&    

Europäisches Patentamt
(19) European Patent Office

Office européen des brevets (11) EP 1 030 829 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C07C 51/42 (2006.01) C07C 51/43 (2006.01)
12.07.2006 Bulletin 2006/28
(86) International application number:
(21) Application number: 98956315.0 PCT/US1998/022942

(22) Date of filing: 29.10.1998 (87) International publication number:

WO 1999/023055 (14.05.1999 Gazette 1999/19)

(54) METHOD AND APPARATUS FOR PREPARING PURIFIED TEREPHTHALIC ACID

VERFAHREN UND VORRICHTUNG ZUR HERSTELLUNG GEREINIGTER TEREPHTHALSÄURE
PROCEDE ET DISPOSITIF DE PREPARATION D’ACIDE TEREPHTALIQUE PURIFIE

(84) Designated Contracting States: • LAMSHING, Wiston

DE ES FR GB IT Katy, TX 77450 (US)

(30) Priority: 31.10.1997 US 962030 (74) Representative: Nash, David Allan

HASELTINE LAKE,
(43) Date of publication of application: Redcliff Quay
30.08.2000 Bulletin 2000/35 120 Redcliff Street
Bristol BS1 6HU (GB)
(73) Proprietor: GTC Technology, Inc
Houston, Texas 77077 (US) (56) References cited:
WO-A-96/40612 GB-A- 818 211
(72) Inventors: US-A- 3 931 305 US-A- 4 380 662
• LEE, Fu-Ming US-A- 5 159 109 US-A- 5 344 969
Katy, TX 77450 (US)
EP 1 030 829 B1

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
a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art.
99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 1 030 829 B1

Description

[0001] The present invention relates to a method for preparing purified terephthalic acid. It also relates to methods for
purifying crude terephthalic acid to produce a purified terephthalic acid product which is a useful starting material for
5 producing polyester resin, which is in turn useful for the production of fibers, film, plastic bottles, and polyester resin
structures, often reinforced by other materials such as glass fiber.

BACKGROUND OF THE INVENTION

10 [0002] Purified terephthalic acid (PTA) is a starting material for the formation of polyester resin, which is, in turn, used
to make many materials of commerce having a variety of utilities. Purified terephthalic acid is formed from "crude"
terephthalic acid conventionally by a number of purification methods, often with the aid of catalysts. The methods for
purifying crude terephthalic acid heretofore available are not completely satisfactory either from an engineering stand-
point, or from an economic standpoint, yet the purity of the purified terephthalic acid is an important determinant of the
15 satisfactoriness of the processes by which the polyester resin is formed.
[0003] A number of reaction systems are known for forming crude terephthalic acid from a variety of starting materials.
The purification aspects of the present invention may be used with substantially any of these reaction systems, but in
accordance with the invention it is preferred that a reaction system involving the oxidation of paraxylene (p-xylene) be
employed, and the use of such a synthesis system forms a part of the present invention.
20 [0004] The problems of existing and prior systems for producing purified terephthalic acid center around the difficulties
in running the reaction systems to produce good yields of crude terephthalic acid economically, compounded by the
difficulties of refining the crude terephthalic acid to eliminate impurities and unwanted components to produce purified
terephthalic acid of a quality suitable as a starting material for producing polyester. Concomitant problems in prior systems
include the high capital investment required for PTA plants, the severity of operating conditions of prior processes, both
25 for the production of crude terephthalic acid, and for its purification, and the need for handling catalyst systems and
reaction solvents, as well as reaction byproducts in a way such that environmental problems are minimized, and loss of
material is also controlled.
[0005] One factor of importance in the production of purified terephthalic acid is the formation of crystals having a size
and shape giving them good handling characteristics, washability and filterability in the PTA manufacturing process, and
30 easier handling and better processability in the polyester process.

SUMMARY OF THE INVENTION

[0006] In accordance with the present invention there is provided a method for producing purified terephthalic acid.
35 In one aspect, the method includes the production of crude terephthalic acid by the oxidation of p-xylene. The oxidation
step produces not only terephthalic acid, but p-toluic acid and 4-carboxybenzaldehyde (4-CBA) as oxidation intermediates
and other impurities from side reactions. The product produced in the oxidation step is a liquid dispersion containing
unreacted starting materials, solvents, if any have been used, oxidation intermediate products, particularly those just
mentioned, and other materials which are not desired in the sought-for purified terephthalic acid. The oxidation step of
40 the present invention is so conducted that the conversion to crude terephthalic acid should be at least about 30% by
weight per pass of p-xylene.
[0007] In further accordance with the invention, the crude terephthalic acid from the oxidizer is first grossly separated
from the other materials from the oxidizer and then it is re-dissolved in a selective crystallization solvent and, optionally,
one or more additional solvents of the invention discussed below. The re-dissolved crude terephthalic acid is then
45 crystallized out of the selective crystallization solvent and additional solvents of the invention in one or, preferably, two
crystallization stages. Provision is made to separate out the crystallized and progressively purified terephthalic acid from
the solvents of the invention, and the filter cake of purified terephthalic acid ultimately obtained is washed with other
solvents of the invention and dried or, alternatively, dried (e.g., using a vacuum dryer), sent to a soaker to remove residual
solvent, and ultimately filtered and dried for storage or for further processing.
50 [0008] Also in accordance with the present invention, any crude TA produced by existing and prior oxidation systems
may be purified. An important advantage of the present invention is that it can process a higher content of oxidation
intermediates, like 4CBA, making it possible to relax oxidation conditions, which reduces p-xylene and acetic acid burning
losses.
[0009] Also in accordance with the present invention, improvements in the crystallization processes just outlined are
55 provided which produce larger, globular crystals that are thought to contain little or no salt of the kind which may tend
to form when the selective crystallization solvent(s) is an organic base. The larger non-salt crystals have the advantage
that they resist destruction by water rinsing and are otherwise easier to recover solvent from, as well as being easier to
rinse for removal of residual impurities.

2
 EP 1 030 829 B1

[0010] The improvements in the crystallization processes comprise flashing solvent from the crystallizing acid by
reducing the pressure on it, preferably both prior to and during the cooling of the saturated acid solution. It is further
preferred to reduce the pressure progressively to lower levels, either in a batch or continuous flow crystallizer, and this
may be arranged to be performed stepwise or continuously. Still further, heat may be added to the crystallizing acid
5 during the application of reduced pressure to increase the rate and quantity of solvent removal, care being taken, however,
to avoid materially increasing the temperature of the crystallizing acid to cause redissolution of the acid and consequent
waste of energy.
[0011] As was mentioned above, in accordance with the invention, crystallization may be performed in multiple stages;
when this form of the invention is used, it is preferred that some or all of the crystallization improvement techniques just
10 discussed be utilized in the second or last stage, although the techniques may also be used to advantage in the first stage.
[0012] Further in accordance with the invention, co-solvents may be used for purifying terephthalic acid by flash
crystallization. A co-solvent having a lower boiling point than the solvent can be used to reduce the flashing temperature
for crystallization and hence the dissolution temperature. With a lower flashing temperature, crystallization can be carried
out under a lower degree of vacuum.
15 [0013] The co-solvents include water, C1 to C5 alcohols, such as methanol or ethanol, C5 to C10 hydrocarbons, such
as p-xylene, and C1 to C10 organic acids, such as formic acid or acetic acid. It is thus possible to include 1 to 50% inert
solvents having boiling points ranging from 25 to 200°C as the co-solvents.
[0014] The invention also contemplates that steps are included to reclaim and recycle the solvents of the invention at
each stage of crystallization and washing, including recycle of some of the recovered materials to the oxidizer. Steps
20 are also taken to closely control the delivery of any objectionable materials to the environment.
[0015] In an important aspect, the present invention is based on several discoveries relating to solvents which are
effective to bring about the purification of crude terephthalic acid through crystallization and separation steps. These
discoveries may be summarized in several ways as follows.
[0016] The selective crystallization solvents useful in the practice of the present invention include those in which (a)
25 the impurities desired to be separated from terephthalic acid to purify it are relatively more soluble in the solvent than is
the terephthalic acid at substantially every temperature within the desired range of temperatures at which the solvent
containing terephthalic acid is to be handled, and (b) the terephthalic acid is more soluble at an elevated temperature
and less soluble at a lower or reduced temperature. It is to be understood that the term "selective crystallization solvent"
is intended to mean solvents useful in the selective crystallization of terephthalic acid as described above and as described
30 in greater detail below and as shown in FIGS. 1 and 2.
[0017] In this connection it should be noted that U.S. Patent No. 3,465,035 mentions that certain organic solvents
(pyridine, dimethyl sulfoxides, dimethyl foramide, and the like) have been used to purify terephthalic acid, but that they
suffer from being unstable in air and easily form addition products with terephthalic acid. This same patent, along with
several others, also teaches the use of acetic acid and water as purification solvents for terephthalic acid. By contrast,
35 the selective crystallization solvents according to the present invention are (a) non-aqueous, (b) non-corrosive, and (c)
essentially non-reactive with terephthalic acid and do not include those prior practices just described. Specifically, water,
acetic (and other alkyl) acid, and the above-mentioned organic solvents are excluded from the selective crystallization
solvents which are contemplated by the present invention.
[0018] In accordance with the invention, the primary preferred selective crystallization solvents are N-methyl pyrro-
40 lidone (NMP) and N,N-dimethyl acetamide (DMAC), for the several reasons discussed below, and for their superior
performance. U.S. Patent 2,949,483, dated August 16, 1960 to Ham, and WO9640612 disclose NMP used to crystallize
terephthalic acid, but does not use the same crystallization temperature range as is preferred in the present invention.
Nor does it suggest flash crystallization or its advantageous results. Tr. Vses. Nauch.-Issled. Proekt. Inst. Monomerov
(1970), 2(2), 26-32; From: Ref. Zh., Khim. 1971, Abstr. No. 1N166; V.N. Kulakov, et al.; entitled "Purification of Aromatic
45 Dicarboxylic Acids Obtained by Liquid-Phase Oxidation of Dialkyl Derivatives of Aromatic Hydrocarbons," very briefly
mentions NMP as a solvent, but says nothing about dissolution or crystallization temperatures or flash crystallization.
[0019] N-methyl pyrrolidone (NMP) and N,N-dimethyl acetamide (DMAC) are the preferred selective crystallization
solvents for the practice of the invention. These solvents are non-aqueous, thermally stable, non-toxic (environmentally
safe), non-corrosive, and commercially available. NMP is the most preferred selective crystallization solvent for the
50 practice of the present invention, because its solubility versus temperature curve for terephthalic acid slopes upwardly
and to the right, which means that terephthalic acid can be dissolved in it at elevated temperatures, and precipitated or
crystallized from it at lower temperatures.
[0020] Although NMP is the most preferred selective crystallization solvent, it is to be understood that DMAC exhibits
similar desirable characteristics and that, in accordance with the present invention, other preferred selective crystallization
55 solvents for purification of crude terephthalic acid can be selected from various polar organic solvents including, but not
intended to be limited to, N-alkyl-2-pyrrolidone (such as N-ethyl pyrrolidone), N-mercaptoalkyl-2-pyrrolidone (such as
N-mercaptoethyl-2-pyrrolidone), N-alkyl-2-thiopyrrolidone (such as N-methyl-2-thiopyrrolidone), and N-hydroxyalkyl-2-
pyrrolidone (such as N-hydroxyethyl-2-pyrrolidone), 1,5-dimethyl pyrrolidone, N-methyl piperidone, N-methyl caprol-

3
 EP 1 030 829 B1

actam, N,N-dimethyl formamide, and N-formyl piperidine, and the like, and mixtures thereof. Still other selective crys-
tallization solvents contemplated by the present invention include, but are not intended to be limited to, sulfolane, methyl
sulfolane, the sulfones, the morpholines (such as, morpholine and N-formyl morpholine), the carbitols, C1 to C12 alcohols,
the ethers, the amines, the amides, and the esters, and the like, and mixtures thereof.
5 [0021] It is preferred that the desired selective crystallization solvent be used in a multi-stage crystallization process
in combination with one or more additional solvents, preferably two such additional solvents, particularly where the crude
terephthalic acid is less than about 98% pure. Preferably, a wash solvent, such as water, p-xylene, acetone, methyl
ethyl ketone (MEK) or methanol is used in the washing of the initial filter cake obtained from the first separation of crude
terephthalic acid from other materials issuing from the oxidizer. In addition, a displacement solvent having a low boiling
10 point, such as, but not intended to be limited to, water, methanol, acetone, MEK may be used. Preferably, water is used
as the displacement solvent in association with the third filter following the second crystallization stage in the preferred
process. The desired displacement solvent displaces the selective crystallization solvent from the resulting filter cake,
whereby substantially only the displacement solvent is present during the soaking process. The soaking process is
preferred to eliminate any possible residual solvent trapped in the TA crystals before the product is subjected to the final
15 filtration and drying steps.
[0022] As described above, NMP and DMAC are the preferred selective crystallization solvents for the practice of the
invention. They are non-aqueous, thermally stable, non-toxic (environmentally safe), non-corrosive, and commercially
available. NMP is a preferred selective crystallization solvent for the practice of the present invention, because, among
other things, its solubility versus temperature curve for terephthalic acid slopes upwardly and to the right, which means
20 that terephthalic acid can be dissolved in it at elevated temperatures, and precipitated or crystallized from it at lower
temperatures. However, the solubility versus temperature curve for terephthalic acid is of a much milder slope than the
solubility curves in NMP for other materials sought to be separated from crude terephthalic acid, such as benzoic acid,
4-carboxybenzaldehyde (4-CBA), and p-toluic acid. As a consequence, when crude terephthalic acid, containing or
associated with unreacted starting materials, solvents (if any), and oxidation intermediate products, such as those
25 mentioned above, or other undesired materials, is dissolved in NMP or DMAC at an elevated temperature, substantially
all the materials are dissolved or at least highly dispersed. Then upon removal of heat and pressure and subsequent
cooling of the NMP or DMAC solution of such dissolved materials, the pure terephthalic acid preferentially crystallizes
out, while the other more soluble materials which may be regarded as impurities for the present purposes remain in
solution in NMP or DMAC. A separation is thus effected between purified terephthalic acid and its associated impurities.
30 NMP or DMAC may be stripped of the impurities in a reclaiming column and recycled into the process, while the impurities
may be recycled to the oxidizer step or otherwise disposed of.
[0023] In accordance with a preferred form of the invention, a method is provided for purifying crude terephthalic acid
from a liquid dispersion thereof also containing impurities selected from unreacted starting materials, solvents, products
of side reactions and/or other undesired materials. It includes preparing first stage purified terephthalic acid from said
35 crude terephthalic acid and redissolving the first stage purified terephthalic acid in a selective crystallization solvent to
form a solution. Second stage purified terephthalic acid is crystallized from the solution by reducing the temperature and
pressure sufficient to flash evaporate solvent from the terephthalic acid of the solution but without cooling the solution
below 50°C. Second stage purified terephthalic acid is then separated from the solution, and the separated second stage
purified terephthalic acid is washed with water. The washed separated second stage purified terephthalic acid is soaked
40 in water between 150°C and 300°C, preferably between 180°C and 250°C, and the water soaked second stage purified
terephthalic acid is then filtered and dried.
[0024] If desired, the terephthalic solution is held from 15 to 60 minutes, preferably 20 to 40 minutes, following the
reduction of temperature and prior to separating the second stage purified terephthalic acid therefrom. Also, the washing
of purified terephthalic acid may be done between one and three times. Similarly, the operation of reducing the temperature
45 and pressure to flash evaporate solvent may be performed stage-wise, in from two to six stages, preferably two to four
stages. Advantageously, the proportion of solvent flash evaporated in the first evaporation stage is restricted to increase
final crystal size.
[0025] In further accordance with the invention, a method is provided for purifying crude terephthalic acid from a liquid
dispersion thereof also containing impurities selected from unreacted starting materials, solvents, products of side re-
50 actions and/or other undesired materials. The method includes filtering the dispersion to form a crude terephthalic acid
filter cake, dissolving the filter cake in a selective crystallization solvent at a temperature above 60°C to form a solution,
crystallizing purified terephthalic acid from the solution by reducing the temperature and/or pressure of said solution but
not below 50 °C, separating said crystallized purified terephthalic acid from the solution, washing the separated purified
terephthalic acid with water, soaking the washed separated purified terephthalic acid with water at 150-300°C, preferably
55 between 180-250°C, and filtering and drying the water soaked purified terephthalic acid.
[0026] In accordance with another aspect of the invention, a method is provided for purifying crude terephthalic acid
from a liquid dispersion thereof also containing impurities selected from unreacted starting materials, solvents, products
of side reactions and/or other undesired materials which includes filtering the dispersion to form a crude terephthalic

4
 EP 1 030 829 B1

acid filter cake, dissolving the filter cake in a selective crystallization solvent at a temperature above 50°C to form a
solution, crystallizing purified terephthalic acid from the solution by reducing the temperature and/or pressure thereof,
separating the crystallized purified terephthalic acid from the solution, redissolving the separated purified terephthalic
acid in a selective crystallization solvent to form a second solution, crystallizing second stage purified terephthalic acid
5 from the second solution by reducing the temperature and pressure sufficient to flash evaporate solvent from the tereph-
thalic acid of the second solution but without cooling that solution below 50°C, and separating the second stage purified
terephthalic acid from the second solution.
[0027] Still another embodiment of the invention includes a method for purifying crude terephthalic acid from a liquid
dispersion thereof also containing impurities selected from unreacted starting materials, solvents, products of side re-
10 actions and/or other undesired materials by filtering the dispersion to form a crude terephthalic acid filter cake, dissolving
the filter cake in a selective crystallization solvent at a temperature above 50°C to form a solution, crystallizing purified
terephthalic acid from the solution by reducing the temperature and/or pressure thereof, separating the crystallized
purified terephthalic acid from the solution, redissolving the separated purified terephthalic acid in a selective crystalli-
zation solvent to form a second solution, crystallizing second stage purified terephthalic acid from the second solution
15 by reducing the temperature and pressure sufficient to flash evaporate solvent from the terephthalic acid of the second
solution but without cooling said solution below 50°C, separating the second stage purified terephthalic acid from the
second solution, washing the separated second stage purified terephthalic acid with water, soaking the washed separated
second stage purified terephthalic acid with water at 150-300°C, preferably between 180-250°C, and filtering and drying
the water soaked second stage purified terephthalic acid.
20 [0028] From the foregoing, it can be seen that an object of the present invention to provide an improved method and
apparatus for producing purified terephthalic acid of a purity desired for use in forming polyester resin and other products,
at an economically attractive rate, and at operating conditions of reduced severity which require a lower capital investment
and simplified processing. The manner in which these and other objects of the invention are attained may be learned
by consideration of the detailed description of the invention which follows, together with the accompanying drawings.
25
BRIEF DESCRIPTION OF THE DRAWINGS

[0029] A more complete understanding of the method and apparatus of the present invention may be obtained by
reference to the following Detailed Description when taken in conjunction with the accompanying Drawings wherein:
30
FIGS. 1 and 2 are plots of solubility versus temperature curves for terephthalic acid and for impurities or side reaction
products commonly associated with crude terephthalic acid in NMP and DMAC, respectively;
FIG. 3 is a plot of pH versus water concentration for NMP, DMAC, and NMP plus salt crystals;
FIG. 4 is a plot of pH versus TPA/solvent weight ratio;
35 FIG. 5 is a plot of the solubility of TPA in water against temperature with flash points for a certain prior art process
indicated;
FIG. 6 shows the particle size distribution obtained by a flash process in accordance with the invention;
FIG. 7 is a plot of flash profiles for various flashing processes;
FIG. 8 shows the cooling curves for various processes, both flash and cooling type;
40 FIG. 9 is a simplified elevational diagram of a crystallizer which may be used in the practice of the invention; and
FIG. 10 is a process block diagram for a preferred process of the invention.

DETAILED DESCRIPTION OF EMBODIMENTS

45 I. Process Description

[0030] The present invention relates to the development of a new PTA manufacturing technology. Compared to the
current widely used PTA technology, this technology provides a lower capital investment in new PTA plant construction,
as well as lower costs of plant operation. It also provides means for current DMT plants to co-produce PTA, to strengthen
50 their competitiveness against newer PTA plants.

Process Summary

[0031] The success of this process is based on the development of a low pressure, low temperature, non-aqueous,
55 highly selective crystallization technology. The crystallization technology can purify the crude terephthalic acid (TA) with
purity as low as from between about 70% (from the oxidizer) to about 98+% in the first-stage crystallizer, and to about
99.99+% in the second-stage crystallizer. This allows the TA oxidizer to be operated at much lower severity than those
of widely used prior art processes. The selective crystallization solvent used in the crystallization process is non-aqueous,

5
 EP 1 030 829 B1

thermally stable, non-toxic (environmentally safe), non-corrosive, and commercially available.

[0032] When carrying out the method according to the present invention, employing NMP or DMAC as the selective
crystallization solvent, the present inventors have demonstrated TA purity levels of up to 99.9+wt% after a first crystal-
lization process, and up to 99.99+wt% after a second crystallization process. In particular, Table 1 illustrates the recovery
5 of 99.95 wt% pure TA after the first crystallization process and 99.997 wt% pure TA after the second crystallization
process, from crude TA (89.89 wt% TA).

10

15

20

25

30

35

40 [0033] Table 2 illustrates the recovery of 99.90wt% pure TA after the first crystallization process and 99.9933wt%
pure TA after the second crystallization process from crude TA (89.89wt% TA) by increasing both the saturation tem-
perature and the crystallization temperature.

45

50

55

6
 EP 1 030 829 B1

10

15

20

25

30

Table 3 illustrates the recovery of 99.9960wt% pure TA (single crystallization process) from crude TA (98.99wt% TA).
35 In addition, each of benzoic, p-Toluic, 4-CBA, MMT and other impurities were at less than 10ppm.

40

45

50

55

7
 EP 1 030 829 B1

10

15

20

25

[0034] Table 4 illustrates the recovery of 99.63wt% pure TA (single crystallization process) from crude TA (83.91wt%
TA) on a large scale basis.

30

35

40

45

50

55 [0035] Table 5 illustrates the recovery of 99.92wt% pure TA (single crystallization process) from crude TA (79.79wt%
TA) on a large scale basis.

8
 EP 1 030 829 B1

10

15

20

25

[0036] Table 6 illustrates the recovery of 99.15wt% pure TA (single crystallization process) from crude TA (83.90wt%
TA) on a large scale basis at a higher saturation temperature of 190°C.

30

35

40

45

50

55
[0037] Table 7 illustrates the recovery of 99.9915wt% pure TA from crude TA (98.50wt% TA) on a large scale basis.
The supersaturation of the crystallization mixture resulted in the formation of substantially larger TA crystals than those
crystals resulting from the processes summarized above. As would be understood by one skilled in the art, the sizes of

9
 EP 1 030 829 B1

TA crystals are an important consideration with respect to separation thereof from solvents and impurities.

10

15

20

25

[0038] Table 8 demonstrates the recovery of 99.45 wt% pure TPA (single crystallization process) from crude TPA
30 (82.92 wt% TPA), using N,N-dimethyl acetamide (DMAC) as the crystallization solvent. The 4-CBA content was reduced
from 6 wt% to 3276 ppm. The range of the operating temperature was very moderate (from 45 to 120°C).

35

40

45

50

55

10
 EP 1 030 829 B1

10

15

20

25

30

35

40

45

[0039] Although for many purposes relatively high dissolution temperatures are preferred, i.e. 140°C-200°C, experi-
ments run at relatively low temperatures with cooling crystallization showed that similar purification may be achieved
compared to complete dissolution at high temperature (160°C or higher):
50
Experiment A:

[0040]

55 (a) Weigh of TA: 254g

(b) Weigh of Crystallization Solvent: 507g
(c) Initial ("saturation") Temperature: 60°C

11
 EP 1 030 829 B1

(continued)
(d) Crystallization Temperature: 45°C

5
(1) Crude TA Composition:
Benzoic p-Toluic 4-CBA TA
210ppm 459ppm 0.78% 99.15%

10
(2) Crystallization Product (Recovery 89.5%)
21ppm 21ppm 548ppm 99.94%

Experiment B:
15
[0041]

(a) Weight of TA: 256g

(b) Weight of Crystallization Solvent: 510g
20 (c) Initial ("saturation") Temperature: 58°C
(d) Crystallization Temperature: 45°C

25
(1) Crude TA Composition:
Benzoic p-Toluic 4-CBA TA: Others:
0.27% 5.3% 2.53% 91.56% 0.34%

(2) Crystallization Product (Recovery: 74.5%):

30 140ppm 0.18% 0.13% 99.67% 31ppm

The use of lower dissolution temperatures may make possible economies in energy consumption in the process.
[0042] As has been discussed, important aspects of this invention are related to the discovery of methods to crystallize
35 terephthalic acid (TA) from organic solution where the solvent tends to form an organic salt with TA. The salt is normally
formed from cooling the solution of an organic solvent or a mixture of organic solvents, which solution is saturated with
TA at higher temperatures. However, the crystal structure of the salt is destroyed when it is washed with water or other
solvents to remove the solvent in the crystal. The washed crystals become very fine powders which are very difficult to
filter and wash in order to remove the impurities in the trapped mother liquor and the residual solvent. Avoidance of such
40 fine powders is desirable.
[0043] As is known, organic solvents easily form addition products with terephthalic acid with the result that difficulties
are encountered in the purification and in recovering pure terephthalic acid. Some of these difficulties can be appreciated
from an integration of various empirical observations. Salt crystals tend to be desirably large (>120-150 microns) but
they are destroyed by contact with water, methanol or acetic acid (otherwise desirable washing agents) and are resolved
45 into very fine crystals (<50 microns), which, as pointed out above, are difficult to handle. Cake formed from salt crystals
is soft and easy to filter, but after water addition, the cake shrinks (its thickness is reduced), becoming a very compact
cake that is very difficult to de-water and rinse for residual solvent removal. If an attempt is made to overcome this
undesirable result by reslurrying the cake after water addition (at room temperature), it is found that a high viscosity
paste forms instead of a slurry, unless solids concentration is held very low (<20%). The paste is difficult to process
50 further. When reslurrying with hot water (60°C or higher) is attempted, it is found that the mix has a high tendency to
form a very stable foam (like shaving foam), which is also very difficult to process. Because of the small particle size
resulting after water addition to salt crystals, the settling characteristics are very poor, and processing rates through the
wash column are very low, requiring very big equipment. Notwithstanding the foregoing difficulties encountered in at-
tempting to rinse residual solvent away from salt crystals, residual solvent removal still remains critical because such
55 solvent can discolor TPA when heated to temperatures of 120°C or higher. This will affect the quality of polyester made
from such material. In addition, regeneration or water wash is needed in order to recover the solvent for reasons of cost.
[0044] Salt crystals can be visually differentiated from TPA crystals because the former are bright, transparent and
slightly pale and the latter are opaque and whiter. Prior workers have reported that the salt contains 2 moles of solvent

12
 EP 1 030 829 B1

for each mol of TPA, which means that the salt formula is TPA:2NMP. Based on the weight formula, TPA is 45% and
NMP is 55% in the salt. Empirically, it has been found that the solvent content of the salt crystals is confined between
55-65%, which confirms that the salt formula postulated by prior workers is correct and the difference is free solvent as
moisture in the cake.
5 [0045] pH measurements at room temperature of NMP and DMAC indicate both solvents are basic (pH is 10.3 and
11 respectively). When TPA is added, pH drops to neutral, and when water is added, the mixture becomes acidic. FIG.
3 is a plot of pH versus water concentration for NMP, DMAC, and NMP plus TPA salt crystals.
[0046] A study of the pH of different TPA-to-solvent mixtures at 30°C showed the same type of behavior, going from
basic to acidic as the proportion of TPA is increased. Around pH of 6.5, TPA starts precipitating, which means solution
10 is saturated. FIG. 4 is a plot of pH versus TPA/solvent weight ratio.
[0047] The TPA used for pH measurements was a commercial PTA product (globular crystals) and the precipitated
crystals were bars and transparent (salt crystals) which indicates that the original TPA crystals were transformed into
salt crystals even at low temperature.
[0048] Based on these observations, an acid-base reaction can be postulated between TPA and the solvent to form
15 the salt: TPA(s)+2NMP(1) →TPA:2NMP(s).
[0049] Studies of melting point determinations of NMP-salt crystals indicated that bright and transparent crystals are
transformed into opaque and white crystals at 50-60°C and remained the same until temperature was >300°C when
some visible vapors were evolved, indicating possible sublimation. The same phenomena was observed for salt crystals
formed from DMAC.
20 [0050] Experiments in which salt crystals were dried to remove the solvent showed weight loss at about 60% of the
original weight which is consistent with the salt formula proposed by earlier workers. In drying tests at temperatures
above 120°C, the material turned brown.
[0051] Heating salt crystals at temperatures between 80-100°C with some agitation forms a slurry with a clear liquid
(NMP) and white, opaque, hard crystals (TPA). Slurry formation was also observed at higher temperatures.
25 [0052] These observations indicate that salt decomposition occurs at a temperature of 60°C or higher into TPA and
NMP. At temperatures below 50°C, the salt is more stable. Therefore, the salt decomposition reaction can be stated as
follows:

30

35 [0053] In accordance with the invention, this concept has been used to set crystallization conditions in order to produce
true TPA crystals which can stand in water and prevent all the problems related to salt regeneration as mentioned before.
[0054] Experiments involving either cooling or flash/cooling of solutions to 60°C crystallization temperature (instead
of 45°C) have confirmed the salt formation/decomposition mechanism postulated above, by producing true TPA crystals
which are not destroyed by water.
40 [0055] Further in accordance with the invention, the solution of an organic solvent (or mixture of organic solvents)
saturated with TA and impurities such as 4-carboxybenzaldehyde (4-CBA), p-toluic acid, etc., is fed to a crystallizer
maintained at a lower pressure (or under vacuum) to allow the solvent (or solvent mixture) to flash instantaneously in a
continuous or batch manner at temperatures maintained above 50°C to avoid salt formation. Then, the solids (nuclei)
generated from solvent flashing are allowed to grow for a certain period of time at the reduced pressure and temperature.
45 It is desirable to subject the saturated solution to a number of solvent flash operations in the same crystallizer or in
several crystallizers connected in series, each at a different reduced pressure (or vacuum), to generate higher TA
recovery and larger TA crystals. It has been found, surprisingly, that the structure of the crystals produced from this
method is not adversely affected by washing with water or other solvents which have significant solubility for the crys-
tallization solvent (or mixture of solvents) or by vacuum drying the crystals to remove solvent. Consequently, it appears
50 that there was no salt formation or at least the salt formation was minimized so that washing with water or other solvent
which can dissolve the crystallization solvent or vacuum drying did not change the size and shape of the TA crystals.
[0056] Flash crystallization is being used commercially for TPA using water as the solvent. This process requires 3-5
flashes to reduce pressure and temperature and achieve a good particle size and distribution (120 microns average).
This type of crystallization takes advantage of the shape of the solubility curve to create a high supersaturation condition,
55 especially in the first flash as reported in the prior art and shown in FIG. 5 which is a plot of the solubility of TPA in water
against temperature.
[0057] In contrast to its behavior in water, the solubility curve of TPA in NMP is very flat, but crystal growth rate is
higher based on flash crystallization procedures using only 4 flashes: larger crystals are obtained (160-170 microns

13
 EP 1 030 829 B1

average). Also, crystals from flash crystallization are larger than those obtained by cooling alone. FIG. 6 shows the
particle size distribution obtained by such a flash process.
[0058] Good control of the flash profile (amount of solvent flash-out after each flash) is important to promote the desired
particle shape and size. Flash crystallization is the only way to produce globular type crystals which have good filtration
5 rates and wash efficiencies, but if too much solvent is flashed-out in the first two flashes, then small globular crystals
are obtained which are somewhat difficult to filter and wash. Selection and control of flash profile thus provides a way
to create the desired or optimum supersaturation conditions with respect to crystal shape and size, as is shown in FIG. 7.
[0059] Preferably, the flash crystallization method using NMP runs under vacuum, because of the low vapor pressure
of the solvent, compared to flash crystallization in acetic acid or water methods that run under pressure. Preferred flash
10 conditions are:

1st flash: 150 mmHg @ 145-150°C, V/F* = 0.26

2nd flash: 80 mmHg @ 120-125°C, V/F = 0.12
3rd flash: 40 mmHg @110-115°C, V/F = 0.07
15
4th flash: 20 mmHg @ 95-100°C, V/F = 0.07
*Amount of solvent flash as a fraction of initial
solvent for each flash.

20 [0060] Experiments were done by both cooling or flash crystallization methods to end points at 60 °C, making true
TPA crystals by both methods, although they are different in shape and size from each other. For flash crystallization,
complete dissolution (29g TPA/100g NMP @ 185°C) is preferred at initial conditions, but, for cooling, some seeding is
required so initial conditions are preferably 43.7g TPA/100g NMP @ 185°C. The crystal shapes obtained by cooling
were a mixture of bar and globular, but predominantly globular and smaller than those produced by flash, as a result of
25 lower supersaturation conditions achieved at the end of the crystallization step by cooling (31g TPA/100g NMP as
suspended solids in cooling compared to 49g TPA/100g NMP in flash). FIG. 8 shows the cooling curves for various
processes, both flash and cooling.
[0061] In accordance with the invention, the holding time to allow crystals to grow is a very important factor. A minimum
of 15 min. and a maximum of 60 min. is preferred, with an optimum around 30 min. This time is enough to achieve a
30 certain equilibrium between the liquid and solid phases and to minimize plugging problems during filtration.
[0062] In summary, these are the results from a number of crystallization tests:

4-CBA in crude (%) FIRST STAGE SECOND STAGE

2-3% 300-500 ppm (cooling) 30-50 ppm (cooling)
35
0.3 ~300 ppm (cooling) <29 ppm (flash)
0.8 ~250 ppm (cooling)
from 200 ppm 4-CBA <20 ppm (flash)
40

[0063] As previously mentioned, organic solvents useful in this invention include, but are not limited to, N-methyl
pyrrolidone (NMP), N,N-dimethyl acetamide (DMAC), 1,5-dimethyl pyrrolidone, N-methyl piperidone, N-methyl caprol-
actam, N,N-dimethyl formamide, N-formyl piperidine, N-alkyl-2-pyrrolidone (such as N-ethyl pyrrolidone), N-mercap-
toalkyl-2-pyrrolidone (such as N-mercaptoethyl-2-pyrrolidone), N-alkyl-2-thiopyrrolidone (such as N-methyl-2-thiopyrro-
45
lidone), and N-hydroxyalkyl-2-pyrrolidone (such as N-hydroxyethyl-2-pyrrolidone).
[0064] In order to remove the residual solvent trapped in the crystals from the final TA product, the washed TA crystals
are preferably fed to a high temperature soaker where water is used to partially or completely dissolve the TA crystals.
[0065] Several attempts to remove residual solvent by vacuum or low temperature drying of salt crystals were done.
The results showed 0.5% of residual solvent still remained, apparently because agglomeration of fine particles occurred,
50
trapping some solvent in between particles of the agglomeration.
[0066] Soaking at 220°C in water at different water to TPA ratios demonstrated that residual solvent can be effectively
and satisfactorily removed without the need for complete dissolution:

55 g TPA/100g water % dissolution residual solvent (ppm)

5.0 80.0 <20
4.4 90.9 <20

14
 EP 1 030 829 B1

(continued)

g TPA/100g water % dissolution residual solvent (ppm)

6.2 64.5 <25
5

[0067] The following examples illustrate the principles and features of the invention.

EXAMPLE 1
10
Cooling Crystallization

[0068] 9761g of NMP was added to a jacketed crystallizer provided with agitation together with 3028g of TA. This
mixture was heated to 180°C under atmospheric pressure until all of the TA was dissolved.
15 [0069] The mixture was then subjected to surface cooling by circulating a cooling medium through the jacket until a
temperature of 45 °C was reached. Then after 15 minutes, the slurry was filtered to separate the solids from the mother
liquor, and the cake was washed with room temperature pure NMP to displace all the mother liquor from the cake.
[0070] A sample was taken from the cake for observation under a microscope. The crystals had a bar-like shape and
a size in the range of 120-150 microns.
20 [0071] In order to remove the solvent from the cake, the cake had to be washed with water or other suitable solvents
which have high solubility of the solvent. Hot water at 80°C was used to wash the cake. However, the bar-like crystals
in the cake were completely destroyed by water and changed into fine powders which looked more like precipitates than
crystals produced by a crystallization process. These fine precipitates are extremely difficult to wash and handle and
the residual solvent removal is complicated.
25
EXAMPLE 2

Flashing Crystallization

30 [0072] The same sample preparation of NMP and TA as in the previous example was used, except that the mixture
was also, prior to the cooling step, subject to a flashing removal of solvent by reducing the pressure from atmospheric
to 125 mmHg of vacuum. In this way, some solvent was vaporized out and condensed through a cooler so the temperature
of the mixture dropped from 180°C to 147°C. The amount of solvent flashed out created a super-saturation condition
so the TA dissolved in NMP crystallizes into the solid phase.
35 [0073] Although the flashing step is done instantaneously, crystallization of TA requires some time to take place, so
the mixture was kept agitated for 30 minutes to form the nuclei and permit them to grow, thus forming a slurry. The slurry
was filtered to separate the solids from the liquid phase, washed with pure NMP at room temperature and observed
under a microscope. The crystal shape was globular instead of bar-like, as it was when using the previous cooling
crystallization method, and very uniform in size but smaller - about 40-60 microns.
40 [0074] Then the cake was washed with hot water at 80°C and, surprisingly, the globular-like crystals were not affected
by water washing (their shape and size were not changed). These globular-like crystals have a very high filtration rate
and effectively rinsing them is much easier.

EXAMPLE 3a
45
Crystal Growth

[0075] To promote crystal growth, the experiment, as in the preceding example, was repeated except that 6174g of
NMP and 1952g of terephthalic acid were used.
50 [0076] Also, the flash pressure was 120 mmHg instead of 125 mmHg and the temperature was 145°C. Then, the
mixture was flashed a second time at 40 mmHg, as described in the preceding example, and the temperature dropped
to 110°C. Thus, more terephthalic acid crystallized. The crystal shape was globular-like and the size was increased to
60-80 microns.

55 EXAMPLE 3b

[0077] The experiment as in Example 3a was repeated except that 7490g ofNMP and 2325g of terephthalic acid were
used. Also, a different pressure profile was followed and two more flashes were added:

15
 EP 1 030 829 B1

first flash: 150 mmHg @ 154°C

second flash: 80 mmHg @ 135°C
third flash: 40 mmHg @ 117°C
5
fourth flash: 20 mmHg @ 101°C

[0078] Observation under a microscope showed that the crystal shape was globular and the size improved significantly.
The final sample contained crystals in the range of 120-150 microns.
10
EXAMPLE 4a and 4b

Flash/Vaporizing Crystallization

15 [0079] The experiment as in Example 3b was repeated except that the temperature of the hot oil circulation through
the jacket was kept 5-10°C above the crystallizer temperature in a way that some vaporization of the solvent occurred
at the same time of the flashing. This procedure resulted in more solvent flashed/vaporized and a lower temperature
profile which increases the recovery of the crystals:

20 FLASH No. EXAMPLE 3b EXAMPLE 4a EXAMPLE 4b

First 154°C 155°C 145°C
150 mmHg 150 mmHg 150 mmHg
755 ml of solvent 1328 ml of solvent 1660 ml of solvent
25 removed by flashing removed by flashing removed by flashing
Second 135°C 135°C 130°C
80 mmHg 80 mmHg 80 mmHg
696 ml of solvent 473 ml of solvent 580 ml of solvent
removed by flashing removed by flashing removed by flashing
30
Third 117°C 110°C 115°C
40 mmHg 40 mmHg 40 mmHg
248 ml of solvent 110 ml of solvent 340 ml of solvent r
removed by flashing removed by flashing emoved by flashing
35
Fourth 101°C 90°C 95°C
20 mmHg 20 mmHg 20 mmHg
135 ml of solvent 155 ml of solvent 430 ml of solvent
removed by flashing removed by flashing removed by flashing
40

[0080] When observed under a microscope, the crystals looked globular-like in shape as described for Example 2
above.

45
EXAMPLE 5

[0081] In this example, the 4-CBA rejection characteristics of the flash crystallization method was compared with that
of crystallization by cooling alone.

50
Flash Crystallization

[0082] The crystallizer was charged with 31g TA/100g solvent. 4-CBA was added to start with a concentration based
on solids of around 2%. The mixture was heated to 185°C and agitated until most of the crystals dissolved. Some crystals
may not have dissolved and these became seeds for crystal growth. The oil bath was set to 155°C. The first vacuum
55
(150 mmHg) was pulled to remove around 15-20% of the liquid in about 15 minutes. Next, the flash vacuum was pulled
to 80 mmHg and 6-8% of the remaining liquid was removed within 5 minutes. In the third flash, 6-8% of the solvent was
removed with a vacuum of 40 mmHg requiring about 6-7 minutes. In the fourth flash, 12% of the solvent was removed
with a vacuum of 20 mmHg requiring about 10-15 minutes. Then the mother liquor was cooled to 50°C as quickly as

16
 EP 1 030 829 B1

possible, taking about 30 minutes. The crystals were then removed from the flask and filtered using a Buchner funnel
and side arm flask. About 200g of 50°C solvent was then poured over to wash the crystals. The crystals were then put
in a pressure filter and dried by passing nitrogen for 30 minutes at 40 psi. The final crystals were analyzed for 4-CBA
content, giving a result of 500 ppm.
5
Cooling Crystallization

[0083] The crystallizer was charged with 31 g TA/100g solvent. 4-CBA was added to start with a concentration based
on solids of 2%. The mixture was heated to 185°C and agitated until most of the crystals dissolved. Some crystals may
10 not have dissolved and these became seeds for crystal growth. Cooling of the mix was started to crystallize the TA from
the solution. The cooling rate was 2°C/min to a final temperature of 50°C. The crystals were then removed from the flask
and filtered using a Buchner funnel and side arm flask. About 200g of 50°C solvent was then poured over to wash the
crystals. The crystals were then put in a pressure filter and dried by passing nitrogen for 30 minutes at 40 psi. These
final crystals were analyzed for 4-CBA content, giving a result of about 500 ppm.
15 [0084] The experiments show that the flash and cooling crystallization processes have substantially the same rejection
capability for 4-CBA.
[0085] According to the invention, a preferred embodiment of the process is divided into five sections:

(1) Oxidation Section:

20
[0086] In this section, p-xylene is oxidized according to the following main reactions:

(a) p-xylene + oxygen ------------> terephthalic acid + water

(b) p-xylene + oxygen ------------ > p-toluic acid + water
25 (c) p-xylene + oxygen -------------> 4-carboxybenzaldehyde (4-CBA) + water

The oxidizer residence time is approximately five hours. Since the oxidizer effluent will contain up to about 30% TA,
mixing in the oxidizer is very important in order to maintain the yield and selectivity, and to prevent fouling and blockages.
The initial mixing of the feed streams may be achieved in a static mixer (outside of the oxidizer). Further mixing may be
30 provided by an air sparger and by external circulation. Depending on the thoroughness of the p-xylene washing step at
the filter (discussed below), the terephthalic acid (TA) in the solid can vary from between about 55% and about 90+%.

(2) Crystallization Section:

35 (A) First Crystallization

[0087] After filtration, the solids from the oxidizer effluent are mixed with the mother liquor and the solvent wash liquid
from the second-stage crystallizer and with additional crystallization solvent. The mixed slurry is dissolved in a slurry
tank at a predetermined temperature, preferably at from between about 140°C and about 200°C. The saturated solution
40 is transferred to a holding tank to remove p-xylene through evaporation. The saturated solution is then fed to a first-
stage batch crystallizer to recover purified TA by flash evaporation of solvent at reduced pressure and/or cooling. After
the crystallization step, the crystallizer content is then dropped to a product holding tank and is pumped continuously to
a filter (or centrifuge) to collect the solids to be recrystallized in the second-stage crystallizer for further purification.

45 (B) Second Crystallization

[0088] The solids generated from the first crystallizer filter are redissolved in a feed dissolver with the crystallization
solvent for the second-stage crystallizer at a predetermined condition, such as at a temperature of from between 140°C
and 200°C. The saturated solution is pumped to the second-stage crystallizer for crystal growth and recovery, again, by
50 flash evaporation of solvent at reduced pressure and/or cooling. Then, the crystallizer content is dropped to a holding
tank for filtration before being sent to the soaker. In the filtration step, the solid (cake) is first washed by the crystallization
solvent to displace mother liquor remaining in the cake. The solid is then washed by a low-boiling solvent to displace
the crystallization solvent in the cake, soaked at high temperature in water to remove any residual solvent, and subse-
quently dried to remove the final liquid from the PTA product. The crystallization solvent alternatively can be displaced
55 by drying the solid using a vacuum dryer and subjecting the cake to a soaking process. The soaking process comprises
partially or completely dissolving the TA in a solvent, crystallizing the product in water at a high temperature and high
pressure to remove residual solvent trapped in the crystals, and recrystallizing, filtering and drying the TA cake.

17
 EP 1 030 829 B1

(3) Mother Liquor/Solvent Recovery Section:

[0089] The mother liquor from the first crystallizer filter is transferred to a solvent recovery column to recover the
crystallization solvent from the column overhead. The impurities, such as p-toluic acid, benzoic acid, 4-carboxybenzal-
5 dehyde (4-CBA) are recovered from the bottom of the column. In order to make sure the column bottom slurry can be
transferred back to the oxidizer, a high-boiling diluent is preferably added to the reboiler.

II. Detailed Process Description and Example

10 [0090] The present invention will be described in terms of the production and recovery of terephthalic acid (TA) from
the air oxidation of p-xylene in the presence of a solution of components of catalysis in dimethyl terephthalate (DMT) or
in benzoic acid solvent system. The oxidizer temperature is preferably between from 150°C and 250°C and the pressure
is from between about 5 and about 30 kg per cm2. Since the oxidizer effluent will contain up to 30% TA, mixing in the
oxidizer is very important in order to maintain the yield and selectivity, and to prevent fouling and blockages. The initial
15 mixing of the feed streams may be achieved in a static mixer (outside of the oxidizer). Further mixing may be provided
by air sparging and external circulation. In the preferred form of the process manganese acetate and cobalt acetate in
aqueous solution are fed to the oxidizer to catalyze the oxidation reactions.
[0091] The effluent from the oxidizer at about 160°C is transferred and filtered via a first filter to separate the solid
from mother liquor (filtrate). During filtering, the solid cake is washed with p-xylene which is heated from 30°C to 100-150
20 °C. The mother liquor is transferred to a first holding tank. The cake washing liquid is removed separately from the first
filter to a second holding tank.
[0092] The washed cake is dropped into a first slurry tank to mix with the following streams: (1) NMP or DMAC (selective
crystallization solvent) wash liquor (heated from 45 to 100-150°C); (2) mother liquor (heated from 50 C to 100-150°C);
and (3) NMP or DMAC (heated from 45°C to 100-150°C).
25 [0093] When a crude TA from existing or prior oxidation systems is used, the p-xylene wash is not necessary, and
the crude TA is dropped into the first slurry tank as described above. Crude TA can contain as much as 2-3% of 4CBA;
thus oxidation conditions may be relaxed, which will result in significantly reduced p-xylene and acetic acid burning losses.
[0094] The above mixture is then transferred from the bottom of the first slurry tank to a first dissolver tank. The content
in the first dissolver tank is then heated indirectly from 100-150°C to 140-200°C by a hot oil heating coil in the first
30 dissolver tank. About 75% of the p-xylene and 100% of the sparging nitrogen in the mixture is vaporized from the first
dissolver tank and removed. Sparging nitrogen is added to the first dissolver tank to assist the removal of p-xylene.
Vapor streams from the first dissolver tank and a crude crystallizer are combined into a stream, condensed by a cooler,
and sent to a first storage tank. The bottom effluent from the first dissolver tank is transferred to the crude crystallizer
batchwise.
35 [0095] The batch content in the crude crystallizer is cooled from 140-200°C to 30-50°C by an external cooler, to
generate the desired super-saturation for TA crystals to grow. To improve the crystal size distribution and solid recovery,
crystal seeding may be helpful. At the conclusion of a batch crystallization cycle, the slurry is dropped into a third holding
tank and transferred to a second filter where it is filtered at a continuous rate.
[0096] During filtering at the second filter, NMP or DMAC is used to wash the cake in the second filter. The mother
40 liquor plus NMP or DMAC wash are combined to be fed to a crystallization solvent recovery column. The washed cake
is dropped into a second dissolver tank where it is mixed with NMP or DMAC to form the supersaturated feed for a pure
crystallizer. NMP or DMAC is heated from 45°C to 140-200°C and is fed to the second dissolver tank.
[0097] The content of the second dissolver tank is transferred batchwise to the pure crystallizer where the pressure
is reduced in the manner described previously and the temperature is reduced from 140-200°C to 50-60°C to induce
45 TA crystal growth. The cooling to promote supersaturation results from the flashing steps. Again, to improve the crystal
size distribution and crystal recovery, crystal seeding may be helpful. At the end of the batch cycle, the slurry is dropped
from the pure crystallizer into a feed tank for the third filter.
[0098] The slurry is continuously fed to the third filter. The mother liquor from the first filter is transferred to a fourth
holding tank. The cake is initially washed with NMP or DMAC at 45°C to displace the remaining mother liquor from the
50 cake, and then the cake is washed with the low-boiling displacement solvent, such as water, to displace NMP or DMAC
from the cake or, alternatively, sent to a vacuum dryer. The NMP or DMAC wash (from a crystallization solvent storage
tank) and the displacement solvent are then added to the third filter. The NMP or DMAC wash liquid is sent to the first
slurry tank, while the displacement solvent is transferred to a fifth holding tank.
[0099] The washed cake from the third filter is passed through a wash column or multistage contactor and counter-
55 current water is added to remove the crystallization solvent. The slurry from the wash column or contactor is then fed
to the soaker where the temperature is raised to from between about 150 - 250°C. to remove trapped solvent from the
crystals. The slurry is finally filtered and dropped to a product dryer where water (moisture) in the cake is removed by
heating and purging with a counter-current flow of heated nitrogen. The dried PTA product is removed from the dryer

18
 EP 1 030 829 B1

and is stored in the product bin.

[0100] The bottom stream from the fifth holding tank (mixture of NMP and displacement solvent), together with the
liquid from the wash column or multi-stage contactor, is transferred through a heater (to heat the stream from 25°C to
80-120°C) to a displacement solvent evaporator. The displacement solvent vapor from the overhead of the displacement
5 solvent evaporator is condensed and sent to the displacement solvent tank. The bottom stream from the displacement
solvent evaporator is split into two streams: one stream to the vent pot and a second stream to the crystallization solvent
tank.
[0101] The mother liquor and NMP or DMAC wash from the second filter are transferred to the crystallization solvent
tank and then are fed to the NMP or DMAC recovery column. This stream is heated from 15-45 °C to 130-170°C before
10 entering the recovery column. The overhead vapor is condensed and sent to a condensate pot. A part of the condensate
at 160-220°C is returned to the recovery column as the reflux. The rest of the overhead product from recovery column
is sent to a crystallization solvent check tank. From the crystallization solvent check tank, the regenerated NMP or DMAC
is pumped to a NMP or DMAC storage tank.
[0102] In order to make sure the slurry in the recovery column reboiler can be transferred back to the oxidizer, high-
15 boiling diluent, such as benzoic acid or DMT, is added to the reboiler. The slurry plus the high-boiling diluent is withdrawn
from the bottom of the recovery column and is sent back to the oxidizer.
[0103] In FIG. 9, there is shown an arrangement of a crystallizer S-2 useful for the practice of the embodiment of the
invention in which heat is added to the crystallizing acid mixture during the times when the pressure is being reduced
to flash solvent. As shown in FIG. 3, crystallizer S-2 is there provided with both a cooling recirculation circuit with
20 exchanger E-8, and a heating recirculation circuit with heater E-8a. Heat is applied to the mixture by heater E-8a during
flashing, and cooling is applied to the mixture at other times by exchanger E-8. Flashed solvent (e.g. NMP or DMAC) is
removed through line 50 for recycling to the recovery column, and the pressure reduction vacuum is also applied to the
crystallizer through line 50.
[0104] FIG. 10 is a process block diagram for a preferred purification process of the invention based on the several
25 considerations discussed herein above.
[0105] This new configuration using soaking instead of water recrystallization reduces capital cost and energy require-
ments.
[0106] Another improvement is to use single stage flash crystallization if 4-CBA in the crude is about 0.3%-0.8% and
4CBA requirements in the final product are between 200-400 ppm.
30

Claims

1. A method for producing purified water-resistant terephthalic acid crystals from a liquid dispersion thereof also con-
35 taining impurities selected from unreacted starting materials, solvents, products of side reactions and/or other un-
desired materials, comprising:

(a) dissolving terephthalic acid in an organic selective recrystallisation solvent to form a solution, wherein the
organic solvent is one which is capable of forming an addition salt with the terephthalic acid; and
40 (b) crystallising purified water-resistant terephthalic acid from said solution by reducing the temperature and
pressure sufficient to flash evaporate solvent from said solution whilst maintaining the solution above 50°C to
cause crystallization whilst avoiding salt formation.

2. A method in accordance with claim 1, further comprising:

45
(c) separating the purified water-resistant terephthalic acid crystals from the solution.
(d) washing said separated purified water-resistant terephthalic acid with water;
(e) soaking said washed, separated purified terephthalic acid with water at a temperature between 150°C and
300°C; and
50 (f) filtering and drying said water soaked purified terephthalic acid.

3. A method in accordance with claim 2 in which said soaking with water is done between 180°C and 250°C.

4. A method in accordance with claim 2 in which said solution is held from 15 to 60 minutes following said reduction
55 of temperature.

5. A method in accordance with claim 2 in which said solution is held between 20 to 40 minutes.

19
 EP 1 030 829 B1

6. A method in accordance with any of claims 2-5 in which said washing of purified terephthalic acid is done from one
to three times.

7. A method in accordance with any preceding claim in which said reducing the temperature and pressure to flash
5 evaporate solvent is performed stage-wise, in from two to six stages.

8. A method in accordance with claim 7 in which said reducing of the temperature and pressure is done in two to four
stages.

10 9. A method in accordance with claim 7 in which the proportion of solvent flash evaporated in the first evaporation
stage is restricted to increase final crystal size.

10. A method in accordance with claim 1 in which said crystallisation is performed in multiple stages.

15 11. A method according to claim 1, wherein the crystallisation is performed in at least two stages, the flash crystallisation
being carried out as the last stage.

12. A method according to claim 11, wherein the flash crystallisation is also carried out in the first stage.

20 13. A method in accordance with claim 1, further comprising, prior to step (a), the steps of:

(1) filtering the liquid dispersion to form a crude terephthalic acid filter cake;
(2) dissolving the filter cake in a selective crystallisation solvent at a temperature between 50°C and 250°C to
form a solution;
25 (3) crystallising purified terephthalic acid from the solution by reducing the temperature and/or pressure thereof;
and
(4) separating the crystallised purified terephthalic acid from the solution.

30 Patentansprüche

1. Verfahren zur Herstellung reiner wasserbeständiger Kristalle von Terephthalsäure aus einer flüssigen Dispersion
hiervon, die zudem Verunreinigungen enthält, ausgewählt aus nicht-umgesetzten Ausgangsmaterialien, Lösungs-
mitteln, Produkten der Nebenreaktionen und/oder anderen unerwünschten Substanzen, umfassend:
35
(a) Lösen von Terephthalsäure in einem selektiven organischen Umkristallisationslösungsmittel unter Erhalt
einer Lösung, wobei das organische Lösungsmittel ein Additionssalz mit der Terephthalsäure bilden kann; und
(b) Kristallisieren reiner wasserbeständiger Terephthalsäure aus der Lösung durch Verringern der Temperatur
und des Drucks soweit, dass das Lösungsmittel aus der Lösung blitzartig verdampft, wobei die man die Lösung
40 über 50°C hält, so dass eine Kristallisation erhalten und zugleich eine Salzbildung vermieden wird.

2. Verfahren nach Anspruch 1, zudem umfassend:

(c) Abtrennen der reinen wasserbeständigen Terephthalsäurekristalle aus der Lösung,

45 (d) Waschen der abgetrennten reinen wasserbeständigen Terephthalsäurekristalle mit Wasser,
(e) Tränken der gewaschenen, abgetrennten, reinen Terephthalsäurekristalle mit Wasser bei einer Temperatur
zwischen 150°C und 300°C und
(f) Abfiltrieren und Trocknen der mit Wasser getränkten reinen Terephthalsäure.

50 3. Verfahren nach Anspruch 2, wobei das Tränken mit Wasser bei einer Temperatur zwischen 180°C und 250°C erfolgt.

4. Verfahren nach Anspruch 2, wobei die Lösung nach der Temperaturabsenkung 15 bis 60 Minuten gehalten wird.

5. Verfahren nach Anspruch 2, wobei die Lösung zwischen 20 bis 40 Minuten gehalten wird.
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6. Verfahren nach einem der Ansprüche 2-5, wobei das Waschen der reinen Terephthalsäure ein- bis dreimal erfolgt.

7. Verfahren nach einem vorhergehenden Anspruch, wobei das Verringern der Temperatur und des Drucks zur blitz-

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artigen Verdampfung des Lösungsmittels stufenweise in zwei bis sechs Stufen erfolgt.

8. Verfahren nach Anspruch 7, wobei das Verringern der Temperatur und des Drucks in zwei bis vier Stufen erfolgt.

5 9. Verfahren nach Anspruch 7, wobei der Anteil des Lösungsmittels, das in der ersten Verdampfungsstufe blitzartig
verdampft wird, eingeschränkt wird, so dass die Größe der Kristalle am Ende zunimmt.

10. Verfahren nach Anspruch 1, wobei die Kristallisation in mehreren Stufen erfolgt.

10 11. Verfahren nach Anspruch 1, wobei die Kristallisation in mindestens zwei Stufen erfolgt und die Blitzkristallisation
als letzte Stufe erfolgt.

12. Verfahren nach Anspruch 11, wobei die Blitzkristallisation auch auf der ersten Stufe erfolgt.

15 13. Verfahren nach Anspruch 1, das vor Schritt (a) zudem folgende Schritte umfasst:

(1) Filtrieren der flüssigen Dispersion unter Erhalt Filterkuchens von roher Terephthalsäure,
(2) Lösen des Filterkuchens in einem selektiven Kristallisationslösungsmittel bei einer Temperatur zwischen
50°C und 250°C unter Bildung einer Lösung,
20 (e) Kristallisieren von reiner Terephthalsäure aus der Lösung durch Verringern von deren Temperatur und/oder
Druck und
(f) Abtrennen der kristallisierten reinen Terephthalsäure aus der Lösung.

25 Revendications

1. Méthode de production de cristaux d’acide téréphtalique résistant à l’eau, purifié, à partir d’une dispersion liquide
de celui, contenant également des impuretés choisies parmi des matières premières n’ayant pas réagi, des solvants,
des produits de réactions secondaires et/ou d’autres matières non désirées, comprenant :
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(a) la dissolution de l’acide téréphtalique dans un solvant organique de recristallisation sélectif pour former une
solution, dans laquelle le solvant organique est un solvant capable de former un sel d’addition avec l’acide
téréphtalique ; et
(b) la cristallisation de l’acide téréphtalique résistant à l’eau, purifié, à partir de ladite solution par réduction
35 suffisante de la température et de la pression pour soumettre le solvant de ladite solution à une évaporation
éclair, tout en maintenant la solution au-dessus de 50°C pour provoquer la cristallisation tout en évitant la
formation d’un sel.

2. Méthode selon la revendication 1, comprenant en outre :

40
(c) la séparation des cristaux d’acide téréphtalique résistant à l’eau, purifié, de la solution ;
(d) le lavage dudit acide téréphtalique résistant à l’eau, purifié, séparé avec de l’eau ;
(e) le trempage dudit acide téréphtalique purifié, séparé, lavé, dans de l’eau à une température entre 150°C et
300°C ; et
45 (f) la filtration et le séchage dudit acide téréphtalique purifié trempé dans l’eau.

3. Méthode selon la revendication 2, dans laquelle ledit trempage dans de l’eau est réalisé entre 180°C et 250°C.

4. Méthode selon la revendication 2, dans laquelle ladite solution est maintenue de 15 à 60 minutes avant ladite
50 réduction de la température.

5. Méthode selon la revendication 2, dans laquelle ladite solution est maintenue entre 20 et 40 minutes.

6. Méthode selon l’une quelconque des revendications 2 à 5, dans laquelle ledit lavage de l’acide téréphtalique purifié
55 est réalisé de une à trois fois.

7. Méthode selon l’une quelconque des revendications précédentes, dans laquelle ladite réduction de température et
de pression pour soumettre le solvant à une évaporation éclair est réalisée par étapes, en deux à six stades.

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8. Méthode selon la revendication 7, dans laquelle ladite réduction de température et de pression est réalisée en deux
à quatre stades.

9. Méthode selon la revendication 7, dans laquelle la proportion de solvant évaporé par évaporation éclair dans la
5 première étape d’évaporation est limitée pour augmenter la dimension finale des cristaux.

10. Méthode selon la revendication 1, dans laquelle ladite cristallisation est réalisée en plusieurs stades.

11. Méthode selon la revendication 1, dans laquelle la cristallisation est réalisée en au moins deux stades, la cristallisation
10 éclair étant réalisée dans le dernier stade.

12. Méthode selon la revendication 11, dans laquelle la cristallisation éclair est réalisée également dans le premier stade.

13. Méthode selon la revendication 1, comprenant en outre, avant l’étape (a), les étapes de :
15
(1) filtration de la dispersion liquide pour former un gâteau de filtration d’acide téréphtalique brut ;
(2) la dissolution du gâteau de filtration dans un solvant de cristallisation sélectif à une température entre 50°C
et 250°C pour former une solution ;
(3) la cristallisation de l’acide téréphtalique purifié à partir de la solution par réduction de la température et/ou
20 de la pression de celle-ci ; et
(4) la séparation de l’acide téréphtalique purifié cristallisé de la solution.

25

30

35

40

45

50

55

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