Bioresource Technology 101 (2010) 62786280

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Short Communication

Hydrogenation of biodiesel using thermoregulated phase-transfer catalyst

for production of fatty alcohols
Shi-wei Liu a, Cong-xia Xie b,*, Rui Jiang b, Shi-tao Yu a, Fu-sheng Liu a
a
b

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

The character of this catalytic process can be described as follows:

At a temperature lower than cloud point (CPT), the catalyst would
remain in the aqueous phase. On heating to a temperature higher
than CPT, the catalyst would transfer into the organic phase. Thus,
the catalyst and the reagents are in the same phase and the reaction is carried out in the organic phase. As soon as the reaction is
completed and the system is cooled to a temperature lower than
CPT, the catalyst would return to the aqueous phase. Therefore,
TRPTC is a monophasic reaction combined with a biphasic separation, which contributes to the separation and reusability of the catalyst, and it has been successfully used in the hydrogenation of
high-carbon olens with excellent conversion and selectivity (Jiang
et al., 1999; Wei et al., 2004). However, the reported hydrogenations mainly use linear olens with little steric hindrance as reagents, no literature about the hydrogenation of carboxylic ester
in presence of TRPTC was found. Here we rst report the hydrogenation of fatty acid methyl ester in presence of TRPTC. It is found
that TRPTC was an efcient catalyst for the hydrogenation. The
mixture of product higher alcohol and unreacted ester was easily
separated from the ionic liquid by decantation, and the desired
product higher alcohol was easily separated from the unreacted ester which could be used as biodiesel by distillation.
2. Methods
2.1. Materials
Tetrahydrofuran, triethylamine and catechol were distilled over
calcium hydride or 3A molecular sieve under reduced pressure,

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S.-w. Liu et al. / Bioresource Technology 101 (2010) 62786280

and poly(ethylene glycol) alkyl ethers were dehydrated by 3A

molecular sieve before use. Fatty acid methyl ester was prepared
from soybean oil by transesterication with methanol at 65 C
for 4 h using 0.2 wt% sodium hydroxide as catalyst. (Saponication
value 188 mg KOH/g, acid number 5 mg KOH/g, value of iodine
(I
V) 135 mg I2/g, hydroxyl value (OH
V) 1 mg KOH/g). Other chemicals used were reagent grade procured commercially and used
without pretreatment.

85% H3PO4): 10.26(s). Cloud points: 112 C. III: IR (KBr disc,

cm 1): m 2924, 2869, 1604, 1489, 953, 694, 757. 1H NMR
(500 MHz, D2O) 1.11.3(m, C15H21C20H41), 3.403.80(s, OCH2),
6.707.4(m, ArH). 31P NMR (200 MHz, D2O, ppm, external standardization: 85% H3PO4): 10.10(s). Cloud points: 106 C. IV: IR
(KBr disc, cm 1): m 2920, 2868, 1110, 951. 1H NMR (500 MHz,
D2O) 1.01.2(m, CH3), 3.23.6(s, OCH2). 31P NMR (200 MHz, D2O,
ppm, external standardization: 85% H3PO4): 7.18 (s). Cloud points:
107 C.

2.2. Preparation of P-ligands

2.3. Hydrogenation of fatty acid methyl ester
The P-ligands IIV (Fig. 1) were synthesized according to the literatures (Jiang et al., 1999; Wei et al., 2004). For example, the general process for the preparation of P-ligand I is following: Under
nitrogen, 0.15 mol phosphorus trichloride was mixed with
0.1 mol catechol under 20 C with an ice bath and reacted for
30 min at room temperature, then another 0.1 mol phosphorus trichloride was added and further reacted for 2 h at 80 C. After that,
the mixture was distilled to remove the unreacted phosphorus trichloride at 80 C under reduced pressure (7090 mm Hg), giving
1,2-phenylene phosphorochloridite with 82.5% yield. Next,
0.01 mol 1,2-phenylene phosphorochloridite was dissolved in the
mixture of tetrahydrofuran and triethylamine (V/V = 3), and
0.075 mol fatty alcohol polyoxyethylene (RO-(CH2CH2O)n-H) dissolved in tetrahydrofuran. Both was mixed and reacted at 5 C
for 6 h, then further reacted at room temperature for 12 h. The
mixture was ltrated to remove ammonium salt, and distilled to
remove the solvents. 100 ml anhydrous ethyl ether was added to
the residue and ltrated to get the white precipitate, giving P-ligand I with 92% yield (Fig. 2). The cloud points were measured
according to the literature (Jiang et al., 1999). I: IR (KBr disc,
cm 1): m 2923, 2860, 1600, 1498, 1467, 1108, 1032, 953, 749. 1H
NMR (500 MHz, D2O, ppm): 01.50(m, C15H21C20H41), 3.04.0(s,
OCH2), 6.77.2(m, ArH). 31P NMR (200 MHz, D2O, ppm, external
standardization: 85% H3PO4): 7.40(s). Cloud points: 103 C. II: IR
(KBr disc, cm 1):m 3056, 1721, 1645, 1455, 997, 950, 699. 1H
NMR (500 MHz, D2O): 1.11.2(m, CH3), 3.53.7(s, OCH2), 7.37.8
(m, ArH). 31P NMR (200 MHz, D2O, ppm, external standardization:

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 OH
V and I
V 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 OH
V and 0 I
V (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

3.2. Effect of metal complex on hydrogenation results

P O CH2CH2O

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, OH
V
and I
V 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

Fig. 2. Synthesis of P-ligand I (n = 1218, R = C15C20).

HCl

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S.-w. Liu et al. / Bioresource Technology 101 (2010) 62786280

Table 1
Effect of catalysts on the reaction results.
Entry

Catalysts

OH
V

I
V

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

performance. Using Pd/IV as catalyst, not only the hydrogenation

of fatty acid methyl ester was of high selectivity to saturated fatty
alcohol, but also the product could be easily separated from the
catalytic system and the catalyst complex was of good reusability.
It is also found that the steric resistance of the nonionic P-ligand, to
a large extent, affects the performance of metal complex. Thus,
more research should be done to synthesize novel nonionic phosphine ligands with little steric resistance in order to extend the
eld of the thermoregulated catalytic system.
Acknowledgments

Table 2
Effect of metal complex on the reaction results.
Entry

Catalysts

OH
V

I
V

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

OH
V

I
V

1
2
3
4
5

163
160
158
156
155

0
0
0
2
3

3.3. Reusability of Pd/IV

When the reaction was nished, the upper organic phase was
separated from aqueous phase by decantation. Then by adding
fresh solvent and reagent, the aqueous phase was directly used
as catalyst and the reusability of the catalytic system was investigated under optimum reaction conditions, the results were given
in Table 3. The results showed that the catalytic system was reused
ve times without an obvious decrease in its catalytic activity.
Therefore, it was indicated that this catalyst system was of good
reusability. The good reusability of this catalytic system was attributed to the good thermally stable and effective phase-transfer performance, which could well avoid the loss of catalyst during the
reaction and separation.
4. Conclusion
The hydrogenation of fatty acid methyl ester was investigated
in presence of thermoregulated phase-transfer catalysts. The thermoregulated catalytic system Pd/IV exhibited an efcient catalytic

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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