New findings on soybean and methylester epoxidation with alumina as the catalyst

Article abstract of DOI:10.1039/c6ra01780k

The activity of a commercial alumina, after a preliminary characterization, was investigated in epoxidation with soybean oil with aqueous hydrogen peroxide. Results show that the γ-alumina was an efficient catalyst. The role of the solvent in the epoxidation reaction in the presence of alumina was investigated. A "no-innocent" solvent role was demonstrated. Moreover, the optimization of the methyl oleate epoxidation reaction with alumina was eventually valuated, varying the type of the solvent and concentration of hydrogen peroxide in order to obtain a product with commercial features.

Full text of DOI:10.1039/c6ra01780k

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New findings on soybean and methylester
epoxidation with alumina as the catalyst
Cite this: RSC Adv., 2016, 6, 31647
ab
a
ab
a
Rosa Turco, Chiara Pischetola, Riccardo Tesser, Salvatore Andini and Martino Di
Serio*
ab
The activity of a commercial alumina, after a preliminary characterization, was investigated in epoxidation
with soybean oil with aqueous hydrogen peroxide. Results show that the g-alumina was an efficient catalyst.
The role of the solvent in the epoxidation reaction in the presence of alumina was investigated. A “no-
innocent” solvent role was demonstrated. Moreover, the optimization of the methyl oleate epoxidation
reaction with alumina was eventually valuated, varying the type of the solvent and concentration of
hydrogen peroxide in order to obtain a product with commercial features.
Received 20th January 2016
Accepted 20th March 2016
DOI: 10.1039/c6ra01780k
www.rsc.org/advances
this case the water would be the only by-product (Fig. 1), and the
catalysts could be easily recovered at the end of the process.
1
. Introduction
The epoxidation reaction of vegetable oils and their derivatives Moreover, the use of a heterogeneous catalyst could allow to
has attracted increasing interest from both the scientic and suppress the oxirane ring opening side reactions, considering
industrial community, because the obtained epoxides are the lack in free acidity in the reaction environment (Fig. 1).
important building blocks for the preparation of chemical
intermediates, which are the basis for a wide variety of hydrogen peroxide as oxidant, have been studied and proposed
Many different catalytic systems for epoxidation, using
3,4
consumer products. They are used directly as plasticizers and in literature. Among them, the titanium silicalite (TS-1) was
stabilizers for PVC resins, as additives in lubricants, and as reported as a milestone for the oxidation of olens with
5
components in plastics. On the industrial scale, oil epoxidation hydrogen peroxide. However, this catalyst is barely active with
is currently performed through the “Prileschajew reaction”, large substrates like oils and methyl esters, due to the small
˚
where the unsaturated oils react with a percaboxylic acid, such pores diameter (5.6 ꢀ 4.7 A) of TS-1. Extensive work was done to
as peracetic or performic, obtained in situ through the acid incorporate Ti(IV) in large molecular sieves pores, leading to
6
catalysed oxidation of the respective organic acid with hydrogen materials such as Ti-MCM-41 and Ti-MCM-48. Recently, some
1
peroxide. The soluble mineral acids, such as H
3
PO
4
and H
2
SO
4
,
niobium–silica based solids were developed and reported in
7
–10
are commonly used as catalysts. However, the use of these acids literature as active catalysts for the epoxidation reaction.
It
involves problems concerning the selectivity of the process, was demonstrated that different synthesis procedures lead to
because they promote the degradation reaction of the produced the presence of different structures and surface distribution of
epoxides, with the formation of detrimental side products. The active sites, inuencing in this way the activity and selectivity in
presence of such by-products, derived by side reactions, in the the epoxidation reaction. However, the majority of the catalysts
commercial epoxidized oils diminishes their attractiveness as
starting materials for further syntheses. Moreover, there are
other severe limitations correlated to this technology, such as
the disposal of salts derived from the nal neutralization of
mineral acids, the corrosion and expensive separation opera-
2
tions. Therefore, the setting up of new sustainable processes
based on the use of green reagents and clean technologies is
imperative to overcome the afore mentioned disadvantages.
For the epoxidation reaction, the use of hydrogen peroxide as
oxidant and a heterogeneous catalyst is attractive, because in
a
Dipartimento di Scienze Chimiche, Universit a` degli Studi di Napoli Federico II,
Complesso Universitario di Monte Sant'Angelo, 80126 Napoli, Italy. E-mail:
diserio@unina.it; Tel: +39 081674414
b
Consorzio Interuniversitario di Reattivit a` Chimica e Catalisi, Via Celso Ulpiani 27,
Fig. 1 Epoxidation and ring opening reactions.
7
0126 Bari, Italy
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2.3. Epoxidation reaction
The epoxidation reactions were carried out in a round-bottom
glass batch reactor (100 mL), put in an oil bath, equipped
with a condenser, a thermometer and a magnetic bar for
vigorous stirring (300 rpm). The temperature was kept constant
ꢂ
3
(
z80 C). In a typical experiment, 600 mg of catalyst, 20 cm of
solvent, 5 g of organic substrate and 6.9 g of hydrogen peroxide
54.9% wt) were used. All the reagents were added in one pot at
(
Scheme 1
the beginning of the reaction. The reaction was conducted in
general for 5 h. Operating conditions different from the refer-
ence ones will be detailed in the forthcoming text. The nal
solution was separated from the catalyst by ltering, and it was
analyzed to evaluate the double bonds conversion and the
selectivity to oxirane rings, determining the Iodine Number
based on transition metals are expensive due to their complex
synthesis. Therefore, the use of no expensive catalyst could be
attractive from the commercial point of view.
The g-alumina was found to be able to activate the hydrogen
peroxide for the oxidation, through the formation of a peroxide
(
I.N.) and the Oxirane Number (O.N.) according to the analytical
18,19
11,12
methods reported in the literature.
site, according to the reaction reported in Scheme 1.
As a matter of fact, a good activity and selectivity towards
1
3,14
2.4. Hydrogen peroxide decomposition
different epoxides was reported.
A moderate performance
15
was also found with methyl esters. However, only preliminary The decomposition reaction was conducted in the same batch
data was reported for the epoxidation of bulk substrates such as reactor used for the epoxidation reactions. To this end, 6.9 g of
16
oil. Therefore, the aim of this work was to carry out a detailed H O were fed to the reactor preloaded with 600 mg of catalyst.
2
2
study on the activity of g-alumina in the soybean oil and methyl The system was heated to reux temperature of solvent (ethyl
esters epoxidation reaction with hydrogen peroxide. Although acetate) and placed under continuous stirring (360 rpm) for 5 h.
the use of alumina in epoxidation is not new, the evaluation of Intermediate samples were collected, and cooled in a bath of
its activity with larger organic substrates represents a novelty in water and ice. The amount of decomposed hydrogen peroxide
this eld. For this purpose a commercial alumina, aer was assessed by iodometric titration according to the method
a preliminary characterization, was tested in epoxidation with described in ref. 2.
soybean oil and the role of the solvent in the epoxidation
reaction in the presence of alumina was investigated. Some
3
. Results and discussion
crucial aspects for the epoxidation reaction were investigated,
such as the type of the solvent, the type of substrate, the
concentration of hydrogen peroxide.
3.1. Alumina characterization
The XRD analysis and the comparison with the standard JCPD
card (00-010-0425) conrmed the presence of g phase for the
investigated alumina. Its textural properties were determined by
nitrogen adsorption–desorption isotherm at 77 K. An adsorp-
tion isotherm of type IV was observed, and the type of hysteresis
2. Experimental procedures
2.1. Materials
Commercial alumina, supplied by Fluka (neutral, activated loop indicates the presence of ink bottle-shaped mesopores. As
aluminum oxide for chromatography, Brockman activity I, reported in Table 1, values of specic surface area and pore
2
ꢁ1
3
ꢁ1
particle size of 0.05–0.15 mm), was used, as received, in the volume equal to 149 m g and 0.27 cm g were obtained,
epoxidation tests. Methyl oleate, (acidity number of 0.64 mg
gsample ) ethyl acetate, acetonitrile and toluene were supplied
respectively. The mean pore diameter is about 4.2 nm.
The chemical composition was determined by XRF and
KOH
ꢁ
1
by Sigma Aldrich and were used as received, without further indicates the main presence of alumina, together with a low
ꢁ
1
purication. Soybean oil, (iodine number of 128 gI2
g
sample
amount of other impurities (Table 1).
ꢁ1
and acidity number of 0.36 mgKOH gsample ), was purchased in
a local food store. The hydrogen peroxide (54.9% wt) was kindly 3.2. Epoxidation of soybean oil
provided by Solvay S.p.A.
3.2.1. Activity of alumina and effect of hydrogen peroxide
decomposition. Table 2 reports in detail the operating condi-
tions adopted for each of the 16 epoxidation tests whose results
2.2. Catalyst characterization
The X-Ray Diffraction (XRD) patterns were determined with are reported in this paper. Tests varied with each other in terms
ꢂ
a Philips 1887 diffractometer, using Cu Ka radiation in a 5–80
2
of substrate nature and amount, type of solvent, amount of
, amount of alumina, reaction time. Table 2 lists the
surface area of the alumina was determined by the BET conversion and selectivity experimental results. They pointed
ꢂ
ꢁ1
q range and at a scan velocity of 0.02 2q s . The specic
2 2
H O
17
method, using nitrogen adsorption isotherms (at 77 K) in out that alumina is an active catalyst in epoxidation with
a Sorptomatic 1990 instrument. X-Ray Fluorescence (XRF) hydrogen peroxide, also in the presence of a more bulky
analysis on the raw materials was performed through a BRUKER substrate like oil. In fact, using ethyl acetate as solvent (Run #1)
Explorer S4 apparatus.
a conversion of double bonds of 56% and a selectivity to oxirane
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Table 1 Principal characteristics of alumina
Chemical composition (% wt)
BET surface
Mean pore
diameters (nm)
Pore volume
2
ꢁ1
3
ꢁ1
a
(m g
)
(cm g
)
CaO
SiO
2
Al
2
O
3
K
2
O
Fe
2
O
3
Na
2
O
L.o.i.
Others
1.67
Fluka
149
4.2
0.27
—
0.11
90.37
0.12
—
0.32
7.00
a
ꢂ
Loss on ignition @ 900 C.
ꢂ
3
Table 2 Operating conditions adopted for the epoxidation reaction at 80 C (in any case, 20 cm of solvent were used), and related conversion
and selectivity results
a
b
H
wt (g)
2
O
2
54.9%
Substrate
(g)
Alumina
(g)
Reaction
time (h)
Conversion
(%)
Selectivity
(%)
Run
Substrate
Solvent
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
Soybean oil
Soybean oil
—
Soybean oil
—
Soybean oil
Methyloleate
Methyloleate
Methyloleate
Soybean oil
—
Methyloleate
Methyloleate
Methyloleate
Methyloleate
Methyloleate
Ethyl acetate
Ethyl acetate
Ethyl acetate
Ethyl acetate
Ethyl acetate
Solution of Run 5
Ethyl acetate
Acetonitrile
Toluene
Acetonitrile
Acetonitrile
Solution of Run 11
Acetonitrile
Acetonitrile
Acetonitrile
Acetonitrile
6.9
6.9
6.9
6.9
6.9
—
6.9
6.9
6.9
6.9
6.9
—
5.0
5.0
—
5.0
—
5.0
5.0
5.0
5.0
5.0
—
5.0
5.0
5.0
5.0
5.0
0.6
0.6
0.6
—
0.6
—
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
5
10
5
56
75
78
0
65
11
57
72
22
6.7
—
0
75
71
70
80
59
64
—
—
—
41
71
81
7.0
4.3
—
—
58
74
77
96
c
5
c
2.5
2.5
5
5
5
0
1
2
3
4
5
6
5
2.5
2.5
5
8
5
d
6.9
6.9
8.1
e
6.9 + 3.4
8
a
b
c
d
Conversion of double bonds. Selectivity to oxirane rings. Conversion of H
2
O
2
.
At the beginning of the reaction 0.1 g of glacial acetic acid was
e
added. Aer 5 h of reaction. The standard deviations relative to conversion and selectivity values are 2.8% and 1.8% respectively.
of 59% were found aer 5 h of reaction. These results are in
20
good agreement with those reported by Suarez et al. for the
methyloleate epoxidation reaction, obtained with an alumina
2
ꢁ1
having similar specic surface area (167 m g ). The activity of
alumina was also studied for longer times in epoxidation reac-
tion (Run #2), obtaining a prole of conversion and selectivity as
shown in Fig. 2. It emerges that the reaction is stopped at
around 75% of conversion (10 h as reaction time), where
a selectivity of 64% was observed, notwithstanding the use of an
excess of hydrogen peroxide (molar ratio hydrogen peroxide/
double bonds ¼ 4). The limit in the conversion could be due
to a loss of hydrogen peroxide ascribable to the parallel
decomposition reaction, because the alumina could also cata-
21
lyze the hydrogen peroxide decomposition. Regarding this
aspect, a specic test has been also performed to evaluate the
H O decomposition in the presence of Al O (Run #3, no
2 2 2 3
Fig. 2 Performance (conversion and selectivity) of the g-alumina
catalyst as a function of reaction time in the epoxidation of soybean oil.
substrate). The obtained results are also reported in Fig. 3. As it Operating conditions are those for Run #2 (Table 2), with a H O /
2
2
can be seen, H
2
O
2
gradually decomposed up to 78% with double bonds molar ratio equal to 4. The standard deviations relative
to conversion and selectivity values are 2.8% and 1.8% respectively.
respect to the initial amount in 5 h, and this explains the strong
loss of activity along with the reaction time. In fact, as long as
the epoxidation goes on, the reactive system loses a part of the
oxidant useful for the reaction and it enriches in water, which is
able to hydrolyze the oxirane ring. These results are in agree-
of the water amount on the epoxidation rate. Actually, a small
amount of water is necessary to rehydrate the surface, indis-
pensable for the activity of alumina in this reaction. However,
12
ment with those by Sheldon et al., who pointed out the key role
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probably involved in undesired side reactions, such as the
decomposition of hydrogen peroxide and the hydrolysis of
1
2
ethyl acetate to acetic acid.
Acetic acid can react with oxirane ring or catalyze the
reaction of water with oxirane rings (ring opening), reducing
the nal yield. Moreover, because of the highly oxidizing
environment, it can be argued that acetic acid forms peracetic
acid, which could then react with the double bonds in the oil,
via Prileschajew reaction, increasing the reaction rate of
double bond epoxidation. To verify these assumptions, dedi-
cated tests (Runs #4–6) were carried out. In particular, Run #4
was performed under the same conditions of Run #1, but
without catalyst. No reaction of double bonds was observed.
Run #5 was performed under the same conditions of Run #3
(
no soybean oil), but the reaction was stopped at 2.5 h. Then,
aer the removal of alumina, the soybean oil was added and
Fig. 3 Hydrogen peroxide decomposition as a function of reaction the reaction was carried out for other 2.5 h (Run #6). A
time in presence of g-alumina catalyst. Operating conditions are those
conversion of 11% and a selectivity of 41%, obtained in this
case, can be attributed to the reaction of formed peracetic acid
with double bonds.
for Run #3 (no substrate, Table 2), with a H
ratio equal to 4.
2 2
O /double bonds molar
an excessive quantity of water, derived by the reaction and the 3.3. Methylesters epoxidation
use of dilute hydrogen peroxide, diminishes the selectivity to
the desired epoxides.
The epoxidation reaction was also performed in ethyl acetate
using methyl oleate instead of soybean oil as substrate (Run #7),
under the same reaction conditions of Run #1. Notwithstanding
the methyl oleate has a smaller dimension than that of
triglycerides of soybean oil (methyl oleate has a molecular
diameter of 2.5 nm while the dimensions of triglycerides fall in
the range of 2.5–5 nm (ref. 33 and 34)), the same conversion of
double bonds (around 56–57%) was found for the two reagents.
This behaviour can be justied considering that the dimensions
of the two reagents are comparable with the mean pore diam-
eter of the catalyst (4.2 nm), and so relevant diffusive restric-
tions have not been observed.
One way to limit this problem may consist in the adding
2 2
drop-by-drop the H O to the reaction mixture, or gradually
22,23
remove water.
.2.2. Role of the solvent. Practically, all the literature
3
works concerning the application of g-alumina as epoxidation
catalyst report the use of a reaction solvent such as ethyl acetate.
The detection of the characteristic odour of acetic acid in the

nal product of the epoxidation reaction, in the presence of
ethyl acetate as solvent, led to the hypothesis that at the reaction
ꢂ
temperature under investigation (80 C) and in the presence of
water coming from hydrogen peroxide, alumina could promote
the hydrolysis of ethyl acetate to acetic acid. The formation of
acetic acid was conrmed by titration of solvent in Run #3 with
a KOH solution and qualitatively by gas chromatographic
analysis. The solvent acidity at the beginning of the reaction was
The selectivity to oxirane in the case of methyl oleate (Run
#7) is higher than the one obtained with soybean oil (Run #1)
(71% vs. 59%). This behaviour can be justied by the presence
in soybean oil of a high concentration of dienes and trienes,
with the resulting oxirane rings being more reactive than in the
ꢁ
1
0
g
.39 mgKOH
g
sample
while at the end it became 2.8 mgKOH
31
case of monoenes.
ꢁ
1
sample
.
With the aim to optimize the synthesis of epoxidized
methylesters, the effect of the solvent was further investigated.
To this end, two other solvents with different polarity in respect
to ethylacetate (3 z 6.0) were tested: acetonitrile (3 z 37) and
toluene (3 z 2.4) (see Table 2). The largest values of double
bonds conversion (72%) and selectivity to oxirane rings (81%)
were obtained with acetonitrile (Run #8), while the worst results
were obtained using toluene as solvent (Run #9, double bonds
conversion ¼ 22%; selectivity to oxirane rings ¼ 7%). This result
can be explained considering the better solubility of both
epoxidation reactants in acetonitrile (methyloleate and
hydrogen peroxide), with respect to the other two solvents. In
particular, while the methyloleate is miscible in all solvents,
hydrogen peroxide and water are completely soluble in aceto-
nitrile, only partially in ethyl acetate and very poorly in
This assumption can be explained considering the
complicated alumina surface with the presence of different
types and strengths of Lewis acid sites, which consist in form
of coordinatively unsaturated aluminium ions and of different
2
4
hydroxyl groups. A lot of studies on this aspect with a large
2
5–27
28,29
variety of techniques such as solid state NMR,
FT-IR
3
0
and theoretical calculations have revealed the presence of
three-, four- and ve coordinate Al ions as Lewis acid sites, and
up to or more than ve types of surface hydroxyls for the
dehydrated aluminas. Most of them are very weak acids and
only one has been shown to be the most reactive. The epoxi-
dation reaction was believed to take part on the alumina
surface through the formation of hydroperoxo species,
involving only weak Lewis acid sites, which consist in 5-coor-
3
+
dinate Al . The strong and medium Lewis acid sites are
32
toluene. Moreover, the lower selectivity found when ethyl
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acetate as solvent was employed (with respect to the acetonitrile
case) can be explained assuming the presence of acetic acid,
4. Conclusions
derived by hydrolysis of ethyl acetate, as discussed above. This In this work, it is shown that common commercial alumina is
acid promotes the degradation of oxirane groups by ring active in the epoxidation of soybean oil with aqueous hydrogen
12,31
opening reaction.
peroxide as oxidant. A “no-innocent” role of solvent, like ethyl
The importance of the solvent choice can be further appre- acetate, is supposed and demonstrated for the epoxidation
ciated considering the results of Run #10, where acetonitrile reaction with hydrogen peroxide as oxidant. As a matter of fact,
was used as solvent in epoxidation reaction of soybean oil. The the ethylacetate is reasonably hydrolyzed and form peracetic
obtained result was worst than in the case of ethyl acetate (Run acid. Moreover, also other parameters have a strong inuence
#
10: double bonds conversion ¼ 6.7%; selectivity to oxirane on the epoxidation reaction.
rings ¼ 4.3%). This behaviour can be explained considering that
It was found that the epoxidation system acetonitrile/
oil is poorly dissolved in acetonitrile. Acetonitrile lls most of alumina, barely reported in literature, is suitable for the effi-
pore volume and therefore hinders the access of the triglyceride cient epoxidation of methyl oleate with hydrogen peroxide.
to reactive sites of the catalyst.
Superior values of conversion and selectivity were found with
However, in the presence of acetonitrile as solvent the acetonitrile, in comparison with the use of other solvents,
hydrolysis by hydrogen peroxide (Radziszewski reaction) to demonstrating the strong inuence of the solvent nature on the
form peroxycarboximidic acid could be feasible, even if an reaction rate. In order to reach high conversion and selectivity
3
5
alkaline environment is required. Because epoxidation of values, it is crucial to work with high oxidizing reactant/
methyl oleate is conducted in neutral reaction medium, the unsaturations molar ratios, with a careful control of the
solvent hydrolysis should not occur. To conrm this, a run hydrogen peroxide feed rate, also considering the parallel
without substrate using acetonitrile as solvent was per- decomposition reaction of hydrogen peroxide.
formed (Run #11) for 2.5 h. Alumina was then removed from
the reaction solution and methyloleate was added (Run #12).
No reaction of double bonds was observed aer additional
Acknowledgements
2
.5 h.
To further demonstrate the “non innocent” role of ethyl
The authors are grateful to Solvay Italy for having provided
hydrogen peroxide. Thanks are due to P.O.R. Campania FERS
acetate a new run (Run #13) with the same condition of Run #8
was performed with adding 0.1 g of glacial acetic acid.
The results are in agreement with the forecasting. As
a matter of fact, we observed a light increase in activity
2007/2013 – BIP – CUP B25C13000290007 for nancial support.
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