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New Oxidation

Process for duction


of Terephthalic Acid
from p-Xylene
YATARO ICHIKAWA
GENTARQ YAMASHITA
MICH IY U KI TO KASH I KI
TEIZO YAMAJI

As polyester fiber production increases,


raw materials TPA and DMT increase in importance

erephthalic acid (TPA) and dimethyl terephthalate Table 111, the methods which belong to the third group
T ( D M T ) are the raw materials for polyester which were thought to be practical for production of high-
are increasing in importance in accordance with the purity terephthalic acid because their reaction could be
increasing production of polyester fiber throughout the carried out under mild conditions (Table IV).
world (Table I). Recent Japanese production of and The cobalt catalyst, on further investigation, had a
drmand for polyester in 1968 and 1971 are shown in profound effect on the reaction temperature, partial
Table 11. pressure of oxygen, and the organic solvents used. This
I n 1962, before we began investigating the present fact suggested these co-oxidation agents are not absolutely
process, the methods listed in Table I11 were being essential for the progress of this oxidation reaction.
used to produce terephthalic acid from p-xylene by Many experiments were carried out which finally
oxidation with niolecular oxygen. At the same time, culminated in a process capable of producing tereph-
studies were begun on the direct mterification method thalic acid from p-xylene on a commercial scale by
using a high-purity terephthalic acid to produce poly- using considerably larger amounts of cobalt catalyst
ester, replacing the usual dimethyl terephthalate ester- than usually thought necessary. The process is outlined
exchange method. I n 1963 the methods were commer- below.
cialized by both Teijin Ltd. and Toyo Rayon Co., Ltd.
Interest in the research on production of terephthalic
acid, therefore, was naturally focused on the production oxidation Reaction
of high-purity terephthalic acid by the air oxidation of The catalyst, especially its amount, has an important
p-xylene. role in the oxidation of this process. The relatioiiship
I n contrast with the two well-established methods in between the one-pass yield of terephthalic acid and the

38 INDUSTRIAL A N D ENGINEERING CHEMISTRY


amount of catalyst used is shown in Figure 1. Im-
provement in the yield was observed by using a larger
amount of catalyst than usual. Maximum yield was TABLE I . POLYESTER FIBER PRODUCTION (1968)
obtained with the amount of the catalyst between 0.4
Rate of
and 0.5 mol Co/mol p-xylene, but no improvement in Production, increase over
the yield was found when a higher amount of the catalyst lo3 metric previous year,
Country tons %
was added. T o find the effect of the cobalt catalyst in
U.S.A. 490 53
this reaction, the reaction mechanism of p-xylene to
West Europe 310 44
terephthalic acid was investigated.
Japan 188 18
It was assumed from the analyses of the samples in the
intermediate steps that the reaction in this process
proceeds by steps shown in Figure 2, involving chain
reactions. T h e p-xylene oxidation mechanism, esti-
mated by analyzing the experimental results with a TABLE II. POLYESTER PRODUCTION I N JAPAN
relatively high content of cobalt catalyst, is thought to be Rate of
as shown in Figure 3. Production increase over
103 metric previous
I n this process the initiation step involves abstraction Year tons year, %
of hydrogen by cobaltic ion, and the propagation step 1968 188 18
consists of oxidation of the substrates by cobaltic ion and 1969 218 16
reduction of radicals and hydroperoxides by cobaltous 1970 251 15
ion. This means that cobalt ions play important roles 1971 286 14
as chain carriers in this reaction. Of course it is esti-
mated that the hydrogen abstraction by peroxy radicals
(Figure 4) occurs as observed in the usual air oxidation,
but it is thought the resulting production is much less
than that achieved by cobaltic ions as shown in Schemes TABLE 111. p-XYLENE OXIDATION METHODS
1 and 4 in Figure 3. Oxidation methods Company
Comparison of the experimental results and the values Bromine-promoted Amoco Chemicals, Mitsui Petro-
calculated using the mechanism suggested by Figure 3 oxidation chemical, Maruzen Oil, I.C.I.
shows good agreement (Figure 5), which gives good Oxidation via func- Hercules, Chemische Werke Witten
tional derivatives
support for use of this reaction mechanism. Oxidation with Mobil Oil, Tennessee Eastman
Examinations were also made on the structure of the co-oxidation
catalyst. From the results of chemical analyses (total agent
amount of Co, Co3+, RCO-, HtO, and C and H ele-
mental analyses), X-ray diffraction, and infrared and
ultraviolet absorption spectra (p-dihydroxy structure),
the structure of the catalyst was estimated to be a bi-
TABLE IV. CHARACTERISTICS O F OXIDATION
nuclear complex of cobaltic and cobaltous ions as shown . W I T H CO-OXIDATION AGENT
in Figure 6. Reaction temperature. . . . . . . . . . . . . . . . .Below 15OOC
Peshanski isolated the compound with a structure Heavy metal catalyst. . . . . . . . . . . . . . . . ..Limited to cobalt
shown in Figure 6 by oxidizing cobaltous acetate with Solvent. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Lower fatty acid
Co-oxidation agents. . . . . . . . . . . . . . . . . . .Used
persulfate. T h e structure of this compound resembles
the catalyst structure in our process, but there is a
definite difference in the point that our catalyst structure
contains Co(I1) and Co(II1) species in the binuclear
complex, while only the Co(II1) species is found in the
complex isolated by Peshanski.
Table V shows the results obtained from the experi- CBA), p-acetoxymethyl benzoic acid, isophthalic acid,
ments carried out under our reaction conditions where benzoic acid, and o-toluic acid, and others are present
the co-oxidizing agents used in the low-temperature air only in trace. These compounds can be converted into
oxidation cited before were added. These additives are terephthalic acid by circulation of the mother liquor to
efficient in the region of low catalyst content and do not the oxidation reactor with the exception of compounds
show any effectiveness in high catalyst content. derived from the impurities of p-xylene-Le., isophthalic
T o show the characteristics of the oxidation in this acid, benzoic acid, o-toluic acid, and acetophenone.
process, the isolated oxidation by-products are listed in For example, p-acetoxymethyl benzoic acid can be
Table VI. These compounds were isolated from a oxidized in the same way as p-xylene in the presence
large amount of concentrated mother liquor of oxidation of cobaltic ion to give terephthalic acid in a high yield
reaction from a pilot operation. with a small amount of 4-carboxybenzaldehyde.
The amount of these compounds decreases in the As the oxidation in this process is carried out under a
order of $-toluic acid, 4-carboxybenzaldehyde (4- mild condition, the by-products (Table VII) found in the

VOL. 6 2 NO. 4 A P R I L 1 9 7 0 39
90

-
0
-1
a Figure 3. Reaction scheme
I 80
t-
r
a
W
a
W
-I
LL
0 70
n
-I
w
>-

6o0 0.2 0.4 0.6 0.8 I:O 1.2 Figure 4. Hydrogen abstraction by peroxy radical

RATIO O F C O ( O A ~ ) ~ * ~TO
H~O
p-XYLENE (MOLE/MOLE)
Figure 7 . Yield dependence on amount of catalyst

L
a
a
I-

REACTION TIME

Figure 2. Reaction steps i n this process Figure 5 . Periodical variation of each component

40 INDUSTRIAL A N D E N G I N E E R I N G CHEMISTRY
oxidation under relatively drastic conditions are not
formed. I n this process, therefore, circulation can
become possible only by removing water from most of the
mother liquor.

Process Description
Figure 7 shows that this process consists of three main
sections, oxidation, purification, and recovery.
Oxidation section. Oxidation is carried out con-
tinuously in one step a t a temperature lower than 1 5 O O C
with the pressure u p to several tens of atmosphere.
Acetic acid is used as solvent plus a relatively large
amount of cobalt catalyst, and oxygen-containing gases,
such as air as the oxidizing gas. The terephthalic acid Figure 6 . Catalyst structure
produced in the oxidation section is transferred to the
purification section after separation from the oxidation
mother liquor. The mother liquor, containing the
catalyst, oxidation intermediates, solvent, and water
produced by the oxidation reaction, is transferred to the
purification section. Over 9 5y0 yield of terephthalic TABLE V. p-XYLENE OXIDATION I N T H I S
acid by oxidation is attained when oxidation of the inter- PROCESS USING CO-OXIDATION AGENTS
mediate products in the recirculation system is included. Co-oxidation
Purification section. The crude terephthalic acid agent Condition Results
transferred from the oxidation section contains a small MEKa Low Co content + HzO Effective
High Co content No improvement
amount of oxidation intermediates, catalyst, and solvent,
but is used without drying in the preliminary purifica- 0 8 Low 0 2 pressure and low Co Effective
content
tion section. It is purified in the liquid phase using the High Co content and high N o improvement
same solvent, acetic acid, as in the oxidation. Most of 0 2 pressure

the impurities are eliminated by the preliminary purifica- AcH Low Co content Effective
High Co content N o improvement
tion, and the fiber grade terephthalic acid is produced
a Methyl ethyl ketone.
by crystallization following a preliminary purification.
Recovery section. Recovery section consists of the
recovery of the solvent and the catalyst. I n the solvent
recovery section, water produced in the oxidation
reaction is eliminated from the oxidation mother liquor TABLE VI. OXIDATION BY-PRODUCTS
which is separated in the oxidation section from the top (THIS PROCESS)
of the distillation column. The water-eliminated oxi- Substance Structural formula Remarks
dated mother liquor is recycled to the oxidation section p-Toluic acid
without further treatment and is used again.
A part of the mother liquor is treated, and impurities 4-Carboxybenz-
produced by the oxidation are separated. The catalyst aldehyde
is almost completely recovered and recycled to the p-iice toxy-
oxidation section. T h e impurities separated in this methylbenzoic
section are the products from the impurities in the raw acid HOW, Impurity
fromp-
material, p-xylene, and the organic and inorganic Isophthalic acid &COOH xylene
impurities produced in all sections.
T h e ratio of mother liquor recycled to the portion Impurity
Benzoic acid @COOH from p-
treated in this section was determined from the results xylene
Impurity
AUTHORS Yataro Ichikawa, Chief of the 70th Research o-Toluic acid &COO. from 16-
xylene
Laboratory, Gentaro Yamashita, Chief of the 3rd Research
Laboratory, and Michiyuki Tokashiki, Chemical Engineer of p-Tolualdeh yde
70th Research Laboratory, are associated with the Products
Development Institute, Teijin Ltd., Iwakuni, Japan; Teizo p-Methylbenzyl
Yamaji formerly Chemist of 70th Research Laboratory, is now acetate
a graduate student at Clarkson College of Technology, Potsdam, Impurity
Acetophenone fromp-
N . Y. This is one of the papers from the Symposium on
xylene
Novel Processes and Technology of the European and Japanese
Chemical Industry, presented at the 758th ACS Meeting in
New York, N . Y., September 7-72, 7969.

VOL. 6 2 NO. 4 A P R I L 1 9 7 0 41
of the pilot plant operation and from that computed
from the accumulation of impurities in the total system.
A continuous pilot plant s>-stem consisting of three
main sections mentioned above was constructed and has
been in operation to collect process and engineering
data for industrial and commercial plants. For this
process, three tentative flows were selected to supply
the best quality product economically, computed on the
basis of results obtained from the laboratory-scale experi-
ment and the pilot plant. Each of these three cases was
optimized by using IBM 7040 and IBM 360 Model 50.
The reaction conditions on an industrial scale were
decided from optimization results and operative effec-
tiveness. The characteristics of this process are sum-
marized below.
In this process, oxidation is carried out under a mild
condition. Therefore, (a) terephthalic acid yield based
upon $-xylene is high, being over 95%; (b) crude
Figure 7. Teijin process terephthalic acid produced by this oxidation process
does not contain coloring impurities such as fluorenone
and biphenyl ketone compounds, so that they are easily
purified to terephthalic acid of good color tone; (c)
impurities that hinder the reaction are not produced in
the oxidation section, so that most of the oxidation
TABLE V I I . OXIDATION BY-PRODUCTS mother liquor can be recycled. This is the important
(OTHER PROCESS) reason why this process is economical in spite of the
By-$roduct Influence Literature fact that a relatively large amount of catalyst is used;
(d) cobalt catalyst alone is used, without any accelera-
H~~C--@[+CC'OH Color Shigeyasu, Ozaki,
J . Chem. Sac. Japan tors or promoters such as bromides, aldehydes, and
0
(Ind. Chem. Sec.), ketones, so that the process system is simplified; ( e )
68, 304 (1965) the mild oxidation condition makes it possible to use
Shigeyasu, Ozaki, stainless steel for the apparatus, with no need for expen-
J . Chem. Sac. Japan sive materials like titanium.
II (Ind. Chem. Sec.),
0 68, 304 (1965) In the purification section the same solvent as the one
for the oxidation section is used. This saves the trouble
Hinder Shigeyasu, Ozaki,
oxidation J . Chem. Sac. Japan
of drying or separating the solvent between the sections
(Ind. Chem. Sec.), and makes the total process simple.
67,1396 (1964) I n the recovery section, most of the oxidation mother
liquor containing the catalyst can be recycled by elimi-
nating water from it, and only a part of it is treated
so efficiently that it is possible to avoid recovery loss in
TABLE V I I I . CONSUMPTION O F spite of the use of a relatively large amount of the catalyst.
RAW MATERIAL§ Economic data. Consumption of main raw ma-
Material Consumption terials is shown in Table VIII. These values were fully
$-Xylene 65 kg/100 kg TPX confirmed by using the pilot plant. The scale-up factors
Solvent Less than 10 kg/100 kg T P A for this process from 50 metric tonsiday to 300 metric
Catalyst Less than 0.10 kg/100 kg TPA tons/day are shown in Table IX. Other economic
data are satisfactory. These data indicated that this
process can fully compete with the conventional pro-
cesses now in operation.
TABLE I X . SCALE-UP FACTORS
Conclusion
(50-300 metric tons/day)
A process for production of high-purity terephthalic
Section Factor acid by air oxidation of @-xylene developed by Teijin
Total 0.65 Ltd. has been outlined, and is completely covered by
Oxidation 0.76 patents submitted by the company. Terephthalic acid
Purification 0.62 produced by this process can also be reacted before the
Recovery 0.50 stage of fiber-grade purification with methanol to form
dimethyl terephthalate or with ethylene oxide to form
his- (P-hydroxyethyl)terephthalate.

42 INDUSTRIAL AND ENGINEERING C H E M I S T R Y

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