Renewable Energy 36 (2011) 437e443

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Renewable Energy
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Review

Biodiesel separation and purification: A review

I.M. Atadashi, M.K. Aroua*, A. Abdul Aziz
Chemical Engineering Department, Faculty of Engineering, University Malaya, 50603 Kuala Lumpur, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: Biodiesel as a biodegradable, sustainable and clean energy has worldwide attracted renewed and
Received 4 January 2010 growing interest in topical years, chiefly due to development in biodiesel fuel and ecological pressures
Accepted 28 July 2010 which include climatic changes. In the production of biodiesel from biomass, separation and purification
Available online 23 August 2010
of biodiesel is a critical technology. Conventional technologies used for biodiesel separation such as
gravitational settling, decantation, filtration and biodiesel purification such as water washing, acid
Keywords:
washing, and washing with ether and absorbents have proven to be inefficient, time and energy
Biodiesel
consumptive, and less cost effective. The involvement of membrane reactor and separative membrane
Transesterification
Separation
shows great promise for the separation and purification of biodiesel. Membrane technology needs to be
Purification explored and exploited to overcome the difficulties usually encountered in the separation and purifi-
Membrane technology cation of biodiesel. In this paper both conventional and most recent membrane technologies used in
refining biodiesel have been critically reviewed. The effects of catalysts, free fatty acids, water content
and oil to methanol ratios on the purity and quality of biodiesel are also examined.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction animal fats and microalgal oil. It is biodegradable, sustainable, and

Increased demand for energy, price hike of crude oil, global
warming due to emission of green house gases, environmental
pollution, and fast diminishing supply of fossil fuels are the major
key factors leading to search for alternative sources of energy. Some
of the most notable alternative sources of energy capable of
replacing fuels include amongst others: water, solar and wind
energy, and biofuels. Currently, 86% of the energy being consumed
worldwide and nearly 100% of energy desired in the transportation
sector is provided by non-renewable fossil fuels [1]. Biofuels
production is being supported by the European Union (EU) with the
objective of increasing fuel supply sources, boosting decarbon-
isation of fuels for transportation, decreasing hazardous gaseous
emission which causes global warming effects, providing more
earning opportunities in rural communities and developing long
term plan for finite fossil fuels replacement. Presently several
countries such as United States, Germany, Australia, Italy, and
Austria are already using biofuels such as biodiesel and bioethanol.
Table 1 presents volume of biodiesel production in different
countries. This trend is expected to continue worldwide with more
countries to use biofuels as source of energy [2].
Biodiesel (fatty acid alkyl esters), a substitute to diesel fuel, is
produced from renewable natural sources such as vegetable oils,
* Corresponding author. Tel.: þ60 3 79674615; fax: þ60 3 79675319.
E-mail address: mk_aroua@um.edu.my (M.K. Aroua).
also environmentally beneficial, thereby providing lower gas
emission profile. Biodiesel is considered to be carbon neutral, as
biodiesel yielding plants such as jatropha curcas, rape plant and
palm trees absorb carbon-dioxide to a greater extent than that
contributed to the atmosphere when used as fuel in diesel engines.
Also, biodiesel has similar physicochemical properties to that of
diesel produced from crude oil and can be used directly to run
existing diesel engines without major modifications or as a mixture
with petroleum diesel and produces less harmful gas emission such
as sulfur oxide. However, the direct use of vegetable oils as fuel in
compression ignition engines is problematic due to their high
viscosity (about 11e17 times greater than diesel fuel) and low
volatility. These oil types do not burn completely and form carbon
deposits in the fuel injectors of diesel engines. The viscosity of
vegetable oils can be better improved with transesterification
reaction, a process which seems to insure very good outcomes in
terms of lowering viscosity and enhancing other physicochemical
properties [3]. Transesterification is a chemical reaction involving
triglycerides and an alcohol of lower molecular weights using
homogeneous or heterogeneous substances as catalyst to yield
biodiesel and glycerol, as presented in Fig. 1.
Even though transesterification reaction catalyzed by alkali
homogeneous catalyst such as sodium and potassium hydroxides
yields higher conversion of vegetable oil to methyl esters in short
time, the reaction has several drawbacks: it is energy intensive;
recovery of glycerol is difficult; the catalyst has to be removed from

0960-1481/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.renene.2010.07.019
438 I.M. Atadashi et al. / Renewable Energy 36 (2011) 437e443

Table 1 mixture is influenced by numerous factors such as intense mixing,

Volume of biodiesel production in different countries [2]. formation of emulsion, solubility of biodiesel in glycerol, and
Country Volume potential (Ml) Production cost (US$ per liter) glycerol in biodiesel [7]. Demirbas [6] reported that supercritical
Malaysia 14,540 0.53 methanol process is non-catalytic, involves a much simpler puri-
Indonesia 7595 0.49 fication of transesterified products, has a lower reaction time, is
Argentina 5255 0.62 more environmentally friendly, and requires lower energy use.
USA 3212 0.7
Though, the reaction requires temperatures of 525e675 K and
Brazil 2567 0.62
Netherlands 2496 0.75 pressures of 35e60 MPa. Another advantage with supercritical
Germany 2024 0.79 methanol is that the conversion gets 95% complete in 10 min [8].
Philippines 1234 0.53 Siti et al. [9] revealed the problems encountered in the use of
Belgium 1213 0.78 chemical catalysts to be high energy and methanol consumptions,
Spain 1073 1.71
and large amount of alkaline wastewater. The use of enzymes such
as lipase has recently received a wider attention and considered to
the product; alkaline wastewater requires treatment and free fatty be an effective way to overcome such problems. Particularly, the
acids (FFA) and water interfere with the reaction [4]. The presence separation of glycerol without complicated treatment. Even though
of water lowers the activity of catalyst, while FFA react with the cost is the major bottle neck associated with enzymatic catalysis.
catalyst to produce saponified product [2]. The formation of soap Sharma et al. [8] stated that methanol has polar hydroxyl group
reduces the biodiesel yield, and causes significant difficulty in which can act as an emulsifier causing emulsification and rendering
product separation and purification. Thus, biodiesel and by- severe difficulties in the separation of the methyl ester layer from
product, glycerol have to be refined by washing with hot deionized water.
water two to three times, leading to high waste of time, energy and
water [3,4]. The major limiting factor to biomass use is the 2.1. Effects of catalyst
technology development for the separation, purification, and
transformation of it into biochemicals and biofuels. Currently, The high consumption of energy and costly separation of the
“down-stream processing” alone accounts for 60e80% of the homogeneous catalyst from the reaction mixture have drawn to the
process cost [5]. Ineffective biodiesel separation and purification need of development of heterogeneous catalysts for trans-
causes severe diesel engines problems such as plugging of filters, esterification reaction, which is easily separated from the reaction
coking on injectors, more carbon deposits, excessive engine wear, mixture and recyclable. Several authors used heterogeneous cata-
oil ring sticking, engine knocking, and thickening and gelling of lysts with the aim of eliminating neutralization and washing steps
lubricating oil [6]. Several different separation and purification of needed for processes using homogeneous catalysts but were faced
biodiesel techniques have been studied. This paper reviews the with major problems such as higher temperature of trans-
technologies employed with emphasis on the most suitable prac- esterification reaction, longer reaction time and lower yield of
tice for effective separation. Membrane separation seems to be the esters [1]. Helwani et al. [10] have discussed the advantages and
most suitable for this purpose and is the focus of this study. disadvantages of using homogeneous catalysts (alkali and acid) and
heterogeneous catalysts (solid and enzymes) in the industrial
2. Conventional biodiesel separation techniques production of biodiesel. Homogeneous catalysts are significant for
industrial biodiesel production because of their easy conversion at
Several researchers had studied extensively numerous conven- moderate temperatures (40e65  C), but are faced with refining
tional techniques for the separation of biodiesel. A brief review for problems. However, heterogeneous catalyst was introduced in the
the biodiesel separation techniques is presented here. Most of the biodiesel production to avoid several neutralization and washing
researchers reported that high-quality biodiesel that is economi- steps needed for processes using homogeneous catalysts. The
cally viable can be achieved when suitable biodiesel separation authors revealed purity of methyl esters to exceed 99%, with yield
process is employed. After transesterification, separation of bio- close to 100%, glycerol as by-product with purity of more than 98%
diesel and by-product, glycerol is usually first carried out. This compared to about 80% from homogeneous process. The overall
process of biodiesel separation is based on the facts that the bio- production economy is improved through the utilization of the by-
diesel and glycerol produced are typically sparingly mutually product, glycerol [1]. Several researches are also currently going on
soluble, and that there is palpable difference in density between with the enzymatic methanolysis using lipases for biodiesel
biodiesel (880 kg/m3) and glycerol (1050 kg/m3, or more) phases production with view of overcoming issues involved in recovery
respectively. More so, this difference in density is sufficiently and treatment of the by-product that requires complex processing
enough for the application of simple techniques such as gravita- equipment. The major problem of enzyme catalyzed process is the
tional settling or centrifugation for the separation of biodiesel and high cost of the lipases as catalyst. In order to reduce the cost,
glycerol phases. In addition, the separation rate of biodiesel enzyme immobilization was introduced for ease of recovery and
reused [2]. They stated that although transesterification reaction
O O catalyzed by lipase provides an attractive alternative, the industrial
|| ||
CH2 - O - C - R1 CH3 - O - C - R1 use of this technology has been retarded as a result of feasibility
| | aspects and some technical challenges. Biodiesel production
| O | O CH2 - OH assessment has shown that, homogeneous base-catalyzed reaction
| || | || | is still much favorable in spite of the difficulties encountered in the
CH - O - C - R2 + 3 CH3OH ↔ CH3 - O - C - R2 + CH - OH
| (Catalyst) | | product separation and purification. The major reason has been
| O | O CH2 - OH that the kinetic rates of homogeneous reaction are much faster than
| || | || heterogeneously catalyzed transesterification reaction and is
CH2 - O - C - R3 CH3 - O - C - R3 economically viable.
Nestor et al. [11] stated that higher amount of FFA has resulted in
Triglyceride Methanol Esters glycerin
excessive soap formation as FFA react with the catalyst, which is
Fig. 1. Transeterification of vegetable oil with methanol. normally sodium and potassium hydroxides via saponification
 I.M. Atadashi et al. / Renewable Energy 36 (2011) 437e443 439

reaction. Soap renders biodiesel purification and catalyst removal O

more challenging. However, homogeneous lewis acids such as
AlCl3, ZnCl3, and excess methanol were tested at higher tempera-
tures and demonstrated that AlCl3 irrespective of the feedstock
type can give higher conversion of esters with better product that
can be easily refined. Boey et al. [12] concluded that use of classical
homogeneous catalysts results in higher yield loss through
saponification as well as from the complicated separation process
due to soap formation. Calcium oxide (CaO) catalyst was employed,
though the reaction time was longer but the elimination of few
purification processes and less wastewater generation compen-
sates the delay, in addition to higher yield and the possibility of
catalyst reusable. Masato et al. [13] noted massive wastewater
discharged due washing of alkali-hydroxide from biodiesel. The
authors tested different heterogeneous catalysts such as H-Y
zeolites, sulfated titanium oxides and cation-exchange resin in the
esterification of FFA and made use of calcium oxide and higher
methanol ratios in the transesterification and achieved biodiesel
yield of 93%. Yomi et al. [14] reported the use of chemical processes
to give high conversion of triglycerides to their corresponding
methyl ester in short reaction time but accompanied with several
drawbacks such as being energy intensive, difficulty in recovering
glycerol, the need for removal of alkaline catalyst, treatment of
wastewater, and the interference of reaction by FFA and water. They
observed that, enzymatic methods can overcome these problems
but have not been industrialized because of the high cost of
enzymes. A lipase continuous three-step flow reaction process was
developed with the aim of reducing cost of enzymes. Thiam and
Subhash [1] stated the removal of homogeneous catalyst to be
sometime difficult and bring extra cost to the final product.
Marchetti and Errazu [15] reported that feedstock with large
amount of FFA is catalyzed using heterogeneous acid catalyst, solid
resins, enzymes or in supercritical process. Transesterification
reaction with basic homogeneous catalysts will promote soap
formation and render product separation difficult. In order to
improve the separation of the phases, a centrifuge was used for
20 min. Hideki et al. [16] found that biodiesel is best produced by
using homogeneous alkaline catalyst but the process is followed
with several drawbacks including difficulty in glycerol recovery and
catalyst removal, in particular several stages such as evaporation of
residual methanol, removal of soap and neutralization etc. The
authors developed enzymatic process using extracellular and
intracellular lipases to overcome the drawbacks and acknowledged
the production cost of lipase to be very high. The significance of
different catalysts in the purification of biodiesel is shown in Table 2.
||
CH2 - O - C - R1 CH3 - OH
| |
| O | O O
| || | || ||
CH - O - C - R2 + H2O → CH3 - O - C - R2 + HO – C - R1
| |
| O | O
| || | ||
CH2 - O - C - R3 CH3 - O - C - R3
Triglyceride Water Diglyceride Fatty acid
Fig. 2. Hydrolysis of a triglyceride to form free fatty acids.
its cost. Van Gerpen et al. [7] stated that due to low solubility of
glycerol in alkyl esters, separation usually takes place rapidly and is
accomplished with settling tank, and that addition of water to the
reaction mixture after transesterification reaction can enhance the
separation of alkyl esters and the by-product, glycerol. In his work,
he revealed that unreacted methanol tends to act as a stabilizer and
can lengthen the separation and that it is advantageous to remove
the unreacted methanol before phase separation.
2.3. Effects of water and free fatty acids
Water and FFA in oils and fats can pose a great problem during
transesterification. When water is present, especially at elevated
temperatures, it can hydrolyze the triglycerides to diglycerides and
form an FFA (Fig. 2). However, the presence of water at average
temperatures leads to formation of excessive soap formation. When
an alkali catalyst such as sodium or potassium hydroxides is
present, the FFA will react to form saponified product (Fig. 3). The
saponified product formations of saturated fatty acids tend to be
strengthened at ambient temperatures and the reaction mixture
may gel and form a semi-solid substance that is very difficult to
recover. The negative effects of excessive soap formation include
amongst others; consumption of the catalyst, reduction of catalyst
effectiveness, difficulty in glycerol separation, and prevention of
crude biodiesel purification [7]. Demirbas [6] reported that even
a little amount of water (0.1%) in the transesterification reaction
will reduce the methyl ester conversion from vegetable oil. At the
same time the presence of water has a significant effect in the yield
of methyl esters when methanol at ambient temperature was
replaced by supercritical methanol [8]. In conventional catalyzed
methods, the presence of water has bad effects on the yields of
methyl esters.

3. Conventional biodiesel purification techniques

2.2. Effects of oil to alcohol ratio
Oils to alcohols ratios play a vital role in determining the purity
of biodiesel. The lower the ratios the lesser the complexity of the
separation and purification processes vice versa. Sharma et al. [8]
reported that increased in molar ratio of methanol to oil ratios
beyond 6:1 neither increase the product yield nor the ester content,
but rather makes the ester recovery process complicated and raises
3.1. Biodiesel purification
The main objective of biodiesel washing is to remove free
glycerol, soap, excess alcohol, and residual catalyst. The drying of
alkyl ester is needed to achieve the stringent limits of biodiesel
specification on the amount of water content in the purified bio-
diesel product. However, there are other treatments used to reduce

Table 2
Comparison of the different technologies to produce biodiesel [10].

Variable Base catalyst Acid catalyst Lipase catalyst Supercritical alcohol Heterogeneous catalyst
Reaction temperature ( C) 60e70 55e80 30e40 239e385 180e220
Free fatty acid in raw materials Saponified products Esters Methyl esters Esters Not sensitive
Water in raw materials Interfere with reaction Interfere with reaction No influence e Not sensitive
Yields of methyl esters Normal Normal Higher Good Normal
Recovery of glycerol Difficult Difficult Easy e Easy
Purification of methyl esters Repeated washing Repeated washing None e Easy
Production cost of catalyst Cheap Cheap Relatively expensive Medium Potentially cheaper
440 I.M. Atadashi et al. / Renewable Energy 36 (2011) 437e443
O evaporate residual water. Ferella et al. [3] stated that formation of soap
|| + KOH
HO - C - (CH2)7 CH=CH(CH2)7CH3
Oleic Acid Potassium Hydroxide
O separation of biodiesel and glycerol underwent simple centrifugation
||
→ K+ -O - C - (CH2)7 CH=CH(CH2)7CH3 + H2O
(Soap) Water
Fig. 3. Formation of soap.
biodiesel colour, remove glycerides, sulfur and phosphorus, from
the fuel. Water has the ability to provide a means for addition of
acid to neutralize the unreacted alkaline homogeneous catalyst.
This process simplifies immediate removal of the salt products. The
unreacted methanol after transesterification reaction should be
removed before the washing stage to minimize the presence of
alcohol in the wastewater effluent. However, some processes
remove the excess methanol after washing with water Von Gerpen
et al. [7]. The authors prevented precipitation of saturated fatty acid
esters using deionized water (120e140  F). Formation of emulsions
is retarded when gentle water washing is applied fostering rapid
and complete phase separation. Calcium and magnesium contam-
ination is eliminated with the help of softened water (slightly
acidic) which has the capability of neutralizing the remaining
unreacted alkali catalysts. Similarly, iron and copper ions removal
get rid of a source of catalysts that reduces the fuel stability [7].
Sharma et al. [8] reported that simple biodiesel purification process
and recovery of high-quality glycerin are the key factors to be
considered to reduce the price of biodiesel fuel and make it
competitive to the conventional diesel fuel.
Transesterification reaction is a reaction that is widely considered
and mostly adopted to produce commercial biodiesel [11]. The
transesterified products undergo different purification techniques in
order to purify biodiesel from glycerol and other by-products.
However, the neutralization of alkali catalyst and the purification
stage performed using a larger amount of water create additional
wastewater which are the major roadblocks of such process. Down-
stream from the reactor, the recovery of the residual alcohol, the
purification of fatty acid alkyl esters from the catalyst and the sepa-
ration of glycerol as a major secondary product are generally desir-
able. In the case when vegetable oils or waste vegetable oil contains
an appreciable amount of FFA, the catalyst during transesterification
reaction is consumed due to neutralization of acids causing decrease
of the reaction rate, and rendering separation and purification diffi-
cult. Harding et al. [17] conducted experimental studies to compare
the simplicity of purification and energy saving of biological process
and that of inorganic chemical process. The authors stated that the
conversion rate are generally slower in the enzymatic catalyze
process but the process has eliminated the restriction imposed on
water content or level of free fatty acid, and avoided saponification
reaction and alcohol recovery. This process made separation of esters
from glycerol, recovery of glycerol and purification of esters much
more easier and economical compared to the conventional chemical
process whose separation and purification processes proved too
complicated and energy consuming. The major conventional bio-
diesel purification techniques are discussed below.
3.1.1. Washing with distilled water
Water washing is generally carried out to remove soap, catalyst,
methanol and other contaminants from biodiesel, using deionized
water. Chongkhong et al. [18] conducted an experimental neutrali-
zation technique instead of distillation to purify the transesterified
product. The process was carried out using 3 M of sodium hydroxide
in water. Then 2%wt of sodium chloride was dissolved in the solution
to remove the soap formation. Water at 60e80  C was used to wash
the ester phase which was allowed to settle and then heated to
due to neutralization of FFA in the vegetable oil or triglyceride by
potassium hydroxide decreases biodiesel yield and quality. In addition
and washing product leads to high utilization of time and water. Jaya
et al. [19] demonstrated simple filtration of cation-exchange resins
catalyst in the production of biodiesel. The ester layer separated was
washed with hot deionized water and dried over anhydrous sodium
sulfate (Na2SO4). Haq et al. [20] noted the application of tetrahydro-
furan (THF) as a co-solvent to enhance the homogeneity of oil and
methanol and to promote more transesterification reactions increases
biodiesel cost of purification. Removal of the co-solvent requires extra
processing equipment. The washing processes conducted consist of
acid neutralization followed by water washing. This was done to
remove sodium hydroxide and other impurities such as excess
methanol, triglyceride, diglyceride and monoglyceride. However, the
glycerol separation and purification at the end of transesterification
reaction were complicated and costly.
Suprihastuti and Aswati [21] investigated biodiesel washing
with water extraction. The process showed that washing biodiesel
by water extraction in a single stage stirred tank reduced the
glycerol content from 0.9331% to at least 0.09% for 20 min washing
time by adding 50% water of biodiesel volume. When the water was
300% of biodiesel volume the glycerol content was less than 0.05%
and the pH was 7.3. To achieve the standard requirement of glycerol
content in biodiesel to be less than 0.02%, the washing was carried
out in multistage process. It was also noted that the rate of mass
transfer of glycerol from the biodiesel into water was affected by
the temperature of extraction and the volume ratio of solvent to
biodiesel. Higher mass transfer rate was achieved on higher bio-
diesel to water volume ratio as well as higher temperature. The
more water added the larger the mass transfer area, so the higher
volumetric mass transfer coefficient. The higher washing temper-
ature gave higher diffusivity of glycerol from biodiesel to water
phase, then the mass transfer coefficient was higher. Praveen et al.
[22] stated that the reaction mixture was separated into an upper
layer of methyl esters and lower layer of glycerol. The methyl esters
are neutralized and vacuum distilled to remove excess methanol.
They introduced an alternative method of glycerol recovery
through conversion of crude glycerol to its mono and diesters using
triglycerides (glycerolysis). Neutralization and water washing are
necessary for total removal of catalyst from the product [22].
3.1.2. Washing with acids
Acids are added to transesterified product to neutralize the
catalyst and decompose the soap formed. This process is followed
with water washing to purify biodiesel from contaminants such as
catalyst, soap, methanol and free glycerol. Sharma and Singh [23]
washed biodiesel with 10% H3PO4 by bubble wash method after
separation from glycerol, and then purified it further by passing air
by aquarium stone for at least 24 h. It was furthermore, treated by
washing with hot distilled water to remove the dissolved impuri-
ties such as catalysts, alcohol, etc. Silica gel was used for the
removal of catalyst from the biodiesel product. Meher et al. [24]
reported the difficulty in the separation and purification of glyc-
erol and esters when higher alcohol to oil ratios is used. The use of
triglyceride of relatively low FFA was emphasized to avoid soap
formation. The products formed were separated using sedimenta-
tion, and the ester phase was distilled at 80  C to remove excess
methanol, followed by numerous washes with distilled water and
treatment with Na2SO4 and filtration.
3.1.3. Washing with solid adsorbent, ether, and water
Absorbents are another means of treating transesterified
product. Absorbent such as Magnesol has the potential of selectively
 I.M. Atadashi et al. / Renewable Energy 36 (2011) 437e443
absorbing hydrophilic materials such as glycerol and mono- and
diglycerides. This treatment, followed by an appropriate filter, has
been shown to be effective in lowering glycerides and total glycerol
levels. Some vegetable oils and many yellow greases and brown
greases leave an objectionable colour in the biodiesel. Activated
carbon bed is an effective way to remove excessive biodiesel colour
[7]. Dube et al. [25] mentioned the use of a solid absorbent, such as
activated clay, activated carbon, activated fiber, etc. to purify the
resultant biodiesel, and also use glycerine as a solvent to wash
impurities. Hot deionized water washing at 50  C was considered to
be the best way to separate and purify biodiesel but with challenging
wastewater treatment problem in the wastewater stream. Meher
et al. [26] adopted overnight separation of biodiesel from glycerol
layer. The catalyst and unused methanol were in the lower
glycerol phase, whereas little amounts of catalysts, methanol and
glycerol were in the upper biodiesel phase. The upper phase was
collected for further purification, and to obtain pure biodiesel,
method of washing with hot distilled water and petroleum ether
(1:1) was performed in the refining process. The biodiesel after
separation was washed using same amount of hot distilled water
(60  C) to remove the unreacted catalysts and glycerol. The moisture
from washed biodiesel was removed by boiling at 120  C for 1 h.
Sharma and Singh [23] stated that the distillation of esters can be
assumed to be completed when the temperature reached 240  8  C
(40  5 mmHg). The biodiesel separated after acidic trans-
esterification reaction was washed with petroleum ether and then
with hot distilled water (50  C) until the washing reached a neutral
pH. The authors gave the relationship for the calculation of biodiesel
yield as follows.
Weight of product
Product yield ¼
Weight of raw oil
4. Biodiesel membrane separation and purification
The membrane equipments mostly produced for the separation
and purification of crude biodiesel seem to exhibit several advan-
tages over the conventional ones such as eradication/minimization
of higher capital cost and other related costs of production, and
provide high specific area of mass transfer. Membrane equipments
for biodiesel refining are usually made from inorganic microporous
ceramic membranes and generally have a lot of applications in
biotechnology. These membranes hold some hope in their use for
biofuels. Some of the most effective devices used for the separation
and purification of crude biodiesel include: Membrane reactor and
separative ceramic membrane.
4.1. Biodiesel separation and purification using membrane reactors
Operations involving membrane technologies in the last years
have shown their potentialities in the rationalization of production
systems [27]. Membrane performance is usually governed by:
selectivity or separation factor and permeability. In the absence of
defects, the selectivity is a function of the material properties at
given operating conditions. The productivity is a function of the
material properties as well as the thickness of the membrane film,
and the lower the thickness, the higher the productivity [28].
Qfiltrate
Permeability; Lp ¼
ADP
Flux of impurity
Selectivity; a ¼
Flux of product
441
Membrane reactors intrinsic characteristics of efficiency, oper-
ational simplicity and flexibility, relatively high selectivity and
permeability, low energy requirements, good stability under a wide
spectrum of operating conditions, environment compatibility, easy
control and scale-up have been confirmed in a numerous variety of
applications and operations, as molecular separations, fraction-
ations, concentrations, purifications, clarifications, emulsifications,
crystallisations, etc [27].
Dube et al. [25] developed a membrane reactor that removed
unreacted vegetable oil from the fatty acid methyl esters (FAMEs)
product after transesterification, yielding high-purity biodiesel
and shifting the reaction equilibrium to the product side. The
authors stated that the novel membrane process was particularly
useful in removing unreacted canola oil from the FAME product
yielding a high-purity biodiesel. Additionally, a novel refining
method using membrane extraction was developed by He et al.
[29]. The authors compare membrane extraction and the tradi-
tional extraction methods of biodiesel refining. The membrane
separation proved to be more effective and efficient over the
conventional dispersed phase separation, in the following ways:
no emulsification formed, no density difference noticed between
fluids for hollow fiber membranes, and the interfacial area was
high. The use of hollow fiber membrane leads to avoidance of
emulsification of water and 99% purity of methyl esters was
recorded. Peigang et al. [30] investigated high-purity FAME
production using vegetable oils and fats with lower and higher FFA
contents such as canola, soybean, palm, brown grease and yellow
grease by means of a membrane reactor. The membrane used in the
reactor system had a 300 kDa MWCO. This property was instru-
mental in providing excellent means of retaining emulsion. High-
quality FAME was achieved which was ascertained by Gas Chro-
matography (GC) analysis based on the ASTM D6584 standard and
the glycerin content of FAME produced was significantly lower
than that produced via a conventional batch transesterification
reaction. FAME quality was reported to be reasonably affected by
the fatty acid composition of the lipid feedstock. The authors noted
absence of glycerin after phase separation and recorded FAME
purity of 79.07e86.36% prior to hot distilled water washing. All the
glycerin was distributed in the methanol/glycerin rich phase
because methanol and glycerin are all hydrophilic. Meanwhile
diglyceride was detected in the FAME-rich phase because of
Diglyceride’s hydrophobicity. To meet American standard of
testing materials (ASTM), FAME-rich phase from the permeate
stream was subjected to six water washes at one-third the volume
of the FAME-rich phase for each wash. They also stated the
potentials and challenges of high temperature membrane reactors.
Peigang et al. [31] studied methanol recycling in the production of
biodiesel in a membrane reactor. The authors reported that
microporous inorganic membrane reactor could selectively
remove FAME, methanol, and glycerol during transesterification
reaction from triglycerides. The reactor is based on the general
principle that oil particles form droplets in hydrophilic environ-
ment. When the reactants are mixed the oil droplets with larger
pore sizes are formed. The smallest calculated oil droplet size in the
membrane reactor was 12 mm and this greatly exceeds most of the
membrane pore sizes (0.01e0.04 mm) employed. This distinct
characteristic enables unreacted vegetable oil to be retained in the
retented stream and permit the removal of the product. A signifi-
cant reduction in the amount of water washing for the treatment of
EAME for higher purity was noticed. The authors stated that in the
same physical enclosure, membrane reactors can be employed to
(1)
carry out a transesterification reaction as well as separation
simultaneously. Li-Hua et al. [32] tested membrane separation
using the ceramic membrane combined with liquideliquid
(2)
extraction for the continuous cross flow rejection of triglycerides
442 I.M. Atadashi et al. / Renewable Energy 36 (2011) 437e443
Table 3
GC results according to ASTM D6584 [30].
Feedstock Biodiesel from membrane reactor (w%)
Total glycerin
Soybean 0.0685
Canola 0.0712
Palm 0.0124
Yellow grease 0.0989
Brown grease 0.104
Canola with methanol recycle 0.0929
a
Does not meet the ASTM standard.
from fatty acid methyl esters mixture. The oil-rich phase was
rejected by the membrane, but the methanol-rich phase perme-
ated and tested to be free of triglycerides. The membrane perfor-
mance was found to be influenced by temperature because it has
an impact on liquideliquid extraction (LLE). The risk of permeating
oil through the membrane increases with increase in the feed
temperature up to 60  C. The authors discovered modified UNIFAC
model not to be capable of simulating the boundary of the LLE at
different temperatures but suggested that the experimental results
obtained to be used for the regression of appropriate model for
oileFAMEemethanol system. Table 3 compares the quantity of
glycerin left in biodiesel during membrane biodiesel purification
and the conventional biodiesel purification [30]. The results show
clearly that the product obtained through membrane purification
contained less glycerin, indicating high biodiesel purity.
4.2. Effect of membrane pore size for biodiesel separation and
purification
The membrane pore size plays a significant role in the sepa-
ration and purification of crude biodiesel. It is important to esti-
mate the minimum particle sizes in the vegetable oilealcohol
emulsion for efficient refining process. Peigang et al. [33] inves-
tigated the effect of membrane pore size on the performance of
a membrane reactor for biodiesel production. The average pore
size for an oil emulsion was determined to be 44 mm with lower
and upper limits of 12 mm and 400 mm respectively. The oil droplet
was found not to pass through the membrane pores because of
their large molecular size relative to membrane pore size. The
membrane provides a barrier to the passage of oleophilic
substances in lipid feedstock. This introduced inherent reliability
in the production of biodiesel that parallels the use of distillation
in petroleum processes.
4.3. Separative ceramic membrane for biodiesel purification
Today, purification of transesterified product posed a great
challenge in commercial production and application of biodiesel
fuel. The development of membrane reactor technology in the
production of biodiesel has reasonably reduced the complicated
separation and purification of crude biodiesel. This technology has
led to the successful separation of the unreacted emulsified oil from
the transesterified products which is a key factor in the production
of biodiesel. Further attempts have been made to purify crude
biodiesel without necessarily using water washing process. Water
washing process proved critical to the production of economically
viable biodiesel. Yong et al [34] investigated refining of biodiesel by
ceramic membrane separation. Different membrane sizes of 0.1 mm,
02 mm and 0.6 mm, temperatures of 30, 40, 50 60, and 70  C, and
transmembrane pressures of 0.05 and 0.2 MPa were tested
respectively. The results of the content of potassium, sodium,
Biodiesel from batch reaction (w%)
Free glycerin Total glycerin Free glycerin
0.00763 e e
0.00654 0.131 0.0124
0.0117 e e
0.00735 0.685a 0.0234a
0.0138 0.797a 0.0171
0.00749 e e
calcium, magnesium and free glycerol recorded were far better
than those obtained when water washing was employed. The
authors stated that the size of the reverse micelle formed by glyc-
erol and soap molecular weight with the mean of 2.21 mm was
larger than that of biodiesel molecular size, and was easier to be
removed during membrane separation. This clearly demonstrated
that application of membrane technology in the purification of
biodiesel will ease the difficulty encountered in conventional bio-
diesel purification. Additionally, the recent use of membranes by
Maria et al. [35] has further demonstrated great efficiency of
membrane technology for the separation and purification of crude
biodiesel.
5. Conclusion and recommendation
Based on the foregoing, the following conclusions and recom-
mendations were made:
1. Even though homogeneous catalyst such as sodium and
potassium hydroxides indicated faster rates in the commercial
biodiesel production. The transesterification reaction involving
these catalysts generates soap leading to great difficulties in the
separation and purification of biodiesel from product mixture.
2. The development of heterogeneous catalysts of lower cost for
the production of biodiesel should be encouraged to overcome
the effects of soap formation. This will immensely contribute in
lowering the cost of biodiesel separation and purification
processes.
3. It is observed that application of water for the purification of
biodiesel leads to higher cost of wastewater treatment,
appreciable energy and time consumptions and low biodiesel
yields.
4. The use of higher oil to methanol ratios in the trans-
esterification reaction was found to contribute significantly to
the higher cost of biodiesel separation and purification.
5. The use of raw materials with water content above the stan-
dard specification resulted in the deactivation of the catalyst
and in some cases promotes soap formations.
6. The use of higher free fatty acids vegetable oils and animal fats
was noticed to promote saponified products thereby contrib-
uting greatly to the difficulties in the separation and purifica-
tion of biodiesel from transesterified products.
7. The introduction of membrane technology to a great extent
minimized the difficulties encountered in the separation and
purification of biodiesel. This technology needs to be thor-
oughly explored and exploited to determine its potential
applications for the separation and purification of biodiesel
product mixture.
8. Scale-up of membrane separation and purification of biodiesel
for commercial application is equally important and needs to
be carried out.
 I.M. Atadashi et al. / Renewable Energy 36 (2011) 437e443 443

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