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Renewable Energy 36 (2011) 437e443

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Review

Biodiesel separation and purication: 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:
Received 4 January 2010
Accepted 28 July 2010
Available online 23 August 2010

Biodiesel as a biodegradable, sustainable and clean energy has worldwide attracted renewed and
growing interest in topical years, chiey due to development in biodiesel fuel and ecological pressures
which include climatic changes. In the production of biodiesel from biomass, separation and purication
of biodiesel is a critical technology. Conventional technologies used for biodiesel separation such as
gravitational settling, decantation, ltration and biodiesel purication such as water washing, acid
washing, and washing with ether and absorbents have proven to be inefcient, time and energy
consumptive, and less cost effective. The involvement of membrane reactor and separative membrane
shows great promise for the separation and purication of biodiesel. Membrane technology needs to be
explored and exploited to overcome the difculties usually encountered in the separation and purication of biodiesel. In this paper both conventional and most recent membrane technologies used in
rening 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.
2010 Elsevier Ltd. All rights reserved.

Keywords:
Biodiesel
Transesterication
Separation
Purication
Membrane technology

1. Introduction
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 decarbonisation 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 nite 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.: 60 3 79674615; fax: 60 3 79675319.
E-mail address: mk_aroua@um.edu.my (M.K. Aroua).
0960-1481/$ e see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.renene.2010.07.019

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


also environmentally benecial, thereby providing lower gas
emission prole. 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 modications 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 transesterication
reaction, a process which seems to insure very good outcomes in
terms of lowering viscosity and enhancing other physicochemical
properties [3]. Transesterication 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 transesterication 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 difcult; the catalyst has to be removed from

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I.M. Atadashi et al. / Renewable Energy 36 (2011) 437e443

Table 1
Volume of biodiesel production in different countries [2].
Country

Volume potential (Ml)

Production cost (US$ per liter)

Malaysia
Indonesia
Argentina
USA
Brazil
Netherlands
Germany
Philippines
Belgium
Spain

14,540
7595
5255
3212
2567
2496
2024
1234
1213
1073

0.53
0.49
0.62
0.7
0.62
0.75
0.79
0.53
0.78
1.71

the product; alkaline wastewater requires treatment and free fatty


acids (FFA) and water interfere with the reaction [4]. The presence
of water lowers the activity of catalyst, while FFA react with the
catalyst to produce saponied product [2]. The formation of soap
reduces the biodiesel yield, and causes signicant difculty in
product separation and purication. Thus, biodiesel and byproduct, glycerol have to be rened by washing with hot deionized
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
technology development for the separation, purication, and
transformation of it into biochemicals and biofuels. Currently,
down-stream processing alone accounts for 60e80% of the
process cost [5]. Ineffective biodiesel separation and purication
causes severe diesel engines problems such as plugging of lters,
coking on injectors, more carbon deposits, excessive engine wear,
oil ring sticking, engine knocking, and thickening and gelling of
lubricating oil [6]. Several different separation and purication of
biodiesel techniques have been studied. This paper reviews the
technologies employed with emphasis on the most suitable practice for effective separation. Membrane separation seems to be the
most suitable for this purpose and is the focus of this study.
2. Conventional biodiesel separation techniques
Several researchers had studied extensively numerous conventional techniques for the separation of biodiesel. A brief review for
the biodiesel separation techniques is presented here. Most of the
researchers reported that high-quality biodiesel that is economically viable can be achieved when suitable biodiesel separation
process is employed. After transesterication, separation of biodiesel and by-product, glycerol is usually rst carried out. This
process of biodiesel separation is based on the facts that the biodiesel and glycerol produced are typically sparingly mutually
soluble, and that there is palpable difference in density between
biodiesel (880 kg/m3) and glycerol (1050 kg/m3, or more) phases
respectively. More so, this difference in density is sufciently
enough for the application of simple techniques such as gravitational settling or centrifugation for the separation of biodiesel and
glycerol phases. In addition, the separation rate of biodiesel
O
||
CH2 - O - C - R1
|
|
O
|
||
CH - O - C - R2 + 3 CH3OH
|
|
O
|
||
CH2 - O - C - R3
Triglyceride

Methanol

(Catalyst)

O
||
CH3 - O - C - R1
|
|
O
|
||
CH3 - O - C - R2
|
|
O
|
||
CH3 - O - C - R3

Esters

Fig. 1. Transeterication of vegetable oil with methanol.

CH2 - OH
|
CH - OH
|
CH2 - OH

glycerin

mixture is inuenced by numerous factors such as intense mixing,


formation of emulsion, solubility of biodiesel in glycerol, and
glycerol in biodiesel [7]. Demirbas [6] reported that supercritical
methanol process is non-catalytic, involves a much simpler purication of transesteried products, has a lower reaction time, is
more environmentally friendly, and requires lower energy use.
Though, the reaction requires temperatures of 525e675 K and
pressures of 35e60 MPa. Another advantage with supercritical
methanol is that the conversion gets 95% complete in 10 min [8].
Siti et al. [9] revealed the problems encountered in the use of
chemical catalysts to be high energy and methanol consumptions,
and large amount of alkaline wastewater. The use of enzymes such
as lipase has recently received a wider attention and considered to
be an effective way to overcome such problems. Particularly, the
separation of glycerol without complicated treatment. Even though
cost is the major bottle neck associated with enzymatic catalysis.
Sharma et al. [8] stated that methanol has polar hydroxyl group
which can act as an emulsier causing emulsication and rendering
severe difculties in the separation of the methyl ester layer from
water.
2.1. Effects of catalyst
The high consumption of energy and costly separation of the
homogeneous catalyst from the reaction mixture have drawn to the
need of development of heterogeneous catalysts for transesterication reaction, which is easily separated from the reaction
mixture and recyclable. Several authors used heterogeneous catalysts with the aim of eliminating neutralization and washing steps
needed for processes using homogeneous catalysts but were faced
with major problems such as higher temperature of transesterication reaction, longer reaction time and lower yield of
esters [1]. Helwani et al. [10] have discussed the advantages and
disadvantages of using homogeneous catalysts (alkali and acid) and
heterogeneous catalysts (solid and enzymes) in the industrial
production of biodiesel. Homogeneous catalysts are signicant for
industrial biodiesel production because of their easy conversion at
moderate temperatures (40e65  C), but are faced with rening
problems. However, heterogeneous catalyst was introduced in the
biodiesel production to avoid several neutralization and washing
steps needed for processes using homogeneous catalysts. The
authors revealed purity of methyl esters to exceed 99%, with yield
close to 100%, glycerol as by-product with purity of more than 98%
compared to about 80% from homogeneous process. The overall
production economy is improved through the utilization of the byproduct, glycerol [1]. Several researches are also currently going on
with the enzymatic methanolysis using lipases for biodiesel
production with view of overcoming issues involved in recovery
and treatment of the by-product that requires complex processing
equipment. The major problem of enzyme catalyzed process is the
high cost of the lipases as catalyst. In order to reduce the cost,
enzyme immobilization was introduced for ease of recovery and
reused [2]. They stated that although transesterication reaction
catalyzed by lipase provides an attractive alternative, the industrial
use of this technology has been retarded as a result of feasibility
aspects and some technical challenges. Biodiesel production
assessment has shown that, homogeneous base-catalyzed reaction
is still much favorable in spite of the difculties encountered in the
product separation and purication. The major reason has been
that the kinetic rates of homogeneous reaction are much faster than
heterogeneously catalyzed transesterication reaction and is
economically viable.
Nestor et al. [11] stated that higher amount of FFA has resulted in
excessive soap formation as FFA react with the catalyst, which is
normally sodium and potassium hydroxides via saponication

I.M. Atadashi et al. / Renewable Energy 36 (2011) 437e443

reaction. Soap renders biodiesel purication and catalyst removal


more challenging. However, homogeneous lewis acids such as
AlCl3, ZnCl3, and excess methanol were tested at higher temperatures and demonstrated that AlCl3 irrespective of the feedstock
type can give higher conversion of esters with better product that
can be easily rened. Boey et al. [12] concluded that use of classical
homogeneous catalysts results in higher yield loss through
saponication 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
purication processes and less wastewater generation compensates 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
esterication of FFA and made use of calcium oxide and higher
methanol ratios in the transesterication 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, difculty 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 ow 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 difcult and bring extra cost to the nal 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. Transesterication
reaction with basic homogeneous catalysts will promote soap
formation and render product separation difcult. 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 difculty 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 signicance of
different catalysts in the purication of biodiesel is shown in Table 2.

439

O
||
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 transesterication 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
transesterication. 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 saponied product (Fig. 3). The
saponied 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 difcult to
recover. The negative effects of excessive soap formation include
amongst others; consumption of the catalyst, reduction of catalyst
effectiveness, difculty in glycerol separation, and prevention of
crude biodiesel purication [7]. Demirbas [6] reported that even
a little amount of water (0.1%) in the transesterication reaction
will reduce the methyl ester conversion from vegetable oil. At the
same time the presence of water has a signicant 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 purication techniques

2.2. Effects of oil to alcohol ratio


3.1. Biodiesel purication
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 purication 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

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
specication on the amount of water content in the puried biodiesel 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)
Free fatty acid in raw materials
Water in raw materials
Yields of methyl esters
Recovery of glycerol
Purication of methyl esters
Production cost of catalyst

60e70
Saponied products
Interfere with reaction
Normal
Difcult
Repeated washing
Cheap

55e80
Esters
Interfere with reaction
Normal
Difcult
Repeated washing
Cheap

30e40
Methyl esters
No inuence
Higher
Easy
None
Relatively expensive

239e385
Esters
e
Good
e
e
Medium

180e220
Not sensitive
Not sensitive
Normal
Easy
Easy
Potentially cheaper

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I.M. Atadashi et al. / Renewable Energy 36 (2011) 437e443

O
||
+ KOH
HO - C - (CH2)7 CH=CH(CH2)7CH3
Oleic Acid
Potassium Hydroxide
O
||
K+ -O - C - (CH2)7 CH=CH(CH2)7CH3 + H2O
Water
(Soap)
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 simplies immediate removal of the salt products. The
unreacted methanol after transesterication reaction should be
removed before the washing stage to minimize the presence of
alcohol in the wastewater efuent. 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 contamination 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 purication 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.
Transesterication reaction is a reaction that is widely considered
and mostly adopted to produce commercial biodiesel [11]. The
transesteried products undergo different purication techniques in
order to purify biodiesel from glycerol and other by-products.
However, the neutralization of alkali catalyst and the purication
stage performed using a larger amount of water create additional
wastewater which are the major roadblocks of such process. Downstream from the reactor, the recovery of the residual alcohol, the
purication of fatty acid alkyl esters from the catalyst and the separation of glycerol as a major secondary product are generally desirable. In the case when vegetable oils or waste vegetable oil contains
an appreciable amount of FFA, the catalyst during transesterication
reaction is consumed due to neutralization of acids causing decrease
of the reaction rate, and rendering separation and purication difcult. Harding et al. [17] conducted experimental studies to compare
the simplicity of purication 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 saponication
reaction and alcohol recovery. This process made separation of esters
from glycerol, recovery of glycerol and purication of esters much
more easier and economical compared to the conventional chemical
process whose separation and purication processes proved too
complicated and energy consuming. The major conventional biodiesel purication 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 neutralization technique instead of distillation to purify the transesteried
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

evaporate residual water. Ferella et al. [3] stated that formation of soap
due to neutralization of FFA in the vegetable oil or triglyceride by
potassium hydroxide decreases biodiesel yield and quality. In addition
separation of biodiesel and glycerol underwent simple centrifugation
and washing product leads to high utilization of time and water. Jaya
et al. [19] demonstrated simple ltration 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 tetrahydrofuran (THF) as a co-solvent to enhance the homogeneity of oil and
methanol and to promote more transesterication reactions increases
biodiesel cost of purication. 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 purication at the end of transesterication
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 biodiesel 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 coefcient. The higher washing temperature gave higher diffusivity of glycerol from biodiesel to water
phase, then the mass transfer coefcient 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 transesteried 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 puried 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 impurities such as catalysts, alcohol, etc. Silica gel was used for the
removal of catalyst from the biodiesel product. Meher et al. [24]
reported the difculty in the separation and purication of glycerol 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 sedimentation, 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 ltration.
3.1.3. Washing with solid adsorbent, ether, and water
Absorbents are another means of treating transesteried
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 lter, 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 ber, 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 purication, and to obtain pure biodiesel,
method of washing with hot distilled water and petroleum ether
(1:1) was performed in the rening 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 transesterication 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.

Product yield

Weight of product
Weight of raw oil

4. Biodiesel membrane separation and purication


The membrane equipments mostly produced for the separation
and purication of crude biodiesel seem to exhibit several advantages over the conventional ones such as eradication/minimization
of higher capital cost and other related costs of production, and
provide high specic area of mass transfer. Membrane equipments
for biodiesel rening 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 purication of crude biodiesel include: Membrane reactor and
separative ceramic membrane.
4.1. Biodiesel separation and purication 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 lm,
and the lower the thickness, the higher the productivity [28].

Permeability;

Selectivity;

Lp

Qfiltrate
ADP

Flux of impurity
Flux of product

(1)

(2)

441

Membrane reactors intrinsic characteristics of efciency, operational simplicity and exibility, 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 conrmed in a numerous variety of
applications and operations, as molecular separations, fractionations, concentrations, purications, clarications, emulsications,
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 transesterication, 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 rening
method using membrane extraction was developed by He et al.
[29]. The authors compare membrane extraction and the traditional extraction methods of biodiesel rening. The membrane
separation proved to be more effective and efcient over the
conventional dispersed phase separation, in the following ways:
no emulsication formed, no density difference noticed between
uids for hollow ber membranes, and the interfacial area was
high. The use of hollow ber membrane leads to avoidance of
emulsication 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 instrumental in providing excellent means of retaining emulsion. Highquality FAME was achieved which was ascertained by Gas Chromatography (GC) analysis based on the ASTM D6584 standard and
the glycerin content of FAME produced was signicantly lower
than that produced via a conventional batch transesterication
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
Diglycerides 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 transesterication
reaction from triglycerides. The reactor is based on the general
principle that oil particles form droplets in hydrophilic environment. 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 signicant 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
carry out a transesterication reaction as well as separation
simultaneously. Li-Hua et al. [32] tested membrane separation
using the ceramic membrane combined with liquideliquid
extraction for the continuous cross ow rejection of triglycerides

442

I.M. Atadashi et al. / Renewable Energy 36 (2011) 437e443

Table 3
GC results according to ASTM D6584 [30].
Feedstock

Soybean
Canola
Palm
Yellow grease
Brown grease
Canola with methanol recycle
a

Biodiesel from membrane reactor (w%)

Biodiesel from batch reaction (w%)

Total glycerin

Free glycerin

Total glycerin

Free glycerin

0.0685
0.0712
0.0124
0.0989
0.104
0.0929

0.00763
0.00654
0.0117
0.00735
0.0138
0.00749

e
0.131
e
0.685a
0.797a
e

e
0.0124
e
0.0234a
0.0171
e

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 permeated and tested to be free of triglycerides. The membrane performance was found to be inuenced 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 modied 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 purication
and the conventional biodiesel purication [30]. The results show
clearly that the product obtained through membrane purication
contained less glycerin, indicating high biodiesel purity.
4.2. Effect of membrane pore size for biodiesel separation and
purication
The membrane pore size plays a signicant role in the separation and purication of crude biodiesel. It is important to estimate the minimum particle sizes in the vegetable oilealcohol
emulsion for efcient rening process. Peigang et al. [33] investigated 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 purication
Today, purication of transesteried 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 purication of crude biodiesel. This technology has
led to the successful separation of the unreacted emulsied oil from
the transesteried 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 rening 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,

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 glycerol 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 purication of
biodiesel will ease the difculty encountered in conventional biodiesel purication. Additionally, the recent use of membranes by
Maria et al. [35] has further demonstrated great efciency of
membrane technology for the separation and purication of crude
biodiesel.
5. Conclusion and recommendation
Based on the foregoing, the following conclusions and recommendations were made:
1. Even though homogeneous catalyst such as sodium and
potassium hydroxides indicated faster rates in the commercial
biodiesel production. The transesterication reaction involving
these catalysts generates soap leading to great difculties in the
separation and purication 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 purication
processes.
3. It is observed that application of water for the purication 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 transesterication reaction was found to contribute signicantly to
the higher cost of biodiesel separation and purication.
5. The use of raw materials with water content above the standard specication 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 saponied products thereby contributing greatly to the difculties in the separation and purication of biodiesel from transesteried products.
7. The introduction of membrane technology to a great extent
minimized the difculties encountered in the separation and
purication of biodiesel. This technology needs to be thoroughly explored and exploited to determine its potential
applications for the separation and purication of biodiesel
product mixture.
8. Scale-up of membrane separation and purication of biodiesel
for commercial application is equally important and needs to
be carried out.

I.M. Atadashi et al. / Renewable Energy 36 (2011) 437e443

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