Int. J. Environ. Sci. Tech.

, 7 (1), 183-213, Winter 2010

ISSN: 1735-1472 A. A. Refaat
© IRSEN, CEERS, IAU

Review Paper

Different techniques for the production of biodiesel from waste

vegetable oil
*A. A. Refaat
Department of Chemical Engineering, Faculty of Engineering, Cairo University, Egypt

Received 13 October 2009; revised 8 November 2009; accepted 20 November 2009; available online 1 December 2009

ABSTRACT: The production of biodiesel from waste vegetable oil offers a triple-facet solution: economic,
environmental and waste management. The new process technologies developed during the last years made it possible
to produce biodiesel from recycled frying oils comparable in quality to that of virgin vegetable oil biodiesel with an
added attractive advantage of being lower in price. Thus, biodiesel produced from recycled frying oils has the same
possibilities to be utilized. While transesterification is well-established and becoming increasingly important, there
remains considerable inefficiencies in existing transesterification processes. There is an imperative need to improve the
existing biodiesel production methods from both economic and environmental viewpoints and to investigate alternative
and innovative production processes. This study highlights the main changes occurring in the oil during frying in order
to identify the characteristics of oil after frying and the anticipated effects of the products formed in the frying process
on biodiesel quality and attempts to review the different techniques used in the production of biodiesel from recycled
oils, stressing the advantages and limitations of each technique and the optimization conditions for each process. The
emerging technologies which can be utilized in this field are also investigated. The quality of biodiesel produced from
waste vegetable oil in previous studies is also reviewed and the performance of engines fueled with this biodiesel and the
characteristics of the exhaust emissions resulting from it are highlighted. The overarching goal is to stimulate further
activities in the field.

Keywords: Engine performance; Exhaust emissions; Innovative technologies; Production optimization;

Transesterification; Waste utilization

INTRODUCTION
The term “waste vegetable oil” (WVO) refers to waterways (Szmigielski et al., 2008). Biodiesel is a
vegetable oil which has been used in food production renewable, biodegradable, environmentally benign,
and which is no longer viable for its intended use. energy efficient, substitution fuel which can fulfill
Waste vegetable oil arises from many different sources, energy security needs without sacrificing engine’s
including domestic, commercial and industrial. Waste operational performance. Thus, it provides a feasible
vegetable oil is a potentially problematic waste stream solution to the twin crises of fossil fuel depletion and
which requires to be properly managed. The disposal environmental degradation.
of waste vegetable oil can be problematic when Any fatty acid source may be used to prepare
disposed, incorrectly, down kitchen sinks, where it can biodiesel. Thus, any animal or plant lipid should be a
quickly cause blockages of sewer pipes when the oil ready substrate for the production of biodiesel. The
solidifies. Properties of degraded used frying oil after use of edible vegetable oils and animal fats for biodiesel
it gets into sewage system are conductive to corrosion production has recently been of great concern because
of metal and concrete elements. It also affects they compete with food materials - the food versus
installations in waste water treatment plants. Thus, it fuel dispute (Pimentel et al., 2009; Srinivasan, 2009).
adds to the cost of treating effluent or pollutes There are concerns that biodiesel feedstock may
compete with food supply in the long-term (Lam et al.,
*Corresponding Author Email: [email protected]
Tel./Fax: +20 12 227 7897 2009; Metzger, 2009). Hence, the recent focus is the
 A. A. Refaat

use of non-edible plant oil source and waste products the waste, maintaining public sewers and treating the
of edible oil industry as the feedstock for biodiesel oily wastewater, but also lower the production cost of
production meeting the international standards. biodiesel significantly.
Quality standards are prerequisites for the commercial From a waste management standpoint, producing
use of any fuel product. Since the implementation of the biodiesel from used frying oil is environmentally
European standard specification EN 14214 in 2004, a beneficial, since it provides a cleaner way for disposing
standardized definition for biodiesel has been agreed as these products; meanwhile, it can yield valuable cuts in
fatty acid methyl esters (FAME) from any kind of CO2 as well as significant tail-pipe pollution gains. CO2
feedstock, including recycled frying oils, under fulfilling is the main contributor of global warming and climate
the given quality specifications. Thus, biodiesel change through the enhanced (Tschakert et al., 2008).
produced from recycled frying oils has the same Relative to the fossil fuels they displace, greenhouse
gas emissions are reduced 41% by the production and
possibilities to be utilized. The new process technologies
combustion of biodiesel (Hill et al., 2006). Biodiesel from
developed during the last years made it possible to
used frying oil leads to a far better life cycle analysis. It
produce biodiesel from recycled frying oils comparable
has to be realized, that the effect of CO2 saving is
in quality to that of virgin vegetable oil biodiesel with an
significantly higher when using used frying oil as
added attractive advantage of being lower in price
feedstock, because here the effects of the agricultural
(Canakci, 2007; Chhetri et al., 2008; Refaat et al., 2008a).
production of vegetable oils is not taken into
From an economic point of view; the production of
consideration. In many researches WVO biodiesel
biodiesel is very feedstock sensitive. Many previous
showed net energy ratio (NER) of 5-6 compared to 2-3
reports estimated the cost of biodiesel production based for rapeseed or soybean biodiesel and 0.8 for petrodiesel
on assumptions, made by their authors, regarding (Rutz and Janssen, 2008). The NER is evaluated by
production volume, feedstock and chemical technology dividing the energy output of the system by the
(Canakci and van Gerpen, 2001; Zhang et al., 2003b; cumulative energy demand of the system. Furthermore
Kulkarni and Dalai, 2006). In all these reports, feedstock the processing of used frying oil into biodiesel is an
cost comprises a very substantial portion of overall ideal alternative to the use as animal feed (Supple et al.,
biodiesel cost. Haas et al. (2006) developed a computer 2002), which is restricted by the law in Europe. The
model to estimate the capital and operating costs of a product therefore has the other benefits of being
moderately-sized industrial biodiesel production facility. removed from the food chain. Limiting factor is the limited
Calculated production costs included the cost of the availability of used cooking oil on the market. Oil
feedstock and of its conversion to biodiesel. Process collection from household, commercial or industrial
economics included the recovery of co-product glycerol sources can be achieved through grease traps (Wong
generated during biodiesel production and its sale The et al., 2007) or through a holistic policy framework (El
model is flexible in that it can be modified to calculate Sheltawy and Refaat, 2009). Industries are adopting
the effects on capital and production costs of changes more energy-efficient technologies to improve its
in feedstock cost, changes in the type of feedstock profitability and competitiveness (Tehrani et al., 2009).
employed, changes in the value of the glycerol co-product This study highlights the main changes occurring in
and changes in process chemistry and technology. The the oil during frying in order to identify the characteristics
authors reported that for biodiesel produced from of oil after frying and the anticipated effects of the
soybean oil, the cost of the oil feedstock accounted for products formed in the frying process on biodiesel
88 % of total estimated production costs (Haas et al., quality and attempts to review the different techniques
2006). Marchetti et al. (2008) used a conceptual design used in the production of biodiesel from recycled oils,
of alternative production plants with a techno-economic stressing the advantages and limitations of each
analysis in order to compare these alternatives. In all technique and the optimization conditions for each
cases, more than 80 % of the production cost is process. The emerging technologies which can be
associated with the feedstock itself and consequently, utilized in this field are also investigated. The quality of
efforts should be focused on developing technologies biodiesel produced from waste vegetable oil in previous
capable of using lower-cost feedstock, such as recycled studies is also reviewed, together with the performance
cooking oils. Reusing of these waste greases can not of engines fueled with this biodiesel and the characteristics
only reduce the burden of the government in disposing of the exhaust emissions resulting from it.

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A.Tech.,
A. Refaat
7 (1), 183-213, Winter 2010

Identifying the characteristics of used frying oils internal standard, is obtained by solid phase extraction.
Used frying oils from restaurants and food industries Then, the non-polar fraction is quantitatively analyzed
have a wide variety of qualities. During the frying in 15 min by high-performance size-exclusion
process, the oil is exposed to high temperatures in the chromatography (HPSEC) and the polar fraction is
presence of air and moisture. Under these conditions, determined by difference of weight. In another study
it may undergo important changes due to hydrolytic, Marmesat et al. (2007b), pointed out that the tests
oxidative and thermal reactions. Changes in the main based on physical properties showed better results
fat constituents are known, although it is not easy to than those based on chemical reactions, as the number
foresee the rate of oil degradation due to the high of false results was lower. Furthermore, they can be
number of variables involved in the frying process. useful to gain information on the changes in the frying
Some of them are linked to the process itself, such as oil quality, as their results showed high correlation
temperature, duration of heating, heating pattern coefficients with the determination of polar compounds.
(continuous or intermittent), turnover rate, etc.; others Amore recent study by Lima et al. (2008) used Fourier
to the food subjected to frying, i.e. lipid composition, Transform Infrared Photoacoustic Spectroscopy
main and minor constituents, etc.; or else to the oil (FTIR-PAS) in identifying or monitoring spectral
used e.g., degree of unsaturation, initial quality and changes induced in the vegetable oils due to a
additives (Rodrigues Machado et al., 2007). Thus, used degradation effect. Besides, the method can be used
frying oils can be highly heterogeneous as compared to contribute to the biodiesel wash process to separate
to crude or refined oils. the glycerol from the biodiesel. The authors argued
The new products formed during frying are that the method is efficient, fast and exhibits some
polymers, dimers, oxidized triglycerides, as well as advantages when compared with conventional
diglycerides and fatty acids. All these groups possess processes, such as attenuated total reflectance (ATR).
higher polarity than that corresponding to the initial Some key parameters were selected for determining
triglycerides and can be easily quantified by means of the viability of the vegetable oil transesterification
adsorption chromatography (Ruiz-Méndez et al., 2008). process. These parameters include: acid value and FFA
The determination of polar fatty acids in biodiesels content, moisture content, viscosity and fatty acid
allows for the exact determination of non-polar esters profile of the used oil. Knothe and Steidley (2009)
and is an interesting alternative to the GC standard preferred to determine the dynamic viscosity rather
method due to its accuracy and to the fact that no than the kinematic viscosity because of non-Newtonian
instrumental techniques are required. From the behavior of some samples. The usual trend for the oils
percentage of polar compounds in used frying oils, the after frying was found to be an increase in the acid
percentage of non-polar and polar methyl esters after value, an increase in viscosity and an altered fatty acid
the production of biodiesel can be roughly deduced profile (Knothe and Steidley, 2009). Fatty acid profile
given the excellent correlation between both of the oil is an important determinant for the properties
determinations (Ruiz-Méndez et al., 2008). of the biodiesel produced. It was shown that the
Used frying oils can be analyzed by adsorption and properties of the various fatty esters are determined
size exclusion chromatography before and after by the structural features of the fatty acid and the
transesterification for non-polar and polar species alcohol moieties that comprise a fatty ester (Refaat,
formed during frying. The determination of polar 2009). In a study conducted by Szmigielski, Maniak et
compounds by adsorption chromatography is the most al. (2008) to assess the usability of used frying rapeseed
accepted method for the analysis of used frying oils oil as a substrate for biofuel production it was shown
due to its high precision and accuracy. However, this that utilization of used frying rapeseed oil as fuel seems
method is expensive and time consuming. In a study to be justified when favorable ratio of saturated and
conducted by Marmesat et al. (2007a), a rapid unsaturated fatty acids in oil fraction, and that this
analytical method to determine polar compounds is property stabilizes as a result of surface contact with
proposed. Starting from milligrams of sample dissolved potato chips (Szmigielski et al., 2008). A further study
in a solution of hexane containing methyl oleate as by the same authors on frying sunflower oil confirmed
internal standard, the non-polar fraction, which the previous findings (Maniak et al., 2009). In both
comprises the non-altered triglycerides (TG) and the studies, it was also shown that the acid value has

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A. A. Refaat

increased after frying. In both studies it was also shown raw product is then centrifuged and washed with water
that the acid value has increased after frying. However, to cleanse it of impurities. This yields methyl or ethyl
the increase in acid value was more prominent in the oil ester (biodiesel), as well as a smaller amount of glycerol,
heated without the presence of potato chips (as shown a valuable by-product used in making soaps, cosmetics
in Figs. 1 and 2). These results were attributed to the and numerous other products.
water fraction introduced into oil with potato chips) Fig. 3 shows the process flow sheet of biodiesel
and from absorption of hydrolysis products on porous production using the conventional mechanical method
surface of potatoes, as it was suggested that the key for base-catalyzed transesterification.
factor affecting changes of the investigated oil are Base-catalyzed transesterification is the most
oxidation transformations. commonly used technique as it is the most economical
Thus, it can be concluded that the identification of process since it requires only low temperatures and
some key parameters (acid value and free fatty acids pressures; produces over 98 % conversion yield
(FFA) content, moisture content, viscosity and fatty (provided the starting oil is low in moisture and FFA)
acid profile of the used oil) is a prerequisite for and involves direct conversion to biodiesel with no
determining the viability of the vegetable oil intermediate compounds; also, no special materials of
transesterification process and is essential to identify construction are needed (Singh et al, 2006).
the right processes that can be performed to achieve Base-catalyzed transesterification, however, has
best results with the yield and purity of the produced some limitations among which are that it is sensitive to
biodiesel, as will be shown, in details, in the following FFA content of the feedstock oils. A high FFA content
sections. (> 1 % w/w) will lead to soap formation which reduces
catalyst efficiency, causes an increase in viscosity,
Base-catalyzed transesterification leads to gel formation and makes the separation of
Transesterification is the general term used to glycerol difficult. Also, the oils used in
describe the important class of organic reactions where transesterification should be substantially anhydrous
an ester is transformed into another through (0.06 % w/w). The presence of water gives rise to
interchange of the alkoxy moiety (Freedman et al., 1986). hydrolysis of some of the produced ester, with
Base-catalyzed transesterification involves stripping consequent soap formation (Leung and Guo, 2006).
the glycerin from the fatty acids with a catalyst such as Other drawbacks of the base-catalyzed
sodium or potassium hydroxide and replacing it with transesterification is that the process is energy
an anhydrous alcohol, usually methanol. The resulting intensive, recovery of glycerol is difficult, alkaline

1.8 0.6

1.6
0.5
Acid value (mgKOH/g)

Acid value (mgKOH/g)

1.4

1.2 0.4

1
0.3
0.8

0.6 0.2
0.4
0.1
0.2

0 0
Raw oil
R a w Oil 1 yc le
1C 2 le s 3 C yc3le s 4 C yc4 le s 5 C yc5le s
2 C yc Raw
Raw oil1 C1yc le 22 3 44 55 66 7 7
Cycles Oil C yc le s C yc le s C yc le s C yc le s C yc le s C yc le s
Cycles
Oil with C hips Oil witho ut C hips Oil with C hips Oil witho ut C hips

Fig. 1: Acid value of rapeseed oil subjected to cyclic heating Fig. 2: Acid value of sunflower oil subjected to cyclic heating
(mg KOH/g) with and without potato chips (Szmigielski (mg KOH/g) with and without potato chips (Maniak et
et al., 2008) al., 2009)

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A. A. 7Refaat
(1), 183-213, Winter 2010

p-14
p-13
p-12

Methanol tank

p-2

Catalyst tank
water
p-1 8
Methanol/biodiesel column p-1 7
p-4 p-16
Methoxide mixer
p-9 p-11
p-3
Biodiesel wash
Pump 1 p-22
p-19 Biodiesel
Oil tank Seperator 1 Seperator 2
Biodisel reactor
p-5 p-10
Filter p-6 p-8 Watewater

Oil preheater
Pump 2
Methanol/Glycerol column
p-15

Crude Glycerol

Fig. 3: Base-catalyzed transesterification process flow sheet

catalyst has to be removed from the product and alkaline If the FFA content exceeds 1 % and if an alkaline
waste water requires treatment (Meher et al., 2006). catalyst must be used, then a greater amount of catalyst
should be added to neutralize the FFA (Kulkarni and
Pretreatment processes Dalai, 2006). However, the correct amount of catalyst
The negative effects of the undesirable compounds should be used because both excess as well as
formed during the frying process can be avoided by insufficient amount of catalyst may cause soap
different types of pretreatment before performing the formation. To determine the correct amount of catalyst
base-catalyzed transesterification. These processes required, a titration must be performed on the oil being
include filtration for removing suspended solids, transesterified. One simple method was presented by
maintaining the oil relatively dry by heating, suitable Sudhir et al. (2007) in which phenolphthalein indicator
absorption/adsorption technique or sometimes by is used. In the titration, 0.1 % of NaOH in distilled water
performing film vacuum evaporation or vacuum filtration. is titrated against the titration sample which is essentially
Other processes include: neutralization, steam injection a solution of 10 mL of Isopropyl alcohol and 1 mL of oil
and column chromatography. sample with 2-3 drops of indicator. The end point of the
To ensure an anhydrous medium the filtered oil can titration is marked when the titration sample turns pink
be subjected to drying by heating it to 100 ºC for at least (magenta) and stays pink for 10 s. The number of
15 min with continuous stirring (Sudhir et al., 2007). In milliliters of 0.1 % NaOH solution needed is equal to the
an earlier study by Felizardo et al. (2006), the authors number of extra grams of pure sodium hydroxide catalyst
performed pretreatment by drying the oil sample over needed to produce the proper reaction to make biodiesel
magnesium sulphate followed by filtration under vacuum from WVO.
to remove any suspended matter and magnesium Supple et al. (2002) investigated the effect of steam
sulphate crystals. The authors mentioned that moisture injection and sedimentation treatment of waste cooking
removal at industrial scale is usually done by vacuum oil on the quality of TG to be used as a raw material for
distillation (0.05 bar) at temperature range of 30-40 ºC. the production of biodiesel. The effect of steam

187
 A. A. Refaat

treatment was evaluated in terms of a number of calcium chloride crystals. Ozbay et al. (2008) carried out
physical and chemical characteristics. Significant a successful venture to reduce the amount of FFA
decreases in the moisture, FFA and PV, as well as through esterification of WVO using ion exchange resins
increased energy value, were observed. GC analysis of and reported that acidic ion exchange resins (Amberlyst-
the treated materials demonstrated little change in either 15 (A-15), Amberlyst-35 (A-35), Amberlyst-16 (A-16) and
the overall composition of the oils or the iodine value. Dowex HCR-W2) can be used to decrease the FFA level
The decreases in moisture from 1.4 to 0.4 % and in FFA of waste cooking oil (WCO).
from 6.27 to 4.28 % were found to correlate strongly
with an increase in yield of ester from 67.5 to 83.5 %. Parameters affecting base-catalyzed tr ansesterification
Cvengros and Cvengrosova (2004), however, The main parameters affecting the base-catalyzed
outlined the general processes of WVO treatment that transesterification process are: alcohol formulation,
consists of a sequence of pretreatment methods to alcohol/oil molar ratio, catalyst formulation and
reduce the FFA, water and polymer content in the oil. concentration, reaction temperature, reaction time,
FFA was removed by neutralization with alkalis (KOH agitation, and the presence of moisture and FFA.
or NaOH) and separated as soaps in the decanter while
high polymer content was treated with activated Alcohol formulation
charcoal and removed by adsorption. Film vacuum Short-chain alcohols such as methanol, ethanol and
evaporation was found to be more suitable for de- butanol are the most frequently employed. Although
acidification and drying. While drying was performed the use of different alcohols presents some differences
under moderate conditions of 159 ºC and 20 mbar, de- with regard to the reaction kinetics, the final yield of
acidification required more severe conditions of 200– esters remains more or less inalterable. Therefore,
280 ºC and 0.1–8 mbar. The reported yield of methyl selection of the alcohol is based on cost and
ester obtained from the treated oil was 96 %. performance consideration (Encinar et al., 2007).
Other pretreatment methods have been reported in Methanol was dominating in most of the literature
literature: In an attempt to regenerate restaurant grease reviewed (Alcantara et al., 2000; Encinar et al., 2005;
before esterification by removing excess FFA, Lee et Felizardo et al., 2006; Refaat et al., 2008a; Yuan et al.,
al. (2002) carried out filtration and column 2008). Methyl, rather than ethyl, ester production was
chromatography. Cooking oil containing 10.6 % FFA modeled because methyl esters are the predominant
and 0.2 % water was purified by passing it through a commercial products, methanol is considerably cheaper
mixture of 50 % aluminum oxide and 50 % magnesium and more available than ethanol (Pinto et al., 2005) and
silicate. The FFA and water contents decreased from the downstream recovery of unreacted alcohol is much
10.6 % to 0.23 % and from 0.2 % to 0.02 wt %, easier (Zhou and Boocock, 2006).
respectively. The conversion of untreated oil before Ethanol maintains its capability of being renewable
column chromatography was observed to have as an advantage. It can be produced from agricultural
increased from 25 % to 96 % when pretreated oil was renewable resources, thereby attaining total
used. Saifuddin and Chua (2004) used filtration and independence from petroleum-based alcohols
drying by using microwave oven at 60 ºC for 10 minutes. (Saifuddin and Chua, 2004; Encinar et al., 2007). In
Issariyakul et al. (2007) carried out pretreatment by addition to the entirely agricultural nature of the ethanol,
centrifugation to remove solid portion of the oil. Water the extra carbon atom brought by the ethanol molecule
was removed by mixing the oil with 10 wt % silica gel slightly increases the heat content and the cetane
(28–200 mesh) followed by stirring and vacuum filtration. number. Also, ethanol, as extraction solvent, is
Yuan et al. (2008) employed distillation as refining preferable to methanol because of its much higher
technique for reduction of FFA content in WVO. Dias et dissolving power for oils. Finally, another important
al. (2008) employed filtration under vacuum after advantage in the use of ethanol is that the ethyl esters
dehydration over night using anhydrous sulfate and have cloud and pour points that are lower than the
finally filtered the oil again under vacuum prior to methyl esters (Encinar et al., 2007). However, the
transesterification. Predojevic (2008) pretreated the oil utilization of ethanol also presents inconveniences.
by drying over calcium chloride and filtered through The base-catalyzed formation of ethyl ester is difficult
cellulose filter to remove any suspended matter and compared to the formation of methyl esters; reaction

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A. A. Refaat

rate with ethanol is slightly slower than with methanol, maximum conversion to the ester occurred with a molar
what is attributed to the more difficult formation of the ratio of 6:1 (Tomasevic and Siler-Marinkovic, 2003;
ethoxide anion (Om Tapanes et al., 2008). Also, the Saifuddin and Chua, 2004; Encinar et al., 2005; Gupta
formation of stable emulsion during ethanolysis is a et al., 2007; Meng et al., 2008; Refaat et al., 2008b).
problem. Methanol and ethanol are not miscible with Transesterification of pretreated waste rapeseed oil
triglycerides at room temperature and the reaction carried out by Yuan et al. (2008) showed a maximum
mixture is usually mechanically stirred to enhance mass conversion at 6.5:1 of methanol to oil ratio, whereas an
transfer. During the curse of reaction, emulsions are earlier study by Leung and Guo (2006) found a maximum
usually formed. In the case of methanolysis, these conversion at a ratio of 7:1. With further increase in
emulsions break down quickly and easily to form a molar ratio the conversion efficiency more or less
lower glycerol rich layer and upper methyl ester rich remains the same (Fig. 4) but the energy required for
layer. In ethanolysis, these emulsions are more stable the recovery of methanol becomes higher (Demirbas,
and severely complicate the separation and purification 2009).
of esters (Zhou and Boocock, 2006; Encinar et al., 2007).
Catalyst formulation
Molar ratio of alcohol to triglyceride
Among the most commonly used alkaline catalysts
One of the most important variables affecting the
in the biodiesel industry are potassium hydroxide (KOH)
yield of ester is the molar ratio of alcohol to triglyceride.
and sodium hydroxide (NaOH) flakes which are
The stoichiometric ratio for transesterification requires
inexpensive and easy to handle in transportation and
three moles of alcohol and one mole of triglyceride to
yield three moles of fatty acid alkyl esters and one storage. They are preferred by small producers. Alkyl
mole of glycerol. However, transesterification is an oxide solutions of sodium methoxide or potassium
equilibrium reaction in which an excess of alcohol is methoxide in methanol, which are now commercially
required to drive the reaction to the right (Ma and available, are the preferred catalysts for large continuous-
Hanna, 1999). However, an excessive amount of alcohol flow production processes (Singh et al., 2006).
makes the recovery of the glycerol difficult, so that the Biodiesel with the best properties was obtained
ideal alcohol/oil ratio has to be established empirically using potassium hydroxide as catalyst in many studies
(Schuchardt et al., 1998). (Tomasevic and Siler-Marinkovic, 2003; Encinar et al.,
For maximum conversion to the ester, a molar ratio of 2005; Encinar et al., 2007; Gupta et al., 2007; Refaat et
6:1 is the most acceptable. Most of the studies on the al., 2008a; Demirbas, 2009). Besides, many other
base-catalyzed transesterification of WVO reported that studies achieved best results using NaOH (Saifuddin

100 90 (b) (Demirbas, 2009)

(a) (Meng et al., 2008)
80
90
Conversion efficiency (%)

70
Yield of biodiesel (%)

80 60

50
70
40

60 30

20
50
10

40 0
0 2 4 6 8 10 0 30 60 90 120 150

M o la ratio
Molar r ra tio(%) MMethanol (%)
e tha no l (%)

Fig. 4: Effect of methanol to oil molar ratio on the transesterification of WVO

189
 Biodiesel production
A. A. Refaat

and Chua, 2004; Felizardo, et al., 2006; Leung and Guo, Catalyst concentration
2006; Chetri et al., 2008; Meng et al., 2008). In the case of the alkaline catalysis, the literature
Encinar et al. (2007) studied the influence of catalyst presents many works relating to this issue. In most of
type on the evolution of esters yield with time and the literature reviewed the results showed that the best-
found that potassium catalyst presented the best suited catalyst concentrations giving the best yields
behavior and also observed that the hydroxides gave and viscosities of the esters are between 0.5 and 1.0 wt
rise to higher percentages than the corresponding %. For higher values the yields were lower.
methoxides (Fig. 5). Catalyst concentration is closely related to the free
These results are very similar to those found in the acidity of the oil. When there is a large free fatty acid
literature in transesterification processes of used frying content, the addition of more potassium hydroxide, or
oil with methanol and other alcohols, that also any other alkaline catalyst, compensates this acidity
concluded that potassium hydroxide was the best and avoids catalyst deactivation (Freedman et al.,
catalyst (Tomasevic and Siler-Marinkovic, 2003; 1986). The addition of an excessive amount of catalyst,
Dorado et al., 2004; Refaat et al., 2008a). however, gives rise to the formation of an emulsion,

80

70

60
Methyl esters (%)

50

40

30

20

10

0
0 20 40 60 80 100 120

Time
T (m(min)
in)

CH
C 3
Na
H3ONa CH
C OK
H3OK
3 Na OH KOH

Fig. 5: Esters yield vs. time. Influence of catalyst type (Encinar et al., 2007)

80

70

60
Methyl esters (%)

50

40

30

20

10

0
0 20 40 60 80 100 120

Time
T (m(min)
in)
[KOH]=0.5% [KOH]=1.0%2 [KOH]=1.5%3

Fig. 6 Esters yield vs. time. Influence of catalyst concentration (Encinar et al., 2007)

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 Int. J. Environ. Sci.A.Tech., 7 (1), 183-213, Winter 2010
A. Refaat

which increases the viscosity and leads to the employed (68oC in case of methanol) so that the reactor
formation of gels. These hinder the glycerol separation does not need to be pressurized (van Gerpen, 2005).
and, hence, reduce the apparent ester yield. The result Thus, the usual temperature used during
of these two opposing effects is an optimal catalyst transesterification in most literature is 60-65 °C. When
concentration that is about 1.0 %. Further increases in the reaction temperature closes or exceeds the boiling
catalyst concentration will not increase the conversion point of methanol (68 °C), the methanol will vaporize
(Fig. 6) and will lead to extra costs because it will be and form a large number of bubbles which may inhibit
necessary to remove it from the reaction medium at the the reaction (Meng et al., 2008).
end (Encinar et al., 2005). Various researches have been carried out to find
These results were confirmed by Chhetri et al. (2008) out the optimum temperature of the transesterification
who carried out transesterification of WVO with NaOH reaction. Refaat et al. (2008 a) reported an optimum
concentrations at 0.2 % increments starting from 0.4 % temperature of 65 °C, while Meng et al. (2008) reported
to 1.2 % and observed that the optimum conversion 50 °C as the optimum temperature (Fig. 7). Yuan et al.
was achieved at 0.8 % NaOH concentration and that (2008) carried out transesterification of waste rapeseed
ester yield decreased with the increase in sodium oil using response surface methodology and observed
hydroxide concentrations. Meng et al.(2008) also used that maximum conversion occurred at 48.2 °C.
NaOH as the catalyst in the transesterification of WCO
and reported that 1wt % (of oil) NaOH is the optimum Reaction time
catalyst concentration. Similarly, Yuan et al. (2008) The completion of the basic-catalyzed
carried out transesterification of waste rapeseed oil transesterification process depends on reaction time.
(using response surface methodology) and obtained Most investigators have observed an optimum reaction
maximum conversion at 1 wt % alkaline catalyst time around 1 h (Tomasevic and Siler-Marinkovic, 2003;
Meng et al., 2008; Refaat et al., 2008 a). It was reported
concentration.
that excess reaction time does not increase the
conversion but favors the backward reaction
Reaction temperature
(hydrolysis of esters) which results in a reduction of
Temperature has no detectable effect on the ultimate
product yield (Leung and Guo, 2006). Felizardo et al.
conversion to ester. However, higher temperatures
(2006) reported, however, that after 1 h of reaction, at
decrease the time required to reach maximum
methanol/oil molar ratio of 4.8 and using a catalyst
conversion (Pinto et al., 2005). Transesterification can
concentration of 0.6 % (by wt of oil) highest yield of
be conducted at various temperatures ranging from
ME was obtained which allowed an efficient separation
room temperature to the boiling point of the alcohol
of the ester phase. Yuan et al. (2008) carried out
transesterification of waste rapeseed oil using response
100
surface methodology and observed that maximum
conversion occurred at 65.4 min.
90
Conversion efficiency (%)

Agitation
80 Since this reaction can only occur in the interfacial
region between the liquids and also due to the fact
70 that fats and alcohols are not totally miscible,
transesterification is a relatively slow process. As a
60
result, vigorous mixing is required to increase the area
50
of contact between the two immiscible phases (Singh
and Fernando, 2006).
40 The agitation intensity appears to be of a particular
0 20 40 60 80 importance for the alcoholysis process. The mass
transfer of triglycerides from the oil phase towards the
R e a c tio n te m pe ra ture (°C )
methanol-oil interface could be a critical step limiting
Fig. 7: Effect of tempera ture on the transesterifica tion of the rate of alcoholysis reaction because the reaction
WVO (Meng et al., 2008) mixture is heterogeneous, consisting of two immiscible

191
 A. A. Refaat

phases. Poor mass transfer between two phases in the of return and a lower biodiesel break-even price (Zhang
initial phase of the reaction results in a slow reaction et al., 2003b).
rate, the reaction being mass transfer controlled Despite its insensitivity to free fatty acids in the
(Noureddini and Zhu, 1997). Therefore, variations in feedstock, acid-catalyzed transesterification has been
mixing intensity are expected to alter the kinetics of the largely ignored mainly because of its relatively slower
transesterification reaction. Stamenkovic et al., (2007) reaction rate (Zhang et al., 2003a). For acid catalyzed
studied the effect of agitation intensity on alkali- conversion of WVO with high FFA content, higher
catalyzed methanolysis of sunflower oil and reported alcohol to oil ratio is required compared to basic
that by using the microphotographic technique, drop catalyzed operation for better yield of biodiesel. Other
size distributions were found to become narrower and disadvantages with this process are acidic effluent, no
shift to smaller sizes with increasing agitation speed reusable catalyst and high cost of equipment (Wang et
as well as with the progress of the methanolysis reaction al., 2006)
at a constant agitation speed. Transesterification of triglycerides is usually
It is evident, from the literature presented above, catalyzed by inorganic acids such as sulfuric acid,
that methanol has been reported to give the best result hydrochloric acid, phosphoric acid and sulfonated
in terms of biodiesel yield and byproduct recovery. organic acids. Freedman et al. (1984) investigated the
The optimum reaction conditions for base-catalyzed transesterification of soybean oil with methanol using
transesterification using methanol (methanolysis) 1 wt% concentrated sulfuric acid (based on oil). They
involve using the alcohol in excess of stoichiometric found that at 65 °C and a molar ratio of 30:1 methanol to
proportion (preferably 100% excess) and using KOH oil, it took 69 h to obtain more than 90 % oil conversion
or NaOH as a catalyst in a concentration of 1% of the to methyl esters. In addition, the authors established
weight of the oil. The temperature positively influences that the rate-limiting step varied over time and three
the biodiesel yield nearly up to about the boiling point regimes, in accordance with the observed reaction rate,
of the alcohol (usually 60-65 oC) if other parameters are could categorize the overall reaction process. Initially,
kept unchanged. Most investigators have observed the reaction was characterized by a mass-transfer
an optimum reaction time around one hour; however, controlled regime that resulted from the low miscibility
excess residence time can negatively influence the of the catalyst and reagents; i.e., the nonpolar oil phase
biodiesel production by favoring the backward was separated from the polar alcohol-acid phase. As
reaction (hydrolysis of esters) which results in a the reaction proceeded and ester products acted as
reduction of product yield. emulsifiers, a second-rate regime emerged, which was
kinetically controlled and characterized by a sudden
Acid-catalyzed transesterification surge in product formation. Finally, the last regime was
As previously stated, one limitation of base-catalyzed reached once equilibrium was approached near reaction
transesterification is its sensitivity to the purity of the completion. Using higher molecular weight alcohols,
reactants, especially to moisture and FFA content. such as butanol, brings about interesting advantages.
Freedman et al. (1986) have pointed out that acid For instance, butanol has better miscibility with the
catalysts are insensitive to FFA and are better than the lipid feedstock than smaller alcohols, contributing to a
alkaline catalysts for vegetable oils with FFA greater less pronounced initial mass-transfer-controlled
than 1 %. In fact, acid catalysts can simultaneously regime. Additionally, the elevated boiling points of
catalyze both esterification and transesterification. larger alcohols enable the liquid reaction system to be
Thus, a great-advantage with acid catalysts is that they operated at higher temperatures while maintaining
can directly produce biodiesel from low-cost lipid moderate pressures. This is an important issue with
feedstock generally associated with high FFA the acid-catalyzed transesterification since higher
concentrations, including waste frying oils (Lotero et reaction temperatures are often required to achieve
al., 2005). Although the base-catalyzed process using faster reaction rates.
virgin vegetable oil had the lowest fixed capital cost, Al-Widyan and Al-Shyoukh (2002) studied the
the acid-catalyzed process using waste cooking oil was transesterification of waste palm oil under different
more economically feasible overall, providing a lower conditions. Sulfuric acid and different concentrations
total manufacturing cost, a more attractive after-tax rate of hydrochloric acid and ethanol at different excess

192
 Int. J. Environ. Sci. A.
Tech., 7 (1), 183-213, Winter 2010
A. Refaat

levels were used. Using higher catalyst concentrations no monoglycerides were detected during the course of
in the range of 1.5–2.25M produced biodiesel with lower the reaction, and diglycerides present in the initial waste
specific gravity in a much shorter reaction time than oil were rapidly converted to FAME.
lower concentrations. They have noticed that product It can be concluded that acid catalysts show better
specific gravity changes with reaction time in a roughly adaptability to FFAs than base catalysts and can
exponential fashion. Compared to HCl, H2SO4 was a catalyze esterification and transesterification
superior catalyst. Also, in the acid catalyzed simultaneously. However, it suffers some shortcomings
transesterification of WVO, Zhang et al. (2003a) used such as high alcohol to oil molar ratio, high catalyst
a high molar ratio (100:1) of alcohol to oil. Higher excess concentration and high temperature. Also, the reaction
level of alcohol consistently led to desirable lower is relatively slow and the catalyst ends up in the by-
values of specific gravity throughout the reaction time. products causing serious separation problems. All
In a more recent study, Zheng et al. (2006) studied the these factors in addition to the serious environmental
optimum process parameters and reaction kinetics in and corrosion-related problems limit their use.
the acid catalyzed transesterification of waste frying
oils, where they reported that the oil:methanol:acid Two-step transesterification
molar ratios and the temperature were the most Both the base-catalyzed and the acid-catalyzed
significant factors affecting the yield of FAME. At 70 transesterification processes have their advantages
°C with oil:methanol:acid molar ratios of 1:245:3.8, and and disadvantages as previously mentioned. Hence,
at 80 °C with oil:methanol:acid molar ratios in the range to avoid the problems associated with the use of these
1:74:1.9–1:245:3.8, the transesterification was catalysts separately, especially the problems of
essentially a pseudo-first-order reaction as a result of saponification in base-catalyzed and slow reaction time
the large excess of methanol which drove the reaction in acid-catalyzed transesterification, many researchers
to completion (99 ± 1 % at 4 h). They observed the have adopted the two-stage transesterification. In the
conversion of waste frying oil to FAME as a function first stage, esterification of FFA present in waste frying
of methanol to oil molar ratio (at three different acid oil is performed using acid to decrease the FFAs to a
concentrations) as shown in Fig. 8. They also reported level less than 1 %. In the second stage,
the effect of temperature on time course of conversion transesterification of the obtained oil is performed using
of waste frying oil to FAME during the course of the an alkaline catalyst.
reaction and observed that in the presence of the large A comparison was held between the traditional acid-
excess of methanol, free fatty acids present in the waste catalyzed transesterification using sulfuric acid as a
oil were very rapidly converted to methyl esters in the catalyst and a two-step method using ferric sulfate (2.0
first few minutes under the above conditions. Little or %) catalyzed reaction followed by alkali (1.0 % potassium

1 1 (b)
(a)
Mole conversion at 240 min
Mole conversion at 240 min

0.9
0.9
0.8

0.7 0.8

0.6
0.7
0.5

0.4 0.6
0 50 100 150 200 250 0 50 100 150 200 250

M e OH: Oil m o le ra tio (%) M e OH: Oil m o le ra tio (%)

1.5%
1.5 %aacid
c id 2.5 % aacid
2.5% 2
c id2 3.5%
3.5 a c id3
% acid 3 1.5%
1.5 % aacid
c id 2.5%
2.5 % a c id2
acid 2 3.5%
3.5 % aacid
c id3
3

Fig. 8: Conversion of waste frying oil to FAME at 240 min, as a function of methanol:oil molar ratios, at acid concentrations of
1.5, 2.5 or 3.5 mol % at (a) 70 °C; and (b) at 80 ° C; stirring speed, 400rpm (Zheng et al., 2006)

193
 A.Biodiesel
A. Refaatproduction

hydroxide) transesterification (Wang et al., 2006). The cooking oil, 4.2 g NaOH and 140 ml methanol were used
feedstock was waste cooking oil with the acid value of in the first step and 1.8 g NaOH and 60 mL methanol
75.92 ± 0.04 mgKOH/g. In both cases methanol was used were used in the second step. All reactions were done at
and a reaction temperature of 95 °C was applied. The 25 °C; the effects of water content and suspended
FAME yield in the two-step method was 97.22 % at the particles on the yield were studied. The yields were
reaction time of 4 h, mole ratio of methanol to TG of 10:1, easily determined by Thermo Gravimetric Analysis (TGA)
compared to 90 %, 10 h and 20:1, respectively in the acid instead of the usual Gas chromatography (GC) and the
method. The authors argued that the two-step process viscosity of products was measured by a viscometer. It
showed advantages of no acidic wastewater, high was found that the two-step process gives a better yield
efficiency, low equipment cost and easy recovery of (96 %) than the one step process (86 %). A more recent
catalyst compared with the limitations of acidic effluent, study was conducted by Wan Omar et al. (2009) in an
no reusable catalyst and high cost of equipment in the attempt to optimize the pre-treatment step of a two-step
traditional acid process. biodiesel production from waste cooking oil. Pre-
Hancsok et al. (2004), in an earlier study, used the treatment with ferric sulphate in acid-catalyzed
combined acid/alkali-catalyzed transesterification (with esterification process preceded transesterification in
cosolvent use) for the production of FAME from used order to reduce the FFA level in the waste cooking oil.
frying oil with FFA 32.5 %, acid value 56 mg KOH/g and The authors investigated the relationship between
iodine value 126 g I2/100 g. Tetrahydrofuran (THF) and reaction temperature, reaction time and methanol to oil
dioxine were used as co-solvents while H2SO4 and sodium molar ratio in the pre-treatment step. Central Composite
methylate were used as catalysts. In the first step a Design (CCD) and Response Surface Methodology
temperature of 60 °C, molar ratio of methanol and THF (RSM) were utilized to determine the best operating
to oil 4:1, concentration of H2SO4 15 % and reaction conditions for the pre-treatment step which were found
time 0.5–6 h. In the second step the temperature and to be 60 °C, 3 h and 7:1 for the reaction temperature,
molar ratio remained the same but 3 % sodium methylate reaction time and methanol to oil molar ratio respectively,
catalyst was used in a reaction time of 2 h. The with (FAME) yield of 81.3 %.
experiments were also repeated with dioxine under the Despite its advantages, the two-stage method also
same conditions. It was observed that the use of co- faces the problem of catalyst removal in both stages.
solvents significantly reduced the FFA content thereby The problem of catalyst removal in the first stage can be
reducing the reaction time during the first stage. With avoided by neutralizing the acid catalyst, using extra
the combined transesterification, an ester yield greater alkaline catalyst in the second stage. However, the use
than 96.5 % was obtained. Fig. 9 shows the change in of extra catalyst will increase the cost of biodiesel.
free fatty acid of the oil during the acidic pre-esterification
in the absence of co-solvent (Fig. 9 a), in the presence Transesterification using heterogeneous catalysts
of THF co-solvent (Fig. 9 b) and in the presence of Heterogeneous (solid) catalysts have the general
dioxane co-solvent (Fig. 9 c). Issariyakul et al. (2006) advantage of easy separation from the reaction medium
studied the transesterification of waste fryer grease and reusability. Heterogeneous catalysis is thus
containing 5–6 % (wt %) FFA and showed that more considered to be a green process. The process requires
than 90 % ester was obtained when two-stage (acid and neither catalyst recovery nor aqueous treatment steps:
alkali catalyzed) method was used compared to ~ 50 % the purification steps of products are then much more
ester in single stage alkaline catalyst. Similar results were simplified and very high yields of methyl esters, close
obtained by Encinar et al. (2007) who showed that the to the theoretical value, are obtained. Glycerin is
two-stage transesterification of waste frying oil was directly produced with high purity levels (at least 98%)
better than the one-stage process and the yields of the and is exempt from any salt contaminants (Bournay et
esters were improved 30 % in relation with the one-stage al., 2005). They are in general much more tolerant to
transesterification. Cayli and Küsefoglu (2008) have, water and FFAs in the feedstock. Furthermore, the use
also, reported the results of comparing one-step and of heterogeneous catalysts does not lead to soap
two-step base-catalyzed room temperature formation, and solid acid catalysts have the capacity
transesterification reaction of used cooking oil. In the to replace strong liquid acids, eliminating corrosion
two-step base catalyzed process, for each 1000 g of used problems and the environmental threat posed by them

194
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Int. J. Environ. Sci. Tech., (1), 183-213, Winter 2010

35 35
(a) in the absence of co-solvent (b) in the presence of THF co-solvent

30 30

Free fatty acid content (%)

Free fatty acid content (%)

25 25

20 20

15 15

10 10

5 5

0 0
0 2 4 6 8 0 2 4 6 8
-5 -5
R e a c tio n tim e (h) R e a c tio n tim e (h)
H FFA A B C
H FFA A B C

35 (c) in the presence of dioxane co-solvent

30
Free fatty acid content (%)

25

20

15

10

0
0 1 2 3 4 5 6 7
-5
R e a c tio n tim e (h)
H FFA A B C

(H FFA=32.5% initial free fatty acid content, A=19.1 % initial free fatty acid content, B = 12.7 % initial free fatty acid content, C=6.5 % initial free
fatty acid content)

Fig. 9: Change in free fatty acid of the oil during the acidic pre-esterification (Hancsok et al., 2004)

thus improving the sustainability of the biodiesel involves used oils. More general and dramatic is catalyst
production process (Cao et al., 2008). However, leaching, which not only can increase the operational
heterogeneously catalyzed transesterification cost as a result of replacing the catalyst but also leads
generally requires more severe operating conditions to product contamination. While purification of the
(relatively elevated temperatures and pressures) and reaction substrates, optimization of process parameters
the performance of heterogeneous catalysts is and inclusion of catalyst-regeneration steps can minimize
generally lower than that of the commonly used the deactivation of heterogeneous catalysts, leaching
homogeneous catalysts. Moreover, one of the main phenomena can be minimized only by altering the
problems with heterogeneous catalysts is their catalyst formulation (Sivasamy et al., 2009).
deactivation with time owing to many possible In general, the use of solid catalysts to produce
phenomena, such as poisoning, coking, sintering and biodiesel requires a better understanding of the factors
leaching (Sivasamy et al., 2009). The problem of that govern their reactivity. To improve the performance
poisoning is particularly evident when the process of these catalysts, it is essential to understand the

195
 A. A. Refaat

correlations between acid and base strength and with increasing the amount of strong acid sites. Hence,
catalytic activity. It is clear that the surface of these proton-exchanged MOR(10) zeolite, which has more
heterogeneous materials should display some acid sites and greater acid strength than other zeolites,
hydrophobic character to promote the preferential exhibited the highest yield of methyl esters (95 %).
adsorption of triglycerides and to avoid deactivation of The authors also reported that dealumination to the
catalytic sites by strong adsorption of polar by-products HMOR zeolite induced decreasing of acid amount and
such as glycerol and water. Furthermore, it is important acid strength, with consequent deactivation of the
to enhance the interaction between the active phase catalyst. They argued that the yields were independent
and the support. This enhancement can be obtained on pore structure of the zeolites.
by tuning the synthesis parameters, for instance, by
designing embedded catalysts (Sivasamy et al., 2009). Heteropolyacids
Thus far, it seems that an ideal solid acid catalyst Heteropolyacids (HPAs) are found to be active solid
should show some underlying characteristics, such acid catalysts for their inherent advantages; such as
as an interconnected system of large pores, a strong Brønsted acidity better than H2SO4, easier
moderate to high concentration of strong acid sites separation and reusability, higher proton mobility and
and a hydrophobic surface (Lotero et al., 2005). Even higher selectivity. Chai et al. (2007) investigated the
though the best catalysts must have several qualities use of heteropolyacid Cs 2.5H 0.5 PW 12 O 40 as a
i.e., catalyze transesterification and esterification, not heterogeneous catalyst for the production of biodiesel.
be deactivated by water, be stable, do not give rise to The results illustrated that the Cs2.5H0.5PW12O40 is an
leaching, be active at low temperature, and have high excellent environmentally benign solid acid catalyst
selectivity (Di Serio et al., 2008). Heterogeneous for the production of biodiesel. It shows almost the
ca ta lysis for biodiesel product ion h as been same activity under the optimized reaction conditions
extensively investigated in the last few years. A great as compared to a conventional homogeneous catalyst
variety of materials have been tested as heterogeneous such as sodium hydroxide or sulfuric acid and can
catalysts for the transesterification of vegetable oils; easily be separated from the products and can be used
a broad classification of these materials is to categorize for several more runs. The most important features of
them as base or acid heterogeneous catalysts. this catalyst are that the catalytic activity is not affected
Compared with solid base catalysts, solid acid by the content of free fatty acids and content of water
catalysts have lower catalytic activity but higher in the vegetable oil and that the esterification can occur
stability, thus, they can be used for feedstock with at a lower temperature (room temperature) and be
large amount of FFAs without catalyst deactivation finished within a shorter time. However, the relative
(Lotero et al., 2005). water tolerance of the catalyst was limited to water
content up to 1%, over which the catalyst lost its
Acid zeolites catalytic activity. As continuation of this work, Cao et
Zeolites can be synthesized with extensive control al. (2008) investigated the transesterification of waste
of acidic/basic and textural properties. The acidic cooking oil with high acid value and high water
properties of zeolites are usually improved by contents, using heteropolyacid H3PW12O40.6H20 (PW12)
protonation, that is, by exchange of the cations as catalyst. The hexahydrate form of PW12 was found
contained in the positively charged alumino-silicate by the authors to be the most promising catalyst which
cage with protons. Furthermore, it is possible to induce exhibited highest ester yield 87 % for transesterification
some hydrophobicity of zeolites by the elimination of of waste cooking oil and ester yield 97 % for
water of hydration (Sivasamy et al., 2009). Koh and esterification of long-chain palmitic acid, respectively.
Chung (2008) have studied the transesterification of The PW12 acid catalyst also showed higher activity
waste frying oil using various zeolite catalysts with under the optimized reaction conditions compared
different acidities and pore structures. Proton- with conventional homogeneous catalyst sulfuric acid
exchanged MOR, MFI, FAU and BEA zeolites were and can easily be separated from the products by
employed in the reaction with silicalite which has no distillation of the excess methanol and can be reused
strong acid sites. The authors found that the yield more times. The most important feature of this catalyst
increased linearly with enhancing the acid strength and that the authors reported is that the catalytic activity

196
 Int. J. Environ. Sci. Tech.,
A. A. 7Refaat
(1), 183-213, Winter 2010

is not affected by the content of free fatty acids and Bronsted and Lewis double acid sites promotes the
the content of water in the waste cooking oil and the conversion of waste cooking oil into biodiesel. The
transesterification can occur at a lower temperature catalytic activity of the ZnPW nanotubes was stable
(65 °C), a lower methanol oil ratio (70:1) and be finished to the presence of free fatty acids or water in the
within a shorter time (14 h). The results illustrated feedstock. The high catalytic activity of the ZnPW
that PW12 acid is an excellent water-tolerant and nanotubes is attributed to the synergistic effect of
environmentally benign acid catalyst for production Lewis acid sites and Bronsted acid sites. Zinc
of biodiesel from waste cooking oil. The most dodecatungstophosphate (Zn 1.2H0.6PW12O40; ZnPW)
important parameters affecting the process are nanotubes, which feature Lewis acid and Bronsted acid
depicted in Fig. 10. sites, were prepared using cellulose fibers as templates.
A more recent study by Li et al. (2009) showed that The structure, acid properties, and catalytic activity of
the use of a ZnPW nanotube catalyst containing the nanotubes as heterogeneous catalysts for biodiesel

90
90 (b)
(a)
80
70
Conversion (%) 80
Conversion (%)

60

50 70
40

30
60
20
10

0 50
6:1 30:1 40:1 50:1 60:1 70:1 80:1 90:1 55 60 65 70 75

M e tha no l/wa s te o il ra tio Reaction temperature (°C)

Influence of molar ratio of methanol to waste frying oil Influence of temperature on the transesterification of waste oil

90
(c) 90 (d)

80
Conversion (%)
Conversion (%)

80
70

70
60

50 60

40
50
8 10 12 14 16
1 2 3 4 5
Reac tio n time (h)
Num be r o f runs
Effect of reaction time on the transesterification of waste frying oil Catalyst activity of transesterification of waste frying oil in five
reaction cycles
Fig. 10: Variables affecting the transesterification of waste frying oil by heteropolyacids: molar ratio of methanol/oil=70:1,
time=14 h, temperature= 65 ºC, PW12 catalyst 0.1 mmol (Cao et al., 2008)

197
 Biodiesel production
A. A. Refaat

production were then studied in detail. The ZnPW highly suited to the production of biodiesel from waste
nanocatalyst exhibited higher catalytic activities for oils containing high FFAs.
the simultaneous esterification and transesterification
of palmitic acid than the parent acid catalyst 12- Sulfated zirconia and mixed metal oxides
tungstophosphoric acid (H3PW12O40). Moreover, the Sulfated zirconia (SO42"/ZrO2), sulfated tin oxide
doubly acidic nanotubes led to markedly enhanced (SO42"/SnO2) and sulfated titanium oxide (SO42"/TiO2)
yields of methyl esters in the conversion of waste have been studied to catalyze the transesterification
cooking oil (containing 26.89 wt % free fatty acids and of vegetable oils owing to their superacidity. These
1 % moisture) to biodiesel. The catalyst could be catalysts have showed good catalytic activities (Furuta
recycled and reused with negligible loss in activity over et al., 2004; Jitputti et al., 2006; Kiss et al., 2006) and
five cycles. The authors concluded that ZnPW good stability when used to catalyze esterification and
nanocatalyst is acid- and water-tolerant and is an transesterification simultaneously. However, they have
environmentally benign heterogeneous catalyst for the not been generally used in the industrial production
production of biodiesel from waste cooking oil. process, mainly because of the high catalyst cost and
difficulty in filtering the small catalyst particles. The
Ion-exchange resins and immobilized sulfonic acids activities of three modified-zirconias (titania zirconia,
Heterogeneous solid catalysts for the effective sulfated zirconia and tungstated zirconia) were
production of biodiesel from waste oils can be prepared evaluated for both esterification and transesterification
by the incomplete carbonization of carbohydrates, such reactions (Lopez et al., 2008). The study provided a
as D-glucose, sucrose, cellulose, and starch, followed quantitative comparison of the rate of
by sulfonation. Zong et al. (2007) have prepared a sugar transesterification and conversion of TGs versus the
catalyst from D-glucose and have investigated its rate of esterification of FFAs under simultaneous
catalytic properties for the production of biodiesel from reaction conditions, which is of great importance when
waste oils. Their results indicated that sugar catalysts using less pure biodiesel feedstocks (as waste cooking
are highly effective, minimally polluting and re-usable oil). As expected, esterification occurred at a much
catalysts that are highly suited to the production of faster rate than transesterification. However, under
biodiesel from waste oils with a high acid value (Zong simultaneous reaction conditions, by virtue of the
et al., 2007). In a preceding study by the same authors, water being produced in esterification and hydrolysis
carbohydrate-derived catalysts have been prepared of the TG taking place, the conversion of the
from various carbohydrates such as D-glucose, triglycerides to ester products was greatly increased.
sucrose, cellulose and starch. They found that the Although the fresh sulfated zirconia (SZ) catalyst was
starch-derived catalyst had the best catalytic found to be the most active for these reactions, its
performance (Lou et al., 2008). The carbohydrate- activity was not easily regenerated. Titania zirconia
derived catalysts exhibited substantially higher (TiZ) was found to have a greater activity for
catalytic activities for both esterification and transesterification than tungstated zirconia (WZ).
transesterification compared to the two typical solid However, the opposite result was found for
acid catalysts (sulphated zirconia and Niobic acid) and esterification. The higher activity of TiZ towards
gave markedly enhanced yield of methyl esters in transesterification is suggested to be due to its base
converting waste cooking oils containing 27.8 wt % sites, which are likely poisoned in the presence of the
high free fatty acids (FFAs) to biodiesel. In addition, carboxylic acid during esterification. WZ was found to
under the optimized reaction conditions, the starch- be the most suitable of these catalysts for carrying out
derived catalyst retained a remarkably high proportion these reactions as it is more active than TiZ for
(about 93 %) of its original catalytic activity even after esterification and can be more easily regenerated than
50 cycles of successive re-use and thus displayed very SZ by simple re-calcination in air.
excellent operational stability. The authors argued that Peng et al. (2008) studied the activity of a solid acid
the results obtained clearly indicate that the catalyst comprising SO42-/TiO2–SiO2 for the production
carbohydrate-derived catalysts, especially the starch- of biodiesel from several low cost feedstocks with high
derived catalyst, are highly effective, recyclable, eco- FFAs. The optimized reaction parameters were reaction
friendly and promising solid acid catalysts that are temperature 200 °C, molar ratio of methanol to oil 9:1

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 Int. J. Environ. Sci. A. A. Refaat
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and catalyst concentration 3 wt %. They reported that production cost (Meher et al., 2006) as well as difficulty
the catalyst showed good stability, can be recycled, during manufacturing due to the need for a careful
easily removed and can simultaneously catalyze control of reaction parameters (Cerveró et al., 2008).
esterification and transesterification. A continuous The enzymatic conversion is based on the use of
process for biodiesel production from cheap raw biocatalysts as lipases that, on one hand, catalyze the
feedstocks was proposed and a 10,000-tons/y biodiesel hydrolysis of fats and vegetable oils with release of
production demonstration plant has been built. glycerol and, on the other hand, in the presence of
Various solid acid catalysts were evaluated by short chain alcohols, favor the formation of linear chain
Jacobson et al. (2008) for the production of biodiesel esters. Enzymes have several advantages over chemical
from low quality oil such as (WCO) containing 15 wt % catalysts such as mild reaction conditions; specificity,
free fatty acids. The authors found that zinc stearate reuse; and enzymes or whole cells can be immobilized,
immobilized on silica gel (ZS/Si) was the most effective can be genetically engineered to improve their
catalyst in simultaneously catalyzing the efficiency, accept new substrates, are more
transesterification of triglycerides and esterification of thermostable and are considered natural, and the
free fatty acid (FFA) present in WCO to methyl esters. reactions they catalyze are considered “green”
They reported that by optimization of reaction reactions (Akoh et al., 2007). The reuse of lipases and
parameters with the most active ZS/Si catalyst at 200 the recovery of their stability, both thermal and
°C, 1:18 oil to alcohol molar ratio and 3 wt % catalysts mechanical, are the most significant issues for making
loading, a maximum ester yield of 98 wt % could be the enzymatic process, whose costs are still too high,
obtained. The catalysts were recycled and reused many more competitive for biodiesel production. A major
times without any loss in activity. The results showed problem with lipase reaction with methanol is enzyme
that the fresh and used ZS/Si catalysts had a similar inactivation by methanol. The stepwise addition of
Zn content of about 6.0 %. The presence of large pores methanol can prevent the inactivation of the lipase and
and the existence of active ZS species (even after allow its continued usability (Watanabe et al., 2001).
reaction for four times) contribute to the overall activity Immobilized lipases permit to achieve this goal (Shimada
and stability of ZS/Si catalyst. Further, studies are in et al., 2002). However, they can be maximally exploited
progress to investigate the correlation between only if operating conditions are optimized; a task which
catalytic activity and concentration, type of acid sites requires knowledge of reaction kinetics and, in general,
in the catalyst. predictions of process performance (De Paola et al.,
Hence, it can be concluded that the use of solid acid 2009)
catalysts can offer many advantages as: they are Engineering of enzymatic biodiesel synthesis
insensitive to FFA content, they can perform processes requires optimization of such factors as:
esterification and transesterification simultaneously, molar ratio of substrates (alcohol:triacylglycerols),
they can be easily separated from the products, they temperature, type of organic solvent (if any) and water
show good stability and can be recycled and they are activity. All of them are correlated with properties of
environmentally friendly. However, the process lipase preparation (Antczak et al., 2009). In addition,
deserves to be further investigated. Positive results knowledge about water content, free fatty acid level,
should be expected if more research efforts are directed percent conversion, acyl migration and substrate flow
to this field. rate in packed bed bioreactors) are required to improve
the yield of biodiesel (Akoh et al., 2007). For the use of
Enzymatic transesterification enzymes, there are some critical factors: There is a
There is a current interest in using enzymatic minimum water content needed by the lipase, below
catalysis to commercially convert vegetable oils and which it does not work; alcohol has an effect on the
fats to FAME as biodiesel fuel, since it is more efficient, reaction, being methanol the most commonly employed;
highly selective, involves less energy consumption the effect of temperature effect is significant because
(reactions can be carried out in mild conditions) and instead of increasing the reaction rate by increasing
produces less side products or waste (environmentally temperature, enzymes can become denatured at high
favorable) (Akoh et al., 2007). However, the drawbacks temperatures; and obviously the raw material is
of enzymatic catalysts are significantly higher important, because not all oils have the same amount

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or type of fatty acids and lipase specificity can become methyl ester yield. Silica gel was proved to be the
more attractive in some oils than in others (Cerveró et optimal adsorbent, affording a ME yield of 92.8% after
al., 2008). 7 h. Moreover, the enzyme preparation displayed a
Chen et al. (2006) have investigated the enzymatic higher stability in waste oil than in corn oil, with 68.4%
conversion of waste cooking oils into biodiesel. of the original enzymatic activity retained after being
Enzymatic conversion using immobilized lipase based reused for 10 batches (Fig. 12).
on Rhizopus orzyae was considered and the Reaction kinetics can be studied through a
technological process was studied focusing on fundamental approach based on kinetics modeling, but
optimization of several process parameters, including other factors than kinetics can also affect the reaction
the molar ratio of methanol to waste oils, biocatalyst progress. An accurate study of the effects and
load and adding method, reaction temperature and water interactions of process operating conditions, such as
content. The results indicated that methanol/oils ratio mixing and reactor fluid-dynamics, on the system
of 4:1, immobilized lipase/oils of 30 wt % and 40 °C are performance is necessary to set the bases of bioreactors
suitable for waste oils under 1 atm. The irreversible design. Fluid-dynamics is a relevant aspect in the
inactivation of the lipase is presumed and a stepwise bioreactor design also because of its influence on mass
addition of methanol to reduce inactivation of transport phenomena. However, the effect of mixing
immobilized lipases was proposed. Under the optimum on process performance is hardly predictable by means
conditions the yield of methyl esters was around 88– of fundamental modelling; in this regard factor analysis
90 %. becomes an efficient tool to evaluate the effect of such
A more recent study by Maceiras et al. (2009) was parameter. It is based on experimental design and
also conducted to investigate the enzymatic conversion optimization with the aim of understanding the effect
of waste cooking oils into biodiesel using immobilized of each significant parameter on the process
lipase Novozym 435 as catalyst. The effects of performance, defined as substrates final conversion or
methanol to oil molar ratio, dosage of enzyme and final products concentration. De Paola et al. (2009) have
reaction time were investigated. The optimum reaction implemented a factor analysis in order to evaluate the
conditions for fresh enzyme were methanol to oil molar effect of operating parameters on yields of biodiesel
ratio of 25:1, 10 % of Novozym 435 based on oil weight production from waste oil. The two variables considered
and reaction period of 4 h at 50 °C obtaining a biodiesel are mixing rate and enzyme loading, since it has been
yield of 89.1 %. Moreover, the reusability of the lipase recognized that they affect process performance
over repeated cycles was also investigated under singularly and through interaction effects. These
standard conditions. Best results were obtained with variables were subjected to a factor analysis and their
the reused enzyme and low oil molar ratio (1:1). From combined effect on the reaction performance was
these results the authors concluded that: (i) Novozym determined. Response surface methodology (RSM) was
435 is not deactivated by methanol in the operating used based on a linear first order model (steepest ascent
conditions used, (ii) external mass transfer can be the method) and on a second order one in proximity of the
limiting step in the oil transesterification working with optimal solution. The authors have established a model
high concentration on immobilized enzyme and (iii) the able to predict reaction performance within the range
excess of methanol interferes with the separation of of mixing rates and enzyme amount considered for
methyl ester causing an apparent lost of product by model formulation and outside of it and showed that
increasing solubility of glycerol (Fig. 11). best performances were obtained at high stirring and
Li et al. (2009) presented an inexpensive self-made high enzyme loading.
immobilized lipase from Penicillium expansum which Using the tools of recombinant DNA technology, it
was shown to be an efficient biocatalyst for biodiesel is possible to increase the supply of suitable lipases
production from waste oil with high acid value in for biodiesel production. Protein engineering and site-
organic solvent. It was revealed that water from the directed mutagenesis may be used to alter the enzyme-
esterification of free fatty acids and methanol prohibited substrate specificity, stereospecificity and
a high methyl ester yield. The authors showed that thermostability, or to increase their catalytic efficiency,
adsorbents could effectively control the concentration which will benefit biodiesel production and lower the
of water in the reaction system, resulting in an improved cost of the overall process (Akoh et al., 2007).

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The enzymatic approach is environmentally friendly, process comprises solubilizing oil in methanol by
considered a “green reaction”, however, the cost of addition of a cosolvent in order to form a one-phase
the final enzymatic product remains a hurdle compared reaction mixture, Tetrahydrofuran (THF) is chosen as a
to the cheaper alternative of using chemical catalysis. cosolvent because its boiling point is close to that of
The process needs to be explored for industrial methanol, so that at the end of the reaction the
production of biodiesel and more work has to be done unreacted methanol and THF can be co-distilled and
to justify its industrial application in the future. recycled. At the 6:1 methanol-oil molar ratio, the
addition of 1.25 volume of tetrahydrofuran per volume
Non-catalytic transesterification of methanol produces an oil dominant one phase
The non-catalyst options were designed to system in which methanolysis speeds up dramatically
overcome the reaction initiation lag time caused by to 5-10 min, at ambient temperatures, atmospheric
poor methanol and oil miscibility. An improved process pressure and without agitation. No catalyst residues
was investigated for methanolysis of vegetable oil. The in either the ester or the glycerol phase (Meher et al,

100 (a) 100 (b)

80 80
Methyl esters yield wt (%)

Methyl esters yield wt (%)

60 60

40 40

20 20

0 0
0 2 4 6 8 0 2 4 6 8

Time (h)
t (h) Time (h)
t (h)
Fig. 11: Effect of enzyme addition on methanolysis WFO at different alcohol–oil molar ratio: (a) 1:1, (b) 25:1. Reaction
conditions: first-step: WFO 2 g; 10 wt % immobilized C. antarctica; reaction temperature 50 o C; reaction time 4 h.
Second step was conducted under the same conditions after 10% of fresh enzyme was added in the reaction mixture
(Maceiras et al., 2009)

100
Relative activity (%)

90

80

70

60
0 2 4 6 8 10

B a tc h

Fig. 12: Operational stability of immobilized PEL. The reaction was performed at 35 o C and 200 rpm by adding one molar
equivalent of methanol into the mixture containing 2 g waste oil, 0.4 g t-amyl alcohol, 0.96 g blue silica gel and 168 U
immobilized PEL. Each one molar equivalent of methanol was added at 1 and 3 h, respectively. The three steps served
as one batch with total reaction time being 7 h (Li et al., 2009)

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2006). The co-solvent increases the rate of reaction by processes were capable of producing biodiesel at high
making the oil soluble in methanol, thus increasing purity, the heterogeneous and supercritical processes
contact of the reactants. were the least complex and had the smallest number of
Another non-catalytic approach is the use of unit operations. Material and energy flows, as well as
methanol at very high temperature and pressure. This sized unit operation blocks, were used to conduct an
is known as supercritical methanol. Under supercritical economic assessment of each process. Total capital
conditions (350-400 ºC and > 80 atm) and at high (42:1) investment, total manufacturing cost and after tax rate-
alcohol to oil ratio, the reaction is complete in about 4 of-return were calculated for each process. The
minutes (Kusdiana and Saka, 2001). In addition to the heterogeneous acid catalyst process had the lowest
high conversion and reaction rates, supercritical total capital investment and manufacturing costs and
transesterification is appealing as it can tolerate had the only positive after tax rate-of-return. The high
feedstock with very high contents of FFAs and water, solvent (glycerol for washing) and catalyst costs of
up to 36 wt % and 30 wt %, respectively (Warabi et al., the alkali-catalyzed process, the large excesses of
2004). The supercritical method is a catalyst-free methanol in homogeneous acid-catalyzed and the
approach which simplifies the recovery of glycerin as supercritical processes resulted in much higher
a co-product for biodiesel production and could manufacturing costs than in the heterogeneous acid
potentially be a solution to many processing problems. catalyst process. The transesterification reactor forms
However, the reactor sizes would be larger compared a large part of the capital cost, especially for the
to the normal method for biodiesel production due to homogeneous acid-catalyzed and the supercritical
the higher amount of alcohol used. Capital and processes in which the large reactor was required to
operating costs are higher and energy consumption contain a large material flow.
higher. van Kasteren and Nisworo (2007) described a
Many researchers have focused on how to decrease conceptual design of a production process in which
the severity of the reaction conditions. Co-solvents, waste cooking oil is converted via supercritical
such as carbon dioxide, hexane and calcium oxide, transesterification with methanol to methyl esters
added into the reaction mixture can decrease the (biodiesel) at industrial scale and concluded that
operating temperature, pressure and the amount of supercritical transesterification can be scaled up to yield
alcohol. Examples of the co-solvents used for this high purity methyl esters (99.8%) and almost pure
glycerol with added advantages of elimination of
purpose are propane (Cao et al., 2005), calcium oxide
pretreatment related capital and operating costs.
(Demirbas, 2007) and carbon dioxide (Han et al., 2005;
Wen et al. (2009) presented a review on supercritical
Yin et al., 2008). Han demonstrated that, with an optimal
fluid technology for biodiesel production indicating
reaction temperature of 280 °C, methanol to oil ratio of
some prominent merits which the SCF technology
24 and CO2 to methanol ratio of 0.1, a 98% yield of
possesses that includes fast kinetics, high fuel
methyl esters (biodiesel) was observed in 10 min at a
production rate, ease of continuous operation and
reaction pressure of 14.3 MPa, which makes the
elimination of the necessity of catalysts. They added
production of biodiesel using supercritical methanol that the harsh operation environment, i.e. the high
viable as an industrial process (Han et al., 2005). temperature and high pressure and its request on the
Whereas Yin showed that with CO2 or hexane as co- materials and associated cost are the main concerns
solvent in the reaction system and at an optimal reaction for its wide application. Demirbas (2009) by comparing
temperature of 160 p C and methanol to oil ratio of 24, the effects of base-catalytic and supercritical methanol
a 98 % yield of methyl esters was observed in 20 min. transesterification of waste cooking oil reached a similar
(Yin et al., 2008). conclusion and pointed out that the great advantages
West et al. (2008) carried out assessment of four of supercritical methanol are: (a) no catalyst required;
biodiesel production processes using HYSYS. The first (b) not sensitive to both water and free fatty acid; (c)
two employed traditional homogeneous alkali and acid free fatty acids in the waste cooking oil are
catalysts. The third and fourth processes used a transesterified simultaneously (Fig. 13).
heterogeneous acid catalyst and a supercritical method It can be concluded that the supercritical technology
to convert a waste vegetable oil feedstock into has been shown to be a promising technique for future
biodiesel. The authors established that while all four large-scale biodiesel production especially from waste

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oil. However, the supercritical technology suffers from exceeds the critical molecular distance necessary to
certain drawbacks including the harsh operation hold the liquid intact, the liquid will break down and
environment and high cost. voids (cavities) will be created, i.e., cavitation bubbles
will form. At high ultrasonic intensities, a small cavity
Emerging technologies in transesterification may grow rapidly through inertial effects. As a result,
Biodiesel production using ultrasonication some bubbles undergo sudden expansion to an
As previously mentioned on discussing the effect unstable size and collapse violently, generating energy
of agitation on the base-catalyzed transesterification for chemical and mechanical effects and may increase
process, the mass transfer of triglycerides from the oil the mass transfer rates by disrupting the interfacial
phase towards the methanol-oil interface could be a boundary layers (known as the liquid jet effect).
critical step limiting the rate of alcoholysis reaction Another effect of ultrasound agitation is acoustic
because the reaction mixture is heterogeneous, streaming mixing, in which a macroscopic flow is
consisting of two immiscible phases. As a result, a induced in the liquid by the absorption of the ultrasonic
vigorous mixing is required to increase the area of wave by the reactive medium (Colucci et al., 2005).
contact between the two immiscible phases and thus Wu et al. (2007) reported that ultrasonic mixing
to produce an emulsion. Low frequency ultrasonic produced smaller droplet sizes than conventional
irradiation is a useful tool for emulsification of agitation, leading to more interfacial area for the reaction
immiscible liquids (Colucci et al., 2005). The collapse to occur. By studying the effect of ultrasonication on
of the cavitation bubbles disrupts the phase boundary droplet size in biodiesel mixtures, the authors concluded
and causes emulsification by ultrasonic jets that that ultrasonication can result in mean droplet sizes
impinge one liquid to another (Hanh et al., 2008). Hence, much lower than those generated by conventional
ultrasonication can provide the mechanical energy for agitation, and can be a more powerful tool in breaking
mixing and the required energy for initiating the methanol into small droplets.
transesterification reaction. Like any sound wave, The ultrasound in the chemical processing enhances
ultrasound alternately compresses and stretches the both the mass transfer and chemical reactions. It offers
molecular spacing of the medium through which it the potential for shorter reaction times, cheaper
passes, causing a series of compression and rarefaction reagents and less extreme physical conditions, leading
cycles. If a large negative pressure gradient is applied to less expensive and smaller chemical plants (Hanh et
to the liquid so that the distance between the molecules al., 2008). Many studies have investigated the effect

100

90

80
Yield of biodiesel (%)

70

60

50

40

30

20

10

0
0 300 600 900 1200 1500 1800
Tim e (s )
Time (s)
520 K 540 K 560 K

Fig. 13: Plots for yield of biodiesel form waste cooking oil vs time at different temperatures using supercritical methanol. Molar
ratio of methanol to waste cooking oil: 41:1 (Demirbas, 2009)

203
 A. A. Refaat

of ultrasonication on the transesterification process frequency of 2.45 GHz, but other frequency allocations
for producing biodiesel and reported the optimum do exist (Mingos and Baghurst, 1991; Fini and Breccia,
reaction conditions (Stavarache et al., 2005; Singh and 1999).
Fernando, 2006; Stavarache et al., 2007 a; Hanh et al., Microwaves, a non-ionizing radiation incapable of
2008; Kelkar et al., 2008). These previous studies breaking bonds, are a form of energy and not heat and
reported excellent ester yields (98-99 %) with a low are manifested as heat through their interaction with
amount of catalyst in much shorter time than the the medium or materials wherein they can be reflected
mechanical stirring. Ultrasonic irradiation also proved (metals), transmitted (good insulators that will not heat)
suitable for large-scale continuous processing of or absorbed (decreasing the available microwave
vegetable oils since relatively simple devices can be energy and rapidly heating the sample) (Varma, 2001).
used to perform the reaction (Stavarache et al., 2007b). Microwaves, representing a non-ionizing radiation,
Refaat and El Sheltawy (2008) compared the use of influence molecular motions such as ion migration or
ultrasonication for fast production of biodiesel from dipole rotations, but not altering the molecular
waste vegetable oil with the conventional base- structure.
catalyzed transesterification and concluded that A molecule possessing a dipole moment is sensitive
transesterification by low frequency ultrasound (20 to external electric fields. Therefore,, when it is exposed
kHz) offered a lot of advantages over the conventional to microwave irradiation, the dipole will attempt to align
classical procedure. It proved to be efficient (biodiesel with the applied electric field by rotation. The applied
yield up to 98-99 %), as well as time and energy saving field provides the energy for this rotation. In the
(dramatic reduction of reaction time to 5 min, compared microwave radiation region, the frequency of the
to one hour or more using conventional batch reactor applied irradiation (2.45 GHz) is low enough so that the
systems and remarkable reduction in static separation dipoles will have time to respond to the alternating
time to 25 min, compared to 8 h). electric field and therefore will rotate. However, the
frequency is not high enough for the rotation to follow
Microwave-enhanced transesterification the oscillating field exactly generating a phase
Thermally driven organic transformations can take difference between the orientation of the field and that
place by conventional heating where the reactants are of the dipole. The continual reorientation of the
slowly activated by an external heat source. Heat is molecules results in friction giving rise to dielectric
driven into the substance, passing first through the heating (Lidstrom et al., 2001). If a molecule is charged,
walls of the vessel in order to reach the solvent and then the electric field component of the microwave
reactants. This is a slow and inefficient method for irradiation will move the ions back and forth through
transferring energy into the reacting system. the sample while also colliding them into each other.
Alternatively, microwave-accelerated heating can be This movement again generates heat. The conductivity
employed where microwaves couple directly with the mechanism is a much stronger interaction than the
molecules of the entire reaction mixture, leading to a dipolar mechanism with regard to the heat generating
rapid rise in temperature. Since the process is not limited capacity (Lidstrom et al., 2001). In the
by the thermal conductivity of the vessel, the result is transesterification process, because the mixture of
an instantaneous localized superheating of any vegetable oil, methanol and potassium hydroxide
substance that will respond to either dipole rotation or contains both polar and ionic components, rapid
ionic conduction - the two fundamental mechanisms heating is observed upon microwave irradiation and
for transferring energy from microwaves to the because the energy interacts with the sample on a
substance(s) being heated (Hayes, 2004). molecular level, very efficient heating can be obtained.
In the electromagnetic radiation spectrum, the To allow for a strict comparison between microwave
microwave radiation region is located between infrared irradiation and conventional heating under similar
radiation and radio waves. Microwaves (MW) have conditions (reaction medium, temperature and
wavelengths of 1mm - 1m, corresponding to frequencies pressure), a monomode microwave reactor should be
between 0.3 - 300 GHz. In general, in order to avoid used. This ensures wave focusing (reliable
interference, industrial and domestic microwave homogeneity in the electric field) and accurate control
apparatus are regulated to 12.2 cm, corresponding to a of the temperature (using an optical fibre or infrared

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Int. J. Environ. Sci. Tech., 7 (1), 183-213, Winter 2010

detection) throughout the reaction (Perreux and Loupy, Performance tests of wvo-based biodiesel
2001). Reflux system has been developed in an effort Operationally, biodiesel performs very similar to low
to use solvents in microwave assisted organic sulfur diesel in terms of power, torque and fuel
synthesis without the risk of explosion. Reflux systems consumption without major modification of engines or
are at minimal risk of explosion because they are infrastructure (van Gerpen, 2005). Compared to
operating at atmospheric pressure and because petroleum diesel, the engine efficiency is not
flammable vapors cannot be released into the significantly affected by using biodiesel (Dorado et
microwave cavity. Several examples of microwave al., 2003a). However, an increase in fuel consumption
irradiated transesterification methods have been is observed. This increase is proportional to the
reported using adapted domestic ovens to use them as decrease in the heating value of biodiesel (Lapuerta et
flow systems (Saiffudin et al., 2004) or batch laboratory al., 2008). Brake specific energy consumption (bsec)
ovens (Mazzocchia et al., 2004) but only moderate or brake thermal efficiency (the inverse of bsec), are
conversions were obtained.. A more recent study used more adequate parameters than the break specific fuel
homogeneous catalysis, both in a batch and in a flow consumption (bsfc) for comparing fuels and for
system (Hernando et al., 2007). Leadbeater and Stencel evaluating the engine capability to be fuelled with
reported the use of microwave heating as a fast, simple biodiesel and biodiesel blends (Cardone et al., 2002).
way to prepare biodiesel in a batch mode (Leadbeater Combustion efficiency remained constant using either
and Stencel, 2006). This was followed by a continuous- biodiesel or diesel fuel (Dorado et al., 2003b). Several
flow approach allowing for the reaction to be run under studies (Dorado et al., 2003a; Pramanik, 2003; Usta,
atmospheric conditions and performed at flow rates of 2005; Ozgunay et al.,2007) which have previously
up to 7.2 L/min using a 4 L reaction vessel. (Barnard et carried out performance tests with biodiesel fuels
al., 2007). In a study by Refaat et al. (2008b) the optimum produced from different resources, stated that biodiesel
parametric conditions obtained from the conventional shows slightly lower performance values in comparison
technique were applied using microwave irradiation in with petroleum diesel fuel performance. Kegl (2008,
order to compare both systems for the production of 2006) reported that because of the lower heating value
biodiesel from neat and waste vegetable oils. The of biodiesel fuel, the engine effective power is reduced
results showed that application of radio frequency by about 5 % and the specific fuel consumption is
microwave energy offers a fast, easy route to this increased by about 10 %, whereas the thermal efficiency
valuable biofuel with advantages of enhancing the is practically the same for both fuels. The temperatures
reaction rate and improving the separation process. of exhaust gases as well as the in-cylinder pressures
From these results it was concluded that using were lower than those obtained with petroleum diesel.
microwave irradiation reduces the reaction time by Agarwal and Agarwal (2007) observed significant
97 % and the separation time by 94 %. The methodology improvement in engine performance and emission
allowed for the use of high free fatty acid content characteristics for the biodiesel-fuelled engine
feedstock, including used cooking oil without prior compared to diesel fuelled engine. Thermal efficiency
pretreatment processes. The authors also proved that of the engine improved, brake specific energy
microwave-enhanced biodiesel is not, at least, inferior consumption reduced and a considerable reduction in
to that produced by the conventional technique. the exhaust smoke opacity was observed.
A study was conducted by El Sheltawy and Refaat The performance of engines fueled with biodiesel
(2008) to compare three options for the production of produced from waste vegetable oil was extensively
biodiesel from neat and waste vegetable oil; the covered in the literature (Dorado, 2003a; Tashtoush et
conventional base-catalyzed transesterification, al., 2003; Volmajer and Kegl, 2003; Najafi et al., 2007;
ultrasonication and microwave-enhanced Lapuerta et al., 2008; Meng et al., 2008; Refaat et al.,
ansesterification. Despite the prominent advantages 2008b; Utlu and Kocak, 2008; Ghobadian et al., 2009)
the ultrasonication and microwave technologies offer Lapuerta et al. (2008) tested two different biodiesel
compared to the conventional base-catalyzed fuels, obtained from waste cooking oils with different
transesterification, yet, these emerging technologies previous uses in a diesel commercial engine either pure
need to be further investigated for possible scale-up or in 30 % and 70 % v/v blends with a reference diesel
for industrial application. fuel. The main objective of their work was to study the

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effect of biodiesel blends on particulate emissions, Compared to mineral diesel, biodiesel generally causes
measured in terms of mass, optical effect (smoke a decrease of unburned HC, CO and PM emissions and
opacity) and size distributions. A sharp decrease was an increase of NOx emission (Tat et al., 2007). The actual
observed in both smoke and particulate matter results, however, vary significantly in dependence on
emissions as the biodiesel concentration was the used fuel, employed engine, and engine operating
increased. The mean particle size was also reduced with regimes (Kegl, 2006). Ramadhas et al. (2005) have found
the biodiesel concentration, but no significant a significant decline in CO emission values with
increases were found in the range of the smallest increasing ratios of the biodiesel to petro-diesel. Results
particles. They concluded that compared to petroleum obtained by Murillo et al. (2007) revealed that the use of
diesel, the engine efficiency is not significantly affected biodiesel resulted in lower emissions of CO (up to 12 %)
by using biodiesel. However, an increase in fuel with an increase in emissions of NOx (up to 20 %, except
consumption is observed. This increase is proportional in one case which presented a slight reduction). Kegl
to the decrease in the heating value of biodiesel. (2008, 2006) indicated that, using biodiesel, harmful
Refaat et al. (2008b) found that the difference in emissions (NOx, CO, smoke and HC) can be reduced to
performance between microwave-enhanced biodiesel some extent by adjusting the injection pump timing
and petroleum diesel was not statistically significant; properly. Numerous reports in the literature deal with
a slight increase in SFC was detected with biodiesel, the study of exhaust emissions from engines fueled with
biodiesel produced from waste vegetable (Dorado,
no significant differences were observed in brake
2003a; Tashtoush et al., 2003; Sudhir et al., 2007;
thermal efficiency and the combustion efficiency
Lapuerta et al., 2008; Meng et al., 2008; Refaat et al.,
remained constant using either microwave-enhanced
2008b; Utlu and Kocak, 2008; Ghobadian et al., 2009).
biodiesel or Diesel fuel.
Lapuerta et al. (2008) found that by using biodiesel
Najafi et al. (2007) noticed that by adding 20 % of
the soot and particulate matter emissions, as well as the
waste vegetable oil methyl ester to petrodiesel fuel the
particle number concentration, decreased sharply, mainly
maximum power and torque increased by 2.7 % and 2.9
due to the oxygen content of the biodiesel, which
%, respectively (Najafi et al., 2007). The same results
improve the oxygen availability in rich-zone flames in
were reconfirmed in a succeeding study by the authors
the combustion chamber. When compared with
(Ghobadian et al., 2009). Utlu and Kocak (2008) reported
petroleum diesel fuel, biodiesel emissions contain less
that although the maximum power values of both Diesel
soot and a greater fraction of the particulate was soluble.
fuel and waste frying oil biodiesel are very close, yet,
The analysis and speciation of the soluble organic
since waste frying oil biodiesel (WFOME) has a lower
fraction of biodiesel particulate suggest that the
heating value, higher density and viscosity, WFOME’s
carcinogenic potential of the biodiesel emissions is
specific fuel consumption is increased as 14.34 % as
probably lower than that of petroleum diesel (Cardone
shown in Fig. 14.
et al., 2002).
Exhaust emissions tests of wvo-based biodiesel Studies on waste vegetable oils include waste olive
Initially, environmentally related research oil by Dorado et al. (2003a; 2003b) revealed that the
concentrated on regulated exhaust gas emissions use of biodiesel resulted in lower emissions of CO
(carbon monoxide, NOx and particulate matter) and it (up to 58.9 %), CO2 (up to 8.6 %, excepting a case
was recognized that there was a substantial reduction in which presented a 7.4 % increase), NO (up to 37.5 %)
these emissions, with the exception of NOx sometimes, and SO2 (up to 57.7 %), with increase in emissions of
when compared with the use of petroleum diesel fuel NO2 (up to 81 %, excepting a case which presented a
with no real penalties in terms of fuel consumption or slight reduction). Biodiesel also presented a slight
engine performance. More recently, additional increase in brake-specific fuel consumption (lower
information on exhaust emissions with potential than 8.5%) that may be tolerated due to the exhaust
environmental and health importance has been studied emission benefits. Combustion efficiency remained
by the characterization of unregulated exhaust emissions constant using either biodiesel or Diesel fuel.
(Cardone et al., 2002). Refaat et al. (2008b) found that evaluation of the
Biodiesel possesses several distinct advantages over data relating to emission values indicated that, despite
petro-diesel regarding exhaust emissions (Kegl, 2008). the small increase in NOx emissions, decreases in

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CO, NO and NO2 emissions as a result of firing (acid value and FFA content, moisture content,
biodiesel were found to be statistically important viscosity and fatty acid profile of the used oil) is a
compared to the emissions when burning diesel. The prerequisite for determining the viability of the
authors pointed out that although the results of the vegetable oil transesterification process and is
power tests of biodiesel are similar to petroleum diesel essential to identify the right processes that can be
fuel performance values, a slight increase in SFC was performed to achieve best results with the yield and
detected with biodiesel. The slight increase in brake- purity of the produced biodiesel.
specific fuel consumption (lower than 8.5%) observed It is evident, from the literature reviewed, that
with biodiesel may be tolerated due to the exhaust methanol has been reported to give the best result in
emission benefits. terms of biodiesel yield and byproduct recovery. The
Ghobadian et al. (2009) confirmed that the optimum reaction conditions for base-catalyzed
concentration of the CO and HC emissions were transesterifica- tion using methanol (methanolysis)
significantly decreased when biodiesel was used. Utlu involve using the alcohol in excess of stoichiometric
and Kocak (2008) showed that the amount of emission proportion (preferably 100 % excess) and using KOH
such as CO, CO2, NOx and smoke darkness of waste or NaOH as a catalyst in a concentration of 1 % of the
frying oils are less than No. 2 diesel fuel (Fig. 15). weight of the oil. The temperature positively influences
Exhaust emissions and performance tests with the biodiesel yield nearly up to about the boiling point
biodiesel fuels derived from used cooking oils have of the alcohol (usually 60-65 ºC) if other parameters
shown that this kind of biodiesel exhibit properties are kept unchanged. Most investigators have observed
similar to that of biodiesel derived from ‘‘classical” an optimum reaction time around one hour; however,
vegetable oil feedstock. excess residence time can negatively influence the
biodiesel production by favoring the backward
CONCLUSION reaction (hydrolysis of esters) which results in a
While transesterification is well-established and reduction of product yield.
becoming increasingly important, there remains Acid catalysts show better adaptability to FFAs than
considerable inefficiencies in existing transesterifica - base catalysts and can catalyze esterification and
tion processes. There is an imperative need to improve transesterification simultaneously. However, it suffers
the existing biodiesel production methods from both some shortcomings such as high alcohol to oil molar
economic and environmental viewpoints and to ratio, high catalyst concentration and high temperature.
investigate alternative and innovative production Also, the reaction is relatively slow and the catalyst
processes. The identification of some key parameters ends up in the by-products causing serious separation

500
(b) Break-specific fuel consumption versus engine speed
Brake-specific fuel consumption (g/kWh)

80
(a) Power versus engine speed
450
70
400
Power (kW)

60 350

50 300

250
40
200
30
150

20 100
1500 2000 2500 3000 3500 4000 4500 1500 2000 2500 3000 3500 4000 4500

Engine s pe e d (rpm ) Engine s pe e d (rpm )

WF OM E No .2 Die s e l WF OM E No.
No .2 2 Diesel
Die s el

Fig. 14: Performance Tests for engines fueled by WVO-based Biodiesel (Utlu and Kocak, 2008)

207
 A. A. Refaat

900 (b) CO emissions versus engine speed

55
(a) Smoke density versus engine speed
800
50
700
Smoke density (%)

45

CO (ppm)
600
40
500
35
400
30
300
25
200
20
1500 2000 2500 3000 3500 4000 4500 100
1500 2000 2500 3000 3500 4000 4500
Engine s peed (rpm) Engine s pe e d (rpm )

WFOME No..22Dies
No Diesel
el WF OM E No.
No .2 2Die
Diesel
s el

12 (c) CO2 emissions versus engine speed 490

(d) Exchange of NOx
480
10 470
NOx (ppm)

460
8
CO2 (%)

450
440
6
430
420
4
410
400
2
1500 2000 2500 3000 3500 4000 4500
1500 2000 2500 3000 3500 4000 4500
Engine s pe e d (rpm )
Engine s pe e d (rpm )
WF OM E N0.2
No. 2Die s el
Diesel
WF OM E No..22Die
No Diesel
s el

Fig. 15: Exhaust emissions from WVO-based biodiesel (Utlu and Kocak, 2008)

problems. All these factors in addition to the serious The enzymatic approach is environmentally friendly,
environmental and corrosion-related problems limit their considered a “green reaction”, however, the cost of
use. Despite its advantages, the two-stage method also the final enzymatic product remains a hurdle compared
faces the problem of catalyst removal in both stages. to the cheaper alternative of using chemical catalysis.
The problem of catalyst removal in the first stage can The process needs to be explored for industrial
be avoided by neutralizing the acid catalyst, using extra production of biodiesel and more work has to be done
alkaline catalyst in the second stage. However, the use to justify its industrial application in the future. Also,
of extra catalyst will increase the cost of biodiesel. The the supercritical technology has been shown to be a
use of solid acid catalysts can offer many advantages promising technique for future large-scale biodiesel
as: they are insensitive to FFA content, they can production especially from waste oil. However, the
perform esterification and transesterification supercritical technology suffers from certain drawbacks
simultaneously, they can be easily separated from the including the harsh operation environment and high
products, they show good stability and can be recycled cost.
and they are environmentally friendly. However, the Despite the prominent advantages the
process deserves to be further investigated. Positive ultrasonication and microwave technologies offer
results should be expected if more research efforts are compared to the conventional base-catalyzed
directed to this field. transesterification, yet, these emerging technology

208
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A. A. 7Refaat
(1), 183-213, Winter 2010

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AUTHOR (S) BIOSKETCHES

Refaat, A. A., B.Sc. (Hons), M.Sc., Teaching assistant, Department of Chemical Engineering, Faculty of Engineering, Cairo University,
Cairo, Egypt. Email: [email protected]

How to cite this article: (Harvard style)

Refaat, A. A., (2010). Different techniques for the production of biodiesel from waste vegetable oil. Int. J. Environ. Sci. Tech., 7 (1),
183-213.

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