CN101209964B - Method for preparing high pure terephthalic acid - Google Patents
Method for preparing high pure terephthalic acid Download PDFInfo
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- CN101209964B CN101209964B CN2007103004339A CN200710300433A CN101209964B CN 101209964 B CN101209964 B CN 101209964B CN 2007103004339 A CN2007103004339 A CN 2007103004339A CN 200710300433 A CN200710300433 A CN 200710300433A CN 101209964 B CN101209964 B CN 101209964B
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Abstract
The present invention provides a method for manufacturing terephthalic acid with high purity, capable of preventing a heat exchanger from blockage due to boiler scale of the terephthalic acid and generation thereof, forming coarse terephthalic acid aqueous solution with high concentration and implementing hydrogenation reaction with high efficiency so as to manufacture PTA availably. The method is characterized in that including: (I) mixing the coarse terephthalic acid obtained by liquid phase oxidation to p-xylene with water to form coarse terephthalic acid slurry, (II) heating the coarse terephthalic acid slurry step by step using a plurality of heat exchangers to form coarse terephthalic acid slurry aqueous solution, (III) implementing hydrogenation treatment to the coarse terephthalicacid slurry aqueous solution, (IV) step down coolling the terephthalic acid slurry aqueous solution after hydrogenation treatment, and seeding out terephthalic acid using a plurality of seedout grooves, (V) implementing solid-liquid separation to the obtained terephthalic acid slurry, wherein the flow rate of the coarse terephthalic acid slurry with less 200 DEG C is above 1.7 m/s in the step (II).
Description
Technical field
The present invention relates to high purity terephthalic acid's method of manufacture; In more detail; The present invention relates to a plurality of heat exchangers with the aqueous slurry of crude terephthalic acid step by step heating for dissolving, when making the crude terephthalic acid aqueous solution, can prevent because the incrustation scale of the terephthalic acid in the heat exchanger forms and the high purity terephthalic acid's of the obstruction that growth causes method of manufacture.
Background technology
Add depress, in the acetate solvate and exist under the condition of the oxide catalysts such as catalyzer that contain cobalt, manganese and bromine; With the gas that contains molecularity oxygen under liquid phase during oxidation of p-xylene; Outside terephthalic acid (below, also be designated as " TA "), also generate as major impurity contain the 4-carboxyl benzaldehyde (below; Also be designated as " 4-CBA ") crude terephthalic acid (below, also be designated as " CTA ").But, in the manufacturing of trevira etc., require high purity terephthalic acid (below, also be designated as " PTA "), therefore to need refining above-mentioned CTA as raw material.
As the process for purification of CTA, known following method promptly, the slurry heating that CTA is suspended in water, forms the aqueous solution, in the presence of hydrogenation catalyst, carries out hydrogen treatment, treatment solution is carried out crystallization is separated out and solid-liquid separation is made PTA.Generally in industry, fully be dissolved in the water in order to make CTA, use a plurality of heat exchangers to carry out step by step mostly, in addition, hydrogen treatment is that the logical liquid of the CTA aqueous solution is implemented (for example, with reference to patent documentation 1～4) in the catalyzer packing layer mostly.But, even fully heat the CTA slurry, still can stop up sometimes in the manufacturing installation, produce variety of issue during continuous operation.For this reason, in order to address these problems people various schemes had been proposed in the past.
For example, flow to the occasion of the packing layer of hydrogenation catalyst, be difficult to realize stable continuous running (with reference to patent documentation 1 and 4) at undissolved terephthaldehyde's acid crystal.In these patent documentations; As countermeasure, following PTA method of manufacture has been proposed, promptly; Partly be provided with by overflow wall at the upper entrance of filling the tower reactor drum and separate the stagnant area that forms; The CTA aqueous solution is supplied with this stagnant area, and after making it to overflow overflow wall, logical liquid is to the catalyzer packing layer that is positioned at this bottom, stagnant area.
On the other hand, heat exchanger inside also can be stopped up sometimes, is difficult to continuous operation stably.When particularly using a plurality of heat exchangers to heat step by step this problem taking place, is seeking improved countermeasure.
[patent documentation 1] spy opens flat 6-128191 communique
[patent documentation 2] spy opens flat 8-208561 communique
[patent documentation 3] spy opens flat 8-225489 communique
[patent documentation 4] spy opens the 2004-203864 communique
Summary of the invention
The present invention accomplishes in order to solve the problem that exists in the above-mentioned prior art; The objective of the invention is to; A kind of high purity terephthalic acid's method of manufacture is provided, can prevents the obstruction that incrustation scale forms and growth causes, form the crude terephthalic acid aqueous solution of high density owing to the terephthalic acid in the heat exchanger; Carry out hydrogenation expeditiously, thereby make PTA effectively.
For addressing the above problem; The inventor has carried out deep research; The result finds; In the occasion of using a plurality of heat exchangers to heat step by step, being blocked in the heat exchanger that slurry temp is the ratio lesser temps below 200 ℃ in the heat exchanger takes place, and this obstruction is that the incrustation scale by terephthalic acid forms and grows and causes.And then find, through being that the flow rate control of CTA slurry in heat exchanger below 200 ℃ is 1.7m/ more than second with temperature, can not taking place because the obstruction that the incrustation scale of the terephthalic acid in the heat exchanger forms and growth causes, thereby accomplish the present invention.
Promptly; High purity terephthalic acid's of the present invention method of manufacture; It is characterized in that; Comprise: the crude terephthalic acid that (I) will obtain through the liquid-phase oxidation of p-Xylol mixes, forms the operation of crude terephthalic acid slurry with water; (II) heat, make its dissolving to form the operation of the crude terephthalic acid aqueous solution with a plurality of heat exchangers step by step to this crude terephthalic acid slurry; (III) this crude terephthalic acid aqueous solution is carried out hydrotreated operation, (IV) separate out aqueous terephthalic acid solution step by step step-down cooling, the crystallization of groove after and separate out the operation of terephthalic acid, (V) terephthalic acid slurry that obtains is carried out the operation of solid-liquid separation hydrogenation with a plurality of crystallizations; Wherein, in above-mentioned operation (II), temperature is that the flow velocity of crude terephthalic acid slurry in heat exchanger below 200 ℃ is that 1.7m/ is more than second.
Preferably, above-mentioned operation (II) comprises at least 1 operation (II-A), and this operation (II-A) is with heating crude terephthalic acid slurry in the steam delivery heat exchanger that is produced by the step-down cooling in the said operation (IV); And then; More preferably comprise 1 operation (II-B) at least; This operation (II-B) will contain the high temperature fluid of steam that in said operation (IV), is produced by the step-down cooling and the phlegma that in the heat exchanger that imports the steam higher than the temperature and pressure of this steam, produces; Import the heat exchanger lower, heating crude terephthalic acid slurry than this heat exchanger temperature.
In addition, above-mentioned heat exchanger is preferably multi tube heat exchanger, and the concentration of the crude terephthalic acid in the above-mentioned crude terephthalic acid slurry is preferably 10～40 weight %.
Through the present invention; Can prevent when heating crude terephthalic acid slurry is made the crude terephthalic acid aqueous solution owing to the incrustation scale formation of the terephthalic acid in the heat exchanger and the obstruction of growing and causing thereof; Form the crude terephthalic acid aqueous solution of high density; Carry out hydrogenation expeditiously, thereby make PTA expeditiously.
Description of drawings
Fig. 1 is the synoptic diagram of the 1st manufacturing installation (n=4).
Fig. 2 is the synoptic diagram of the 2nd manufacturing installation (n=4).
Fig. 3 is the synoptic diagram of the 3rd manufacturing installation (n=4).
Fig. 4 is the synoptic diagram of the 4th manufacturing installation (n=4).
Nomenclature
1 tempering tank
21 first multi tube heat exchangers (i=1)
22 second multi tube heat exchangers (i=2)
23 the 3rd multi tube heat exchangers (i=3)
24 the 4th multi tube heat exchangers (i=4)
3 heat exchangers
4 hydrogenation grooves
Groove (i=1) is separated out in 51 first crystallizations
Groove (i=2) is separated out in 52 second crystallizations
Groove (i=3) is separated out in 53 the 3rd crystallizations
Groove (i=4) is separated out in 54 the 4th crystallizations
6 equipment for separating liquid from solid
71～74 pressure regulator valves
8 phlegma accumulator tanks
9 steam pipe arrangements
10 phlegma pipe arrangements
The CTA crude terephthalic acid
The PTA high purity terephthalic acid
Embodiment
High purity terephthalic acid's of the present invention method of manufacture; Comprise: the crude terephthalic acid that (I) will obtain through the liquid-phase oxidation of p-Xylol mixes, forms the operation of crude terephthalic acid slurry with water; (II) heat, make its dissolving to form the operation of the crude terephthalic acid aqueous solution with a plurality of heat exchangers step by step to this crude terephthalic acid slurry; (III) this crude terephthalic acid aqueous solution is carried out hydrotreated operation; (IV) aqueous terephthalic acid solution after the hydrogenation is separated out in a plurality of crystallizations carry out step-down cooling step by step in the groove, the operation of terephthalic acid is separated out in crystallization, (V) terephthalic acid slurry that obtains is carried out the operation of solid-liquid separation.
(I) slurry forms operation
In this operation, the crude terephthalic acid that will obtain through the liquid-phase oxidation of p-Xylol mixes with water, forms the crude terephthalic acid slurry.The liquid-phase oxidation of p-Xylol can be utilized in that normally used oxidation reactor carries out in the manufacturing of terephthalic acid.Described oxidation reactor is preferentially selected raw material, catalyzer, solvents such as the p-Xylol of can packing into for use, in these raw materials of supply etc., is blown into air, carries out the oxidation reactor of liquid-phase oxidation continuously.
The liquid-phase oxidation of above-mentioned p-Xylol uses solvent and catalyzer to carry out usually.As above-mentioned solvent, but lipid acid such as illustration acetic acid, propionic acid, butanic acid, isopropylformic acid, positive valeric acid, pivalic, caproic acid, or the mixture of they and water.Wherein, the mixed solvent of preferred acetic acid or acetic acid and water.
As above-mentioned catalyzer, can enumerate heavy metal, bromine and their compound, as heavy metal, can enumerate nickel, cobalt, iron, chromium, manganese etc.These catalyzer preferably use with the form that is dissolved in the reactive system.As above-mentioned catalyzer, the preferred merging used cobalt cpd and manganic compound and bromine compounds, and with respect to solvent, the usage quantity of cobalt cpd is converted into cobalt and is generally 10～10000ppm, is preferably 100～3000ppm.In addition, manganic compound is preferably 0.001～10 with manganese with respect to the atomic ratio measuring of cobalt, and more preferably 0.001～2, bromine compounds is preferably 0.001～10 with bromine with respect to the atomic ratio measuring of cobalt, and more preferably 0.001～5.
The liquid-phase oxidation of p-Xylol uses the gas that contains molecularity oxygen to carry out usually.As such oxygen-containing gas, usually use the air of oxygen that for example used air or enrichment with the dilution oxygen of oxygen with inert gas dilution.The temperature of oxidizing reaction is generally 150～270 ℃, is preferably 170～220 ℃, and pressure is that mixture can keep more than the pressure of liquid phase under temperature of reaction at least, is generally 0.5～4MPa (gauge pressure).And then the reaction times is depended on the size of device etc., is generally 20 minutes～180 minutes degree as the residence time.Moisture concentration in the reactive system is generally 3～30 weight %, is preferably 5～15 weight %.
CTA by above-mentioned liquid phase oxidation reaction obtains separates from the mother liquor of liquid phase oxidation reaction through solid-liquid separation, reclaims.Usually the 4-CBA that contains 0.1～0.4 weight % degree among the CTA that reclaims.In tempering tank, these CTA are mixed, form the CTA slurry with water.Above-mentioned tempering tank can use normally used tempering tank in the manufacturing of terephthalic acid.The CTA concentration of above-mentioned CTA slurry is generally 10～40 weight %, is preferably 20～30 weight %.
(II) aqueous solution forms operation
Terephthalic acid is low-solubility in water at normal temperatures and pressures, in order to improve the solubleness in water, needs to form HTHP.In this operation, at first, above-mentioned CTA slurry is pressurizeed with topping-up pump, then, heat, dissolve CTA step by step with a plurality of heat exchangers, form the CTA aqueous solution.As heat exchanger, can use normally used heat exchanger in the manufacturing of terephthalic acid, preferably use multi tube heat exchanger.
High temperature fluid, particularly steam are imported in these heat exchangers, and these high temperature fluids and/or steam and above-mentioned CTA slurry carry out heat exchange, and above-mentioned CTA slurry is heated, and the CTA dissolving forms the CTA aqueous solution.Also can high temperature fluid and/or the steam from other path be imported in the above-mentioned heat exchanger, preferred import after state operation (IV) crystallization separate out the steam that produces by the step-down cooling in the groove (below, this operation is called " operation (II-A) ").In addition, can also and use the operation [" operation (II-C) "] of using well heater (heater) to wait other well heaters.This operation (II-C) can be used as preheating procedure be arranged on above-mentioned operation (II-A) and after state operation (II-B) before, perhaps, also can be used as the post-heating operation be arranged on above-mentioned operation (II-A) and after state operation (II-B) afterwards.
And then; In the present invention; Preferably, at least 1 in above-mentioned heat exchanger, import after state operation (IV) crystallization separate out the steam [operation (II-A)] that produces by the step-down cooling in the groove; In at least 1 in remaining heat exchanger, import contain after state operation (IV) crystallization separate out the steam that produces by the step-down cooling in the groove and at the high temperature fluid [operation (II-B)] of the phlegma that more generates in the pyritous heat exchanger than this heat exchanger.At this moment, this steam and high temperature fluid and above-mentioned CTA slurry carry out heat exchange, heat above-mentioned CTA slurry, and steam and high temperature fluid become the highly compressed phlegma, are commonly used to the heating source as more cryogenic heat exchanger.Particularly, will import the phlegma of vapor condensation of the heat exchanger of operation (II-A), and import after the step-down to separate out in the steam that produces in the groove and form high temperature fluid, import the more cryogenic heat exchanger of heat exchanger than operation (II-A) in the crystallization of operation (IV).The pressure of the phlegma of step-down, with the pressure of the steam that imports phlegma be same degree.
Consider from the angle of effciency of energy transfer, preferably, in operation (II), only contain 1 above-mentioned operation (II-A).
Heating temperature in above-mentioned operation (II-A) and the operation (II-B), the temperature of the steam that produces according to operation (IV) is confirmed.In addition, the pressure of the steam that also produces according to operation (IV) of the pressure of the steam of importing and high temperature fluid is confirmed.
In this operation, in order fully to dissolve CTA, the CTA aqueous solution is heated to more than 230 ℃ usually, preferably is heated to 240～300 ℃.Intrasystem pressure during heating so long as can make the aqueous solution keep above the getting final product of pressure of liquid phase basically, has no particular limits, and is generally 1～11MPa (gauge pressure), is preferably 3～9MPa (gauge pressure).
The concentration of the CTA aqueous solution of making like this, the concentration decision by above-mentioned CTA slurry is generally 10～40 weight %, is preferably 20～30 weight %.
In this operation of the present invention (II), be that the flow rate control of CTA slurry in heat exchanger below 200 ℃ is 1.7m/ more than second with temperature, preferably be controlled to be 2.0m/ more than second, more preferably be controlled to be 2.2m/ more than second.In order fully to dissolve terephthalic acid, the upper limit of flow velocity is preferably 10.0m/ below second, and more preferably 5.5m/ is below second.With temperature be the flow rate control of CTA slurry in heat exchanger below 200 ℃ in above-mentioned scope, can prevent to make the CTA aqueous solution expeditiously because the incrustation scale in the heat exchanger generates the obstruction that causes.
(III) hydrogen treatment operation
In this operation,, make the 4-CBA that contains in the CTA aqueous solution be reduced to 4-tolyl acid (4-MBA) with implementing hydrogen treatment in the above-mentioned CTA aqueous solution importing hydrogenation groove.
Above-mentioned hydrogenation groove, so long as have the catalyst layer of having filled hydrogenation catalyst, the reactive tank that under catalyzer and CTA aqueous solution state of contact, can supply with hydrogen gets final product, not special restriction such as its shape, structure.As preferred hydrogenation groove; Can enumerate inside and have the stagnant catalyst layer of having filled solid catalyst; And have the aqueous solution introduction channel and the aqueous solution derivation passage that can make logical liquid to this catalyst layer of the CTA aqueous solution, and then has the hydrogenation groove of the hydrogen feed path that can supply with hydrogen.The logical liquid direction of the CTA aqueous solution is restriction not, can to the upper reaches, also can be to dirty.Preferably, for this reason, preferably aqueous solution introduction channel is arranged at the top of hydrogenation groove, the aqueous solution is derived passage be arranged at the bottom to the dirty liquid that leads to.In addition, preferably supply with hydrogen, for this reason, preferably the hydrogen feed path is arranged at the top of hydrogenation groove by top.
As hydrogenation catalyst; Can use the hydrogenation catalyst that in the past used; For example can enumerate: palladium, ruthenium, rhodium, osmium, iridium, platinum, platinum black, palladium black, iron, cobalt-nickel etc. preferably are supported at it on carrier, preferably are supported on the adsorptive supports such as gac can form the solid catalyst of immovable bed.
As concrete hydrogenation treatment method; For example; The CTA aqueous solution is imported in the hydrogenation groove, one side make its through catalyst layer, one side with common 1.5 times more than the mole of the 4-CBA in the CTA aqueous solution, be preferably 2 times of flow hydrogen supplies more than the mole, carry out hydrogenation.Temperature of reaction during hydrogenation is generally more than 230 ℃, is preferably 255～300 ℃, and pressure is generally 1～11MPa, is preferably 3～9MPa (gauge pressure), and the hydrogen dividing potential drop is generally more than the 0.05MPa, is preferably 0.05～2MPa.
Through such hydrogen treatment, the 4-CBA among the CTA is reduced to water-soluble 4-MBA.On the other hand because TA is insoluble in water, usually through below 300 ℃, be preferably and carry out under 100～280 ℃ the temperature that crystallization is separated out and solid-liquid separation, can from the CTA aqueous solution, separate 4-MBA, obtain PTA.
(IV) operation is separated out in crystallization
In this operation, the CTA aqueous solution after the above-mentioned hydrogenation (below be called " CTA hydrogen treatment liquid ") is separated out step-down cooling step by step in the groove in a plurality of crystallizations, TA is separated out in crystallization.Separate out groove as crystallization, can use in the manufacturing of terephthalic acid normally used crystallization to separate out groove.Particularly, separate out in the groove, import above-mentioned CTA hydrogen treatment liquid,, cool off the method for CTA hydrogen treatment liquid (step-down cooling) simultaneously the pressure decompression of CTA hydrogen treatment liquid in the crystallization that is set at the pressure condition lower than the pressure of above-mentioned CTA hydrogen treatment liquid.In the present invention, use a plurality of crystallizations to separate out groove, the pressure of CTA hydrogen treatment liquid is reduced pressure step by step, reduce the temperature of CTA hydrogen treatment liquid simultaneously step by step.Thus, terephthalic acid is separated out in crystallization, forms the TA slurry.
When as above-mentioned, carrying out the step-down cooling, the part gasification of separating out the water medium in the CTA hydrogen treatment liquid in the groove in each crystallization produces steam.Preferably, as above-mentioned, this steam is imported in the heat exchanger of above-mentioned operation (II), be used as the heating source of CTA slurry.Particularly; Consider preferably from the angle of effciency of energy transfer; To separate out the steam that produces through the step-down cooling in the groove in the highest temperature highly compressed crystallization that above-mentioned crystallization is separated out in the groove, not import, import individually in the heat exchanger of operation (II) by the phlegma that generates in the heat exchanger.
The temperature of the CTA hydrogen treatment liquid that is cooled through step-down cooling and the steam of generation can suit to determine by the pressure when being adjusted at each crystallization and separating out step-down cooling in the groove.
(V) solid-liquid separation process
In this operation, above-mentioned TA slurry is carried out solid-liquid separation, from mother liquor, separate, reclaim PTA.Solid-liquid separation can use normally used equipment for separating liquid from solid in the manufacturing of terephthalic acid such as filter, separating centrifuge to implement.
In addition, also can once more above-mentioned PTA be suspended in water, make the foreign matter that is attached in the PTA crystallization move to aqueous phase, carry out solid-liquid separation and drying then.
< manufacturing installation >
High purity terephthalic acid's of the present invention method of manufacture; Can use following manufacturing installation to carry out: groove and the equipment for separating liquid from solid manufacturing installation by this high purity terephthalic acid who is connected in series is in proper order separated out in tempering tank, a plurality of heat exchanger, reactive tank, a plurality of crystallization, and it has n heat exchanger and groove is separated out in n crystallization.The present invention does not hinder the recovery of heat that utilizes the heat exchanger beyond the said n heat exchanger.That is, shown in Fig. 1～4, that works and use the recovery of heat that utilizes other thermals source like heat exchanger 3.In addition, such heat exchanger can be a plurality of.
< the 1st manufacturing installation >
In the 1st manufacturing installation, heat exchanger is separated out groove with crystallization and is not connected, and can not utilize crystallization to separate out the steam that groove produces.But import the steam (with reference to Fig. 1 (occasion of n=4)) that produces by other paths in this occasion heat exchanger.
< the 2nd manufacturing installation >
In the 2nd manufacturing installation, at least 1 heat exchanger and this crystallization are separated out groove and are connected to import crystallization and separate out the steam that groove is produced.Remaining heat exchanger can be connected with other thermal source lead-in path; Also can pass through other heater heats of well heater (heater) etc.; Consider that from the angle of effciency of energy transfer preferred whole heat exchanger is separated out groove with crystallization and is connected (with reference to Fig. 2 (occasion of n=4)).
Separate out the occasion that groove is connected in a plurality of heat exchangers and crystallization, consider from the angle of effciency of energy transfer, preferably the heat exchanger of the highest temperature in these heat exchangers is separated out groove with the crystallization of highest temperature highly compressed and is connected.
< the 3rd, the 4th manufacturing installation >
In the 3rd and the 4th manufacturing installation, at least 1 heat exchanger and this crystallization are separated out groove and are connected to import crystallization and separate out the steam that groove is produced.
In addition; In remaining heat exchanger at least 1; Separate out groove through steam pipe arrangement and crystallization and be connected, in the way of this steam pipe arrangement, be connected with the phlegma pipe arrangement that is connected with the heat exchanger higher, in the way of this phlegma pipe arrangement, be provided with pressure regulator valve than this heat exchanger temperature and pressure.Thus, the phlegma that heat exchanger is generated imports crystallization and separates out in the steam that groove produces, and forms high temperature fluid, imports than this heat exchanger this high temperature fluid more in the heat exchanger of low-temp low-pressure.Compare with the above-mentioned the 1st and the 2nd manufacturing installation, the effciency of energy transfer of the 3rd and the 4th such manufacturing installation is better, thereby preferentially selects for use.
Consider that from the angle of effciency of energy transfer preferably, the heat exchanger of the highest temperature in the above-mentioned heat exchanger is separated out groove with the crystallization of highest temperature highly compressed and is connected.
In addition, preferably, at least 1 of above-mentioned heat exchanger (below; This heat exchanger is called " heat exchanger α ") with crystallization separate out groove (below; Groove is separated out in this crystallization is called " groove α is separated out in crystallization ") connect, than heat exchanger α at least 1 in the heat exchanger of low-temp low-pressure (below, this heat exchanger is called " heat exchanger β ") more; Through the steam pipe arrangement be different from crystallization separate out the crystallization of groove α separate out groove (below; Groove is separated out in this crystallization is called " groove β is separated out in crystallization ") connect, in the way of this steam pipe arrangement, be connected with the phlegma pipe arrangement that is connected with heat exchanger α, in the way of this phlegma pipe arrangement, be provided with pressure regulator valve.
Consider that from the angle of effciency of energy transfer more preferably, in manufacturing installation of the present invention, only separating out the heat exchanger that groove is connected with crystallization is 1.
The concrete example of such manufacturing installation (occasion of n=4) is shown among Fig. 3 and Fig. 4.The 3rd manufacturing installation shown in Figure 3; Enumerated following manufacturing installation: heat exchanger (n) is separated out groove (1) through pipe arrangement and crystallization and is connected; Separate out groove (n-i+1) from the heat exchanger (i) of low temperature one side i number (i is the integer more than 1, below the n-1) through steam pipe arrangement and crystallization and be connected, in the way of this steam pipe arrangement, be connected with the phlegma pipe arrangement (with reference to Fig. 3) that is connected with heat exchanger (i+1).Preferably, in the phlegma pipe arrangement, pressure regulator valve is set.
The 4th manufacturing installation shown in Figure 4; Enumerated following manufacturing installation: heat exchanger (n) is separated out groove (1) through pipe arrangement and crystallization and is connected; Heat exchanger (i) is separated out groove (n-i+1) through steam pipe arrangement and crystallization and is connected, and in the way of this steam pipe arrangement, is connected with the phlegma pipe arrangement (i is the integer more than 1, below the n-1) that is connected with heat exchanger (i+2).In such occasion, also preferably in the phlegma pipe arrangement, pressure regulator valve is set.
Below; Steam that groove produces is separated out in crystallization during for the manufacturing installation manufacturing high purity terephthalic acid that utilizes the 3rd or the 4th and the method for utilizing of phlegma describes; Specifically, groove is separated out in n (n is the integer 2 or more) crystallization in operation (IV), using, the method for utilizing when in operation (II), using n utilization separated out the groove generation by this n crystallization steam as the heat exchanger of heating source describes.
Separate out groove with the crystallization of highest temperature highly compressed and separate out groove (1) as crystallization, low temperature side order for crystallization separate out groove (2), crystallization separate out groove (3) ..., crystallization separates out groove (n-1), separate out groove with the crystallization of lowest temperature low pressure and separate out groove (n) as crystallization.In addition, with the heat exchanger of lowest temperature as heat exchanger (1), high temperature side be in proper order heat exchanger (2), heat exchanger (3) ..., heat exchanger (n-1), the heat exchanger of the highest temperature is heat exchanger (n).
Usually, separate out the steam that produces by the step-down cooling in the groove (1), consider, preferably do not import the phlegma that in heat exchanger, generates, and import to individually in the heat exchanger (n) from the angle of effciency of energy transfer in the crystallization of highest temperature highly compressed.
In addition; Will be than heat exchanger (i) (i is more than 1, below the n-1 integer) the highly compressed phlegma that generates of pyritous heat exchanger (i+1) more; Importing is the steam that produced by step-down cooling of i number partial crystallization groove from low temperature side; Form high temperature fluid, importing this high temperature fluid from low temperature side is as heating source i number the heat exchanger (i).At this, be that groove is separated out in i number crystallization from low temperature side, if be n-i+ 1 number from the high temperature side number.Therefore, be i number the heat exchanger (i) from low temperature side, import crystallization and separate out the steam that groove (n-i+1) produces and the high temperature fluid of the cold, high pressure lime set of heat exchanger (i+1) generation.Forming the occasion of this high temperature fluid, preferably, reducing the pressure of phlegma, then, with this phlegma import with than in the heat exchanger steam pipe arrangement that more heat exchanger of low-pressure low-temperature is connected that generates this phlegma.
In addition, the former operation is equivalent to operation (II-A), and the latter's operation is equivalent to operation (II-B).
In method of manufacture of the present invention, operation (II-A) and operation (II-B) are not limited to above-mentioned operation, and for example, operation (II-B) also can be following operation.
Will be than heat exchanger (i) (i is more than 1, below the n-1 integer) the highly compressed phlegma that generates of pyritous heat exchanger (i+2) more; Importing is that i number crystallization is separated out the steam that groove produces by the step-down cooling from low temperature side; Form high temperature fluid, importing this high temperature fluid from low temperature side is as heating source i number the heat exchanger (i).With likewise above-mentioned, be that groove is separated out in i number crystallization from low temperature side, if be n-i+ 1 number from the high temperature side number.Therefore, can be i number the heat exchanger (i) from low temperature side also, import crystallization and separate out the steam that groove (n-i+1) produces and the high temperature fluid of the cold, high pressure lime set of heat exchanger (i+2) generation.In such occasion, when forming high temperature fluid, preferably reduce the pressure of phlegma, then, with this phlegma import with than in the heat exchanger steam pipe arrangement that more heat exchanger of low-pressure low-temperature is connected that generates this phlegma.
Embodiment
Below, through embodiment the present invention is described, but the present invention is not limited to this embodiment.The flow velocity of the CTA slurry in first to fourth multi tube heat exchanger of present embodiment, if be 1 with the value in first multi tube heat exchanger, then their flow velocity such as the following stated.
First multi tube heat exchanger 1.0
Second multi tube heat exchanger 0.95～1.1
The 3rd multi tube heat exchanger 0.95～1.1
The 4th multi tube heat exchanger 0.95～1.1
Use the manufacturing installation (n=4) that groove is separated out in 4 multi tube heat exchangers and 4 crystallizations that has as shown in Figure 2; The CTA slurry that with CTA concentration is 30 weight % is supplied with heat exchanger with the flow velocity shown in the table 1; Heating as following; After the CTA aqueous solution that obtains carried out hydrogen treatment,, make the high purity terephthalic acid with CTA treatment solution step-down cooling.In addition, under meter and regulating valve are set,, calculate the flow velocity of CTA slurry by the volume meter of this flow and heat exchanger through the flow of this under meter mensuration CTA slurry in the front of first heat exchanger (i=1).In addition, under the different in flow rate condition, made the high purity terephthalic acid respectively 2 months.
With the 4th crystallization separate out 143 ℃ of the temperature that groove (i=4) produces, the steam of pressure 0.4MPa imports first heat exchanger (i=1).With the 3rd crystallization separate out 182 ℃ of the temperature that groove (i=3) produces, the steam of pressure 1.1MPa imports second heat exchanger (i=2).With second crystallization separate out 207 ℃ of the temperature that groove (i=2) produces, the steam of pressure 1.8MPa imports the 3rd heat exchanger (i=3).With first crystallization separate out 220 ℃ of the temperature that groove (i=1) produces, the steam of pressure 2.3MPa imports the 4th heat exchanger (i=4).With the phlegma after each heat exchanger heat exchange, be depressured to 100 ℃ of temperature, pressure 0.1MPa respectively after, be recovered in the phlegma accumulator tank.
Under the flow velocity in office, the temperature of the CTA slurry of first heat exchanger outlet is 130 ℃～135 ℃, and the temperature of the CTA slurry of second heat exchanger outlet is 180 ℃～185 ℃, and the temperature of the CTA slurry of the 3rd heat exchanger outlet is 200 ℃～205 ℃.
The pressure-losses lift velocity of the CTA slurry from first heat exchanger to second heat exchanger is shown in Table 1.Find that the pressure-losses slightly rises, but do not find the obstruction in the heat exchanger.
Table 1 table 1
| CTA slurry mean flow rate [m/ second] | Pressure-losses lift velocity [MPa/ days] |
| 2.0 | 0.0019 |
| 2.1 | 0.0017 |
In addition, the effciency of energy transfer in the above-mentioned method of manufacture is estimated in the available energy loss (exergy loss) that produces during the phlegma step-down through heat exchanger is generated.The result is shown in Table 2.
Table 2
| Step-down place (left side: before the step-down, the right side: after the step-down) | Temperature before the step-down (℃) | Temperature after the step-down (℃) | High temperature fluid discharging amount (ton/hr) | Available energy loss (GJ/hr) |
| Three sections heat exchanger entrances of the 4th section heat exchanger outlet-Di | 220 | 100 | 30 | 1.72 |
| The 3rd section heat exchanger outlet-second section heat exchanger entrance | 207 | 100 | 3 | 0.14 |
| Second section heat exchanger outlet-first section heat exchanger entrance | 182 | 100 | 5 | 0.14 |
| First section heat exchanger outlet-phlegma accumulator tank | 143 | 100 | 5 | 0.04 |
| Add up to | 43 | 2.04 |
Use the manufacturing installation (n=4) that groove is separated out in 4 multi tube heat exchangers and 4 crystallizations that has as shown in Figure 3; The CTA slurry that with CTA concentration is 30 weight % is supplied with heat exchanger with the flow velocity shown in the table 3; Heat by the following stated; After the CTA aqueous solution that obtains carried out hydrogen treatment,, made the high purity terephthalic acid 1 month with CTA treatment solution step-down cooling.In addition, the flow velocity of CTA slurry and embodiment 1 likewise calculate.
Will the phlegma step-down after the heat exchange in second heat exchanger (i=2); The temperature (143 ℃) and the pressure (0.4MPa) that make it to separate out with the 4th crystallization the steam that groove (i=4) produces equate; Then; Import the 4th crystallization and separate out in the steam that groove produces and form high temperature fluid, this high temperature fluid is imported first heat exchanger (i=1).Will the phlegma step-down after the heat exchange in the 3rd heat exchanger (i=3); The temperature (182 ℃) and the pressure (1.1MPa) that make it to separate out with the 3rd crystallization the steam that groove (i=3) produces equate; Import the 3rd crystallization then and separate out in the steam that groove produces and form high temperature fluid, this high temperature fluid is imported second heat exchanger (i=2).Will the phlegma step-down after the heat exchange in the 4th heat exchanger (i=4); The temperature (207 ℃) and the pressure (1.8MPa) that make it to separate out with second crystallization steam that groove (i=2) produces equate; Import second crystallization then and separate out in the steam that groove produces and form high temperature fluid, this high temperature fluid is imported the 3rd heat exchanger (i=3).With first crystallization separate out 220 ℃ of the temperature that groove (i=1) produces, the steam of pressure 2.3MPa imports the 4th heat exchanger (i=4).In addition, with the phlegma step-down that first heat exchanger produces, making its temperature is that 100 ℃, pressure are 0.1Mpa, is recovered to then in the phlegma accumulator tank.
Under the flow velocity in office, the temperature of the CTA slurry of first heat exchanger outlet is 120 ℃～125 ℃, and the temperature of the CTA slurry of second heat exchanger outlet is 160 ℃～165 ℃, and the temperature of the CTA slurry of the 3rd heat exchanger outlet is 200 ℃～205 ℃.
The pressure-losses lift velocity of the CTA slurry from first heat exchanger to second heat exchanger is shown in Table 3.Find that the slight pressure-losses rises, but do not find the obstruction in the heat exchanger.
Table 3 table 3
| CTA slurry mean flow rate [m/ second] | Pressure-losses lift velocity [MPa/ days] |
| 2.4 | 0.0013 |
The effciency of energy transfer in the above-mentioned method of manufacture is estimated in the available energy loss (exergy loss) that produces when in addition, utilizing the phlegma step-down that heat exchanger is generated.The result is shown in Table 4.
Table 4
| Step-down place (before the step-down of left side, after the step-down of right side) | Temperature before the step-down (℃) | Temperature after the step-down (℃) | High temperature fluid discharging amount (ton/hr) | Available energy loss (GJ/hr) |
| Three sections heat exchanger entrances of the 4th section heat exchanger outlet-Di | 220 | 207 | 30 | 0.03 |
| The 3rd section heat exchanger outlet-second section heat exchanger entrance | 207 | 182 | 33 | 0.08 |
| Second section heat exchanger outlet-first section heat exchanger entrance | 182 | 143 | 38 | 0.21 |
| First section heat exchanger outlet-phlegma accumulator tank | 143 | 100 | 43 | 0.35 |
| Add up to | - | 0.67 |
Use the manufacturing installation (n=4) that groove is separated out in 4 multi tube heat exchangers and 4 crystallizations that has as shown in Figure 3; The CTA slurry that with CTA concentration is 30 weight % is supplied with heat exchanger with the flow velocity shown in the table 5; Heat by being described below; After the CTA aqueous solution that obtains carried out hydrogen treatment,, make the high purity terephthalic acid with CTA treatment solution step-down cooling.In addition, the flow velocity of CTA slurry and embodiment 1 likewise calculate.Under the different in flow rate condition, made the high purity terephthalic acid respectively 2 months.
Will the phlegma step-down after the heat exchange in second heat exchanger (i=2); The temperature (143 ℃) and the pressure (0.4MPa) that make it to separate out with the 4th crystallization the steam that groove (i=4) produces equate; Import the 4th crystallization then and separate out in the steam that groove produces and form high temperature fluid, this high temperature fluid is imported first heat exchanger (i=1).Will the phlegma step-down after the heat exchange in the 3rd heat exchanger (i=3); The temperature (182 ℃) and the pressure (1.1MPa) that make it to separate out with the 3rd crystallization the steam that groove (i=3) produces equate; Import the 3rd crystallization then and separate out in the steam that groove produces and form high temperature fluid, this high temperature fluid is imported second heat exchanger (i=2).Will the phlegma step-down after the heat exchange in the 4th heat exchanger (i=4); The temperature (207 ℃) and the pressure (1.8MPa) that make it to separate out with second crystallization steam that groove (i=2) produces equate; Import second crystallization then and separate out in the steam that groove produces and form high temperature fluid, this high temperature fluid is imported the 3rd heat exchanger (i=3).With first crystallization separate out 220 ℃ of the temperature that groove (i=1) produces, the steam of pressure 2.3MPa imports the 4th heat exchanger (i=4).In addition, with the phlegma step-down that first heat exchanger produces, making its temperature is that 100 ℃, pressure are 0.1Mpa, is recovered to then in the phlegma accumulator tank.
Under the flow velocity in office, the temperature of the CTA slurry of first heat exchanger outlet is 115 ℃～120 ℃, and the temperature of the CTA slurry of second heat exchanger outlet is 130 ℃～135 ℃, and the temperature of the CTA slurry of the 3rd heat exchanger outlet is 200 ℃～205 ℃.
The pressure-losses lift velocity of the CTA slurry from first heat exchanger to second heat exchanger is shown in Table 5.Find that the slight pressure-losses rises, but do not find the obstruction in the heat exchanger.
Table 5
| CTA slurry mean flow rate [m/ second] | Pressure-losses lift velocity [MPa/ days] |
| 3.0 | 0.0012 |
| 3.1 | 0.0010 |
| 3.2 | 0.0006 |
In addition, when the effciency of energy transfer in the above-mentioned method of manufacture is estimated in the available energy loss (exergy loss) that produces when utilizing the phlegma step-down that heat exchanger is generated, identical with embodiment 2.
Comparative example 1
Except the flow velocity of the CTA slurry in the heat exchanger is changed into 1.6m/ second, when making the high purity terephthalic acid, less than 1 month, with just encountering difficulties in the CTA slurry delivery heat exchanger with embodiment 1 is same.When checking the inside of heat exchanger, find inner the obstruction.
Claims (12)
1. a high purity terephthalic acid method of manufacture; It is characterized in that; Comprise: the crude terephthalic acid that (I) will obtain through the liquid-phase oxidation of p-Xylol mixes, forms the operation of crude terephthalic acid slurry with water; (II) heat, make its dissolving to form the operation of the crude terephthalic acid aqueous solution with a plurality of heat exchangers step by step to this crude terephthalic acid slurry; (III) this crude terephthalic acid aqueous solution is carried out hydrotreated operation, (IV) separate out aqueous terephthalic acid solution step by step step-down cooling, the crystallization of groove after and separate out the operation of terephthalic acid, (V) terephthalic acid slurry that obtains is carried out the operation of solid-liquid separation hydrogenation with a plurality of crystallizations; Wherein, in said operation (II), temperature is that the flow velocity of crude terephthalic acid slurry in heat exchanger below 200 ℃ is that 1.7m/ is more than second.
2. high purity terephthalic acid's according to claim 1 method of manufacture; It is characterized in that; Said operation (II) comprises at least 1 operation (II-A), and this operation (II-A) heats the crude terephthalic acid slurry with the steam delivery heat exchanger that is produced by the step-down cooling in the said operation (IV).
3. high purity terephthalic acid's according to claim 2 method of manufacture; It is characterized in that; Said operation (II) further comprises at least 1 operation (II-B); This operation (II-B) will contain the high temperature fluid of the phlegma that produces in steam that is produced by the step-down cooling in the said operation (IV) and the heat exchanger that imports the steam higher than the temperature and pressure of this steam, import the heat exchanger lower than this heat exchanger temperature, heating crude terephthalic acid slurry.
4. high purity terephthalic acid's according to claim 1 method of manufacture, said heat exchanger is a multi tube heat exchanger.
5. high purity terephthalic acid's according to claim 2 method of manufacture, said heat exchanger is a multi tube heat exchanger.
6. high purity terephthalic acid's according to claim 3 method of manufacture, said heat exchanger is a multi tube heat exchanger.
7. high purity terephthalic acid's according to claim 1 method of manufacture is characterized in that, the concentration of the crude terephthalic acid in the said crude terephthalic acid slurry is 10～40 weight %.
8. high purity terephthalic acid's according to claim 2 method of manufacture is characterized in that, the concentration of the crude terephthalic acid in the said crude terephthalic acid slurry is 10～40 weight %.
9. high purity terephthalic acid's according to claim 3 method of manufacture is characterized in that, the concentration of the crude terephthalic acid in the said crude terephthalic acid slurry is 10～40 weight %.
10. high purity terephthalic acid's according to claim 4 method of manufacture is characterized in that, the concentration of the crude terephthalic acid in the said crude terephthalic acid slurry is 10～40 weight %.
11. high purity terephthalic acid's according to claim 5 method of manufacture is characterized in that, the concentration of the crude terephthalic acid in the said crude terephthalic acid slurry is 10～40 weight %.
12. high purity terephthalic acid's according to claim 6 method of manufacture is characterized in that, the concentration of the crude terephthalic acid in the said crude terephthalic acid slurry is 10～40 weight %.
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