Review

pubs.acs.org/IECR

Intensification Approaches for Biodiesel Synthesis from Waste

Cooking Oil: A Review
Ganesh L. Maddikeri, Aniruddha B. Pandit, and Parag R. Gogate*
Chemical Engineering Department, Institute of Chemical Technology, Matunga, Mumbai 40019, India

ABSTRACT: The use of biodiesel as an alternative fuel has become more attractive recently because of its environmental
benefits such as nontoxicity and biodegradability. However, due to the unfavorable economics and other problems for design and
operation of large scale reactors, commercialization of biodiesel has not been significantly effective. The specific challenges in the
synthesis route based on transesterification include higher separation times, high operating cost, high energy consumption, and
low production efficiency due to equilibrium limitations. The present work highlights the potential use of waste cooking oil as a
cheap and economical feedstock discussing the advantages of the process and limitations for transesterification reaction.
Improvements in the synthesis process based on the different pretreatment methods and process intensifying techniques are
discussed with specific reference to transesterification of waste cooking oil. Different physical and chemical pretreatment methods
required for the preparation of feedstock include filtration, drying, acidic esterification, adsorption, crystallization, and distillation
for the removal of fatty acids and other contaminants. The critical review also highlights the different process intensification
techniques such as cavitational reactors, microwave irradiation, microchannel reactor, oscillatory flow reactor, use of cosolvent,
and supercritical transesterification process that can be used for biodiesel production process with an objective of enhancing the
reaction rate, reduction in the molar ratio of alcohol to oil, and energy input by intensifying the transport processes and
overcoming the equilibrium limitations. Guidelines for the selection of optimum operating parameters have also been given with
comparative analysis of the different approaches of process intensification. Finally, some recommendations have been made for
the possible research that needs to be done for successful commercialization of biodiesel synthesis.

1. INTRODUCTION
Increases in population and industrialization have given rise to a
significant increase in worldwide fuel consumption, also
resulting in significant air pollution which is one of the most
serious environmental problems all over the world.1 In addition
to the significant air pollution from the coal-fired power
stations, heavy vehicles based on diesel engines are also known
to release huge quantum of air contaminants such as NOx, SOx,
CO, particulate matter, and volatile organic compounds.2 Also,
experts suggest that current oil and gas reserves would suffice to
last only a few more decades. So, there is a need for an
alternative clean fuel for diesel engines to meet the rising
energy demand and also to reduce environmental pollution.
One of the alternative and viable options for compression-
ignition engines is use of biodiesel fuel. Biodiesel is a renewable
diesel fuel composed of fatty acid alkyl ester that can be
synthesized by transesterification, i.e. chemically combining any
natural oil or fat with an alcohol. Many vegetable oils, animal
fats, and recycled cooking greases can be transformed into
biodiesel. Biodiesel has several advantages such as biodegrad-
ability, nontoxicity, lower harmful emissions, high flash point,
excellent lubricity, and superior cetane number, and can be
derived from agricultural surplus, which can also help to
improve rural economies.3 Moreover, it is essentially free of
sulfur, and engines fueled by biodiesel emit significantly less
particulate matter, unburnt hydrocarbons, and carbon mon-
oxide as compared to engines operating on conventional fossil
fuels.4 Biodiesel can be used neat or as a diesel additive, but is
typically used as a fuel additive to petroleum diesel in
compression ignition (diesel) engines because of the differences
in the higher heating values (HHVs). The HHVs of biodiesel
(39−41 MJ/kg) are lower than those of gasoline (46 MJ/kg),
petro-diesel (43 MJ/kg), or petroleum (42 MJ/kg), but higher
than those of coal (32−37 MJ/kg). However, it is estimated
that the cost of biodiesel is approximately 1.5−2 times higher
than that of diesel fuel. The high price of biodiesel is due to the
higher costs of the feed stock and associated technical
challenges related to biodiesel production using the generally
preferred transesterification route. Use of waste cooking oil,
which is much less expensive than pure vegetable oil, as a
promising alternative feed stock and the recovery of high-
quality glycerol as a byproduct can be the primary options that
can be considered for favorable economics.5,6
The properties of biodiesel depend on the physicochemical
properties of feedstock and the production method. 7
Physicochemical properties of waste cooking oil are dependent
on the extent of usage of vegetable oil. Pretreatment of waste
vegetable oil is important and essentially required before it is
used in transesterification process because the free fatty acid in
waste vegetable oil can react with the alkaline catalyst resulting
in soap formation. The soap formation during the trans-
esterification reaction prevents the glycerol separation,
drastically reducing the ester yield, and can also create
operational problems in the reactor/separation units. It has
been reported that transesterification is not feasible if the free
fatty acid content in the oil is more than 1−2%.8,9 Different
Received: June 25, 2012
Revised: October 4, 2012
Accepted: October 16, 2012
Published: October 16, 2012

© 2012 American Chemical Society 14610 dx.doi.org/10.1021/ie301675j | Ind. Eng. Chem. Res. 2012, 51, 14610−14628
Industrial & Engineering Chemistry Research
Figure 1. Graphical representation of financial contribution of the major parameters in production of biodiesel.12
methods that can be used for the pretreatment of waste
vegetable oil include esterification, crystallization, adsorption,
and distillation, mainly for the treatment or removal of free
fatty acids.
Today, the majority of biodiesel is produced by trans-
esterification (also called alcoholysis) of vegetable oils in batch
reactors (such as stirred tanks) in the presence of alkali, acid, or
enzyme as catalyst or under supercritical conditions to form
esters and glycerol. These production processes may take 2−24
h to obtain very high oil conversion and fatty acid methyl ester
yield. Although it takes only a couple of minutes for the
transesterification reaction to be completed under supercritical
conditions, high temperature (>300 °C) and high pressure
(>40 MPa) have to be used.10 There are some technical
challenges related to biodiesel production via transesterification
such as (a) lower rates of synthesis typically attributed to mass
transfer limitations due to heterogeneous nature of the reaction
system, and (b) requirement of high molar ratio (alcohol to oil)
as transesterification itself is a reversible reaction. Both these
facts result in high operating cost and energy consumption and
hence low production efficiency for the biodiesel production.
To overcome these problems, different process intensifying
approaches can be used to improve the mixing, mass and heat
transfer between two liquid phases in transesterification
reaction.
The objective of the present work is to give an overview of
the pretreatment processes for treating waste cooking oil to
reduce the free fatty acid content with an objective of making it
a suitable feedstock for transesterification reaction. Also, a
review of different process intensification approaches which can
reduce the production costs of biodiesel synthesis by enhancing
heat, mass, and momentum transfer in the physical process is
presented.
2. WASTE COOKING OIL AS POTENTIAL FEEDSTOCK
FOR BIODIESEL PRODUCTION
Waste cooking oil mainly consists of animal and/or vegetable
matter that has been used in cooking or preparation of foods.
Most of this oil is used for deep-frying process, after which it is
no longer suitable for human consumption. Patil et
al.11reported that 4.1 kg (9 pound) of waste cooking oil is
generated per person per year. Today's world population is
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Review
around 7 billion, so around 29 million tons of waste cooking oil
is generated per year. Disposal of waste cooking oil creates a
significant challenge because of dumping problems and possible
pollution of the water and land resources. Previously, waste
edible oil was used as an ingredient in animal feed. However,
since 2002, the European Union (EU) has banned the use of
this oil in fodder making,7 which is likely to be extended
worldwide.
The raw material cost typically contributes about 70−80% of
the total cost of production for biodiesel. A limit of 75% for the
cost of raw materials has also been reported12,13 (Figure 1).
Waste cooking oil, which is much less expensive than virgin
refined vegetable oil, can be used as a possible feedstock.
Annually, a total of more than 15 million tons of waste cooking
oil is generated from selected countries in the world as shown
in Table 1.14
Table 1. Quantity of Waste Cooking Oil Produced in
Selected Countries14
country quantity (million tons/year)
China 4.5
Malaysia 0.5
United States 10.0
Taiwan 0.07
Europe 0.7−10
UK 0.2
Canada 0.12
Japan 0.45−0.57
Ireland 0.153
India is a leading consumer of edible oil and the
consumption during 2009−2010 was 16.7 million tons.15 It is
reported that nearly 10% of edible oil is being thrown out as
waste as it cannot be reused.16 If we assume that 10% of the
edible oil is consumed in hotels and restaurants, then the total
waste cooking oil available in 2009−2010 would be about 0.167
million tons. Assuming that with adequate incentives, 70% of
the waste cooking oil could be recovered, the available feed
stock could be approximately 0.12 million tons. If India plans a
10% mix in the total diesel consumption (60.14 million tons
during 2009−2010),17 6 million tons of biodiesel will be
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Industrial & Engineering Chemistry Research Review

required. With the available quantity of used cooking oil, nearly unsaturated aldehydes, ketones, hydrocarbons, lactones, alco-
about 0.114 million tons of biodiesel can be generated. In India, hols, acids, and esters. In the case of hydrolytic reaction, the
nearly 1.9% of diesel oil can be replaced by using the biodiesel steam produced during the processing of food containing water
generated from used cooking oil. In India during 2009−2010, causes the hydrolysis of triglycerides, resulting in the formation
biodiesel production was 1 million tons.18 The available used of free fatty acid, glycerol, monoglycerides, and diglycerides.20
cooking oil thus can form a useful contributing feedstock for High free fatty acid level, i.e. quantum of free fatty acids
the current biodiesel production. All these data indicate that the greater than 1 mg/g KOH, results in generation of high
used cooking oil can be a potential source for biodiesel amounts of undesirable soap simultaneously with trans-
production. Waste oils, such as used frying oil, trap grease, and estrification reaction. In the alkali-catalyzed process, the
soap stock (byproduct of vegetable oil refineries), which are presence of free fatty acid (greater than 1 mg/g KOH) and
available cheaply, can also be considered as a sustainable water in the oil can cause high amounts of undesirable soap
feedstock for the biodiesel synthesis. formation, also consuming some quantity of alkaline catalyst
and reduces the effectiveness, all of which result in a lower
3. QUALITY OF WASTE COOKING OIL AND conversion. Therefore, for the feedstock with high free fatty
IMPORTANCE OF PRETREATMENT acids, it is essential to have a pretreatment stage before
Waste cooking oil is generated from the process of oil frying, subjecting it to transesterification process.21
i.e. oil is heated in air in the presence of light at a temperature
of 160−200 °C for relatively long period of time, beyond which 4. PRETREATMENT PROCESS FOR WASTE COOKING
it cannot be used for edible purposes and needs to be disposed. OIL
Frying under such conditions results in major physical and Pretreatment of waste cooking oil consists of physical treatment
chemical changes in the oil altering the physiochemical for removing the suspended solid contaminants and chemical
properties as compared to the virgin oil (Table 2).19 The treatment processes mainly for deacidification. A flow sheet
giving the different approaches for pretreatment of waste
Table 2. Physical and Chemical Properties of Used Frying cooking oil is shown in Figure 2. Issariyakul et al.22 have
Oil and Neat Canola Oil19 reported the treatment of waste cooking oil using centrifugation
for the removal of solid portions of the oil. Water was removed
property used frying oil neat canola oil
by mixing used cooking oil (UCO) with 10 wt % silica gel (28−
acid value (mg KOH/g) 2.1 <0.5 200 mesh) followed by stirring and vacuum filtration. Dias et
kinematic viscosity at 40 ° (cSt) 35.3 30.2 al.23 filtered UCO under vacuum after dehydration overnight
fatty acid composition (wt %) using anhydrous sulfate, and finally filtered it again under
myristic (C14:0) 0.9 0.1 vacuum prior to transesterification.
palmitic (C16:0) 20.4 5.5 Esterification produces either methyl ester or triglyceride
palmitoleic (C16:1) 4.6 1.1 depending on the alcohol used for esterification. If esterification
stearic (C18:0) 4.8 2.2 of free fatty acid is carried out with methanol in the presence of
oleic (C18:1) 52.9 55 acid catalyst, methyl esters are obtained. Similarly, conversion
linoleic (C18:2) 13.5 24 of free fatty acids carried out using glycerol at high temperature
linolenic (C18:3) 0.8 8.8 (240−280 °C) with or without esterification catalysts (in an
arachidic (C20:0) 0.12 0.7 inert atmosphere to oppose oxidation) gives mono-, di-, or
eicosenic (C20:1) 0.84 1.4 triglycerides.24 Free fatty acid is removed from waste vegetable
behenic (C22:0) 0.03 0.5 oil as soap by treating it with alkali such as KOH or NaOH.
erucic (C22:1) 0.07 0.4 Meher et al.25 reduced the acid value to 0.6 by neutralization of
tetracosanic (C24:0) 0.04 0.3 free fatty acid content from Karanja oil with alkali. Similarly,
mean molecular weight (g/mol) 856 882
Cvengros et al.20 followed a stepwise procedure for the
pretreatment of used cooking oil. Free fatty acid was removed
observed changes in physicochemical properties of oil differ by neutralization using alkali (KOH or NaOH) as soaps while
from oil to oil, depending on their composition and the degree high polymer content was treated with activated carbon and
of heating. Physical changes such as increase in viscosity and removed by adsorption.
specific heat, a change in the surface tension and color, and an Adsorption processes for the separation are gaining a wider
increase in the tendency of foaming, generally occur during the importance as an efficient and low energy operation for the
course of frying.7 Chemical changes due to the thermolytic, removal of free fatty acid from waste vegetable oil. Toeneboehn
oxidative, and hydrolytic reaction also occur during the frying of et al.26 used silica hydrogel for the removal of sulfur-containing
oil. A thermolytic reaction occurs in the absence of oxygen at compounds from fatty materials. Removal of free fatty acids and
high temperatures. A series of alkanes, alkenes, lower fatty acids, moisture was carried out by heating the oil under reduced
symmetric ketones, oxopropyl esters, CO, and CO2 are pressure followed by a two stage adsorption with basic-treated
produced from the saturated fatty acids in the oil. From the activated carbon and a hydrophilic adsorbent such as activated
unsaturated fatty acids, basically diametric compounds such as alumina and silica gel, respectively.27 Lee et al.28 used column
dehydrodimers, saturated dimers, and polycyclic compounds chromatography containing 50% magnesium silicate and 50%
are formed. In addition, dimers and trimers may be formed aluminum oxide (basic) to reduce the free fatty acids and water
when unsaturated fatty acids react with other unsaturated fatty content from waste cooking oil from 10.6 to 0.23 wt % and
acids through Diels−Alder reaction. Oxidative reaction occurs from 0.2% to 0.02 wt %, respectively.
when oxygen in air comes in contact with the oil or fat and Separation of fatty acids can also be achieved based on the
reacts mainly with unsaturated acyl-glycerols resulting in the difference in their solidification points. At low temperature, fats
formation of various oxidation products such as saturated and and oils that solidify can settle at the bottom of the equipment.
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Industrial & Engineering Chemistry Research Review

Figure 2. Schematic flow sheet for different pretreament techniques for waste cooking oil.

Scheme 1a

a
Major steps of the transesterification reaction mechanism. (1) Conversion of triglyceride to diglyceride. (2) Conversion of diglyceride to
monoglycerides. (3) Conversion of monoglyceride to glycerol. (4) Overall transesterification reaction.

Due to impure product, melt crystallization is not used in the method has been modified suitably under controlled conditions
oil industry for individual fatty acids separations. However, this and has become an industrial tool for partial separation of fatty
14613 dx.doi.org/10.1021/ie301675j | Ind. Eng. Chem. Res. 2012, 51, 14610−14628
Industrial & Engineering Chemistry Research
acids. Temperature-controlled crystallization has been used in
the industry to separate the oleic acid rich fraction from a
mixture of oleic and linoleic acids. The main disadvantage of
this process is poor separation, as the separation is only based
on the solidification point, resulting in the contamination of
each fraction of the acids with high levels of other acid
impurities.
The distillation technique (physical refining or steam
refining) has a dominant role in separation technology because
of its simplicity and universal applicability. Simple distillation
accomplishes the removal of odor or color bodies while
maintaining the original composition of the feedstock. Steam
injection reduces the boiling points of the compounds and
allows them to evaporate at lower temperatures, preferably
below the temperatures at which the deterioration of the
material becomes appreciable. Application of such treatments
on waste cooking oil can also reduce the moisture content
(from 1.4% to 0.4%), free fatty acid (from 6.3% to 4.3%), and
viscosity, and increase its energy value.29 Vacuum distillation
gives clear separation of triglyceride from impurities such as
water and free fatty acid.20 Cvengro et al.20 performed drying at
159 °C and at 20 mbar pressure and deacidification at 200−280
°C and 0.1−8 milli bar pressure.
Overall, it is recommended that based on the quality and
properties of waste cooking oil due to frying of virgin oil, both
physical and chemical treatment will be required. Physical
treatment includes filtration for removing suspended solids and
repeated water washing for the separation of water-soluble salt
impurities present in the waste cooking oil. Chemical
pretreatment processes involve acidic esterification, saponifica-
tion, adsorption, and distillation for the reduction of free fatty
acid content.
5. MECHANISM OF BIODIESEL PRODUCTION
Biodiesel synthesis from waste cooking oil by transesterification
reaction, which is also known as alcoholysis, is the reaction of
vegetable oil or fat with an alcohol to form esters and glycerol.
For complete transesterification reaction, stoichiometrically 3:1
molar ratio of alcohol to oil is required. In practice, to have a
maximum ester yield, this ratio needs to be higher than the
stoichiometric ratio. Because the reaction is reversible, excess
alcohol is used to shift the equilibrium to the product side.
Alcohols mainly used for this purpose are primary and
secondary monohydric aliphatic alcohols having 1−8 carbon
atoms. The most widely used alcohols are methanol and
ethanol though some applications also report the use of iso-
propanol as the synthesized isopropyl esters also have
commercial value. Among these two, methanol finds frequent
application in commercial use because of its lower cost. Rate of
transesterification reaction depends on the active ions for the
initiation of reaction and more significantly on the interfacial
contact between oil and methanol. Catalyst is used to create the
initial active ions resulting in an improvement in the reaction
rate and yield. The transesterification reaction can be catalyzed
by alkalis, acids, or enzymes.
Biodiesel is produced by transesterification reaction convert-
ing large branched triglycerides into smaller straight-chain
molecules of methyl esters, using an alkali or acid as catalyst.
There are three stepwise reactions with intermediate formation
of diglycerides and monoglycerides resulting in the production
of three moles of methyl esters and one mole of glycerol.30
Three major steps of the transesterification reaction mechanism
can be given as shown in Scheme 1.
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Transesterification can be further classified as alkali-catalyzed,
acid−alkaline-catalyzed (two stage), heterogeneous catalyst,
noncatalyzed super critical methanol, or enzyme-catalyzed
transesterification processes. A schematic flow diagram of the
biodiesel production from used cooking oil is shown in Figure
3. The methods used for biodiesel production from used
Figure 3. Schematic flow diagram of the biodiesel production from
waste cooking oil.
cooking oil are similar to that of conventional transesterification
processes once the waste oil is pretreated appropriately.
Selection of a particular process will depend on the amount
of free fatty acid and water content of the used cooking oil due
to the inherent advantages and disadvantages of different
processes. Lee et al.31 analyzed three continuous biodiesel
processes with a production capacity of 40 000 tonne/yr,
including a conventional alkali-catalyzed process using both
fresh and waste vegetable oil and a supercritical methanol
process using waste vegetable oil as the raw material. It has
been reported that the alkali-catalyzed transesterification
process is most effective in converting triglycerides into esters
when free fatty acid level is less than 1%. It is the most widely
used process because it requires only moderate temperatures
and lower pressures and also there is high conversion efficiency
(98%). This process requires only a short time and there is a
direct conversion of biodiesel without any intermediate steps.
However, it becomes less effective when the free fatty acid level
exceeds 1% because the FFA reacts with the most alkaline
catalysts and forms soap which inhibits the separation of ester
from glycerine and in turn reduces the conversion rate. Acid-
catalyzed transesterification process does not yield soap due to
the absence of alkali however the reaction is significantly slower
than the alkali-catalyzed reaction. Another major problem with
the use of acid catalyst is the formation of water which stays in
the reaction mixture and finally stops the reaction well before
reaching completion.32 The two-stage acid- and- alkali-catalyzed
transesterification can be used to avoid the problems associated
with the separate use of base or acid catalysts such as
saponification and slow reaction time.33 In the first stage,
esterification of FFA present in waste cooking oil is carried out
using acid to decrease the FFA level to less than 1%. In the
second stage, transesterification of the treated waste cooking oil
is performed using an alkaline catalyst. Despite its advantages,
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the two-stage method also faces the problem of catalyst removal
in both stages. The problem of catalyst removal in the first stage
can be avoided by neutralizing the acid catalyst, using extra
alkaline catalyst in the second stage. However, the use of extra
catalyst increases the processing cost for the second stage. The
use of heterogeneous catalyst does not yield soap. Most solid
catalysts are alkali or coated alkaline oxides offering large
surface area. However, this process requires higher pressures
and temperatures than the homogeneous catalyzed process
with an excess amount of methanol.34 To overcome the
limitations of acid- and base-catalyzed transesterification
processes, a new method called noncatalyzed supercritical
methanol transesterification process has been developed.35 This
requires a very short time (only 4 min) for the completion of
the transesterification process under supercritical conditions
(temperature 350−400 °C and pressure more than 80 bar). It
avoids the complications of purification in the last stages.
However, it requires a very high alcohol to oil (42:1) ratio and
higher capital and operating costs. It also consumes more
power. Another limitation of this process is that it neither
explains nor verifies any compliance of the free glycerol content
to less than 0.02% as established in the ASTM D6584 or other
equivalent International standard for the synthesized biodiesel.
Enzyme-catalyzed transesterification process is a promising
alternative method to all chemical-catalyzed reactions for the
production of biodiesel from waste cooking oil. However,
yields, reaction times, and costs are still suboptimal compared
to alkaline-catalyzed transesterification process.36
The characteristic properties of biodiesel obtained from the
fresh oils and from waste cooking oil are similar. The important
characteristic properties of biodiesel obtained from waste frying
palm oil and those of fossil diesel fuel are summarized in Table
3.37 Cetane index of biodiesel is very much higher than fossil
high operation costs and energy consumption, and low
efficiency in the downstream processing, different new
technologies for process intensification can be applied. We
now discuss such technologies which have shown considerable
promise in biodiesel synthesis.
6.1. Cavitational Reactors. Cavitational reactors are a
novel and promising form of multiphase reactors, based on the
principle of release of large magnitude of energy due to the
violent collapse of the cavities. Cavitation occurs at millions of
locations in the reactor simultaneously and generates local
conditions of very high local temperatures and pressures (few
thousand atmospheres pressure and few thousands Kelvin
temperature) with bulk ambient conditions.38 These cavita-
tional effects are mainly responsible for the intensification of
physical and chemical processing applications limited by mass
transfer. Physical effects such as liquid streaming associated
with intense turbulence and chemical effects such as generation
of hot spots and reactive free radicals are mainly responsible for
intensification of different physical and chemical processing
applications.38 Cavitational reactors use acoustic energy
(sonochemical reactor) or flow energy (hydrodynamic
cavitation reactor) to generate cavitational events. Broadly
speaking, sonochemical reactors can be classified into indirect
and direct irradiation type. In the former, sonication is
performed in a reaction vessel (usually Erlenmeyer or round-
bottom flask) immersed in an ultrasonic cleaning bath, and in
direct irradiation the reaction vessel is equipped with an
ultrasonic processing probe (Figure 4), known as horn,

Table 3. Test Fuel Properties37

properties fossil diesel biodiesel procedure
cetane index N47 62 ASTM D613
high heating value (MJ/kg) 39.87 ASTM D240
specific gravity at 15.6/15.6 °C 0.81−0.87 0.8772 ASTM D1298
viscosity at 40 °C (cSt) 1.8−4.1 6.317 ASTM D445
pour point (°C) b10 10.0 ASTM D97
Figure 4. Experimental setup for the transesterification reaction using
ultrasonic horn.43 1. Condenser. 2. Transducer. 3. Ultrasonic reactor
sulfur content (wt %) b0.05 b0.0082 ASTM D4294
(500 mL). 4. Stand support. 5. Temperature sensor. 6. Ultrasonic
carbon residue (wt %) b0.05 0.05 ASTM D4530
generator.
water and sediment (vol %) b0.5 Trace ASTM D2709
copper strip corrosion b1 1a ASTM D130
sonotrode, or sonoprobe, which is immersed directly into the
flash point (°C) N52 130 ASTM D93
reaction mixture. In the hydrodynamic cavitation (Figure 5)
distillation 90% recovered (°C) b357 337.1 ASTM D86
reactor, cavitation is generated by the passage of the liquid
through a constriction such as a valve, orifice plate, or venturi,
diesel but its heating value is 39.9MJ/kg which is about 86.8% etc.
of the fossil diesel. The viscosity of biodiesel at 40 °C is 6.3 cSt In a sonochemical reactor, frequency of irradiation is a critical
which is slightly higher than the fossil diesel. The high viscosity parameter for deciding the extent of physical or chemical
of biodiesel may be due to the presence of trace amount of effects. The high-frequency operation (typically in the range of
triglyceride or monoglyceride. The pour point of the biodiesel 200−500 kHz) creates more chemical effects, which can be
is very similar to fossil diesel. Biodiesel is safer in transportation effectively used in wastewater treatment and chemical synthesis
and storage as its flash point exceeds that of fossil diesel. applications. Low-frequency operation (in the range of 10−100
Carbon residue is also lower than the fossil diesel. kHz, more specifically 20−50 kHz which is readily available) is
useful for maximizing the physical effects by improving the
6. PROCESS-INTENSIFYING TECHNOLOGIES FOR mass transfer which is typically achieved by maximizing the
BIODIESEL PRODUCTION FROM WASTE COOKING interfacial surface area between the immiscible reactants. In
OIL case of biodiesel synthesis, since dominant physical effects are
To overcome the main bottlenecks associated with traditional required for intensification, it is recommended to use low-
processes for biodiesel production such as long residence time, frequency reactors with the operating frequency in the range of
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Industrial & Engineering Chemistry Research Review

ratio of 6:1, potassium hydroxide as the catalyst (1 wt %/wt),

Figure 5. Schematic representation of the experimental setup for
hydrodynamic Cavitation reactor.48
20−50 kHz.39 The use of cavitational reactors is not only
efficient and time saving but also economically viable as it
requires low quantity of catalyst and only one-third to half of
the energy that is consumed by mechanical agitation.
Many researchers have used direct immersion type of
sonochemical reactors (i.e., ultrasonic horn) for the trans-
esterification of waste vegetable oil. Ultrasound has been
employed for intensification of biodiesel production from waste
cooking oil by transesterification reactions catalyzed by acid,
base, or enzyme catalysts as summarized in Table 4.
The homogeneous acid-catalyzed reaction is significantly
slower than the homogeneous base-catalyzed reaction.40
Alkaline metal alkoxides and hydroxides are the most often
used base catalysts. The former are considered to be the most
active catalysts, since they give very high yields (>98%) in short
reaction times (30 min) even if they are applied at low
concentrations (0.5 mol %). Many researchers have succeeded
in speeding up the reaction rate by carrying out homogeneous
base-catalyzed methanolysis of waste cooking oil in the
presence of a low-frequency direct sonication reactor. For
instance, Refaat et al.41 studied base-catalyzed transesterifica-
tion of waste cooking oils at two catalyst loadings (0.5% and
1.0% KOH wt/wt), two reaction temperatures (25 and 65 °C),
and three alcohol-to-oil molar ratios (3:1, 6:1, and 9:1) using
low-frequency ultrasound (20 kHz) and compared the results
with the conventional classical approach. It has been reported
that the best yield was obtained using a methanol/oil molar
and 65 °C temperature. It was concluded that trans-
esterification by low-frequency ultrasound (20 kHz) offered a
lot of advantages over the conventional classical procedure. Use
of sonochemical reactors proved to be efficient giving biodiesel
yield up to 98−99% and resulting in substantial time and
energy savings (dramatic reduction of reaction time to 5 min,
compared to one hour or more using conventional batch
reactor systems, and a remarkable reduction in static separation
time to 25 min, compared to 8 h).
Babajide et al.42 conducted transesterification of waste
cooking oil using ultrasound homogenizer with 20 kHz
frequency and power output of 400 W at different catalyst
loadings and reaction times. It has been reported that ultrasonic
homogenization proved suitable for large-scale processing of
waste cooking oils resulting in a better yield of 90% and higher
conversion efficiency of 98%. The effective mass transfer in the
ultrasonic field enhanced the rate of transesterification reaction
compared to mechanical mixing (stirring conditions).
Hingu et al.43 investigated the transesterification of used
frying oil using low-frequency ultrasonic reactor (20 kHz)
(Figure 4). Effects of different operating parameters such as
alcohol−oil molar ratio, catalyst concentration, temperature,
power, ultrasonic pulse, and horn position on the extent of
conversion of oil have been investigated and efficacy of using
ultrasound has been compared with the conventional stirring
approach based on the use of a six-blade turbine with diameter
of 1.5 cm operating at 1000 rpm. The optimum conditions
were established as molar ratio of alcohol to oil as 6:1, catalyst
concentration of 1 wt %, temperature as 45 °C, and ultrasound
power as 200 W with an irradiation time of 40 min. It has been
reported that acoustic cavitation results in 89.5% conversion
whereas the conventional stirring method results in much lower
extent of conversion (57.5%) over similar time of operation as
40 min. This can be attributed to the fact that as the reaction is
mass transfer controlled, the micro level turbulence generated
due to the oscillation and collapse of cavitational bubbles
results into the higher availability of the interfacial area and
hence higher conversion.
The use of heterogeneous catalysts significantly simplifies the
process of separation and purification of the products, reduces
environmental problems, allows reuse of the catalyst by easy
regeneration, and contributes to favorable economics.44
Undesired saponification reactions can be avoided by using
heterogeneous acid catalysts. They enable the transesterification
of vegetable oils or animal fats containing high contents of free

Table 4. Biodiesel Production by Transesterification Reaction from Waste Cooking Oil Using Ultrasound Methoda
reaction condition optimized condition
sr freq. T
no. alcohol (MR) catalyst (CL in %) T (°C) (kHz) power (watt) MR CL (°C) performance ref
1 methanol (65 mL for Mg/MCM-41, Mg−Al 60 24 200 65 mL for fatty 10 60 conversion = 97% 46
fatty acid weight of 5g) hydrotalcite, mesoporous acid weight of 5g
K/ZrO2 (10)
2 methanol (4:1−7:1) KOH(0.5−1.25) 35−55 25 150−250 6:1 1 45 conversion = 43
89.62%
3 methanol (6:1) KOH(0.5−1.5) 30−70 20 400 6:1 0.75 30 conversion = 98% 42
yield = 90
4 methanol (3:1−9:1) KOH(0.5−1.0) 25−65 20 100 6:1 1 65 yield = 98−99 41
5 methanol (∼4.6:1) NaOH(1.0−2.0) 60 24 200 ∼4.6:1 2 60 yield = 95 95
6 propanol Novozyme 435 40−45 28 100 3:1 conversion = 47
94.86

a
MR = Molar ratio of alcohol to oil. CL = catalyst loading. T = temperature. freq. = frequency of ultrasound.

14616 dx.doi.org/10.1021/ie301675j | Ind. Eng. Chem. Res. 2012, 51, 14610−14628

Industrial & Engineering Chemistry Research
fatty acids, such as deep-frying oils from restaurants and food
processing. Biodiesel synthesis using solid catalysts could
potentially lead to cheaper production because of the reuse
of the heterogeneous catalyst,45 which can be easily separated.
Georgogianni et al.46 carried out transesterification reaction
of soybean frying oil with methanol, in the presence of different
heterogeneous catalysts (Mg MCM-41, Mg−Al hydrotalcite,
and K+ impregnated zirconia), using low frequency ultra-
sonication (24 kHz) and mechanical stirring (600 rpm) for the
production of biodiesel. It has been reported that the Mg−Al
hydrotalcite catalyst showed particularly the highest activity
(conversion 97%) and the catalyst activity of ZrO2 in the
transesterification reaction increased as the catalyst was
enriched with more potassium cations. Use of ultrasonication
significantly accelerated the transesterification reaction with a
treatment time of 5 h as compared to the reaction time of 24 h
in the case of mechanical stirring.
Very few research studies are available on the use of
ultrasound irradiation in enzyme-catalyzed biodiesel produc-
tion. Only Novozym 435, a commercial lipase preparation from
Candida Antarctica, has been tested in the studies on
ultrasound-assisted transesterification reactions of soybean
and high acid value waste oil with methanol and propanol,
respectively. Wang et al.47 optimized ultrasound-assisted
enzyme-catalyzed biodiesel production from high acid value
waste oil and 1-propanol by esterification and transesterification
with respect to the amount of lipase, propanol-to-oil molar
ratio, and frequency and power of ultrasound. Immobilized
lipase Novozym 435 was utilized as a biocatalyst. Under
optimal conditions, such as 8% loading of Novozym 435, the
propanol-to-oil molar ratio of 3:1, the frequency and power of
ultrasound of 28 kHz and 100 W, and the temperature of 40−
45 °C, the conversion of 94.86% to propyl oleate was achieved
in 50 min. Ultrasound tends to reduce the adsorption of
biodiesel and glycerol on the surface of immobilized Novozym
435. As a result, Novozym 435 can be recycled to use with
clean appearances, good decentralizations, no agglomeration,
easy washing, and higher operational stability. Also, it was
noticed that short-chain linear and branched alcohols (C1−C5)
showed high conversion to fatty acid alkyl ester.
Ghayal et al.48 studied alkali-catalyzed transesterification of
waste cooking oil for biodiesel production using hydrodynamic
cavitation. They investigated the effect of operating pressure (1,
1.5, 2, 3 bar) and flow geometry (such as hole size, number of
holes, and total perimeter of holes on a cavitating orifice plate)
of orifice plate on the rate of reaction. It has been reported that
the rate of transesterification reaction increases with an increase
in the operating pressure and results in a reduction in the
reaction time. With an increase in the operating pressure, the
flow rate through orifice plate increases. As the amount of
liquid passing per unit time through the orifice increases, the
number of passes of liquid through cavitating zone increases,
due to which liquid experiences the cavitating zone for a longer
time and hence results in better conversion. Also, increase in
the upstream pressure leads to an increase in the pressure drop
across the orifice plate, due to which the collapse intensity of
cavity increases. Thus, there is an increase in the magnitude of
pressure generated due to cavitation which assists the mass
transfer between two immiscible phases of the reaction mixture
resulting in higher extents of conversion. It is seen that at lower
upstream pressure (1 and 1.5 bar) there is considerable
difference in the reaction rate for all geometric configurations
but there is no significant difference in reaction rate at higher
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operating pressure (2 and 3 bar). The increase in the rate of
reaction may occur due to an increase in cavitation effect when
operating pressure is increased from 1 to 2 bar and beyond that
there is no significant improvement in the cavitation effect with
operating pressure or when the condition of chocked cavitation
occurs. The observed results can also be attributed to the fact
that due to the complete elimination of mass transfer resistance
at higher operating pressure, inherent reaction kinetics becomes
rate controlling. At higher pressure, as the transesterification
reaction proceeds, the viscosity of reaction mixture reduces
rapidly. As viscosity reduces the flow rate increases. The
increase in flow rate results in decreasing cavitation number. Up
to a certain value of increasing flow rate, there is a considerable
decrease in cavitation number, beyond that there is only a
marginal decrease in the cavitation number (only a marginal
increase in the extent of cavitation will be observed). Therefore,
there may be no significant improvement in cavitation effects
beyond a certain high value of flow rate. It has been also
reported that in the case of the plates having the same flow
areas (78.58 mm2), the conversion for the plate 1 (25 holes of
2-mm diameter) which has a larger value of α (ratio of total
perimeter of holes to total area of opening) is more as
compared to plate 2 (1 hole of 10-mm diameter) which has the
lower value of α at constant (1.5 bar) pressure. A higher value
of α (by increasing number and minimizing diameter of holes)
increases the cavity generating spots (i.e., shear layer area) and
frequency of turbulence (i.e., energy released per cavity)
resulting in reduced mass transfer resistance due to the
generation of better degree of emulsification. In the case of
plates having the same value of β, i.e. ratio of diameter of hole
to pipe diameter, the conversion is higher for plate 4 (20 holes
of 3-mm diameter) having more holes as compared to plate 3
(16 holes of 3-mm diameter) having fewer holes at constant
inlet pressure. This is because as number of holes increases,
total perimeter increases resulting in larger shear area being
available in the system which leads to better conversion due to
higher cavitational effects. Overall, it has been reported that a
hydrodynamic cavitation reactor gives more than 95%
conversion in 10 min of operation time whereas the
conventional stirred reactor gives only 60% of conversion in
60 min of operation. Thus, the microlevel turbulence of high
intensity generated by cavitating bubbles in hydrodynamic
cavitation reactor is very effective in eliminating the mass
transfer resistance of the reaction. The oscillation of cavitation
bubbles provides more interfacial area for mass transfer and
their sudden collapse generates the high intensity turbulence in
flowing liquid, enhancing rates of transport processes and hence
higher conversion is obtained as compared to the conventional
stirred reactor.
Since the energy required for biodiesel production represents
a significant part of the overall energy input, the use of
ultrasonic reactors with better performance than currently
employed reactors can reduce the production cost, enhancing
the chances for large-scale commercialization of biodiesel
production.49 Sonochemical reactor design depends on the
objective of obtaining maximum and uniform spatial distribu-
tion of cavitational activity with possibly continuous mode of
operation. Typically, on a larger scale of operation, it will be a
requirement that multiple transducers will have to be used
considering the local nature of cavitational events. Typically,
flow cell types of arrangements are more suitable for large scale
operation as this definitely gives flexibility in terms of the
continuous operation and also gives an option of arranging the
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Industrial & Engineering Chemistry Research
transducers on the wall of the reactor on opposite faces so that
standing wave patterns can be generated. Typically, hexagonal
or rectangular cross sections have been reported to yield
excellent distribution of the cavitational activity and are
recommended for large-scale operation.39 The number and
location of the transducers also affects the hydrodynamic
behavior and the mixing characteristics in the reactor which can
be of prime importance especially for biodiesel synthesis, which
is limited by mass transfer. While maintaining the geometric
similarity for the design of large-scale sonochemical reactors, it
is also important to maintain similar conditions of hydro-
dynamics and mixing characteristics in the reactor so as to
achieve the desired objectives.
6.2. Microwave Reactors. In the case of microwave-
assisted transesterification, use of microwave irradiation helps in
transferring the energy directly to the reactants and accelerates
the rate of chemical reactions, reducing the reaction time from
hours to minutes or even a few seconds in some cases.
Microwaves are basically electromagnetic waves propagating
between 300 MHz and 300 GHz containing electric and
magnetic components and acting perpendicularly to each other
and also to the direction of propagation. In microwave, the
electric component is responsible for heating. Microwaves are
between radio waves and infrared radiations with wavelengths
in the range of about 1 mm to 1 m.50
Heat transfer in the case of conventional heating occurs via
conduction and radiation from the source and via conduction
and convection within the material. This has significant
drawbacks due to the dependency on the thermal conductivity
of materials, specific heat, and density.51 Apart from that,
conventional heating is rather slow and heat is not distributed
uniformly in a reaction vessel, resulting in a higher energy (than
the theoretical value) requirement for a particular chemical
reaction.52 Microwaves can interact directly with a sample
matrix by two mechanisms, viz. dipolar rotation and ionic
conduction. When exposed to microwave frequencies, dipoles
in the sample align themselves in the direction of applied
electric field. As the electric field rapidly oscillates, the dipole
tries to rapidly realign to the electric field via rotation. Heat is
generated by the frictional forces between the randomly
rotating polar molecules and the surrounding media. In ionic
conduction, the dissolved charged particles oscillate back and
forth under the influence of applied microwave field. When the
electric field direction changes, the larger ions dissipate their
kinetic energy as heat as they slow down and change direction
via friction at molecular levels. Both mechanisms contribute to
localized superheating leading to high temperature and pressure
gradients.53
In the transesterification process, the mixture contains
vegetable oil or fatty acid and alcohol which have polar and
ionic components and hence microwave irradiation can play an
active role in heating the reactants to the required temperature
quickly and efficiently.54
Several reports concerning the usage of microwave
irradiation in transesterification are available in recent years
and some of them use waste vegetable oil as reaction feed stock.
Barnard et al.54 studied the continuous-flow preparation of
biodiesel from used vegetable oil using a commercially available
multimode microwave apparatus consisting of a continuous
microwave power delivery system with an operator-selectable
power output from 0 to 1600 W. Experiments were carried out
using 2 and 4 L reaction vessels at flow rates of up to 7.2 L/min
of methanol and a 1:6 molar ratio of oil/alcohol. Energy
14618
Review
consumption calculations suggest that the continuous-flow
microwave methodology for the transesterification reaction is
more energy-efficient than using a conventional heated
apparatus. Quantitatively, the microwave process has an energy
requirement of 26.0 kJ/L of biodiesel as compared to 94.2 kJ/L
required for the conventional mode of heating. Similarly,
Lertsathapornsuk et al.37 investigated microwave (modified
800-W kitchen microwave oven) assisted continuous biodiesel
production (Figure 6) from waste frying palm oil and also
Figure 6. Schematic diagram of continuous microwave reactor.37
evaluated its performance in a 100-kW diesel generator. It has
been reported that continuous conversion of waste frying palm
oil to ethyl ester was 97% at ethanol to oil molar ratio of 12:1
with catalyst loading of 3.0% NaOH (in ethanol) and 30 s
residence time. Also, the energy consumption for microwave-
assisted continuous transesterification process was about 269
kJ/L, while the energy consumption for conventional heating
process was 799 kJ/L. Engine efficiency of a 100-kW diesel
generator powered by biodiesel (B100) (without any
modification of the engine) was 0.26 ± 0.03% lower than
that powered by conventional diesel, while the specific fuel
consumption was 12.73 ± 0.03% higher. Hydrocarbons and
carbon monoxide emissions were decreased by 25.11 ± 0.03%
and 17.96 ± 0.12%, respectively.
Yaakob et al.55 investigated the effect of transesterification
reaction parameters such as quantity of the catalyst, reaction
temperature, and time on the biodiesel yield and purity from
waste frying palm oil using microwave operated at power and
frequency of 1250 W and 2.45 GHz, respectively. The obtained
results indicate that the maximum yield (88.63%) and purity
(99.45%) of biodiesel was observed with the optimized process
parameters as reaction temperature of 65 °C, time of 7 min,
and catalyst concentration as 1% by weight.
In another work,56 ethyl esters were produced from a feed
material of esterified crude palm oil (CPO) with 1.7 wt % of
free fatty acid content using microwave heating (Sharp model
R235 compact microwave oven working at 2.45 GHz with a
power of 800 W). It was found that transesterification process
using microwave heating resulted in a yield of 85% and its fuel
properties were within the limits prescribed by American
standards at optimum conditions of molar ratio of oil to ethanol
as 1:8.5, 1.5 wt %/wt KOH/oil as a catalyst loading, reaction
time of 5 min, and microwave power of 70 W. Koberg et al.57
carried out transesterification of used cooking oil to biodiesel,
based on microwave dielectric irradiation as a driving force for
the transesterification reaction in the presence of SrO as a
catalyst. The transesterification was carried out with and
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Industrial & Engineering Chemistry Research
without magnetic stirring. It has been reported that 99.8%
conversion of used cooking oil is obtained under MW
irradiation of 1100 W output with magnetic stirring in only
10 s.
Refaat et al.58 studied the performance of transesterification
process carried out by conventional and microwave techniques
(using a microwave oven with output microwave power up to
1200 W, controlled via microprocessor) for the production of
biodiesel from waste cooking oil and investigated the effects of
reaction time, separation time, and yield. They reported that
microwave-assisted transesterification showed optimum per-
formance at a temperature of 65 °C, a methanol/oil molar ratio
of 6:1, and potassium hydroxide loading as 1%. The application
of radio frequency microwave energy decreased the reaction
time from 60 to 2 min and separation time from 480 to 30 min
and increased yield from 96% to 100% as compared to the
conventional technique for biodiesel production.
Chen et al.59 have also compared the yield of biodiesel from
waste cooking oil using microwave and conventional heating
source in the presence of sodium methoxide as catalyst and the
important results have been given in Table 5. The maximum
Table 5. Comparison of Biodiesel Yields from Waste
Cooking Oil under Conventional Heating and Microwave
Heating Systems59
method reaction time (min) yield (%)
conventional heating 30 86.3
45 91.5
60 93.4
75 94.2
90 96.6
microwave heating 1 94.6
2 95.8
3 97.9
4 96.6
5 92.7
yields of biodiesel from waste cooking oil under conventional
heating and microwave heating were 96.6% and 97.5%,
respectively. Microwave-assisted heating causes direct absorp-
tion of the radiation by the OH group of the reactant which
produces a volumetrically distributed heat source within the
system. The OH group is directly excited by the microwave
radiation, causing the increase in the local temperature around
the OH group to be much higher than that of the activation
energy needed for the transesterification. This results in
microwave heating giving a significantly higher yield of
biodiesel in shorter reaction time compared to conventional
heating.
To summarize, use of microwaves can give significant
intensification as compared to the traditional methods for
transesterification of waste cooking oil, allowing better yields
and conversions into biodiesel in a short time and,
consequently, less energy consumption as compared to the
conventional heating systems. Also, microwave irradiation
requires no stirring and cooling facility and hence also reduces
volatilization of alcohol. It is also reported that use of
continuous-flow microwave methodology for the transester-
ification reaction gives a more energy-efficient process than
using a conventional heating apparatus. One of the major
drawbacks associated with microwave synthesis is that scale-up
of the system from laboratory scale operation to industrial scale
14619
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production is not easy. The most significant limitation for the
scale-up of this technology is the penetration depth of
microwave radiation into the absorbing materials, which is
only a few centimeters, depending on their dielectric properties.
The safety aspect is another reason for not having ready
acceptability of microwave reactors in industry.
6.3. Oscillatory Flow Reactors. The oscillatory flow
reactor (OFR) is a novel type of continuous flow reactor
consisting of a tube containing equally spaced orifice plate
baffles where the oscillations are applied in an axial direction
within the tube. There is a net flow through the reactor, but
superimposed upon this, usually by reciprocating pistons at
either end of the reactor, is an oscillatory motion, which is
relatively large compared to the net flow. In OFR, mixing due
to the oscillating motion of liquid intensifies the process by
improving mixing as well as other transport properties, such as
heat transfer,60 mass transfer,61 plug flow type residence time
distribution,62 and multiphase suspensions.63 When a bulk fluid
is introduced into the OFR, radial mixing is enhanced due to
the oscillatory motion. The interaction of the orifice plate with
the oscillating fluid causes periodic creation and destruction of
toroidal vortices above and below each baffle plate. These
represent extremely efficient mixing patterns, which also result
in significant enhancements in the mass and heat transfer.
When there are enough plates in series, the overall residence
time distribution is close to that of plug flow. Unlike
conventional plug flow reactors in which the plug flow is
caused by net flow, the plug flow achieved in an oscillatory flow
reactor is due to long residence times because the degree of
mixing is not directly dependent upon the Reynolds number of
the bulk flow through it, but is mainly related to the oscillatory
conditions. This offers the oscillatory flow reactor an important
process intensification approach as it allows “long” (e.g., greater
than 15 min) reactions to be performed in a plug flow reactor
of relatively small length-to-diameter ratio.64 The shear rates in
such reactors have been shown to be very uniform and the
radial and axial velocities are very similar. Hence the oscillatory
flow reactor can be designed with a short length-to-diameter
ratio to improve the economy of biodiesel production due to
smaller “footprint”, lower capital and pumping costs, and easier
control.
Harvey et al.65 conducted alkaline transesterification of waste
cooking oil and pure rapeseed oil in a continuous oscillatory
flow reactor (OFR) to produce biodiesel in a pilot-scale plant.
The reaction was performed at a temperature of 20−70 °C,
residence time of 10−30 min, and molar ratio of methanol to
oil was maintained at 1.5:1. Reaction samples were analyzed for
cetane number and glycerides to investigate the effect of
temperature and residence time on the conversion. It has been
reported that a residence time of 10 min at 50 °C does not
produce the required conversion, as unreacted triglyceride
remains in the product, and the level of diglyceride is high. It
was found that up to 99% conversion of biodiesel was achieved
after 30 min at 50 °C. Thus, cetane numbers can be seen to
increase with increasing residence time and temperature,
attributed to the fact that the degree of conversion increases
with these parameters. An in-depth study on OFR in
transesterification with heterogeneous catalyst is definitely
needed as OFR is ideal for suspending solid catalysts or
polymer-supported catalysts. One of the advantages of this
technology is the low molar ratio of methanol to oil used in this
technology, reducing the operating cost significantly. This can
be attributed to reduced backmixing overcoming the
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Industrial & Engineering Chemistry Research
equilibrium limitations to a larger extent. The short length-to-
diameter ratio of this reactor also results in decreased capital
costs. The OFR allows these processes to be converted to
continuous, thereby intensifying the process. Conversion to
continuous processing should improve the economics of the
process, as the improved mixing should generate a better
product (rendering the downstream separation processes
easier), at lower residence time (reduction in reactor volume).
These improvements can decrease the price of biodiesel,
possibly making it a more realistic competitor to fossil diesel.
Skelton et al.64 also studied the development of the
oscillatory flow based process for the production of biodiesel
from used cooking oil. The synthesis of biodiesel was carried
out in a jacketed 25-mm oscillatory flow reactor with a loop
length of about 3 m. The processing rate was 3 L per hour at a
residence time of 30 min. In the actual process, used
commercial cooking oil and methanol are preheated and fed
to the loop by metering pumps and temperature is held
constant by a hot oil filled jacket. The apparatus can operate at
pressures of up to 3 bar g. The product is depressurized and fed
to a simple vertical gravity separator with a glass wool
coalescence pack. The biodiesel phase then passes to a simple
OFR based washing column with settling sections for product
and wash water at the top and bottom, respectively. From
there, the product passes through a sand-packed coalescer
followed by drying in a salt column. To give a reasonable scale-
up from the existing apparatus, processing rates between 20 and
30 L/h should be used. While a bigger ratio can be desirable for
design purposes it was not considered practicable for
operational reasons. Finally, it has been reported that oscillatory
flow mixing technology is well suited for the production of
biodiesel from used commercial cooking oil.
6.4. Microchannel Reactors. Microreactors and micro-
mixers have gained considerable attention, especially in
chemical processes because of their higher transport rates,
safer environment for highly exothermic or explosive chemical
reactions, compact design, and simpler process control.
Microchannel reactors are compact reactors that have channels
with diameters in the micro range (typical dimensions of
microchannel are in the range of 10−500 μm). Reducing
dimensions of the reaction system increases the surface to
volume ratio of microreactors (microchannel: 10 000−50 000
m2/m3; laboratory vessel: 1000 m2/m3; and production vessel:
100 m2/m3) which result in high mass and heat transfer.66 Heat
transfer coefficients measured in microreactors have been
reported to be a maximum of 25 000 W/(m2 K).67 Besides that,
microreactors provide excellent mass and heat transfer, shorter
residence time, and smaller amounts of reagents, catalyst, and
waste products compared to that of macroscale reactors. Also,
microreactors are lightweight with compact system design,
laminar flow, effective mixing, short molecular diffusion
distance, better process control, and small energy consump-
tion.67,68
Jovanovich et al.69 filed a patent on embodiments of methods
for using a microreactor to produce biodiesel. Tranesterification
can be carried out between oil (which includes soy, inedible
tallow and grease, corn, edible tallow and lard, cotton, rapeseed,
sunflower, canola, peanut, safflower, and combinations of
thereof) and alcohol (typically lower aliphatic which includes
methanol, ethanol, amyl alcohol, or combinations thereof) in
the presence of catalyst (such as metal oxides, metal hydroxides,
metal carbonates, alcoholic metal carbonates, alkoxides, mineral
acids, and enzymes). It has been reported that oil conversion to
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biodiesel typically increases with increasing mean residence
time in the microreactor. While the claims of the patents
cannot be verified, use of microreactors certainly offers one of
the process intensification approaches. Recently, KOH-
catalyzed synthesis of biodiesel has been investigated in
capillary microreactors, with unrefined rapeseed oil and
cottonseed oil as raw materials.70 The influence of the
methanol to oil molar ratio, the residence time, the catalyst
concentration, the reaction temperature, and the dimension of
the capillary (ID 0.25 or 0.53 mm) on the production of
biodiesel has been investigated. It has been reported that the
yield of methyl esters is 99.4% at the residence time of 5.89 min
with KOH concentration of 1% and methanol to oil molar ratio
of 6:1 at 60 °C in capillary microreactor with inner diameter of
0.25 mm. The authors also observed that the reaction
temperature was not an important factor influencing the yield
of methyl ester but the inner diameter of the microchannel
reactor had a strong influence on the transesterification reaction
because mass transfer area in a microreactor with a smaller
dimension is much larger than that with a larger dimension.
Thus, it could be concluded that higher methyl ester yield is
obtained at even shorter residence time for the microchannel
reactor with the smaller inner diameter. Though no study with
waste cooking oil was observed, credence to the results can be
obtained based on these results with virgin vegetable oil.
A microreactor having a single microchannel might be used
to make biodiesel at laboratory scale, but increasing output
especially at commercial scale, may require using devices having
plural microchannels, plural microreactors, or both.69 During
scale-up, conventional reactors requires plant designers to
increase the size of each reactor unit. This makes scale-up
expensive, time-consuming, and sometimes extremely difficult.
In contrast, the microchannel reactors can be shop-fabricated,
and the microchannel-based plants can be constructed more
quickly and easily with guarantees that desired features of basic
unit will remain unchanged while increasing the total system
capacity. Also, in a microreactor plant, continuous operation is
uninterrupted with the replacement of the failed microreactor,
while the other parallel units continue production.66
Different types of microstructured mixers with various
operating principles and parameters have been designed and
successfully applied in microreactor technology for biodiesel
production. The modifications are used to decrease diffusion
lengths and to increase interfacial area between phases in
microchannel. Guari et al.71 studied transesterification of
sunflower oil to produce biodiesel using T-type (inner diameter
1 mm; length 160 mm) microstructured mixer. It has been
reported that residence time of 112 s is required for complete
conversion of sunflower oil to biodiesel. Wen et al.72 used
zigzag type microstructured mixer for continuous alkali-based
biodiesel production from sunflower oil. This type of reactor
was shown to intensify the biodiesel production process by
obtaining smaller droplets compared to that of T- or Y-type
microstructured mixer. It has been reported that 99.5% yield of
biodiesel is obtained in residence time of 25 s using optimized
zigzag type microstructured reactor.
Sun et al.73 developed a two-step process for fast acid-
catalyzed biodiesel production from high acid value oil in a
microstructured reactor, which was assembled with a micro-
mixer and connected with a 0.6-mm ID stainless steel capillary.
Esterification of oleic acid with methanol was carried out to find
suitable reaction conditions. In the first step of esterification, it
has been reported that the oleic acid conversion was reduced
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Industrial & Engineering Chemistry Research
significantly from 99.1 to 10.4% with an increase in the water
content from 0.01 to 5 wt % (Table 6), since the presence of
Table 6. Effect of Water Content on Oleic Acid
Conversiona73
water content (%) oleic acid conversion (%)
0.01 99.1
0.5 90.3
1 75.4
2 55.8
5 10.4
a
Reactions were carried out with a methanol to oleic acid molar ratio
of 30, and a catalyst concentration of 3 wt % at 100 °C in 5 min.
more water leads to a movement of the reaction equilibrium in
the reverse direction and loss in acid strength of catalytic
protons. The acid value of the oil was reduced from 160 to 1.1
mg KOH/g with methanol to acid molar ratio of 30:1, H2SO4
concentration of 3 wt %, and residence time of 7 min at 100 °C
in the first step. The final FAME yield reached 99.5% with a
methanol to triglyceride molar ratio of 20:1, H 2 SO 4
concentration of 3 wt %, and residence time of 5 min at 120
°C in the second step. Finally, they concluded that biodiesel
production from high acid value oil can be continuously
achieved with high yields by acid-catalyzed transesterification in
microstructured reactors with total reaction times of less than
15 min.
6.5. Cosolvent. Biodiesel can be produced through
transesterification reaction74 in which vegetable oils or animal
fats react with short chain alcohol (e.g., methanol). The
transesterification reaction can be either catalytic or non-
catalytic, but these processes are relatively time-consuming to
drive the reaction toward completion. This is because of lower
solubility of the reactant (i.e., oil in alcohol) used in
transesterification reaction causing mass transfer limitation,
especially at the initial phases of the reaction. Cosolvent plays
an important role in transesterification process in increasing the
yield of biodiesel production. Different cosolvents can be used
to accelerate transesterification reaction such as hexane,
heptane, ether, cyclohexane, CO2, diethyl ether, toluene,
propane, and tetrahydrofuran (THF) which can improve the
mass transfer rate between oil and alcohol phase.75−77
Introducing a cosolvent into the transesterification process
changes the reaction mixture from a two-phase system to a
single-phase system due to an increase in the mutual solubility
of alcohol and vegetable oil at low reaction temperatures, based
on the concept “like to dissolve like”. The cosolvents form
hydrogen bonds with polar compounds (such as alcohols), and
also contain sufficient nonpolar hydrocarbon groups to dissolve
the high molecular weight oils and fats.78 The mass transfer in
the one-phase reaction is superior to that in the two-phase
reaction, due to an increase in the contact surface, and hence
production of biodiesel can be intensified by the addition of
cosolvent into transesterification process.
Presence of cosolvent also helps to separate the phases
(biodiesel and glycerol) more easily. The separation of the
glycerol-rich phase is faster than in the cosolvent-free system.
Besides, when hexane is used as a cosolvent, the formation of
soap is significantly reduced.77 It was also indicated that the
addition of cosolvent could improve both supercritical and
subcritical methanol transesterification because the use of
cosolvents can decrease the critical point of the reaction
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mixture and allow the reaction to be carried out under milder
conditions, enhancing the mutual solubility of the oil−alcohol
mixture, reducing the transport limitations, and increasing the
reaction rates.79 However, the primary concerns with this
method are the additional complexity of recovering and
recycling the cosolvent, although this can be simplified by
choosing a cosolvent with a boiling point near that of the
alcohol being used.
Park et al.78 investigated the feasibility of fatty acid methyl
ester (FAME) as a cosolvent to increase the mass transfer
between soybean oil and methanol. The influence of the initial
addition of 0, 5, and 10 wt % of FAME to oil on the FAME
production rate was studied. It has been reported that as the
amount of FAME added was increased, the time required for
the formation of the single-phase system decreased due to the
increase in the miscibility of oil in methanol. It has been
concluded that introduction of FAME as a cosolvent increases
the reaction rate. Thus the production rate of biodiesel can be
improved by recycling a portion of FAME as cosolvent into the
reaction mixture of transesterification process.
Li et al.80 studied the effect of pure organic (which include
polar and nonpolar) and cosolvent (mixture of strong and weak
hydrophobic solvent) on the yield of biodiesel preparation
catalyzed by lipase. It has been reported that polar organic
solvents deprive the lipase molecules of their essential water
thus deactivating the biocatalyst and making it unable to be
reused. In the case of hydrophobic solvents, good dissolution
occur between two substrates to accelerate the rate of reaction,
but hydrophobic solvents dissolve little methanol, and excessive
insoluble methanol deactivates the lipase significantly. It was
observed that the biodiesel yields were higher in the presence of
cosolvent as compared to other pure organic solvents. This is
because cosolvent medium can dissolve both methanol and
glycerol to eliminate the negative effects thoroughly. There was
practically no loss in the activity of lipase even after being
recycled 30 times.
Solid acid catalysts are normally used to catalyze the
transesterification of oil with high free fatty acid to biodiesel.
Lam et al.81 used biodiesel itself as cosolvent for the
transesterification reaction of waste cooking oil with methanol
catalyzed by SO2− 4 /SnO2SiO2 (solid acid catalyst). It was
found that with the use of biodiesel as a cosolvent, a high
FAME yield of 88.2% (almost 30% higher than without using
cosolvent) can be obtained in a shorter reaction time (1.5 h).
In the case of a homogeneous base catalyst, such as KOH,
the addition of a cosolvent to the reaction mixture can enhance
the reaction rate, due to the promotion of diffusion by
homogenization. However, the FAME yields decreased to some
extent after the addition of either a liquid cosolvent (THF) or a
gas cosolvent (DME) when using a heterogeneous catalyst in
the transesterification of waste cooking oil.82 In the presence of
heterogeneous catalysts, the glycerol drops formed in the
homogeneous reaction mixture readily adhere to the catalyst
particles, causing them to agglomerate. As a result at the end of
the reaction, the agglomerated catalyst particles adhered to
glycerol were found to be deposited on the reactor wall and
were found to be deactivated as a result of agglomeration.
Similarly, Sabudak et al.83 used tetrahydrofuran (THF) as
cosolvent in transesterification reaction of waste frying oil and
reported that the highest yield obtained was 90%. From an
economic point of view, they conclude that the use of THF in
transesterification of biodiesel production is not feasible as
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Scheme 2Hydrolysis (eq 5) and esterification (eq 6) reactions.
THF is applied mainly to increase the solubility of methanol in
oil.
6.6. Supercritical Transesterification Process. Super-
critical fluid transesterification can be considered an an
interesting alternative to the conventional approach (acid- or
alkali-catalyzed) since it can be conducted without using any
catalyst, avoiding the complications of purification in the
downstream processing. In the case of a supercritical fluid
process, the reactor pressure and temperature are manipulated
to influence the thermophysical properties of solvent
(methanol), such as dielectric constant, viscosity, specific
gravity, and polarity. Liquid methanol is a polar solvent and
has hydrogen bonding between the hydroxide oxygen and the
hydroxide hydrogen to form methanol clusters. In supercritical
methanol, with increasing temperature, the degree of hydrogen
bonding decreases resulting in a reduction in the polarity of
methanol, which in turn increases the solubility of oil in
methanol. Because of the hydrophobic nature of nonpolar
triglycerides, they are well-solvated in supercritical methanol to
form a single phase oil/methanol mixture. The higher solubility
of oil in methanol increases the rate of formation of methyl
esters dramatically in the supercritical state. The ionic product,
which is an important parameter for chemical reactions, can
also be improved by increasing the pressure. Therefore, in the
supercritical methanol treatment of vegetable oil, methanol not
only acts as a solvent but also as an acid catalyst, thereby
avoiding the requirement of any external catalyst.
Among all the supercritical alcohols (methanol, ethanol, 1-
propanol, 1-butanol, 1-octanol), it has been reported that the
rate of transesterification is maximum when supercritical
methanol is used.84 The supercritical methanol method is
determined to be more water-tolerant than the conventional
method using an alkaline catalyst. Tan et al.85 studied the
transesterification process under supercritical method in
presence of water in oil. It has been reported that yield of
biodiesel in supercritical methanol is positively affected by the
presence of water in oil. The yield increases steadily with
increasing amount of water content. This observation can be
best explained by a two-step process, as shown in eqs 5 and 6 in
Scheme 2, which consists of hydrolysis and esterification
reactions, respectively, instead of conventional transesterifica-
tion reaction between triglycerides.
In supercritical methanol reaction, the presence of water in
the reaction mixture induces the hydrolysis of triglycerides,
which produces FFA and glycerol, and subsequently leads to
the former being esterified with methanol to produce FAME
and water. Overall the yield increases steadily as simultaneous
reactions of transesterification, hydrolysis, and esterification
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take place in the supercritical conditions. Tan et al.86 utilized
waste palm cooking oil as the source of triglycerides for
biodiesel production using supercritical methanol. The effect of
different parameters that influence the reaction, including
reaction time (5−25 min), temperature (300−380 °C) and the
molar ratio of alcohol to oil (20:1−60:1), were investigated.
Results show that 80% yield was obtained under optimum
conditions (reaction time 20 min, temperature 350 °C, and
molar ratio 40:1) using low-cost oils as a feedstock. It has been
reported that the total production costs of biodiesel can be
reduced significantly through the supercritical methanol
process, provided heat integration is adapted in the process.
Demirbas et al.87compared the effects of alkali-catalyzed and
supercritical methanol transesterification of waste cooking oil
and reported that supercritical transesterification offers great
advantage over alkali-catalyzed transesterification to eliminate
the pretreatment and operating costs.
Conversion of waste cooking oil to biodiesel has been
studied by Patil et al.88 using ferric sulfate and supercritical
methanol processes. This process resulted in a feedstock to
biodiesel conversion yield of about 85−96% in a reaction time
of 2 h using a ferric sulfate catalyst, and 50−65% in only 15 min
of reaction time using supercritical methanol transesterification
method. The results revealed that the supercritical method is
probably a promising alternative method to the traditional two-
step transesterification process using a ferric sulfate catalyst for
waste cooking oil conversion.
A conceptual design for supercritical transesterification
process for continuous biodiesel production from waste
cooking oil has been reported by Van Kasteren and Nisworo89
for three plant capacities (125 000, 80 000, and 8000 TPA). It
has been concluded that biodiesel by supercritical trans-
esterification can be scaled up resulting in high purity of
methyl esters (99.8%) and almost pure glycerol (96.4%)
attained as byproduct with added advantages of elimination of
pretreatment related capital and operating costs.
Campanelli et al.90 used methyl acetate instead of methanol
for supercritical synthesis of glycerol-free biodiesel from edible,
nonedible, and waste cooking oils. The results demonstrate that
the oil composition does not significantly influence the
biodiesel yield because all the oils achieved complete
conversion after 50 min at 345 °C, 20 MPa with methyl
acetate:oil molar ratio equal to 42:1.
Anitescu et al.91 studied the volatility of biodiesel fuel
samples produced by supercritical transesterification of
triglyceride feedstock of chicken fat using the advanced
distillation curve method. They reported that biodiesel fuels
produced by supercritical transesterification at ∼400 °C exhibit
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Industrial & Engineering Chemistry Research
higher overall volatility and cetane number when compared to
commercial biodiesel samples produced by conventional
catalytic transesterification. This is attributed to the fact that
high temperatures (∼ 400 °C) of the supercritical trans-
esterification process partially decomposed the polyunsaturated
fatty acid methyl esters (FAMEs) to lower molecular FAMEs
(∼C6−C15) and ∼C10−C17 hydrocarbons. These lighter fuel
components shifted the first portion of the distillation curve
towards petrodiesel.
As compared to base-catalyzed transesterification, super-
critical methanol transesterification has the following advan-
tages: (a) no catalyst requirement; (b) no sensitivity to either
water and free fatty acid; and (c) free fatty acids in the waste
cooking oil are esterified simultaneously. However, the
supercritical technology suffers from certain drawbacks
including the requirement of high temperature (350 °C) and
high pressure (45 MPa). In addition, this method requires a
large amount of methanol (1:42 molar ratio of oil to alcohol).
In presence of substantial quantity of fatty acid, the material of
construction could also be an issue at these extreme operating
conditions.
6.7. Comparison of Process-Intensifying Technology
for Biodiesel Production from Waste Cooking Oil.
Different process intensification techniques for biodiesel
synthesis from transesterification reaction have been discussed
in the earlier sections based on the working principle, reactor
details, operating parameters, and yields in comparison with the
conventional technique. Now the comparative analysis of the
different process-intensifying techniques has been performed
based on advantages and limitations for its use for biodiesel
production using transesterification reactions.
The use of cavitational reactors in transesterification reaction
is not only efficient and time saving but also economically
viable as it requires a low quantity of catalyst and only one-third
to half of the energy that is consumed by mechanical agitation.
Use of sonochemical reactors has proved to be efficient, giving
biodiesel yield up to 98−99% and resulting in substantial time
and energy saving (dramatic reduction in reaction time
accompanied by a simultaneous reduction in static separation
time). Sonochemical reactors suffer from disadvantages of scale-
up and inefficient operation at large scale. The alternate mode
of generating cavitating conditions, i.e. hydrodynamic cavita-
tion, is the phenomenon where cavities are created due to
pressure reduction by passing liquid through a constriction
(orifice plate or venturi) and this has been found to give higher
conversion and cavitational yields (quantum of product per unit
energy supplied into the reactor) as compared to the acoustic
cavitation. It has been reported that conversion for the
transesterification of waste frying oil using acoustic cavitation
was 85% after 40 min of the reaction time at optimized
conditions which is less than the conversion obtained using
hydrodynamic cavitation reactor, i.e. more than 95% within 10
min.48 The cavitational yield has also been reported to be
higher (about 10−15 times) for hydrodynamic mode of
cavitation (1.53 × 10−4 to 3.1 × 10−4 g/J) as compared to
the acoustic mode of cavitation (1.33 × 10−5 to 5.33 × 10−5 g/
J) for biodiesel production through transesterification reac-
tion.92 It has been established that hydrodynamic cavitation is
about 40 times more efficient than acoustic cavitation and 160−
400 times more efficient than the conventional agitation/
heating/refluxing method. The scale-up of hydrodynamic
cavitation reactors also appears to be easy considering the
fact that lot of information is available on the turbulence
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characteristics downstream of the constrictions in the fluid flow
and the only energy dissipating device in the hydrodynamic
cavitation reactor configuration is the pump used for the
recirculation of the reaction mixture.93
In the case of microwave-assisted transesterification, use of
microwave irradiation helps in transferring the energy directly
to the reactants and accelerates the rate of transesterification
reactions, reducing the reaction time from hours to minutes.
Microwave energy offers numerous potential processing
advantages over the conventional heating methods to provide
a rapid and volumetric heating to an absorbing medium.
Microwaves can interact directly with a sample matrix by two
mechanisms viz. dipolar rotation and ionic conduction. Both
mechanisms contribute to localized superheating leading to
high temperature and pressure gradients. Energy consumption
calculations suggest that transesterification reaction assisted
with microwave methodology is more energy-efficient than
using a conventional heating apparatus. Quantitatively, the
microwave process has an energy requirement of 26.0 kJ/L of
biodiesel as compared to 94.2 kJ/L required for the
conventional mode of heating.54 However, the use of
microwaves to produce products at a large scale is a challenging
problem. A few studies on continuous reactions under the
influence of microwave irradiation have been successful but a
perennial problem in the manufacturing of microwave systems
is the difficulty to obtain hybrid devices that incorporate
distinct materials with different functionalities. In most of the
cases, cumbersome prototyping and high investment needed
for manufacturing are additional problems that add to the cost
of the final product. Exposure to high levels of microwave
radiation is also known to cause health problems including
cataracts and burns, according to the National Health and
Medical Research Council. The thermal effect is almost
instantaneous at the molecular level. This effect, however, is
limited to a small area near the surface of the dielectric material
because microwaves have a penetration depth which depends
on the polarity of the compound and are completely absorbed
at the boundary. Hence, there are also possibilities of formation
of localized hot spots due to uneven heating. It is, therefore,
essential that such reactions are studied in controlled
conditions of microwave energy supply. This is an important
factor for scaling up the reactors for large-scale applications.
The oscillatory flow reactor contains combination of the
baffles and the oscillatory motion which provide uniform
mixing by the formation of periodic vortices in the bulk fluid,
resulting in a remarkable increase in mass and heat transfer,
while maintaining plug flow. The enhanced mass transfer makes
such a reactor highly advantageous when applied to reactions
having mass-transfer and equilibrium limitations such as
transesterification reaction. Mass transfer limitations in the
two-phase biodiesel production can be eliminated if effective
mixing methodologies are applied to increase interfacial area by
deformation, break-up, and redispersion of droplets into a
continuous phase. Similarly reduced backmixing allows the
equilibrium limitations to be partially overcome. One of the
advantages of using oscillatory flow reactor is that the fluid
mechanics are controllable by oscillation conditions (frequency
and amplitude) and independent of net flow Reynolds number.
In the case of tubular continuous reactor the residence time and
net mass flow rate are optimized, which in turn optimizes
mixing conditions (i.e., fluid turbulence). On the other hand, in
the case of oscillatory flow reactor the residence time and plug
flow performance are optimized with the help of oscillations
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Industrial & Engineering Chemistry Research
hence heat and mass transfer are totally independent of the net
mass flow rate through the tubes; this means that ideal mixing
conditions can be achieved at very low net mass flow rates. A
wider range of operating conditions and residence times can be
achieved (high turn-up or turn-down ratios) also maintaining a
very small footprint and high throughputs. Oscillatory flow
reactor can be applied to both batch and continuous
transesterification of waste cooking oil for biodiesel production.
The cost of maintenance of oscillatory flow reactor is high due
to presence of moving parts such as oscillatory baffles.
Microreactors are usually defined as miniaturized reaction
vessels fabricated, at least partially, by methods of micro-
technology and precision engineering. Microchannel reactors
have high volume/surface ratio, short diffusion distance
requirement for the reactants, laminar flow, effective mixing,
fast response time, easy integration, and small footprint, which
are ideal for portable power. In addition, enhanced mass and
heat transport properties are also widely recognized as
advantages of microreactors. These characteristics have been
advantageously used in biodiesel production from waste
cooking oil at milder conditions. Recently, the yield of methyl
esters of 99.4% was obtained at the residence time of 5.89 min
with KOH concentration of 1% and methanol to oil molar ratio
of 6 at 60 °C carried out in capillary microreactor.70 A major
disadvantage of using microreactors for the biodiesel synthesis
is that for the required volumes of biodiesel (bulk chemicals),
the capital costs are expected to be significantly higher as
compared to the other process intensification approaches.
Another problem that may occur in a microchannel reactor
when used for transesterification reaction is the clogging of
microchannels by either contaminants present in reaction
media or formation of small quantity of soap. In case of
clogging, the flow distribution inside the microreactor changes
and cannot guarantee the adequate transport of the product.
Mechanical pumping may generate a pulsating flow which can
be another disadvantage in the use of microchannel reactor for
transesterification reaction.
The noncatalyst options for transesterification are designed
to overcome the reaction initiation lag time caused by poor
methanol and oil miscibility. Introducing a cosolvent into the
transesterification process changes the reaction mixture from a
two-phase system to a single-phase system due to increase in
the mutual solubility of alcohol and vegetable oil at low reaction
temperatures. This is in agreement with a kinetic study that
clearly indicates that the reaction rate constant for trans-
esterification increases significantly when the cosolvent is
added.78 The presence of cosolvent helps to separate the phases
(biodiesel and glycerol) more easily. However, a disadvantage
of the use of cosolvent is that it must be separated from the
final product after the completion of the reaction. Although it
can be distilled together with methanol, further separation
between methanol and cosolvent is difficult since they have
similar boiling points. It should be noted that methanol is
normally purified before it can be recycled for subsequent
transesterification reaction. So this factor creates a big
economical barrier as the cost of separation of methanol and
the cosolvent is significant and it translates into additional
production cost while the residual solvent in the biodiesel
product can affect the compliance with the international
standards.
Tranesterification reaction of waste cooking oil by super-
critical methanol for biodiesel production has some advantages
which include (a) glycerides and free fatty acids are reacted
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with equivalent rates; (b) the homogeneous phase eliminates
diffusion problems; (c) the process tolerates higher percentage
of water in the feedstock; (d) the catalyst removal step is
eliminated; and (e) if high methanol/oil ratio is used, total
conversion of the oil can be achieved in a few minutes. Despite
having all these advantages, the supercritical methanol method
has some serious disadvantages, which include (1) the process
operates at very high pressures (25−40 MPa); (2) the high
temperatures (350−400 °C) bring along proportionally high
heating and cooling costs; (3) high methanol:oil ratios (usually
set at 42:1) entails higher costs for the evaporation of the
unreacted methanol; and (4) the process does not answer the
problem of reduction in free glycerol to less than 0.20% as
required according to the international standards.
Based on the critical assessment of the literature, few
guidelines have been given for the analysis of process-
intensifying techniques in transesterification reaction for
biodiesel production in achieving desired goals in industrial
operation. Among all the mentioned process-intensification
approaches, individual techniques have inherent limitations
when considered for large-scale applications except hydro-
dynamic cavitation reactor for biodiesel production. In the case
of hydrodynamic cavitation equipments, scale-up appears to be
much easier due to the fact that knowledge regarding the
conditions downstream of the constriction is easily available,
scale-up ratios required are lower, and centrifugal pumps
operate with higher energy efficiency at larger scales of
operation.
6.8. Hybrid Processes Based on Combination of
Microwave Irradiation and Cavitational Reactor. The
improvement in process-intensifying technology for heteroge-
neous system (such as oil and alcohol) based on the use of
combination or sequential approach of different intensification
techniques such as microwave, ultrasound, or hydrodynamic
cavitation can further accelerate the chemical reactions and
other processing applications significantly. The dramatic
acceleration effect may be attributed to a combination of
enforced heat transfer due to microwave irradiation and
intensive mass transfer at phase interfaces caused by ultrasonic
or hydrodynamic cavitation. In transesterification reactions, the
rate-determining step is the mass transfer at the interface
between two phases i.e. oil and alcohol. With sonication, the
liquid jet caused by cavitation propagates across the bubble
toward the phase boundary at a velocity estimated at several
hundreds of meters per second, and violently hits the surface.
The intense agitation leads to the mutual injection of droplets
of one liquid into the other, resulting in the formation of fine
emulsions. Microwave irradiations compliment these effects by
way of enhanced heating as well as by absorption of the
molecules resulting in significantly enhanced rates of trans-
esterification reactions. The main advantage of microwave
heating is the instantaneous heating of liquids due to dipolar
rotation and ionic conduction which contributes to localized
superheating leading to high temperature and pressure
gradients, which is not the case in conventional heating.
The combination of microwave with ultrasound technique
can improve the process chemistry, yield, and reduce the
processing time by 10−15 fold as compared to the individual
operations.39 Hsiao et al.94 employed ultrasonic mixing and
closed microwave irradiation to intensify transesterification of
soybean oil. Reactions were carried out at methanol/oil molar
ratio of 6:1; amount of catalyst as 1.0 wt %, and reaction
temperature of 333 K.
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Industrial & Engineering Chemistry Research
Table 7 shows the effects of ultrasonic mixing and closed
microwave irradiation on the conversion of soybean oil. The
Table 7. Effects of Ultrasonic Mixing and Microwave
Irradiation on Conversion Rate94
ultrasonic mixing time microwave irradiation time conversion rate
(min) (min) (%)
0a 1 11.2
2 13.1
5 20.0
10 21.0
1 0b 44.1
2 59.2
5 72.5
10 90.2
1 1 91.6
1 2 97.7
a
The reaction was assisted by closed microwave irradiation alone and
without ultrasonic mixing. bThe reaction was assisted by ultrasonic
mixing alone and without microwave irradiation.
conversion was significantly high with ultrasonic mixing for 1
min and closed microwave irradiation for 1 (91.6%) and 2
(97.7%) min. It has been reported that ultrasonic mixing causes
cavitation near the phase boundary between the soybean oil
and methanol. In summary, if the soybean oil and methanol are
not thoroughly mixed (without ultrasonic mixing), the
conversion rate achieved under the assistance of closed
microwave irradiation alone was low. Similarly, for trans-
esterification without closed microwave irradiation, the
conversion rate achieved by ultrasonic mixing alone within
short reaction time was also low. On the contrary, if the
soybean oil and methanol are thoroughly mixed after ultrasonic
mixing for 1 min, the conversion rate achieved by 2-min closed
microwave irradiation was very high. In short, the optimal
procedure was 1-min ultrasonic mixing and 2-min closed
microwave irradiation. The discussed effects for pure oil can be
equally applicable for the waste cooking oil though no literature
reports were observed to the best of our knowledge.
7. SCOPE FOR FUTURE WORK
In this section, the most important lacunae of the chosen
promising process intensification techniques (possible com-
bined operation of microwave and cavitational reactors) have
been discussed highlighting the need for future work required
with an objective of successful commercial-scale operation.
Microwave reactors provide uneven heating and also the
scale-up of the magnetron in the microwave reactor poses a
challenge. There is a need to develop designs operating on
continuous basis with orientation of magnetrons in such a way
that there are not many limitations on the material of
construction. Also, the work should be directed in evaluation
of pilot-scale continuous reactors for the application of
biodiesel synthesis from sustainable feed stocks to establish
some degree of confidence in the design engineers.
In case of cavitational reactors, hydrodynamic mode of
cavitation is found to be more energy efficient as compared to
the acoustic mode of cavitation based on cavitational yield
which is defined as the yield of product per unit of supplied
energy to the system. Unlike acoustic cavitation, the efficiency
of the pumps increases with the capacity and hence better
cavitational yield can be achieved with larger scale of operation.
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Most of the literature related to the use of hydrodynamic
cavitation for biodiesel production is based on orifice plate as
the cavitating device and not many studies have been reported
with the use of sustainable feed stock or a mixed feed stock,
which can be a reality in a large-scale production unit.
Additional studies are required for the application of hydro-
dynamic cavitation reactors based on the use of different
cavitating devices to increase the cavitation yield. Application to
a variety of sustainable feed stocks also needs to be evaluated.
Test rigs involving the combination of microwave, sonochem-
ical, and hydrodynamic cavitation reactors can be developed
and optimized with respect to the time of operation so that
energy efficient operation can be carried out. Considering scale-
up and better energy efficiency of hydraulic equipment,
hydrodynamic cavitation holds a potential for large-scale
applications in cavitationally assisted chemical and/or physical
transformations.
8. CONCLUSIONS
Depending on the undesired content of the waste cooking oil,
different pretreatment methods should be adopted before the
transesterification process for biodiesel production. The
separation of suspended solids from waste cooking oil can be
effectively carried out by filtration whereas the removal of
soluble salts by water washing, and moisture removal by
drying/adsorption will be required based on the quality of the
feed material. Free fatty acid removal by acidic esterification
and/or vacuum distillation/stripping and/or adsorption
technique can be achieved based on the FFA content.
Pretreatment is necessary as the impurities can deactivate
catalysts and create problems in the separation of pure
products. Scaling up of a laboratory-scale process involving
immiscible phases to commercial scale is not an easy task due
to mass and heat transfer limitation. Nevertheless, recent
advances in technologies such as ultrasonic reactors, microwave
irradiation, oscillatory flow reactor, microchannel rector,
addition of cosolvent, and supercritical uncatalyzed trans-
esterification have shown high potential in overcoming this
limitation. These technologies not only facilitate transester-
ification reaction in terms of increasing mixing intensity, heat,
and mass transfer rate, but also prove to be more energy-
efficient as compared to the conventional heating and mixing
based transesterification process. In cavitational reactors, the
collapse of cavity or bubbles produces conditions of high
temperature and pressure associated with local turbulence
resulting in enhanced reaction rate. Microwave reactors utilize
microwave irradiation to transfer energy directly to the
reactants and thus accelerate the rate of chemical reaction.
Microchannel reactors improve heat and mass transfer rates due
to short diffusion distance and high volume/surface area
increasing the reaction rates. Oscillatory baffled reactors
enhance radial mixing and transport processes by independent
and controlled oscillatory motion. Use of cosolvents in
transesterification processes changes the heterogeneous nature
of the reaction mixture to a homogeneous phase. In the
presence of cosolvent, the increase in the mutual solubility of
alcohol and WCO at low reaction temperatures results in an
increase in the mass transfer due to an increase in the contact
surface, and hence the production of biodiesel increases.
Supercritical transesterification requires very short time (few
min) for the completion of the reaction under supercritical
conditions (temperature 350−400 °C and pressure more than
80 bar). It avoids the complications of separation of catalyst in
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Industrial & Engineering Chemistry Research
the last stages. However, it requires a high alcohol to oil (42:1)
ratio and higher capital and operating cost. Overall, among the
different process intensifying approaches, cavitational reactors
such as hydrodynamic cavitation reactors have very high energy
efficiency and also potential for easy scale-up and commerci-
alization for biodiesel production.
The fuel properties of biodiesel derived from used cooking
oil are in accordance with the ASTM standards. Thus, biodiesel
produced from used cooking oil can be used in diesel engines
without any engine modifications. Overall, it can be said that
the process-intensifying techniques offer considerable promise
for the intensification of biodiesel production from sustainable
raw materials. Cost of biodiesel can be reduced by using low
cost feedstock such as waste cooking oil and incorporating
process-intensifying techniques in transesterification processes
for biodiesel production. The use of low-cost feedstock and
process-intensifying techniques for biodiesel can reduce the
production cost significantly.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: pr.gogate@ictmumbai.edu.in. Tel.: +91-22-33612024.
Fax: +91-22-3361 1020.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
G.L.M. is thankful to University Grants Commission, Govern-
ment of India for financial assistance. GLM would also like to
acknowledge the help of B.N. Rekha in preparation of the
manuscript.
■
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