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Indian Journal of Chemistry

Vol. 39A April2000, pp. 439-441
Catalytic liquid phase oxidation of p-xylene
using transition metal substituted
polyoxometalates
Nirupa A Alekar, Sarada Gopinathan & C Gopinathan •
Inorganic and Catalysi s Di vision, National Chemical Laboratory,
Pune 411 008, India
Received 30 March 1999; revised 26 October 1999
Liquid phase oxidation of p- xylene has been carried out in the
presence of potassium sal ts of monosubstituted heteropoly
compounds with tungsten as the addenda atom and having the
general formulae [XW
11
ML0
39
]K·•.x H
2
0 where X = P and Si ,
M"+ = Co
2
+, Cu
2
+ and Mn
2
+ and L = H
2
0. The reactions are
carried out in a halide free environment using ai r as the oxidant
and water as the solvent at a temperature of 180°C. High values of
p-xylene conversion to the order of 70% are obtained using
K
6
[SiW
11
Co(H
2
0 )0
39
].14 H
2
0 as catalyst The silicotungstate
derivatives have been found to be more efficient catalysts than the
phosphotungstate analogues for the oxidation of p-xylene. The
product obtained is mainly p-toluic and terephthalic acids with
minor quantities of p-tolualdehyde and p-methyl benzylalcohol.
Influence of reaction parameters such as temperature, solvents and
catalyst concentration on the oxidati on reacti on and its effect on
product distributi on have been exami ned.
Industrially p-xylene is oxidized in acetic acid
medium in the presence of a Co-Mn-Br catalyst to
produce terephthalic acid. Various catalytic
procedures for thi s oxidati on of p-xylene to
terephthalic acid have been described in patent
literature as th is is an industrially important reacti on.
US patent No. 4892,970, assigned to Amoco
Corporation, describes a process for the oxidation of
p-xylene selectively to terephthalic acid in the
presence of a mixture of cobalt acetate, manganese
acetate and HBr as catalysts and acetic acid as
solvent. Zaidi has reported the use of low
concentrations of cobalt acetate and sodium bromide
as catalysts in the liquid phase oxidation of p-xylene
by air at a temperature of 60-105° to afford onl y p-
toluic acid
1
• A major di sadvantage of the above
described process is the necessity to combat the
corrosive nature of cobalt/ manganese/ bromide/
acetic acid mi xtures and consequent increase in cost
of capital equipment. Another di sadvantage is the loss
of about I 0 parts by weight of acetic acid per I 00
parts of aromatic carboxylic acid produced, by
conversion to carbon dioxide. Other reports · on
oxidation of p-xylene include the use of transition
I I f F
3+ C 2+ N·2+ C 3+ . b. ..
meta sa ts o e , u , 1 or r m com matton
with cobalt salts as catalysts. Cobalt catalyzed p-
xylene oxidation in aqueous medium at temperature
in the range I 00-150° in the presence of phase
transfer catalysts has also been reported
2
. This
process yielded mainly p-toluic acid as the oxidation
product. In this paper we report the liquid phase
oxidation of p-xylene using transttton metal
substituted Keggin type heteropoly anion in a halide
free system in aqueous medium to give a mixture of
p-toluic and terephthalic acids.
Experimental
p-Xylene, I ,2-dichloroethane and 70% aqueous
tert- butyl hydroperoxide were procured from Aldrich
and were used as such for the reactions. The catalysts
K
5
[PW11Co(H20 )0 39]. 16 H20 ,
Ks[PW11Mn(H20)039]. 15 H20,
K
5
[PW11Cu(H20)039]. 23 H20 ,
  14 HzO,
K
6
[SiW11Mn(H
2
0)0
3
9]. 21 H20 and


14 HzO,
were freshl y prepared by methods described below.
Preparation of K6[Si W
11
Co(H20 )0J9].14 H
2
0
Hydrated 12-silicotungstic acid (11 .5g) was
dissolved in water (25 rnl) containing glacial acetic
aci d (3 rnl ). The pH was adjusted to 6 with potassium
bicarbonate. The solution was boi led and cobalt
acetate tetrahydrate (0.8 g in one ml water) was added
with stirring, followed by the addition of potassium
acetate ( 15 g in 8 ml water and 0.5 rn1 glaci al acetic
acid). The hot solution was filtered and kept in a
refri gerator overnight. Deep red crystals separated
were ai r-dri ed. The yield of the potassium salt was
about I 0 g. Similarly K
6
[SiW
11
Mn(H
2
0 )0
39
]. 21 H
2
0
and K
6
[SiW"Cu(H20)0
3
9].14 H20 were prepared in
good yields.
The phosphotungstate salts were also obtained by
the above procedure except that the pH of the
solution was adjusted to 5 using potassium
bicarbonate before the addition of the corresponding
transition· metal salts.
440 INDIAN J CHEM, SEC. A, APRIL 2000
IR spectra of the catalysts as nujol mulls were
recorded on a Shimadzu FfiR 8201 instrument.
The thermal analysis was done on a Seiko
instrument model TG/DTG 32. The gaseous reaction
products were analyzed on a Shimadzu GC-14B with
thermal conductivity detector having Porapak N
column. The liquid product was analyzed on Hewlett
Packard GC, model 5890 using SE-52 megabore
capillary column for separation.
Th:! oxidation reaction
The reaction was carried out in a stainless steel 300
rnl capacity Parr autoclave. The reactants, p-xylene
(15 g, 140 mmol), water (15 g) tert-butyl
hydroperoxide as the initiator (0.3 g) and the catalyst
(0.096 mmol) were taken in the autoclave. The
reactor was pressurised with air upto 400 psi and kept
at 180° with stirring (600 rpm). After an induction
period of 2 h, a sudden drop in pressure was observed
suggesting the commencement of the oxidation
reaction; heating and stirring were maintained till
there was no further pressure drop. The autoclave was
then cooled to 0°C and gaseous products were
released through a gas holder, collected and analysed.
The reactor was further repressurised with air upto
400 psi and the reaction was continued at 180°C. This
operation was repeated once more. The solid product
(6.5 g) was separated by filtration. A sample of the
solid product was analysed by esterification by the
following procedure: the solid product (0.1g) was
dissolved in methanol (5 rnl) and BF
3
.MeOH (14%
solution, 2 rnl) was added and the mixture was then
refluxed for 6 h. After cooling the sample, water was
added and the esters formed were extracted with
dich1oromethane and analysed by GC.
The filtrate portion of the oxidation product
consisted of two layers: one was the aqueous layer
while the second was organic. Both the layers were
separated and analysed.
Results and discussion
IR spectra of the transition metal substituted
phosphotunrstate complexes show the absorption
bands characteristic of Keggin structure,. viz. peaks at
10'74 cm·
1
, 943 cm·
1
, 920 cm·
1
and 810 crn·
1
respectixe4' ilue to v .fP-D=(W)], v ( W-0
1
) and the
two v ( W -Ob-W)
3
• Further the presence of a shoulder
near 1074 cm·
1
could be attributed to the stretching.
frequency of P-0-(M) bond, thus indicating the
presence of transition metal ion in the
heteropolyanion. The IR spectra of tlhe analogues
silicotungstate salts exhibited peaks at 1000 em·\
960 cm·
1
, 900 cm·
1
and 796 cm·
1
which were
attributed respectively to v(W-Ot), v(Si--0-W) and to
the types of bridging (W-0-W). The transition metal
absorption could not be resolved as these absorptions
overlap with the (W-0-W) peaks.
The UV -visible spectrum of these catalysts were
taken in water medium. The spectrum of the cobalt
substituted c:atalyslt exhibited two
absorption bands, one at 248 nm due to W f--0
charge transfers and another at 532 nm because of the
typical d-d transitions. The cobalt substituted
silicotungstate also showed two corresponding bands
at 250 and 546 nm respectively. The manganese
substituted phosphotungstate showed absorption
peaks at 248 and 540 nm while the silicotungstate salt
exhibited peaks at 250 and 530 nm.
The transition metal substituted heteropolyanions
Table l-Air oxidation of p-xylene catalysed by transition metal substituted heteropolyanions
Conversion Product selectivity%
Catalyst mol% A B c D
K
5
[PW
11
Co(Hz0)039]. 16 HzO 52.28 61.65 21.45 15.45 0.99
K
5
[PW
11
Mn(Hz0)03
9
]. 15 HzO 54.36 68.42 21.74 9.83
Ks[PWt
1
Cu(Hz0)039l · 23 HzO 50.01 51.39 24.72 18.82 5.05
K
6
[SiW
11
Co(H
2
0)0
39
]. 14 H
2
0 70.45 60.64 24.53 13.27 1.54
K
6
[SiW
1
tMn(Hz0)039l · 21 HzO 51.13 65.04 22.21 11 .27 1.46
K
6
[SiW
11
Cu(H
2
0)0
39
]. 14 H
2
0 65.72 52.53 23.00 23.62 0.85
Reaction temp.l80"C, p-xylene 15 g, water 15 g.
A: p- toluic acid; B: p- tolualdehyde; C: p•methyl benzyl     D: terephthalic acid
NOTES 441
of the type K5[PW1IM(H20)039] and
  (M = Co
2
+, Mn
2
+ and Cu
2
+)
have been found to be good catalysts for the aerial
oxidation of p-xylene in water medium. Oxidation
reactions were carried out under identical conditions
using these catalystS\ and the results are tabulated in
Table 1. The results reveal that the silicotungstate
analogues give 10-20% more catalytic efficiency for
p-xylene conversion compared to phosphotungstate
analogues. Among the catalysts studied the cobalt
substituted silicotungstate, K
6
[SiW
11
Co(H
2
0)0
3
o]. l4
H
2
0 gives maximum activity as seen from the higher
p-xylene conversion. Under the set experimental
conditions, the major oxidation product was p-toluic
acid. Other products included p-tolualdehyde, p-
methyl benzyl alcohol and terephthalic acid.
Effect of reaction parameters on p-xylene oxidation
Oxidation of p-xylene was carried out using the
catalyst

 

H20 between the
temperature range 140-200°C. Maximum molar
conversion upto 85% was observed at 200°C with 64
% selecti vity for p-toluic acid.
The effect of catalyst concentration on the
oxidation of p-xylene has been studied. Different
concentration of the catalyst were scanned for
optimum activitl. Maximum conversion was
observed when the molar ratio of the substrate to the
catalyst was 1470. Molar conversion upto 70.45 %
with good product selectivity was observed at this
concentration level.
Solvents such as 1 ,2-dichloroethane and water
were used for the oxidation purpose at 180°C. A
solventless reaction was also carried out. The reaction
in aqueous medium gave the maximum conversion.
References
I Zaidi S A H, Appl Catal, 27( 1986) 99.
2 Harustiak M, Hronec M & llavsky 1, 1 mol Cat, 48( 1988)
335.
3 Claude R 0, Cchiccioli D & Rene T, 1 chem Res (S) (1977)
46.
4 Sheldon R A & Kochi J K, Metal Catalyzed oxidation of
organic compounds ( Academic Press, New York) 1981, p 45.