KR100807762B1 - Method for producing terephthalic acid - Google Patents

Abstract

Provided are a terephthalic acid production method capable of efficiently obtaining terephthalic acid and controlling the particle size distribution of a crystal, and a terephthalic acid having a narrow particle size distribution. For this purpose, when terephthalic acid aqueous solution is refine | purified with a platinum group metal catalyst, and then crystallization of terephthalic acid from aqueous solution, crystallization is formed in substantially trapezoidal plate shape, and it performs in the stirring tank provided with the stirring blade which can change a rotation speed in the tank bottom. Thereby, terephthalic acid is obtained efficiently, and terephthalic acid crystal which is excellent in powder characteristic, slurry characteristic, and reactivity, and which can control particle size distribution of a crystal is obtained.

Description

Production method of terephthalic acid {METHOD FOR PRODUCING TEREPHTHALIC ACID}

The present invention relates to a method for producing terephthalic acid, and more particularly, to a method for producing terephthalic acid, which is suitable as a raw material for producing polyester such as polyethylene terephthalate. The present invention also relates to a terephthalic acid having a narrow particle size distribution produced using the preparation method thereof.

Crude terephthalic acid obtained by the oxidation of paraxylene usually contains a relatively large amount of various impurities including 4-carboxybenzaldehyde (abbreviated as "4CBA"), and after purification, it is used as a raw material of polyester. Doing.

As such a method for purifying crude terephthalic acid, a method of dissolving the crude terephthalic acid in an aqueous medium and contacting with a platinum group metal catalyst under high pressure and high temperature is known (for example, JP-A 6-329583). Several methods are known.

As the oxidation reaction of paraxylene, a method is generally employed in which paraxylene is reacted with molecular oxygen in an acetic acid solvent, for example, in the presence of a catalyst containing cobalt, manganese and bromine under a temperature condition of 170 to 230 ° C. . Terephthalic acid obtained by this method usually contains 1000 to 10,000 ppm of 4-carboxybenzaldehyde as weight impurities. This terephthalic acid is mixed with water to make a slurry of 10 to 40% by weight. Next, the slurry is pressurized to a pressure slightly higher than the reaction pressure by a boost pump, sent to a heat dissolving step to form a terephthalic acid aqueous solution.

This aqueous terephthalic acid solution is passed through a tower reactor filled with a catalyst containing a platinum group metal. As a catalyst containing a platinum group metal, palladium, ruthenium, rhodium, osmium, iridium, platinum and the like, or metal oxides thereof are used. Although these metals or metal oxides can be used as a catalyst as they are, they are used by being supported on a carrier such as activated carbon, which is insoluble in aqueous terephthalic acid solution.

Purification of terephthalic acid by the platinum group metal catalyst can be carried out only by contacting the aqueous terephthalic acid solution with the catalyst, but it is advantageous to carry out in the presence of a reducing agent. Usually, hydrogen is used as the reducing agent, aqueous terephthalic acid solution and hydrogen gas are supplied to the reactor, and brought into contact with the catalyst under a temperature condition of 220 to 320 캜, preferably 260 to 300 캜. The hydrogen gas may be supplied at a ratio of 0.05 to 10 Nm 3, preferably 0.1 to 3 Nm 3 with respect to 1000 kg of terephthalic acid aqueous solution.

Terephthalic acid after the purification step is sent to a crystallization step to crystallize terephthalic acid by pressure-pressure cooling. Crystallization is usually carried out in multiple stages, and finally cooled to a temperature at which most of the terephthalic acid is precipitated, and the resulting crystals are solid-liquid separated by centrifugation or the like and dried. Usually, an average particle diameter is determined by adjusting the crystallization temperature and average residence time of a 1st crystallization tank and a 2nd crystallization tank, and usually obtain high purity terephthalic acid of 50-150 micrometers.

As a crystallization apparatus applied to the production of conventional terephthalic acid, as shown in FIG. 4, a predetermined distance between a lower end of the rotary shaft (b) and an inner bottom surface of the crystallization tank (a) is shown at the center of the crystallization tank (a). Are arranged so as to have a gap between them, and a stirring blade (c) such as an inclined paddle type turbine blade is attached to the lower end of the rotating shaft (b), and a baffle plate is provided on the inner surface of the crystallization tank (a). As shown in FIG. 5, the apparatus having (d) installed therein, or, as shown in FIG. 5, the rotation shaft f is placed at the center of the crystallization tank e, and a gap of a predetermined distance is formed between the lower end and the inner bottom surface of the crystallization tank e. It is arranged side by side, and a stirring blade (g) such as an inclined paddle blade is attached to the lower end of the rotating shaft (f), and a baffle plate (d) is provided on the inner surface of the crystallization tank (e). The device which provided the impingement plate h in the vicinity of the front-end | tip of the said stirring blade g is known The.

In the conventional crystallization apparatus, the rotational flow of the aqueous solution of terephthalic acid occurs at the tip of the stirring blade due to the rotation of the stirring blade. As a result, the slurry is stagnated at the center of the inner bottom of the crystallization tank at the center of the stirring blade, thereby causing clogging or the like. .

On the other hand, in recent years, the method of manufacturing polyester, especially polyethylene terephthalate by the so-called direct polymerization method which directly reacts with terephthalic acid and glycols is performed. In the direct polymerization method, terephthalic acid is mixed with glycols such as ethylene glycol and sent to the reaction system in the form of a slurry to be provided for the reaction. In this process, the particle size distribution and the average particle diameter of the terephthalic acid particles greatly influence the handling, transport, mixing with ethylene glycols, and reaction uniformity of terephthalic acid.

In general, those having a wide particle size distribution ranging from large particle size to small particle size tend to improve slurry characteristics with ethylene glycol, and are suitable for mixing with ethylene glycol, and the average particle diameter is usually 50 to 150 μm. Range. On the contrary, if the ratio of the large particle size such that the particle size exceeds 250 mu m is excessively increased, terephthalic acid is likely to remain as unreacted powder during the direct polymerization method, and as a result, it is necessary to lengthen the reaction time. It turns out that there are problems such as an increase in living things. On the other hand, if the proportion of the fine powder such as less than 50 µm is excessively increased, it has been found that there is a problem such as that it takes time for handling or transporting the product.

Therefore, it is difficult to produce terephthalic acid which satisfies all of handling, transport, mixing of ethylene glycols, and reaction uniformity of terephthalic acid, and thus, the apparatus, scale, and operation method of a so-called direct polymerization apparatus for directly reacting with terephthalic acid and glycols. In some cases, the required quality may vary.

[Initiation of invention]

The present invention provides a method for producing terephthalic acid, which is capable of efficiently obtaining terephthalic acid by preventing stagnation of a slurry occurring in a central portion of a bottom of a crystallization tank, and being capable of dividing the required particle size distribution of a terephthalic acid particle directly in a crystallization tank. For the purpose of The present invention also provides terephthalic acid having a narrow particle size distribution produced using the preparation method thereof.

The present invention provides the following method, for example.

(1) When terephthalic acid is crystallized from an aqueous solution of terephthalic acid, the preparation of terephthalic acid using a crystallization apparatus provided with a stirrer having a stirring blade close to the inner bottom surface and a baffle plate extending in the vertical direction on the inner surface of the crystallization tank is provided. Way.

(2) The shape of the stirring blade is formed in a plate shape in which the length in the vertical direction is long at the center of the crystallization tank, and the length in the vertical direction is gradually shortened toward the periphery of the crystallization tank. The manufacturing method of terephthalic acid of description).

(3) The method for producing terephthalic acid according to (1) or (2), wherein the opening of the inflow pipe of the aqueous solution of terephthalic acid connected to the crystallization tank is formed upward in the crystallization tank.

(4) Said (1)-() in which the ratio (c / R) of the clearance (c) between the lower end of the said stirring blade and the inner bottom face of the said crystallization tank and the blade diameter (R) of the said stirring blade is a range of 0.005-0.10. The manufacturing method of terephthalic acid in any one of 3).

(5) Crystallization of terephthalic acid in a crystallization tank composed of a plurality of crystallization tanks connected in series, and having a stirrer close to the inner bottom surface of the crystallization tank and a baffle plate extending in the vertical direction on the inner surface of the crystallization tank. Crystallizing at least 50 weight% of the quantity, The manufacturing method of the terephthalic acid in any one of said (1)-(4) characterized by the above-mentioned.

(6) The method for producing terephthalic acid according to any one of (1) to (5), wherein the stirring power of the stirring blade of the first crystallization tank is 0.01 to 10 kPa / m 3.

(7) When the inner diameter of the first crystallization tank is D and the blade diameter is R, the stirring blade diameter (R) is (0.3 to 0.8) D, and the shape of the blade is (0.1 to 3.0) R and a plurality of stirring blades having (0 to 0.5) R in the vertical direction at the tip of the blade are used. The method for producing terephthalic acid according to the above (2).

(8) Zoterephthalic acid is dissolved in an aqueous medium, purified by contact with a platinum group metal catalyst under a temperature condition of 260 to 320 ° C, and cooled stepwise in a plurality of crystallization tanks connected in series with terephthalic acid from the aqueous solution of terephthalic acid. When crystallization by crystallization, the crystallization temperature in the first crystallization tank is set to 240 to 260 ° C, stirring is carried out with a stirring blade in the range of 0.01 to 10 kPa / m 3, and then the crystallization temperature in the second crystallization tank is 180. It is -230 degreeC, and this crystallization temperature is 20-60 degreeC lower than the crystallization temperature of a 1st crystallization tank, The manufacturing method of the terephthalic acid in any one of said (1)-(7) characterized by the above-mentioned.

(9) The method for producing terephthalic acid according to any one of the above (1) to (8), wherein the particle size distribution of the terephthalic acid particles is classified and produced by changing the stirring power to change the rotation speed of the stirring blades.

(10) A terephthalic acid having an average particle diameter of 50 to 150 µm and a standard deviation of 30 to 50.

(11) A terephthalic acid characterized by having an average particle diameter of 50 to 150 µm and a standard deviation of 30 to 50 produced by any one of the methods (1) to (9).

A first embodiment of the present invention will be described with reference to FIG. 1. Although FIG. 1 is an example in which the motor is provided in the crystallization tank upper part, you may install in a crystallization tank bottom part.

1 represents a crystallization tank, the rotating shaft 2 was lined up in the center part in the said crystallization tank 1, and the stirring blade 3 was attached to the lower end part of the said rotating shaft 2.

Here, each of the plurality of wing bodies 3a of the stirring blade 3 has a large trapezoidal shape in which the width of the base portion side up-down direction adjacent to the rotation shaft 2 is large, and the width gradually decreases toward the tip side. It is formed in plate shape, and the lower end of each wing body 3a is affixed close to the inner bottom face of the said crystallization tank 1. As shown in FIG.

That is, when the inner diameter of the crystallization tank is D and the blade diameter is R, the stirring blade diameter (R) is (0.3 to 0.8) D, preferably (0.4 to 0.6) D, and the shape of the blade is up and down at the center part side. The length in the direction is (0.1 to 3.0) R, preferably (0.3 to 0.7) R, more preferably (0.4 to 0.6) R, and the length in the vertical direction at the tip of the wing is (0 to 0.5) R, preferably Preferably, a plurality of stirring blades of (0.1 to 0.3) R is used.

The ratio (c / R) of the clearance (c) between the lower end of the stirring blade and the inner bottom surface of the crystallization tank and the blade diameter (R) of the stirring blade is in the range of 0.005 to 0.10, preferably 0.01 to 0.05, more preferably Preferably it is the range of 0.01-0.03.

Moreover, the some baffle plate 4 extended in the up-down direction is being fixed to the inner surface of the said crystallization tank 1, The lower end of the said baffle plate 4 is close to the inner bottom surface of the said crystallization tank 1. .

When producing terephthalic acid in a plurality of crystallization tanks connected in series, the entire crystallization tank of terephthalic acid is provided in a crystallization tank having a stirrer in which stirring blades are close to the inner bottom surface and a baffle plate extending in the vertical direction on the inner surface of the crystallization tank. It is preferable to crystallize at least 50% by weight, preferably at least 70% by weight, of the crystallization amount.

In FIG. 1, 5 shows the inflow pipe of the aqueous solution of terephthalic acid connected to the said crystallization tank 1, 6 shows the outflow pipe of this aqueous solution connected to the said crystallization tank 1. As shown in FIG.

Therefore, when the stirring blade 3 which drives the rotating shaft 2 by the drive of a motor (not shown), and the lower end approaches the inner bottom surface of the crystallization tank 1, the terephthalic acid in the said crystallization tank 1 is rotated. The aqueous solution is crystallized by the respective wing bodies 3a having a narrow upper and lower widths while being pressed by the respective wing bodies 3a having a larger upper and lower width at the base portion side in the lower portion of the crystallization tank 1 toward the tip portion. Along the inner bottom of (1), there is a concentrated outward flow, and then the aqueous solution is a high velocity upward flow along the baffle plate (4) whose lower end is close to the inner bottom, and then the crystallization tank (1) It flows toward the central part of and becomes a downward flow from the said central part, and becomes a circulation flow (C).

As the operation conditions, the stirring power of the crystallization tank 1 is preferably 0.01 to 10 kPa / m 3, more preferably 0.1 to 1.0 kPa / m 3, and the stirring power is in the range of 0.15 to 0.7 kPa / m 3. Carried out in.

Therefore, the aqueous solution becomes a slurry at the central portion of the inner bottom surface of the crystallization tank 1, and does not become stagnant, and at the same time, it is a non-uniform and high velocity flow in the peripheral portion near the inner surface of the crystallization tank 1. Crystallization does not occur, and crystals of uniform particle size are obtained efficiently.

And as mentioned above, since there is no stagnation as a slurry, even if the stirring blade 3 is rotated at low speed, the slurry is not seen, so the rotation speed of the stirring blade 3 can be controlled in a wide range, and thus the stagnation time. In addition, it is possible to control the classification effect, so that artificial production of crystals having a uniform particle size distribution or a variety of particle diameter distributions becomes possible.

For example, terephthalic acid having a narrow particle size distribution such that the average particle diameter is in the range of 50 to 150 µm, preferably 80 to 110 µm and the standard deviation is 30 to 50 can be obtained. For example, in that case, stirring power is 0.01-10 mW / m <3>, Preferably it is 0.1-1.0 mW / m <3>.

The standard deviation is obtained by the following equation. That is, when the mean value (X), standard deviation (s), representative value (X ₀ ), interval width (h), frequency (f), number of data (N), u = (XX ₀ ) / h,

medium; X = X ₀ + ∑ (u × f) / N × h

Standard Deviation; s = h × √ (1 / (N-1) × {Σ (u ² × f) − (∑uf) ² / N}).

In addition, although the example which formed the stirring blade 3 with the six blade bodies 3a was shown in this embodiment, it is not limited to this, You may form with two or more blade bodies 3a.

Further, the crude terephthalic acid is dissolved in an aqueous medium, purified by contacting with a platinum group metal catalyst under a temperature condition of 260 to 320 ° C, and stepwise in a plurality of crystallization tanks in which terephthalic acid is connected in series from the aqueous solution of terephthalic acid. At the time of cooling and crystallizing, the crystallization temperature in the first crystallization tank is set to 240 to 260 ° C, stirring is carried out with a stirring blade in the range of 0.01 to 10 kPa / m 3, and the crystallization temperature in the second crystallization tank is then changed. The manufacturing method of terephthalic acid which uses 180-230 degreeC is preferable.

In this case, it is preferable to make the crystallization temperature in a 2nd crystallization tank 20-60 degreeC lower than the crystallization temperature of a 1st crystallization tank, and to make 180-230 degreeC the crystallization temperature in a 2nd crystallization tank by changing stirring power.

FIG. 2: shows 2nd Embodiment of this invention, and in the said embodiment, the front-end | tip part of the inflow pipe 5 in the crystallization tank 1 of the said 1st embodiment is upwards in the said crystallization tank 1 And the opening 5a of the inflow pipe 5 is formed upward, and the outflow pipe 6 is also bent upwardly in the crystallization tank 1 to be bent to form the opening 5a of the inflow pipe 5 and the outflow. The opening 6a of the tube 6 was formed upward.

Thus, the terephthalic acid aqueous solution flows upward in the solution flowing upward from the periphery in the crystallization tank 1 from the opening 5a of the inflow pipe 5 so that vapor does not directly wind the blade to the stirring blade 3 Since the discharge efficiency of the aqueous solution in () does not decrease, and the opening 6a of the outflow pipe 6 also faces upward, the aqueous solution rising from the periphery in the crystallization tank 1 does not directly flow in and discharges. It is possible to lengthen, and crystallized crystallized in the aqueous solution which reached above the opening 6a flows downward, flows into the opening 6a, and discharges it from the discharge pipe 6. Thus, a uniform crystal having a predetermined particle size or more is obtained.

Fig. 3 shows a third embodiment of the present invention. In this embodiment, the tip end portion of the inflow pipe 5 according to the first embodiment is bent upwardly in the crystallization tank 1 to be folded to form the inflow. The opening 5a of the pipe 5 is formed upward, and an inverted cone flow dispersion 5b is provided above the opening 5a, and the tip end of the outlet pipe 6 is bent downward. It formed by folding and closing the cross section of the said tip part, and the opening 6b was formed in the direction opposite to the inner surface of the said crystallization tank 1 at the side surface of the said tip part.

Thus, the aqueous solution of terephthalic acid is dispersed by the inverted conical flow dispersion 5b after outflowing from the opening 5a of the inflow pipe 5, and dispersed and introduced into the aqueous solution in the crystallization tank 1, so that the wings of the wafer It is possible to prevent the winding of the furnace, to improve the discharge efficiency of the aqueous solution by the stirring blades 3, and to obtain an initial dispersing action using the incoming energy. In addition, the opening 6b of the outflow pipe 6 is located at the position where the crystallized particles rise with and with the aqueous solution at the periphery of the inner bottom surface of the crystallization tank 1, so that crystals having a predetermined particle size or more are determined. Particles are reliably sucked under negative pressure in the opening 6b.

1 is a cross-sectional view of the first embodiment of the present invention.

It is sectional drawing of the principal part of 2nd Embodiment of this invention.

It is sectional drawing of the principal part of 3rd Embodiment of this invention.

4 is a cross-sectional view of an example of a conventional manufacturing apparatus.

5 is a cross-sectional view of another example of a conventional manufacturing apparatus.

6 is a graph showing the relationship between the stirring power and the particle size distribution of terephthalic acid in the crystallization tank of the production apparatus of the present invention and the conventional production apparatus.

<Explanation of Codes>

1: crystallization tank 2: rotating shaft

3: stirring blade 3a: wing body

4: baffle plate 5: inlet pipe

5a: opening 5b: flow dispersion

6: outlet tube 6a; 6b: opening

a: stirring tank b: rotating shaft

c: stirring blade d: baffle plate

e: crystallization tank f: axis of rotation

g: stirring blade h: collision plate

i: inlet pipe j: outlet pipe

Best Mode for Carrying Out the Invention

Hereinafter, although an Example demonstrates this invention, this invention is not limited to an Example.

(Example 1)

The present inventor will specifically explain the experiment when the above-mentioned conventional manufacturing apparatus and the manufacturing apparatus of the third embodiment of the present invention are continuously operated.

A water slurry of high purity terephthalic acid having a particle diameter distribution of 74 to 149 µm was prepared, and the slurry was pressurized in a dissolution tank and connected in three series of crystallization tanks having the same capacity from an aqueous solution of terephthalic acid dissolved completely at 220 ° C. Crystallization was performed.

In this case, when the inner diameter of the first crystallization tank is D and the blade diameter is R, the stirring blade diameter R is 0.5D, and the shape of the blade is 0.5R in the vertical direction at the center portion side, and at the blade tip portion. The stirring blade which consists of six wings which consist of 0.15R of the length of an up-down direction was used. The ratio (c / R) of the clearance (c) between the lower end of the stirring blade and the inner bottom surface of the crystallization tank and the blade diameter (R) of the stirring blade was 0.02. Moreover, the rotation speed was changeable and crystallization was performed at 0.2 and 0.7 dl / m <3>. On the other hand, as a 2nd crystallization tank, the stirring blade which has the inclined paddle blade of four blades was used constantly with 0.7 kW / m <3> of stirring powers.

The temperature of the first crystallization tank and the second crystallization tank is controlled to be 160 ° C of the first crystallization tank temperature and 120 ° C of the second crystallization tank so that about 70% by weight and about 99% by weight of the total amount of terephthalic acid precipitates, respectively 3 crystallization tank was temperature-controlled so that it might become 100 degreeC.

The result of the physical property test regarding terephthalic acid particle | grains is shown. In FIG. 6, the difference between an Example and a comparative example uses the inclined paddle blade | wing whose blade diameter is 0.5D in a comparative example, and all other operating conditions are the same as an Example. In addition, the particle size used the laser diffraction scattering particle size distribution analyzer.

The average particle diameter when the stirring power was 0.2 kPa / m 3 was 190.7 µm, and the standard deviation was 61.1. Moreover, when the stirring power was 0.7 kPa / m <3>, the average particle diameter was 134 micrometers and the standard deviation was 46.9, and terephthalic acid with a narrow particle size distribution was obtained.

As described above, according to the present invention, it is possible to efficiently obtain the crystal of terephthalic acid and also to control the particle diameter of the crystal.

Claims (12)

When crystallizing terephthalic acid from an aqueous solution of terephthalic acid, a crystallizer is provided with an agitator in which stirring blades are placed close to the inner bottom surface, and a baffle plate extending in the vertical direction on the inner surface of the crystallization tank. A method for producing terephthalic acid using a crystallization apparatus in which the ratio (c / R) of the clearance (c) between the inner bottom of the crystallization tank and the blade diameter (R) of the stirring blade is in the range of 0.005 to 0.10. The shape of the stirring vane is formed in a plate shape in which the length in the vertical direction is long at the center of the crystallization tank, and the length in the vertical direction is gradually shortened toward the periphery of the crystallization tank. Method for producing terephthalic acid. The method for producing terephthalic acid according to claim 1 or 2, wherein the opening of the inflow pipe of the aqueous solution of terephthalic acid connected to the crystallization tank is formed upward in the crystallization tank. delete The crystallization tank according to claim 1 or 2, wherein the crystallization tank comprises a plurality of crystallization tanks connected in series, including a first crystallization tank and a second crystallization tank connected in series with the first crystallization tank. The first crystallization tank has a stirrer having the stirring blade close to the inner bottom, and a baffle plate extending in the vertical direction is provided on the inner surface of the crystallization tank, and in the first crystallization tank, at least 50 weight of the total crystallization amount of terephthalic acid in the first crystallization tank. Crystallization of%, the method for producing terephthalic acid. The method for producing terephthalic acid according to claim 5, wherein the stirring power of the stirring blades of the first crystallization tank is 0.01 to 10 mW / m 3. The inner diameter of the crystallization tank is set to D and the stirring blade diameter R, wherein the stirring blade diameter R is (0.3 to 0.8) D, and the shape of the blade has a length in the vertical direction at the center side ( 0.1 to 3.0) R, and a plurality of stirring blades having a length of (0 to 0.5) R in the vertical direction at the wing tip are used. The crude terephthalic acid according to claim 5, which is dissolved in an aqueous medium, and purified by contacting with a platinum group metal catalyst under a temperature condition of 260 to 320 ° C, and terephthalic acid is purified from the aqueous solution of terephthalic acid in the first crystallization tank. And crystallization temperature in the first crystallization tank is 240 to 260 ° C. when the crystallization is carried out stepwise by cooling in a plurality of crystallization tanks connected in series including the second crystallization tank connected in series to the first crystallization tank. The stirring blade was stirred with a stirring blade in a range of 0.01 to 10 Pa / m 3, and the crystallization temperature in the second crystallization tank was set to 180 to 230 ° C., and the crystallization temperature was lower than that of the first crystallization tank. 20-60 degreeC can be made low, The manufacturing method of terephthalic acid characterized by the above-mentioned. The preparation of terephthalic acid according to any one of claims 1 to 7, wherein the particle size distribution of the terephthalic acid particles is produced separately by changing the stirring power to change the rotation speed of the stirring blades. Way. delete delete 6. The stirring blade diameter (R) is (0.3 to 0.8) D, and the shape of the blade is in the up-down direction at the central portion, when the inner diameter of the first crystallization tank is D and the stirring blade diameter is R. A method for producing terephthalic acid, characterized in that a plurality of stirring blades having a length of (0.1 to 3.0) R and a length of (0 to 0.5) R in the vertical direction at the tip of the blade are used.

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