperm = ∑i = 1 Fpermi
n QF = FF *hF = FF *Cp*(TF − TRef )
Fret = ∑i = 1 Freti
Ji Energy content taken away by retentate is
Z permi =
Fperm
Freti Qret = Fret *hret = Fret *Cp*(Tret − TRef )
Zreti =
Fret
ZpermEth / ZpermWat Energy required to vaporize permeate is
αEth / Wat =

437
Z FEth / Z F Wat Q vap = FPerm*∆hvap
The overall energy balance equation of pervaporation is
FF *hF − Fperm*hperm − Fret *hret = 0
Solution Diffusion Model version
• Modified Di xi, f α (pperm / pi, sat )
Basic equation Ji = (x m− i, f i, f Free Volume Theory
• E l 1 + (α − 1) xi, f
1 D (pi, f − pi, perm ) 1 1⎞
Ji = * i* where, Di = D*i exp ( i ⎛⎜ − ⎟)

1+
Di i pi, sat R Tref T Basic equation
Qo pi, sat i
⎝ ⎠ • ∂lna1 . dv1 f (0 . T ) β1 (T ) β2 (T )
J1 = −ρ1 D1* Where, D1 = RTA1exp (− ⎛ + φ1 + φ2 ⎞ )−1
∂lnv1 . dc ⎝ E1 E1 β1 ⎠
Modified version
1 Di *exp (B * xi, F ) (pi, F − pi, perm )
•
J = * *
i Di *exp (B * xi, F )
1+ i pi, sat
Qo pi, sat i
Modified version
• Modified version
1 Di, exp (pi, F − pi, perm ) E 1
• −E ω1 V1 + εω2 V2
Ji = * * where, Di, exp = Di exp(€ixi )exp ( i ⎛ ⎜ −
1⎞
⎟)
Di = Qo (1 − ∅1 )2 (1 − 2σ ∅1) exp K
)
Di, exp R Tref T RT
( ) exp (− K11
ω1 (K21 − Tg1 + T ) + 12 ω2 (K22 − Tg 2 + T )
1+ i pi, sat
⎝ ⎠ θ θ
Qo pi, sat i

• Modified version
E 1 1 ⎞⎞ E 1 1 ⎞⎞ E 1 1 ⎞⎞
⎜
− ⎟ ⎟*(x ⎜ − ⎟ ⎟*(x ⎜ − ⎟ ⎟*(x
Ji = Qiref exp ⎜⎛ i ⎛
R T T i i pi, sat ) Ji = Qiref exp ⎜⎛ i ⎛
R T T i i pi, sat − yi pperm ); Ji = Qiref exp ⎜⎛ i ⎛
R T T i i pi, sat − yi, SL1 pz − SL1 )
⎝ ⎝ ref ⎠⎠ ⎝ ⎝ ref ⎠⎠ ⎝ ⎝ ref ⎠⎠
Renewable and Sustainable Energy Reviews 105 (2019) 427–443
A. Khalid, et al. Renewable and Sustainable Energy Reviews 105 (2019) 427–443

been verified.
and modified by
Recently used

4.2. Modeling of pervaporation for separation of components of

[134,135]

[137,138]
[66,129]
fermentation broth

The fundamentals and novel equations for pervaporation modeling

are shown in Table 4. Furthermore, the basic and modified versions of

Single or binary
the solution-diffusion model and free volume theory are presented.
components
permeating

Aspen Tech provides one of the most widely used tools for simulating
Number of

Ternary or
quarterly
chemical unit operations and processes [123] (Table 3). The membrane
Multi

module is not present in Aspen's in-built library. A few options are

available for carrying out this task. Liquido Do et al. [124] developed a
Proposed By

pervaporation software based on FORTRAN language. This model cal-

culates parameters using the solution-diffusion mechanism, whereas
[132]

[133]

[136]
the activity coefficients are determined using the UNIFAC method. Si-
milarly, custom modeling can be performed using Microsoft excel VBA
coding, FORTRAN language, or Aspen custom modeler. Once the model
Theoretical

is developed, it can be exported to the Aspen interface for further stu-

Nature of

empirical

empirical

dies and integration with other units. gPROMS model builder is another
model

Semi-

Semi-

advanced simulation tool for developing models based on governing

equations. After model development, the gPROMS file can be extracted
Lacks the understanding of how and

to a compatible simulator such as CAPE-OPEN, where the free-of-charge

Require experimentally determined
Modified models accommodate the

increases, complexity of equations

membrane performance based on

where actual phase change takes

steady-state environment provides an opportunity to study developed

Prediction of multi-component
concentration changes on flux

Applicable to non-ideal multi-

As the number of components

single-component experiment

Requires numeric solution of

unit operations with other in-built models.

Describes the phase change

Pervaporation modeling involves two parts: the flux model that

effect of temperature and

describes component transport, and a model to depict energy flow. The

diffusion parameter
component system

mass and energy flow can be modeled either in one dimension or in two
Pros. and cons.

dimensions by explaining the axial variation or both the axial and radial
phenomenon
parameters

variations, respectively. In recent years, semi-empirical trans-mem-

enhances

brane models have gained much attention. These models are based on
place

calculation of the flux across the module. Flux is a direct representation

of the membrane efficiency and is thus used further for capital cost
travel from feed side to permeate side under the influence of
Based on thermodynamically irreversible system, components
Vapor permeate travels from liquid-vapor boundary to pore

calculation for membrane-based systems.

Straight cylindrical pores are present across the membrane
Diffusion of components across the membrane thickness

Jaimes et al. [125] first developed transport equations for the per-
concentration gradient (driving force) and friction force
Liquid permeate travels from pore inlet to liquid-vapor

vaporation model by using the basic idea of Rautenbach et al. [126];

(because of component interaction in the system)
Sorption of feed components to membrane layer

afterwards this model was termed as solution diffusion model. This

model is based on three steps: sorption of the component to the mem-
Desorption of components to permeate side

brane surface, diffusion of the component through the membrane,

desorption, and evaporation of the component to the permeate side (as
represented in Fig. 4).
This model requires knowledge of a basic parameter, such as the
permeability, from experimentation. Valentínyi et al. [66] re-
Evaporation takes place

commended improvement of the basic model given by Jaimes et al.

[125] and tested the model for hydrophilic membranes. In this im-
proved model, the change in the transport coefficient is considered as
Transfer steps

an exponential function of the concentration of the permeating com-

boundary

pound. Lovasz et al. [129] reported a generalized methodology for

outlet

pervaporation modeling based on basic solution-diffusion equations.

Ashraf et al. [127] used a semi-empirical flux model to calculate the
flux, PSI profile, temperature, and concentration over the membrane
between feed side and permeate side
Component concentration difference

feed side and permeate side along

Concentration difference between

length. This model represents the flux as a function of the temperature,

pressure and partial pressure of
Difference between saturation

and for a solution, it only requires the experimental feed temperature,

Comparison of available pervaporation models.

with coupled diffusion effect

composition, and one parameter from the feed side, such as the
component in feed side

permeate composition. Jain et al. [130] studied pervaporation using a

solution-diffusion approach for a spiral-wound module. Further, in this
study, equations were derived based on the mass and energy balance to
Driving force

predict variations in the operating parameters along the axial direction

and solved in MATLAB. Based on these models, the effect of different
parameters on the pervaporation performance is explained and the
scale-up problem is addressed.
Zhuang et al. [95] studied the performance of a mixed matrix
Solution diffusion

Maxwell Stephan
Pore flow theory

membrane for a water-ethanol mixture using models proposed by

Theory

Maxwell et al. [131] based on Maxwell-Stephan theory. Although the

Model

Maxwell model is proposed for evaluating mixed matrix membranes in

Table 5

Model

gas separation processes, due to the closeness of gas separation and

pervaporation principles, researchers have used this model for the latter

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A. Khalid, et al. Renewable and Sustainable Energy Reviews 105 (2019) 427–443

as well. In this model, the permeability of the key component is broken one at the upstream end, supplying an ethanol-enriched feed to the
down into the permeability in the dispersed and continuous phases. dephlegmator, the second at downstream end, providing the final
In recent years, the solution diffusion model has gained the status of overhead product through drying [55].
“most studied pervaporation modeling approach,” as shown in Table 5. It is well accepted that membrane-based solo or hybrid systems have
However, some other approaches, i.e. great potential over conventional technologies [142]. However, the
Flory-Huggins theory [139], the pore flow model, and the hydro- industrialization of these systems is still limited due to several chal-
phobic sorption distillation (HSD) model [140], are also utilized in the lenges, such as the membrane production cost, difficulties in large-scale
literature. Lipnizki et al.[141] explained all available empirical, semi- module fabrication, membrane material reliability in harsh environ-
empirical, and theoretical models to demonstrate sorption, diffusion, ments, tendency towards aging, and complex process design [143,144].
and trans-membrane mass transfer. However, the existing literature is Continuous intense effort is required to design and fabricate mem-
still immature in terms of describing the separation procedure, which branes with high flux and separation capability for product separation.
restricts the development of highly efficient membranes. Therefore,
exhaustive efforts are required to design excellent membranes for
ethanol recovery. 5. Challenges and future prospects

Separation of bioethanol from fermentation broths is the most en-

4.3. Commercialization status ergy intensive step and contributes the most to the overall cost of the
bioethanol production process. Therefore, it is desired to select an ef-
Pervaporation is not a newly developed technique; it was first used ficient separation technology to commercialize bioethanol production.
in the mid-50 s. However, its commercialization remained a challenge Over the past few decades, many alternatives to conventional distilla-
due to difficulties in fabricating the pervaporation membrane. tion have been proposed. This review covers recent developments in
Furthermore, the trade-off between membrane selectivity and perme- ethanol separation from fermentation broth with the focus on mem-
ability poses a limitation to achieve either a higher quality or flux, as brane-based separation. In the production of bioethanol, syngas derived
one parameter will be compromised while enhancing other. Companies from biomass is fermented, yielding a very low concentration aqueous
invested to make this process an industrially successful technology. ethanol, from which ethanol can be recovered using the above-dis-
However, the economics of these plants was quite prohibitive; thus, no cussed techniques. It is challenging to evaluate technological options
great success was achieved. However, in the twenty-first century, ex- for bioethanol dehydration due to inconsistent and diverse information
citing breakthroughs were made in the economical commercialization regarding the feed composition, interaction parameter values, ther-
of pervaporation. Table 6 shows the companies supplying pervapora- modynamic model applied, heat integration, compressor efficiency,
tion membranes worldwide. reboiler duty, efficiency factors in generating steam and electricity,
All these companies are providing commercial-scale and lab-scale overall energy requirement, and cost correlations (including mem-
pervaporation modules. According to their websites, a wide variety of branes, solvent replacement, and adsorbent if any), etc. Hence, it is
separation markets is covered, including water-organic separation and imperative to use only similar operating conditions, required energy
organic-organic separation. These membranes provide high flux, high values, and cost estimations to evaluate bioethanol separation alter-
temperature resistance, and high selectivity. A number of modules exist natives to facilitate industrial implementation.
for pervaporation including tubular, spiral-wound, plate and frame, and Fig. 7 shows an economic comparison of different hybrid bioethanol
hollow fiber. Successful operation of the hollow fiber module for separation techniques reported in the literature. As compared to non-
azeotropic mixture separation is considered as the biggest breakthrough membrane techniques such as LLE (liquid-liquid extraction) and PSA
in the last decade. Membrane Technology & Research Inc. (MTR), to- (pressure swing absorption), membrane based techniques such as VP
gether with The United States Environmental & Protection Agency (vapor permeation), pervaporation, and RO (reverse osmosis) have
(USEPA), developed a technology termed BioSep for small rural-scale shown lower unit cost per kg of ethanol with reference to conventional
ethanol production. This technology utilizes a pervaporation module, extractive distillation approach. However, because of their working
dephlegmator, and another pervaporation module in series after the principle constraints, VP can only be employed to enrich azeotropic
fermenter. A 10 wt% ethanol feed coming from the fermenter is first vapor stream leaving the top of the distillation, whereas, RO can only
enriched to 30–40 wt% in the pervaporation module. Further con- be used to initially enhance the purity of stream entering the distilla-
centration enhancement up to formation of the azeotropic mixture tion. Moreover, pervaporation has shown the potential to be employed
(95 wt%) is achieved in the dephlegmator. The final fuel-grade ethanol in various schemes, i.e., pervaporation-distillation, distillation-perva-
(99 wt%) is obtained by using the pervaporation module that breaks the poration, and distillation-pervaporation-distillation hybrids. Among
azeotrope. Hence, the system makes use of two pervaporation modules; these, maximum economic benefit is obtained when distillation-

Table 6
Companies dealing in pervaporation membranes.
Company and website Applications

Pervatech (Netherlands) http://pervaporation-membranes.com/ Dehydration of solvents azeotrope separation

Sulzer (Switzerland) https://www.sulzer.com/en Removal of water or methanol from solvent mixtures, Splitting of azeotropes and dehydration
of aroma components
PolyAn (Berlin) https://www.poly-an.de/ Membranes for the organophilic Pervaporation
i3 Nanotech (USA) http://www.i3nanotec.com/ Dehydration of organic-water mixtures, Concentration of dilute organic mixtures, Separation of
organic-organic mixtures
Perm select (USA) http://permselect.com/ Butanol separation
Mega Vision Membrane (China) http://www.china-membrane.com/doce/brief. Isopropanol and ethanol dehydration
htm
SepraTek (Korea) http://www.sepratek.com/home/en/ Dehydration of alcohols and jet fuels
Buss-SMS-Canzler GmbH (Germany) https://www.sms-vt.com/ Dehydration of alcohol, bio ethanol and fuel ethanol
Kings Membrane energy technology with https://en.kingmembrane.com.tw Purification and dehydration of recycled Ethanol and Isopropanol Alcohol (IPA)
Mulder Trading and Energy Efficiency Solutions (Netherlands) http://www. Sea water desalination, Process water cleaning
mutrees.com/

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A. Khalid, et al. Renewable and Sustainable Energy Reviews 105 (2019) 427–443

Fig. 7. Ethanol purity vs unit cost per kg of ethanol produced for various bioethanol dehydration schemes. For calculation, 360 working days were assumed in each
year, whereas, total annual cost (TAC) of the separation unit was divided by ethanol produced to obtain per kg cost in mentioned case studies. From left to right
(scheme-1 [145], scheme-2 [145], scheme-3 [111,146], scheme-4 [146], scheme-5 [13], scheme-6 [147], scheme-7 [148], scheme-8 [149], scheme-9 [62], scheme-
10 [150]. Dist: Distillation, ExD: Extractive distillation, PSA: Pressure swing absorption, LLE: liquid-liquid extraction, VP: vapor permeation, HSM: HiGee stripper
membrane, RO: Reverse osmosis, SS: Steam stripping. * Purity data not available.

pervaporation (pervaporation replacing the azeotropic distillation in life at a satisfactory level. This achievement would help to reduce the
conventional process) hybrid is used. The maximum reported cost costs of membrane-based separation to make them competitive with
saving e.g., 49% (Table 3) is attributed to elimination of two columns other technologies. Apart from finding new material, modification in
i.e., azeotropic column as well as solvent recovery column. On the other preparation method of existing materials may also result in better
hand, integration of pervaporation at the upstream of distillation results performance. Effective synthesis methods focusing on consistent
in comparatively lesser economic benefit mainly due to; requirement of membrane microstructure must be developed to utilize this technology
larger number of heaters to pre heat the feed stream, and use of larger in a better way. With continued development of membranes having
number of membrane modules to meet the ethanol recovery require- higher permeability, ethanol-water selectivity, longer life, greater re-
ment. Hence, it is recommended to retrofit the PV with distillation in sistance to fouling, and lower cost, scale-up to industrial acceptance can
the existing bioethanol production industries, while companies working be achieved [11].
on new technology development for bioethanol separation should In most of the reported literature, only binary mixtures of ethanol-
benefit from the advantages of membrane based hybrid systems. water have been utilized for studying several issues. Development of an
Moreover, efforts are required for penetration of membrane based accurate pervaporation model to determine realistic design parameters
technologies in the global market. require use of realistic fermentation broth feed compositions. Acetic
Great progress has been made in improving the energy efficiency of acid, dissolved carbon dioxide, and other higher alcohols present even
these hybrid distillation-membrane separation processes compared in trace amounts have the potential to affect the energy requirement of
with distillation alone for the recovery or dehydration of bioethanol. the process. Therefore a realistic fermentation broth should be used for
However, several issues such as shorter lifetime, low separation factor, accurate assessment of membrane behavior. Furthermore, a thermo-
membrane fouling, and the high cost of membranes are yet to climb dynamic model capable of accommodating the experimental data to the
over, for technology commercialization. In the last decade, perva- maximum possible extent is required to obtain reliable results. The
poration has made enormous progress as several challenges have been existing literature on models is still immature in terms of providing
addressed. Although pervaporation is an energy efficient process, its correct descriptions of the separation phenomena, which limits the
industrial application is still limited. This is mainly due to lack of development of high-performance membranes. Most of the available
economical and sustainable large-scale membrane modules capable of pervaporation models require the empirical determination of a few
operating under industrial feed conditions [12]. Therefore, significant parameters for specific membrane application. This in turn restricts the
effort must be directed towards the design and fabrication of pressure- applicability of the model. Hence, efforts are required to develop a
and temperature-resistant modules. The feed temperature and vacuum universal model which can describe the separation phenomena with
pressure should be optimized to lessen the operating cost. The real enhanced accuracy and the capability of representing various mem-
quest is to develop next-generation ethanol dehydration pervaporation brane types and operation conditions. Apart from modeling, optimiza-
membranes that can provide higher permeance and sustain higher tion is another aspect of achieving better process performance. By
temperatures while maintaining the process selectivity and operating adopting modernized optimization tools an enormous energy saving

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A. Khalid, et al. Renewable and Sustainable Energy Reviews 105 (2019) 427–443

can be achieved in existing pervaporation models. Thus, efforts are Technology Program of the Korea Institute of Energy Technology
required to apply the optimization algorithms with an aim to save every Evaluation and Planning (KETEP) grants from the Ministry of Trade,
joule of energy. Industry and Energy (No. 20173010092460). This work was also sup-
Reported studies related to simulation have mainly focused on the ported by the Priority Research Centers Program through the National
design aspects, whereas little literature is available on pervaporation Research Foundation of Korea (NRF) funded by the Ministry of
process control. Lack of design and control data is another major bot- Education (2014R1A6A1031189), the Basic Science Research Program
tleneck in the widespread implementation of bioethanol production. Foundation of Korea (NRF) funded by the Ministry of Education
Therefore, more studies on the control and dynamic simulation of new (2018R1A2B6001566) and Basic Science Research Program through
separation technologies are vital for widespread bioethanol production the National Research Foundation (NRF) of Korea funded by the
on the industrial scale. Thus far, pervaporation is far from the practi- Ministry of Science and ICT ( 2017R1A2B4007804).
cality and economical limits. There is great opportunity for the devel-
opment of processes for fabricating membranes having higher flux and Declaration
selectivity, as well as computational tools for accurately predicting the
process dynamics and membrane structure and performance. The authors declare no competing financial interest.
The bioethanol industry has not yet employed hybrid processes of
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