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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech
Short Communication
College of Chemical Engineering, Qingdao University of Science and Technology, No. 53 Zhengzhou Road, Qingdao 266042, China
College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, No. 53 Zhengzhou Road, Qingdao 266042, China
a r t i c l e
i n f o
Article history:
Received 6 January 2010
Received in revised form 25 February 2010
Accepted 3 March 2010
Available online 24 March 2010
Keywords:
Thermoregulated phase-transfer catalyst
Biodiesel
Fatty alcohol
Hydrogenation
a b s t r a c t
The hydrogenation of biodiesel was investigated in presence of thermoregulated phase-transfer catalysts
to produce fatty alcohols. The thermoregulated catalytic system Pd/IV (IV: P-ligand, tri-(methoxyl polyethylene glycol)-phosphite) exhibited an efcient catalytic performance for the hydrogenation. It was
also found that the steric resistance of the P-ligand, to a large extent, affected the performance of catalytic
system. Using Pd/IV as catalyst, the product could be easily separated from the catalytic system and the
catalyst was of good reusability. Thus, a clean and environmentally friendly strategy for the production of
fatty alcohol is provided.
2010 Published by Elsevier Ltd.
1. Introduction
Natural fats are converted into biodiesel in typical process of
methanolysis. This process seems now more attractive because of
a growing interest in an ecological diesel fuel. However, due to
the higher raw material cost, biodiesel is difcult to compete with
petroleum diesel. Therefore, new method must be found to enlarge
the value of biodiesel. Fatty alcohol, produced by the hydrogenation
of fatty acid methyl ester, is an important chemical raw material
and widely used in the elds of detergents, plasticizers, synthetic bers, surfactants and cosmetics (Bryan, 2009; Krzysztof et al., 2003).
At present, the hydrogenation popularly uses supported ruthenium
and rhodium (Miyake et al., 2009), copper chromite (Deepak et al.,
1999), palladium (Agustn et al., 2006), zinc, ferrum and thulium
oxide catalysts (Buchold, 1983). The drawbacks of these processes
are much more catalyst requirements, higher reaction temperature
and higher hydrogen pressure, especially, inactivation of catalyst.
Therefore, to design and synthesize a catalytic system which is stable, easily separable and reusable has been pursued.
Based on the property of cloud point of nonionic P-ligands, a novel aqueous biphasic homogeneous catalysis system termed as
thermoregulated phase-transfer catalysis (TRPTC) was proposed
in recent years (Jiang et al., 2002; Jin et al., 1997; Kevin, 2009;
Jin and Wang, 2005). The introduction of TRPTC is free from the
shortcomings of classical biphasic catalysis, in which the scope of
application is restrained by the water-solubility of the substrate.
* Corresponding author. Tel.: +86 532 84022864; fax: +86 532 84022719.
E-mail address: xiecongxia@126.com (C.-x. Xie).
0960-8524/$ - see front matter 2010 Published by Elsevier Ltd.
doi:10.1016/j.biortech.2010.03.016
6279
P O CH2CH2O
P O CH2CH2O
The mixture of 2.5 g fatty acid methyl ester, 3 mg metal chloride, 1 g ligand, 2.5 g water and 2.5 g toluene was reacted in a
100 ml stainless-steel autoclave with 7 MPa H2 at 200 C for 4 h.
After that, the reactor was cooled to room temperature and depressurized. The upper organic phase was separated from the aqueous
phase by decantation and distilled under reduced pressure to obtain the product higher alcohol. The OHV and IV of the product
were measured according to the literature (Wang, 1993). All results were repeated at least ve times (10 times for Pd/IV).
3. Results and discussion
3.1. Effect of different catalysts on hydrogenation results
As can be seen from Table 1, some examined thermoregulated
phase-transfer catalysts exhibited better catalytic performance
than traditional catalysts Pd/C and PdCl2. This may be due to that,
at the reaction temperature, the catalyst is soluble in organic
phase, and the reaction proceeds homogeneously, while Pd/C and
PdCl2 are used as catalysts, the reaction is carried out in the solidliquid two-phase system (Wang et al., 2002; Zhang et al.,
1999). It was indicated that the hydrogenation of fatty acid methyl
ester could be smoothly carried out in presence of thermoregulated phase-transfer catalysts. Among the investigated thermoregulated phase-transfer catalysts, Pd/IV showed the best catalytic
performance with 160 OHV and 0 IV (theoretical hydroxyl value
203 mg KOH/g, which was calculated according to the reference
Wang, 1993), but the results of others were not satised. This
may be because of the steric resistance of P-ligand. With increasing
the volume/size of the substituent group of the P-ligand, the steric
resistance of the catalyst complex was higher, which handicaps the
progress of hydrogenation reaction.
CH3
II
O CH2CH2O
III
CH3
As shown in Table 2, the TRPTC Pd/IV exhibited efcient catalytic performances for hydrogenation of fatty acid methyl ester,
but the others were poor. Especially using Ni/IV as catalyst, OHV
and IV were only 5 and 106, respectively, which indicated that
the hydrogenation was almost no occurred. This may be because
of the differently catalytic activity of the metal complexes, and this
result is in line with that reported in literature (Szollosi et al.,
1996).
IV
R = C15 - C20 , n = 12 - 18
Fig. 1. The structure of the used P-ligands.
OH
OH
O
PCl3
O
P Cl
O
P Cl
2HCl
O
O
HO CH2CH2O n R
P O
O
CH2CH2O nR
HCl
6280
Table 1
Effect of catalysts on the reaction results.
Entry
Catalysts
OHV
IV
1
2
3
4
5
6
7
PdCl2 (3 mg)
Co(CH3COO)2(3 mg)
Pd/C (5%, 60 mg)
Pd/I
Pd/II
Pd/III
Pd/IV
0
0
71
93
19
10
160
3
115
50
60
89
90
0
Table 2
Effect of metal complex on the reaction results.
Entry
Catalysts
OHV
IV
1
2
3
4
5
Pd/IV
Rh/IV
Ni/IV
Co/IV
Ru/IV
160
84
5
65
72
0
39
106
62
51
Table 3
The reusability of catalytic system.
Times
OHV
IV
1
2
3
4
5
163
160
158
156
155
0
0
0
2
3
This work was supported by Shangdong Province Natural Science Foundation (No. Y2007B53) and Qingdao University of Science and Technology Fetching in talent Research fund start-up
projects.
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