Journal of Industrial and Engineering Chemistry 19 (2013) 14–26

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Journal of Industrial and Engineering Chemistry

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Review

The effects of catalysts in biodiesel production: A review

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

A R T I C L E I N F O A B S T R A C T

Article history: Biodiesel fuel has shown great promise as an alternative to petro-diesel fuel. Biodiesel production is
Received 9 May 2011 widely conducted through transesterification reaction, catalyzed by homogeneous catalysts or
Accepted 14 July 2011 heterogeneous catalysts. The most notable catalyst used in producing biodiesel is the homogeneous
Available online 20 July 2012
alkaline catalyst such as NaOH, KOH, CH3ONa and CH3OK. The choice of these catalysts is due to their
higher kinetic reaction rates. However because of high cost of refined feedstocks and difficulties
Keywords: associated with use of homogeneous alkaline catalysts to transesterify low quality feedstocks for
Biodiesel
biodiesel production, development of various heterogeneous catalysts are now on the increase.
Production
Alkaline catalyst
Development of heterogeneous catalyst such as solid and enzymes catalysts could overcome most of the
Acid catalyst problems associated with homogeneous catalysts. Therefore this study critically analyzes the effects of
Solid catalyst different catalysts used for producing biodiesel using findings available in the open literature. Also, this
critical review could allow identification of research areas to explore and improve the catalysts
performance commonly employed in producing biodiesel fuel.
ß 2012 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2. Biodiesel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.1. Techniques for biodiesel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.2. Feedstocks for biodiesel production. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3. The effects of homogeneous catalyst in biodiesel production . . . . . . . . . . . . . . . . . ........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.1. The effects of alkaline catalysts in biodiesel production. . . . . . . . . . . . . . . . ........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.2. The effects of acid catalysts in biodiesel production. . . . . . . . . . . . . . . . . . . ........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.3. The effects of homogeneous catalysts on the yield of biodiesel fuel . . . . . . ........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4. The effects of heterogeneous catalysts in biodiesel production. . . . . . . . . . . . . . . . ........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.1. The effects of solid alkaline and acid catalysts in biodiesel production . . . . ........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.1.1. The effects of solid alkaline catalysts in biodiesel production. . . . ........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.1.2. The effects of solid acid catalysts in biodiesel production. . . . . . . ........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.2. The effects of enzymes catalysts in biodiesel production . . . . . . . . . . . . . . . ........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
4.3. The effects of heterogeneous catalysts on the yield of biodiesel . . . . . . . . . ........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
5. The advantages and disadvantages of homogeneous catalysts and heterogeneous catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
6. Conclusions and recommendations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

1. Introduction
Energy is the prime mover for socio-economic development.
The World’s economic growth is affected by climatic change, fuel
* Corresponding author. Tel.: +60 3 79674615; fax: +60 3 79675319.
E-mail address: mk_aroua@um.edu.my (M.K. Aroua).
price hike, and the gradual depletion of fossil fuel reserves.
Therefore, to increase energy security for economic development,
the need to search for an alternative source of energy such as
biodiesel is necessary [1,2]. Biodiesel is renewable, sustainable,
biodegradable, and emits low greenhouse gases [3,4]. As well, the
oxygen content of 11–15% in the molecular structure speed up the
combustion process in compression ignition engines and decreases
pollutants such as soot, fine particles, and carbon monoxide (CO)

1226-086X/$ – see front matter ß 2012 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2012.07.009
 I.M. Atadashi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 14–26 15

O O cost of refined feedstocks, account to over 70% of the overall cost of

|| || biodiesel production [21]. As a result, different kinds of low quality
CH2 - O - C - R1 R4 - O - C - R1
feedstocks such as: waste cooking oils, used cooking oil, greases
| +
| O O CH2 - OH (yellow and brown), and non-edible oils have being investigated
| || || | [13,22]. The price of low quality feedstocks such as waste cooking
CH - O - C - R2 + 3 R4OH R4 - O - C - R2 + CH - OH oil is 2–3 times lower than refined oils. Nonetheless, the feedstocks
| (KOH) + | contains higher amount of FFAs and water contents. This features
| O O CH2 - OH makes their processing challenging [23,24]. Therefore to augment
| || ||
CH2 - O - C - R3 R4- O - C - R3 their processing difficulties, acid-catalyzed transesterification is
first employed to decrease the content of FFAs before performing
Triglyceride alcohol Alkyl Esters glycerin alkali-catalyzed transesterification [19]. Thus adopting two-step
transesterification technique could provide large biodiesel con-
Fig. 1. Transesterification reaction of triglycerides via alkaline catalyst.
version of up to 98% [25].
Recently heterogeneous catalysts such as solid catalysts and
[5,6]. Thus, biodiesel is a potential substitute to replace/supple- enzyme catalysts are employed to catalyze transesterification
ment petro-diesel fuel [7,8]. reaction for producing biodiesel. Heterogeneous catalysts offers
Biodiesel fuel is produced via transesterification of refined many advantages over homogeneous catalysts such as; simple
vegetable oil, waste cooking oil, and used frying oil using alkaline catalyst recovery, catalyst reusability, simple product purification,
catalysts [9–12] as shown in Fig. 1. The nature of catalyst employed less energy and water consumption, less added cost of purification,
during transesterification reaction is crucial in converting trigly- and simple glycerol recovery. Besides, most of the heterogeneous
cerides to biodiesel. As a result different catalysts have being catalysts used especially solid alkaline catalysts have provided
explored for converting triglycerides to biodiesel fuel. The catalysts high yields [26], though faced with problem of leaching [27]. Also,
usually employed to catalyze transesterification reaction are the stability of enzymes catalysts in non-aqueous media is
homogeneous catalysts and heterogeneous catalysts. Convention- significant to its excellent catalytic activity, this improves
ally, homogeneous alkaline catalysts such as NaOH, KOH, CH3ONa, transesterification and esterification during biodiesel production
and CH3OK are more often used in producing biodiesel [13]. The [28], and providing high biodiesel yield (95 wt%) [29]. However,
catalytic performance of these catalysts and their ability to the problem mostly associated with enzymes catalysts is the cost
perform under moderate conditions has led to their choice [14]. of the enzymes, but immobilization of the catalyst could mitigate
Among these homogeneous alkaline catalysts, CH3ONa is most the cost [30]. Therefore, to achieve biodiesel that is economically
active, providing biodiesel yield above 98 wt% in short reaction feasible, development of active and cheap catalysts for effective
time (30 min) [15,16]. However because of low price, industrial transesterification of different kinds of feedstocks is necessary
biodiesel production process mostly employs NaOH and KOH [14]. [31]. In this regards, this study extensively examined and reported
The process involving these catalysts needs high-quality feed- the effects of different catalysts in producing biodiesel fuel.
stocks, thus the free fatty acid (FFAs) level of the feedstocks should
not exceed 3 wt%, beyond which the reaction will not occur. In 2. Biodiesel production
addition, water content of the feedstocks is critical, as a result the
feedstocks used in alkali-catalyzed transesterification have to 2.1. Techniques for biodiesel production
anhydrous [14,17]. Thus, presence of water leads to hydrolysis of
oils to FFAs. Fig. 2 shows water hydrolysis of fats and oils to form Biodiesel is usually produced through different techniques such
free fatty acid. The FFAs react with alkaline catalysts to produce as direct/blends [32,33], microemulsion [34,35], pyrolysis [36,37]
soaps formation. Fig. 3 presents soaps formation in homogeneous and transesterification [38,39]. As stated earlier, alkali-catalyzed
alkali-catalyzed transesterification. Soaps formation consumes the transesterification is the most adopted technique for producing
catalyst, deactivates it and makes biodiesel purification process biodiesel, this method usually needs refined feedstocks containing
difficult [13,18]. Therefore, preparation of biodiesel by low quality less FFAs content otherwise it will result to much soaps formation.
feedstocks containing huge quantity of FFAs and water needs For alkali-catalyzed transesterification, if the feedstocks contains
sound technology [19]. However, high cost of refined feedstocks high amount of FFAs then it has undergo pretreatment steps before
result in high price of biodiesel compared to diesel fuel [15,20]. The transesterification [40]. Hideki et al. [14] and Ramadhas et al. [25]
recommended acid value of feedstocks to be less than 4.0 mg KOH/g
before performing alkaline transesterification. Although, Canakci
CH2 - O - CO - R1 CH2 - OH and Gerpen [41] and Mittelbach [42] stated that before alkali-
| |
catalyzed transesterification, the acid value of a feedstock has to be
| | O
| | || 2.0 mg KOH/g. Nonetheless, the use of heterogeneous catalysts in
CH - O - CO - R2 + H2O CH - O - CO - R2 + HO - C-R1 biodiesel production has reduced the effects of using low quality
| | feedstocks, especially enzymes catalysts that has the potential of
| | converting FFAs into biodiesel, besides high purity by-products [14].
| |
CH2 - O - CO - R3 CH2 - O - CO- R3
2.2. Feedstocks for biodiesel production
Triglyceride Water Diglyceride Free fatty acid
Biodiesel production is achieved via different kinds of feed-
Fig. 2. Water hydrolysis of fats and oils to form free fatty acid (FFAs). stocks. The nature of feedstock used is dependent on the
geographical position and climate of the place. For instance
O Europe employs sunflower and rapeseed oils, palm oil predomi-
|| + KOH R1 - COOK + H2O
nates in tropical countries, soybean in United States and canola oil
R1- C -OH
Free fatty acid Potassium hydroxide (Soap) Water in Canada [43]. Singh and Singh [44] reported the major feedstocks
employed in producing biodiesel are cotton seed, palm oil,
Fig. 3. Soap formation in homogeneous alkali-catalyzed transesterification. sunflower, soybean, canola, rapeseed, and Jatropha curcas.
16 I.M. Atadashi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 14–26

Table 1 Table 3
Level of FFAs recommended for alkali-catalyzed transesterification. FFAs levels in feedstocks.

FFAs recommended (%) Reference Feedstocks FFA levels References

1 Demirbas [16] Trap grease 50–100% Sharma and Singh [3]

1 Chongkhong et al. [19] Refined vegetable oils <0.05% Davies [71]
<3 Ramadhas et al. [25] Finished greases 8.8–25.5% Canakci [41]
<0.5 Adam Khan [35] Crude soybean oil 0.4–0.7% Canakci [41]
<3 Canakci and Van Gerpan [41] Restaurant waste grease 0.7–41.8% Canakci [41]
<0.5 Zhang et al. [45] Waste palm oil >20% Balat and Balat [23]
<0.5 Martino et al. [47] Municipal sludge Up to 65% Bryan [58]
2 Sahoo et al. [48] Animal fat 5–30% Davies [71], Van Gerpen [69]
<1 Ma and Hanna [49] Trap grease 75–100% Davies [71], Van Gerpen [69]
<2 Huang and Chang [50] Use cooking oil 2–7% Van Gerpen [69]
0.5 Szczesna Antczak et al. [51] Waste oil 46.75% Nie [70]
1 Marchetti et al. [52]
<1 Tiwari et al. [53]

oils. Since biodiesel fuels from refined oils are costly when
compared to petro-diesel fuel. Besides, the application of such
Additionally, Zhang et al. [45] remarked that employing feedstocks feedstocks in biodiesel production could minimize competition
such as waste frying oils, non-edible oils, and animal fats, as between demand of edible vegetable oils and cost of biofuel [27]. In
feedstocks could be useful in producing biodiesel. Although, addition, application of vegetable oils as sources of biodiesel needs
Banerjee and Chakraborty [46] stated that FFAs contents in the great efforts to either develop more productive plant species with a
waste cooking oil should be kept within certain limit for reaction high yield of oil or to increase oilseeds’ production [72].
involving both acid- and alkali-catalyzed transesterification Further, many studies have reported microalgal oil as feed-
reactions. Otherwise these substances may cause severe difficul- stocks for producing biodiesel [73–78]. Demirbas [79] noted that
ties in refining of biodiesel products. Table 1 presents the microalgal oil is the only feedstock that can meet the global
recommended FFAs values for alkali-catalyzed transesterification demand for transport fuels. The author also reported that soon,
method. While Table 2 shows FFAs contents of different vegetable microalgal oil will become the most important feedstocks for
oils. In addition, Table 3 presents FFAs levels of most of the biofuel production. Singh and Gu [80] reported that microalgae
feedstocks used to produce biodiesel. The cost of feedstocks feedstocks are receiving great attention as sources of energy
decreases as FFAs content increases. In case of industrial biodiesel because of their quick growth potential coupled with reasonably
production, there is need for low-cost (high FFAs) feedstocks such high lipid, carbohydrate and nutrients contents. In addition,
as used cooking oils, waste cooking oils, and non-edible vegetable Demirbas [81] highlighted that microalgae possess much quicker
growth-rates than terrestrial crops. The author noted the per unit
Table 2 area yield of oil from algae is estimated to be from 20,000 to
Values of FFAs content of different vegetable oils. 80,000 l per acre, per year. In deed this is 7–31 times more than the
Vegetable oils FFA levels (%) Reference
next best crop, palm oil. Table 4 presents lipid content in the dry
biomass of various species of microalgae [82].
Polanga oil 22.0 Sahoo et al. [48]
Cottonseed oil 0.11 Sahoo et al. [48]
Tobacco oil 35.0 Veljkovic et al. [54]
Spent bleaching earth 24.1 Huang and Chang [50] Table 4
Rubber oil 17.0 Ramadhas et al. [25] Lipid content in the dry biomass of various species of microalgae [82].
Palm fatty acid distillate (PFAD) 93 Chongkong et al. [19]
Species Lipid content (% dryweight)
Pongamia pinnata 20 Naik et al. [55]
Palm oil 5.3 Balat and Balat [23] Botyococcus braunii 25–80
Rape seed oil 2.0 Balat and Balat [23] Chlamydomonas reinhardtii 21
Tall oil 100 Demirbas [56] Chlorella emersonii 28–32
Jatropha oil 14.0 Tiwari et al. [54], Bryan [57] Chlorella protothecoides 57.9
Tung oil 9.55 Bryan [57] Chlorella pyrenoidosa 46.7
Soybean soapstock >90 Bryan [57] Chlorella vulgaris 14–22
Ponagamia oil 0.64 Sureshkumar et al. [58] Crypthecodinium cohnii 20
Pongamia oil 2.69 Kaul et al. [59] Cylindrotheca sp. 16–37
Salvadora oil 1.76 Kaul et al. [59] Dunaliella primolecta 23
Moringa oleifera 2.9 Rashid et al. [60] Dunaliella salina 6
Karanja oil 2.53 Sharma and Singh [61] Dunaliella tertiolecta 35.6
Sorghum bug oil 10.5 Mariod et al. [62] Euglena gracilis 14–20
Mahua oil 21.0 Puhan et al. [63] Hormidium sp. 38
Mahua oil 19.0 Ghadge and Raheman [64] Isochrysis sp. 25–33
Madhuca indica 20.0 Kumari et al. [65] Monallanthus salina >20
Zanthoxylum bungeanum 45.5 Zhang and Jiang [66] Nannochloris sp. 30–50
Acid oil 59.3 Haas et al. [67] Nannochloropsis sp. 31–68
Karanja oil 2.53 Meher et al. [68] Neochloris oleoabundans 35–54
Trap grease 50–100% Sharma and Singh [3] Nitzschia sp. 45–47
Finished greases 8.8–25.5% Canakci [41] Phaeodactylum tricornutum 20–30
Crude soybean oil 0.4–0.7% Canakci [41] Pleurochrysis carterae 30–50
Restaurant waste grease 0.7–41.8% Canakci [41] Prymnesium parvum 22–38
Waste palm oil >20% Balat and Balat [23] Scenedesmus dimorphus 16–40
Municipal sludge Up to 65% Bryan [57] Scenedesmus obliquus 12–14
Animal fat 5–30% Van Gerpen [69] Schizochytrium sp. 50–77
Trap grease 75–100% Van Gerpen [69] Spirulina maxima 6–7
Use cooking oil 2–7% Van Gerpen [69] Spirulina platensis 4–9
Waste oil 46.75% Nie [70] Tetraselmis sueica 15–23
 I.M. Atadashi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 14–26
Base catalysed SN2 Transesterification
H-O-H CH -O-H
3 K-O-H
CH3-O
Fig. 4. Mechanism of base-catalyzed transesterification reaction.
Also to highlight the significance of microalgae as feedstock for
biodiesel production, Tran et al. [83] have reviewed biodiesel
production via microalgal oil. The authors noted that catalysts such
as acid, base and zeolites catalysts can used in catalyzing
transesterification involving microalgal oil as feedstocks.
3. The effects of homogeneous catalyst in biodiesel production
3.1. The effects of alkaline catalysts in biodiesel production
Application of alkali-catalyzed transesterification reaction
provide faster rate, nearly 4000 times faster than that catalyzed
by the same amount of an acid catalyst [14]. Some of the alkaline
catalysts used for the transesterification reaction include among
others; NaOH [19,84], KOH [85,86], and sodium methoxide [16,84].
Other alkaline catalysts include; sodium ethoxide [57], potassium
methoxide [3,13], sodium propoxide [57], sodium butoxide [31]
and carbonates [31,87], etc. Based on biodiesel yield, CH3ONa or
CH3OK are better and more suitable catalyst than NaOH and KOH.
Thus, CH3ONa and CH3OK are more suitable due to their ability to
dissociate into CH3O and Na+ and CH3O and K+ respectively.
Besides, the catalysts do not form water during transesterification
reaction [3]. For these reason, alkaline catalyst is mostly preferred
in commercial production of biodiesel fuel [13]. Transesterification
of refined oils with less than 0.5 wt% FFAs via chemical catalysts
could lead to high-quality biodiesel fuel with better yield within
short time of 30–60 min [88]. Fig. 4 presents the mechanism of
base-catalyzed transesterification reaction [71]. Vicente et al. [89]
have compared different basic catalysts (sodium hydroxide,
potassium hydroxide, sodium methoxide and potassium methox-
ide) to produce biodiesel fuel using sunflower oil. The reactions
were conducted at temperature of 65 8C, methanol to oil molar
ratio of 6:1 and basic catalyst by weight of vegetable oil of 1%. They
17
C
O Gly'
O
C
O Gly'
-
CH3-O
C O Gly'
H
O-CH3
H-O-H
O
C
HO-Gly'
CH3-O
HO-CH 3
-OH
achieved 85.9 and 91.67 wt% yield of esters for NaOH and KOH and
99.33 and 98.46 wt% yields of esters for CH3ONa and CH3OK
respectively. The authors recorded 98 wt% yields of esters for
methoxides after separation and purification steps were complet-
ed. Further, less yields losses and negligible ester dissolution in
glycerol were observed with methoxides compared to hydroxides.
Umer et al. [90] used alkali catalyst to produce sunflower oil
methyl esters. They reported notable yield of 97.1 wt% at 60 8C. In
addition, alkaline catalysts concentrations ranging from 0.5–1 wt%
could yield 94–99 wt% conversion of vegetable oils to alkyl esters.
However, increase in catalyst concentration above 1 wt% does not
increase the conversion but could add to extra costs of production.
Since it is essential to get rid of the catalyst from the products after
the reaction is completed [91,92].
Chung [93] transesterified V. fordii and C. japonica seed oils with
methanol using alkaline catalysts (KOH, NaOH, and CH3ONa) to
produce biodiesel. The authors noted that KOH provided higher
catalytic activity to the seed oils in the reaction. The optimum
reaction conditions used were: 6:1 molar ratio of methanol to the
seed oils, 1 wt% loading amount of catalyst, 65 8C reaction
temperature, and reaction time of 3 h. The biodiesel contents of
the C. japonica and V. fordii seed oils under these reaction
conditions were 97.7% and 96.1% on KOH catalyst. Figs. 5 and 6
shows the effects of alkaline catalysts on feedstocks contain high
amount of water and FFAs [94]. The lesser the water and FFAs
contents the better yield vice versa. In another study, Sahoo et al.
[48] employed alkaline transesterification after reducing the FFAs
value from 44 mg KOH/g a below 4 mg KOH/g through acid
catalyzed transesterification. The author found that 1.5 wt% of
KOH was adequate to obtained maximum biodiesel yield.
Marchetti and Errazu [95] revealed that ethanol and sulfuric acid
are suitable to carry out both direct esterification and transester-
ification reactions simultaneously. These processes could
18 I.M. Atadashi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 14–26

Alkaline catalyst
separation time of 30 min. Also, Saifuddin and Chua [97]
optimized transesterification of used frying oil to ethyl ester
110
using microwave irradiation. They used a microwave oven
equipped with non-contact infrared continuous feedback tem-
100
perature system and magnetic stirrer to heat the oil and the
alcohol at 60 8C. Twenty five percent (25%) of an exit power of
90 750 W was used to irradiate the reaction mixture. The authors
Methyl esters (%)

experimented different concentrations of sodium methoxide

80 (0.3 wt% to 0.5 wt%) and achieved maximum conversion (87 wt%)
at 0.5 wt%. During transesterification process, both sodium
70 ethoxide and potassium hydroxide provided good conversions.
However, due simplicity in products phase separation, sodium
60 ethoxide was viewed as most promising catalyst for producing
biodiesel. Besides, microwave-assisted transesterification pro-
50 cess dramatically reduced the reaction time from 75 min to 4 min
at 60 8C, thus saving great time. Additionally during transester-
40 ification, irradiation times must be controlled and the levels of
0 5 10 15 20 25 30 35
radiation power should not be too high, to avoid destruction of
Water content (%)
organic molecules.
Fig. 5. Graph of methyl esters yield against water content in transesterification Moreover, to determine optimum operating parameters such as
reaction. catalyst concentration, Ferella et al. [98] studied transesterification
reaction of rapeseed oil for biodiesel production using response
surface methodology (RSM). They employed a 500 ml jacketed
Alkaline catakyst stirred (at 600 rpm) reactor tank. At optimum conditions of
temperature of 50 8C, KOH concentration of 0.6% (w/w), reaction
105 time of 90 min, and 60 methanol to KOH ratio by weight, large
amount of triglycerides, diglycerides and monoglycerides were
100
converted into biodiesel. As well, the final concentrations were
95 0.05% triglycerides, 0.09% diglycerides and 0.36% monoglycerides
and the triglyceride conversion was 98–99%.
Methyl esters (%)

90 The effects of catalysts such as NaOH on transesterification of

85
80
75
70
65
0 1 2 3 4 5
FFA (%)
Fig. 6. Graph of methyl esters yield against FFA in transesterification reaction.
effectively convert waste cooking oil containing high amount of
FFAs ranging from 3% to 40% to biodiesel. The authors noted the
FFAs content was reduced via esterification process from 10.684%
to a value close to 0.54 wt%. Though, the final FFAs concentration
was slightly more than the recommendable quantity. They
reported minimized soaps formation during alkali-catalyzed
transesterification reaction.
Further, to improve biodiesel production process, Refaat et al.
[96] studied microwave irradiation technique to produce
biodiesel. They employed sunflower oil (used 3 times at a
cooking temperature of 130 8C) and methanol to oil ratio of 6:1 in
the presence of 1 wt% of potassium hydroxide at 65 8C. The
authors used a normal pressure glass reactor 500 ml flask and
reflux condenser. Using the microwave system, the vegetable oil
was preheated to a desired temperature of 65 8C. The mixture of
alcohol and catalyst then charged into the flask through the
condenser. The power output adjusted to 500 W and under reflux
the mixture irradiated via different reaction times of 0.5, 1, 1.5, 2,
2.5, 3 and 6 min. Using microwave irradiation technique, reaction
time was reduced by 97% and the separation time reduced by 94%.
They recorded biodiesel yield of 100% within 2 min and
rapeseed oil under supercritical/subcritical conditions were also
studied by He et al. [99]. The authors employed little quantity of
NaOH as catalyst and achieved excellent biodiesel yield with no
soaps formation.
3.2. The effects of acid catalysts in biodiesel production
The most notable acids commonly employed in transester-
ification reaction include among others; sulfuric acid [13,19,100],
6
sulfonic acid [14], hydrochloric acid [16], organic sulfonic acid
[14], ferric sulfate [13], etc. Among these acids, hydrochloric acid,
sulfonic acid and sulfuric acid are usually favored as catalysts for
the production of biodiesel. The catalyst and the alcohol are
vigorously mixed with a stirrer in a small reactor. The oil is first
charged into the biodiesel reactor and then the mixture of
catalyst/alcohol is fed into the oil. Brønsted acids preferably
sulfuric acid or sulfonic acid is used to catalyze the reaction.
Although the catalysts give high yield of biodiesel, but the reaction
rates are slow. The alcohol to oil molar ratio is the main factor
influencing the reaction. Therefore addition of excess alcohol
speeds up the reaction and favors the formation biodiesel
products. The steps involve during acid-catalyzed transesterifica-
tion are: (1) initial protonation of the acid to give an oxonium ion
(2) the oxonium ion and an alcohol undergo an exchange reaction
to give the intermediate (3) and this in turn can lose a proton to
become an ester. Reversibility of each of the above step is possible
but the equilibrium point of the reaction is displaced in the
presence of excess large alcohol, by allowing esterification to
advance to completion [16]. Leung et al. [40] reported that
esterification by acid-catalysis makes the best use of the FFAs in
the animal fats and vegetable oils and converts them into fatty
acid alkyl esters. The authors noted that one-step esterification
pretreatment may not reduce the FFAs efficiently, if the acid value
of the oils or fats is very high. This is because of the high content of
water produced during the reaction. In this case, addition of
 I.M. Atadashi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 14–26 19

Table 5
Reaction yield as function of the homogeneous catalyst weight.

Feedstock Catalyst Conc. (wt/v/v) Reaction time (h) Reaction temp (8C) Yield/conv. (w/w%) Molar ratios Reference

Waste tallow (chicken) H2SO4 1.25 24 50 99.01  0.71 1:30 [85]

Palm fatty acid H2SO4 – 2 70 99.6 7.2:1 [19]
Sunflower oil KOH 0.55 – 70 96 – [104]
Jojoba oil-wax Sodium methoxide 1 4 60 55 7.5:1 [105]
Brassica carinata KOH – – – 98.27 – [106]
Canola oil KOH 0.5 0.33 25 86.1 6:1 [107]
Jatropha curcas KOH 1 30 92 – [108]
Cottonseed oils Sodium hydroxide 0.5 1 55 77 – [109]
Roselle oil Potassium hydroxide 1.5 1 60 99.4 8:1 [110]
Rubber seed oil (Hevea brasiliensis) NaOH 1 1 60 84.46 6:1 [111]
Mahua oil (Madhuca indica) NaOH 1 2 60 92 6:1 [63]
Mahua oil H2SO4/KOH 1/0.7 1 60 98 6:1 [64]
Sunflower frying oil KOH 1 0.5 25 max 6:1 [112]
Tobacco seed oil NaOH 1.5 1.5 55 max 3:1 [113]
Rice bran oil Sulfuric acid 2 8 100 98 – [21]
Used frying oil KOH 1 2 60 72.5 12:1 [12]
Waste cooking oils KOH 0.75 0.33–2 30–50 88–90% 7:1–8:1 [11]
Jatropha oil H2SO4/KOH 0.25–1.5/0.5 2 60 90–95 6:1/9:1 [114]
Karanja oil KOH 1 3 65 97–98 6:1 [115]

mixture of alcohol and sulfuric acid into the oils or fats three times
(three-step pre-esterification) is required. The time needed for
this process is about 2 h and removal of water is necessary by a
separation funnel before adding the mixture into the oils or fats
for esterification again. Further, Palligarnai and Briggs [24]
reported sulfuric acid catalyzed transesterification to provide a
few advantages over base-catalyzed technique such as one-step
process as opposed to a two-step transesterification. The authors
also reported that feedstock with a high FFAs content could be
easily handle, downstream separation is straightforward, and a
high-quality glycerol byproduct is achievable.
Additionally, Soriano Jr. et al. [101] studied transesterification
of canola oil to produce biodiesel via homogeneous Lewis acid
(AlCl3 and ZnCl2) as catalyst. The reaction occurred in a round
bottom flask submerged in an oil bath equipped with a reflux
condenser, temperature controller and a magnetic stirrer. The
authors reported use of variable parameters such as: reaction time
(6, 18, 24 h), methanol to oil molar ratio (6, 12, 24, 42 and 60),
reaction temperature (75, 110 8C). And tetrahydrofuran (THF) as
co-solvent (1:1 methanol to THF by weight in runs with THF), and
catalyst (AlCl3 or ZnCl2). In all the runs, the catalyst amount was
kept at 5% based on the weight of oil. 1H NMR monitored
converting canola oil into fatty acid methyl esters. Thus the best
conditions with AlCl3 were 24:1 molar ratio at 110 8C and 18 h
reaction time with THF as co-solvent provided a conversion of 98%.
AlCl3 was far more active compare to ZnCl2 due to its higher acidity.
In another study, Cardoso et al. [102] discussed the effects of Lewis
acid on the transesterification process in producing biodiesel. The
authors have introduced an inexpensive Lewis acid Tin(II) chloride
dihydrate (SnCl2
2H2O), and evaluated its potential as catalyst on
the ethanolysis of oleic acid of fats and vegetable oils. The catalytic
tests were carried out in triplicate with a molar ratio fatty acid:
catalyst (100:1), reaction time of 2 h. Using these conditions, the
process provided more than 90% biodiesel yield with a high
selectivity of more than 93%.
3.3. The effects of homogeneous catalysts on the yield of biodiesel fuel
The nature of catalyst used plays a great role during
transformation of vegetable oil to biodiesel [103]. As a result,
catalyst is among the key factors determining the rate and yield of
biodiesel during biodiesel production process [17,46]. Thus, Table
5 presents reaction yield as function of the homogeneous catalyst
weight. The data obtained shows that production of biodiesel via
homogeneous catalyst could yield more than 99%.
4. The effects of heterogeneous catalysts in biodiesel
production
Despite the problems surrounding alkali-catalyzed transester-
ification, the process is still favorable in producing biodiesel fuel.
The main reason is due to their faster kinetic rate and economic
viability [116]. Recently several researches were conducted on
heterogeneous catalysts with the aim of finding solutions to
problems caused by using homogeneous catalysts in producing
biodiesel. As a result a good number of heterogeneous catalysts
were explored and many of the catalysts have displayed very good
catalytic performances [27]. Some of these catalysts include among
others; oxides [117], hydrotalcides [118], zeolites [119], etc.
Currently, majority of heterogeneous catalysts used in producing
biodiesel are either oxides of alkali or oxides of alkaline earth
metals supported over large surface area [15]. Further, biodiesel is
commercially produced using heterogeneous catalyst through the
Esterfip-H process. This biodiesel process is commercialized by
Axens. The process needs neither catalyst recovery nor aqueous
treatment steps, which are major bottlenecks from the current
homogeneous catalytic processes. Additionally the Esterfip-H
process displays high biodiesel yields and directly produces salt-
free glycerol at purities exceeding 98% compared to 80% glycerol
purity from homogeneous catalyzed process [120].
Thus, the effects of these catalysts are discussed as follows.
4.1. The effects of solid alkaline and acid catalysts in biodiesel
production
Semwal et al. [121] reported that many studies on solid acidic
catalysts for producing biodiesel were carried out, however lower
reaction rates and unfavorable side reactions have limited their
uses. The authors noted that a good number of investigations on
basic heterogeneous catalysts were also conducted but their
activity gets degraded in the presence of water. They stated that
acid–base catalysts are among the most promising catalysts to
employ in biodiesel production; this is because they can catalyze
both esterification and transesterification simultaneously. Further,
Lee and Shiro [122] reported simultaneous esterification and
transesterification of waste cooking oil using solid catalyst ZnO–
La2O3, which combines acid (ZnO) and base sites (La2O3). Although
the process provided high conversion of 96% in 3 h, but like
zirconia, lanthanum is a rare and expensive metal, therefore cost of
the catalyst would prohibit it high use in the production of
biodiesel. Further gelular resin catalysts having covalently bound
20 I.M. Atadashi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 14–26
sulfonic groups are developed and employed to simultaneously
esterify and transesterify variety of feedstocks including beef
tallow and soybean oil of high acid number. The authors noted the
key factors influencing the feasibility and performance of solid
catalysts, are durability, catalytic activity and cost of production.
Therefore the main challenges to R&D in using solid catalyst in
production of biodiesel are exploring the impacts of those chemical
properties of supports on the catalytic activity. And designing
specifically tailored deactivation–prevention and/or renewal
techniques for each catalyst and developing less expensive
supports.
4.1.1. The effects of solid alkaline catalysts in biodiesel production
In recent times there is a great development in the preparation
of solid alkaline catalysts for producing biodiesel. Solid alkaline
catalysts such as CaO provides many advantages for instance
higher activity, long catalyst life times, and could run under only
moderate reaction conditions [123]. However, use of CaO in
biodiesel production presents slow reaction rate [31]. Antunes
et al. [124] noted that like homogeneous catalysts, solid alkaline
catalysts present more catalytic activity than solid acid catalysts.
Meher et al. [115] examined methanolysis of karanja oil via solid
basic catalysts. They remarked that increased in FFAs content of
karanja oil from 0.48 to 5.75% decreased the yield of biodiesel
produced decrease from 94.9 to 90.3 wt%. The authors achieved an
acid value of 0.36 mg KOH/g and an ester content of 98.6 wt%, after
purification of the esters. The properties of the esters produced met
both American and European standard specifications for biodiesel
fuels.
Also, Liu et al. [125] have produced biodiesel fuel from
soybean oil using CaO as a solid base catalyst. The authors
reported that use of CaO as a catalyst could provide a numbers of
advantages such as: high activity, lengthen catalyst life and
moderate condition of reaction. In a similarly study, Masato et al.
[123] produced biodiesel fuel via solid base-catalyzed transes-
terification at a reaction time of 1 h and obtained esters yield of
93 wt% for CaO, 12 wt% for Ca(OH)2, and 0% for CaCO3. The
authors stated that CaO will probably provide good productivity
as NaOH as well as easy recovery of products and environmental
benignity. They used CaO to transesterify waste cooking oil with
an acid value of 5.1 mg KOH/g. The yield of esters was above 99%
at a reaction time of 2 h. But a fraction of the catalyst transformed
into calcium soap. Thus, solving this problem will entail removal
of FFAs before transesterification reaction. The authors also
noted that due to neutralization reaction of the catalyst,
concentration of calcium in the produced biodiesel increased
from 187 ppm to 3065 ppm. Conversely, Lim et al. [126] noted
that transesterification reaction involving CaO needs longer
reaction time. But the benefits gained from the process such as
elimination of neutralization process, less waste generation and
prospect of catalyst reusability compensates the delay. The
authors also achieved biodiesel purity of 98.6  0.8% within 2.5 h.
Besides for CaO catalyst, the process generated 90.4% biodiesel
yield compared to biodiesel yield of 45.5% for NaOH and 61.0% for
KOH catalysts. Further, it was observed that compared to biodiesel
yield of 80% under anhydrous conditions using CaO, addition of
2.03 wt% water into the reaction medium of 8 wt% catalysts, 12:1
alcohol/oil molar ratio and at 3 h of reaction time, could provide
biodiesel yield above 95%. Besides the catalyst active sites were
found not to leach and the activity of the catalyst was stable after 20
cycles of the reaction [27].
Similarly, Puna et al. [127] conducted an experimental study to
produce biodiesel via CaO and CaO modified with Li catalysts. Both
catalysts showed good catalytic performances with high activity
and stability. In fact yields of biodiesel were higher than 92% in two
consecutive reaction batches without expensive intermediate
reactivation procedures. As a result, the catalysts are suitable for
producing biodiesel. In another study, Sharma et al. [128]
remarked that the regeneration and reuse of CaO for many times
(for instance, 20 runs) makes the catalyst most favorite among the
oxides. These characteristics are useful from economic analysis.
Further, moderate conversion and yield could be obtained using
mixed oxides as catalyst therefore oxides of calcium and
magnesium are preferred. Besides presence of some amount of
water/moisture in the reaction mixture has fewer effects on the
activity of CaO, this reduces pretreatment cost of feedstock and
alcohol. However, Hsin et al. [129] reported that the high solubility
of CaO in methanol makes it a less attractive candidate for
recyclable heterogeneous catalysis. Consequently the authors have
produced biodiesel fuel from soybean oil (SBO) and poultry fat
using new calcium containing silicate mixed oxide-based hetero-
geneous catalysts. The catalysts are; PME-templated calcium
containing silicate mixed oxide catalysts (PMCS 1–9) and
mesoporous calcium containing silicates (CS 1–9). The authors
reported transesterification of SBO via PMCS-5 consisting of total
surface area of 150 m2/g to provide 100% yield within 2 h. This
catalyst could be recycled and reused for 8 times after regeneration
by calcinations. They remarked that transesterification of soybean
oil using CS-9 improved the reaction kinetics by a factor of 6. Also
this catalyst could be recycled and reused for 3 times without any
decrease in reactivity for poultry fat and 9 times for soybean oil.
Additionally, Zabeti et al. [130] optimized biodiesel yields
produced using transesterification of palm oil via CaO/Al2O3. They
used a 150 ml glass jacketed reactor equipped with a water-cooled
condenser and a magnetic stirrer (1000 rpm) to perform the
experiments for 5 h. The estimated optimal reaction conditions
achieved were; reaction temperature of 65 8C, catalyst content of
6 wt% and alcohol/oil molar ratio of 12:1, and achieved a
corresponding yield of 98.64 wt%. The authors reported that the
values achieved from ICP-MS showed little leaching of CaO/Al2O3
active species into the reaction medium and the catalyst
successfully reused for two successive cycles. To further, examine
the potential of solid alkaline catalysts, Ilgen and Akin [131]
studied different heterogeneous catalysts such as K2CO3/g-Al2O3,
Na2CO3/g-Al2O3, LiOH/g-Al2O3, NaOH/g-Al2O3, g-Al2O3, and KOH/
g-Al2O3and reported FAME yield of 89.40%.
In recent years hydrotalcites materials are receiving great
attention because they can be applied as precursors [132] and as
catalyst [133]. Hydrotalcite-like compounds (HTlcs) are a category
of anionic and basic clays referred as layered double hydroxides
(LDH) with the formula Mg6Al2(OH)16CO3
4H2O [15]. Thus
production of biodiesel was experimented using different hydro-
talcites such as activated Mg–Al hydrotalcites [133,134]. Zeng et al.
[135] have examined activation of Mg–Al hydrotalcite catalysts for
rape oil, and achieved 90.5% conversion. The production of
biodiesel from soybean oil via Mg–Al hydrotalcite was patented
by Siano et al. [136]. The ratio of Mg/Al was found to affect the
performance of the catalyst. And the catalytic activity was highest
at 3–8 ratio of Mg/Al. The authors remarked that the catalyst is best
suitable for oils containing up to 10,000 ppm quantity of water.
They achieved 92% conversion at a reaction condition: reaction
time of 1 h, temperature of 180 8C, catalyst concentration of 5 wt%
and alcohol/oil weight ratio of 0.45. Similarly the catalytic
performance of Mg–Al hydrotalcite for the transesterification of
vegetable oil to biodiesel was investigated by Di Serio et al. [137].
The authors noted that at higher reaction temperatures (215–
225 8C); Mg–Al hydrotalcite displayed high catalytic activity. The
transesterification was then conducted at methanol/oil weight
ratio of 0.45 and catalyst concentration of 1 wt%, and esters yield of
94 wt% was achieved. Xie et al. [138] have experimented
methanolysis of soybean using Mg–Al hydrotalcite as solid base
catalyst. The synthesis of the Mg–Al hydrotalcite was carried out
 I.M. Atadashi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 14–26
by employing co-precipitation technique of aqueous solution of
NaOH, Na2CO3, Al(NO3)3
9H2O, and Mg(NO3)2
6H2O under intense
stirring. Increased in catalytic performance and improved basicity
were observed by improving temperature of calcinations to 500 8C.
But the catalyst showed very low catalytic activity. And a
conversion of 67% was recorded at an operating condition of
9 h, catalyst concentration 7.5 wt%, temperature of 65 8C, and
alcohol/oil molar ratio of 15:1. Further, Georgogianni et al. [118]
have employed heterogeneous catalyst to produce biodiesel fuel
using used frying oil. The authors conducted comparison between
the catalytic activities of MgO supported on MCM-41 and Mg–Al
hydrotalcite base catalyst in the production of biodiesel fuel from
soybean frying oil with alcohol (methanol). They reported the
conversion of oil to biodiesel to be 97% and 85% respectively after
24 h under the same reaction conditions. Further the hydrotalcite
showed greater activity which was attributed to its high basicity.
Even though Mg-MCM 41 has higher specific surface area of
1289 m2/g compared to the low specific surface area of Mg–Al
hydrotalcite of 82 m2/g.
Also, Wen et al. [139] have synthesized fatty acid methyl esters
from vegetable oil with methanol catalyzed by Li-doped magne-
sium oxide catalysts. A number of Li-doped MgO samples were
prepared by the incipient wetness impregnation with the Li/Mg
molar ratio in the range of 0.02–0.15. The catalyst weight was
varied in the range of 3–15 wt% (methanol/oil molar ratio of 12,
temperature of 338 K, residence time of 2 h). The results showed
that the formation of strong base sites was principally promoted by
adding Li. This results to an increase of fatty acid methyl esters
synthesis. In addition the catalyst with Li/Mg molar ratio of 0.08
and calcined at 823 K exhibits the highest biodiesel yield of 93.9%
at 333 K with the molar ratio of methanol/soybean oil of 12 and the
catalyst amount of 9 wt%. The use of the catalyst for the second and
third cycle decreased the fatty acid methyl esters yield from 79.3%
and 71.0%, respectively. The biodiesel conversion decreases with
further increasing Li/Mg molar ratio above 0.08, which is most
likely attributed to the separated lithium hydroxide formed by
excess Li ions and a concomitant decrease of BET values. The metal
leaching from the Li-doped MgO catalysts was detected. The
leaching from the catalyst and the agglomeration of crystallites
caused the deactivation of the catalyst during the initial reaction
cycles.
Furthermore, Suppes et al. [119] have transesterified soybean
oil with zeolites (ETS-10 zeolite, NaX faujasite zeolite) and metal
catalysts. The transesterification reaction was performed at 6:1
molar ratio of alcohol and temperatures of 60, 120, and 150 8C. The
conversion to esters increases from 60 to 150 8C with an average
conversion of 90% achieved at 125 8C. Thus, ETS-10 gave better
conversions of triglycerides than zeolite-X type catalysts. This was
attributed to the higher activity of ETS-10 zeolites and larger pore
structures that improved intra-particle diffusion. The catalyst
activity was not affected after reused. However, FFAs loadings in
excess of 25% quench the catalyst activity. Meyer et al. [140]
conducted experimental studies on heterogeneous catalysts to
produce biodiesel. The reaction occurred at temperature of 90 8C
and a methanol to triglyceride ratio of 9:1. The authors stated that
among the studied catalysts the potassium exchanged low silica
zeolite of the faujasite type (K-LSX) has shown the best results and
reached ester formation of over 90 wt% after 1 h. The result
obtained was comparable to those of homogeneous catalysts such
as alkali metal hydroxides. Another study conducted by Marı́a et al.
[141] examined different zeolite catalysts such as NaX for the
parent zeolite in sodium form: 0.3MNaX, 1MNaX, 3MNaX,
3MNaXB, and samples from mordenite and beta zeolite were
named as 3NaM and 3Nab for the transesterification of sunflower
oil with alcohol (methanol). Hence, zeolite X provided greater
activity compared to other zeolites (mordenite and beta) due to its
21
higher concentration of super-basic sites. The authors reported
that biodiesel contents of 93.5 and 95.1 wt% were achieved at 60 8C
for zeolite X with and without sodium bentonite, respectively.
Though, during the course of the reaction, the active species were
observed to be leached out to the product [141]. Additionally,
Supamathanon et al. [142] have transesterified jatropha oil using
heterogeneous catalysts consisting of potassium supported on NaY
(K/NaY) with potassium loading of 4, 8 and 12 wt% to produce
biodiesel. The experiments were conducted in a 50 ml round-
bottom flask equipped with a water-cooled condenser and heated
with a water bath. They remarked that under reaction temperature
of 65 8C, methanol to oil molar ratio of 16:1 and at a reaction time
of 3 h, the catalyst with 12 wt% of potassium loading yielded
optimum biodiesel yield of 73.4%.
4.1.2. The effects of solid acid catalysts in biodiesel production
The replacement of homogenous catalysts by the solid acid
catalysts is useful for green chemistry [143]. Helwani et al. [15]
reported that compared to homogeneous acid, solid acid catalysts
are preferred although their catalytic activities are low. This is due
to fact that they contain a multiple sites with different strength of
Bronsted or Lewis acidity. Kathlene et al. [144] reported solid acid
catalysts to have strong capacity to substitute liquid acids, thus
wiping out separation, corrosion and environmental problems. The
authors evaluated different solid catalysts for the production of
biodiesel from high FFAs feedstocks (waste cooking oil). The
catalysts investigated include; zinc stearate/SiO2, MoO3/ZrO2,
WO3/ZrO2, WO3/ZrO2–Al2O3, MoO3/SiO2, TPA/ZrO2, and zinc
ethanoate/SiO2. They stated that zinc stearate immobilized on
silica gel was most active and stable. The catalyst recycled several
times at optimized conditions of reaction temperature of 470 K,
1:18 molar ratio of oil to alcohol, and 3 wt% catalyst loading
without being deactivated. The authors recorded a maximum ester
content of 98 wt%. Catalyst recycling reduces the biodiesel
processing cost. In another study, Ngo et al. [145] have esterified
FFAs in greases (12–40 wt% FFA) using a diphenylammonium
triflate acid catalyst immobilized onto two robust and highly
porous solid silica supports (MCM-48 and SBA-15). The authors
evaluated the catalytic activities of the catalysts. The catalysts
were reported to be effective for the esterification of FFAs in
greases with a conversion to biodiesel of 95–99%, resulting in a
pretreated grease with a final FFAs content of <1 wt%. Also, Furuta
et al. [146] studied biodiesel fuel production via transesterification
using soybean oil and methanol with solid superacid catalysts
sulfated tin oxide (SO4/SnO2) and zirconium oxide (SO4/ZrO2) and
tungstated zirconia (WO3/ZrO2) at 200–300 8C. And conducted
esterification of n-octanoic acid with methanol at 175–200 8C in
fixed bed reactor under atmospheric pressure. The authors noted
that out of the catalysts prepared, tungstated zirconia–alumina
catalyst (WZA) showed high performance, yielding over 90%
conversion for esterification processes. Although detail analysis for
the acidity of WZA has not yet been determine.
Besides, Kitiyanan et al. [147] studied transesterification of
palm and coconut oils using solid catalysts such as KNO3/ZrO2,
KNO3/KL zeolite, SO42 /ZrO2, SO42 /SnO2, and ZrO2, ZnO. The
authors noted that transesterification of crude palm kernel oil
using SO42 /SnO2 and SO4/ZrO2catalysts provided highest yield of
methyl esters (90.3 wt%). The purities of the esters were 95.4 wt%
for SO42 /SnO2 and 95.8 wt% for SO42 /ZrO2, respectively. Howev-
er, for ZnO the highest content of the esters was 98.9 wt%. In
addition, owing to the availability of enough acid site strength,
solid acid catalysts for example sulfated zirconia, tungstated
zirconia and Nafion-NR50 were selected to catalyze transester-
ification [147,148]. However, due to its acid strength, the
selectivity of Nafion-NR50 towards biodiesel and glycerol produc-
tion was higher, compared to both sulfated zirconia and tungstated
22 I.M. Atadashi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 14–26
zirconia [149]. Nonetheless, Chai et al. [150] remarked that the
major drawbacks of Nafion as catalyst to produce biodiesel, is it
lower catalytic activity and high cost compared to liquid acids.
Further, application of amberlystTM BD20 catalyst has provided
more impetus for the development of biodiesel fuel. The
amberlystTM BD20 process can effectively convert any feedstock
containing 0.5–100% FFAs to biodiesel. Further amberlystTM BD20
presents fast solid esterification catalyst. Besides high biodiesel
yield can be obtained with improved biodiesel and glycerol purity
[151]. Additionally the search for a suitable solid catalyst has lead
to the development of vanadium phosphate catalyst by Di Serio
et al. [152] for biodiesel production. The authors reported 2–4 m2/g
as specific surface area of the catalyst. However, despite the surface
area of the catalyst is low, the catalyst was found to be active in
producing biodiesel from soybean oil. They reported ester yield of
80% at 150 8C and observed catalysts deactivation at elevated
temperatures owing to reduction of V5+ to V3+ with the alcohol
(methanol). Although regenerating process of the catalyst after use
is simple and could be achieved without complexities.
Also, zeolites are used as a catalyst for esterification and as a
support material for transesterification catalysts [2,142]. Zeolites
are microporous crystalline solids with well defined structures and
that they contain aluminum, silicon and oxygen in their framework
and cations. As catalysts, unlike the compositionally equivalent
amorphous catalysts, zeolites demonstrate substantial acid
activity and shape selective features [153–155]. Chung et al.
[153] employed different Si/Al molar ratio to remove FFAs in waste
frying oil by esterification with methanol using different zeolite
catalysts. The catalysts used include mordenite (MOR), faujasite
(FAU), beta (BEA) zeolites, ZSM-5 (MFI), and silicalite. The pore
structure and the acidic properties of the zeolites were particular
useful in the removal of FFAs. These properties influenced the
catalytic activity in FFAs removal. High conversion of FFAs was
comparatively induced by strong acid sites of zeolites. The MFI
zeolite induced an improvement of the FFAs removal efficiency by
cracking to the FFAs in its pore structure owing to its constricted
pore mouth. Converting FFAs on HMFI and HMOR zeolites provided
80% at a reaction temperature of 60 8C. In addition, HMOR zeolites
showed almost a similar conversion of FFAs with different Si/Al
molar ratio, but with decreased in acidity. Decreased in acid
strength of the zeolites lowered the catalytic performance for FFAs
removal [156].
4.2. The effects of enzymes catalysts in biodiesel production
Transesterification reaction can be catalyzed with enzymes
catalysts such as Candida antarctica lipase [28], Pseudomonas
cepacia [157], Candida sp. 99–125 [28,158], Pseudomonas fluor-
escens [157], Rhizomucor miehei and Chromobacterium viscosum
[20,159] and Rhizopus oryzae lipase [160]. Casimir et al. [161] noted
that biodiesel can be excellently produced via enzymatic-
transesterification reactions involving lipases. They suggested
that large quantities of lipases can be produced using recombinant
DNA technology. The authors believed that application of
immobilized lipase may reduce the overall cost of biodiesel
production and lower downstream processing problems. Besides,
enzymatic approach is environmentally friendly [161]. Watanabe
et al. [29] explored use of immobilized Candida antarctica lipase for
continuous production of biodiesel fuel from vegetable oil. The
transesterification of vegetable oil was conducted using 4%
immobilized Candida lipase as a catalyst at 30 8C in a 20- or 50-
ml screw-capped vessel, shaking at 130 oscillations/min. The
authors noted the activity of Candida antarctica lipase was not
affected in a mixture of vegetable oil and more than 1:2 molar
equivalent of methanol against the total fatty acids. They
discovered inactivation of the lipase to be eradicated via three
consecutive additions of 1:3 molar equivalent of methanol. And
then developed a three-step methanolysis by which over 95% of
the oil triacylglycerols (TAG) transformed to their corresponding
esters.
Additionally, Shah et al. [30] have prepared biodiesel from
jatropha oil using lipase catalyst. The authors have screened
pancreas porcine, candida rugosa, Chromobacterium viscosum and
in a solvent-free system for the production of biodiesel. They
employed a screw-capped vial and jatropha seed oil (0.5 g) and
ethanol were taken in the ratio of 1:4 (mol mol 1). Also 50 mg of
enzyme preparation (tuned or immobilized) was added and
incubated at 40 8C with constant shaking at 200 rpm. The
immobilization of lipase (Chromobacterium viscosum) on Celite-
545 improved yield of esters from 62% to 71% by free tuned enzyme
preparation with a process time of 8 h at 40 8C. Additionally to
explore more information on the use of enzymes for the production
of biodiesel, Tan et al. [28] reviewed biodiesel production using
immobilized lipase. The immobilized lipase as biocatalyst draws
great interest because that process is environmentally friendly.
The authors noted different techniques for lipase immobilization,
such as covalent bonding, cross-linking, encapsulation, entrap-
ment and adsorption. Lipase immobilization technique is com-
monly used to increase the stability of lipase in biodiesel
production. They stated that, for biodiesel (fatty acid methyl
esters) preparation, at least a stoichiometric amount of methanol is
needed for the complete conversion of triglycerides to their
resultant fatty acid methyl ester. But, methanolysis is reduced
considerably by adding >1/2 molar equivalent of methanol at the
commencement of the enzymatic process. Usually, the polar short
chain alcohols causes inactivation of enzymes and this is the major
obstacle for the enzymatic-transesterification reaction. Therefore
to overcome this difficulty one of these options is selected: acyl
acceptor alterations, solvent engineering and methanol stepwise
addition. The authors reported that biodiesel yield of 97 wt% was
obtained after 24 h at temperature of 50 8C with a reaction mixture
containing 13.5% methanol, 32.5% t-butanol, 54% oil and
0.017 g enzyme (g oil) 1. With the same mixture, a 95% biodiesel
yield was achieved using a one step fixed bed continuous reactor
with a flow rate of 9.6 ml h 1 (g enzyme) 1. The authors concluded
that low cost of immobilized Candida sp. 99–125 lipases is rather
competitive for industrial use [28]. More so, Hideki et al. [14] noted
use of enzymatic-catalyzed transesterification to avoid problems
associated with homogeneous catalysts. Therefore the production
processes are compared in Figs. 7 and 8. The authors reported
conversion of high FFAs feedstocks to biodiesel using immobilized
antarctica lipase (Novozym-435) with ease of separation process.
4.3. The effects of heterogeneous catalysts on the yield of biodiesel
As earlier stated great efforts have being made by several
researchers and industries to explore and exploit use of heteroge-
neous catalysts in the production of biodiesel. Some of the reasons
for the recent growth and development of heterogeneous catalysts
include among others: biodiesel yield of 98 wt% and simplicity in
catalyst separation process [130], high-purity by-products, less
cost of separation and low energy consumption [31]. Table 6
presents reaction yield as function of the heterogeneous catalyst
weight.
5. The advantages and disadvantages of homogeneous
catalysts and heterogeneous catalysts
The choice of catalyst to use in the production of economically
viable biodiesel fuel is one of the most critical issues that are being
discussed by futurists and industries [117]. As discussed earlier,
NaOH and KOH are mostly preferred because they are cheaper than
 I.M. Atadashi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 14–26 23

Alcohol for recycling

Vegetable
Crude
oils/Animal
biodiesel
fats Centrifuge/settler
Transesterification for separation of Neutralization Distillation/ Drying
Alcohol
Reaction crude biodiesel process/water Evaporation Facility
products washing
Alkali
Waste
Crude water
glycerin/ Mineral acid (H3PO4) Finished
impurities product
Pure glycerin for (biodiesel)
Mineral acid (H2SO4) Glycerin purification
Storage/recycling/sale

Free Fatty Acid (FFAs)

Fig. 7. Traditional alkali biodiesel production.

Fats and oils

Separation/purification Upper layer
Alcohol Finished biodiesel
Transesterification reaction of transesterified
product for
products
Enzymes consumption

Lower layer

Pure glycerin
Glycerin purification
for sale

Fig. 8. Enzymatic biodiesel production.

alkoxides, but are less active [17]. Leung and Guo [38] revealed that
industrially, separation of esters is much easier when KOH catalyst
is used compared to NaOH or CH3ONa. Because potassium soap
formation is much softer and does not sink into glycerol phase.
Owing to this reason, KOH is most often employed to produce
biodiesel from waste recycled feedstocks [38]. Saka and Isayama
[170] reported that even though the alkaline catalyst technique has
the advantage of using moderate reaction conditions, several water
washings are needed to remove the catalysts. Zhang et al. [45]
conducted economic analysis of four continuous processes to
produce biodiesel such as alkali- and acid-catalyzed processes,
with virgin vegetable oil and waste cooking oil. The authors
revealed that acid-catalyzed transesterification with waste cook-
ing oil were more economically viable. The process gave lesser
total production cost, a more attractive after-tax rate of return and
a less biodiesel break-even price.

Table 6
Reaction yield as function of the heterogeneous catalyst weight.

Feedstock Catalyst Conc (wt) Reaction time (h) Reaction temp (8C) Yield (w/w%) Molar ratios Reference

Soybean oil CaO 25 1 – 93 – [121]

Vegetable oil M(3-hydroxy-2-methyl-4-pyrone)2(H2O)2 3 60 93 – [162]
Sunflower oil CaO/SBA-14 5 160 95 12 [163]
Sunflower Zeolite X 4.2 – 60 95.1 – [164]
Soybean oil ETS-10 zeolite 0.03 24 125 90 – [119]
Palm oil CaO/Al2O3 3.5 5 65 98.64 12:1 [26]
Waste bleaching earths Rhizopus oryzae 96 35 55 1:4 [160]
Soybean Na/NaOH/g-Al2O3 1 2 60 96 9:1 [165]
Crude palm kernel oil SO42 /ZrO2 1 1 200 90.3 6:1 [144]
Waste cooking oil ZS/Si 3 10 200 98 1:18 [166]
Soybean oil Lipase 0.9 6.3 36.5 92.2 3.4:1 [159]
Palm oil CaO/Al2O3 3.5 5 65 95% 12:1 [130]
Canola oil Nano-g-Al2O3 8 65 97.7  2.1 15:1 [167]
Mixture of soybean and Candida lipase 4 24 30 93 1:3 [29]
rapeseed oils
Jatropha oil Chromobacterium viscosum lipase 5 8 40 92 1:4 [30]
Soybean oil Pseudomonas cepacia lipase 47.5 1 35 67 mol% 1:7.5 [168]
Sunflower oil WO3/ZrO2 3 5 200 97 20:1 [169]
24 I.M. Atadashi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 14–26

Table 7
Advantages and disadvantages of homogeneous catalysts and heterogeneous catalysts.

Type of catalyst Example Merits Demerits Ref.

Homogeneous catalyst
Alkaline catalysts: NaOH, KOH, CH3ONa, CH3OK
Acid catalysts: H2SO4
Heterogeneous catalysts
Solid alkaline catalysts MgO, CaO, ZnO KOH/NaY,
and solid acid catalyst CaO/MgO, Al2O3–SnO, KOH/K2CO3,
Al2O3–ZnO, Ca(NO3)2/Al2O3,
CaO/Al2O3, KOH/Al2O3, Al2O3/KI
Sr(NO3)2/ZnO, ZrO2/SO42 TiO2/SO4 2 .
ETS-10 zeolite, zeolite HY, and zeolite X
Enzymes catalysts: Candida antarctica B lipase, Rhizomucor
meihei lipase, candida rugosa Pseudonas
cepacia, M. meihei (Lypozyme), M. meihei
(Lypozyme IM60), Aspergillus niger.
P. fluorescens, R. Oryzae
Less corrosive, high reaction rate
Zero soap formation, the catalyst
can be used to catalyze both
esterification and
transesterification
simultaneously
Environmentally friendly, easily
ecycle, less discharges, less
separation difficulty, high
purity glycerol, lower cost of separation
Insignificant leaching of CaO/Al2O3
Zero saponification products
nonpolluting, easily separable,
lesser separation cost, high
purity glycerol and biodiesel
products, environmentally benign
Simple glycerol recovery
Formation of saponified product, [13,17,98,153,
emulsion formation, high water 170,177–179]
and energy consumption, huge,
high wastewater discharges,
high purification cost. Feedstocks
are limited to 0.5 wt FFAs,
not recycle
More waste as a result of [31,177,180]
neutralization, recycling difficulty,
high purification cost, energy
consuming, low reaction rates
Leaching effects, catalysts [15,27,47,150,
preparation is complicated 152,162,172,
and expense relatively slow rates 174,175,181,
182]
[26,130]
Catalysts inhibition by water [14,40,161,
180,183]
High cost of enzymes [29,30]

In contrast both alkali- and acid catalyzed transesterification
are associated with a number of problems. Madras et al. [171]
reported that alkali-catalyzed transesterification present high cost
of biodiesel production and large energy consumption during
down-stream biodiesel refining process. Ferella et al. [98] stated
that potassium hydroxide produces soaps formation by neutraliz-
ing FFAs. Additionally, due to the tendencies to produce soaps
formation and mono- and di-glycerides during transesterification,
direct use of sodium and potassium alkylates as catalysts is raising
serious issues in the industries. The soaps formations cause
formation of gels and makes separation and purification of
biodiesel hard. Also, Cardoso et al. [102] reported that the
problems associated with H2SO4 catalyst include much reactor
corrosion and huge wastewater discharges resulting from the
neutralization of mineral acid. Another investigation conducted by
Helwani et al. [15] revealed that application of homogeneous
catalysts in biodiesel production presents difficulty in biodiesel
product separation and makes recovery of used catalyst cumber-
some. The authors reported that biodiesel production via
homogeneous alkaline catalysts needs multi-steps of production
and purification, since such catalysts do not tolerate presence of
moisture or FFAs. In addition, there are many notable issues
surrounding the existing transesterification processes such as;
difficulties in processing low quality feedstocks and refining of
transesterified products [40].
Further heterogeneous catalysts provide many advantages
compared to homogeneous catalysts such as: catalyst re-usability,
less separation and purification difficulties, high purity glycerol
(above 99%), and catalyst recoverability [117,172]. Additionally
no neutralization step is required [173]. Thus, in biodiesel
production, the overall economy can be improved through the
use or sale of by-product, glycerol [117]. Mariscal et al. [172]
reported that heterogeneous catalysts are less corrosive, leading
to safer, less costly, and more environmentally friendly opera-
tions. Watanabe et al. [29] reported enzymatic-transesterification
reaction to overcome problems associated with chemical pro-
cesses. Palligarnai and Briggs [24] found glycerol from enzymatic-
catalyzed transesterification not to show negative effects on
biodiesel fuel property. The authors stated that the major
advantage of employing enzyme catalysts is lack of soaps
formation. They reported application of insoluble solid catalysts
(immobilized enzymes) to speed up catalyst removal from both
glycerol and alkyl esters. Zabeti et al. [27] showed solid-catalyzed
transesterification reaction to yield biodiesel products with no
catalyst impurities. Therefore absence of leaching improves
separation process and lowers the cost of final refining. Martino
et al. [47] noted that heterogeneous catalysts can be separated
more easily, besides low processing costs and zero waste streams.
Hameed et al. [174] stated that heterogeneous catalysts are
searched over time to achieve environmentally benign and
economically viable biodiesel production and purification pro-
cesses. However, issues such as leaching of catalysts especially
when solid alkaline catalysts such as CaO, MgO, La2O3, ZnO, SrO,
Li-promoted CaO, CaCO3, Ba(OH)2, KxX/Al2O3 (X-halide ion or
other mono/di-valent anion), Zinc aluminates, Metal salts of
amino acids, Mg–Al hydrocalcites and K- and Cs-exchanged
zeolites are used in producing biodiesel creates great deal of
concern during separation process. The leaching of active sites of
solid alkaline catalysts into liquids results from its characteristic
changed turning it partly ‘‘homogeneous’’. This changed in the
properties of the catalysts affects biodiesel quality, makes catalyst
separation and biodiesel purification difficult, thus bringing extra
cost of production [15]. Mariscal et al. [172] reported significant
leaching of potassium during transesterification of triglyceride via
K/c-Al2O3 catalysts. The authors reported 99 wt% biodiesel yield
which was attributed to homogeneous contribution from active
basic species dissolved in the methanol. In addition, the
homogeneity of this catalyst complicates its separation process.
Also leaching of solid acid catalyst (sulfate species) was reported
to restrict its reusability [175]. Moreover, a study carried out by
Lee et al. [176] remarked that leaching of base active species
caused great negative effects on the degree of purity of biodiesel
and glycerol. Another investigation conducted through optimiza-
tion of catalytic activity of CaO/Al2O3 for producing biodiesel with
response surface methodology showed insignificant leaching of
catalyst into the reaction medium [26,130]. Table 7 summarizes
the merits and demerits of homogeneous catalysts and
heterogeneous catalysts for biodiesel production.
 I.M. Atadashi et al. / Journal of Industrial and Engineering Chemistry 19 (2013) 14–26
6. Conclusions and recommendations
Based on the foregoing the following conclusions and recom-
mendations were made:
1. Use of high FFAs feedstocks to produce biodiesel is more
economically viable, though it has great negative effects on the
catalyst. Besides refining of crude biodiesel produced from low
quality feedstock with alkaline catalysts is complicated.
2. It was found that acid-catalyzed transesterification reaction
needs higher alcohol to oil molar ratios. In addition the reaction
was reported to cause large corrosion effects on the production
facilities.
3. It observed that biodiesel can be conveniently produced from
low quality feedstocks using heterogeneous catalysts. Especial-
ly, enzymatic-catalyzed transesterification reaction that was
discovered to converts FFAs to biodiesel fuel.
4. The conversion of FFAs to biodiesel was found to increase the
yield of biodiesel and simplify the separation of catalyst form
crude biodiesel mixture.
5. To make biodiesel production process cost effective, the
chemistry of heterogeneous catalysts such as solid alkaline
catalysts needs to be thoroughly explored, developed and use
consistently in producing biodiesel. Further the catalysts were
found provide biodiesel yield similar those obtained from
homogeneous alkaline catalysts.
6. Tremendous effort should be made to exploit ways of improving
the kinetic rate of CaO catalysts, since its catalytic activity is
high, its catalyst life time is long and it operates under only mild
reaction conditions.
7. Development of enzymes catalyst as a more environmentally
benign process is necessary due to the prevailing environmental
needs. Besides the process is potentially sound providing high-
quality biodiesel fuel that can compete favorably with petro-
diesel fuel.
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