Sodium stannate promoted double bond cleavage of oleic acid by hydrogen peroxide over a heterogeneous WO3 catalyst

Article abstract of DOI:10.1039/c8gc00949j

The production of valuable mono- and dicarboxylic acids from abundant and renewable vegetable oil sources is of great industrial interest. It is demonstrated by a simple and eco-friendly heterogeneous catalytic system for direct oleic acid (OA) cleavage by hydrogen peroxide to produce azelaic acid (AA) and nonanoic acid (NA). Commercially available tungsten oxide was used as a heterogeneous catalyst without any modification or pretreatment, and sodium stannate was used as a H₂O₂ stabilizer to improve the efficiency of the oxidant. The sodium stannate additive notably improved the product yields and it could be recycled together with the tungsten oxide catalyst. Isolated product yields up to 89% for azelaic acid and 65% for nonanoic acid were achieved from oleic acid in this simple system, which should be among the best results for oleic acid cleavage in heterogeneous systems. This strategy is also applicable for other catalytic systems for the cleavage of OA or its derivatives. This work provides a potential method for the large scale upgrading of oleic acid.

Full text of DOI:10.1039/c8gc00949j

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DOI: 10.1039/C8GC00949J
Journal Name
ARTICLE
Sodium Stannate Promoted Double Bond Cleavage of Oleic
Acid by Hydrogen Peroxide over Heterogeneous WO3
Catalyst
Received 00th January
2
0xx,
Accepted 00th January
0xx
*
Xiukai Li, Joel Choo Ping Syong and Yugen Zhang
2
The production of valuable mono- and dicarboxylic acids from abundant and renewable vegetable oil sources
is of great industrial interest. It is demonstrated a simple and eco-friendly heterogeneous catalytic system for
direct oleic acid (OA) cleavage by hydrogen peroxide to produce azelaic acid (AA) and nonanoic acid (NA).
Commercially available tungsten oxide was used as the heterogeneous catalyst without any modification or
DOI: 10.1039/x0xx00000x
www.rsc.org/
2 2
pretreatment, and sodium stannate was used as an H O stabilizer to improve the efficiency of the oxidant.
The sodium stannate additive notably improved the product yields and it could be recycled together with the
tungsten oxide catalyst. Isolated product yields up to 89% for azelaic acid and 65% for nonanoic acid were
achieved from oleic acid in this simple system, which should be among the best results for oleic acid cleavage
in heterogeneous systems. This strategy is also applicable for other catalytic systems for the cleavage of OA
or its derivatives. This work provides a potential method for the large scale upgrading of oleic acid.
Renewable biomass feedstock is a potential alternative to fossil
Though the ozonolysis of oleic acid (OA) into azelaic acid (AA)
resources for the production of chemicals and fuels. Oils from and nonanoic acid (NA) is efficient and has already been
vegetable origins are abundant, nontoxic, and biodegradable, industrialized on a large scale, the use of hazardous ozone as an
making them very promising candidates for the sustainable oxidant is obviously a big challenge for safety and environmental
chemical industry. In fact, the nonfood consumption of vegetable management. As such, safer, greener, and economically viable
[1]
oils has increased steadily in the past two decades. The hydrolysis processes for oleic acid cleavage are highly sought-after.
of triglycerides (the main constituents of vegetable oils and animal Noncatalytic and catalytic systems with oxidants alternative to
fats) generates glycerol and various saturated and unsaturated fatty ozone have therefore been explored extensively. Reagents such as
acids such as palmitic acid, oleic acid, and linolenic acid. The fatty nitric acid, organic peracids, potassium monopersulfate, potassium
acid products as well as glycerol have functional groups possible for permanganate, sodium periodate, and sodium hypochlorite were
further derivatization and chemical modification. The oxidative used as strong oxidants for oleic acid cleavage in homogeneous
[
1a, 2a, c, 3]
cleavage of unsaturated fatty acid at the C=C bond for the systems with or without the aid of a catalyst;
however,
production of shorter-carbon-chain monocarboxylic acids and these oxidants are not eco-friendly. Transition metal-based catalytic
[
1a, 2]
dicarboxylic acids is of particlular interest.
ozonolysis of oleic acid enables the production of azelaic acid (C9 oxidants are more attractive. Fe, W, Mo, and Ru organometallic
dicarboxylic acid) and nonanoic acid (C9 monocarboxylic acid) complexes are homogeneous catalysts, activating O or H for
Among those, the quaternary ammonium
salts of W-based heteropoly acids gave the best product yield
For instance, the systems with molecular oxygen and hydrogen peroxide as green
2
2 2
O
[2d-f]
[1a, 2a, 4]
(
Scheme 1),
both acid products being useful intermediates for oleic acid cleavage.
the manufacture of polymers and a variety of materials.
[
4d-h]
varying from 80t97% in two phase reaction systems.
Besides
the direct cleavage of oleic acid, there have also been trials on the
two-step conversions of oleic acid via 9,10-dihydroxysteric acid
[5]
(
DSA) as an intermediate. Oleic acid was first dihydroxylated to
DSA by in the presence of H WO , then DSA was further
cleaved by sodium hypochlorite or molecular oxygen in the
presence of homogeneous cobalt catalysts.
Au/AlO catalyst could cleave DSA to afford a high yield of azelaic
acid (86%) and nonanoic acid (99%) under 5 bar of O ; however, the
catalyst recyclability suffered from the problem of Au leaching.
H
2
O
2
2
4
[5b]
Scheme 1. Oxidative cleavage of oleic acid into aldehydes and
[5a, c, d]
A heterogeneous
carboxylic acids.
3
2
[5e, f]
Dr. X. Li, Joel Choo Ping Syong, Dr. Y.G. Zhang.
Institute of Bioengineering and Nanotechnology, 31 Biopolis Way, The Nanos,
Singapore 138669, Singapore. E-mail: ygzhang@ibn.a-star.edu.sg
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
Compared with the one-step processes, the two-step processes
were more complicated and afforded comparable or even lower
product yield.
This journal is © The Royal Society of Chemistry 20xx
J. Name, 2016, 00, 1-3 | 1
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The direct cleavage of oleic acid in heterogeneous catalytic of sodium stannate with the tungsten oxide catalyst resulted in
systems is preferred for better simplicity of the system and easier product yields improving to 51.1% for NA and 42.0% for AA (Entry 5,
post-treatment. However, so far there have been quite limited Table 1). It is also noted that the addition of sodium stannate did
reports on such heterogeneous systems probably because of the not change the product distribution. Other tin-containing
[6]
poor catalyst performances. About 80% product yield was compounds were not as effective as sodium stannate (9všŒ]ꢂ• ò>ô).
achieved from methyl oleate cleavage over ruthenium Our control reaction (Entry 9, Table 1) revealed that sodium
nanoparticles supported on hydroxyapatite, however, with NaIO
4
as stannate itself is inactive for oleic acid cleavage. To study the
Using Cr/Co/Mn- thermal decomposition of H in the presence of sodium stannate
and supported/unsupported stabilizer, we carried out the tests at 130 °C without oleic acid and
as catalysts, only 30% yield of azelaic acid and nonanoic acid WO in the system (Figure 1). It turned out that 91% of H
were produced from oleic acid oxidation by molecular oxygen or remained in 4 h and 66% of H remained in 16 h. This is a sharp
hydrogen peroxide. Surfactant-functionalized WO and MoO contrast to the fact that H was almost fully decomposed in 4 h at
nanoparticles afforded higher product yield (near 80%) due to the 130 °C in the absence of sodium stannate. Thus, it is feasible to
[7]
the oxidant instead of greener O
2
and H
2
O
2
.
2 2
O
[6c]
doped MCM-41 molecular sieves
[
3
6e]
WO
3
2 2
O
2 2
O
3
3
2 2
O
[6a, d, 8]
better compatibility of catalysts in the reaction system.
2 2
improve OA cleavage by adding sodium stannate as a H O stabilizer
Sophisticated procedures were carried out to synthesize such into the reaction system. Similar positive effects of adding H
2
O
2
[
12]
nanoparticles with hydrophobic surfaces. Thus, all the current stabilizer were also observed in Fenton oxidations.
catalytic sytems are restricted for the large-scale cleavage of oleic
acid.
Table 1 The oxidative cleavage of OA by H
2
O
2
in the presence of
In this work, we report a simple system for direct oleic acid commercial WO
3
catalyst and tin additives.
cleavage by hydrogen peroxide employing commercial tungsten
oxide as a catalyst and sodium stannate as an additive. The
tungsten oxide is easily avaliable in large amounts and it was used
without any modification or pretreatment. Sodium stannate served
[a]
Yield (%)
Conv.
-al-
(%)
AA
Entry Catalyst Additive
C
8
-
C
9
9
C -al NA
acid
acid
as an H
2
O
2
stabilizer and it promoted the reaction notably. An
1
2
3
4
5
6
7
8
9
-
-
1.8 4.7 3.6 2.7 1.2 60.0
3.2 2.9 14.6 1.5 10.6 53.2
4.6 11.7 28.1 10.8 20.9 76.1
5.0 3.9 38.1 2.0 22.9 100.0
2.4 1.3 51.1 2.6 42.0 100.0
0.0 0.0 37.2 0.0 27.1 100.0
7.1 7.5 32.2 6.7 24.7 100.0
5.0 7.6 24.4 6.0 17.0 100.0
2.7 0.6 5.4 0.0 3.9 52.7
[
b]
c]
isolated yield up to 89% for AA was achieved from this simple
WO3
WO3
-
[
system, in contrast to the 30t80% yield for AA from other
-
[6a, 6c-e, 8]
heterogeneous systems.
Moreover, both the tungsten oxide
WO
WO
WO
WO
WO
-
3
3
3
3
3
-
catalyst and the sodium stannate additive could be recycled. This
work provides a possible strategy for improving product yields from
2 3
Na SnO
Sn(OH)
SnO
SnCl
Na SnO
4
2 2
oleic acid and its derivatives by H O oxidation. This work may also
2
open up the study of new W/Sn-based catalysts for this reaction.
Tungsten-based catalysts are attractive for oleic acid cleavage in
4
[4d-h, 6a, e, 8]
2
3
both the homogeneous and heterogeneous systems.
The
OA 283 mg (1 mmol), WO
mL, 31% H 1 mL, 130 °C 4 h. [a] GC yield; [b] 60 °C 4 h; [c] 100 °C
4 h. C -acid: octanoic acid; C
3 2 3
30 mg, Na SnO 10 mg, tert-butanol 4
use of tungsten oxide as a solid catalyst for oleic acid cleavage by
hydrogen peroxide usually requires a reaction temperature above
2 2
O
[
6a, e, 8]
8
9
-al: nonanal; NA: nonanoic acid; C
9
-al-
1
00 °C to achieve high OA conversion.
reports the results of OA cleavage by hydrogen peroxide in the
presence of commercial WO catalyst under different reaction
tempratures. The WO was in a monoclinic crystal structure and had
micron particle sizes. rapid sample derivatization method
esterification in BF -methanol) was used to speed up GC analysis
Çꢀꢁoꢂ í ~9všŒ]ꢂ• î>ð•
acid: 9-oxononanoate; AA: azelaic acid.
3
3
A
100
[9]
in the presence of Na SnO3
(
3
2
in our preliminary catalyst screening and reaction optimization,
with the extents of esterification at 70% for AA and 85% for NA,
respectively. One can see that both OA conversion and the
apparent yields for NA and AA increased with the reaction
temperature. Full OA conversion was achieved at the reaction
temperature of 130 °C, and the apparent yields for NA and AA were
80
60
40
3
8.1% and 22.9%, respectively. Octanoic acid, suberic acid, nonanal
20
and 9-oxononanoate were observed as the major side products. As
the decomposition of hydrogen peroxide at above 130 °C is rapid
in the absence of Na SnO3
2
0
[
10]
and dangerous,
30 °C. As we envision that suppressing the rapid decomposition of
hydrogen peroxide might improve reaction efficiency, we added
stabilizers into the system. Different types of stabilizers were
screened (Table 1 & S1), including inorganic acids, inorganic salts,
reaction temperatures should be capped at
0
5
10
15
20
1
Time / h
Figure 1. Rate of H
Na SnO . Na SnO
2
O
2
decomposition in the presence or absence of
10 mg, tert-butanol 4 mL, 31% H 1 mL, 130 °C.
2 2
H O
2
3
2
3
2 2
O
[11]
metal oxides, and chelating agents. Most of the stabilizers did
not give positive effects except sodium stannate. The combination
2
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Journal Name
A
60
50
40
30
20
10
NA
AA
B 60
NA
AA
50
40
30
20
10
80
100
120
140
160
0
5
10
15
Temperature / èC
Na SnO / mg
2 3
D
140
20
100
C 60
NA
AA
1
50
40
30
20
10
0
8
6
4
2
0
0
0
0
2
Amount of H O2
1 mL
1.5 mL
2 mL
0
5
10 15 20 25 30 35 40 45 50
0
2
4
6
8
10
12
WO / mg
3
Time / h
o
1 mL, 130 C, reaction
Figure 3. Deferred reaction conditions: OA 283 mg (1 mmol), WO
time 12 h. (A) The temperature dependence of OA cleavage by H
3
30 mg, Na
2
SnO
3
10 mg, tert-butanol 4 mL, H
2
O
2
2
O
2
in the presence of WO
3
and Na SnO
2 2
. (D) The loading amount of H O
2
3
. (B) The changing of loading
amount of Na
2
SnO
3
at 4 h reaction time. (C) The changing of loading amount of WO
3
and the reaction time.
in micron sizes (Figure 5A). After the first round of catalytic reaction,
the cubes broke into smaller irregular particles (Figure 5B). After
seven rounds of recyclability testing, the catalyst morphology
changed into uniform nanoparticles (Figure 5C). The XRD analysis
60
50
40
30
20
10
0
NA
AA
(Figure S1) shows that the fresh WO
3
catalyst is in a monoclinic
crystal structure. After several runs of reaction for OA cleavage, the
[
14]
catalyst gradually changed to monoclinic WO2.72
between WO and aqueous H is profound under solvothermal
conditions. WO could be converted to various hydrates and
.
The interaction
3
2 2
O
3
[8]
tungsten-peroxo complexes under the conditions, and this would
induce the restacking and phase transition of the crystals, and also
the changes in sample morphology. Because the tungsten-peroxo
complexes are the active oxidants for OA cleavage and their
1
2
3
4
5
6
7
Recycle sequence
Figure 4. The recyclability tests for WO and Na
formation is independent of the crystal structure of WO
3 3
, WO with
[8]
2 2
various crystal structures can activate H O for this reaction. The
3
2
SnO
3
. OA 283 mg (1
tungsten-peroxo complexes are unstable and gradually
decomposed, converting to the oxygen-deficient metal oxide after
prolonged reaction. The catalyst after the seventh reaction was
subjected to the energy dispersive X-ray analysis (EDXA). The
elemental mapping spectra (Figure 5D & E) for the used catalyst
show that both W and Sn were uniformly dispersed over the sample,
confirming that the tin additive was recovered together with the
2
3 2 2
mmol), catalyst 30 mg, Na SnO 10 mg, tert-butanol 4 mL, H O 1
mL, 130 °C 4 h. Catalyst was separated by centrifuge and washed
with tert-butanol twice for the next test.
Catalyst recyclability was tested for OA cleavage with the results
reported in Figure 4. In seven runs of use and reuse of the catalyst,
the product yields dropped slightly for NA and AA. Since the
product yields in the recycled reactions are higher than that in the
WO
3
catalyst. The elemental emission spectrum (Figure 5F)
indicates that the W/Sn ratio (2.1 in molar) in the used catalyst is
close to the initial ratio (2.7) in the first round of reaction. It is
reaction with WO
that the Na SnO
fresh and the used catalysts were characterized by scanning
electron microscopy (SEM). The fresh WO catalyst contains cubes
3
catalyst alone (Entry 4, Table 1), we assumed
2
3
additive was recycled together with WO . The
3
noteworthy that Na
2
SnO
3
is soluble in tert-butanol/water mixture
catalyst. We presume
but it can be recycled together with the WO
3
3
4
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3
Figure 5. The SEM image and the EDX mapping. (A) Fresh WO catalyst. (B) Catalyst after the first round of reaction shown in Figure 4. (C)
/ꢀšꢀoÇ•š ꢀ(šꢂŒ šZꢂ •ꢂÀꢂvšZ Œ}µvꢃ }( Œꢂꢀꢄš]}v •Z}Áv ]v C]PµŒꢂ ðX ~5 > C• ÇZꢂ ꢂvꢂŒPÇ ꢃ]•‰ꢂŒ•]Àꢂ ó-ray analysis (EDXA) for the catalyst after the
seventh round of reaction shown in Figure 4.
catalyst and the Na
2 3
SnO additive can be recycled without
that there might be certain interactions between the WO
3
hydrate remarkable loss in activity. It is proposed that the interaction
and the Na
dehydration between the Na
could graft Na SnO onto the surface of WO
binding between WO and Na SnO
Na SnO together with WO . The WO
.1>2.7) is a bifunctional material; WO
activate H
attached to the WO
2 3
2
SnO hydrate. For instance, the intermolecular between the WO3 hydrate and the Na SnO3 hydrate enabled the
2
SnO
3
hydrate and the WO
3
hydrate good recyclability of the catalyst and the additive.
2
3
3
(Scheme S1). Such
3
2
3
enabled the recyclability of Acknowledgements
2
3
3
3
-Na
2
SnO
is the active phase to
SnO species
stabilizer. This
3
composite (W/Sn @
This work was supported by the Institute of Bioengineering and
Nanotechnology (Biomedical Research Council, Agency for Science,
Technology and Research (A*STAR), Singapore).
2
3
2
O
2
for oleic acid cleavage, while the Na
surface serves as a H
2
3
3
2
O
2
observation may open the door for the design of new W-Sn based
compounds as bifunctional catalysts for OA cleavage.
Notes and references
As we have demonstrated that adding Na
2 3
SnO could improve [1] a) A. E. Kerenkan, F. Beland and T. O. Do, Catal. Sci. Technol.
the yield for AA and NA from oleic acid cleavage, we further scaled 2016, 6, 971-987. b) M. Wang, J. Ma, H. Liu, N. Luo, Z. Zhao and F.
Wang, ACS Catal. 2018, 8U îíîõ>îíòñX
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Gebbink, Catal. Sci. Technol. 2014, 4, 2182-2209; b) A. Kockritz and
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P. C. A. Bruijnincx, B. M. Weckhuysen and R. Gebbink, Rsc Adv. 2013,
up the reaction (8 mmol of OA) to verify the efficiency of this
protocol (Supporting Information). After product isolation and
purification, AA was achieved at 89% yield as a white solid (Figure
S2), and NA was achieved at 65% yield as a clear liquid (Figure S3);
the results should be among the best for oleic acid cleavage in
[
3
Polyaniline Nanocomposite as Catalyst for Heterogeneous
, 6606-6613; d) B. G. Khadijeh, A. Nilofar and M. A. Yarmo in V
2 5
O -
[
6a, 6c-e, 8]
heterogeneous systems.
The isolated yields, especially that
A
for AA, are higher than those from GC analysis, because the extent
of esterification for a dicarboxylic acid is lower than that for a
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Haji, A. Aziz, M. Y. M. Sulaiman, B. Ahmad, K. N. Ismail, A. R.
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monocarboxylic acid by the rapid sample derivatization method.
Conclusions
2
008, 110, 812-824; g) K. Kawasaki, F. Jin, A. Kishita, K. Tohji and H.
In conclusion, we have demonstrated
a very simple
Enomoto in Partial hydrothermal oxidation of high molecular weight
unsaturated carboxylic acids for upgrading of biodiesel fuel, Vol. 898
Eds.: K. Tohji, N. Tsuchiya and B. Jeyadevan), 2007, pp. 159.
heterogeneous catalytic system for direct oleic acid cleavage to
produce shorter carbon chain carboxylic acids by
Commercially available WO was used as the catalyst and Na
was used as an additive to stabilize H . The Na SnO
H
2
O
2
.
3
2
SnO
3
[
3] a) A. Kockritz, M. Blumenstein and A. Martin, Eur. J. Lipid Sci.
2
O
2
2
3
additive did Technol. 2010, 112, 58-63; b) P. Spannring, I. Prat, M. Costas, M.
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Mieloszynski, J. M. Lecuire and N. Oget, Tetrahedron Lett. 2005, 46,
201-3203.
other catalytic systems for the cleavage of OA and its derivatives. In
a scale-up reaction, azelaic acid and nonanoic acid were produced
3
at isolated yields of 89% and 65% from this system. The WO
3
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