Applied Catalysis A: General 182 (1999) 9196

Oxidation of para-xylene over zeolite-encapsulated

copper and manganese complexes
Chandra R. Jacob, Saji P. Varkey, Paul Ratnasamy*
National Chemical Laboratory, Pune 411 008, India
Received 19 August 1998; received in revised form 20 November 1998; accepted 25 November 1998

Abstract
Salen, saltin and salcyhexen complexes of copper and manganese, encapsulated in the cavities of zeolite NaX have
been investigated as catalysts for the aerobic oxidation of para-xylene in the absence of added halogen promoters and using
tertiary-butyl hydroperoxide as the initiator at low temperatures. Signicant conversion levels (upto 5060%) are attained.
The major products include toluic acid, toluyl aldehyde and toluyl alcohol. The zeolite-encapsulated complexes did not
undergo any colour change during the reaction and could be easily separated and reused many times. In contrast, the
neat complexes, while they were active in the rst cycle, were completely destroyed during the run and changed colour.
They, however, gave lower conversions compared to the encapsulated catalysts. Conversion increases when electronwithdrawing substituents (like Cl, Br and NO2) are substituted in the aromatic ring. # 1999 Elsevier Science B.V. All rights
reserved.
Keywords: Copper salens; Manganese salens; Oxidation catalysts; Zeolite encapsulation; Xylene oxidation; Terephthalic acid; Toluic
acid

1. Introduction
The oxidation of p-xylene to terephthalic acid is of
major industrial interest. Since terephthalic acid
(TPA) is used chiey for polyethylene terephthalate,
it also experienced the same dramatic growth as the
polyester bre and lm material during the last three
decades. Terephthalic acid and dimethyl terephthalate
are the starting materials for the manufacture of
polyesters used mainly in bres (currently more than
90% worldwide). A smaller amount is used in polyester resins for the manufacture of lms, paints and
*Corresponding author. Tel.: +91-212-334761; fax: +91-212330233; e-mail: prs@ems.ncl.res.in

adhesives. Terephthalic acid is extremely insoluble

even in hot water (1008C) and the usual organic
solvents, and does not melt, so that it could not be
prepared on a large scale with purity sufcient for
polycondensation. The crude terephthalic acid was
therefore converted into its dimethyl ester, which
was then brought to bre grade by crystallisation
and distillation. In 1963, Teijin and Toray were successful in using a classical process with improved
technology to manufacture pure terephthalic acid that
was polycondensable with ethylene glycol. Since then
other processes have been developed for producing
bre grade terephthalic acid, which in comparison to
dimethyl terephthalate (DMT), have become more
important especially in Western Europe and Japan.

0926-860X/99/$ see front matter # 1999 Elsevier Science B.V. All rights reserved.
PII: S0926-860X(98)00427-X

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C.R. Jacob et al. / Applied Catalysis A: General 182 (1999) 9196

The most important commercial route for

TPA manufacture is the liquid phase oxidation of
p-xylene. However, if no special precautions are
taken, the oxidation of p-xylene stops at p-toluic
acid. Several methods are available to convert the
second methyl group (in p-toluic acid) into a carboxyl
group.
 The carboxyl group of p-toluic acid is esterified
with methanol in a separate step, or if methanol is
used as solvent for the oxidation, the esterification
occurs simultaneously, and the second methyl
group is then oxidised.
 In addition to the metal salt catalyst (Mn or Co), a
cocatalyst or promoter such as a bromine compound (such as NaBr) is used.
 In a co-oxidation process, an auxiliary substance
which is capable of supplying hydroperoxides is
simultaneously oxidised. Acetaldehyde, paraldehyde and methylethyl ketone are all used as cooxidisable substances. The first method yields,
dimethyl terephthalate while the other two are
used to manufacture the pure terephthalic acid
(PTA). There are four improvements desirable
in the presently used process of p-xylene oxidation
to PTA: (1) replacement of the homogeneous by
solid heterogeneous catalysts, (2) replacement of
the corrosive bromine compounds by non-corrosive compounds, (3) elimination or replacement of
the acetic acid solvent used in the current processes, and (4) lowering of the temperature of
oxidation from the currently used values of
423473 K. All these improvements can reduce
significantly, the cost of production of PTA.
The ultimate aim of our work is to achieve all the
above mentioned objectives. The present paper
describes our results in the rst stage of the process,
namely, the conversion of p-xylene to p-toluic acid.
The aerobic oxidation of p-xylene was conducted
using copper and manganese salens, saltins and salcyhexens encapsulated in zeolite-X as catalysts and
tertiary-butyl hydroperoxide (TBHP) instead of Br
as a promoter in the absence of any solvent. The
main product is the p-toluic acid, the intermediate
in the production of terephthalic acid. The feasibility
of using a solid, non-Br-containing catalyst in
the absence of any solvent including acetic acid, at
least for the rst stage of p-xylene oxidation, is
established.

2. Experimental
2.1. Materials
p-Xylene and tertiary-butyl hydroperoxide were
obtained from Aldrich. The salens were prepared by
the methods described earlier [1].
2.1.1. Synthesis of chloro manganese(III) saltin
complexes (saltinsalicylaldehyde1,3propylenediamine)(Mn(III)saltin)
Preparation of salicylaldehyde1,3-propylenediamine (saltin). Salicylaldehyde (4.88 g, 0.02 mol)
was mixed with 150 ml of distilled ethanol in a
500 ml round bottom ask, which was stirred using
a magnetic stirrer. 1,3-Propylenediamine (0.749 g,
0.01 mol) dissolved in 25 ml of distilled ethanol
was added drop by drop using a dropping funnel to
the above solution. The contents were reuxed for 1 h
to get a yellow solid precipitate of saltin, which was
cooled, ltered, washed with petroleum ether and
dried. The saltin was then recrystallised from ethanol
(yield 4.23 g). The substituted saltins were prepared
using substituted salicylaldehyde instead of salicylaldehyde.
Preparation of ClMn(III) saltin. Manganese acetate
tetrahydrate (2.4 g, 0.01 mol) dissolved in ethanol
(20 ml) was reacted with an ethanol (20 ml) solution
of saltin (2.82 g, 0.01 mol) by reuxing for 1 h.
Lithium chloride (0.635 g, 0.015 mol) was then added
to the reuxing solution and the reaction continued for
another 0.5 h. Cooling the mixture to 273 K afforded
ClMn(III) saltin as dark brown crystals. The crystals
were ltered, washed thoroughly with cold water and
dried in vacuo (yield 2.17 g). The substituted Mn
saltins were prepared using substituted salicylaldehyde instead of salicylaldehyde.
2.1.2. Synthesis of chloro manganese(III)
salicyhexen complexes (salicyhexen
salicylaldehyde1,2-cyclohexanediamine)
(Mn(III) salicyhexen)
Preparation of salicyhexen. Salicylaldehyde
(4.88 g, 0.02 mol) was mixed with 150 ml of distilled
ethanol in a 250 ml round bottom ask, which was
stirred using a magnetic stirrer. 1,2-Cyclohexanediamine (1.75 g, 0.01 mol) dissolved in 25 ml of distilled
ethanol was added drop by drop using a dropping

C.R. Jacob et al. / Applied Catalysis A: General 182 (1999) 9196

funnel to the above solution. The contents were

reuxed for 1 h to get a yellow solid precipitate of
salicyhexen, which was cooled, ltered, washed with
petroleum ether and dried. The salicyhexen was then
recrystallised from ethanol (yield 5.9 g). The substituted salicyhexen were prepared using substituted
salicylaldehyde instead of salicylaldehyde.
Preparation of ClMn(III) salcyhexen. Manganese
acetate tetrahydrate (2.4 g, 0.01 mol) dissolved in
ethanol (20 ml) was reacted with an ethanol (20 ml)
solution of salicyhexen (3.75 g, 0.01 mol) by reuxing
for 1 h. Lithium chloride (0.635 g, 0.015 mol) was
then added to the reuxing solution and the reaction
continued for another 0.5 h. Cooling the mixture to
273 K afforded ClMn(III) salicyhexen as dark brown
crystals. The crystals were ltered, washed thoroughly
with cold water and dried in vacuo (yield3 g). The
substituted Mn salicyhexens were prepared using
substituted salicylaldehyde instead of salicylaldehyde.
The salen, saltin and salcyhexen complexes were
encapsulated in zeolite NaX by the `zeolite synthesis'
method described earlier [1]. The silicate gel was
prepared from 1.0 g of fumed silica, 3.2 g of NaOH,
0.3 g of the salen/saltin/salcyhexen complex of copper
or manganese and 8.0 ml of H2O and stirred for
30 min. To the above solution, sodium aluminate
(prepared from 9 g of Al(I-OPr)3, 3.2 g of NaOH
and 36 ml of H2O) was added. The resulting gel
was then transferred to a polypropylene bottle and
aged at room temperature with stirring for 24 h and
then heated at 363 K for 24 h. The mixture was then
allowed to cool to room temperature and diluted with
copious amounts of deionised water. The solid crystals
were isolated by centrifugation at 8000 rpm for 2 h.
This solid was dried at 363 K for 24 h in air and
extracted (Soxhlet) with acetonitrile for 72 h. It was
nally dried at 363 K under vacuum (103 Torr) for
15 h.
2.2. Procedures
The oxidation reactions were carried out in an
autoclave of 300 ml volume. In a typical experiment,
30 g of p-xylene, 0.5 g of solid catalyst and 0.5 g of
tertiary-butyl hydroperoxide were taken in an autoclave and pressurised with air to 33 bar. The reaction
mixture was stirred continuously at 403 K for 18 h.
After the completion of the reaction, the autoclave was

93

cooled and the catalyst was removed by hot ltration.

The resultant ltrate was cooled to crystallise p-toluic
acid which was removed by ltration. The nal ltrate
contains p-toluyl aldehyde, p-tolyl alcohol, 4-carboxybenzyl alcohol, 4-carboxybenzaldehyde and unreacted p-xylene. There was only a trace of other
acids (like terephthalic acid) in the solid products.
The acids formed were esteried and analysed as
methyl esters by the procedure given below: 300 ml
of the sample was taken in a glass vial. Two ml of 14%
boron triuoride (BF3) in methanol was added to the
glass vial which was stoppered with a teon lined
stopper and heated for 1 h at 353 K. The sample was
cooled to room temperature and 2 ml of Milli-Q
reagent water was added with mild shaking. Two
ml of HPLC grade dichloromethane (S.D. Fine Chemicals) was added before the GC analysis. The identity of the products was further conrmed by GCMS
(Schimadzu QCMC-QP 2000A). The liquid products
of the oxidation reaction were analysed in a gas
chromatography (Shimadzu GC 14B) equipped with
an SE-32 column and a ame ionisation detector.
3. Results and discussion
The oxidation of p-xylene is negligible in the
absence of Cu/Mn catalysts conrming that under
the conditions of the experiments, the oxidation is
indeed catalytic in nature. In the case of the encapsulated catalysts, Cu and Mn was not detected in the
reaction products by atomic absorption spectroscopy
indicating that oxidation of p-xylene by dissolved
copper and manganese complexes leached out from
the zeolite matrix is negligible. The zeolites alone
without the copper and manganese complexes were
also catalytically inactive. Since the concentration of
uncomplexed Cu and Mn ions in the catalysts is also
negligible [1], their contribution to catalytic activity
may be neglected. Further evidence to conrm that the
oxidation of p-xylene is indeed catalysed to a signicant extent by the solid zeolite catalyst containing
the encapsulated metal complex and not by the free
complex dissolved in solution was obtained as follows: In one set of two identical experiments, the solid
catalyst (MnSalen-X) was removed by centrifugation
after a reaction time of 6 h. While the conversion of
p-xylene proceeded further in the presence of the solid

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C.R. Jacob et al. / Applied Catalysis A: General 182 (1999) 9196

Table 1
Aerial oxidation of p-xylene by Cu/Mn (salens/substituted salens)-X
Catalyst

p-Xylene
converion (wt%)

Products (wt%)
A

MnSalen-X
MnBr2Salen-X
MnCl2Salen-X
Mn(NO2)2Salen-X
MnBr4Salen-X
MnCl4Salen-X
CuSalen-X
CuBr2Salen-X
CuCl2Salen-X
Cu(NO2)2Salen-X
CuBr4Salen-X
CuCl4Salen-X

52
53.5
57.9
59.9
61.0
61.8
44.2
46.5
47.1
49.6
45.2
42.6

18.6
23.5
24.2
25.3
27.2
27.9
20.8
18.9
18.4
19.6
17.0
15.2

17.7
15.7
17.0
20.4
18.0
17.4
13.0
16.7
16.2
15.0
15.7
14.2

12.0
12.3
11.3
11.9
13.5
12.6
6.0
6.3
7.1
9.8
9.3
8.4

3.7
2.0
4.4
2.3
2.3
3.8
4.4
4.6
5.4
5.2
3.2
4.8

Ap-toluic acid, Btoluyl aldehyde, Cp-toluyl alcohol, Dothers, mainly 4-carboxybenzyl alcohol, 4-carboxybenzaldehhyde and traces of
terephthalic acid. Reaction conditions: 30 g p-xylene, 0.5 g catalyst, 0.5 g TBHP, air33 bar, 403 K, 18 h.

The following points may be noted:

1. The major products of oxidation of p-xylene are
p-toluic acid, toluyl aldehyde and toluyl alcohol;
further oxidation to terephthalic acid does not
occur to any signicant extent.
2. The zeolite-encapsulated complexes did not
undergo any colour change during the reaction
and could be easily separated and reused many
times. In contrast, the neat complexes, while they
were active in the first cycle, were completely
destroyed during the first run and changed colour.
3. The neat complexes gave low conversions compared to the encapsulated catalysts. This may be a
consequence of (2) above, since, due to the continuous degradation of the catalyst, the effective

catalyst, there was no further conversion of p-xylene

when the catalyst was removed from the reaction
system. In the absence of the catalyst, molecular
oxygen as well as TBHP, are unable to oxidise
p-xylene to any signicant extent. While the oxidation
proceeded in the presence of either air or TBHP alone,
conversion levels were low (less than 10%). A synergistic enhancement of the rate was observed when
both were present. The results of the oxidation of
p-xylene using O2 (in air) as the oxidant and tertiarybutyl hydroperoxides as the initiator at 403 K over the
various encapsulated copper and manganese salens are
presented in Table 1. The corresponding results for the
saltin and salcyhexen complexes are presented in
Tables 2 and 3, respectively.
Table 2
Aerial oxidation of p-xylene by ClMn(III) (saltin/substituted saltin) -X
Catalyst

MnSaltin-X
MnBr2Saltin-X
MnCl2Saltin-X
Mn(NO2)2Satin-X
MnBr4Saltin-X
MnCl4Saltin-X

p-Xylene
conversion (wt%)

Products (wt%)
A

46.2
46.4
45.9
48.9
47.1
49.9

15.6
14.4
15.1
17.0
13.9
16.7

18.4
20.0
18.8
19.2
21.5
18.1

10.6
9.7
10.0
10.5
8.5
11.8

0.6
2.3
2.0
2.2
3.2
3.3

Ap-toluic acid, Btoluyl aldehyde, Cp-toluyl alcohol, Dothers, mainly 4-carboxybenzyl alcohol, 4-carboxybenzaldehhyde and traces of
terephthalic acid. Reaction conditions: 30 g p-xylene, 0.5 g catalyst, 0.5 g TBHP, 403 K, 18 h.

C.R. Jacob et al. / Applied Catalysis A: General 182 (1999) 9196

95

Table 3
Oxidation of p-xylene by ClMn(III) (Salcyhexen/substituted salcyhexen)-X
Catalyst

p-Xylene
conversion (wt%)

Products (wt%)
A

MnSalcyhexen
MnBr2Salcyhexen
MnCl2Salcyhexen
Mn(NO2)2Salcyhexen
MnBr4Salcyhexen
MnCl4Salcyhexen

43.5
46.0
47.2
45.1
48.6
46.4

14.4
15.1
14.2
14.9
17.8
14.0

17.4
18.9
21.2
18.3
18.4
20.2

10.2
9.8
8.7
9.9
10.4
9.2

1.5
2.2
3.1
2.0
2.0
3.0

Ap-toluic acid, Btoluyl aldehyde, Cp-toluyl alcohol, Dothers, mainly 4-carboxybenzyl alcohol, 4-carboxybenzaldehyde and traces of
terephthalic acid. Reaction conditions: 30 g p-xylene, 0.5 g catalyst, 0.5 g TBHP, 403 K, 18 h.

concentration of the catalyst will be lower than that

taken initially.
4. The salen/saltin/salcyhexen ligands alone in the
absence of Cu/Mn metal were not catalytically
active.
5. Conversion increases when electron-withdrawing
substituents (like Cl, Br, and NO2) are substituted
in the ring (Tables 13).
6. The activity of p-xylene oxidation decreases in the
series salen>saltin>salcyhexen.
7. Substitution of electron-withdrawing groups like
the halogen or NO2 group in the aromatic ring
enhances the activity.
While terephthalic acid is the main product formed
in the homogeneous oxidation by cobalt and manganese acetate salts, the reaction stops at toluic acid in
the case of encapsulated salen/saltin/salcyhexen complexes. There may be several causes for this: (1) The
toluic acid may precipitate out and block the pores of
the zeolite preventing the ingress of further quantities
of p-xylene. (2) The toluic acid may coordinate with
the manganese or copper ion and thereby poison the
active site. Conversion of the toluic acid to the ester
and further oxidation of the remaining methyl group
may be a feasible route to terephthalic acid.
The interaction of TBHP with the metal complex
generates species which can play a role analogous to
Br ions in the reaction cycle. A radical-chain autoxidation mechanism is likely to be operative where the
role of the catalyst is to generate radicals by catalysing
the decomposition of tertiary-butyl hydroperoxide. In
fact, Lyons and Ellis [2,3] had earlier reported that
iron pentauorophenyl porphyrins, which are efcient

catalysts for tertiary-butyl hydroperoxide decomposition to tertiary-butanol at ambient temperatures are

also efcient in oxidising isobutane to tertiary-butyl
alcohol without the requirement of a coreductant. Our
results on the catalyst activity of encapsulated MN2O2
(MCu, Mn) complexes (like the salens) in oxidising
various substrates using O2 as the oxidant and TBHP
as the initiator is similar to the behaviour of polyhalogenated iron or manganese porphyrins in hydroxylation of alkanes and aromatics [2,3].
4. Summary and conclusions
The aerobic oxidation of p-xylene using the salen,
saltin and salcyhexen complexes of copper and manganese encapsulated in zeolite NaX has been investigated. When the oxidation is carried out using
tertiary-butyl hydroperoxide as the initiator, signicant conversion levels (in the range of 5060 wt%)
were achieved. The major products were toluic acid,
toluyl alcohol and toluyl aldehyde. Only traces of
terephthalic acid were observed in the product. The
zeolite-encapsulated complexes did not undergo any
colour change during the reaction and could be easily
separated and reused many times. In contrast, the neat
complexes, while they were active in the rst cycle,
were completely destroyed during the run and changed colour. The neat complexes however, gave low
conversions compared to the encapsulated catalysts.
Conversion increases when electron-withdrawing substituents (like Cl, Br and NO2) are substituted in the
aromatic ring.

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C.R. Jacob et al. / Applied Catalysis A: General 182 (1999) 9196

Acknowledgements
Saji P. Varkey thanks DST for a Young Scientist
Award fellowship. We thank members of the Physical
Chemistry and Catalysis Division for help and support.

References
[1] C.R. Jacob, S.P. Varkey, P. Ratnasamy, Appl. Catal. A 168
(1998) 353364.
[2] P.E. Ellis Jr., J.E. Lyons, Coord. Chem. Rev. 105 (1990) 181.
[3] J.E. Lyons, P.E. Ellis Jr., H.K. Myer Jr., R.W. Wagner, J.
Catal. 141 (1993) 311.