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DOI 10.1007/s11244-010-9460-5
ORIGINAL PAPER
1 Introduction
Due to growing worldwide demand for energy and its
resulting impact on the environment, it is becoming
This well established process, introduced in the nineteenth century, has been used to exploit the fatty acid and
triglyceride content of a variety of natural oils for biodiesel
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Fig. 1 Reaction mechanism of
base catalyzed
transesterification [17, 19]
(1)
ROH
R O
+B
OR
(2)
R2
OH
R1
R O
R2
R1
O
O
R3
R3
O
O
OR
(3)
R2
OH
O
O
R1
R2
R3
R3
O
(4)
O
-
R2
O
O
B H
R2
OH
fuel over the years. Among these renewable oils and fats
are soybean oil [5], rapeseed oil [6], cotton seed oil [7],
sunflower seed oil [8], jojoba oil [9], waste cooking oil
[10], chicken fat [11], lard [12], and beef tallow [3].
Typical alcohols used as the reactant in this biodiesel
process include methanol [5], ethanol [13] and butanol
[14], with methanol being the most widely used because of
its lower cost.
Some of the first industrial processes to create biodiesel
relied on either strong base or strong acid homogeneous
catalysts for this transesterification reaction. Examples of
the base catalyst are potassium hydroxide [9, 13] and
sodium hydroxide [14, 15], while sulfuric acid has been
used as an acid catalyst [16]. The reaction mechanism for
strong base catalyzed transesterification is shown in Fig. 1
[1719]. Lee et al. [19] described the first step in the
synthesis of alkyl esters as the formation of an alkoxide ion
(RO) through proton transfer from the alcohol using the
base catalyst; the alkoxide ion then attacks a carbonyl
carbon on the triglyceride molecule and forms a tetrahedral
intermediate ion (step 2). This ion rearranges to generate a
diglyceride ion and alkyl ester molecule (step 3). The
diglyceride ion reacts with the protonated base catalyst,
O
R3
123
OR
R1
R3
O
723
+
OH
(1)
R2
R1
O
H
R1
R2
O
O
O
R3
R3
O
+
OH
O
(2)
R2
R1
HO
R4
R2
R4 OH
R1
O
R3
R3
O
HO
(3)
R2
H
O
R4
R1
OH
R2
O
O
R4
R1
O
R3
R3
O
these same homogeneous catalysts, by virtue of the associated production process, face a variety of technical hurdles that limit their use for biodiesel production and
eventually may cause the demise of the early biodiesel
producers. Homogeneous catalysts are normally limited to
batch-mode processing [21]. In addition, other steps in the
biodiesel production process also require time consuming
and costly processing. These steps include oil pretreatment,
catalytic transesterification, separation of fatty acid/methyl
ester (FAME) from crude glycerin, neutralization of waste
homogeneous catalyst, distillation of accessory methanol,
water washing of the FAME phase, and vacuum drying of
the desired products [22]. Each of these steps introduce
additional processing time and cost. As an example, separation of the products from the spent waste catalyst
require a post treatment with large volumes of water to
neutralize the used catalyst in the product mixture. This
creates an additional process burden by generating waste
water that must be treated before release into the environment [22].
Other difficulties with using homogeneous catalysts
center on their sensitivity to free fatty acid (FFA) and water
in the source oil. FFAs react with basic catalysts (NaOH,
KOH) to form soaps when the FFA and water content are
above 0.50 and 0.06%, respectively [5, 23]. This soap
formation complicates the glycerol separation, and reduces
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724
heterogeneous processes can be run in either batch or continuous mode giving the producers the option to continue
with their current batch reactors or retrofit their operations
with a packed bed continuous flow reactor operation. Heterogeneous catalysts in either mode are in a separate phase
from the reaction products, thereby removing costly and
time consuming water washing and neutralization steps to
separate and recover the spent catalyst. Additionally, contaminated water from that process is greatly reduced and the
need for waste water treatment minimized.
The greatest advantage of the heterogeneous approach
over the homogeneous method is the prolonged lifetime of
the heterogeneous catalysts for FAME production. This
attribute is generally related to the stability of the microcrystal structure of the catalyst surface. Poisoning and
leaching of catalyst components can change the bulk and
surface structure of the catalyst and cause catalyst deactivation quickly if the catalyst is not formulated properly.
The above three factorscatalytic activity, catalyst life
and oil flexibilityhave a tremendous impact on the cost
of biodiesel. Because of this, we have undertaken a review
of the past and current heterogeneous catalyst technology
with these aspects as the focus. In this paper, the reported
heterogeneous catalysts are separated into two categories
based on their operation temperature. For reaction temperatures lower than the flash point of biodiesel (130 C),
we refer to this type of catalyst as a low temperature catalyst. For reaction temperatures greater than 130 C, we
classified these catalysts as high temperature catalysts.
These catalysts are characterized by the need for additional
safety considerations and require more energy intensive
operations. To further reduce the field of catalysts for this
review, only heterogeneous catalyst technologies which
provide the potential for decreasing the biodiesel process
cost and feedstock cost will be discussed.
123
Binding energy
of O 1s (eV)
Biodiesel yield
(%)
c-Al2O3
538.8
NaOH/ c-Al2O3
538.5
60
Na/ c-Al2O3
537.5
70
Na/NaOH/ c-Al2O3
535.5
78
Reaction conditions: Methanol/oil molar ratio is 6:1, reaction temperature is 60 C, and stirring speed is 300 rpm. All data are taken
from literature [29]
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726
123
crude soybean oil, crude palm oil and waste cooking oil,
which satisfy the limitation of water content lower than
10% and FFA lower than 3.5%, showed a FAME yield in
excess of 95% within 3 h. For the oils with a high FFA
content, dilution with refined oil will lower the FFA content of the mixture again allowing the use of a CaOLa2O3
catalyst to produce a high FAME yield.
Equally important to the usefulness of a catalyst is its
lifetime. Reddy et al. [61] found that nanocrystalline calcium oxide particles deactivated after eight cycles with
soybean oil and after only three cycles with higher FFA
content poultry fat. Similarly, Kawashima et al. [57, 58]
found evidence of decreased FAME activity with CaTiO3
and CaZrO3 catalysts after as few as three cycles.
To overcome these limitations, therefore, it is important
to understand the mechanism of catalyst deactivation. In
general, there are three pathways by which catalyst deactivation can occur: poisoning, blocking of reactant fragments and lixiviation. Many studies have already paid close
attention to poisoning due to high levels of either FFA or
water present in raw materials [65, 70], so they will not be
discussed here. But little research has been performed that
focuses on the effects of exposing a stored catalyst to CO2,
moisture, and O2 present in the air. As stated by Busca
[69], base catalysts can easily react with these components
of ambient air to form very stable surface species like
carbonate, hydroxide, and epoxide which cover the basic
sites and deactivate the base catalysts. Yan et al. [70] found
that when comparing the activity of a fresh CaOLa2O3
catalyst to one exposed to air for 12 h, the yield of FAME
sharply decreased from 96.8 to 34.5%, and the total base
amount decreased from 14.0 to 1.5 mmol CO2/g. They
later attributed this decrease in activity to moisture and
CO2 in air restructuring the surface of CaOLa2O3 catalyst
from metal oxides to hydroxide and carbonate. Other
research groups have found that the reused base catalysts
have a lower basic strength and a lower activity than fresh
the catalysts [71, 72]. This was explained by the blockage
of active surface sites on the catalyst by strongly adsorbed
intermediates or product species. In particular, Martyanov
and Sayari [63] studied reused catalysts (CaO, Ca(OCH3)2)
and found that surface adsorbed butyric acids were the
most likely species responsible for the catalyst deactivation
in their experiments.
Catalyst lixiviation or leaching is another frequently
encountered pathway for catalyst deactivation. Many
researchers have studied the leaching of catalyst components into reaction mixtures. Kouzu et al. using a pure CaO
catalyst [71] found that the calcium concentration would be
as high as 3065 ppm in the FAME when waste cooking oil
was used as the source oil. Later Kouzu et al. [72] showed
calcium in the products of transesterified refined soybean
oil. In that case, he found that the calcium content in
727
Not only inorganic bases, but also some organic bases were
also tested for biodiesel production [78, 79], especially for
base resin catalysts. Shibasaki-Kitakawa et al. [80] investigated the transesterification of triolein with ethanol using
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728
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about 92% after 8 hs reaction. Furthermore, the starchderived solid acid catalyst proved exceptionally stable
under reaction conditions.
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730
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731
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732
100
Water addition
(%)
60 min
90 min
150 min
70
52
88
93
94
60
1.03
50
80
90
96
3.12
22
74
89
93
5.07
13
57
78
90
90
Yield of FAME %
80
50
40
30
20
10
0
100
0
10
12
14
16
18
FAME content %
Recycle times
100
80
80
60
40
20
60
0
0
20
40
60
80
100
120
140
160
180
200
40
20
0
0
10
20
30
40
50
60
70
80
Time (day)
Fig. 3 FAME yield (a) in the batch reactor using the recycled
Zn3La1 catalyst. Note the catalyst was reused for 17 times. The
average yield of soybean methyl esters is 93.7% (b) in the continuous
reactor. Note that this catalyst has run for 70 days, and the average
yield of FAME during stable stage is 92.3% [127]
10 min
20 min
40 min
10
16
52
83
88
93
5.20
38
72
83
95
92
10.13
73
83
88
92
92
15.21
89
95
98
92
30.56
75
85
93
95
01
60 min
90 min
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Fig. 4 FAME yield of crude corn oil from DDGs, crude algae oil,
crude coconut oil, crude palm oil, crude soybean oil, waste cooking
oil, food grade soybean oil and food grade soybean oil with 3% water
and 5% oleic acid addition. Reaction conditions: 126 g of oil, 180 g
of methanol, 3 g of catalyst, 200 C, 500 psi, in the batch stir reactor.
Note that all of these oils was converted into FAME within 3 h [127]
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Table 4 Fatty acid composition and TAN of food grade soybean oil, crude soybean oil, crude palm oil, waste cooking oil, crude corn oil from
DDGs, crude algae oil and crude coconut oil [127]
Crude soybean
oil (%)
Crude palm
oil (%)
Waste cooking
oil (%)
Crude algae
oil (%)
Crude coconut
oil (%)
C 12:0
49.13
C 14: 0
0.27
0.21
2.72
19.63
13.05
0.39
41.92
0.23
20.91
10.62
10.12
1.79
C 16: 0
C 16: 1
11.07
0.09
11.58
0.18
11.50
0
C 18: 0
3.62
4.17
3.85
4.26
4.77
6.95
2.83
C 18: 1
20.26
22.75
42.44
24.84
26.26
33.33
7.59
C 18: 2
57.60
52.78
11.30
53.55
56.20
18.45
2.75
C 18: 3
7.36
6.59
0.04
5.60
1.27
1.16
0.15
Others
6.86
6.01
TAN
0.03
6.62
0.48
7.56
26.38
8.48
100
600
Yield of FAME %
80
500
400
Yield of FAME
La content in FAME phase
Zn content in FAME phase
60
300
40
200
100
20
0
0
0
10
20
30
40
50
60
70
80
Time (day)
100
1800
80
1400
1600
Yield of FAME %
25.19
Food grade
soybean oil (%)
1200
Yield of FAME
La content in glycerine phase
Zn content in glycerine phase
60
1000
800
600
40
400
200
20
Fatty acid
components
0
-200
0
0
10
20
30
40
50
60
70
80
Time (day)
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Triglyceride
Transesterification
Water
Hydrolysis
FFA
Esterification
Hydrolysis
catalysts can be divided into two types, solid base and solid
acid catalysts, according to their active center. Both Lewis
acidbase sites and Bronsted acidbase sites have the
ability to catalyze the oil transesterification reaction.
Therefore, catalyst activity is closely related to the acid/
base strength. Other texture properties of the catalyst also
impact the catalysts activity, such as specific surface area,
pore size, pore volume and active site concentration.
Modification of reaction conditions, such as increasing
reaction temperature (130250 C), pressure (100
1000 psi), catalyst quantity (310 wt%), and methanol/oil
molar ratio (10:142:1) is effective for obtaining high
FAME yields. Reported catalysts, operating at high temperature, exhibit a low base or acid strength which many
research groups have demonstrated is the basis for
improved activity, improved tolerance to FFA and water,
and extended catalyst lifetimes. Within these high temperature catalysts, two catalysts stand out as leading technologies: one is the ZnOAl2O3 catalyst from IFP and the
other is the ZnOLa2O3 catalyst developed at Wayne State
University. Additional work is still required to find ways to
rejuvenate or re-active catalysts that have failed because of
poisoning, leaching, or loss of surface area. Finally, the
most recognized drawbacks of heterogeneous catalysts are
their slow reaction rates in comparison to homogeneous
catalysts. Perhaps, by enhancing the number and type of
active sites and intensifying reaction conditions, to minimize mass transfer limitations, these catalysts may be able
to overcome this limitation as well.
References
1. Clark SJ, Wagner L, Schrock MD (1984) J Am Chem Soc
61:1632
2. Ma F, Hanna MA (1999) Bioresour Technol 70:1
123
735
71. Kouzu M, Kasuno T, Tajika M, Sugimoto Y, Yamanaka S,
Hidaka J (2008) Fuel 87:2798
72. Kouzu M, Yamanaka SY, Hidaka JS, Tsunomori M (2009) Appl
Catal A 355:94
73. Granados ML, Poves MDZ, Alonso DM, Mariscal R, Galisteo
FC, Moreno-Tost R, Santamara J, Fierro LG (2007) Appl Catal
B 73:317
74. Granados ML, Alonso DM, Sadaba I, Mariscal R, Ocon P
(2009) Appl Catal B 89:265
75. Xie W, Peng H, Chen L (2006) J Mol Catal A 246:24
76. Li E, Xu ZP, Rudolph V (2009) Appl Catal A 88:42
77. Fraile JM, Garca Nuria, Mayoral JA, Pires E, Roldan L (2009)
Appl Catal A 364:87
78. Schuchardt U, Vargas RM, Gelbard G (1995) J Mol Catal A
99:65
79. Schuchardt U, Vargas RM, Gelbard G (1996) J Mol Catal A
109:37
80. Shibasaki-Kitakawa N, Honda H, Kuribayashi H, Toda T, Fukumura T, Yonemoto T (2007) Bioresour Technol 98:416
81. Vicente G, Coteron A, Martinez M, Aracil J (1988) Ind Corps
Prod 8:29
82. Kim M, Salley S, Ng KYS (2008) Energy Fuels 22:3594
83. Xie J, Zheng X, Dong A, Xiao Z, Zhang J (2008) Green Chem
11:355
84. Yang L, Zhang A, Zheng X (2009) Energy Fuels 23:3859
85. Nakatani N, Takamori H, Takeda K, Sakugawa H (2009) Bioresour Technol 100:1510
86. Wei Z, Xu C, Li B (2009) Bioresour Technol 100:2883
87. Kiss AA, Dimian AC, Rothenberg G (2006) Adv Synth Catal
348:75
88. Gore RB, Thomson WJ (1998) Appl Catal A 168:23
89. Suwannakarna K, Loteroa E, Lu JGGC Jr (2008) J Catal
255:279
90. Du Y, Liu S, Ji Y, Zhang Y, Wei S, Liu F, Xiao FS (2008) Catal
Lett 124:133
lvarez M, Aguilar DH, Quintan P (2008) J
91. Garca J, Lopez T, A
Non-Cryst Solids 354:729
92. Yadav GD, Nair JJ (1999) Microporous Mesoporous Mater 33:1
93. Yadav GD, Murkute AD (2004) J Catal 224:218
94. Alsalme A, Kozhevnikova EF, Kozhevnikov IV (2008) Appl
Catal A 349:170
95. Pesaresi L, Brown DR, Lee AF, Montero JM, Williams H,
Wilson K (2009) Appl Catal A 360:50
96. Narasimharao K, Brown DR, Lee AF, Newman AD, Siril PF,
Tavener SJ, Wilson K (2007) J Catal 248:226
97. Katada N, Hatanaka T, Ota M, Yamada K, Okumura K, Niwa M
(2009) Appl Catal A 362:164
98. Rezende SMD, Castro MD, Garcia M, Coutinho FMB, Silva PL Jr,
da Silva San Gil RA, Lachter ER (2008) Appl Catal A 349:198
99. Lotero E, Liu Y, Lopez DE, Suwannakarn K, Bruce DA,
Goodwin JG Jr (2005) Ind Eng Chem 44:5353
100. Lopez DE, Goodwin JG Jr, Bruce DA, Furuta S (2008) Appl
Catal A 339:76
101. Soldi RA, Oliveira ARS, Ramos LP, Cesar-Oliveira MAF
(2009) Appl Catal A: Gen 361:42
102. Hara M, Yoshida T, Takagaki A, Takata T, Kondo JN, Hayashi
S, Domen K (2004) Angew Chem Int 43:2955
103. Toda M, Takagaki A, Okamura M, Kondo JN, Hayashi S,
Domen K, Hara M (2005) Nature 438:178
104. Takagaki A, Toda M, Okamura M, Kondo JN, Hayashi S,
Domen K, Hara M (2006) Catal Today 116:157
105. Zong MH, Duan ZQ, Lou WY, Smith TJ, Wu H (2007) Green
Chem 9:434
106. Lou W-Y, Zong M-H, Duan Z-Q (2008) Bioresour Technol
99:8752
123
736
107. Demirbas A (2007) Energy Conv Manag 48:937
108. Suppes GJ, Bockwinkel K, Lucas S, Botts JB, Mason MH,
Heppert JA (2001) J Am Oil Chem Sci 78:139
109. Barakos N, Pasias S, Papayannakos N (2008) Bioresour Technol
99:5037
110. Chen XR, Ju YH, Mou CY (2007) J Phys Chem 111:18731
111. Furuta S, Matsuhashi H, Arata K (2004) Catal Commun 5:721
112. Jitputti J, Kitiyanan B, Rangsunvigit P, Bunyakiat K, Attanatho
L, Jenvanitpanjakul P (2006) Chem Eng J 116:61
113. Melero JA, Bautista LF, Morales G, Iglesias J, Briones D (2009)
Energy Fuels 23:539
114. Shu Q, Zhang Q, Xu G, Wang J (2009) Food Bioprod Process
87:164
115. Shu Q, Zhang Q, Xu G, Nawaz Z, Wang D, Wang J (2009) Fuel
Process Technol 90:1002
116. Sunita G, Devassy BM, Vinu A, Sawant DP, Balasubramanian
VV, Halligudi SB (2008) Catal Commun 9:696
117. Kulkarni MG, Gopinath R, Meher LC, Dalai AK (2006) Green
Chem 8:1056
123