US 20080275271A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2008/0275271 A1
Hashmi et al. (43) Pub. Date: Nov. 6, 2008
(54) PROCESS FOR PREPARING PURIFED Publication Classification
TEREPHTHALCACD
(51) Int. Cl.
(76) Inventors: Syed Mohammed Azar Hashmi, CD7C5L/42 (2006.01)
Riyadh (SA); Sulaiman
Al-Luhaidan, Riyadh (SA) (52) U.S. Cl. ........................................................ 562/486
Correspondence Address:
SABIC AMERICAS, INC. (57) ABSTRACT
16OO INDUSTRIAL BILVD. The present invention relates to a process for preparing puri
SUGAR LAND, TX 77.478 (US) fied terephthalic acid IPTA), comprising the steps: dissolv
ing crude terephthalic acid CTA in an aqueous medium in a
(21) Appl. No.: 11/793,288 reactor; hydrogenating CTA at a temperature of about 260
(22) PCT Fled: Dec. 9, 2005 320° C. and a pressure of about 1100-1300 psig using a
hydrogenation catalyst, crystallizing terephthalic acid in the
(86) PCT NO.: PCT/B2005/003722 reactor by lowering the temperature of the solution to about
160° C. without evaporation cooling; transferring the content
S371 (c)(1), of the reactor to a filtration unit; filtrating the content at a
(2), (4) Date: Feb. 4, 2008 temperature of about 140-160° C. and a pressure of about
40-100 psig, preferably 80-100 psig to obtain a filter cake,
(30) Foreign Application Priority Data washing the filter cake obtained with water having a tempera
ture of about 140-160° C. in the filtration unit; and drying the
Dec. 15, 2004 (EP) .................................. O4O296,154 filter cake.

Comparison of 4-CBA contents

CTA Batch Batch-2 Batch-3 Batched Batch-5 Batch-5a On-spec,

Time 4h Time=6h Times8h Timeu8h Time sBh Timesh PTA
Patent Application Publication Nov. 6, 2008 Sheet 1 of 2 US 2008/0275271 A1

Fig. 1: Comparison of 4-CBA contents

CTA Batch- Batch-2 Batch-S Batch-4 Batch-5 Batch-Sa OnvSpec,

Times4h Time-6h Times8h Timeu8h Times8h Tineash PTA

Fig. 2: Comparison of p-Toluic contents

2500
2000

SOO

1000

500

Batch-6 Batch-7 Batch-8 Batch-9 On-Spec-PTA

Fig. 3: Comparison of p-Toluic acid

250

200

150
100
50

s 5:
Batch-8 B3th9 Bitch10 Batch-08 On-Spec-PTA
Patent Application Publication Nov. 6, 2008 Sheet 2 of 2 US 2008/0275271 A1

Fig. 4: Comparison of Metal Contents

TTANUM ON-SPEC-PTA

Fig.5: Comparison of Color Properties

DELTAY

b-VALUE

APHA COLOUR
w

".
DUPLess PACKED On-Spec PTA
US 2008/0275271 A1 Nov. 6, 2008

PROCESS FOR PREPARNG PURIFED 0006 Moreover, U.S. Pat. No. 5,767,311 discloses a
TEREPHTHALCACD method for purifying crude terephthalic acid from a liquid
dispersion thereof, wherein the method does not include a
hydrogenation step, but the crude terephthalic acid is only
0001. The present invention relates to a process for pre purified by crystallization and filtration steps.
paring purified terephthalic acid. 0007. The known processes for preparing pure tereph
0002 Purified terephthalic acid (PTA) is a commodity thalic acid are connected with the disadvantages that, mostly,
petrochemical of great commercial importance. It is used as a the catalytic hydrogenation of CTA is carried out in a fixed
key raw material for the production of various types of poly bed and requires low concentration of feed. Further, hydro
genation and crystallization are often performed separately in
mers. The world production capacity for PTA is above 25 different reactors, and also several stage crystallization is
million metric tons per year. Polymer grade or purified common. Additionally, crystallization is performed by evapo
terephthalic acid is the starting material for polyethylene ration cooling (depressurisation) of the water Solvent which
terephthalate, which is the principal polymer for polyester results in build-up on the wall of crystallization reactors.
fibres, polyester films, and resins for bottles and the like Finally, also hot filtration and hot washing is often done
containers. Purified terephthalic acid is produced commer separately and by reslurrying Solid product obtained after hot
cially from relatively less pure, technical grade or crude filtration. Therefore, loss of material occurs and also load on
terephthalic acid (CTA). Crude terephthalic acid may be waste water and energy.
obtained by oxidation of p-Xylene usually containing rela 0008. It is an object of the present invention to provide a
tively large amounts of various impurities. Such impurities process for preparing pure terephthalic acid which overcomes
may include the following. The organic impurities present in the drawbacks of the prior art.
CTA include partially oxidized products, such as 4-carboxy 0009. This object is achieved by a process for preparing
benzaldehyde (-3000 ppm) and p-toluic acid (-500 ppm) purified terephthalic acid (PTA), comprising the steps:
being a hydrogenation product of 4-carboxybenzaldehyde. 0.010 i) dissolving crude terephthalic acid (CTA) in an
Color impurities may include benzil, fluorenone and/or aqueous medium in a reactor;
anthraquinone (~30 ppm). Metal impurities include iron and 0.011 ii) hydrogenating CTA at a temperature of about
other metals (-85 ppm). In addition, moisture (-0.2%) and 260-320° C. and a pressure of about 1100-1300 psig
ash (~100 ppm) may be present as impurities. Table-1 below using an hydrogenation catalyst;
shows the specification of crude and pure terephthalic acid. 0012 iii) crystallizing terephthalic acid in the reactor by
The specification of PTA is the one which is necessary to be lowering the temperature of the solution to about 160°C.
useful as starting material for polymerization without evaporation cooling;
TABLE 1.
0013 iv) transferring the content of the reactor to a
filtration unit;
Specification of CTA and PTA 0.014 v) filtrating the content at a temperature of about
140-160° C. and a pressure of about 40-100 psig, pref
PROPERTY UNITS CTA PTA erably 80-100 psig to obtain a filter cake:
Purity % 99.7 99.95 0.015 vi) washing the filter cake obtained with water
4-CBA ppm 2SOO &25 having a temperature of about 140-160° C. in the filtra
P-Toluic Acid ppm 500 &150 tion unit; and
APHA Color HU 50 &10
AY 30 &10 0016 vii) drying the filter cake.
b-Value 9 &2.5 0017 Preferably, the process is carried out in a batch reac
ASH ppm 1OO &10 tOr.
Moisture % O.2 <0.1
Total Metals ppm 85 &10
0018 Still preferred, in steps i)-iii) the reactor content is
agitated with a stirrer at about 250-400 rpm.
0019. In one embodiment, within the reactor a basket is
0003 PTA may be commercially produced by catalytic disposed containing the hydrogenation catalyst.
hydrogenation of the intermediate crude terephthalic acid 0020 Preferably the basket is made of titanium or duplex
over palladium catalyst Supported on carbon. The hydroge stainless steel.
nation reaction is performed in an aqueous solvent at high 0021. It is further preferred that the hydrogenation catalyst
temperature of 280° C. and high pressure of 80 bar. This is contains a platinum group metal selected from the group
followed by crystallization, hot filtration hot washing and consisting of palladium, ruthenium, rhodium, osmium, iri
drying to obtain PTA having a purity of more than 99.95% dium, and platinum, or an oxide of Such a metal.
0004 U.S. Pat. No. 5,567,842 discloses a process for pro 0022. It is preferred that the hydrogenation catalyst is sup
ducing pure terephthalic acid, wherein the hydrogenation ported on a carrier.
step is carried out in a continuous fixed bed reactor, where 0023. Most preferred the hydrogenation catalyst is palla
upon the slurry is fed to multiple crystallizers wherein the dium on a carrier of active carbon.
temperature is lowered stepwise by pressure release cooling. 0024. In one embodiment, the aqueous medium is water,
0005 U.S. Pat. No. 3.584,039 discloses a process for pro preferably demineralized water.
ducing pure terephthalic acid in a batch reactor. Again, the 0025. Further, it is advantageous that the time for hydro
hydrogenation reactor is cooled by releasing the pressure genation in Step i) is at least six hours, preferably at least seven
which vaporizes water from the solution and cools the solu hours, most preferably at least eight hours.
tion, thereby precipitating terephthalic acid crystals. The 0026. It is preferred that in step ii) the lowering of the
obtained terephthalic acid crystals are filtered at room tem temperature is done at a rate of about 1°C/min, to a tempera
perature. ture of about 160° C.
US 2008/0275271 A1 Nov. 6, 2008

0027. Most preferably, after a temperature of about 160° 0043 FIG.3 is a comparison of p-toluic acid contents after
C. in step iii) has been reached, the reactor is depressurized by hot washing in a process of the present invention;
evaporation to a pressure of about 100 psi.g. 0044 FIG. 4 is a comparison of metal contents using dif
0028 Still preferred is that the temperature is maintained ferent metals as material for the catalyst basket within a
after the temperature of about 160° C. has been reached. process of the invention; and
0029. In one embodiment the transfer in step iv) is done 0045 FIG. 5 is a comparison of color properties of pure
via a transfer line which is kept at a temperature of about
180-2500 C. terephthalic acid obtained by a process of the present inven
0030. It is advantageous that the water used in step vi) is tion.
heated in the reactor at a pressure of about 100 psig. 0046 Chemicals: The quantity and source of the chemi
0031. It is still preferred that in step ii) lowering of the cals used in each batch carried out for the conversion of CTA
temperature is achieved by passing coolant through coolant to PTA are as follows: a hydrogenation reaction was per
circulation coils disposed at and/or in the reactor. formed in a hydrogenation reactor using 1.25 kg of commer
0032. Preferably, the coolant is water, preferably chilled cial CTA and 32 gm of palladium catalyst on a carbon Support
water having a temperature of about 10-15°C. (commercially available from Sud-Chemie or Engelhard).
0033 Finally, it is preferred that the content of PTA in step The purity of hydrogen gas used was 99% and demineralised
i) is between about 5-60 weight percent, based on the total water of specific conductance of less than 1 was used.
weight of PTA and aqueous medium. 0047. Feed preparation: A feed mixture for hydrogenation
0034 Surprisingly, it was found for the process of the reaction was prepared by feeding first water into the reactor
present invention that several advantages may be achieved, if by applying vacuum. This was followed by manual addition
the process utilizes the following steps: of 1.25 kg of CTA powder to the reactor using a funnel. This
0035) crystallizing the terephthalic acid in the hydroge mixture was then agitated at 320 rpm to give a slurry contain
nation reactor by lowering the temperature without ing about 13.5 weight percent of terephthalic acid. Nitrogen
evaporation cooling to a temperature of about 160° C.
and gas was then added to the reactor twice up to 50 psig and the
0036 transferring the content of the hydrogenation reaction mixture was agitated for 5 minutes, and then the gas
reactor to a unit where both filtration and washing may was released by opening a vent valve, keeping a nitrogen
be carried out. Further, it is advantageous to utilize a pressure of 10 psig in the reactor. Inside the hydrogenation
continuously stirred hydrogenation reactor in contrast to reactor a catalyst basket containing the hydrogenation cata
the fixed bed reactor used in the prior art. lyst is fixed, for example at a cooling coil within the reactor.
0037. As the cooling of the hydrogenated terephthalic acid 0048 Hydrogenating: Hydrogenation of CTA to convert
Solution is performed via a lowering of reaction temperature the main impurity of 4-carboxybenzaldehyde (4-CBA) into
and not by depressurizing, no build-up on the wall of the p-toluic acid was carried out at a temperature of 285°C., and
hydrogenation reactor is observed. Further, hot filtration and the pressure of the reactor was maintained at 1200 psig, i.e.
hot washing is carried out in one filtration unit without reslur above the partial pressure of water to maintain a liquid phase
rying the Solid product obtained, so that the loss of material and to ensure an adequate Supply of hydrogen. The hydroge
may be controlled. nation reaction was carried out for different time periods,
0038. As outlined above, the cooling for crystallization is during which hydrogen was supplied, when the pressure
effected only by lowering the temperature and not by depres decreased and reached the partial pressure of water, in order
Surization. However, during cooling the pressure is automati to keep the pressure almost constant.
cally lowered to about 250-300 psig. After a cooling tempera 0049 Crystallizing: After the time period of the hydroge
ture of about 160° C. is obtained, the pressure may then nation reaction was over, the beater of the hydrogenation
preferably be lowered further by depressurizing to 100 psi. reactor was switched off, and the temperature of the reactor
This avoids shock cooling and produces a product having was lowered to 160° C. by passing chilled water of a tempera
good quality, articles with good morphology and a product ture of about 10-15° C. through water circulation coils at
with high purity. The particle size distribution of the PTA is and/or in the hydrogenation reactor. In general, the decrease
narrow with few fine (dust) particles. The particles also have in temperature is very slow at a rate of about 1° C. per minute.
good strength. Further, a depressurization at a lower tempera During the crystallization the agitator was kept on at 320 rpm.
ture has other advantages, such as a carry over of crystals to When a temperature of 160° C. was reached the heater was
the vent line is prevented, thus avoiding blockages which is a Switched on again to avoid further lowering of the tempera
common problem with some commercial plants. ture. After a temperature of 160° C. was reached, depressur
0039. It is also preferred that the temperature of the trans ization was carried out to bring the reactor pressure to about
fer line is kept higher than the temperature of the crystalliza 100 psi. Depressurization at this temperature will not result in
tion reactor and the hot filtration unit. This avoids plugging as a significant loss of PTA product, but only hydrogen gases
a result of flash cooling in the transfer line. that were added to built up the pressure, will be released.
0040. Additional advantages and features will become 0050 Hot filtrating: The hot filtration for removing
apparent from the following detailed description of examples p-toluic acid from an aqueous slurry of terephthalic acid was
for a process for preparing pure terephthalic acid, with refer carried out using a Sparkler filter unit. Nitrogen gas was first
ence to the accompanying drawings, wherein: flushed through the filter unit and a pressure of about 80 psig
0041 FIG. 1 shows a comparison of 4-carboxybenzalde was kept in the filtration unit. The content of the reactor was
hyde contents using different hydrogenation times in a pro then transferred via a transfer line to the filtration unit. The
cess of the present invention; content of the reactor was fed continuously, however, the
0042 FIG. 2 is a comparison of p-toluic acid contents after pressure in the filter unit was maintained at 80 psig by slowly
hot filtration in a process of the present invention; controlling a drain valve of the hydrogenation reactor. The
US 2008/0275271 A1 Nov. 6, 2008

filtration unit was kept at a temperature of about 140-160°C., temperature of the transfer line was about 100°C. The analy
and the transfer line was kept at a temperature of about 180 sis showed that the hot filtration is not successful and some
2009 C. amount of p-toluic acid is crystallized with PTA. Batch-8 and
0051 Hot washing: About 6 litres of demineralised water batch-9 were carried out in a similar manner except that the
was heated to a temperature of 160° C. in the hydrogenation transfer line temperature was increased to 220°C. The analy
reactor. The hot water at a temperature of 160° C. and a sis showed that after the hot filtration the content of p-toluic
pressure of about 100 psig was then fed to the filtration: unit acid is reduced to 160 and 220 ppm, respectively. These result
containing the filter cake. The hot water was fed continuously show that the amended hot filtration is successful and p-toluic
to the filter, however, the pressure in the filter unit was main acid contents may be reduced significantly.
tained at about 80 psig by controlling the drain valve of the 0059 Optimization of hot washing conditions: In on-spec
reactor. Also in the washing process, the temperature of the PTA the p-toluic acid content should be less than 150 ppm.
transfer line was kept at a temperature of about 180-200° C. Therefore washing of the PTA cake with hot water was car
0052. After the washing process, the filter cake obtained ried out to reduce the amount of p-toluic acid further. FIG. 3
may be removed from the filtration unit and/or may be dried shows the results of hot filtration and hot washing experi
to dryness, as desired. ments which were carried out for several batches obtained in
0053. In the following description, possibilities for opti a process of the present invention. The content of p-toluic acid
mizing the major processing steps to produce pure tereph in batch-8 after hot filtration was 160 ppm and was reduced
thalic acid having required purity (on-spec PTA) are illus after hot washing to about 97 ppm. Similarly, the content of
trated. p-toluic acid in batch-9 was 200 ppm after hot filtration and
0054 Optimization of hydrogenation conditions: The was reduced after hot washing to 98 ppm. Likewise, more
major impurity present in CTA is 4-carboxybenzaldehyde. experiments were carried out by performing both hot filtra
The 4-CBA causes undesirable coloring of the polymer as a tion and hot washing and the analysis of PTA obtained
consequence of its thermal instability during polymerization. showed that the content of p-toluic acid is always on-spec
Therefore, parameters for reducing 4-CBA have been stud (<150 ppm).
ied. 0060 Removal of metallic impurities: Metallic impurities
0055 FIG. 1 shows the results of five batches of tereph act as poison for the antimony catalyst during the polymer
thalic acid obtained in a process of the present invention, ization reaction of purified terephthalic acid. In pure tereph
carried out by varying the reaction in order to reduce the thalic acid the total metal content should be < 10 ppm. FIG. 4
content of 4-CBA from 2500 ppm (off-spec) to <25 ppm shows the metal analysis of several batches obtained in a
(on-spec). process of the present invention using different metal mate
0056. The hydrogenation reaction in batch-1 and batch-2 rials as catalyst baskets, namely SS-316, Duplex-SS and Tita
was carried out for a period of 4 hours and 6 hours at 285°C. nium. The PTA obtained showed a very high total metal
temperature and 1200 psig pressure. The analysis showed that content with SS-316, as SS-316 is not a suitable material of
hydrogenation is incomplete in both batches. The 4-CBA construction for carrying out a purification process of crude
content present in the PTA obtained was 500 ppm and about terephthalic acid. The total metal contents was on-spec using
60 ppm respectively. In batch-2 the content of 4-CBA titanium and duplex-SS as material for the catalyst basket.
decreased significantly with increase in reaction time for two 0061 Removal of color impurities: Color impurities
hours, but the content was still off-spec. The hydrogenation present in CTA lower the melting point of polyester and/or
reaction in batch-3 was carried out for 4 period of 8 hours at cause coloration of the polyester. In fact, some impurities that
285° C. temperature and 1200 psig pressure. The analysis are contained in the crude terephthalic acid are color-forming
showed that hydrogenation is complete. The 4-CBA contents precursors. Therefore, the effect of known and potential color
present in the PTA obtained was only 5 ppm. The hydroge impurities on PTA prepared in a batch process according to
nation reaction in batch-4, batch-5 and batch-5a was carried the present invention, were investigated. Three optical prop
out under similar operation conditions as in batch-3 to con erties, i.e. delta Y. b-value and APHA color were investigated.
firm the optimized parameters obtained. The analysis A delta-Y value of >10, b-value of >2.5 and APHA color
revealed a 4-CBA content of 5.2, 6.8 and 5.1 ppm for these value of >10 (HU) indicates that the sample is heavily con
batches, respectively. Further, it could be demonstrated in taminated and is not a commercially accepted product. FIG.5
additional experiments, that at a pressure below 1110 psi the shows results of optical properties, i.e. delta Y. b-value and
hydrogenation was incomplete, and the 4-CBA content was APHA color for several PTA batches obtained in the process
higher than 25 ppm. Similar results may be obtained using a of the present invention using different materials for the cata
temperature outside the range of about 260-320°C. lyst basket. In this regard, duplex is the metallurgy of catalyst
0057. Optimization of hot filtration condition: A further basket used during the hydrogenation reaction. The capacity
major impurity present in CTA is p-toluic acid. P-toluic acid of the basket is bigger than the amount of catalyst used during
acts as polymerization terminator and slows down the poly hydrogenation reaction. Therefore, under high pressure and
merization rate and decreases the average molecular weight agitation catalyst pellets move inside the catalyst basket and
of the polymer. FIG. 2 shows the results of hot filtration Some get crushed and impart colour to the product. Therefore,
experiments which were carried out for different batches the colour of PTA product was affected. In duplex packed
obtained in a process of the present invention, as outlined basket, Some inert material was used to fill the remaining
above. space inside the catalyst basket so that the catalyst pellets
0058. In batch-6 PTA was obtained without hot filtration were fixed and not moveable.
and the p-toluic acid content was about 2200 ppm. The trans 0062. The features disclosed in the foregoing description,
fer line in batch-6 was not heated or heat traced. In batch-7 in the claims and/or in the accompanying drawings may, both
PTA was obtained by performing hot filtration and the separately and in any combination thereof, be material for
p-toluic acid content was about 800 ppm. In batch-7 the realizing the invention in diverse forms thereof.
US 2008/0275271 A1 Nov. 6, 2008

1. A process for preparing purified terephthalic acid (PTA), 8. The process according to claim 7, wherein the hydroge
comprising the steps: nation catalyst is palladium on a carrier of active carbon.
viii) dissolving crude terephthalic acid (CTA) in an aque 9. The process according to claim 1, wherein the aqueous
ous medium in a reactor; medium is water.
ix) hydrogenating CTA at a temperature of about 260-320° 10. The process according to claim 1, wherein the time for
C. and a pressure of about 1100-1300 psig using an hydrogenation in step ii) is at least six hours.
hydrogenation catalyst; 11. The process according to claim 1, wherein in step iii)
X) crystallizing terephthalic acid in the reactor by lowering the lowering of the temperature is done at a rate of about 1°
the temperature of the hydrogenated CTA in the aqueous C./min, to a temperature of about 160° C.
medium to about 160° C. without evaporation cooling: 12. The process according to claim 1, wherein, after a
xi) transferring the content of the reactor to a filtration unit; temperature of about 160° C. in step iii) has been reached, the
xii) filtrating the content at a temperature of about 140 reactor is depressurized by evaporations to a pressure of about
160° C. and a pressure of about 40-100 psig to obtain a 100 psig.
filter cake 13. The process according to claim 1, wherein the tempera
xiii) washing the filter cake obtained with water having a ture is maintained after the temperature of about 160° C. has
temperature of about 140-160° C. in the filtration unit; been reached.
xiv) drying the filter cake. 14. The process according to claim 1, wherein the transfer
2. The process according to claim 1, wherein the process is in step iv) is done via a transfer line which is dept at a
carried out in a batch reactor. temperature of about 180-250°.
3. The process according to claim 1, wherein in stepsi)-iii) 15. The process according to claim 1, wherein the water
the reactor content is agitated with a stirrer at about 250-400 used in step vi) is heated in the reactor at a pressure of about
rpm.
100 psig.
16. The process according to claim 1, wherein in step iii)
4. The process according to claim 1, wherein within the lowering of the temperature is achieved by passing coolant
reactor a basket is disposed containing the hydrogenation through coolant circulation coils disposed at and/or in the
catalyst. reactOr.
5. The process according to claim 4, wherein the basket is 17. The process according to claim 16, wherein the coolant
made of titanium or duplex-stainless steel. is water, preferably chilled water having a temperature of
6. The process according to claim 1, wherein the hydroge about 10-15° C.
nation catalyst contains a platinum group metal selected from 18. The process according to claim 1, wherein the content
the group consisting of palladium, ruthenium, rhodium, of CTA in step i) is between 5-60 weight percent, based on the
osmium, iridium, and platinum, or an oxide of Such a metal. total weight of PTA and aqueous medium.
7. The process according to claim 6, wherein the hydroge
nation catalyst is Supported on a carrier c c c c c