Epoxidation of Biodiesel with Hydrogen Peroxide over Ti-Containing

Silicate Catalysts
Nicole Wilde, Christian Worch, Wladimir Suprun, Roger Glser*
Institute of Chemical Technology, Universitt Leipzig, Linnstr. 3, 04103 Leipzig, Germany

Electronic Supplementary Information (ESI)

1 Synthesis and characterization of selected products for gas chromatographic analysis

For analytical purposes, selected products were synthesized, characterized by GC-MS (GC
Varian 3800, Varian Saturn 2000, 70 eV IE), 1H-NMR (400 MHz, BRUKER AVANCE
DRX-400) and

13

C-NMR spectroscopy (100 MHz, BRUKER AVANCE DRX-400). These

substances were used for product analysis by co-injection via GC. Epoxide directly derived
from catalytic reaction. Here, diol and ketone were obtained by converting the prepared
epoxide.

Methyl 9,10-epoxy stearate

Methyl 9,10-epoxy stearate was isolated from catalytic product mixtures. After removing of
the solid catalyst by centrifugation, the volatile part of the reaction mixture was removed by
evaporation under vacuum. The resulting pale yellow oil was purified by column
chromatography (silica gel, n-hexane/ethylacetate 9:1).1H-NMR: / ppm = 0.82 (t, 3H, CH3
(C18)), 1.22 1.59 (m, 26 H, CH2 (C 3-8, 11-17)), 2.42 (t, 2 H, CH2 (C2)), 2.83 (t, 2 H, CHO
(C9,10) epoxide), 3.60 (s, 3 H, CH3 (C19) methyl ester)-

13

C-NMR: / ppm = 14.09 (C18,

methyl end), 22.68-34.05 (CH2 (C2-8, 11-17)), 51.39 (C19, methyl ester), 57.13/ 57.18 (C
9,10, epoxide), 174.17 ( C1, carbonyl group)- MS (m/z): 55 (100), 74 (55), 109 (59), 127 (36),
155 (58), 171 (21), 199 (10), 245 (11), 263 (8).

-2Methyl 9-,10-dihydroxy stearate

Methyl 9-,10-dihydroxy stearate was prepared by acid catalyzed ring opening of the purified
methyl 9,10-epoxy stearate [20]. To a solution of methyl 9,10-epoxy stearate (0.85 g, 1 eq.,
2.72 mmol) and tetrahydrofuran (Sigma-Aldrich, > 99%), deionized water was added. Under
vigorous stirring at 298 K, 0.1 ml perchloric acid (Fluka, 70 wt% aqueous solution) was
added dropwise. After 6 h, 80 ml of deionized water and 80 ml of diethyl ether were added.
The phases were separated and the organic phase was washed three times with 40 ml of
saturated sodium bicarbonate solution and dried over sodium sulfate. The solvent was
removed under reduced pressure. Further purification by column chromatography (silica gel,
n-hexane/ethylacetate 10:1) yielded the product as slightly yellowish oil. 1H-NMR: / ppm =
0.88 (t, 3H, CH3 (C18)), 1.27 1.66 (m, 26 H, CH2 (C 3-8, 11-17)), 2.28 (t, 2 H, CH2 (C2),
3.39/ 3.40 (m, 2 H, COH (C9/C10) diol), 3.66 (s, 3 H, CH 3 (C19) methyl ester)- 13C-NMR: /
ppm = 14.15 (C18, methyl end), 22.72-34.12 (CH2 (C2-8, C11-17)), 51.39 (C19, methyl
ester), 74.49/74.54 ((C9/C10) diol ), 174.43 ( C1, carbonyl group) - MS (m/z): 55 (48), 83
(33), 109 (65), 138 (25), 155 (100), 187 (40), 244 (48), 273 (8), 281 (5).

Methyl 9-/10-keto stearate

Methyl 9,10-epoxy stearate (0.85 g, 1 eq., 2.72 mmol) was dissolved in anhydrous benzene
(Sigma-Aldrich, > 99,9 %) under nitrogen atmosphere and cooled in an ice bath. Boron
trifluoride (3.7 eq., 10.1 mmol, Sigma-Aldrich, 50 wt.-% in diethylether) was added dropwise.
The resulting yellow solution was vigorously stirred for 1 h at 298 K. Thereafter, 20 ml of
deionized water and 20 ml diethyl ether (Sigma-Aldrich,> 99.9%) were added. The phases
were separated and the organic phase was washed three times with 30 ml of saturated sodium
bicarbonate solution and dried over sodium sulfate. The solvent was removed under reduced
pressure. Further purification by column chromatography (silica gel, n-hexane/ethylacetate
10:1) yielded the product as a slightly yellowish oil. 1H-NMR: / ppm = 0.88 (t, 3H, CH3

-3(C18)), 1.26 1.62 (m, 24 H, CH2 (C 3-7, 11-17/ C 3-8, 12-17 )), 2.31/ 2.37 (m, t, 6 H, CH2
(C2, C8, C10/ C9, C11)), 3.66 (s, 3 H, CH3 (C19) methyl ester)-

13

C-NMR: / ppm = 14.2

(C18, methyl end), 22.8-42.9 (CH2 (C2-8, 10-17/ C 2-9, C11-17)), 51.58 (C19, methyl ester),
174.17 ( C1, carbonyl group), 211.8 (C9 / C10) - MS (m/z): 43 (78), 55 (100), 71 (33), 83
(88), 111 (38), 125 (73), 153 (45), 170 (25), 199 (13), 263 (12).
Remark: Due to the fact that only the product mixture of Methyl 9-/10-keto stearate could be
obtained, some signals are overlapped and the assignment of the signals was only rough. The
signals for C1, C19 and C18 have the same chemical shift, because they are more than 7
bonds far from C9 and C10 and thus chemically equivalent. The atoms C9 and C10 have the
same chemical environment and occur at one signal in the spectrum.

2 Gas chromatographic product analysis

Table 1: Retention times of detected components in gas chromatographic analysis
component
acetonitrile
chlorbenzene (internal standart)
nonylaldehyde (C-C-cleavage-product 1)
methyl 9-oxononanoate (C-C-cleavage-product 2)
methyloleate
methyl 9,10-epoxy stearate (epoxide)
methyl keto stearate (1 & 2)*
methyl 9,10-dihydroxy stearate (diol)
* methyl 9- keto stearate / methyl 10-keto stearate

tR / min
2.7
2.9
3.7
6.6
18.2
21.5
21.9
24.0

-4-

Intensity / a.u.

3 Catalyst characterization

MoOx-SiO2

TiOx-SiO2

10

20

30

40

50

60

70

80

2/
Figure 1: Powder X-ray diffractograms of MoOx-SiO2 and TiOx-SiO2.

Intensity / a.u.

MoOx-Al2O3

WOx-Al2O3

10

20

30

40

50

60

2/
Figure 2: Powder X-ray diffractograms of MoOx-Al2O3 and WOx-Al2O3.

70

K-M-units

-5-

TiOx-SiO2
Ti-MCM-41

200

300

400

500

600

700

800

Wavelength / nm

Intensity / a.u.

Figure 3: DR-UV-Vis spectra of TiOx-SiO2 and Ti-MCM-41.

TS-1_s_60

TS-1_s_20

10

20

30

40

50

60

70

80

2/
Figure 4: Powder X-ray diffractograms of TS-1 with stacked morphology (TS-1_s_60 and
TS-1_s_20 from microwave irradiation during synthesis at different times).

-6-

2 m
Figure 5: SEM image of TS-1_s_60 with stacked morphology.

4 Determination of the activation energy

-3.6

-3.8

ln [r 0 / (mol l

-1

-1

h )]

-3.7

-3.9
-4.0
-4.1
-4.2
-4.3
-4.4
0.0028

0.0030

0.0032
-1

-1

T /K

Figure 6:

Arrhenius plot for determination of the activation energy of the epoxidation of

methyl oleate over TS-1 (ind.) in acetonitrile.

-7For determination of the activation energy, the initial reaction rates for the temperatures of
313 - 333 K were considered. The point for 323 K was not taken into account as considerably
larger amounts of side-products were formed. The activation energy was determined to be
21.8 kJ mol-1.

5 Calculation of the Thiele Modulus and the effective diffusivity

(1)

(2)

(3)

The effective factor was calculated by dividing the observed initial reaction rate for a given
maximum catalyst particle size L (see Figure 4, right part, of main manuscript) by the initial
rate without diffusion limitation r0,kin. The latter was assumed to be the one for catalyst
particles with a size less than 50 m. Then, for each maximum catalyst particle size L, the
effective diffusivity D eff was obtained by inserting the Thiele Modulus , provided by
equation (2), into equation (3). The (volumetric) rate constant k is given by assuming a first
order reaction in methyl oleate and, thus, by division of the initial rate without diffusion
limitation r0,kin by the initial concentration of methyl oleate, i.e., 0.03 mol l-1. The overall
effective diffusion coefficient is give as the arithmetic average of the diffusion coefficients for
each maximum particle size and amounts to Deff = 5.710-11 m2 s-1.