Epoxidation of unsaturated fatty esters over large-pore Ti-containing

molecular sieves as catalysts: important role of the hydrophobichydrophilic

properties of the molecular sieve
M. A. Camblor, A. Corma,* P. Esteve, A. Martnez and S. Valencia
Instituto de Tecnologa Qumica, CSIC-UPV, Avda de los Naranjos s/n, 46071 Valencia, Spain
Ti-b and Ti-MCM-41 catalysts are able to epoxidize methyl
oleate using hydrogen peroxide or tert-butyl hydroperoxide
as oxygen donors with high conversions and epoxide
selectivities.
Epoxidized fatty acids and their derivatives are useful commer-
cial chemicals used, e.g. as stabilizers in halogen-containing
polymers, as additives in lubricants, in the manufacture of
cosmetics and pharmaceuticals, fungicidal and algicidal solu-
tions, and in wood treatment.
15
In existing industrial processes
the epoxide is produced by reacting the unsaturated compound
with a peracid either preformed
6
or synthesized in situ
7
with an
organic acid, usually acetic or formic acid, and hydrogen
peroxide. Using this procedure, the yields to epoxide are
relativelly low as a consequence of the low H
2
O
2
selectivities.
Thus, it would be interesting to replace the processes based on
peracids by a more desirable catalytic one.
812
Recently, it has been shown that the incorporation of Ti into
the framework of zeolites produce oxidation catalysts with
unique shape-selective properties.
13
Large-pore Ti-b zeolite
14
and the mesoporous material Ti-MCM-41,
15
when properly
prepared, are active for the selective oxidation of bulky
substrates that can not diffuse inside the Ti-silicalite chan-
nels.
1617
Because of their oxidation properties and the
advantages related to the use of solid catalysts in industrial
processes, Ti-b and Ti-MCM-41 could open new possibilities in
the field of fatty acids and esters if they could selectively
epoxidize the double bound, forming stable epoxides.
Here we report a new and interesting application of large-
pore zeolites containing Ti in the framework such as the
selective epoxidation of unsaturated fatty acids using organic
and inorganic peroxides. We will show that the hydrophobic
hydrophilic properties of the zeolite play an important role
when, as in this case, the organic reactant has two moieties with
different polarities and an aqueous solution of H
2
O
2
is used as
oxidant.
Hydrophilic Ti-b samples were prepared as follows: samples
1 and 2 were synthesized by diluting tetraethylammonium
hydroxide (TEAOH) (35%, Aldrich, Na < 1 ppm, K < 47 ppm)
with the required amount of water to which tetraethyl-
orthotitanate (TEOTi, Alfa) and tetraethylorthosilicate (TEOS,
Merck) were added at room temperature with stirring. Finally, a
solution of aluminium nitrate (Merck) was also added. Sample
4 was prepared by the hydrolysis of TEOS in an aqueous
solution of TEAOH and H
2
O
2
(35%, Fluka) under stirring.
TEOTi was added and the mixture was left under stirring to
allow the evaporation of the ethanol produced. Finally,
dealuminated zeolite-b seeds were added under stirring (4 g of
solid per 100 g of total SiO
2
in the reaction mixture). Sample 3
was synthesized in the same way but using non-dealuminated
zeolite-b seeds which determined the total Al content of the
reaction mixture.
A hydrophobic Ti-b sample (sample 5) was prepared as
follows: TEOS was hydrolysed in an aqueous solution contain-
ing TEAOH and H
2
O
2
followed by the hydrolysis of TEOTi and
allowing evaporation of ethanol and water to the resultant clear
solution, water lost in the evaporation and the appropriate
amount of HF (48%) were added.
The chemical composition of the gels are listed in Table 1.
After crystallization at 413 K and rotation at 60 rpm, the solids
were separated, washed until pH = 9, dried at 353 K and
calcined at 853 K.
A Ti-MCM-41 sample was synthesised as follows: an
aqueous solution of tetramethylammonium silicate (25%
TMAOH, 10% SiO
2
, Aldrich) was added to an aqueous solution
containing 29.0% hexadecyltrimethylammonium bromide
(CTAB, Merck). When the solution was homogenized, amor-
phous silica (Aerosil 200, Degussa) and titanium isopropoxide
(Alfa) were added. The molar chemical composition of the
synthesis mixture was: SiO
2
: 0.15 CTAB: 24.3 H
2
O: 0.26
TMAOH: 0.016 TiO
2
. The gel was heated at 413 K under static
conditions. After filtering, the solid was washed, dried and
calcined at 813 K for 1 h in a flow of N
2
, followed by 6 h in air.
The Ti content of the final solid was 2.5 mass% expressed as
TiO
2
.
Reactions were carried out batchwise in a 5 ml round-
bottomed flask with continuous stirring. The flask contained the
catalyst (30 mg), the substrate (1 mmol of methyl oleate), the
solvent, when used (2 ml), and the peroxide (0.25 mmol).
Products were analysed by capillary gas chromatography (25 m,
5% methylphenylsilicone) and their identification was estab-
lished by GCMS. Unreacted peroxide was determined by
iodometric titration.
Table 2 shows the results obtained in the epoxidation of
methyl oleate with hydrogen peroxide on Ti-b and Ti-MCM-41
catalysts. As can be seen, higher conversions and H
2
O
2
Table 1 Chemical composition of Ti-b samples
Gel synthesis Solid
Sample SiO
2
/TiO
2
SiO
2
/Al
2
O
3
TEAOH/SiO
2
H
2
O
2
/SiO
2
H
2
O
2
/SiO
2
HF/SiO
2
Si/Al %TiO
2
1
a
60 769 0.54 10.0 112 3.92
2 60 400 0.55 12.0 138 4.04
3 60 1660 0.55 6.3 0.34 590 2.96
4 60 0.55 6.8 0.34 H 2.36
5 25 0.56 7.5 0.34 0.62 H 2.10
a
Aerosil (Degussa) used as silica source.
Chem. Commun., 1997 795
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selectivities were obtained on Ti-b. It has been reported
18
that
polar solvents, such as methanol or acetonitrile, enhance the
activity of hydrophilic materials as epoxidation catalysts.
However, the higher hydrophility of Ti-MCM-41, as compared
to Ti-b, has a detrimental effect because it decreases the
adsorption of the organic substrate and, consequently, it favours
H
2
O
2
decomposition.
17
The epoxide is practically the only product obtained in
acetonitrile with both catalysts while the epoxide selectivities
are lower in methanol. In the case of Ti-b, the Al atoms present
in the zeolite framework generate surface acid groups which
catalyse the ring opening of the epoxide by addition of a protic
molecule. When decreasing the zeolite acidity, i.e. decreasing
the Al content in the catalyst, the epoxide selectivity increases
(Table 3). This increase is even larger when the hydrophobic Ti-
b, sample 5, is used. When there are no Al atoms in the catalyst
framework (Al-free Ti-b and Ti-MCM-41), opening of the
oxirane ring still occurs. This means that there are sites other
than those associated with the Al framework which are able to
catalyse the side reaction. These acid sites have been assigned to
peroxo or hydroperoxo species formed by the interaction of
hydrogen peroxide with Ti atoms in the zeolite.
19,20
The
selectivity to the epoxide is significantly improved (ca. 90%)
when the Al-free Ti-b sample is washed with an aqueous
solution containing Na
+
cations (Table 3), although the activity
of the catalyst slightly decreased.
As the presence of water inhibits the catalytic activity of Ti-
MCM-41, the epoxidation of methyl oleate was also carried out
using tert-butyl hydroperoxide (TBHP) as oxygen donor (Table
4). In this case, no solvent is needed to perform the epoxidation,
with corresponding savings in reactor volume and separation
costs. Under such reactions conditions Ti-MCM-41 was a
highly effective catalyst with high conversions and selectivities
to the epoxide and TBHP (ca. 91 and 99%, respectively). Ti-b
is also able to epoxidize methyl oleate using TBHP as oxidant.
Although the reaction rate is slower with respect to H
2
O
2
due to
steric restrictions to the formation of the transition state, the
epoxide and TBHP selectivities are > 80%.
In conclusion, hydrophobic Ti-b/H
2
O
2
and Ti-MCM-
41/TBHP have been demonstrated to be effective catalytic
systems to prepare epoxidized fatty esters with high conversions
and selectivities to epoxide.
The authors thank CICYT, project MAT 94-0359-C02-01
and project PL-921686 for financial support. P. E. thanks the
Generalidad Valenciana for a scholarship.
References
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Received in Cambridge, UK, 20th January 1997; Com.
7/00448F
Table 2 Epoxidation of methyl oleate with H
2
O
2
over Ti-b and Ti-MCM-41
catalysts
a
Oleate
Conv. Epoxide H
2
O
2
H
2
O
2
(% of selectivity conv. selectivity
Catalyst Solvent max.) (%) (%) (%)
Ti-b
b
MeCN 45.3 97.2 89.6 50.6
MeOH 40.1 31.8 62.0 64.6
Ti-MCM-41 MeCN 26.7 88.3 86.7 30.8
MeOH 21.9 42.9 81.8 26.7
a
Reaction conditions: 296 mg methyl oleate, 2 ml solvent, 24 mg H
2
O
2
(35
mass%), 30 mg catalyst. 50 C, 8 h.
b
Sample 1.
Table 3 Effect of Al content on Ti-b catalysts for the epoxidation of methyl
oleate with H
2
O
2
a
Chemical Oleate Epoxide H
2
O
2
composition conv. selec- H
2
O
2
selec-
(% of tivity conv. tivity
Sample Si/Al %TiO
2
max.) (%) (%) (%)
2 138 4.04 65.4 10.8 87.7 74.6
3 590 2.96 64.2 20.4 80.3 79.9
4 H 2.36 78.6 34.9 90.2 87.2
5 H 2.10 56.6 64.6 63.1 90.4
Na-Ti-b (4) H 2.36 59.1 90.1 85.2 69.4
a
Reaction conditions as in Table 2. Methanol used as solvent.
Table 4 Epoxidation of methyl oleate with TBHP over Ti-b and Ti-MCM-
41 catalysts
a
Epoxide TBHP
Oleate conv. selectivity TBHP conv. selectivity
Catalyst (% of max.) (%) (%) (%)
Ti-b
b
49.3 97.4 51.9 95.0
Ti-MCM-41 64.6 91.1 65.3 98.9
a
Reaction conditions: 296 mg methyl oleate, 112 mg TBHP (80% in tert-
butyl peroxide), 30 mg catalyst. 70 C, 8 h.
b
Sample 5.
796 Chem. Commun., 1997
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