Documente Academic
Documente Profesional
Documente Cultură
DOI 10.1007/s10562-009-0227-1
Received: 24 October 2009 / Accepted: 12 November 2009 / Published online: 25 November 2009
Springer Science+Business Media, LLC 2009
Abstract The aerobic oxidation of p-toluic acid to terephthalic acid over tetra(p-chlorophenylporphinato)manganese (T(p-Cl)PPMnCl)/cobalt acetate was reported for the
first time. The co-catalysis of T(p-Cl)PPMnCl/Co(OAc)2
was also studied. The studies indicated that the PTA oxidation was influenced by the catalyst composition, catalyst
concentrations and reaction conditions. A preliminary
mechanism of this co-catalyzed oxidation reaction was
proposed based on experimental observations.
Keywords Metalloporphyrin Cobalt acetate
co-Catalysis p-Toluic acid Oxidation Terephthalic acid
1 Introduction
The preparation of terephthalic acid (TPA) via the aerobic
oxidation of p-xylene (PX) is a very important industrial
process from both economical and environmental aspects
[1, 2]. In practice, the oxidation of PX with air to TPA is
now carried out in HOAc (80%) using Co(OAc)2/
Mn(OAc)2/HBr as catalysts on an industrial scale worldwide. The low concentration of the reactants and the use of
the bromide make the low efficiency and high environmental impact and corrosion of reactors becoming the
major shortcomings [3, 4]. The development of new PX
oxidation processes fitting the requirements of green
chemistry still remains a challenge.
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2 Experimental
Y. Xiao et al.
+ O2
123
COOH
CH3
COOH
PTA
COOH
T(p-Cl)PPMnCl / Co(OAc)2
acetic acid
T, P
COOH
TPA
CHO
4-CBA
157
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158
Y. Xiao et al.
Catalyst composition
Conversion (%)
Selectivity (%)
TPA
CBA
Co(OAc)2
39.0
92.0
8.0
Co(OAc)2
43.7
94.1
5.9
Co(OAc)2
45.1
94.3
T(p-Cl)PPMnCl
1.1
Co(OAc)2/T(p-Cl)PPMnCl
42.0
92.7
7.3
Co(OAc)2/T(p-Cl)PPMnCl
51.9
94.5
5.5
Co(OAc)2/T(p-Cl)PPMnCl
57.1
95.5
4.5
Co(OAc)2/Mn(OAc)2
45.6
94.5
5.5
Temperature (8C)
1.37 9 10
2.74 9 10
5.48 9 102
1.10 9 103
Conversion (%)
Selectivity (%)
TPA
CBA
14.6
81.8
18.2
160
47.8
94.8
5.2
51.9
94.5
5.5
45.4
93.8
6.2
Conversion (%)
Selectivity (%)
TPA
CBA
3.2
45.3
94.1
5.9
9.7
46.8
94.3
5.7
13.0
48.9
94.3
5.7
16.2
51.9
94.5
5.5
22.7
47.1
93.9
6.1
[20]. Similar phenomena were also observed in our previous works [6, 15].
3.4 Effect of Reaction Temperature
The influence of reaction temperature on the oxidation
reaction was investigated and the results were shown in
Table 4. When the temperature was below 210 C, the
PTA conversion and TPA selectivity enhanced with the
increasing of the temperature, and there was a sharp
123
5.7
100
Conversion (%)
Selectivity (%)
TPA
CBA
11.5
82.6
17.4
180
44.1
94.9
5.1
190
51.9
94.5
5.5
210
220
56.4
52.9
97.6
97.1
2.4
2.9
159
Conversion (%)
Selectivity (%)
TPA
CBA
35
33.4
92.7
7.3
50
51.9
94.5
5.5
65
62.9
96.8
3.4
80
50.8
95.5
4.5
90
26.3
92.0
8.0
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160
Y. Xiao et al.
4 Conclusions
The PTA was oxidized to TPA with air by the catalysis of
T(p-Cl)PPMnCl/Co(OAc)2, The aerobic oxidation of PTA
was influenced by the catalyst composition and the concentrations of the catalyst as well as reaction conditions.
Both the PTA conversion and TPA yield increased significantly when the a small amount of T(p-Cl)PPMnCl was
added to the PTA-O2-Co(OAc)2 system. By the use of
548 ppm Co(OAc)2 and 16 ppm T(p-Cl)PPMnCl as the
catalysts, PTA oxidation under the optimum conditions of
190 C, 1.2 MPa and 160 L h-1 airflow produced TPA at
96.8% selectivity and 62.9% conversion of PTA in 5 h. For
the co-catalysis between metalloporphyrin and cobalt
acetate, the function of T(p-Cl)PPMnCl might be to
Table 6 Comparison of the catalytic power between Co(OAc)3 and Co(OAc)2 in combination with metalloporphyrin
Catalyst
Co2? (mol)
Co3? (mol)
Conversion (%)
Selectivity (%)
TPA
CBA
Co(OAc)2/T(p-Cl)PPMnCl
4.01 9 10-4
51.9
94.5
5.5
Co(OAc)2/Co(OAc)3/T(p-Cl)PPMnCl
2.98 9 10-4
1.03 9 10-4
56.8
96.5
3.5
Reaction conditions: PTA, 100 g; T(p-Cl)PPMnCl, 16.2 ppm; air pressure, 1.2 MPa; 190 C; air flow, 160 L h-1; reaction time, 5 h
Scheme 2 Preliminary
mechanism of co-catalysis
between T(p-Cl)PPMnCl and
Co(OAc)2 in the aerobic
oxidation of PTA to TPA
HOOC-Ph-CH3
T(p-Cl)PPMnCl, O2
a
Co2+
HOOC-Ph-CH2OOH
-OH-
HOOC-PhCH2O
HOOC-PhCH3
c
Co3+
HOOC-PhCH2
- 1/2 O2
O2
HOOC-Ph-COOH
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[O]
HOOC-Ph-CHO
Co2+
H
HOOCH-PhCH2OO
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