Accepted Manuscript

Title: The Effects of Catalysts in Biodiesel Production: A

Review

Authors: I.M. Atadashi, M.K. Aroua, A.R. Abdul Aziz,

N.M.N. Sulaiman

PII: S1226-086X(12)00233-X
DOI: doi:10.1016/j.jiec.2012.07.009
Reference: JIEC 1004

To appear in:

Please cite this article as: I.M. Atadashi, M.K. Aroua, A.R.A. Aziz, N.M.N. Sulaiman,
The Effects of Catalysts in Biodiesel Production: A Review, Journal of Industrial and
Engineering Chemistry (2010), doi:10.1016/j.jiec.2012.07.009

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The Effects of Catalysts in Biodiesel Production: A Review (Article No: IE2011-183)

I.M. Atadashi, M.K. Aroua*, A.R. Abdul Aziz, N.M.N. Sulaiman

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Chemical Engineering Department, Faculty of Engineering, University Malaya 50603 Kuala Lumpur, Malaysia

*Corresponding author. Tel: +603-79674615, Fax: +603-79675319

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Email address: mk_aroua@um.edu.my

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Abstract

Biodiesel fuel has shown great promise as an alternative to petro-diesel fuel. Biodiesel production is widely conducted through
pt
transesterification reaction, catalyzed by homogeneous catalysts or heterogeneous catalysts. The most notable catalyst used in
producing biodiesel is the homogeneous alkaline catalyst such as NaOH, KOH, CH3ONa and CH3OK. The choice of these catalysts is
ce

due to their higher kinetic reaction rates. However because of high cost of refined feedstocks and difficulties associated with use of
homogeneous alkaline catalysts to transesterify low quality feedstocks for biodiesel production, development of various heterogeneous
Ac

catalysts are now on the increase. Development of heterogeneous catalyst such as solid and enzymes catalysts could overcome most of
the problems associated with homogeneous catalysts. Therefore this study critically analyzes the effects of 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.

Key words: Biodiesel, Production, alkaline catalyst, acid catalyst, solid catalyst

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1. Introduction catalysts and heterogeneous catalysts. Conventionally,
homogeneous alkaline catalysts such as NaOH, KOH,
Energy is the prime mover for socio-economic
CH3ONa, and CH3OK are more often used in producing

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development. The World’s economic growth is affected by
biodiesel [13]. The catalytic performance of these catalysts and
climatic change, fuel price hike, and the gradual depletion of
their ability to perform under moderate conditions has led to
fossil fuel reserves. Therefore, to increase energy security for

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their choice [14]. Among these homogeneous alkaline
economic development, the need to search for an alternative
catalysts, CH3ONa is most active, providing biodiesel yield
source of energy such as biodiesel is necessary [1,2]. Biodiesel
above 98wt% in short reaction time (30min) [15,16]. However

ed
is renewable, sustainable, biodegradable, and emits low
because of low price, industrial biodiesel production process
greenhouse gases [3,4]. As well, the oxygen content of 11–15%
mostly employs NaOH and KOH [14]. The process involving
in the molecular structure speed up the combustion process in
pt
these catalysts needs high-quality feedstocks, thus the free fatty
compression ignition engines and decreases pollutants such as
acid (FFAs) level of the feedstocks should not exceed 3wt%,
soot, fine particles, and carbon monoxide (CO) [5,6]. Thus,
ce

beyond which the reaction will not occur. In addition, water

biodiesel is a potential substitute to replace/supplement petro-
content of the feedstocks is critical, as a result the feedstocks
diesel fuel [7,8].
Ac

used in alkali-catalyzed transesterification have to anhydrous

Biodiesel fuel is produced via transesterification of
[14,17]. Thus, presence of water leads to hydrolysis of oils to
refined vegetable oil, waste cooking oil, and used frying oil
FFAs. Figure 2 shows water hydrolysis of fats and oils to form
using alkaline catalysts [9-12] as shown in Figure 1. The
free fatty acid. The FFAs react with alkaline catalysts to
nature of catalyst employed during transesterification reaction
produce soaps formation. Figure 3 presents soaps formation in
is crucial in converting triglycerides to biodiesel. As a result
homogeneous alkali-catalyzed transesterification. Soaps
different catalysts have being explored for converting
formation consumes the catalyst, deactivates it and makes
triglycerides to biodiesel fuel. The catalysts usually employed
biodiesel purification process difficult [13,18]. Therefore,
to catalyze transesterification reaction are homogeneous

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O O
|| ||

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CH2 - O - C - R1 R 4 - O - C - R1
| +
| O O CH2 - OH
| || || |

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CH - O - C - R2 + 3 R4OH ↔ R 4 - O - C - R2 + CH - OH
| (KOH) + |
| O O CH2 - OH
| || ||

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CH2 - O - C - R3 R4- O - C - R3

Triglyceride alcohol Alkyl Esters glycerin

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Figure 1: Transesterification reaction of triglycerides via alkaline catalyst
pt
O
|| + KOH → R1 – COOK + H2O
R1- C -OH
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Free fatty acid Potassium hydroxide (Soap) Water

CH2 - O - CO - R1 CH2 - OH
| | Figure 3: Soap formation in homogeneous alkali-catalyzed
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| | O
| | ||
CH - O - CO - R2 + H2O CH - O - CO - R2 + HO - C-R1
| |
| |
| |
CH2 - O - CO - R3 CH2 - O - CO- R3

Triglyceride Water Diglyceride Free fatty acid

Figure 2: Water hydrolysis of fats and oils to form free fatty acid (FFAs)

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preparation of biodiesel by low quality feedstocks containing
huge quantity of FFAs and water needs sound technology [19].
However, high cost of refined feedstocks result in high price of
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homogeneous catalysts such as; simple catalyst recovery,
catalyst reusability, simple product purification, less energy
and water consumption, less added cost of purification, and

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biodiesel compared to diesel fuel [15,20]. The cost of refined simple glycerol recovery etc. Besides, most of the
feedstocks, account to over 70% of the overall cost of biodiesel heterogeneous catalysts used especially solid alkaline catalysts

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production [21]. As a result, different kinds of low quality have provided high yields [26], though faced with problem of
feedstocks such as: waste cooking oils, used cooking oil, leaching [27]. Also, the stability of enzymes catalysts in non-
greases (yellow and brown), and non-edible oils have being aqueous media is significant to its excellent catalytic activity,

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investigated [13,22]. The price of low quality feedstocks such
as waste cooking oil is 2-3 times lower than refined oils.
this improves tranessterification and esterification during
biodiesel production [28], and providing high biodiesel yield
pt
Nonetheless, the feedstocks contains higher amount of FFAs (95wt%) [29]. However, the problem mostly associated with
and water contents. This features makes their processing enzymes catalysts is the cost of the enzymes, but
ce

challenging [23,24]. Therefore to augment their processing immobilization of the catalyst could mitigate the cost [30].
difficulties, acid-catalyzed transesterification is first employed Therefore, to achieve biodiesel that is economically feasible,
Ac

to decrease the content of FFAs before performing alkali- development of active and cheap catalysts for effective
catalyzed transesterification [19]. Thus adopting two-step transesterification of different kinds of feedstocks is necessary
transesterification technique could provide large biodiesel [31]. In this regards, this study extensively examined and
conversion of up to 98% [25]. reported the effects of different catalysts in producing biodiesel
Recently heterogeneous catalysts such as solid catalysts fuel.
and enzyme catalysts are employed to catalyze
transesterification reaction for producing biodiesel.
Heterogeneous catalysts offers many advantages over

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2. Biodiesel Production
2.1 Techniques for biodiesel production
Biodiesel is usually produced through different
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techniques such as direct/blends [32,33], microemulsion
[34,35], pyrolysis [36,37] and transesterification [38,39]. As
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stated earlier, alkali-catalyzed transesterification is the most
adopted technique for producing biodiesel, this method usually
needs refined feedstocks containing less FFAs content
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otherwise it will result to much soaps formation. For alkali-
catalyzed transesterification, if the feedstocks contains high
pt
amount of FFAs then it has undergo pretreatment steps before
transesterification [40]. Hideki et al. [14] and Ramadhas et al.
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[25] recommended acid value of feedstocks to be less than
4.0mg KOH/g before performing alkaline transesterification.
Ac
Although, Canakci and Gerpen [41] and Mittelbach [42] stated
that before alkali-catalyzed transesterification, the acid value of
a feedstock has to be 2.0 mg KOH/g. Nonetheless, the use of
heterogeneous catalysts in 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].
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2.2 Feedstocks for Biodiesel Production.
Biodiesel production is achieved via different kinds of
feedstocks. The nature of feesdstock used is dependent on the
geographical position and climate of the place. For instance
Europe employs sunflower and rapeseed oils, palm oil
predominates in tropical countries, soybean in United States
and canola oil in Canada [43]. Singh and Singh [44] reported
the major feedstocks employed in producing biodiesel are
cotton seed, palm oil, sunflower, soybean, canola, rapeseed,
and Jatropha curcas. Additionally, Zhang et al. [45] remarked
that employing feedstocks such as waste frying oils, non-
edible oils, and animal fats, as feedstocks could be useful in
producing biodiesel. Although, Banerjee and Chakraborty
[46] stated that FFAs contents in the waste cooking oil
should be kept within certain limit for reaction involving both
acid- and alkali-catalyzed transesterification reactions.
Otherwise these substances may cause severe difficulties in
refining of biodiesel products. Table 1 presents the
recommended FFAs values for alkali-catalyzed
transesterification method. While Table 2 shows FFAs
contents of different vegetable oils. In addition, Table 3
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Table 1: Level of FFAs recommended for alkali-catalyzed transesterification

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presents FFAs levels of most of the feedstoks used to produce
FFAs recommended (%) Reference biodiesel. The cost of feedstocks decreases as FFAs content
increases. In case of industrial biodiesel production, there is

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<1 Demirbas [16]
need for low-cost (high FFAs) feedstocks such as used
<1 Chongkhong et al. [19]
cooking oils, waste cooking oils, and non-edible vegetable
<3 Ramadhas et al [25]

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oils. Since biodiesel fuels from refined oils are costly when
<0.5 Adam Khan [35] compared to petro-diesel fuel. Besides, the application of such
<3 Canakci and Van Gerpan [41] feedstocks in biodiesel production could minimize
<0.5
<0.5 ed
Zhang et al. [45]
Martino et al. [47]
competition between demand of edible vegetable oils and cost
of biofuel [27]. In addition, application of vegetable oils as
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sources of biodiesel needs great efforts to either develop more
<2 Sahoo et al. [48]
productive plant species with a high yield of oil or to increase
<1 Ma and Hanna [49]
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oilseeds’ production [73].

<2 Huang and Chang [50]
Further, many studies have reported microalgal oil as
<0.5 Szczesna Antczak et al. [51]
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feedstocks for producing biodiesel [74-79]. Demirbas [80]

<1 Marchetti et al. [52] noted that microalgal oil is the only feedstock that can meet
<1 Tiwari et al. [53] the global demand for transport fuels. The author also
reported that soon, microalgal oil will become the most
important feedstocks for biofuel production. Singh and Gu
[81] reported that microalgae feedstocks are receiving great
attention as sources of energy because of their quick growth
potential coupled with reasonably high lipid, carbohydrate

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Table 2: Values of FFAs content of different vegetable oils

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Vegetable oils FFA Levels (%) Reference
Polanga oil 22.0 Sahoo et al. [48]
Cottonseed oil 0.11 Sahoo et al. [48]

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Tobacco oil 35.0 Veljkovic et al. [54]
spent bleaching earth 24.1 Huang and Chang [50]
Rubber oil 17.0 Ramadhas et al.[25]
palm fatty acid distillate (PFAD) 93 Chongkong et al. [19]
Pongamia pinnata < 20 Naik et al. [55]

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Palm oil 5.3 Balat and Balat [56]
Rape seed oil 2.0 Balat and Balat [56]
Tall oil 100 Demirbas [57]
Jatropha oil 14.0 Tiwari et al. [54], Bryan [58]

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tung oil 9.55 Bryan [58]
Soybean soapstock >90 Bryan [58]
Pongamia oil 0.64 Sureshkumar et al [59]
Pongamia oil 2.69 Kaul et al. [60]
Salvadora oil 1.76 Kaul et al. [60]
pt
Moringa oleifera 2.9 Rashid et al. [61]
Karanja oil 2.53 Sharma and Singh [62]
Sorghum bug oil 10.5 Mariod et al. [63]
ce

Mahua oil 21.0 Puhan et al. [64]

Mahua oil 19.0 Ghadge and Raheman [65]
Madhuca indica 20.0 Kumari et al. [66]
Zanthoxylum bungeanum 45.5 Zhang and Jiang [67]
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Acid oil 59.3 Haas et al. [68]

Karanja oil 2.53 Meher et al. [69]
Trap grease 50-100 Sharma and Singh [3]
Finished greases 8.8 - 25 Canakci [41]
Crude soybean oil 0.4-07 Canakci [41]
Restaurant waste grease 0.7 - 41.8 Canakci [41]
Waste palm oil >20 Balat and Balat [56]
Municipal sludge Up to 65 Bryan [58]
Animal fat 5-30 Van Gerpen [70]
Trap grease 75-100 Van Gerpen [70]
Use cooking oil 2-7 Van Gerpen [70]
Waste oil 46.75 Nie [71]

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Table 3: FFAs levels in Feedstocks

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crop, palm oil. Table 4 presents lipid content in the dry
Feedstocks FFA Levels References
biomass of various species of microalgae [83].
Trap grease 50-100% [3]

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Table 4: Lipid content in the dry biomass of various species of microalgae [83]
Refined vegetable oils < 0.05% [72]
Species Lipid content (% dryweight)
Finished greases 8.8% - 25.5% [41]
Botyococcus braunii 25–80

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Crude soybean oil 0.4-0.7% [41]
Chlamydomonas reinhardtii 21
Restaurant waste grease 0.7% - 41.8% [41] Chlorella emersonii 28–32
Chlorella protothecoides 57.9
Waste palm oil >20% [56] Chlorella pyrenoidosa 46.7

Municipal sludge

Animal fat
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Up to 65%

5-30%
[59]

[7072]
Chlorella vulgaris
Crypthecodinium cohnii
Cylindrotheca sp.
Dunaliella primolecta
14–22
20
16–37
23
pt
Dunaliella salina 6
Trap grease 75-100% [70,72]
Dunaliella tertiolecta 35.6
Euglena gracilis 14–20
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Use cooking oil 2-7% [70]

Hormidium sp. 38
Waste oil 46.75% [71] Isochrysis sp. 25–33
Monallanthus salina >20
Nannochloris sp. 30–50
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Nannochloropsis sp. 31–68

Neochloris oleoabundans 35–54
Nitzschia sp. 45–47
and nutrients contents. In addition, Demirbas [82] highlighted Phaeodactylum tricornutum 20–30
that microalgae possess much quicker growth-rates than Pleurochrysis carterae 30–50
Prymnesium parvum 22–38
terrestrial crops. The author noted the per unit area yield of oil Scenedesmus dimorphus 16–40
Scenedesmus obliquus 12–14
from algae is estimated to be from 20,000 to 80,000 l per acre,
Schizochytrium sp. 50–77
per year. In deed this is 7–31 times more than the next best Spirulina maxima 6–7
Spirulina platensis 4–9
Tetraselmis sueica 15–23

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Also to highlight the significance of microalgae as feedstock
for biodiesel production, Tran et al. [84] have reviewed
biodiesel production via microalgal oil. The authors noted that
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transesterification reaction [3]. For these reason, alkaline
catalyst is mostly preferred in commercial production of
biodiesel fuel [13]. Transesterification of refined oils with less

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catalysts such as acid, base and zeolites catalysts can used in than 0.5 wt% FFAs via chemical catalysts could lead to high-
catalyzing transesterification involving microalgal oil as quality biodiesel fuel with better yield within short time of 30–

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feedstocks. 60 min [89]. Figure 4 presents the mechanism of base-
3. The Effects of Homogeneous Catalyst in Biodiesel catalyzed transesterification reaction [72]. Vicente et al. [90]
Production have compared different basic catalysts (sodium hydroxide,

Application of
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3.1 The effects of alkaline catalysts in biodiesel production

alkali-catalyzed transesterification
potassium hydroxide, sodium methoxide and potassium
methoxide,) to produce biodiesel fuel using sunflower oil. The
pt
reactions were conducted at temperature of 65oC, methanol to
reaction provide faster rate, nearly 4000 times faster than that
oil molar ratio of 6:1 and basic catalyst by weight of vegetable
catalyzed by the same amount of an acid catalyst [14]. Some of
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oil of 1%. They achieved 85.9 and 91.67 wt% yield of esters
the alkaline catalysts used for the transesterification reaction
for NaOH and KOH and 99.33 and 98.4 6 wt% yields of esters
include among others; NaOH [19,85], KOH [86,87], and
Ac

for CH3ONa and CH3OK respectively. The authors recorded 98

sodium methoxide [16,85]. Other alkaline catalysts include;
wt% yields of esters for methoxides after separation and
sodium ethoxide [58], potassium methoxide [3,13], sodium
purification steps were completed. Further, less yields losses
propoxide [58], sodium butoxide [31] and carbonates [31,88]
and negligible ester dissolution in glycerol were observed with
etc. Based on biodiesel yield, CH3ONa or CH3OK are better
methoxides compared to hydroxides. Umer et al. [91] used
and more suitable catalyst than NaOH and KOH. Thus,
alkali catalyst to produce sunflower oil methyl esters. They
CH3ONa and CH3OK are more suitable due to their ability to
- + - +
reported notable yield of 97.1wt% at 60oC. In addition, alkaline
dissociate into CH3O and Na and CH3O and K respectively.
catalysts concentrations ranging from 0.5–1wt% could yield
Besides, the catalysts do not form water during

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94–99wt% conversion of vegetable oils to alkyl esters.
However, increase in catalyst concentration above 1wt% does
not increase the conversion but could add to extra costs of
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Chung et al. [94] 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

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production. Since it is essential to get rid of the catalyst from provided higher catalytic activity to the seed oils in the
the products after the reaction is completed [92,93]. reaction. The optimum reaction conditions used were: 6:1

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Base catalysed SN2 Transesterification molar ratio of methanol to the seed oils, 1 wt% loading amount
O
of catalyst, 65oC reaction temperature, and reaction time of
C 3hrs. The biodiesel contents of the C. japonica and V. fordii

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O Gly'

H-O-H CH -O-H seed oils under these reaction conditions were 97.7% and
3 K-O-H
O 96.1% on KOH catalyst. Figure 5 and 6 shows the effects of
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C alkaline catalysts on feedstocks contain high amount of water
O Gly '
-
and FFAs [95]. The lesser the water and FFAs contents the
ce

CH -O
3
better yield vice versa. In another study, Sahoo et al. [48]
employed alkaline transesterification after reducing the FFAs
Ac

O value from 44 mg KOH/g a below 4 mg KOH/g through acid

C O Gly' catalyzed transesterification. The author found that 1.5 wt% of
CH -O
H KOH was adequate to obtained maximum biodiesel yield.
3 O-CH
H-O-H
3
Marchetti and Errazu [96] revealed that ethanol and sulfuric
O acid are suitable to carry out both direct esterification and
C
HO-Gly' transesterification reactions simultaneously. These processes
CH -O
3 HO- CH
3 could effectively convert waste cooking oil containing high
- OH
amount of FFAs ranging from 3% to 40% to biodiesel. The
Figure 4: Mechanism of base-catalyzed transesterification reaction

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authors noted the FFAs content was reduced via esterification Alkaline catakyst

process from 10.684% to a value close to 0.54wt%. Though,

the final FFAs concentration was slightly more than the 105

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recommendable quantity. They reported minimized soaps 100

formation during alkali-catalyzed transesterification reaction.

95

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Alkaline catalyst

Methyl esters (%)

90

110
85

100

90 ed 80

75
pt
Methyl esters (%)

80 70
ce

70 65
0 1 2 3 4 5 6

60 FFA (%)

Figure M: Graph of Methyl esters yield against FFA in transesterification reaction

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50 Figure 6: Graph of methyl esters yield against FFA in

transesterification reaction.
40
0 5 10 15 20 25 30 35
Further, to improve biodiesel production process, Refaat et al.
Water content (%)
[97] studied microwave irradiation technique to produce
Figure
Figure 5: Graph
N: Graph of methylofesters
methyl esters
yield against yield
water against
content water reaction
in transesterification
biodiesel. They employed sunflower oil (used 3 times at a
content in transesterification reaction.
cooking temperature of 130°C) and methanol to oil ratio of 6:1
in the presence of 1wt% of potassium hydroxide at 65oC. The
authors used a normal pressure glass reactor 500 mL flask and

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reflux condenser. Using the microwave system, the vegetable Besides, microwave-assisted transesterification process
oil was preheated to a desired temperature of 65oC. The dramatically reduced the reaction time from 75 min to 4 min at
mixture of alcohol and catalyst then charged into the flask 60oC, thus saving great time. Additionally during

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through the condenser. The power output adjusted to 500 watt transesterification, irradiation times must be controlled and the
and under reflux the mixture irradiated via different reaction levels of radiation power should not be too high, to avoid

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times of 0.5, 1, 1.5, 2, 2.5, 3 and 6 min. Using microwave destruction of organic molecules.
irradiation technique, reaction time was reduced by 97% and Moreover, to determine optimum operating parameters
the separation time reduced by 94%. They recorded biodiesel such as catalyst concentration, Ferella et al. [99] studied

ed
yield of 100% within 2 min and separation time of 30 min.
Also, Saifuddin and Chua [98] optimized transesterification of
transesterification reaction of rapeseed oil for biodiesel
production using response surface methodology (RSM). They
pt
used frying oil to ethyl ester using microwave irradiation. They employed a 500 ml jacketed stirred (at 600 rpm) reactor tank.
used a microwave oven equipped with non-contact infrared At optimum conditions of temperature of 50oC, KOH
ce

continuous feedback temperature system and magnetic stirrer concentration of 0.6% w/w, reaction time of 90 min, and 60
to heat the oil and the alcohol at 60oC. Twenty five percent methanol to KOH ratio by weight, large amount of
Ac

(25%) of an exit power of 750 W was used to irradiate the triglycerides, diglycerides and monoglycerides were converted
reaction mixture. The authors experimented different into biodiesel. As well, the final concentrations were 0.05%
concentrations of sodium methoxide (0.3wt% to 0.5wt%) and triglicerides, 0.09% diglycerides and 0.36% monoglycerides
achieved maximum conversion (87wt%) at 0.5wt%. During and the triglyceride conversion was 98–99%.
transesterification process, both sodium ethoxide and The effects of catalysts such as NaOH on
potassium hydroxide provided good conversions. However, transesterification of rapeseed oil under supercritical/subcritical
due simplicity in products phase separation, sodium ethoxide conditions were also studied by He et al. [100]. The authors
was viewed as most promising catalyst for producing biodiesel.

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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
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The most notable acids commonly employed in
transesterification reaction include among others; sulfuric acid
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[13,19,101], sulfonic acid [14] hydrochloric acid [16] organic
sulfonic acid [14] and ferric sulphate [13] etc. Among these
acids, hydrochloric acid, sulfonic acid and sulfuric acid are
ed
usually favoured as catalysts for the production of biodiesel.
The catalyst and the alcohol are vigorously mixed with a stirrer
pt
in a small reactor. The oil is first charged into the biodiesel
reactor and then the mixture of catalyst/alcohol is fed into the
ce
oil. Brønsted acids preferably sulfuric acid or sulfonic acid is
used to catalyze the reaction. Although the catalysts give high
Ac
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
favours the formation biodiesel products. The steps involve
during acid-catalyzed transesterification 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
13 
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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 mixture of alcohol and sulphuric acid into
the oils or fats three times (three-step pre-esterification) is
required. The time needed for this process is about 2hrs 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.
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Additionally, Soriano Jr. et al. [102] studied catalytic tests were carried out in triplicate with a molar ratio
transesterification of canola oil to produce biodiesel via fatty acid: catalyst (100:1), reaction time of 2 hrs. Using these
homogeneous Lewis acid (AlCl3 and ZnCl2) as catalyst. The conditions, the process provided more than 90% biodiesel yield

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reaction occurred in a round bottom flask submerged in an oil with a high selectivity of more than 93%.
bath equipped with a reflux condenser, temperature controller 3.3 The effects of homogeneous catalysts on the yield of

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and a magnetic stirrer. The authors reported use of variable biodiesel fuel.
parameters such as: reaction time (6,18,24hr), methanol to oil The nature of catalyst used plays a great role during
molar ratio (6,12,24,42 and 60), reaction temperature transformation of vegetable oil to biodiesel [104]. As a result,

ed
(75,110oC). And tetrahydrofuran (THF) as co-solvent (1:1
methanol to THF by weight in runs with THF), and catalyst
catalyst is among the key factors determining the rate and
yield of biodiesel during biodiesel production process [17,46].
pt
(AlCl3 or ZnCl2). In all the runs, the catalyst amount was kept Thus, Table 5 presents reaction yield as function of the
at 5% based on the weight of oil. 1H NMR monitored homogeneous catalyst weight. The data obtained shows that
ce

converting canola oil into fatty acid methyl esters. Thus the production of biodiesel via homogeneous catalyst could yield
best conditions with AlCl3 were 24:1 molar ratio at 110oC and more than 99%.
Ac

18hr reaction time with THF as co-solvent provided a 4. The Effects of Heterogeneous Catalysts in Biodiesel
conversion of 98%. AlCl3 was far more active compare to Production
ZnCl2 due to its higher acidity. In another study, Cardoso et al. Despite the problems surrounding alkali-catalyzed
[103] discussed the effects of Lewis acid on the transesterification, the process is still favourable in producing
transesterification process in producing biodiesel. The authors biodiesel fuel. The main reason is due to their faster kinetic rate
have introduced an inexpensive Lewis acid (Tin(II) chloride and economic viability [117]. Recently several researches were
dihydrate (SnCl2·2H2O), and evaluated its potential as catalyst conducted on heterogeneous catalysts with the aim of finding
on the ethanolysis of oleic acid of fats and vegetable oils. The solutions to problems caused by using homogeneous catalysts

14 
 
Page 14 of 40
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Table 5: Reaction Yield as Function of the Homogeneous Catalyst Weight

us
Feedstock Catalyst Conc. (wt/v/v) Reaction time (hr) Reaction temp (oC) Yield/conv. (w/w%) Molar ratios Reference

-Waste tallow H2SO4 1.25 24 50 99.01 ± 0.71 1:30 [86]

(chicken)

an
-Palm fatty acid H2SO4 - 2 70 99.6 7.2:1 [19]
- Sunflower oil KOH 0.55 - 70 96 - [105]
- Jojoba oil-wax Sodium methoxide 1 4 60 55 7.5:1 [106]
-Brassica carinata KOH - - - 98.27 - [107]

M
- Canola oil KOH 0.5 0.33 25 86.1 6:1 [108]
- Jatropha curcas KOH 1 30 92 - [109]
-Cottonseed oils Sodium hydroxide 0.5 1 55 77 - [110]
- Roselle oil potassium hydroxide 1.5 1 60 99.4 8:1 [111]

ed
- rubber seed oil NaOH 1 1 60 84.46 6:1 [112]
(Hevea brasiliensis)
-Mahua oil NaOH 1 2 60 92 6:1 [64]
(Madhuca Indica)
pt
-Mahua oil H2SO4 /KOH 1/0.7 1 60 98 6:1 [65]
-Sunflower frying oil KOH 1 0.5 25 max 6:1 [113]
-Tobacco seed oil NaOH 1.5 1.5 55 max 3:1 [114]
-Rice bran oil Sulfuric acid 2 8 100 98 - [21]
ce

-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 [115]
-Karanja oil KOH 1 3 65 97–98 6:1 [116]
Ac

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 [118],
hydrotalcides [119], zeolites [120] 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

15 
 
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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%
an
glycerol purity from homogeneous catalyzed process [121].
Thus, the effects of these catalysts are discussed as
M
follows:
4.1 The effects of solid alkaline and acid catalysts in
biodiesel production
ed
Semwal et al. [122] reported that many studies on solid
acidic catalysts for producing biodiesel were carried out,
pt
however lower reaction rates and unfavorable side reactions
have limited their uses. The authors noted that a good number
ce
of investigations on basic heterogeneous catalysts were also
conducted but their activity gets degraded in the presence of
Ac
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 [123]
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 3hrs, but like
16 
i
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 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 [124]. However,
Page 16 of 40

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use of CaO in biodiesel production presents slow reaction rate
[31]. Antunes et al. [125] noted that like homogeneous
catalysts, solid alkaline catalysts present more catalytic activity
an
than solid acid catalysts. Meher et al. [116] examined
methanolysis of karanja oil via solid basic catalysts. They remarked
M
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
ed
0.36 mg KOH/g and an ester content of 98.6 wt%, after
purification of the esters. The properties of the esters produced
pt
met both American and European standard specifications for
biodiesel fuels.
ce
Also, Liu et al. [126] have produced biodiesel fuel from
soybean oil using CaO as a solid base catalyst. The authors
Ac
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. [124] produced biodiesel fuel via solid base-catalyzed
transesterification at a reaction time of 1hr and obtained esters
yield of 93wt% for CaO, 12wt% 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
17 
i
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 2hrs. 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. [127] 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
2.5hrs. 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 3hr of reaction time, could provide biodiesel yield
above 95%. Besides the catalyst active sites were found not to
Page 17 of 40

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leach and the activity of the catalyst was stable after 20 cycles
of the reaction [27].
Similarly, Puna et al. [128] conducted an experimental
an
study to produce biodiesel via CaO and CaO modified with Li
catalysts. Both catalysts showed good catalytic performances
M
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
ed
catalysts are suitable for producing biodiesel. In another study,
Sharma et al. [129] remarked that the regeneration and resuse
pt
of CaO for many times (for instance, 20 runs) makes the
catalyst most favourite among the oxides. These characteristics
ce
are useful from economic analysis. Further, moderate
conversion and yield could be obtained using mixed oxides as
Ac
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 [130] 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
18 
i
poultry fat using new calcium containing silicate mixed oxide-
based heterogeneous catalysts. The catalysts are; PME-
templated calcium containing silicate mixed oxide catalysts
(PMCS 1-9) and mesoporous calcium containing silicates
(CS1-9). The authors reported transesterification of SBO via
PMCS-5 consisting of total surface area of 150 m2/g to provide
100% yield within 2hrs. 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. [131] 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 5hrs. The estimated
optimal reaction conditions achieved were; reaction
temperature of 65°C, catalyst content of 6 wt% and alcohol/oil
molar ratio of 12:1, and achieved a corresponding yield of
98.64wt%. The authors reported that the values achieved from
Page 18 of 40

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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
an
solid alkaline catalysts, Ilgen and Akin [132] studied different
heterogeneous catalysts such as K2CO3/γ-Al2O3,Na2CO3/γ-
M
Al2O3,LiOH/γ-Al2O3,NaOH/γ-Al2O3, γ−Al2O3, and KOH/γ-
Al2O3and reported FAME yield of 89.40%.
In recent years hydrotalcites materials are receiving
ed
great attention because they can be applied as precursors [134]
and as catalyst [135]. Hydrotalcite-like compounds (HTlcs) are
pt
a category of anionic and basic clays referred as layered double
hydroxides (LDH) with the formula Mg6Al2(OH)16CO3.4H2O
ce
[15]. Thus production of biodiesel was experimented using
different hydrotalcites such as activated Mg–Al hydrotalcites
Ac
[135,136]. Zeng et al. [137] 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. [138]. The
ratio of Mg/Al was found to affect the performance of the
catalyst. And the catalytic activity was highest at 3 to 8 ratio of
Mg/Al. The authors remarked that the catalyst is best suitable
for oils containing up to 10,000ppm quantity of water. They
19 
i
achieved 92% conversion at a reaction condition: reaction time
of 1hr, temperature of 180 °C, catalyst concentration of 5wt.%
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.
[139]. The authors noted that at higher reaction temperatures
(215–225°C); Mg–Al hydrotalcite displayed high catalytic
activity. The transesterification was then conducted at
methanol/oil weight ratio of 0.45 and catalyst concentration of
1wt%, and esters yield of 94wt% was achieved. Xie et al. [140]
have experimented methanolysis of soybean using Mg–Al
hydrotalcite as solid base catalyst. The synthesis of the Mg–Al
hydrotalcite was carried out 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 500oC.
But the catalyst showed very low catalytic activity. And a
conversion of 67% was recorded at an operating condition of
9hrs, catalyst concentration 7.5 wt%, temperature of 65°C, and
alcohol/oil molar ratio of 15:1. Further, Georgogianni et al.
[119] have employed heterogeneous catalyst to produce
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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
an
production of biodiesel fuel from soybean frying oil with
alcohol (methanol). They reported the conversion of oil to
M
biodiesel to be 97% and 85% respectively after 24hrs under the
same reaction conditions. Further the hydrotalcite showed
greater activity which was attributed to its high basicity. Even
2
ed
though Mg-MCM 41 has higher specific surface area of 1289
m /g compared to the low specific surface area of Mg–Al
pt
hydrotalcite of 82m2/g.
Also, Wen et al. [141] have synthesized fatty acid
ce
methyl esters from vegetable oil with methanol catalyzed by
Li-doped magnesium oxide catalysts. A number of Li-doped
Ac
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 hrs). 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
20 
i
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. [120] 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 150oC. The conversion to esters increases from
60-150oC with an average conversion of 90% achieved at
125oC. 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
Page 20 of 40

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affected after reused. However, FFAs loadings in excess of
25% quench the catalyst activity. Meyer et al. [142] conducted
experimental studies on heterogeneous catalysts to produce
an
biodiesel. The reaction occurred at temperature of 90°C and a
methanol to triglyceride ratio of 9:1. The authors stated that
M
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 1hr. The
ed
result obtained was comparable to those of homogeneous
catalysts such as alkali metal hydroxides. Another study
pt
conducted by Marı´a et al. [143] examined different zeolite
catalysts such as NaX for the parent zeolite in sodium form:
ce
0.3MNaX, 1MNaX, 3MNaX, 3MNaXB, and samples from
modenite and beta zeolite were named as 3NaM and 3Nab for
Ac
the transesterification of sunflower oil with alcohol (methanol).
Hence, zeolite X provided greater activity compared to other
zeolites (mordenite and beta) due to its higher concentration of
super-basic sites. The authors reported that biodiesel contents
of 93.5 and 95.1 wt% were achieved at 60oC 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 [143]. Additionally, Supamathanon
21 
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et al. [144] 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 65oC, methanol to oil molar ratio of
16:1 and at a reaction time of 3hrs, 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 [145]. 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. [146] 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
Page 21 of 40
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include; Zinc stearate/SiO2, MoO3/ZrO2, WO3/ZrO2, in fixed bed reactor under atmospheric pressure. The authors
WO3/ZrO2–Al2O3, MoO3/SiO2, TPA/ZrO2, and Zinc noted that out of the catalysts prepared, tungstated zirconia–
ethanoate/SiO2. They stated that zinc stearate immobilized on alumina catalyst (WZA) showed high performance, yielding

an
silica gel was most active and stable. The catalyst recycled over 90% conversion for esterification processes. Although
several times at optimized conditions of reaction temperature detail analysis for the acidity of WZA has not yet been

M
of 470 K, 1:18 molar ratio of oil to alcohol, and 3wt% catalyst determine.
loading without being deactivated. The authors recorded a Besides, Kitiyananet al. [149] studied transesterification
maximum ester content of 98 wt%. Catalyst recycling reduces of palm and coconut oils using solid catalysts such as

ed
the biodiesel processing cost. In another study, Ngo et al. [147]
have esterified FFAs in greases (12–40 wt% FFA) using a
KNO3/ZrO2, KNO3/KL zeolite, SO42-/ZrO2, SO42-/SnO2, and
ZrO2, ZnO. The authors noted that transesterification of crude
pt
diphenylammonium triflate acid catalyst immobilized onto two palm kernel oil using SO42−/SnO2 and SO4/ZrO2catalysts
robust and highly porous solid silica supports (MCM-48 and provided highest yield of methyl esters (90.3 wt%). The
ce

SBA-15). The authors evaluated the catalytic activities of the purities of the esters were 95.4wt% for SO42−/SnO2 and
catalysts. The catalysts were reported to be effective for the 95.8wt% for SO42−/ZrO2, respectively. However, for ZnO the
Ac

esterification of FFAs in greases with a conversion to biodiesel highest content of the esters was 98.9wt%. In addition, owing
of 95–99%, resulting in a pretreated grease with a final FFAs to the availability of enough acid site strength, solid acid
content of <1 wt%. Also, Furuta et al. [148] studied biodiesel catalysts for example sulfated zirconia, tungstated zirconia and
fuel production via transesterification using soybean oil and Nafion-NR50 were selected to catalyze transesterification
methanol with solid superacid catalysts (sulfated tin oxide [149,150]. However, due to its acid strength, the selectivity of
(SO4/SnO2) and zirconium oxide (SO4/ZrO2) and tungstated Nafion-NR50 towards biodiesel and glycerol production was
o
zirconia (WO3/ZrO2) at 200-300 C. And conducted higher, compared to both sulfated zirconia and tungstated
esterififcation of n-octanoic acid with methanol at 175–200oC zirconia [151]. Nonetheless, Chai, et al. [152] remarked that

22 
 
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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
an
provided more impetus for the development of biodiesel fuel.
The amberlysttm BD20 process can effectively convert any
M
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
ed
glycerol purity [153]. Additionally the search for a suitable solid
catalyst has lead to the development of vanadium phosphate
pt
catalyst by Di Serio et al. [154] for biodiesel production. The
2
authors reported 2–4 m /g as specific surface area of the
ce
catalyst. However, despite the surface area of the catalyst is
low, the catalyst was found to be active in producing biodiesel
Ac
from soybean oil. They reported ester yield of 80% at 150 °C
and observed catalysts deactivation at elevated temperatures
5+ 3+
owing to reduction of V to V 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
[2,144]. Zeolites are microporous crystalline solids with well
defined structures and that they contain aluminum, silicon and
23 
i
oxygen in their framework and cations. As catalysts, unlike the
compositionally equivalent amorphous catalysts, zeolites
demonstrate substantial acid activity and shape selective
features [155,156,157]. Chung et al. [155] 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 60oC. 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 [158].
4.2 The Effects of Enzymes catalysts in biodiesel production
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Transesterification reaction can be catalyzed with
enzymes catalysts such as Candida Antarctica lipase [28],
Pseudomonas cepacia [159], candida sp. 99–125 [28,160],
i
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

an
Pseudomonas fluorescens [159], Rhizomucor Miehei and (TAG) transformed to their corresponding esters.
Chromobacterium viscosum [20,161] and Rhizopus oryzae
Additionally, Shah et al. [30] have prepared biodiesel

M
lipase [162] etc. Casimir et al. [163] noted that biodiesel can be
from jatropha oil using lipase catalyst. The authors have
excellently produced via enzymatic-transesterification
screened pancreas porcine, candida rugosa, chromobacterium
reactions involving lipases. They suggested that large

ed
viscosum and in a solvent-free system for the production of
quantities of lipases can be produced using recombinant DNA
biodiesel. They employed a screw-capped vial and jatropha
technology. The authors believed that application of
seed oil (0.5 g) and ethanol were taken in the ratio of 1:4 (mol
pt
immobilized lipase may reduce the overall cost of biodiesel
mol-1). Also 50 mg of enzyme preparation (tuned or
production and lower downstream processing problems.
immobilized) was added and incubated at 40°C with constant
ce

Besides, enzymatic approach is environmentally friendly [163].

shaking at 200 rpm. The immobilization of lipase
Watanabe et al. [29] explored use of immobilized candida
(Chromobacterium viscosum) on Celite-545 improved yield of
Ac

antarctica lipase for continuous production of biodiesel fuel

esters from 62% to 71% by free tuned enzyme preparation with
from vegetable oil. The transesterification of vegetable oil was
a process time of 8hr at 40°C. Additionally to explore more
conducted using 4% immobilized Candida lipase as a catalyst
information on the use of enzymes for the production of
at 30°C in a 20- or 50-mL screw-capped vessel, shaking at 130
biodiesel, Tan et al. [28] reviewed biodiesel production using
oscillations/min. The authors noted the activity of candida
immobilized lipase. The immobilized lipase as biocatalyst
antarctica lipase was not affected in a mixture of vegetable oil
draws great interest because that process is environmentally
and more than 1:2 molar equivalent of methanol against the
friendly. The authors noted different techniques for lipase
total fatty acids. They discovered inactivation of the lipase to
immobilization, such as covalent bonding, cross-linking,

24 
 
Page 24 of 40
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encapsulation, entrapment and adsorption. Lipase enzymatic-catalyzed transesterification to avoid problems
immobilization technique is commonly used to increase the associated with homogeneous catalysts. Therefore the
stability of lipase in biodiesel production. They stated that, for production processes are compared in Figures 7 and 8. The

an
biodiesel (fatty acid methyl esters) preparation, at least a authors reported conversion of high FFAs feedstocks to
stoichiometric amount of methanol is needed for the complete biodiesel using immobilized antarctica lipase (Novozym-435)

M
conversion of triglycerides to their resultant fatty acid methyl with ease of separation process.
ester. But, methanolysis is reduced considerably by adding
4.3 The effects of heterogeneous catalysts on the yield of
>1/2 molar equivalent of methanol at the commencement of the

ed
biodiesel
enzymatic process. Usually, the polar short chain alcohols
As earlier stated great efforts have being made by
causes inactivation of enzymes and this is the major obstacle
several researchers and industries to explore and exploit use of
pt
for the enzymatic-transesterification reaction. Therefore to
heterogeneous catalysts in the production of biodiesel. Some of
overcome this difficulty one of these options is selected: acyl
the reasons for the recent growth and development of
ce

acceptor alterations, solvent engineering and methanol

heterogeneous catalysts include among others: biodiesel yield
stepwise addition. The authors reported that biodiesel yield of
of 98wt% and simplicity in catalyst separation process [131],
Ac

97wt% was obtained after 24 hrs at temperature of 50°C with a

high-purity by-products, less cost of separation and low energy
reaction mixture containing 13.5% methanol, 32.5% t-butanol,
consumption [31]. Table 6 presents reaction yield as function
54% oil and 0.017 g enzyme (g oil)−1. With the same mixture,
of the heterogeneous catalyst weight.
a 95% biodiesel yield was achieved using a one step fixed bed
5. The Advantages and Disadvantages of Homogeneous
continuous reactor with a flow rate of 9.6 ml h−1 (g
Catalysts and Heterogeneous Catalysts
enzyme)−1. The authors concluded that low cost of
immobilized Candida sp. 99–125 lipases is rather competitive The choice of catalyst to use in the production of economically
for industrial use [28]. More so, Hideki et al. [14] noted use of viable biodiesel fuel is one of the most critical issues that are

25 
 
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Vegetable Alcohol for recycling
        
oils/Animal
Centrifuge/settler Crude
fats

an
Transesterification for separation of biodiesel Neutralization Drying
Alcohol Distillation/
Reaction crude biodiesel process/water Evaporation Facility
        Alkali products washing

M
Waste
Crude water
glycerin/ Mineral acid (H3PO4) Finished
impurities

ed
product
Pure glycerin for (biodiesel)
Mineral acid (H2SO4) Glycerin purification
Storage/recyling/sale
pt
Free Fatty Acid (FFAs)
ce

Figure 7: Traditional alkali biodiesel production

Ac

  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

Figure 8: Enzymatic biodiesel production 

26 
 
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Table 6: Reaction Yield as Function of the Heterogeneous Catalyst Weight

us
Feedstock Catalyst Conc (wt) Reaction time (hr) Reaction temp (oC) Yield ((w/w%) Molar ratios Reference

-Soybean oil CaO 25 1 - 93 - [122]

an
-vegetable oil M(3-hydroxy-2-
methyl-4-pyrone)2(H2O)2 3 60 93 - [164]
Sunflower oil CaO/SBA-14 5 160 95 12 [165]
-Sunflower zeolite X 4.2 - 60 95.1 - [166]
- Soybean oil ETS-10 zeolite 0.03 24 125 90 - [120]

M
- Palm oil CaO/Al2O3 3.5 5 65 98.64 12:1 [26]
-Waste bleaching earths Rhizopus oryzae 96 35 55 1:4 [162]

-Soybean Na/NaOH/ -Al2O3 1 2 60 96 9:1 [167]

-Crude palm kernel oil SO42−/ZrO2

-Waste cooking oil ZS/Si ed 1

3
1

10
200

200
90.3

98
6:1

1:18
[146]

[168]
pt
- Soybean oil lipase 0.9 6.3 36.5 92.2 3.4:1 [161]
- Palm oil CaO/Al2O3 3.5 5 65 95% 12:1 [131]
canola oil nano-g-Al2O3 8 65 97.7+ 2.1 15:1 [169]
ce

-Mixture of soybean
and rapeseed oils Candida lipase 4 24 30 93 1:3 [29]
-Jatropha oil Chromobacterium viscosum lipase 5 8 40 92 1:4 [30]
-Soybean oil Pseudomonas cepacia lipase 47.5 1 35 67mol% 1:7.5 [170]
Ac

-sunflower oil WO3/ZrO2 3 5 200 97 20:1 [171]

being discussed by futurists and industries [118]. As discussed
earlier, NaOH and KOH are mostly preferred because they are
cheaper than 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 [172] 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

27 
 
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virgin vegetable oil and waste cooking oil. The authors
revealed that acid-catalyzed transesterification with waste
cooking oil were more economically viable. The process gave
i
homogeneous catalysts in biodiesel production presents
difficulty in biodiesel product separation and makes recovery
of used catalyst cumbersome. The authors reported that

an
lesser total production cost, a more attractive after-tax rate of biodiesel production via homogeneous alkaline catalysts needs
return and a less biodiesel break-even price. multi-steps of production and purification, since such catalysts

M
In contrast both alkali- and acid catalyzed do not tolerate presence of moisture or FFAs. In addition, there
transesterification are associated with a number of problems. are many notable issues surrounding the existing
Madras et al. [173] reported that alkali-catalyzed transesterification processes such as; difficulties in processing

ed
transesterification present high cost of biodiesel production and
large energy consumption during down-stream biodiesel
low quality feedstocks and refining of transesterified products
[40].
pt
refining process. Ferella et al. [99] stated that potassium Further heterogeneous catalysts provide many
hydroxide produces soaps formation by neutralizing FFAs. advantages compared to homogeneous catalysts such as:
ce

Additionally, due to the tendencies to produce soaps formation catalyst re-usability, less separation and purification
and mono- and di-glycerides during transesterification, direct difficulties, high purity glycerol (above 99%), and catalyst
Ac

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. [103] 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
recoverability etc [118, 174]. Additionally no neutralization
step is required [175]. Thus, in biodiesel production, the
overall economy can be improved through the use or sale of
by-product, glycerol [118]. Mariscal et al. [174] reported that
heterogeneous catalysts are less corrosive, leading to safer,
less costly, and more environmentally friendly operations.
Watanabe et al. [29] reported enzymatic-transesterification
reaction to overcome problems associated with chemical

28 
 
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processes. Palligarnai and Briggs [24] found glycerol from
enzymatic-catalyzed transesterification not to show negative
effects on biodiesel fuel property. The authors stated that the
i
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

an
major advantage of employing enzyme catalysts is lack of properties of the catalysts affects biodiesel quality, makes
soaps formation. They reported application of insoluble solid catalyst separation and biodiesel purification difficult, thus

M
catalysts (immobilized enzymes) to speed up catalyst removal bringing extra cost of production [15]. Mariscal et al. [174]
from both glycerol and alkyl esters. Zabeti et al. [27] showed reported significant leaching of potassium during
solid-catalyzed transesterification reaction to yield biodiesel transesterification of triglyceride via K/c-Al2O3 catalysts. The

ed
products with no catalyst impurities. Therefore absence of
leaching improves separation process and lowers the cost of
authors reported 99wt% biodiesel yield which was attributed
to homogeneous contribution from active basic species
pt
final refining. Martino et al. [47] noted that heterogeneous dissolved in the methanol. In addition, the homogeneity of this
catalysts can be separated more easily, besides low processing catalyst complicates its separation process. Also leaching of
ce

costs and zero waste streams. Hameed et al. [176] stated that solid acid catalyst (sulfate species) was reported to restrict its
heterogeneous catalysts are searched over time to achieve reusability [177]. Moreover, a study carried out by Lee et al.
Ac

environmentally benign and economically viable biodiesel [178] remarked that leaching of base active species caused
production and purification processes. However, issues such great negative effects on the degree of purity of biodiesel and
as leaching of catalysts especially when solid alkaline glycerol. Another investigation conducted through
catalysts such as CaO, MgO, La2O3, ZnO, SrO, Li-promoted optimization of catalytic activity of CaO/Al2O3 for producing
CaO, CaCO3, Ba(OH)2, KxX/Al2O3 (X-halide ion or other biodiesel with response surface methodology showed
mono/di-valent anion), Zinc aluminates, Metal salts of amino insignificant leaching of catalyst into the reaction medium
acids, Mg–Al hydrocalcites and K- and Cs-exchanged zeolites [26,131]. Table 7 summarizes the merits and demerits of
are used in producing biodiesel creates great deal of concern homogeneous catalysts and heterogeneous catalysts for

29 
 
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biodiesel production.
Table 7: Advantages and Disadvantages of Homogeneous Catalysts and Heterogeneous Catalysts
an
Type of catalyst Example
Homogeneous catalyst
M
Alkaline catalysts: NaOH, KOH,
CH3ONa,CH3OK
ed
pt
Acid catalysts: H2SO4
ce
Ac
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.
i
cr
us
Merits Demerits Ref.
Less corrosive, Formation of saponified [13,17,99,155]
high reaction rate product, emulsion formation, 172,179,180,]
high water and energy 181]
consumption, huge, high
wastewater discharges,
high purification cost
Feedstocks are limited to
0.5wt FFAs, not recycle
Zero soap formation, More waste as a result [31,179,182]
The catalyst can be of neutralization,
Used to catalyze both recycling difficulty,
esterification and trans high purification cost,
esterification simultaneously. energy consuming.,
low reaction rates
Environmentally friendly, Leaching effects, [15,27,47,152,
easily recycle, less discharges, catalysts preparation 154,164, 174,
less separation difficulty, is complicated and expense 176, 177
high purity glycerol, lower relatively slow rates 183,184]
cost of separation.
Insignificant leaching of [26,131]
CaO/Al2O3
30 
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Enzymes catalysts: Candida antarctica Zero saponification products Catalysts inhibition by [14,40, 1163,
B lipase, Rhizomucor nonpolluting, easily separable, water. 182,185]
meihei lipase, candida rugosa lesser separation cost, high
Pseudonas cepacia, M. meihei purity glycerol and

an
(Lypozyme), M. meihei
(Lypozyme IM60),
Aspergillus niger.
P. fluorescens, R. Oryzae
biodiesel products,
environmentally benign
Simple glycerol recovery High cost of enzymes [29,30]

M
transesterification reaction that was discovered to
converts FFAs to biodiesel fuel.

ed
6. Conclusions and Recommendations
4. The conversion of FFAs to biodiesel was found to
Based on the foregoing the following conclusions and increase the yield of biodiesel and simplify the
recommendations were made:
pt
separation of catalyst form crude biodiesel mixture.
1. Use of high FFAs feedstocks to produce biodiesel is 5. To make biodiesel production process cost effective,
ce

more economically viable, though it has great negative the chemistry of heterogeneous catalysts such as solid
effects on the catalyst. Besides refining of crude alkaline catalysts needs to be thoroughly explored,
biodiesel produced from low quality feedstock with developed and use consistently in producing biodiesel.
Ac

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. Especially, enzymatic-catalyzed
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.

31 
 
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7. Development of enzymes catalyst as a more [9]. A.B. Chhetri, K.C. Watts, M.R. Islam, Energies 1 (2008) 3.
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an
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