Catalytic hydroxylation of phenol over Cu-ZSM-5

Aída Luz Villa, César Augusto Caro, and Consuelo Montes de C.

Department of Chemical Engineering, Universidad de Antioquia, Medellín,
Colombia, AA 1226

Introduction
Catechol and hydroquinone are two high value phenolic derivatives widely used as
photography chemicals, antioxidants, polymerization inhibitors and also in pesticides,
flavoring agents, and medicine [1]. As other oxidation reactions, phenol
hydroxylation has been usually carried out using stoichiometric oxidants. Because of
the problems associated with updated methodologies, one of the major goals of
chemistry research is the replacement of wasteful and toxic stoichiometric oxidants
by ecologically friendly technologies. Therefore, phenol direct hydroxylation with
H2O2 is of great interest to chemists nowadays. Hydroxylation of phenol with H2O2
using microporous titanosilicate, TS-1 and its commercial utilization by Enichem
workers is a major advance in this area [2]. In the search for other transition metals, it
has been reported [3] that copper sites are active in phenol hydroxylation due to their
ability to activate H2O2 and to form free radicals. The redox properties of copper are
significantly modified by the type of matrix, its concentration and the presence of co-
cations associated with the system. Copper containing porous materials appear to be
promising catalysts for phenol hydroxylation with H2O2 [4]. However, little is known
about the effect of the Si/Al ratio on catalyst activity and product distribution. In this
work, we report the synthesis and catalytic behavior of Cu-ZSM-5 for the partial
oxidation of phenol with hydrogen peroxide. Special emphasis is given to the
influence of Cu content and Si/Al ratio on its activity.

Results and Discussion

Several catalysts were synthesised following a procedure reported in the literature [5].
The molar ratios were: H2O/Si = 45, TPABr/Si = 0.26, CH3NH2/Si = 2.14, Si/Al = 17
- ∝, Si/Cu = 47 - ∝. The synthesized materials were highly crystalline and exhibited
the characteristic MFI structure as determined by XRD.

Phenol hydroxylation was carried out in a 25 ml glass reactor equipped with a

thermocouple, reflux condenser, and a magnetic stirrer. Catalyst, aqueous phenol
solution (1 mmol/ml), water (as solvent) and aqueous H2O2 (35%) were sucessively
added into the reactor. The reaction conditions were: catalyst: phenol = 20 : 1
(mg/mmol), phenol : H2O2 = 3 : 1 and 1 : 1 (molar ratio), H2O (4 g), T = 80ºC.
Products were analyzed on a Varian 3800 GC equipped with a SPB-50 (0.25 mm ID,
30 m, 0.25 µm) capillary column, interfaced to a SATURN 2000 mass detector (EI
mode). Table 1 lists typical results of the effect of copper and Si/Al ratio of
synthesized Cu-ZSM-5 materials on phenol hydroxylation.
Table 1. Effect of Cu and Si/Al ratio on phenol hydroxylation over Cu-ZSM-5.

Catalyst %Cu Si/Al Substrate:oxidant ratio = 3:1 Substrate:oxidant ratio= 1:1

Conv. Product selectivity Conv Product selectivity
% %
Cat HQ Cat/HQ Cat HQ Cat/HQ
CCu-10 0.05 87 12.1 57.9 42.1 1.4 30.8 65.6 34.4 1.9
CCu-11 0.05 126 10.5 57.0 43.0 1.3 41.7 64.4 35.6 1.8
CCu-18 0.14 ∝ 9.4 62.4 36.9 1.7 25.4a 68.1 31.9 2.1
CCu-17 0.31 ∝ 11.9 57.3 42.7 1.3 36.1 67.7 32.3 2.1
a
CCu-13 0.35 119 10.7 60.0 40.0 1.5 29.0 63.9 36.1 1.8
CCu-15 0.59 97 8.6 63.0 37.0 1.7 32.0 64.9 35.1 1.9
CCu-5 0.67 32 8.6 54.9 45.1 1.2 21.2 67.2 32.8 2.1
CCu-19 0.74 ∝ 13.3 61.3 38.7 1.6 32.5 65.3 34.7 1.9
CCu-6 0.90 31 8.7 61.0 39.0 1.6 26.8 66.2 34.1 1.9
CCu14 1.15 78 11.7 57.3 42.7 1.3 35.6 62.7 37.2 1.7
CCu-7 1.83 17 8.2 53.1 46.9 1.1 25.8 62.5 37.5 1.7
Catalyst: 20 mg; water: 4 ml, temperature: 80°C; time: 4 h. Cv: conversion, Cat: catechol, HQ:
hydroquinone. Product selectivity was calculated as: Cat (or HQ)/(Cat + HQ). abenzoquinone traces.

The main products obtained where catechol and hydroquinone though traces of
benzoquinone were observed on CCu-18 and CCu-13. As shown in table 1 the ratio
of Cat/HQ increases with decreasing substrate:oxidant ratios (S:O). The highest
Cat/HQ ratio is around 2 with a S:O of 1:1. These results are in agreement with those
found in the case of titanosilicates in phenol hydroxylation with H2O2 [2]. The
relative concentration of catechol was found to be higher at larger concentration of
H2O2. In this case, diffusion limitations become more severe at higher H2O2
concentrations, leading to more surface reaction and catechol formation. Phenol
conversion tends to decrease with copper contents. This decrease may be attributed to
pore blockage at higher Cu loadings. The activity of Cu-ZSM-5 materials increases
with the Si/Al ratio. Therefore, the relative hydrophobicity/hydrophilicity plays an
important role. The effect of other parameters such as reaction time and temperature,
catalyst amount, as well as, the regeneration of the catalyst will also be discussed in
this contribution.

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