Renewable and Sustainable Energy Reviews 30 (2014) 388–400

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Renewable and Sustainable Energy Reviews

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

A review of membrane technology for bioethanol production

Ping Wei a, Li-Hua Cheng b, Lin Zhang a,n, Xin-Hua Xu b, Huan-lin Chen a, Cong-jie Gao a,c
a
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Department of Chemical and Biological Engineering, Zhejiang University,
Hangzhou 310027, PR China
b
Department of Environmental Engineering, Zhejiang University, Hangzhou 310058, PR China
c
National Engineering Research Center for Liquid Separation Membranes, Hangzhou 310012, PR China

art ic l e i nf o a b s t r a c t

Article history: Bio-ethanol as a clean and renewable fuel has gained more attention; however greater energy inputs
Received 22 October 2012 make a slow progress in industry. Membrane technology has potential in the bioethanol production
Received in revised form process as a highly selective and energy-saving separation process. This review presented membrane
11 September 2013
technologies applied in three aspects: (i) microalgae harvesting, (ii) sugar concentration and detoxifica-
Accepted 19 October 2013
Available online 12 November 2013
tion, (iii) bioethanol recovery. The performance of different membrane processes was summarized and
compared. The advantages and limitations of membrane technologies for these applications are
Keywords: discussed, and it was thought that the hybrid process has great potential in improving membrane
Bioethanol efficiency.
Membrane technology
& 2013 Elsevier Ltd. All rights reserved.
Hybrid process

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
2. Membrane technology applied in bioethanol production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
3. Membrane technology for microalgae harvesting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
3.1. Membrane material for microalgae harvesting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
3.2. Membrane fouling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
4. Membrane technologies for fermentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 392
5. Membrane technology for ethanol recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
5.1. Membrane distillation for ethanol recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
5.2. Pervaporation for ethanol recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
5.2.1. Membrane material for ethanol recovery from broth by pervaporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
5.2.2. Hybrid pervaporation and fermentation process for improving ethanol yields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397

1. Introduction hybrids and natural gas-based cars are still a long way from
becoming mainstream vehicles [5].
The increasing energy crisis and growing environmental con- Bio-ethanol as a clean and renewable fuel has gained more
cerns in recent years have driven the development of technologies attention. It can be produced from all kinds of renewable materials
to allow for the substitution of fossil fuels with renewable energy such as corn, sorghum, cellulose and algae biomass. On the basis of
[1–4]. Several alternatives are currently being explored, including the raw material used for its production, bioethanol is divided into
a range of carbon-free and renewable sources (photovoltaics, wind first-, second- and third-generation bioethanol [1]. The classification
and nuclear power, hydrogen) in an attempt to replace natural gas, of bioethanol is shown in Fig. 1. Burning ethanol instead of gasoline
coal and oil in the electricity generation sector. However, there is reduces global warming emissions of 20% from corn ethanol and 85%
no such equivalent in transportation, since fuel cells, electric/ from cellulosic ethanol while entirely eliminating the release of acid
rain-causing sulfur dioxide [6]. Meanwhile, bio-ethanol can be added
to gasoline for transportation which has been applied in several
n
Corresponding author. Tel.: þ 86 571 87952121; fax: þ86 571 87953802. countries. In Brazil, more than 15% of cars can run on pure ethanol
E-mail address: linzhang@zju.edu.cn (L. Zhang). [7,8]. However, bio-ethanol production involves many processes such

1364-0321/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.rser.2013.10.017
 P. Wei et al. / Renewable and Sustainable Energy Reviews 30 (2014) 388–400 389

Fig. 1. Classification of bioethanol [17].

Fig. 2. Application of membrane processes for three generations of bioethanol production.

as pretreatment, fermentation, recovery and the refining process [9]. bioethanol synthesis. By the use of MF/UF, it is possible to recover
A total of 5.99 kJ of fossil energy is expended to produce 4.19 kJ of microalgae. For second and third generation bioethanol, pretreat-
ethanol. The largest energy inputs in corn-ethanol production are for ment is a necessary step to make the carbohydrates in the biomass
the steam and electricity used in the fermentation/distillation process accessible for conversion. The second potential membrane appli-
[10]. Bioethanol will not be significant without improvements in this cation is the purification and concentration of prehydrolyzates
process and reduced energy requirements. Membrane separation after pretreatment and before fermentation. MD, NF and RO can
technologies have gained more and more attention due to their concentrate the sugar solution and remove inhibitors to fermenta-
reduced energy requirements, lower labor costs, lower floor space tion. Regarding recovering the enzyme and other value-added
requirements and wide flexibility of operation [11]. This technology production, an NF process has been considered, combined with UF.
has applied in many processes of bioethanol production instead of the After fermentation, low concentration bioethanol is sent for
traditional process [12–16]. The aim of this article is to present a state- pervaporation and pre-concentration. Fermentation and perva-
of-the-art review on the applications of membrane technologies poration have been integrated in order to perform continuous
for bioethanol production such as microfiltration (MF), ultrafiltration fermentation. During the hybrid process, UF and NF can be used
(UF), nanofiltration (NF), membrane distillation (MD) and pervapora- to remove fermentation inhibitors and yeast. The section part will
tion (PV). We also discuss the problems confronted with every provide a detailed introduction for each membrane process.
membrane process.

3. Membrane technology for microalgae harvesting

2. Membrane technology applied in bioethanol production
Microalgae is getting more and more attention as a raw
An overview of ethanol production with potential membrane material for bioethanol production as it provides carbohydrates
applications is depicted in Fig. 2. The first potential membrane and proteins that can be used as carbon sources for fermentation.
application is the harvesting of microalgae for third generation Meanwhile, microalgae cells have a very short harvesting cycle
390 P. Wei et al. / Renewable and Sustainable Energy Reviews 30 (2014) 388–400

(1–10 days) compared with other feedstocks (harvest once or for microalgae harvesting [33–35]. They investigated 11 commer-
twice a year) and thus provide enough supplies to meet ethanol cial polymeric membranes for harvesting the cyanobacterium
production demands. On the other hand, algal biomass avoids the Arthrospira platensis by cross-flow MF and UF techniques. Hydro-
issues met with first- and second- generation bioethanol, namely philic membranes seemed more efficient than the others in terms
food–fuel competition and land-use change [18]. of steady-state permeation flux. Furthermore, such membranes
However, algal biomass harvesting is a challenge because of were easier to clean, partly because the negative charge decreased
the small size of algal cells (3–30 mm in diameter), their similar membrane fouling and cake formation, which represent the
density to water and the large volumes of water that must be majority of the total resistance; this can be removed by a single
handled to recover the biomass. Recovery of the biomass from the rinsing step. In addition, they evaluated 14 inorganic membranes
broth has been claimed to contribute 20–30% of the total cost for the separation of Arthrospira platensis from a diluted culture
of producing the biomass [19]. Therefore, a suitable harvesting medium. The UF membrane ATZ-50kD exhibited the best permea-
technology is very important for bioethanol production using algal tion flux and cleanability.
biomass. Generally, microalgae harvesting can be undertaken by According to the above studies, it can be concluded that
the technologies as shown in Table 1. As can be seen, membrane hydrophilic organic and inorganic UF membranes are more sui-
filtration is known to be not energy intensive compared to other table to microalgae harvesting.
methods, as this technology is isothermal and involves no phase
change. Meanwhile, it offers the advantages of almost complete 3.2. Membrane fouling
retention of biomass as well as potential disinfection via the
removal of protozoa and viruses [20,21]. Furthermore, no chemi- Although membrane filtration is a better technology for micro-
cals such as coagulants or flocculants are required, thus preventing algae harvesting, the flux will decline due to membrane fouling,
their accumulation in the biomass or the recycling streams that which limits the large-scale application of membrane technology.
exist in a coagulation–flocculation process [22]. Especially for Therefore, understanding membrane fouling by the biomass
smaller algae cells (o 30 mm), membrane filtration is a technically and developing anti-fouling strategies are critically important for
viable alternative to conventional filtration. Membrane filtration sustainable biomass concentration using membrane technology.
applied in microalgae harvesting was first reported in 1995. However, only a few reports on the algae/water separation process
Petrusevski et al. [23] investigated the capability of a tangential have described the fouling of membranes and solutions to mitigate
flow filtration (TFF) system, equipped with a 0.45 mm pore-size fouling [36–40]. Membrane fouling is mainly caused by bacteria,
membrane to concentrate algae from large volumes of reservoir algae, inorganic colloids and organic material such as proteins and
water. An overall algal biomass recovery of 70–89% was found. polysaccharides. On the other hand, several studies have devel-
Although membrane filtration has many advantages compared to oped potential options for membrane fouling control. There are
other technologies, studies have found that membrane fouling will different techniques to limit the fouling phenomenon, among
be severe under some operational conditions. Therefore, it is very which are the use of the proper membrane material and altered
important to choose the proper membrane material and operation operation conditions. Available membrane materials have been
model for membrane filtration. summarized in Section 3.1.
The enhancement of membrane shear-rates has long been
3.1. Membrane material for microalgae harvesting recognized as one of the most efficient factors for fouling control.
Increasing the cross-flow velocity decreases membrane fouling
Micro- and ultrafiltration have been proven to be effective to [38]. Thus, controlled hydrodynamic conditions, such as a low TMP
harvest microalgae. Membranes prepared from different materials and low shear rate, are required in order to limit fouling and cell
could provide variable harvesting performance, but there is no damage [41–44]. Rios et al. [45] used a rotational-dynamic filtra-
criterion regarding the membrane material for microalgae har- tion system to harvest Phaeodactilum tricornutum microalgae. They
vesting. Rossi et al. has performed studies on membrane materials studied the effect of rotational speeds and TMP on membrane

Table 1
Description of microalgae harvesting technologies.

Process Description Solids Recovery Chemicals Energy usage Limitations

concentration [24]
after harvesting
[24]

Coagulation/ Based on the — 66–98% Yes Low energy requirement for Only as preparatory
flocculation microalgae cells that slow mixing; varies largely step prior; Flocculants
carry a negative is expensive at high
charge dose [25]
Flotation Based on the trapping 3–6% 50–90% Yes High dissolved air Limited evidence of its
of algae cells using flotation10–20 kWh/m3 [27] technical or economic
dispersed micro-air viability [28]
bubbles [26]
Gravity Based on Stoke's law 0.5–3% 10–90% No Very high 8 kWh/m3 [30] Only suitable for large
sedimentation [29] (ca. 470 mm)
microalgae [31]
Centrifugal Based on Stoke's law 12–22% 490% No Energy intensive High energy costs
[29] higher maintenance
requirements [32]
Membrane Based on molecule 5–27% 90–100% No 0.4 kWh/m3 Membrane fouling
filtration size
Electrophoresis Based on microalgae Depends on the Varies Yes Varies Electrodes need to be
techniques able to behave as process replaced periodically
colloid particles
Table 2
Summary of the membrane process applied in sugar concentration and inhibitors removal.

Inhibitors/ Membrane Separation mechanism Scale Driven force Membrane Operation Flux Rejection (%) Disadvantages Advantages Reference
sugar process a b
conditionse (L m  2 h  1)

c
Material Configuration pH T P (bar)
d
(1C)

Sucrose VMD Relative volatility L Vapor pressure PP T – 40 0.0067 0.45 4 98% Low flux and no special Utilize low low-level [60]

P. Wei et al. / Renewable and Sustainable Energy Reviews 30 (2014) 388–400

difference membrane material heat
Sugar VMD L Vapor pressure PVDF F 65 – 8.46 99.5 [63]
difference
Glucose NF Size exclusion L Pressure Proprietary F 2.9 25 24.5 120.8 100 Membrane fouling High rejection and [51]
high flux
Glucose NF L Pressure PVA – – 30 13.78 15 99 [68]
Glucose NF L Pressure PVA – 5.6 50 17.5 60 99 [64]
Glucose NF L Pressure PA – 10 25 13 26.5 99.2 [67]
Glucose NF L Pressure PA – 3 25 11.5 39.8 95 [67]
Xylose NF L Pressure Proprietary F 2.9 25 24.5 120.8 96.4 [51]
Xylose NF P Pressure PA F – 28– 20 24 99.1 [56]
30
Xylose NF P Pressure CTA F – 28– 20 32 66.7 [56]
30
Xylose NF L Pressure PA – 10 25 13 26.5 99.5 [67]
Xylose NF L Pressure PA – 3 25 11.5 39.8 86.8 [67]
Xylose NF P Pressure Proprietar S 2.9 25 24.5 – 85 [71]
Xylose RO Size exclusion and L Pressure PA P 2.93 25 20 23.62 99.67 [74]
solution-diffusion
Glucose RO L Pressure PA P 2.93 25 20 23.62 99.78 [74]
Glucose RO L Pressure Aromatic PA – 2 21 25 – 48 [75]
Glucose RO L Pressure Aromatic – 2 21 25 – 82 [75]
polyamide
Acetate NF Donnan effect L Pressure PVA – – 30 13.78 15 60 The rejection depends on Low energy [68]
pH consumption High
flux
Acetic NF L Pressure Proprietary F 2.9 25 24.5/ 120.8/142.4  19.0—  14.9/ [51]
acid 34.3  31.8—  27.7
Acetic NF P Pressure Proprietar S 9.1 24.5 90 [71]
acid
Acetate NF L Pressure PVA – 5.6 50 17.5 60 40 [64]
Acetic RO L Pressure PA P 2.93 25 20 23.62 52.53 [74]
acid
Acetic RO L Pressure PA P 9.88 25 20 – 99.28 [74]
acid
Acetic RO L Pressure CA – 2 21 25 – 25 [75]
acid
Acetic RO L Pressure CA – 2 21 25 – 5 [75]
acid
Furfural VMD Relative volatility L Vapor pressure PVDF F 4.53 70 6.42 100 High rejection [63]
difference
Furfural NF Size exclusion L Pressure PA – 10 25 13 26.5 31.8 Relative low rejection [67]

391
392 P. Wei et al. / Renewable and Sustainable Energy Reviews 30 (2014) 388–400

fouling. As the speed increased, the flux increased due to reduced

Reference

membrane fouling caused by concentration polarization. Mean-

[67]

[77]
[77]
[77]
[51]
while, it can be stated that fouling effects which reduce the
permeability of the membrane increase when the TMP also
increases. Zhang et al. [46] developed an efficient technology for
High rejection harvesting of algal biomass using membrane filtration and estab-
lished anti-fouling strategies. Air-assisted backwash with an air
consumption
Low energy
Advantages

scour and higher cross-flow velocity can control membrane foul-

High flux

ing. Bilad et al. [47] developed a method to harvesting microalgal

biomass using submerged MF membranes. They used an improved
flux-step method (IFM) to characterize the membrane fouling.
The IFM results suggested lower degrees of fouling compared to
conventional submerged MBRs within the range of operational
parameters.
The harvesting of microalgae by membrane filtration is still
Disadvantages

under development.

4. Membrane technologies for fermentation

 20—8.5/  24.6

Every generation bioethanol will go through the process of

Rejection (%)

saccharification and fermentation. However, for the second- and

third-generation bioethanols based on biomass, the simple sugar
—  5.0

4 80
4 80

PVDF ¼poly(vinylidene fluoride), PP ¼ polypropylene, PVA¼ polyvinylalcohol, PA ¼ polyamide, CTA ¼cellulose triacetate, CA¼ cellulose acetate.

concentration in prehydrolyzates is often low due to the different

3.6

50

pretreatment processes and hydrolysis efficiency [48]. Moreover,

(L m  2 h  1)

120.8/142.4

pretreatment of biomass using steam explosion or dilute acid

results in fermentation inhibitors that will inhibit the subsequent
39.8
Flux

fermentation [49]. Low-concentration fermentable sugars in the

–
–
–

prehydrolyzates and fermentation inhibitors lead to low ethanol

concentrations, which in turn leads to high operational cost and
24.5/
34.3
11.5

40
40
40

energy consumption for subsequent purification steps. Therefore,

conditionse

in order to enhance the effectiveness of prehydrolyzate fermenta-

Operation

25
25

28
28
28

tion, the prehydrolyzate should be detoxified to remove inhibitors

and concentrated to increase sugar concentration prior to being
2.9
3

–
–
–

used for ethanol fermentation.

The conventional methods for sugar concentration or detoxifica-
tion include evaporation, solvent extraction, overliming, activated
charcoal adsorption and ion exchange. However, most of these
methods have the disadvantage of adding high processing costs,
–
F

F
F
F

complicating the lignocellulose-to-ethanol production process, gen-

Proprietary
Membrane

erating additional waste products, requiring long processing times

VMD¼ vacuum membrane distillation, NF ¼ nanofiltration, RO¼ reverse osmosis.

and/or losing sugars [50–55]. The most important point is that

conventional methods cannot concentrate sugar whilst removing
PA

PA
PA
PA

inhibitors. Membranes as a separation technology can solve these

two issues. Furthermore, studies have demonstrated that the capital
Driven force

investment for the membrane process and operating costs were

Pressure
Pressure

Pressure
Pressure
Pressure

lower than evaporator installation [56]. The present membrane

configurations applied in these aspects include membrane distilla-
tion, nanofiltration, reverse osmosis, ultrafiltration. Table 2 summar-
Separation mechanism Scale

ized the membrane process applied in this application.

L
L

L
L
L
b

Membrane distillation is a thermally driven process in which a

F¼ flat, P ¼ plate, S¼spiral wound, T ¼tubular.

microporous hydrophobic membrane acts as a physical support to

separate a warm solution containing either a liquid or a gas
mixture. A schematic diagram of membrane distillation is shown
in Fig. 3. The different MD process configurations (direct contact,
air gap and vacuum) have been used to concentrate sugar solu-
L¼ laboratory; P ¼ pilot scale.

T=temperature, P=pressure.

tions and remove inhibitors. The rejection of sugar can almost

achieve 100%. The flux depends on the membrane type, feed flow
rate, feed temperature and initial sugar concentration [57–60].
Inhibitors/ Membrane
process a

Furthermore, the MD process can utilize low-level heat or alter-

Table 2 (continued )

native energy sources such as waste hot steam and water,

RO
RO
RO
NF
NF

geothermal or solar energy [61,62]. In our previous studies [63],

we attempted to use vacuum membrane distillation (VMD) to
Acetone
Furfural
Furfural

Furfural
Phenols

concentrate sugar and remove inhibitors utilizing solar energy.

sugar

Under the optimal conditions of a velocity of 1.0 m/s and a

d
b

e
a

temperature of 65 1C, glucose rejection was 99.5% and the flux

 P. Wei et al. / Renewable and Sustainable Energy Reviews 30 (2014) 388–400 393

due to the increased molecular weight cut-off, resulting from

the greater intramembrane electrostatic repulsion at negatively
charged state in higher pH value [67,69–71]. The rejection of acid
will increase with the pH increasing. For instance, Weng et al.
[51,71] used Desal-5 DK NF membranes to separate acetic acid
from xylose. They found that there was a tremendous increase in
acetic acid retention with increasing pH values. For example, at
24.5 bar, acetic acid retention increased from 3% at pH 2.9 to
more than 90% at pH 9.1. This is consistent with the studies by Han
and Cheryan [68] who reported a 60% increase in acetic acid
retention when the pH was raised from 2.7 to 6.8 with an NTR729
NF membrane. Choi et al. [72] also reported a significant influence
of pH level on the retention of various organic acids during NF.
This occurs due to the Donnan effect coming from the electrical
interactions between charged ions and membrane, which limits
the transport of ions [73]. Therefore, it is a critical step to control
pH in order to obtain high performance for retaining negatively
charged ions.
Fig. 3. Schematic of membrane distillation to concentrate sugars and remove
Reverse osmosis also had attracted great attention for their
inhibitors.
unique ability to separate and purify process streams. Applications
of reverse osmosis for sugar concentration and inhibitors separa-
tion from lignocelluloses hydrolyzates were studied in recent
was 8.46 L m  2 h  1. Meanwhile, this process exhibited certain years. As the inhibitor with the highest content in hydrolyzates,
potential for removing inhibitors, the furfural can be removed a lot of works focus on removal acetic acid from hydrolyzates
completely. [68,74–76]. Acetic acid was firstly separated by Han et al. [68] from
The main disadvantages of MD are the danger of membrane an acetic acid–glucose model solution by using RO membranes,
wetting which can be reduced by using dilute solutions and the and acetate rejection of 40% and glucose rejection of 99% were
low removal efficiencies for some inhibitors. These disadvantages obtained, respectively. Meanwhile, RO has applied in removing
limit the industrialization of MD. other inhibitors. Sagehashi et al. [77] employed RO membranes to
Nanofiltration has drawn great interest in biorefineries due separate phenols and furfural from the aqueous solution derived
to its low energy consumption and unique separation properties. from the superheated steam pyrolysis of biomass, and the solution
Nanofiltration has a molecular weight cutoff (MWCO) between was concentrated effectively by reverse osmosis separation. Sev-
200 and 1000 g/mol, allowing the retention of soluble compounds eral researchers also reported the separation of carboxylic acids or
with molecular weights up to 150–250 g/mol and divalent ions furans from sugars in dilute-acid hydrolyzates or fast pyrolysis bio-
[64]. The main compounds in the lignocellulosic ethanol fermen- oils by using RO membranes [78,79]. Similarly to NF, size exclusion
tation broth include monosaccharides, aliphatic acids, furan deriva- and the Donnan effect are two main mechanisms for molecular
tives and phenolic compounds. The molecular weight of inhibitors separation [80]. Therefore, the rejection of solutes is influenced
is between 40 and 120 g/mol, while that of monosaccharides is by the operating conditions, such as feed pH, solute concentration,
more than 150 g/mol. Therefore, nanofiltration can remove inhibi- pressure and temperature. Different from NF, the separation
tors from the broth and retain the sugars to concentrate the sugar mechanism of RO includes solution–diffusion. The rejection of
solution. monosaccharide retention seems independent of the feed pH
Liu et al. [65] applied NF membranes with a molecular weight values and the operation temperature. For the uncharged mole-
cut-off of 100 g/mol for the purification of hydrolyzates from the cules, the dominating factors of retention were the solution–
hot-water extraction of woody biomass and found that acetic acid, diffusion mechanism that is the major separation mechanism in
methanol, furfural, hydrolxymethylfurfural and formic acid could nonporous, dense polyamide layer of reverse osmosis membranes
all be preferentially removed from the sugar stream. The rejection [74]. Therefore, although NF was concluded as the standard
efficiency of sugar was about 0.993. Han and Cheryan [64] membrane process for sugar concentration and inhibitors separa-
investigated the recycling of glucose and processing of acetate tion from lignocelluloses hydrolyzates in previous study, Zhou
from a fermentation broth by NF. They found that the separation et al. [76] compared the NF and RO membranes performances on
factor of acetate over glucose in calcium magnesium acetate broth separating acetic acid from model hydrolyzates solution in a
was approximately 40 using a NTR 729 NF membrane. Murthy comprehensive way. The results showed that RO membranes are
et al. [56] reported an increase in the concentration of xylose from much more effective than NF membranes for retaining monosac-
2% to 10% in the reaction liquor produced by dilute acid hydrolysis charides and decrease the concentration of acetic acid. It can be
of rice husk using NF. Operational costs were reduced by greater predicted that RO will play an important role in such application.
than 75%. Sjöman et al. [66] investigated the separation of xylose On the other hand, there are a lot of microorganisms and other
from glucose in hemicellulose hydrolyte using Desal-5 DK, Desal-5 value-added chemicals such as cellulase in an enzymatic hydro-
DL and NF270 membranes. They reported that the separation lyzate which should be recycled to improve the economic viability
factors of xylose over glucose ranged from 1.5 to 3.8, despite the of the enzymatic hydrolysis of biomass. This issue can be tackled
small molecular mass differences between xylose (150 g/mol) and by ultrafiltration technology. Table 3 summarizes the ultrafiltra-
glucose (180 g/mol). tion applied in recovery cellaluse and other value production. The
In theory, NF can remove all inhibitors and completely retain results demonstrated that the UF membranes showed almost 100%
sugars. However, the rejection of solutes is significantly influenced rejection of cellulases as no enzyme was detected in the permeate
by the operating conditions, such as feed concentration, feed pH, in several cases [81–84]. Meanwhile the UF membranes also
solute concentration, pressure and temperature [64,67,68]. Espe- exhibited good performance for enzyme activity recovery. UF was
cially pH has an important effect on separating sugar and acids. applied in recovering other value chemicals and obtained good
For sugars, the retention decrease for uncharged solutes by NF was performance. For instance, Chaiklahan [85] used PES membrane
394 P. Wei et al. / Renewable and Sustainable Energy Reviews 30 (2014) 388–400

Table 3
Summary of ultrafiltration applied in enzyme and other value production recovery.

Type of recovery material Membrane MWCO (kDa) Membrane Membrane flux Rejection (%) Recovery of enzyme Reference
material a configuration (L m  2 h  1) activity (%)

Cellulase “Onozuka” R-10 RC 10 Fat sheet – 100 42 [82]

NOVO Celluclast L PS 10 Fat sheet – – – [88,89]
NOVO A/S – 10 – – High 69/99.5 [79]
Cellulase plus β-glucosidase – 10 – – – 20.1/41 [90]
ABS cellulase PS/PES 10,30,100/30,50 Fat sheet  53  /49,64 98,95,60/98,94 – [84]
Cellulase enzyme PES 50 Fat sheet 30–1200 100 – [81]
Celluclast plus Novozym 188 PES 5 Fat sheet – – 39.3/17.9 [91]
Cellulase plus cellobiase PES 10 Fat sheet – – 60–66.6/76.4–88 [92]
Cellulas PES 5,10,30 – 26.5 89.4/73.9/79.7 –
Protein RC 5100 – 31/44 80 – [93]
Protein PES 5100 – 29/41 80 – [93]
Phycocyanin Modified PES 50,70,100 50–75,75–110 99,97.5,94.2 – [85]
Surfactin RC/PES 30 – 10–40/30–130 90/96 – [94]

a
RC¼ regenerated cellulose, PS¼ polysulfone, PES ¼ polyethersulfone.

with MWCO at 50 kDa, 69 kPa to retain phycocyanin. A retention membrane distillation [99–106], pervaporation [107–109] and the
rate of 99% was found to be optimal and food grade phycocyanin pervaporation–distillation hybrid process [110–113].
with the purity around 1.0 containing c-phycocyanin as the major
component was obtained.
In order to improve the recovery efficiency, Qi et al. [86] first 5.1. Membrane distillation for ethanol recovery
proposed combined technology. Studies have shown [87] that, in
the UF stage, the cellulase in the hydrolyzate suspension was Considering that partial pressure of ethanol is higher than that
recovered in the retentate and could be used for a subsequent of water, ethanol vapor can transfer preferentially through the
round of hydrolysis of the cellulosic substrate. Glucose was membrane pores. Meanwhile based on the mechanism of mem-
completely transmitted through the UF membrane and could be brane distillation, it can be used to separate ethanol and water. The
collected in the permeate, which could be further concentrated by selectivity is determined by ethanol volatility [114]. Franken et al.
NF to increase the glucose concentration. In the NF stage, when [115] first confirmed the possible use of direct contact tubular
the ultrafiltered hydrolyzate was treated by NF270 at 13.1 l/m2 h, membrane distillation module for separating ethanol from etha-
the glucose concentration increased to 110.2 g/l from 30.2 g/l, nol–water mixture. There are very few studies about separating
while the permeate could be collected for water reuse and simple ethanol–water solution using membrane distillation
recycling. [115,116]. Membrane distillation for ethanol recovery focuses on
coupled with fermentation and results showed that the ethanol
productivity improved due to the inhibitors was removed. Direct
5. Membrane technology for ethanol recovery membrane distillation and air gap membrane distillation coupled
with fermentation are common configuration for ethanol produc-
For typical corn-to-ethanol processes, the final fermentor tion. Udriot et al. [100] integrated direct membrane distillation
contains ethanol over 10 wt%. However, the microorganisms used with fermentation for the separation of ethanol from
for fermentation can tolerate a maximum concentration of the culture medium. The results showed 87% increase in ethanol
bioethanol of 10 wt%. Therefore, the ethanol must be removed productivity from 0.99 to 1.85 g L  1 h  1. Tomaszewska et al. [117]
for continuous production. On other hand, bioethanol from cellu- showed that the production rate was in the range of 2.5–
losic biomass likely provides lower product concentrations 4 g dm  3 h  1 in the case of fermentation combined with the
(o5 wt%) than bioethanol from corn. To save energy and costs, MD whereas in the classical batch fermentation from saccharose
the ethanol should be concentrated before the next refining this rate was lower and amounted to 0.8–2 g dm  3 h  1. Lewan-
process. The conventional method to remove and concentrate dowicz et al. [104] reported that ethanol production increased by
ethanol is distillation. Unfortunately, this is also the aspect of 15.5% due to facilitation of the continuous process, more complete
distillation which is not attractive, as reported by Leland [95] fermentation of sugars, lowering the osmotic pressure in the
fermentation broth, decreasing glycerol synthesis level and
(1) The energy requirement is significantly higher at low alcohol increasing yeast cells number and viability. In addition to improve
feed concentrations ( o4 wt%) compared to higher concentra- the ethanol productivity, membrane performance is another
tions [96]. research focus. Studies indicate that the temperature has an
(2) At 101.3 kPa, ethanol–water forms an azeotrope at 95.6 wt% important influence on membrane flux [101,104,105]. The mem-
ethanol. Higher concentrations of ethanol cannot be obtained brane flux increases as the feed temperature increases due to
through simple distillation. membrane swell. It was found that there was no clear influence of
(3) The process operates at high temperatures (unless under the feed temperature on the separation factor. Garc´ıa-Payo et al.
vacuum), much higher than typical optimum fermentor tem- [101] investigated the effect of operating parameter on membrane
peratures and usually at temperatures lethal to microorgan- performance for the air gap membrane distillation. Although
isms, which causes the deactivation of proteins and enzymes membrane distillation for ethanol production can overcome the
and prevents the reuse of salts and microorganisms [97]. disadvantages of conventional batch production. Current studies
have been confined to lab-scale, and larger scale performance
Thereby, opening the door to other technologies based on needs to be further investigated. Moreover the membrane selec-
membranes which can save energy and cost in ethanol production tivity is relative low (1–7), developing high performance mem-
is a good choice, such as reverse osmosis, ultrafiltration [98], brane material is another focus for membrane distillation.
Table 4
Summary of membranes used for ethanol recovery.

Membrane typea Flux Selectivity Advantages Disadvantages Reference

Organic (g m  2 h  1) α

Silicon Unmodified PDMS 1–1000 1–10.8 Relative cheap Easily prepared Poor film-forming ability; relatively low permselectivity; [128–
-containing poor mechanical properties; considerable swelling 130]
polymer Modified PDMS Cross- Vinyl-PDMS 850 8.0 Improved Mechanical properties The flux and selectivity cannot increase simultaneously [131]
link and film-forming ability
Acetoxysily- 251 10.8 [132]
PDMS
Graft PDMS-g- 1300 5.1 [133]
PVDF

P. Wei et al. / Renewable and Sustainable Energy Reviews 30 (2014) 388–400

PDMS-g-PPP 19 40 [134]
Block PDMS/PS/ 4500 6.8 [135]
PHS
IPN b 160 5.5 [136]
– 9 [137]
PDMS- 231–252 7–9 [138]
polyetherimide
hollow fiber
POMS 380 5 – – [139]
PTMSP 340–440 9–26 Selectivity is relatively higher Tendency to physical and/or chemical aging Performance [140–
depends on polymerization conditions 142]
Fluoro — Plasma-polymerized PFP 500 10 Selectivity is relatively higher High cost; low permeability [143]
containing Styrene-fluoroalkyl acrylate graft 5 45.9 High flux [130,144]
polymer copolymers PVDF hollow fiber
3500–8800 5–8 [98,145]
Other polymer poly(ether block amide) 118 2.5 Low selectivity [146]
PDMS-imide 560 10.6 [147]
Liquid membrane (LM) TOA-LM – 80 Low permeability Easy liquid loss [148]
Inorganic Zeolite 100 11.5 High ethanol selectivity; High About 10–50 times more expensive than the equivalent [149]
ZSM-5 223 47 chemical resistance, polymeric ones Defect-free commercial-scale inorganic [150]
thermal membranes are difficult to manufacture
Silicalite-1 220–2550 64–218 Stability [130]
Mixed matrix zeolite 51 16.5 Combine the advantages of inorganic Poor incompatibility Poor dispersion of particles [151]
membrane Silicalite-1 150 16.5–59 and organic membrane in polymer [152–
154]
Polyphosphazene nanotubes 119 10 [155]
Carbon black – 9 [156]
Fumed silica – 7.0 [157]

a
PDMS¼ polydimethylsiloxane, PVDF ¼ polyvinylidene fluoride, PPP¼ poly(1-phenyl-1-propyne), PS ¼ polystyrene, POMS ¼ polyoctylmethyl siloxane, PTMSP ¼poly(1-trimethylsilyl-1-propyne), PFP¼ perfluoropropane.
b
IPN¼ interpenetrating polymer networks.

395
396 P. Wei et al. / Renewable and Sustainable Energy Reviews 30 (2014) 388–400

5.2. Pervaporation for ethanol recovery membrane materials are essential for pervaporation applications
in the recovery of ethanol from broth.
As opposed to membrane distillation, pervaporation systems
are available for commercial applications in the removing of water
5.2.2. Hybrid pervaporation and fermentation process for improving
from concentrated alcohol solutions. Furthermore, a lot of work
ethanol yields
has been reported about membrane materials and process
Continuous fermentation is more attractive than the batch process
[11,118–125]. However, pervaporation for ethanol recovery is at
owing to its higher productivity, better process control and improved
pilot stage. Considering that knowledge of dehydration by perva-
yields. However, traditional continuous fermentation has the inherent
poration is relatively mature, the potential for using pervaporation
limitations of cell wash-out and product inhibition, which seriously
for ethanol recovery from dilute fermentation broth will be
affect the productivity of the process. One way to improve the
reviewed in this section.
productivity of such product-inhibited fermentations is continuous
Pervaporation is a method for the separation of mixtures of
in situ removal of ethanol. Compared with traditional techniques such
liquids by partial vaporization through a non-porous membrane.
as gas stripping and adsorption, pervaporation is simple, highly
The separation mechanism is a solution–diffusion model. For
selective and non-toxic to fermentative microorganisms. It is also
ethanol recovery, the control process is the solution since the
potentially cheaper than distillation. Therefore, hybrid membrane
kinetic diameter of ethanol (0.57 nm) is larger than that of water
pervaporation with fermentation is regarded as a promising technol-
(0.32 nm). Therefore, choosing the proper membrane material for
ogy [167–170].
the separation system is very important.
For the technical application of the hybrid pervaporation-
bioreactor process, two coupling modes have been designed. In
the first, pervaporation is performed externally, while in the
5.2.1. Membrane material for ethanol recovery from broth by
second, the pervaporation unit is directly integrated into the
pervaporation
reactor. A schematic of the two coupling mode is shown in
According to the pervaporation mechanism, hydrophobic
Fig. 4. Lipnizki et al. [171] discussed the advantages and disadvan-
membranes can be used that will leave water in the retentate
tages of these arrangements, and suggested the use of an external
whilst allowing ethanol to pass through. There are two main
pervaporation unit due to its high efficiency and easy mainte-
classes into which most pervaporation membranes can be placed:
nance. Table 5 gives an overview of studies on the hybrid
polymeric membranes and inorganic membranes. Polymeric
fermentation and pervaporation process. Obviously, ethanol pro-
membranes are widely used today in ethanol recovery. Inorganic
ductivity has been improved by utilizing a hybrid fermentation–
membranes, fabricated from zeolites and silicalite-1, have increas-
pervaporation process compared with batch fermentation.
ingly become a focus of research. A third class of membranes is
Meanwhile, several studies have focused on the economic assess-
commonly termed mixed matrix membranes. The membrane
ment of the hybrid fermentation–pervaporation process for bioetha-
materials that can be used for ethanol recovery have been
nol production in terms of the investment and production cost. Most
reported by Peng and Zhan [126,127]. The performance compar-
studies have come to a positive conclusion regarding the economic
ison of different membrane materials is summarized in Table 4
potential of hybrid pervaporation-bioreactor processes for high etha-
according to the factors (flux and selectivity) that characterize
nol productivity and low energy consumption. However, these reports
pervaporation performance. A comprehensive analysis of the
have demonstrated that the total ethanol production cost of the
pervaporation performance of polydimethylsiloxane (PDMS)
hybrid fermentation–pervaporation process was slightly higher than
shows that it is superior to the other membrane materials. PDMS
conventional continuous fermentation due to the relatively high cost
will, at least in the near term, continue to be the dominant organic
of the pervaporation unit [158,172–174].
membrane material used for the recovery of ethanol from water.
Luccio et al. [175] investigated the effect of membrane costs
According to the analysis of O'Brien et al. [158], a couple of
on the process economics of ethanol and fructose production by
systems would be cost-competitive if the performance of the
selective hybrid fermentation and pervaporation. For a complete
pervaporation membranes could be modestly improved so as to
plant installation, the highest allowable membrane cost to main-
exhibit a flux of 150 g m  2 h  1 and a separation factor of 10.3
tain economic feasibility was around $500/m2, while the adapta-
for ethanol to water. As can be seen in Table 4, most of the
tion of an existing plant allowed for a cost of up to $800/m2,
membranes can meet this requirement. However, from the analy-
considering a minimum return rate of return on the investment of
sis of energy consumption, a separation factor of a membrane
17%. Improving the performance of the membrane is a crucial step
greater than at least 20 is needed [159]. This is the main reason for
to reduce production costs. Wasewar et al. [176] investigated the
why polymeric membranes remain unindustrialized. Although the
separation factor of organic membranes is over 20 and these offer
a number of advantages over polymeric membranes, such as
solvent resistance and the ability to operate at higher tempera-
tures, these are more difficult to produce on a large scale
industrially and are often expensive. In addition, another reason
for continued disuse is performance degradation within the actual
separation system [160]. This performance degradation is mainly
caused by complex components in the fermentation broth. The PV module
influence of fermentation components on membrane performance
during pervaporation has been investigated by several authors
[161–166]. Despite this, sometimes contradictory results have
PV
been found between different studies and concrete explanations Permeate
for the observed behavior re-missing. However, it is clear that
membrane performance can be significantly affected by the pre- 2
1 Permeate
sence of fermentation by-products, even in small amounts, which
limits the commercial applicability of a pervaporation system. Fig. 4. Configuration of the hybrid fermentation and pervaporation process with
Therefore, exploiting and designing higher performance, reliable (1) an external pervaporation unit and (2) an internal pervaporation unit.
 P. Wei et al. / Renewable and Sustainable Energy Reviews 30 (2014) 388–400 397

Table 5
An overview of studies about the fermentation and pervaporation hybrid process from the literature.

Feed Micro-organisms Couple Membranes Flux Separation Ethanol productivity Ethanol productivity coupled Reference
mode membrane modules (kg m  2 h  1) factor without PV (g L  1 h  1) with PV (g L  1 h  1)
a

Glucose Baker's yeast External PDMS/PP or PTFE 3.96 5.8–9.0 1.6 6.3 ( þ293.75%) [179]
tubular
Dextrose Saccharomyces External PDMS/PS, tubular 0.56 5 10 30 ( þ200%) [180]
cerevisiae
Glucose Baker's yeast External PDMS/PS hollow 0.39–0.81 2.5–5.7 4.5 8.8 (95.6%) [177]
fiber
Lactose Saccharomyces External PDMS coated on PS 0.05–0.18 4–12 12 15 ( þ25%) [181]
cerevisiae tubular
Glucose Saccharomyces External LTV SR/PS flat sheet 1.2 5.5 1.74/1.76 2.75/3.25 (84.6%) [182]
cerevisiae
Glucose Saccharomyces External PDMS/PS flat sheet 0.25–0.63 1.8–6.5 2.92 4.9–7.8 (67.8–167%) [183]
cerevisiae ATCC 4126
Glucose Saccharomyces External Composite PDMS flat 0.135/0.091 7.7/8.2 0.54/0.52 Z 0.23/ Z 0.38 [184]
cerevisiae sheet
Lactose Saccharomyces External PDMS–PAN 2.6–3.5 48 – 0.9 [185]
cerevisiae B4
Glucose yeast External PDMS/PA flat sheet 0.3–0.69 5.0–7.2 3.21 9.6 (199%) [186]
Glucose yeast External PDMS/PA flat sheet 0.774 4.85 0.7 1.39 (98.57%) [187]

a
PDMS ¼polydimethylsiloxane, PP ¼poly(1-phenyl-1-propyne), PTFE ¼ polytetrafluoroethylene, LTV SR ¼LTV silicone rubber, PS ¼ polysulphone, PAN¼ polyacrylonitrile,
PA ¼polyamide.

effect of membrane flux and selectivity on the ethanol production solved. A hybrid fermentation and pervaporation process would be
cost. A 22% reduction in the direct production cost of ethanol was advantageous in ethanol production with the development of an
found when the flux was increased by 200%. A 10% decrease in the adequately performing membrane. We thought that further stu-
direct production cost of ethanol was observed when the separa- dies should focus on optimizing the hybrid process by integration
tion factor increased by 20% and costs decreased by 35% for a 100% with UF to enhance ethanol productivity and reduce the cost, and
increase in the separation factor. Therefore, developing higher a particular challenge to research in this field is the transition from
performance and more reliable membranes will significantly pilot studies to industrial operations.
reduce the ethanol production cost.
During the hybrid process, cells and other by-products will lead
to membrane fouling. To reduce the effect of fouling, microfiltra-
tion can be used to retain the remains of cells in the fermentation Acknowledgments
broth. In addition, Groot et al. [177,178] compared the different
process alternatives and concluded that continuous ethanol pro- This work is supported by the National Basic Research Program
duction with recycling of the microorganism using microfiltration of China (2011CB710804), National Hi-Tech Research and Devel-
leads to the lowest production costs. The costs were 15% lower in opment Program of China (2012AA023203, 2011AA02A208,
comparison to the batch process. 2009AA02Z208), Postdoctoral Research plan of Zhejiang Province
In summary, the hybrid fermentation and pervaporation process (BSH1302043), and the State Key Laboratory of Motor Vehicle
will have good potential in ethanol production with the develop- Biofuel Technology (2013008).
ment of a high performance membrane. Meanwhile, further studies
should focus on optimizing hybrid process integration with UF to
enhance the ethanol productivity and reduce costs. References

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