Journal of Molecular Catalysis, 71 (1992) 373-381 373
M2799
Hydroxylation of phenol over TS-2, a titanium silicate
molecular sieve
J. Sudhakar Reddy, S. Sivasanker and P. Ratnasamy
Catalysis Division, National Chemical Laboratory, Pune 8 (India)
(Received July 7, 1991; accepted October 4, 1991)
Abstract
The influence of different process parameters on the hydroxylation of phenol with H202
over the titanium silicate molecular sieve TS-2 has been investigated. Apart from the
primary products v/s., p- and o-dihydroxybenzenes, the corresponding quinones are also
formed. Higher Ti contents in the catalyst (TS-2) and higher catalyst concentrations
lower the formation of the secondary oxidation products. Solvents have an influence on
the relative amounts of the two dihydroxybenzenes in the product. H202 efficiency of
up to 74% is obtainable at ~ 2896 phenol conversion to dihydroxybenzenes.
Introduction
The titanium silicate molecular sieve, TS-1, [1, 2] with an MFI structure
has been reported to catalyze a number of reactions, such as hydroxylation
of aromatics [3, 4], selective oxidation of alkanes [5], ammoximation of
cyclohexanone [6[ and rearrangement of cyclohexanone oxime [7]. A more
recent discovery is the titanium silicate molecular sieve, TS-2 [8, 9], which
has an MEL structure. This material has also been reported to catalyze the
ammoximation of cyclohexanone [ 10] and the selective oxidation of n-hexane
[11].
The first commercial process utilizing titanium silicate (TS-1) as a catalyst
was the hydroxylation of phenol to hydroquinone and catechol, introduced
by Enichem, Italy [2, 12]. Some aspects of the TS-l-catalyzed hydroxylation
reaction have been revealed recently [2, 12 ]. We have investigated the reaction
using TS-2 as the catalyst, and present the results in this paper.
Experimental
The titanittm silicate molecular sieve with MEL structure (TS-2) was
synthesized by mixing tetrabutylammonium hydroxide, tetraethylorthosilicate
and titanium butoxide and autoclaving the mixture at 443 K for 48 h. The
details of the synthesis and characterization of this new titanium silicate
have already been reported elsewhere [8, 9]. The as-synthesized TS-2 was
filtered, washed, dried and calcined in dry air for 16 h at 823 K.
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