Europaisches Patentamt

(19) European Patent Office

Office europeen
peen des brevets
brevets EP 0 579 715 B1

(12) E U R O P E A N PATENT S P E C I F I C A T I O N

(45) Date of publication and mention (51) Intel e C07C 5 1 / 4 3

of the grant of the patent:
27.08.1997 Bulletin 1997/35 (86) International application number:
PCT/US92/02910
(21) Application number: 92909320.1
(87) International publication number:
(22) Date of filing: 09.04.1992 WO 92/18454 (29.10.1992 Gazette 1992/27)

(54) PROCESS FOR RECOVERY OF PURIFIED TEREPHTHALIC ACID

VERFAHREN ZUR RUCKGEWINNUNG VON GEREINIGTER TEREPHTALSAURE
PROCEDE DE RECUPERATION D'ACIDE TEREPHTALIQUE PURIFIE

(84) Designated Contracting States: • GRAZIANO, Diane, Jean

AT BE CH DE DK ES FR GB GR IT LI LU MC NL SE Claredon Hills, IL 60514 (US)
• SCHILLER, Sandra, K.
(30) Priority: 12.04.1991 US 685218 Naperville, IL 60594 (US)
• GRIMM, Roger, John
(43) Date of publication of application: Glen Ellyn, IL 60187 (US)
26.01.1994 Bulletin 1994/04
(74) Representative: Ritter, Stephen David et al
(73) Proprietor: AMOCO CORPORATION Mathys & Squire
Chicago, IL 60680-0703 (US) 100 Grays Inn Road
London WC1X8AL (GB)
(72) Inventors:
• STREICH, Debra, Jean (56) References cited:
Naperville, IL 60540 (US) EP-A- 0 073 076 EP-A- 0 305 898
US-A- 3 497 552

DO

O)
Is-
LO Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give
notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in
o
a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art.
a.
99(1) European Patent Convention).
LU
Printed byJouve, 75001 PARIS(FR)
 EP0 579 715B1

Description

The field of the invention relates to an improved process for recovery of purified terephthalic acid (hereinafter PTA)
from an aqueous slurry containing a solution of p-toluic acid. Purified terephthalic acid is prepared wherein the con-
5 centration of p-toluic acid is less than 200 parts per million by weight (ppmw). In the oxidation of paraxylene to tereph-
thalic acid, 4-carboxybenzaldehyde is produced as an intermediate. In the purification of the terephthalic acid in the
presence of water, the 4-carboxybenzaldehyde is hydrogenated to a more water soluble derivative, p-toluic acid. The
purified terephthalic acid containing residual p-toluic acid is washed with water to remove residual soluble p-toluic acid.
The wash water containing the p-toluic acid is recycled or discarded to waste treatment facilities. A process of flooded
10 water washing under pressure of the purified terephthalic acid operates to reduce amount of wash water, to decrease
content of residual impurities in purified terephthalic acid, and/or, to decrease the load on downstream waste treatment
capacity. This invention substitutes the pressure centrifugation, reslurry, atmospheric pressure flashing and atmos-
pheric pressure separation steps utilized in prior art processes to recover purified terephthalic acid from an aqueous
slurry by-a single unit operation, i.e., pressure filtration, with consequent lower equipment costs.
15
Background Of The Invention

Usually, terephthalic acid is produced by a liquid phase oxidation of p-xylene and/or p-toluic acid. Terephthalic acid
is of great commercial importance and is widely used for the production of various-different polymers, such as fiber-
20 forming -polyesters. A process for preparing polyesters of terephthalic acid, particularly polyethylene terephthalate,
comprises a direct condensation of terephthalic acid with the respective polyalcohol. For example, terephthalic acid is
reacted with ethylene glycol to form bis(P-hydroxyethyl) terephthalate which is then polymerized in a second stage.
This direct condensation process is simpler than other known methods such as transesterification of dimethyl tereph-
thalate with the appropriate glycol. However, the direct esterification requires the use of medium or highly purified
25 terephthalic acid. In order to be suitable for the production of polyester fibers, terephthalic acid must be substantially
free of any contaminants which lower the melting point of the polyester and/or cause coloration of the polyester. In
fact, some impurities which are contained in crude terephthalic acid are color-forming precursors.
All these impurities have not yet been identified. However, 4-carboxybenzaldehyde which is an intermediate oxi-
dation product and which in the following is abbreviated as 4-CBA, generally is found in crude terephthalic acid. It is
30 known that the degree to which coloration in the polyester is induced is less if the 4-CBA content of the terephthalic
acid is low. While pure 4-CBA itself does not necessarily promote coloring during polymerization, this impurity is a
convenient tracer for evaluating the degree to which terephthalic acid has been refined. A process which can reduce
the 4-CBA content of terephthalic acid reduces also the content of color-forming precursors.
Commercial crude terephthalic acid contains on a weight basis from 800 to 7,000 parts per million (ppm) 4-car-
35 boxybenzaldehyde and 200 to 1,500 ppm p-toluic acid as the main impurities. Crude terephthalic acid also contains
lesser amounts, 20-200 ppm range, of yellow color aromatic compounds having the structures of benzil, fluorenone or
anthraquinone which are characteristically yellow compounds as impurities resulting from coupling side reactions oc-
curring during the oxidation of p-xylene.
U.S. Pat. No. 3,584,039 issued to Delbert H. Meyer teaches a feasible, commercially useful method for purification
40 of such commercially available crude terephthalic acid products by treating liquid phase solutions thereof in water at
temperatures of 200°-374°C with hydrogen in the presence of a solid hydrogenation catalyst (e.g. metallic palladium
on carbon support) and crystallizing terephthalic acid from catalyst-free liquid phase solutions at temperatures in the
range of 50°C to 150°C. The catalytic hydrogen treatment converts 4-carboxybenzaldehyde to p-toluic acid and de-
colorizes the terephthalic acid.
45 British Pat. No. 1,152,575 is directed to the development of the Meyer Patent method for its commercial application
providing improved modes of conduct for the entire process from the step of dissolving crude terephthalic acid through
the step of crystallizing terephthalic acid from the hydrogen treated aqueous solution. With respect to said crystalliza-
tion, said British patent teaches the use of solvent evaporation to effect the cooling necessary to precipitate crystalline
terephthalic acid but cautions that conduct of such evaporative cooling should avoid shock cooling of the solution as
so would occur by instantaneous flash evaporation of solvent because such shock cooling coprecipitates dissolved im-
purities which contaminate terephthalic acid product. To prevent the contaminating effect of such shock cooling, the
British patent teaches that the evaporative cooling should be controlled by evaporation against equilibrium back pres-
sure, for example, by throttling of steam vapor exhaust at the equilibrium pressure. This is in effect a controlled rate
evaporative cooling.
55 Crystallization by controlled rate evaporative cooling is, according to the above British patent, applied to continuous
crystallization conducted in three series connected stages under the conditions described to effect in 3.4 hours a 150°C
temperature drop from 277°C initial solution temperature to the third stage temperature of 109°C. This mode of con-
ducting said crystallization provided an average cooling rate of 1.48°F (0.82°C) per minute that was not only inordinately

2
 EP0 579 715B1

slow but, when applied to aqueous solutions of terephthalic acid of 2,400 ppm p-toluic acid content, also provided a
terephthalic acid product containing 1,200 ppm p-toluic acid. Such product would not be acceptable for direct reaction
with ethylene glycol for polyester fiber manufacture.
U.S. Pat. No. 3,452,088 repeats the caution against shock cooling and teaches a further improvement for the
5 continuous controlled rate evaporative cooling technique as applied to crystallizing terephthalic acid from aqueous
solutions also containing dissolved p-toluic acid. The improvement consists of limiting the final crystallization temper-
ature and/or crystalline product separation temperature to the temperature range of 121° to 149°C to prevent p-toluic
acid contamination of crystallizing terephthalic acid. By using such final crystallization and/or product separation tem-
peratures of 121° to 149°C terephthalic acid could be and was commercially obtained with 150 ppm and less p-toluic
10 acid from feed solutions containing 500 to 6,000 ppm p-toluic acid at a somewhat faster cooling rate of 3°-4°F (1 .7 -
2.2°C) per minute. But such faster controlled rate evaporation process does not provide a useful basis for devising still
faster continuous flash evaporative crystallization to overcome the p-toluic acid contamination problem mentioned in
both the British and U.S. patents.
U.S. Pat. No. 3,497,552 discloses a procedure for purifying impure terephthalic acid by crystallization from an
is aqueous solution at 150-300°C. The solution is continuously cooled in a series of connected cooling zone stages
having a receiver and external recycle loop. Three flowing streams consisting of injected water, a feed stream and a
stream from the lower portion of the receiver are combined and the injected water is sufficient to provide the required
cooling.
Crystallization by flash evaporation of solvent has, in general, been long known and used to take advantage of
20 the substantially instantaneous decrease in both temperature and pressure and attendant substantially instantaneous
evaporation of solvent as the hot solution of solute is introduced into the crystallization vessel operated at a lower
temperature and pressure. Advantageously, the rapidly vaporized portion of the liquid solvent flashed to the vapor
phase permits rapid removal of solvent vapor. Both crystallization and crystal growth occur rapidly with the cooling and
concentrating caused by flashing the solution to the lower temperature. Growth of crystals is substantially entirely the
25 result of the lower temperature and is independent of residence time. Crystal size in a crystallization vessel where
solvent is flash evaporated can, as is well known, be enhanced by circulation of slurry of crystals throughout the lower
portion of the crystallization vessel. For example, one means for accomplishing such circulation in a stirred crystalli-
zation zone is to withdraw a portion of the slurry from near its upper level and introduce, e.g., by pumping, the withdrawn
slurry up through the bottom of the stirred slurry.
30 However, use of flash solvent evaporation induced crystallization of terephthalic acid (TA) from aqueous solution
also containing dissolved p-toluic acid in amounts of 500 to 6,000 ppm based on TA can, without proper conduct thereof,
bring into play the p-toluic acid contamination phenomenon alluded to in the British patent and more generally described
in the later U.S. patent. Such contamination phenomenon is somewhat anomalous because, in spite of the fact that
there is retained more than enough solvent water to prevent saturation or supersaturation with respect to p-toluic acid,
35 p-toluic acid nevertheless comes out of solution. Said later U.S. patent suggests that the contamination phenomenon
is in some way dependent on the rate of crystallization and the final temperature of crystallization and product separation
and not solely on p-toluic acid concentration in the solution.
From plots of TA saturation and supersaturation (TA concentrations vs. temperature) and the guidance provided
by teachings in the aforementioned related British and United States patents, one might devise a continuous TA crys-
40 tallization process having a number of crystallization stages in series with each stage operated at a temperature lower
than the preceding stage and, for smooth operation approximating batchwise crystallization, having a temperature
profile substantially following the TA saturation plot. Such a devised continuous crystallization process would have at
least about 40 rate-dependent crystallization stages. However, because of the number of stages and their time con-
suming operation, such a continuous crystallization would not be economically attractive or feasible for commercial
45 application.
It is therefore an object of this invention to provide a method for displacing p-toluic acid from a slurry of purified
terephthalic acid in an aqueous medium wherein the aqueous medium containing the p-toluic acid is displaced from
the slurry of purified terephthalic acid by a positive displacement method using pressure filtration of the purified tereph-
thalic acid in a method of flooded water washing, also termed plug flow washing, of the filter cake, at high temperature
so and pressure, followed by release of the pressure with consequent lower temperature and, ultimately, to a condition
of atmospheric pressure. The concentration of p-toluic acid retained in the purified terephthalic acid is equal to or less
than 200 ppmw.
It is an object of this invention to provide a method for displacing p-toluic acid from a slurry of purified terephthalic
acid in an aqueous medium wherein the p-toluic acid is displaced from the slurry of purified terephthalic acid by a
55 positive displacement method using filtration of the purified terephthalic acid slurry under high temperature and pressure
wherein the concentration of p-toluic acid retained in the filter cake is equal to or less than 200 ppmw and pressure is
reduced to atmospheric pressure.
It is further an object of this invention to provide an improved process for preparation of purified terephthalic acid

3
 EP0 579 715B1

containing 200 ppmw, or less, of p-toluic acid and the purified terephthalic acid is at atmospheric pressure, and is
thereby in a state to be processed by a dryer at atmospheric pressure.

Summary of the Invention

5
A process of producing purified terephthalic acid (TA) having 200 ppm or less p-toluic acid content by weight (i.e.,
fiber-grade quality TA) has been discovered which is applicable to aqueous slurries of TA having 500-6,000 ppm by
weight of p-toluic acid in solution. The aqueous slurry containing the crystallized TA and an aqueous solution of dis-
solved p-toluic acid is filtered. The filter cake is subject to a process for positive displacement of the aqueous solution
10 of the p-toluic acid at a temperature of at from 38°C to 205°C and at a pressure differential of from 0.5 psi to 65 psi
(3.4 - 448 kPa) over the system pressure. The aqueous solution containing the soluble p-toluic acid is displaced by
water under pressure from the filter cake of crystalline TA by pressure filtration at high temperature. The solution of p-
toluic acid remaining in the filter cake is displaced by water under pressure. Pressure flash evaporation of water re-
maining in the filter cake occurs upon release of the system pressure and a consequent lower temperature to atmos-
15 pheric pressure. The crystalline product of terephthalic acid containing 200 ppm or less p-toluic acid is thereupon
subjected to drying equipment under atmospheric pressure to obtain desired product.
More specifically, the invention provides a process for the preparation of purified terephthalic acid containing p-
toluic acid present in a concentration equal to or less than 200 parts per million by weight (ppmw) which process
comprises:
20
(a) introducing into a filter cell or a series of filter cells in a filtration zone at a temperature within the range of about
38°C to 205°C at a system pressure of from atmospheric to 235 psig (101 -1 620 kPa) an aqueous slurry comprising
purified terephthalic acid present as crystals and p-toluic acid present as an aqueous solution and as a co-crys-
tallized form with crystals of said purified terephthalic acid, said filter cell or series of filter cells maintained in
25 suitable position whereby each filter cell develops a filter cake or filter cakes upon introduction of said slurry into
each said cell;
(b) transporting each said filter cell containing said filter cake from said filter zone to a wash zone;
(c) introducing a water stream into each said filter cell to form a reservoir of water in each filter cell over said filter
cake or filter cakes, wherein said water stream is at a pressure gradient of at least 0.5 psi (3.4 kPa) over said
30 system pressure and a temperature in the range of from 38°C to 205°C;
(d) washing said filter cake with water for a period sufficient to reduce concentration of p-toluic acid to equal to or
less than 200 ppmw;
(e) transporting each said filter cell containing washed filter cake to a pressure release zone wherein said system
pressure is released to a range from atmospheric to about 90 psig (620 kPa) to reduce temperature of said filter
35 cake to a temperature equal to or less than 166°C; and
(f) discharging said washed filter cake comprising purified terephthalic acid from each said filter cell wherein con-
centration of p-toluic acid in said purified terephthalic acid is equal to or less than 200 ppmw.

Details of the Invention

40
In an embodiment of this invention, an alkyl aromatic, such as paraxylene and/or p-toluic acid, is oxidized in an
acetic acid medium with molecular oxygen in the presence of a catalyst system containing bromine and one or more
heavy metals such as cobalt, manganese and the like. Although this method is well-known in the art and is commercially
used, the oxidation reaction results in impurities which can be removed or rendered colorless to obtain a fiber-grade
45 terephthalic acid. The principal use of captive and non-captive terephthalic acid is and has been for the manufacture
of high molecular weight polyesters for fiber and film manufacture.
From U.S. Patent 3,584,039, it is known that fiber grade terephthalic acid can be prepared by purifying crude
terephthalic acid by means of a reduction procedure. The process is essentially comprised of treating an aqueous
solution of crude terephthalic acid with hydrogen in the presence of a supported or unsupported Group VIII metal
so catalyst wherein the metal and the support are insoluble in the solution under the working conditions. By this process,
intermediate oxidation products, such as 4-carboxybenzaldehyde (4-CBA) and other coloring impurities in terephthalic
acid are reduced and form removable products. Purified terephthalic acid is then recovered by crystallization and dried.
Although the above procedure has various advantages, problems remain in that the contamination of purified
terephthalic acid with p-toluic acid is a cooling rate dependent phenomenon rather than a temperature dependent
55 phenomenon. Flash temperature reduction occasioned by release of pressure operates to precipitate p-toluic acid from
the solution of purified terephthalic acid upon crystalline purified terephthalic acid. However, solubility of p-toluic acid
remains high in the aqueous medium at a temperature of from 38°C to 205°C.
Surprisingly, it has been found that positive displacement of the aqueous solution of p-toluic acid from a filter cake

4
 EP0 579 715B1

of crystalline purified terephthalic acid effectively displaces the p-toluic acid from contact with the purified terephthalic
acid by displacing the aqueous solution of p-toluic acid with water at high temperature and pressure. The pressure is
then released to an ambient atmospheric condition. The concentration of p-toluic acid retained in the crystalline purified
terephthalic acid thereupon has been found to be equal to or less than 200 ppmw.
5 In the process of the instant invention, the purified terephthalic acid crystals from a crystallizer in the aqueous
medium are filtered at a temperature of at least 38°C, preferably from 100°C to about 205°C at a pressure of at least
about 0.5 psig, preferably within the range of from 40 psig to 110 psig (275 - 758 kPa) to develop a filter cake.
The aqueous slurry containing crystals of purified terephthalic acid is introduced into a filter cell, or a series of filter
cells, physically situated to permit a filter cake to develop of a sufficiency and distribution to cover the area of the filter
10 cell to hinder or prevent the development of channeling of wash water. Suitably, a filter cake of at least 0.5 inch (1 .27
cm) in depth to 8 inches (20 cm), preferably at least 1 inch in depth (2.54 cm), more preferably 2 to 4 inches (5-10
cm) in depth is developed over the area of the filter cell. The aqueous mother liquor can be recovered and treated to
recover p-toluic acid and/or sent to waste treatment facilities.
Upon obtaining a suitable or preferred height of filter cake, 0.5 inch to 8 inches, the cake leaves the filtration zone
is and enters a washing zone where the cake is washed with a water stream at a pressure gradient to allow a reservoir
buildup of water over the filter cake to a suitable depth, preferably to a minimum depth of 0.25 inch (6.3 mm). A pressure
gradient of at least 0.5 psi over the system pressure, preferably from 5 psi to 65 psi over the system pressure, is
thereupon applied to the water stream to displace the aqueous solution of p-toluic acid from the filter cake in a positive
displacement method. The water-washed cake of purified terephthalic acid is thereupon subject to release of system
20 pressure to a pressure within the range of from atmospheric pressure to about 90 psig (101 - 620 kPa) with attendant
reduction of system temperature to a temperature equal to or less than about 166°C. The water-washed purified tereph-
thalic acid is thereupon dried under atmospheric pressure.
A minimum cake depth of purified terephthalic acid of at least 0.5 inch is suitable to obtain a filter cake of sufficient
compactness to furnish a wash vehicle, i.e. the filter cake, from which a solution containing a solute can be removed
25 efficiently by displacement washing. If cake depth is less than about 0.5 inch (1 .27 cm), retention of solution containing
a solute by the filter cake is increased significantly despite application of wash water at increased pressure. Because
of the loss of efficiency in displacement washing of the filter cake by water to remove a solution containing a dissolved
solute, a minimum filter cake depth of at least 0.5 inch (1 .27 cm), of purified terephthalic acid is preferred.
A minimum liquid height above the cake surface is required to ensure that displacement washing occurs. This
30 height must be sufficient to ensure that the cake surface is completely covered with liquid. If the cake surface is not
covered with water, bypassing of the wash liquor can occur without complete displacement of mother liquor from the
interior of the cake. Because of irregularities in the cake surface, a minimum liquid height of 0.25 inch (6.3 mm) is
preferred over the cake surface.
It has been found that positive displacement of an aqueous solution of p-toluic acid using water as the displacing
35 medium in a filtration cycle at high temperature and pressure permits an efficient exchange of the p-toluic acid solution
for a medium comprising water and recovery of the purified terephthalic acid from the aqueous component of the slurry
which contains soluble p-toluic acid. The positive displacement of the solution of p-toluic acid from the filter cake of
purified terephthalic acid at elevated temperature and pressure diminishes the co-crystallization of p-toluic acid with
the crystallization of purified terephthalic acid at a pressure equal to or less than 235 psig (1620 kPa) and a temperature
40 equal to or less than 205°C upon release of the system pressure and decrease of system temperature.
Because of the insolubility of p-toluic acid in water at temperatures below 38°C and pressures below 10 psig (68.9
kPa), typical filtration techniques are unsuitable to remove p-toluic acid from the filter cake. Although the solubility
problem can be partially overcome by filtration at elevated temperature and pressure, filtration and water washing are
typically less successful in removing p-toluic acid from crystalline purified terephthalic acid wherein a vacuum is used
45 or wherein pressure filtration is used without use of a method of plug flow washing or flooded water washing. Such
vacuum or pressure filtration procedures can result in the channeling of the cake and the water wash does not penetrate
the cake.
In the process of the instant invention it has been found that unexpected efficiencies of removal of p-toluic acid
can be obtained by pressure displacement washing of the filter cake comprising purified terephthalic acid. P-Toluic
so acid in purified terephthalic acid can be reduced to 200 ppmw, or less.
From an engineering standpoint, the added stages of the pressure filter allow the pressure to be decreased to
atmospheric pressure, thus alleviating problems caused by solids discharge to a dryer operating at atmospheric pres-
sure. In an embodiment of the process of the instant invention, a rotary valve can be used to decrease system pressure
to atmospheric pressure.
55 Utilization of added stages of pressure displacement washing can decrease the amount of water required to reduce
the level of p-toluic acid retained in the cake of purified terephthalic, as has been demonstrated by the reduction of
water required by utilization of added stages of positive displacement washing to reduce the amount of water required
to reduce the level of acetic acid retained from an aqueous solution of acetic acid.

5
 EP0 579 715B1

It is convenient therefore that a suitable number of stages of positive displacement washing be used to minimize
total water used in displacement washing to reduce need for downstream waste treatment facilities. Accordingly, for
the process of the instant invention for positive displacement of p-toluic acid from mother liquor retained in filter cake
of purified terephthalic acid to obtain a level equal to or less than 200 ppm in the cake by filtration, a multi-stage
5 displacement washing of the purified terephthalic acid can be used.
It is of course understood that a multi-stage displacement washing procedure can be replaced by a single stage
displacement washing procedure wherein the quantity of wash water is sufficient to obtain a level equal to or less than
200 ppm of p-toluic acid retained in the purified terephthalic acid. Additionally, a procedure of counter-current washing
can be useful if reduction of the amount of wash water is determined to be advantageous.
10 In the process of the instant invention, a p-toluic acid slurry containing crystals of purified terephthalic acid is
introduced into one or more of a series of filter cells physically situated to permit a filter cake of requisite thickness to
develop by passage of a stream of the slurry of purified terephthalic acid. Upon obtaining a minimum height of filter
cake, 0.5 to 8 inches, the cake leaves the filtration zone and enters a washing zone where the cake is washed with a
water stream. Pressure is applied thereupon to the water stream to displace the p-toluic acid in the mother liquor
is retained in the filter cake by positive pressure. Upon displacement of the water reservoir through the filter cake, the
filter cake is discharged from the filter by suitable means and the cycle is repeated. The ratio of wash area to cake
formation area is within the range of from about 1:20 to about 20:1 to reduce the level of p-toluic acid in the filter cake.
The system pressure is thereupon released and the washed filter cake is discharged from the filter.
Equipment for performing the requisite cycle can comprise a series of filter cells maintained in a suitable position
20 to permit a water flood to develop over the filter cells. Suitable equipment can comprise a rotary drum filter with multiple
filter cells, and fitted with means for discharging washed filter cake from the filter cells. Control means are required for
introducing a stream comprising purified terephthalic acid in a p-toluic acid solution to develop a filter cake to transport
the filter cake from the filtration zone to a washing zone where the filter cake is washed by a stream of water, wherein
the water is under pressure to cause positive displacement of the p-toluic acid in the mother liquor retained in the
25 purified terephthalic acid. The filter cake can be washed for as many times as required to develop a minimum concen-
tration of p-toluic acid in the filter cake before discharging the washed filter cake from the rotary drum filter.
A suitable rotary drum filter which can be adapted to the requirements of the instant invented process is a BHS-
FEST (™) pressure filter, BHS-WERK, Sonthofen, D-8972, Sonthofen, West Germany, although other filters which can
accomplish the required cycle of operation can be used, such as a belt filter from Pannevis, b.v, Utrecht, Holland, or
30 other suppliers.
In the operation of the BHS-FEST™ filter, a rotary drum contains a series of filter cells located on the periphery of
the rotating drum. As the drum rotates, the filter cells receive an aqueous slurry of purified terephthalic acid and soluble
p-toluic acid and a filter cake builds to a requisite depth. Upon rotation of the drum, the filter cake leaves the filtration
zone and enters the washing zone to build a reservoir of water over the filter cake to a required depth. The applied
35 pressure to the water reservoir forces the water through the filter cake to displace the p-toluic acid retained in the water
upon the crystals of purified terephthalic acid. Upon further rotation of the drum, the wash cycle can be repeated at
least one more time if necessary, after which the system pressure is released with attendant temperature decrease to
an ambient condition. The filter cake is thereupon charged from the drum by application of an inert gas under pressure.
A similar sequence of operations occurs with use of a belt filter.
40
Example I

The following example illustrates the process of the instant invention using a BHS-FEST (™) filter.
Slurry, containing 45% crystallized PTA solids and mother liquor, is fed to a BHS-FEST (™) rotary pressure filter
45 at 60 psig pressure, and 149°C temperature. A BHS-FEST (™) filter is employed to separate the solids from the mother
liquor, wash the solids, remove excess cake moisture, and discharge the solids at atmospheric pressure. The filter
housing is divided into five chambers to perform five different operations - filtration/cake formation, displacement wash,
cake drying, cake discharge, and filter cloth rinse. The filter drum, operating at speeds ranging from 0.5 to 2.0 rpm, is
divided into twenty filter cells. The total filter cloth area available on the drum is about 1.3 ft2. Slurry capacity is about
so 360, 720 and 1440 Ibs/hr flow rate when the filter operator is at 0.5, 1.0 and 2.0 rpm, respectively.
As the filter operates continuously, all of the operations - filtration/cake formation, displacement wash, cake drying/
discharge, and filter cloth rinse-occur simultaneously. The operation is described by illustrating the history of one filter
cell.
The filter cell rotates into the filtration/cake formation chamber. The feed slurry, containing about 45% PTA solids
55 and about 1,000 ppmw p-toluic acid, is pumped continuously into the chamber at about 60 psig pressure. As the filter
cell rotates through the chamber, the solids build up on the filter cloth to a 1 inch cake thickness. The mother liquor
passes through the filter cloth into an internal pipe in the filter. The pressure of the mother liquor in this internal pipe
ranges from about 30 to about 50 psig (206 - 344 kPa). The mother liquor is sent to p-toluic acid recovery facilities

6
 EP0 579 715B1

and/or waste treatment.

The filter cell, now containing a formed cake, leaves the filtration/cake formation chamber and rotates into the
displacement chamber. Clean water is pumped continuously into the chamber at a pressure of 60 psig (414 kPa) and
149°C. This useful temperature range for the clean water is 82°C to 149°C. This water, via the effectiveness of dis-
5 placement washing, effectively removes p-toluic acid from the filter cake. Wash water which has passed through the
cake is now at a pressure of 30 to 50 psig. This water is collected separately from the mother liquor and used elsewhere
in the PTA process.
The washed cake in the filter cell leaves the displacement wash chamber and enters the cake driving chamber.
Compressed inert gas, at a pressure of about 60 psig (41 3 kPa), is introduced continuously into the drying chamber
10 to remove excess water from the filter cake.
The filter cell then rotates from the drying chamber into the cake discharge chamber. In contrast to the other
described chambers, this chamber operates at ambient pressure. Because of the pressure drop from the cake drying
chamber to the cake discharge chamber, some additional moisture is flashed from the cake. The cake is then discharged
from the filter at a flow rate of about 190, 380, or 760 Ib/hr (42, 83 or 168 kg/h) for a filter speed of about 0.5, 1.0 or
is 2.0 rpm, respectively. The final cake has a p-toluic acid concentration of 200 ppmw or less on a dry-cake basis.
After discharging the cake, the filter cell is rinsed with water in the filter cloth rinse chamber to remove any traces
of undischarged cake. The filter cell then enters the filtration/cake formation chamber and repeats the process.
Data for relevant experiments are indicated in Table I. The wash ratio indicates the amount of clean water used
to displacement wash the cake from p-toluic acid, measured as a ratio of cake flow rate. The blow ratio indicates the
20 amount of compressed inert gas used to dry the cake prior to discharge, measured as a ratio of cake flow rate.

Table I
Example Fitter Wash Ratio Wash Blow Ratio Delta Form Cake P-Toluic
Number Speed lb water/lb Temp deg SCFH/lb Pressure Wetness Acid on
25 PTA C PTA psi wt% Cake, ppm
rpm
2 0.531 0.773 88 0.855 19 14.7 112
3 0.531 2.783 127 0.855 18 12.4 106
4 1.03 1.241 126 0.441 9 12.2 103
5 1.03 0.381 88 0.441 17 14.5 113
6 1.97 1.151 90 0.231 11 17.5 111
7 1.97 0.436 133 0.231 14 11.7 113
*SI conversions
35
Blow Ratio
SCFH/h/lb PTA 0.855 0.441 0.231
m3/h/kgPTA 0.0534 0.0277 0.0145

Delta Form Pressures

psi 19 18 9 17 11 14
kPa 130 124 62 117 75 96

Example 8

The following example illustrates the process of the instant invention using a beltfilter.
Slurry, containing 48% crystallized PTA solids and mother liquor, is fed to a pressurized beltfilter at a 780 Ibs/hr
flow rate, 90 psi (620 kPa) pressure, and 166°C temperature. The beltfilter performs operations in three zones - sep-
aration of solids from the mother liquor, displacement washing, and drying.
The slurry is fed to the first section of the belt, where the solids and mother liquor are separated. The solids form
a continuous 3 inch thick cake on the belt. The mother liquor filtrate passes through the filter cloth and is pumped either
to p-toluic acid recovery facilities and/or waste treatment.
The continuous cake is then conveyed into the displacement washing zone. This zone also operates at 90 psig
(620 kPa) and 166°C. In this zone, clean water is fed above the cake at a flow rate which maintains a liquid level above

7
 EP0 579 715B1

the cake.
After the displacement washing zone, the continuous cake enters the cake drying zone. The excess water is
allowed to drain from the cake and inert gas is introduced to further remove the moisture. This zone also operates at
90 psig (620 kPa) and 166 °C.
5 The dried cake, now containing only 200 ppmw or less p-toluic acid on a dry basis, is discharged from the belt into
a pressure reducing device(s), such as a sealed screw conveyor or a series of rotary valves. The PTA cake, now at
atmospheric pressure, is then transferred to an atmospheric dryer.

10 Claims

1. A process for the preparation of purified terephthalic acid containing p-toluic acid present in a concentration equal
to or less than 200 parts per million by weight (ppmw) which process comprises:

is (a) introducing into a filter cell or a series of filter cells in a filtration zone at a temperature within the range of
from 38°C to 205°C at a system pressure of from atmospheric to 235 psig (101 - 1620 kPa) an aqueous slurry
comprising purified terephthalic acid present as crystals and p-toluic acid present as an aqueous solution and
as a co-crystallized form with crystals of said purified terephthalic acid, said filter cell or series of filter cells
maintained in suitable position whereby each filter cell develops a filter cake or filter cakes upon introduction
20 of said slurry into each said cell;
(b) transporting each said filter cell containing said filter cake from said filter zone to a wash zone;
(c) introducing a water stream into each said filter cell to form a reservoir of water in each filter cell over said
filter cake or filter cakes, wherein said water stream is at a pressure gradient of at least 0.5 psi (3.4 kPa) over
said system pressure and a temperature in the range of from 38°C to 205°C;
25 (d) washing said filter cake with water for a period sufficient to reduce concentration of p-toluic acid to equal
to or less than 200 ppmw;
(e) transporting each said filter cell containing washed filter cake to a pressure release zone wherein said
system pressure is released to a range from atmospheric to 90 psig (620 kPa) to reduce temperature of said
filter cake to a temperature equal to or less than 166°C; and
30 (f) discharging said washed filter cake comprising purified terephthalic acid from each said filter cell wherein
concentration of p-toluic acid in said purified terephthalic acid is equal to or less than 200 ppmw.

2. The process of Claim 1 wherein said filter cake is at least 0.5 inches (12 mm) in depth.

35 3. The process of Claim 1 wherein said reservoir of water over said filter cake is at least 0.25 inches (6.35 mm) in depth.

4. The process of Claim 1 wherein said water from washing said filter cake is recovered as wash water and is recycled
upstream to slurry crude terephthalic acid or discarded to waste treatment facilities.

40 5. The process of Claim 1 wherein said water stream is at a pressure within the range of from 0.5 psi to 65 psi (3.4
- 448 kPa) over said system pressure.

6. The process of Claim 1 wherein said water stream is at a pressure within the range of from 5 psi to 65 psi (34 -
448 kPa) over said system pressure.
45
7. The pressure of Claim 1 wherein depth of said filter cake is in the range of from 0.5 inches to 8 inches (12.7 to
203 mm).

8. The process of Claim 1 wherein depth of said filter cake is in the range of from 1 inch to 4 inches (25.4 to 101 mm).
50
9. The process of Claim 1 wherein depth of said filter cake is in the range of from 2 inches to 4 inches (50.8 to 101 mm).

10. The process of Claim 1 wherein said system pressure is in the range of from 0.5 psig to 110 psig (34 - 758 kPa).

55 11. The process of Claim 1 wherein said system pressure is in the range of from 40 psig to 65 psig (275 - 448 kPa).

12. The process of Claim 1 wherein said temperature of said water stream is in the range of from 100°C to 205°C.

8
 EP0 579 715B1

Patentanspriiche

1. Verfahren zur Herstellung von gereinigter Terephthalsaure, welche p-Toluylsaure enthalt, die in einer Konzentration
von gleich oder weniger als 200 Gewichtsteilen auf eine Million (ppmw) vorhanden ist, welches Verfahren die
5 folgenden Schritte umfaBt:

(a) Einleiten in eine Filterzelle oder eine Reihe an Filterzellen in eine Filtrationszone bei einer Temperatur
innerhalb des Bereichs von 38°C bis 205°C bei einem Systemdruck von Atmospharendruck bis 235 psig (101
- 1620 kPa) einer waBrigen Aufschlammung, welche als Kristalle vorkommende gereinigte Terephthalsaure
10 und als eine waBrige Losung und als mit den Kristallen der gereinigten Terephthalsaure in cokristallisierter
Form vorkommende p-Toluylsaure enthalt, wobei die Filterzelle oder die Reihe an Filterzellen in einer geeig-
neten Position gehalten werden, wobei jede Filterzelle beim Einleiten der Aufschlammung in jede Filterzelle
einen oder mehrere Filterkuchen entwickelt;

is (b) Transportieren jeder Filterzelle, welche den Filterkuchen enthalt, von der Filtrationszone zu einer Wasch-
zone;

(c) Einleiten eines Wasserstroms in jede Filterzelle, urn in jeder Filterzelle iiber dem oder den Filterkuchen
ein Wasserreservoir auszubilden, wobei der Wasserstrom einen Druckgradienten von mindestens 0,5 psi (3,4
20 kPa) iiber dem Systemdruck und eine Temperatur im Bereich von 38°C bis 205°C besitzt;

(d) Waschen des Filterkuchens mit Wasser wahrend eines Zeitraums, der ausreicht, die Konzentration an p-
Toluylsaure auf gleich oder weniger als 200 ppmw zu reduzieren;

25 (e) Transportieren jeder Filterzelle, welche den gewaschenen Filterkuchen enthalt, zu einer Druckentspan-
nungszone, in welcher der Systemdruck auf einen Bereich von Atmospharendruck bis 90 psig (620 kPa) ent-
spannt wird, urn die Temperatur des Filterkuchens auf eine Temperatur von gleich oder weniger als 166°C zu
verringern; und

30 (f) Entnehmen des gewaschenen Filterkuchens, welcher gereinigte Terephthalsaure enthalt, aus jeder Filter-
zelle, wobei die Konzentration an p-Toluylsaure in der gereinigten Terephthalsaure gleich oder weniger als
200 ppmw betragt.

2. Verfahren gemaB Anspruch 1, wobei der Filterkuchen eine Tiefe von mindestens 0,5 inch (12 mm) besitzt.
35
3. Verfahren gemaB Anspruch 1, wobei das Reservoir an Wasser iiber dem Filterkuchen eine Tiefe von mindestens
0,25 inch (6,35 mm) besitzt.

4. Verfahren gemaB Anspruch 1, wobei das Wasser vom Waschen des Filterkuchens als Waschwasser riickgewon-
40 nen wird und stromaufwarts zum Aufschlammen von Roh-Terephthalsaure riickgefiihrtoderzu Abfallbehandlungs-
anlagen ausgesondert wird.

5. Verfahren gemaB Anspruch 1, wobei der Wasserstrom einen Druck innerhalb des Bereichs von 0,5 psi bis 65 psi
(3,4 - 448 kPa) iiber dem Systemdruck besitzt.
45
6. Verfahren gemaB Anspruch 1, wobei der Wasserstrom einen Druck innerhalb des Bereichs von 5 psi bis 65 psi
(34 - 448 kPa) iiber dem Systemdruck besitzt.

7. Verfahren gemaB Anspruch 1, wobei der Filterkuchen im Bereich von 0,5 inch bis 8 inch (12,7 bis 203 mm) liegt.
50
8. Verfahren gemaB Anspruch 1, wobei der Filterkuchen im Bereich von 1 inch bis 4 inch (25,4 bis 101 mm) liegt.

9. Verfahren gemaB Anspruch 1, wobei der Filterkuchen im Bereich von 2 inch bis 4 inch (50,8 bis 101 mm) liegt.

55 10. Verfahren gemaB Anspruch 1, wobei der Systemdruck im Bereich von 0,5 psig bis 110 psig (3,4 - 758 kPa) liegt.

11. Verfahren gemaB Anspruch 1, wobei der Systemdruck im Bereich von 40 psig bis 65 psig (275 - 448 kPa) liegt.

9
 EP0 579 715B1

12. Verfahren gema(3 Anspruch 1, wobei die Temperatur des Wasserstroms im Bereich von 100°C bis 205°C liegt.

Revendications
5
1. Procede de preparation d'acide terephtalique purifie contenant de I'acide p-toluidique present a une concentration
egale ou inferieure a 200 parties par million, en poids (ppmp), lequel procede comprend :

(a) I'introduction dans une cellule filtrante ou dans une serie de cellules filtrantes, dans une zone de filtration,
10 a une temperature comprise dans I'intervalle 38°C-205°C, a un systeme de pression allant de la pression
atmospherique a 235 psig (101 a 1.620 kPa), d'une suspension aqueuse contenant de I'acide terephtalique
present sous forme de cristaux, et de I'acide p-toluidique present sous la forme d'une solution aqueuse, et
sous une forme co-cristallisee avec des cristaux dudit acide terephtalique purifie, ladite cellule filtrante ou
serie de cellules de filtrantes etant maintenue dans une position adequate grace a laquelle chaque cellule
is filtrante produit un (ou des) gateau(x) de filtration lors de I'introduction de ladite suspension dans chacune
desdites cellules ;
(b) le transport de chacune desdites cellules filtrantes contenant ledit gateau de filtration, depuis ladite zone
de filtration, vers une zone de lavage ;
(c) I'introduction d'un courant d'eau dans chacune desdites cellules filtrantes de facon a former un reservoir
20 d'eau dans chaque cellule filtrante, sur le (ou les) gateau(x) de filtration, dans laquelle ledit courant d'eau est
a un gradient de pression d'au moins 0,5 psi (3,4 kPa) au dessus dudit systeme de pression, et a une tempe-
rature comprise entre 38°C et 205°C ;
(d) le lavage a I'eau dudit gateau de filtration pendant une periode de temps suffisante pour reduire la con-
centration de I'acide p-toluidique a une valeur egale ou inferieure a 200 ppmp ;
25 (e) le transport de chacune desdites cellules filtrantes contenant ledit gateau de filtration lave, vers une zone
de relachement de pression, dans laquelle ledit systeme de pression est ramene dans un intervalle compris
entre la pression atmospherique et 90 psig (620 kPa), pour reduire la temperature dudit gateau de filtration a
une temperature egale ou inferieure a 166°C ; et
(f) le dechargement dudit gateau de filtration lave contenant I'acide terephtalique purifie, provenant de chacune
30 desdites cellules filtrantes, dans lequel la concentration de I'acide p-toluidique dans ledit acide terephtalique
purifie est egale ou inferieure a 200 ppmp.

2. Procede selon la revendication 1, dans lequel ledit gateau de filtration, a une profondeur d'au moins 0,5 pouce
(12 mm).
35
3. Procede selon la revendication 1, dans lequel ledit reservoir d'eau sur ledit gateau de filtration, a une profondeur
d'au moins 0,25 pouce (6,35 mm).

4. Procede selon la revendication 1, dans lequel ladite eau provenant du lavage dudit gateau de filtration, est recu-
40 peree sous forme d'eau de lavage, et est recyclee en amont de la suspension d'acide terephtalique brut, ou rejetee
vers la station de traitement des eaux usees.

5. Procede selon la revendication 1, dans lequel ledit courant d'eau est a une pression comprise dans I'intervalle
0,5-65 psi (3,4 a 448 kPa) au dessus dudit systeme de pression.
45
6. Procede selon la revendication 1, dans lequel ledit courant d'eau est a une pression comprise dans I'intervalle
5-65 psi (34 a 448 kPa) au dessus dudit systeme de pression.

7. Procede selon la revendication 1, dans lequel la profondeur dudit gateau de filtration est comprise entre 0,5 pouce
50 et 8 pouces (12,7 a 203 mm).

8. Procede selon la revendication 1, dans lequel la profondeur dudit gateau de filtration est comprise entre 1 pouce
et 4 pouces (25,4 a 101 mm).

55 9. Procede selon la revendication 1, dans lequel la profondeur dudit gateau de filtration est comprise entre 2 pouces
et 4 pouces (50,8 a 101 mm).

10. Procede selon la revendication 1, dans lequel ledit systeme de pression est dans I'intervalle compris entre 0,5

10
 EP0 579 715B1

psig et 110 psig (3,4 et 758 kPa).

Procede selon la revendication 1, dans lequel ledit systeme de pression est dans I'intervalle compris entre 40 psig
et 110 psig (275 et 758 kPa).

Procede selon la revendication 1, dans lequel ladite temperature dudit courant d'eau est comprise entre 100°C et
205°C.

11