performed with the utilization of a mathematical method of
experimental design. The optimal parameters of the following
functions have been determined: the selectivity of transfor-
mation to 2-methylepichlorohydrin in relation to methallyl
chloride consumed, the selectivity of transformation to
organic compounds in relation to hydrogen peroxide con-
sumed, the conversions of methallyl chloride and hydrogen
peroxide.
a PTFE insert. The autoclave was charged with reagents in
the following order: MAC, hydrogen peroxide, methanol
(solvent), and the catalyst. After closing the lid, the autoclave
was fixed in a shaker holder and was placed in a temperature-
controlled silicone oil bath ((0.1 °C) for the desired period.
The mass balance was performed after completing the
reaction. The following functions describing the process were
calculated: the selectivity of transformation to 2-methylepi-
chlorohydrin in relation to MAC consumed, the selectivity
of transformation to organic compounds in relation to H2O2
consumed, and the conversion of MAC and H2O2.
The quantitative analyses of 2-methylepichlorohydrin
were performed chromatographically by the external standard
method. A Chrom 5 apparatus equipped with a flame-
ionization detector (FID) and a column packed with Chro-
mosorb 101 (60/80 mesh) were used. The column temper-
ature was programmed in the following way: isothermally
at 170 °C for 6 min, followed by an increase of temperature
at the rate of 15 °C/min, isothermally at 200 °C for 10 min,
and then an increase at the rate of 20 °C/min, isothermally
at 225 °C for 14 min, and finally cooling to 170 °C.
Hydrogen peroxide consumption was determined iodometri-
cally.21
2. Experimental Section
2.1. Preparation of TS-1 Catalyst and its Character-
istics. The TS-1 catalyst was prepared by a method of
Thangaraj et al.18 Tetraethyl orthosilicate (Fluka) and tetra-
butyl orthotitanate (Fluka) were used as raw materials,
whereas tetrapropylammonium hydroxide [TPAOH (Fluka)]
was used as the template agent. The gel crystallization was
carried out under the static conditions at 175 °C for 8 days.
After the separation of crystals from the parent liquid, they
were dried at 120 °C for 12 h followed by calcination in a
furnace at 550 °C for 24 h. The calcinated catalyst was
activated by washing with a 10% aqueous solution of
ammonium acetate at 80 °C and recalcinated at 550 °C for
24 h.
The catalyst characterization was performed by using
conventional techniques. The chemical composition of the
catalyst was established by means of X-ray fluorescence
spectroscopy (XRF) on a VRA 30 spectrometer. The catalyst
contained 1.7 wt % Ti. The crystalline structure of the sample
was confirmed by X-ray diffraction spectroscopy (XRD)
using a Siemens D5000 diffractometer with Cu KR radiation
of wavelength 0.154 nm. The XRD pattern was obtained
between 5° and 50° 2θ. The spectrum was identical with
XRD patterns reported by Perego et al. and Thangaraj et
al.19,20 The FT-IR spectrum of the TS-1 catalyst was recorded
on a JASCO FT/IR-430 instrument using the KBr pellet
technique. The catalyst concentration in KBr amounted to
1.4 wt %. The absorption band at ∼960 cm-1 was found for
this spectrum. The UV-vis spectrum was recorded on a
SPECORD M40 instrument. The UV-vis spectrum reveals
the characteristic band at wavelength of 220 nm, which
confirms the incorporation of titanium into the crystalline
structure of silica. There was no additional band associated
with the presence of extraframework Ti. The morphology
of the crystals was determined on the basis of the SEM
micrographs taken on a JEOL JSM-6100 scanning micro-
scope. The uniform orthorhombic crystallites with a size in
the range 0.6-0.8 µm were prepared.
3. Results and Discussion
The side reactions that accompanied the main reaction
occurred in the epoxidation of methallyl chloride with a 30
wt % solution of hydrogen peroxide over the TS-1 titanium
silicalite catalyst and are presented in Scheme 1.
2-Methylepichlorohydrin (MEP) is susceptible to the
attack of the nucleophilic molecules, such as water and
methanol. As a result of the reaction with water 1-chloro-
2-methylpropane-2,3-diol is formed, which undergoes a
further hydrolysis with the formation of 2-methylglycerol.
2-Methylepichlorohydrin reacting with methanol forms 3-chlo-
ro-2-methoxy-2-methylpropane-1-ol and 1-chloro-3-meth-
oxy-2-methylpropane-2-ol. Moreover, the hydrolysis of MAC
to methallyl alcohol may proceeds in an aqueous medium.
The MAC forms additional byproducts: 2-methylglycerol,
2-methylacrolein, and dimethallyl ether.
The determination of the influence of technological
parameters on the course of the epoxidation process makes
it possible to limit the amount of byproducts. The selected
parameters were studied in the following ranges: temperature
20-120 °C, molar ratio of MAC/H2O2 1.0-5.0 mol/mol,
methanol concentration 5-90 wt %, the TS-1 catalyst
concentration 0.1-2.0 wt %, and reaction time 30-300 min.
The optimisation of the technological parameters of MAC
epoxidation was performed according to the mathematical
method of experimental design using a rotatable-uniform
design.22-25 Experimental design and the calculations were
2.2. Epoxidation Procedure, Apparatus and Analytical
Methods. The epoxidation of methallyl chloride was carried
out using the following reagents: methallyl chloride (MAC)
(98 wt %, Fluka), hydrogen peroxide (30 wt % aqueous
solution, POCh, Gliwice), methanol (analytical grade, POCh,
Gliwice), and TS-1 catalyst. The epoxidation was performed
in a 7-cm3 capacity stainless steel autoclave equipped with
(21) Brill, W. F. J. Am. Chem. Soc. 1963, 85, 141.
(22) Montgomery, D. C. Design and analysis of experiments; John Wiley &
Sons: New York, 1976.
(23) Nalimow, W. W.; Czernowa, N. A. Statystyczne metody planowania
doœwiadczen˜; WNT, Warszawa, 1967.
(24) Achnazarowa, S. £.; Kafarow, W. W. Optymalizacja eksperymentu w chemii
i technologii chemicznej; WNT, Warszawa, 1982.
(18) Thangaraj, A.; Kumar, R.; Ratnasamy, P. Appl. Catal. 1990, 57, L1-L3.
(19) Perego, G.; Bellussi, G.; Corno, C.; Taramasso, M.; Buonomo, F.; Esposito,
A. Stud. Surf. Sci. Catal. 1986, 28, 129.
(20) Thangaraj, A.; Kumar, R.; Mirajkar, S. P.; Ratnasamy, P. J. Catal. 1991,
130, 1.
(25) Polan˜ski, Z.; Go´recka-Polan˜ska, R. Cadex: Esdet 2.2, Podreˆcznik uz˘yt-
kownika; Zakład Posteˆpu Technicznego i Wdroz˘en˜, Krako´w, 1992.
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Vol. 10, No. 3, 2006 / Organic Process Research & Development