Studies in Surface Science and Catalysis, volume 159 293

Hyun-Ku Rhee, In-Sik Nam and Jong Moon Park (Editors)

© 2006 Elsevier B.V. All rights reserved

Terephthalic Acid Hydropurification over Pd/C Catalyst

J.-H. Zhou*, G-Z. Sheii, J. Zhu, W.-K. Yuan
UNILAB, State Key Laboratory of Chemical Engineering, ECUST, Meilong Rd. 130,
Shanghai, 200237, P. R. China *jhzhou@ecust.edu.cn
1. INTRODUCTION

Terephthalic acid (p-TA or TA), a raw material for polyethylene terephthalate (PET)
production, is one of the most important chemicals in petrochemical industry. Crude
terephthalic acid (CTA), commonly produced by homogeneous liquid phase p-xylene
oxidation, contains impurities such as 4-carboxybenzaldehyde (4-CBA, 2000-5000 ppm) and
several colored polyaromatics that should be removed to obtain purified terephthalic acid
(PTA). PTA is manufactured by hydropurification of CTA over carbon supported palladium
catalyst (Pd/C) in current industry [1].
Although the process is of significance, it has not well studied. Since the initial
development of the CTA hydropurification process in 1960s', only a few papers have been
published, mainly regarding catalyst deactivation [2]. Recently, Samsung Corporation, in
collaboration with Russian scientists, developed a novel carbon material-CCM supported
palladium-ruthenium catalyst and its application to this process [3]. However, pathways and
kinetics of CTA hydrogenation, which are crucial to industrialization, are not reported
hitherto.
In this paper, the pathways, side reactions, as well as kinetics of CTA hydrogenation
process over Pd/C will be presented.
2. EXPERIMENTAL

1 flow meter; 2 N2 cylinder; 3 H2 cylinder; 4 autoclave; 5 mixer; 6 pressure sensor; 7 temperature sensor; 8
check valve; 9 back pressure valve; 10 buffer tank; 11 special sampling device
Fig.l. Schematic of the experimental setup
Experiments were carried out in a batch autoclave (Type 4571, Parr Corp., USA) with
varying hydrogen partial pressures and temperatures. An industrial 0.5%Pd7C (CBA-300)
294

catalyst, manufactured by Engelhard Corporation, was used for CTA purification. Considering
barriers encountered in smooth sampling, only was the 4-CBA added into the autoclave as
reactant. Actually, our preliminary experiments indicate that the behavior of reaction was
almost not affected by TA, even though the latter had a small effect on the reaction rate. Fig. 1
shows the schematic diagram of the experiment. Samples were analyzed by HPLC [4].
3. RESULTS AND DISCUSSION

3.1. Mechanism of the hydropurification of CTA over Pd/C

It has been commonly understood that during the hydropurification process, CTA is first
dissolved in water at about 280 °C; then the CTA stream, mixed with dissolved hydrogen,
flows through the Pd/C bed, wherein 4-CBA is hydrogenated to p-toluic acid (PT) and is
washed out in the subsequent process. The reaction scheme can be illustrated in Fig.2.

H2O

Fig.2. Reaction occurs during the purification. Fig.3. Mechanism of the hydropurification of CTA
over Pd/C.
However, our experiments, combined with our thermodynamic analysis, have revealed
that the previously mentioned view is not the case, but more complex than expected. Rather,
the purification processes undergo two reactions in parallel: hydrogenation and
decarbonylation. CTA hydrogenation is actually a complex reaction system as illustrated in
Fig.3. Hydrogenation is a tandem process, in which 4-CBA is hydrogenated first to
4-hydroxymethylbenzoic acid (4-HMBA) and subsequently to PT. Simultaneously, 4-CBA is
decarbonylated to benzoic acid (BA) over the Pd/C. Fortunately, it is much easier for the
intermediate hydrogenation product (4-HMBA with a solubility > 1 g/100 g H2O) and
decarbonylation product (BA with a solubility of 0.29 g/ 100 g H2O) to be dissolved in water.
Thus it is also much easier to wash them out than PT whose solubility is 0.035g/100gH2O at
room temperature. Therefore, paradoxically, this concomitant side reaction does not harm the
purification itself. Furthermore, analysis of samples from an industrial reactor of Yangtze
petrochemical Corporation, SINOPEC, further confirmed the above path and pathways for the
CTA purification system.
3.2. Kinetic feature
As has been elucidated, 4-CBA undergoes complex reactions in the course of
purification, during which the hydrogenation inevitably competes with the decarbonylation.
At the same time, although the BA is easy to be washed out, the concomitant CO during
decarbonylation is a poison to Pd/C catalyst.
Experiments were carefully designed to study the effect of the oxygen concentration in
the system on the competition between hydrogenation and decarbonylation, as being shown in
 295

Fig.4. First, the reaction system was filled with about 2 MPa nitrogen at room temperature
then heated to 220 °C (Curve A in Fig.4). Understandably, there must be some dissolved
oxygen in solution under such a condition. Secondly, the system was flushed with nitrogen
three times under the room temperature, filled with about 2 MPa nitrogen and 0.2 MPa
hydrogen and afterwards heated to 220 °C (Curve B in Fig.4). Most of the dissolved oxygen
in the solution was displaced by nitrogen during the flush. Thus, the oxygen concentration
under such a treatment was much lower than that under condition A. Thirdly, the system was
flushed with hydrogen three times at room temperature, filled with 2MPa hydrogen and then
heated to 220 °C (Curve C in Fig.4). There was almost no oxygen in the reaction system
under condition C. It is indicated from Fig.4 that the decarbonylation reaction was
significantly influenced by the oxygen concentration in the solution. The dissolved trace
amount of oxygen facilitated decarbonylation whereas the hydrogen in the system inhibited it,
which may attributes to the consumption of CO by the dissolved oxygen. The more oxygen
was in the reaction system, the more rapid the decarbonylation occurred.

10 4-CBA
—4-CBA
, - , 11000
000
'
concentration of BA (ppm)

9 -•-4-HMBA
4-HMBA
PH
800
— A 8 - ^ 4-MBA
4-MB A
concentration (mol/L)
B 7 -*- total
& 800-
600 C 6
» 600. 5

8 400-
400 4
3
§ 200-
200 2
B 1
0 0
0 5 10 15
15 20 25 30 0 10 20 30 40 50
time (min) time (min)

Fig.4. Decarbonylation of 4-CBA under Fig.5. Evolution of the reactant and product
different oxygen concentrations (220 °C, 2 g with time (60-100 mesh catalyst, 120°C,
20-60 mesh catalyst) 0.7MPa hydrogen, lOOOrpm)
The hydrogen process feature was also analyzed. Fig.5 presents a typical plot of the
change of reactant and product distribution with time during the hydrogenation. It is obvious
that the hydrogenation of 4-CBA was very rapid, even though the reaction temperature was
only 120 °C which was much lower than the industrial one (about 280°C), the 4-CBA
conversion reached 99% in 7 minutes. The intermediate 4-HMBA's concentration first
increased to a maximum, and followed with a gradual lowering. This fact is likely to verify
the proposed mechanism of the CTA hydrogenation process. Hydrogenation of 4-CBA to
4-HMBA was much more rapid than the subsequent hydrogenation of 4-HMBA to PT. Our
thermodynamic analysis indicated that reaction free energy for 4-CBA to 4-HMBA and that
from 4-HMBA to PT were about -11.5 and -93.26 kJ/mol, respectively. This means that the
equilibrium constant of the former reaction is much lower than that of the latter one, which
was unexpected.
3.3. Apparent kinetics of 4-CBA hydrogenation
The 4-CBA's concentration that is left in the system is of most interest in
industrialization. For this reason, the dependence of the rate of 4-CBA disappearance on
reaction conditions was carefully investigated. Reaction conditions included hydrogen
atmosphere, temperature and catalyst particle size. It is believed that the hydrogen atmosphere
296

has little effect on hydrogenation reaction within the industrially acknowledged boundary.
However, the hydrogenation rate is sensitive to agitation speed, temperature and catalyst
particle size, implying obvious diffusion resistance existing in the hydropurification process.
As a result, apparent kinetic equations for the 4-CBA's hydrogenation under different
conditions can be obtained from the experimental data. The activation energy and reaction
order were estimated based on the power-law kinetics under various conditions, as have been
given in Table 1. When the catalyst particle size was decreased from 4-8 mesh to 140-180
mesh, the apparent reaction order did not change much (from 1.23 to 1.17). On the other hand,
the apparent reaction activation was increased from 28.0 to 45.0 kJ/mol, which is significant.
The greater the particle size is, the smaller the activation is, which attribute to the fact that
the diffusion activation is normally smaller than the reaction activation.
Table 1 Reaction order and activation energy of 4-CBA hydrogenation
Catalyst particle (mesh) Temperature range (°C ) Ea (kJ/mol) Reaction order n
140-180 110-150 45.0 1.17
60-100 120-150 31.1 1.15
20-60 170-215 29.5 1.20
4-8 250-280 28.0 1.23

4. CONCLUSION

1) Experimental studies, combined with thermodynamic analysis, indicate that the CTA
hydropurification process is a complex reaction system including both parallel and tandem
reactions wherein 4-CBA hydrogenation is exothermic and its paralleled decarbonylation is
endothermic.
2) The 4-CBA decarbonylation does not weaken much the function for purification. However,
it undoubtedly competes with its hydrogenation. The competition is greatly influenced by the
amount of the dissolved oxygen in the system. The more is the dissolved oxygen, the easier
the decarbonylation takes place. However, the hydrogen has an opposite effect.
3) Unlike what has long been accepted, hydrogenation of 4-CBA is composed of a series of
reactions rather than a single one. 4-CBA is hydrogenated first to 4-HMBA in a very rapid
manner and then to 4-PT in a much slower manner. However, the equilibrium constant of the
first reaction was much smaller than that of the second one, which is not expected.
4) Although hydrogenation of 4-CBA over Pd/C is very fast, there is strong diffusion
resistance. Furthermore, apparent kinetic equations on different catalyst particle sizes have
been obtained from experimental data.
Acknowledgement: This work is financially supported by NSFC(No. 20490200), Shanghai
Science & Technology Committee (No.036505010) and SINOPEC.
References:
[1] I. P. Wheaton, S. A. Cerefice, US Patent No. 4 476 242 (1984).
[2] L. Shen, W. Mao, Shiyou Huagong, 20(1991), 234.
[3] S. H. Jhung, A. V. Romanenko, K. H. Lee, et al, Applied Catalysis A: General, 225(2002), 131.
[4] L. G. Chen, J. H. Zhou, Journal of East China University of Sci. and Tech., 30 (2004), 719.