CN101255110A - Method for preparing terephthalic acid - Google Patents
Method for preparing terephthalic acid Download PDFInfo
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- CN101255110A CN101255110A CNA2008100065212A CN200810006521A CN101255110A CN 101255110 A CN101255110 A CN 101255110A CN A2008100065212 A CNA2008100065212 A CN A2008100065212A CN 200810006521 A CN200810006521 A CN 200810006521A CN 101255110 A CN101255110 A CN 101255110A
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Abstract
The invention provides a preparation of terephthalic acid, which uses a displacement tower having a simple structure without a rack. The preparation is capable of running continuously and stably while keeping high displacement efficiency, as well as of producing high-quality, especially low-hue value high-pure terephthalic acid.
Description
Technical field
The present invention relates to contain the preparation method that the 1st dispersion medium in the 1st dispersion medium and the terephthalic acid crystalline magma utilizes the terephthalic acid of the 2nd replacing dispersion medium.
Background technology
Terephthalic acid is by being that the liquid phase oxidation reaction to the phenylene compound of representative prepares with the p-Xylol.This liquid phase oxidation reaction uses acetate as solvent usually, uses the catalyzer that suitably adds promotor such as bromide or acetaldehyde in metal catalysts such as cobalt, manganese as catalyzer.But, contain by products such as oxidizing reaction intermediate, M-nitro benzoic acids such as 4-carboxyl benzaldehyde or p-methylbenzoic acid and various tint permanence impurity etc. in the resultant of reaction of this liquid phase oxidation reaction, so for from this resultant of reaction, separating the crude terephthalic acid that obtains, for fear of the sneaking into and obtain highly purified terephthalic acid of above-mentioned impurity, need the effectively refining technology.
Have as the purification techniques of the crude terephthalic acid that obtains from liquid phase oxidation reaction is known, under high temperature, high pressure, be dissolved in crude terephthalic acid in water or the aqueous acetic acid, carry out catalytic hydrogenation processing, decarbonylation processing, oxide treatment, recrystallize, perhaps carry out method of high temperature dip treating etc. with terephthalic acid crystallising part dissolved dispersion state.In these methods, any method all needs terephthaldehyde's acid crystal from the isolating operation of slurries in order to remove impurity.
Above-mentioned impurity in the slurries at high temperature almost all is dissolved in the dispersion medium, but with terephthaldehyde's acid crystal when slurries separate, when slurries were cooled to 100 ℃ of left and right sides, these impurity were blended in terephthaldehyde's acid crystal, were difficult to obtain highly purified terephthaldehyde's acid crystal.Therefore, behind the liquid phase oxidation reaction with highly purified terephthaldehyde's acid crystal when slurries separate, need under high temperature, pressurized conditions, carry out.
As with terephthaldehyde's acid crystal from the isolating method of slurries the most frequently used be centrifugal separation, for the situation of slurries behind the liquid phase oxidation reaction or the slurries after the refinement treatment, also can use centrifugal separation.But, be difficult to carry out the crystalline washing in centrifugation or after the centrifugation, exist the dispersion medium adhesion amount in the crystallization to become many problems easily in addition.
On the other hand, as the method for removing above-mentioned impurity, proposed to utilize the method for replacing (referring to Patent Document 1) that the terephthalic acid crystalline that is produced by gravity is depositional, use the dispersion medium of displacement tower recently from above-mentioned terephthalic acid crystalline slurries.And, for fear of the channel or the back mixing of displacement tower inner fluid, improve the displacement efficiency of dispersion medium, proposed to be provided with the technology (referring to Patent Document 2) of shelf in displacement tower inside.But, the operation of slurries and shelf is set on the displacement tower of gravity settling causes the accumulation on the shelf, the obstruction or the dilatational strain of aperture portion easily utilizing, so for steady running, exist to need very a lot of difficulties such as big labour, therefore need further to improve in order to improve displacement efficiency.
Therefore, the inventor has proposed a kind of displacement tower in the past, it is by being provided with whipping appts below the displacement tower, and make terephthaldehyde's acid content in the slurries of lower region be higher than terephthaldehyde's acid content in the slurries of region intermediate, thereby realize not needing the simple structure of shelf, and have high displacement efficiency (referring to Patent Document 3).But, this displacement tower has: (i) introducing port of the slurries that form by terephthaldehyde's acid crystal and the 1st dispersion medium, (ii) the 2nd dispersion medium introducing port, (iii) take out the relief outlet of the displacement slurries that form by terephthaldehyde's acid crystal and the 2nd dispersion medium, (iv) take out four gangways such as relief outlet of the 1st dispersion medium, so traffic management is very loaded down with trivial details, while be difficult to keep high displacement efficiency to continue runs steadily.Particularly the internal diameter for the displacement tower is the displacement tower of the actual device size more than the 1m, the displacement efficiency of the dispersion medium that is difficult to more to keep high.
And the inventor has also proposed in this displacement tower, by the dramatic temperature variation zone position in the temperature distribution of vertical direction in the control displacement tower, the method (referring to Patent Document 4) of steady running displacement tower.By with the index of temperature variation zone position as operating condition, can the steady running state, but wish higher displacement efficiency at present, and the also not record of this method.
Connect the stirrer that extends to the steel basin bottom behind the lower part wall for stir shaft, known have in the oxidation reactor that is used in the aromatic carboxylic acid preparation or the partial crystallization groove (referring to Patent Document 5 and 6).The stir shaft that above-mentioned stirrer and in the past groove top have drive unit and a through slot upper wall is arranged on the stirrer of the total length of oxidation reactor or partial crystallization groove and compares, simple in structure and miniaturization, vibration and driving power are little, and effectively utilize the upper space of oxidation reactor or partial crystallization groove, but record is not applicable in the replacing dispersion medium tower.
Patent documentation 1: the spy opens clear 55-87744 communique
Patent documentation 2: the spy opens clear 57-53431 communique
Patent documentation 3: the spy opens flat 8-231465 communique
Patent documentation 4: the spy opens flat 10-45667 communique
Patent documentation 5: the spy opens the 2000-44510 communique
Patent documentation 6: the spy opens the 2002-275122 communique
Summary of the invention
Therefore, the object of the invention provides the preparation method of terephthalic acid, this preparation method utilizes the displacement tower of the simple structure that does not need shelf to prepare high purity terephthalic acid's method, this method keeps high by the displacement efficiency with the dispersion medium in the slurries, thereby can improve the quality of the terephthalic acid that obtains, particularly can reduce hue value, and can turn round sustainedly and stably.
The inventor furthers investigate in order to solve above-mentioned purpose, and it found that, by utilizing the replacing dispersion medium of displacement tower under given conditions, can obtain high displacement efficiency, and manageable, finishes the present invention thus.
Just, the present invention relates to the preparation method of terephthalic acid, this preparation method will contain the preparation method of the dispersion medium utilization displacement tower metathetical terephthalic acid in the 1st dispersion medium and the terephthalic acid crystalline slurries (to call magma in the following text), wherein, the mixed solution of this displacement tower inside comprises upper area (zone of magma introducing port top), region intermediate (zone of upper surface) from the magma introducing port to the aftermentioned borderline region, borderline region (zone between region intermediate and the aftermentioned lower region), and lower region (zone of the below of the lower surface of borderline region), and this preparation method satisfies following condition (1)-(3);
Condition (1): the internal diameter of displacement tower is 1-7m;
Condition (2): the height L of region intermediate
AFor the 0.3-4 of the internal diameter of displacement tower doubly, and height L
B(height from the lower surface of borderline region to the agitating wing of whipping appts, perhaps height under the situation of not using agitating wing) from the lower surface of borderline region to the bottom tangent line of displacement tower for the 0.3-1.5 of the internal diameter of displacement tower doubly;
Condition (3): the height L of borderline region is 0.1-1m;
This preparation method carries out following operation under following condition (4): import magma from the lower surface of the upper area of this displacement tower, the 2nd dispersion medium is imported to the lower region of this displacement tower, mainly take out the 1st dispersion medium from the upper area of this displacement tower, the lower region from this displacement tower takes out the slurries (to call the displacement slurries in the following text) that contain terephthaldehyde's acid crystal and the 2nd dispersion medium simultaneously;
Condition (4): 15≤X≤500
[in the following formula, X represents the variable quantity (quality %/rice) of terephthaldehyde's acid content of per unit height in the borderline region, with formula (C
B-C
A)/L represents, described C
ATerephthaldehyde's acid content (quality %) in the mid-way of expression region intermediate, described C
BTerephthaldehyde's acid content (quality %) in the mid-way of expression lower region, L represents the height (rice) of borderline region.]
According to the present invention, from by effectively removing impurity the terephthalic acid crystalline slurries that the catalytic hydrogenation processing of the liquid phase oxidation reaction of phenylene compound, crude terephthalic acid, recrystallize processing etc. are obtained, can obtain highly purified, the second best in quality, the low terephthalic acid of hue value particularly.
Description of drawings
Fig. 1 represents an example of displacement tower of the present invention;
Fig. 2 represents to replace an example of the position relation of upper area, region intermediate, borderline region, lower region and whipping appts in the tower;
Fig. 3 represents the example with the displacement tower of outside Recycle design stirring, an example of the position relation of the lower surface of expression borderline region and bottom tangent line;
Fig. 4 represents an example of the displacement tower that the stir shaft of whipping appts contacts with borderline region.
Description of reference numerals
1: the displacement tower
2: magma receives inlet
3: the magma introducing port
4: breaker plate
5: the 1 dispersion medium conveying ends
6: the 2 dispersion medium introducing ports
7: displacement slurries conveying end
8: former stock tank
9: the 1 dispersion medium grooves (overflow dispersion medium groove)
10: the displacement slurry tank
11: the 2 dispersion medium grooves
12: the magma liquid-feeding pump
13: whipping appts
14: the 2 dispersion medium liquid-feeding pumps
15: heat exchanger
16: on-line densimeter
17: heat exchanger
18: upper area
19: region intermediate
20: lower region
21: the mid-way of borderline region
22: upper area
23: region intermediate
24: lower region
25: borderline region
26: the upper surface of borderline region
27: the lower surface of borderline region
28: stir pump
29: displacement slurries circulation line return port
30: magma introducing port (dispersion) with ring
D: the internal diameter of displacement tower
L
A: the height of region intermediate
L: the height of borderline region
L
B: the height from the lower surface of borderline region to the agitating wing of whipping appts, perhaps height under the situation of not using agitating wing from the lower surface of borderline region to the bottom tangent line of displacement tower
Embodiment
The preparation method of the terephthalic acid that the present invention relates to, this preparation method will contain the preparation method of the dispersion medium utilization displacement tower metathetical terephthalic acid in the 1st dispersion medium and terephthalic acid (following also can abbreviate TA as) the crystalline slurries (to call magma in the following text), wherein, the mixed solution of this displacement tower inside comprises upper area (zone of magma introducing port top), region intermediate (zone of upper surface) from the magma introducing port to the aftermentioned borderline region, borderline region (zone between region intermediate and the aftermentioned lower region), and lower region (zone of the bottom tangent line of agitating wing from the lower surface of borderline region to whipping appts or displacement tower), and this preparation method satisfies following condition (1)-(3);
Condition (1): the internal diameter of displacement tower is 1-7m;
Condition (2): the height L of region intermediate
AFor the 0.3-4 of the internal diameter of displacement tower doubly, and the height L of lower region
BFor the 0.3-1.5 of the internal diameter of displacement tower doubly;
Condition (3): the height L of borderline region is 0.1-1m;
This preparation method carries out following operation under following condition (4): import magma from the lower surface of the upper area of this displacement tower, the 2nd dispersion medium is imported to the lower region of this displacement tower, mainly take out the 1st dispersion medium from the upper area of this displacement tower, the lower region from this displacement tower takes out the slurries (to call the displacement slurries in the following text) that contain TA crystallization and the 2nd dispersion medium simultaneously;
Condition (4): 15≤X≤500
[in the formula, X represents the variable quantity (quality %/rice) of the TA content of per unit height in the borderline region, with formula (C
B-C
A)/L represents, described C
ATA content (quality %) in the mid-way of expression region intermediate, described C
BTA content (quality %) in the mid-way of expression lower region, L represents the height (rice) of borderline region.]
Magma can be used by what the liquid phase oxidation reaction to the phenylene compound obtained and contain TA crystalline slurries.
Below to this liquid phase oxidation reaction simple declaration.
Liquid phase oxidation reaction can be enumerated, for example, at the catalyzer that forms by heavy metal compound and bromide at least and moisture concentration be about 1-15 quality % aqueous acetic acid in the presence of, utilize the gas that contains oxygen molecule, make the method that the phenylene compound is reacted., the phenylene compound is meant that 1 and 4 of benzene has substituent compound here, described substituting group can be enumerated for example alkyl such as methyl, ethyl, propyl group, butyl etc.Particularly, as to the preferred p-Xylol of phenylene compound.
As a kind of heavy metal compound of catalyst component must be at least a in cobalt compound and the manganic compound, can also use nickel compound, cerium compound, zirconium compounds etc. together as required.Organic acid salt, oxyhydroxide, halogenide, carbonate of these metals etc. be can enumerate as cobalt compound, manganic compound, nickel compound, cerium compound, zirconium compounds, acetate and bromide are particularly suitable for using.The concrete example of described heavy metal compound can be enumerated, cobaltous acetate, cobaltous hydroxide, cobaltous fluoride, cobalt chloride, cobaltous bromide, cobaltous iodide, cobaltous carbonate, manganous acetate, manganous hydroxide, manganous fluoride, Manganous chloride tetrahydrate, Manganese dibromide, manganese iodide, manganous carbonate, nickelous acetate, nickel hydroxide, nickelous fluoride, nickelous chloride, nickelous bromide, nickelous iodide, nickelous carbonate, cerous acetate, cerous hydroxide, cerium fluoride, Cerium II Chloride, comprise cerium bromide, cerous iodide, cerous carbonate, zirconium acetate, zirconium hydroxide, Zirconium tetrafluoride, zirconium chloride, zirconium bromide, iodate zirconium, zirconium carbonate etc.
As a kind of bromide of catalyst component so long as in reaction system, be dissolved in the aqueous acetic acid, produce the bromide of bromide ion, can use anyly, for example can enumerate organic bromides such as inorganic bromides such as hydrogen bromide, Sodium Bromide, cobaltous bromide and monobromo-acetic acid, tetrabromoethane.Wherein, be fit to use hydrogen bromide, cobaltous bromide, Manganese dibromide, more preferably use hydrogen bromide is dissolved in Hydrogen bromide in the aqueous solution.
The temperature of reaction of liquid phase oxidation reaction is preferably 160-230 ℃, more preferably 180-210 ℃.Reaction pressure is preferably 0.78-3.04MPa, more preferably 0.98-1.86MPa usually so long as can make reaction system keep the pressure of liquid phase to get final product in above-mentioned temperature of reaction.
Can enumerate for example oxygen, the oxygen-rich air of air, usefulness inert gas dilution as the gas that contains oxygen molecule, but usually preferred air is considered in slave unit aspect and cost aspect.
Can be used as magma of the present invention with containing the TA crystalline slurries that obtain by aforesaid method.In addition, also can implement known catalytic hydrogenation to the thick TA that obtains by described liquid phase oxidation reaction (for example handles, the special public clear 41-16860 communique of reference), decarbonylation (is for example handled, with reference to No. the 3456001st, United States Patent (USP)), oxide treatment (for example, the special public clear 52-46212 communique of reference), recrystallize (is for example handled, open clear 49-102636 communique with reference to the spy), the high temperature dip treating (for example, open clear 54-90136 communique with reference to the spy) etc. refinement treatment, with the slurries that obtain as the magma utilization.
Among the present invention, the TA content in the magma is preferably 20-45 quality %, more preferably 30-40 quality % usually.In addition, magma preferably imports under 140-240 ℃ in the displacement tower, more preferably imports down at 170-210 ℃, further preferably imports down at 180-200 ℃.
Be not particularly limited as the 1st dispersion medium, preferably can make water or aqueous acetic acid, the moisture concentration of aqueous acetic acid is preferably 1-15 quality %.Particularly, when the slurries behind the above-mentioned liquid phase oxidation reaction were directly used as magma, the aqueous acetic acid of the about 1-15 quality of moisture concentration % became the 1st dispersion medium.At this moment, described the 1st dispersion medium contains impurity, and this impurity is specially the by product of oxidizing reaction intermediate, M-nitro benzoic acid of 4-carboxyl benzaldehyde or p-methylbenzoic acid etc. etc. and various tint permanence impurity etc.
On the other hand, the moisture concentration that is preferably water or aqueous acetic acid, particularly aqueous acetic acid usually with the 2nd dispersion medium of the 1st replacing dispersion medium is preferably 1-15 quality %.The 2nd dispersion medium is to reach the abundant purified of preferred use on the basis of purpose of the present invention.In addition, the 2nd dispersion medium preferably imports under 60-220 ℃ in the displacement tower, more preferably imports under 100-200 ℃ in the displacement tower, further preferably imports under 140-180 ℃ in the displacement tower.When the temperature of the 2nd dispersion medium was lower than the temperature of magma, the slurry specific gravity of lower region described later was higher than the proportion of magma, can stably implement the present invention, so preferred.
The upper area of displacement tower is meant the zone of the introducing port top of magma, being the liquid phase that is mainly formed by the 1st dispersion medium (can contain the 2nd dispersion medium), is the residual state (the TA crystallization in the magma is deposited to region intermediate described later and lower region) of the 1st dispersion medium from the magma that the lower surface of upper area imports.By the 1st dispersion medium is taken out from upper area continuously or off and on, thereby the above-mentioned impurity in the magma can be taken out with the 1st dispersion medium.In order effectively to carry out the taking-up operation of the 1st dispersion medium, till the introducing port of magma preferably extends to the below of conveying end height of the 1st dispersion medium from cat head.The importing flow of the 1st dispersion medium in the magma is preferably with the ratio of the taking-up flow of the 1st dispersion medium, mass ratio in time per unit, the importing flow of the 1st dispersion medium in the magma: taking-up flow=1 of the 1st dispersion medium: 1-1: 1.5, more preferably 1: 1.01-1: 1.2.
Consider that from the dispersion state of magma introducing port is preferably tubular.In addition, consider that the peristome of introducing port is preferred to be provided with downwards from the contact efficiency that improves magma and the 2nd dispersion medium.And, the liquid flow point preferably is set in the front of peristome looses with breaker plate (barrier plate).Utilize this breaker plate, magma extensively and evenly can be imported in the displacement tower, the replacement operator of dispersion medium is carried out more effectively.
Region intermediate below the introducing port of magma is that TA crystallization from the magma that the lower surface of upper area imports is by the zone of gravity to lower region free setting described later.The temperature of this region intermediate is preferably 70-230 ℃, and more preferably 100-220 ℃, more preferably 150-200 ℃.
Lower region is that the TA crystallization from middle regional subsidence is mixed with the 2nd dispersion medium, forms the zone of homogeneously dispersed state.The temperature of this lower region is preferably 60-220 ℃, and more preferably 100-200 ℃, more preferably 150-180 ℃.
Lower region at the displacement tower has the introducing port of the 2nd dispersion medium, also has the conveying end of the displacement slurries that form with the 2nd replacing dispersion medium.And, when using whipping appts, preferably it is arranged near the tangent line of bottom or below.Because the 2nd dispersion medium does not contain the TA crystallization and proportion is low, so for thorough mixing the 2nd dispersion medium and displacement slurries, the introducing port of the 2nd dispersion medium preferably is arranged on the below of lower region.In addition, because the displacement slurries are high specific gravity,, preferably be arranged on as far as possible position away from the introducing port of the 2nd dispersion medium so the conveying end of displacement slurries also preferably is arranged on the below of lower region.
In addition, the ratio of the taking-up flow of the 2nd dispersion medium in the importing flow of described the 2nd dispersion medium and the displacement slurries, mass ratio in time per unit, the importing flow of the 2nd dispersion medium: the taking-up flow of 2nd dispersion medium of displacement in the slurries is preferably 1: 1-1.5: 1, more preferably 1.01: 1-1.2: 1.
Utilize above-mentioned whipping appts to stir lower region, and regulate the importing flow of the 2nd dispersion medium and the taking-up flow of displacement slurries, make the TA content (C in the lower region
B) [measuring in the mid-way of lower region] be higher than the TA content (C in the region intermediate
A) [mid-way at region intermediate is measured], thereby form borderline region between region intermediate and the lower region.Here, C
ABe preferably 1-40 quality %, more preferably 3-20 quality %.In addition, C
BMore than or equal to C
A, and be preferably 6-51 quality %, more preferably 10-45 quality %.Mix with the 2nd dispersion medium owing to exist described borderline region, the 1st dispersion medium to be difficult to cross borderline region, its result can keep high displacement efficiency.In order to obtain high displacement efficiency, preferably the TA content with lower region exceeds more than the TA content 5 quality % of region intermediate.In addition, the position of this borderline region can be improved by importing flow that increases by the 2nd dispersion medium or the taking-up flow that reduces the displacement slurries.Be adjusted into more than the certain altitude by position, can keep, improve displacement efficiency borderline region.
Whipping appts is so long as in fact with the device of homogenizing in the lower region, just be not particularly limited.Can use the various stirrers that have agitating wing, also can use the outer loop device that produces mixed flow at lower region.Agitating wing can be enumerated spiral paddle, the turbine wing, the blade wing, the disc turbine wing, the tilting blade wing etc.Under the situation of using the outer loop device, circulation tube is arranged on displacement tower outside, takes out the interior liquid of lower region, turns back in the lower region by recycle pump.In this outer loop process, preferably can also get involved whipping appts with agitating wing.In addition, in order to help to stir, also preferably add baffle plate (baffle) in displacement tower bottom.Stirrer with agitating wing does not need the groove integral body of oxidation reactor or partial crystallization groove is stirred, so not need be two sections, three sections to agitating wing, in addition, owing to only stir the part zone of lower region, so do not need strong mixing power.
Among the present invention, the 1st dispersion medium of magma carries out in borderline region with the effect of the 2nd replacing dispersion medium.In order to obtain higher and more stable displacement efficiency, be necessary the stable borderline region that forms.From then on viewpoint is considered, whipping appts is when having the stirrer of agitating wing, and the stir shaft that for example supports agitating wing does not preferably pass borderline region from the top of displacement tower and extends to lower region.When in above-mentioned borderline region, having stir shaft, borderline region is discontinuous, the influence of moving because of the vibration of the rotation influence of stir shaft, stir shaft and the heat by stir shaft, make and the borderline region confusion be difficult to the stability boundaris zone as adhering to TA crystalline influence etc. on the influence of the wall of stir shaft and the stir shaft.Therefore, preferably utilize whipping appts the Contact Boundary zone, that be not arranged on displacement tower downside to stir, or preferably use the outer loop device.
When between region intermediate and lower region, having temperature head, also can effectively form borderline region.This be since as the acetate of dispersion medium and water be temperature high specific gravity is more little more, when middle regional temperature was higher than lower region, the mobile of dispersion medium tailed off in borderline region, borderline region is stable.Therefore, the temperature of region intermediate is preferably higher more than 3 ℃ than the temperature of lower region, and is more preferably high more than 5 ℃, more preferably more than 10 ℃.The temperature of region intermediate determines according to the input heat of the rising flow part of the input heat of magma and the 2nd dispersion medium, and the temperature of lower region determines according to the heat that settled TA crystallization in the input heat of the 2nd dispersion medium and the displacement tower is had.
By the importing flow of regulating the 2nd dispersion medium and the taking-up flow of replacing slurries, the TA content of may command displacement slurries.These Flow-rate adjustment are related to steady running, very important, the adjusting of taking-up flow of the importing flow of the 2nd dispersion medium and displacement slurries can influence the relativeness of the TA content of the TA content of lower region and region intermediate, and its result is related to the displacement efficiency of dispersion medium and the operation difficulty or ease of displacement slurries.The TA content of described region intermediate determines according to the TA crystalline treatment capacity in the displacement tower.TA crystalline treatment capacity is meant and will imports to the result of the TA crystallization import volume of displacement tower divided by the sectional area of the region intermediate of displacement tower as magma.In addition, the taking-up flow that the TA content of lower region can import flow and displacement slurries according to the stirring and the 2nd dispersion medium of the whipping appts that is arranged on displacement tower bottom is set arbitrarily in as the scope that evenly slurries of content can exist.
The displacement tower that uses among the present invention is the device that is used for commercial-scale TA preparation, and its internal diameter is [condition (1)] in the scope of 1-7m.The processing power of displacement tower is owing to mainly determine according to the TA crystallization treatment amount of per unit sectional area, so the internal diameter for preparing the throughput decision displacement tower of equipment according to TA gets final product.If when the TA crystallization more than the processing power is handled, the TA crystalline free setting in the region intermediate is hindered, and reduces displacement efficiency.
The shape of displacement tower is preferably cylinder, can enumerate sphere, ellipse or taper shape etc., particularly lower roof plate for upper plate and lower roof plate and be preferably the ellipse that easily lower region is formed homogeneously dispersed state.The displacement tower that uses among the present invention does not need shelf etc., so accumulation of TA crystalline or obstruction can not occur.But, must not negate the setting of shelf among the present invention.
In addition, the operating temperature of displacement tower so long as the temperature below the boiling point of each dispersion medium of running under the pressure get final product.
The height L of the region intermediate of displacement tower
A(rice) is meant that importing position (the introducing port position of magma) from magma is to the distance of the upper surface of borderline region.
For the stability boundaris zone, be necessary to keep to make the distance of the TA crystallization free setting that imports in the displacement tower.Therefore, height L
A(rice) is necessary to be set in the 0.3-4 scope [condition (2)] doubly of displacement tower internal diameter, is preferably 0.5-2.2 times of displacement tower internal diameter.As height L
ADuring 0.3 times of (rice) is not enough displacement tower internal diameter, the TA crystallization can not free setting, and the magma that flies out from the introducing port of magma can chaotic borderline region, and the tendency that reduces displacement efficiency is arranged.On the other hand, as height L
AWhen (rice) surpassed 4 times that replace the tower internal diameter, the displacement tower became very big, so be difficult to actual deviceization.
Height L among the present invention
B(rice) is, as mentioned above, be equivalent to distance, perhaps do not use under the situation of agitating wing, be equivalent to distance from the lower surface of borderline region to the bottom tangent line of displacement tower in the situation of utilizing the outer loop device etc. from the lower surface of borderline region to the agitating wing of whipping appts.In addition, the bottom tangent line is meant the vertical tube part of displacement tower and the boundary line of lower roof plate.
For the stability boundaris zone, be necessary that the TA crystallization keeps homogeneously dispersed state in the high lower region of TA content, the maintenance borderline region does not rock or does not fluctuate.
Therefore, height L
B(rice) is necessary to be set in the 0.3-1.5 scope [condition (2)] doubly of displacement tower internal diameter, is preferably the 0.5-1 scope doubly of displacement tower internal diameter.As height L
BDuring 0.3 times of (rice) is not enough displacement tower internal diameter, under the situation of using agitating wing, from the discharging current or the rotating fluid of agitating wing borderline region is exerted an influence, chaotic borderline region is so reduce displacement efficiency.In addition, under the situation of using the outer loop device, be necessary the home position of circulation line is descended, because from of the taking-up generation detrimentally affect of circulation line return port round-robin discharging current to the displacement slurries, so can not evenly keep the TA content in the lower region, its result reduces displacement efficiency.On the other hand, as height L
BWhen (rice) surpasses 1.5 times of displacement tower internal diameter, reduce the stirring efficiency in the lower region, the TA crystallization in can not the homodisperse lower region, its result reduces displacement efficiency.In addition, under the situation of using the outer loop device, the displacement tower becomes very big, is difficult to actual deviceization, so not preferred.
Among the present invention, the mixed solution with displacement tower inside forms borderline region between region intermediate and lower region.The position of described borderline region determines according to importing flow and TA content, the importing flow of the 2nd dispersion medium and the taking-up flow and the TA content of displacement slurries of magma.
The height L of borderline region determines according to the temperature head of poor, the region intermediate of the TA content of displacement tower internal diameter, region intermediate and lower region and lower region, TA crystalline particle diameter etc.In order to obtain high displacement efficiency, be necessary that by the above-mentioned condition of suitable decision the height L that makes borderline region is the scope [condition (3)] of 0.1-1m.
The present invention is necessary to make the variable quantity X (quality %/rice) of the TA content of the per unit height in the borderline region to satisfy following condition (4) in order to increase substantially displacement efficiency.
Condition (4): 15≤X≤500
[in the following formula, X formula (C
B-C
A)/L represents, described C
A, C
BAnd L is the same.]
X is meant across what the meaning of the TA of the TA of the region intermediate of borderline region content and lower region content.When X less than 15, can not obtain very high displacement efficiency.The minimum value of considering L is 0.1, C
AAnd C
BDuring for separately preferable range, C
BAnd C
APoor (C
B-C
A) maximum value be 50, so the maximum value of variable quantity X is an actual value---500.
X is preferably the scope of 16-500, more preferably the scope of 30-400, the more preferably scope of 30-200.By the importing flow of regulating above-mentioned the 2nd dispersion medium and the taking-up flow of replacing slurries, can make variable quantity X remain on above-mentioned scope.
In the displacement tower of the present invention, the faint of the 2nd dispersion medium is set in preferred this displacement tower from bottom to top flows.This is in order to prevent that the 1st dispersion medium is diffused into the lower region of displacement tower.The velocity of flow from bottom to top of the 2nd dispersion medium is so that the rising flow of the 2nd dispersion medium is represented divided by " riser speed (the void tower standard) " of the sectional area of displacement tower.Described riser speed is preferably 0.01-1.2m/h, 0.3-1.2m/h more preferably, and 0.6-1m/h more preferably,
Example below in conjunction with device that uses among Fig. 1 to 3 couple of the present invention and method of replacing dispersion medium is carried out simple declaration.In addition, magma is to contain by to the liquid phase oxidation reaction of phenylene compound or the terephthalic acid crystalline slurries that the crude terephthalic acid refinement treatment is obtained.
With reference to figure 1, magma is to utilize magma liquid-feeding pump 12 to import via the magma introducing port 3 of displacement tower 1 from former stock tank 8.At this moment, utilize the breaker plate 4 of the front end that is positioned at magma introducing port 3, magma spreads in the displacement tower.
In the magma of scattering, the TA crystallization is deposited to the below of displacement tower 1, and the 1st dispersion medium and fine TA crystalline particle are to take out from the 1st dispersion medium conveying end 5, overflow in the 1st dispersion medium groove (overflow dispersion medium groove) 9.
With reference to figure 2, dispersive TA crystallization is through region intermediate 23, and free setting arrives lower region 24, and near the whipping appts 13 of bottom tangent line that is set at the displacement tower stirs.Therefore, TA content is even in the lower region 24, and compares TA content height with region intermediate 23.
With reference to figure 1, the 2 dispersion medium is via the 2nd dispersion medium liquid-feeding pump 14, from the 2nd dispersion medium introducing port 6 importings of displacement tower lower side from the 2nd dispersion medium groove 11.In addition, the slurries of lower region are taken out from displacement slurries conveying end 7, the displacement slurries that taken out are transported in the displacement slurry tank 10.
With reference to figure 2, when stating operation on the implementation, borderline region 25 is formed between region intermediate 23 and the lower region 24.This borderline region exists upper surface 26 that contacts with region intermediate 23 and the lower surface 27 that contacts with lower region 24, the height L with certain limit.
With reference to figure 3, under the situation of using the outer loop device, stir pump 28 circulations from the displacement slurries utilization that displacement slurries conveying end 7 takes out, will replace slurries from circulation line return port 29 and turn back to lower region.Therefore, TA content is even in the lower region 24, and compares TA content height with region intermediate 23.This round-robin displacement slurries part is taken out, be transported in the displacement slurry tank 10.
Embodiment
Describe the present invention in detail below by embodiment, but the present invention is not limited to these embodiment.In addition, the rate of displacement of the dispersion medium of obtaining in the following examples is that the M-nitro benzoic acid amount that the displacement back is contained from the dispersion medium of the 1st dispersion medium conveying end 5 overflows is with respect to the calculated value of the M-nitro benzoic acid amount that contains as by product in the magma dispersion medium.
In addition, the hue value (OD of terephthalic acid
340) mensuration implement as follows.
Hue value (the OD of＜terephthalic acid
340) measuring method
Utilize the spectrophotometric determination hue value of following specification.
Machine: spectrophotometer U-3010 (the Ha イ テ of Co., Ltd. Hitachi Network ノ ロ ジ one ズ system)
Wavelength: 340nm
Box: quartzy system, optical path length 50mm
Measuring method: the terephthalic acid of 3.2g as sample, is dissolved in the aqueous sodium hydroxide solution of 2mol/L of 40ml, and the solution that obtains joins in the box, measures the absorbancy under the 340nm.But, when sample dissolution, exist under the sedimentary situation, utilize the centrifugation sedimentation, supernatant liquor is joined in the box, measure absorbancy.
(preparation example 1)
In aqueous acetic acid, with p-Xylol in the presence of the catalyzer that forms by manganese and bromine, (temperature of reaction is 200 ℃ to utilize air to carry out liquid phase oxidation reaction, reaction pressure is 16 normal atmosphere), obtain thick TA slurries (TA content is 34 quality %, is 11 quality % as the moisture concentration of the aqueous acetic acid of the 1st dispersion medium), the thick TA slurries that obtain are imported in the partial crystallization groove that is connected in series, relief pressure successively, be cooled to 190 ℃ after, supply in the former stock tank 8.
Utilize the equipment of Fig. 1, will have the long structure of vertical direction, internal diameter is that the titanium system tubular tower of 1.5m is as replacing tower 1.
To import to the lower region of displacement tower as the water conservancy of the 2nd dispersion medium with the 2nd dispersion medium liquid-feeding pump 14.In this process, utilize heat exchanger 15 160 ℃ of heating down.Make displacement tower 1 for full liquid status,, start whipping appts 13 simultaneously from the 1st dispersion medium conveying end 5 overflow waters.
Then, utilize magma liquid-feeding pump 12 to begin to import the magma of preparation in the preparation example 1.At this moment, magma is to utilize heat exchanger 17 to import in the displacement tower 1 after the heating down at 190 ℃.After having confirmed to form the high lower region 24 of TA content below the displacement tower 1, begin to take out the displacement slurries.
Each imports flow and takes out flow as follows.
The importing flow of magma: 13.90t/h
The importing flow of the 2nd dispersion medium: 9.93t/h
The taking-up flow of the 1st dispersion medium: 10.40t/h
The taking-up flow of displacement slurries: 13.42t/h
At this moment, the TA content of magma is 34.1 quality %, and the TA content of displacement slurries is 33.6 quality %, and the riser speed of the dispersion medium of displacement tower inside is 0.63m/h.
Can confirm the height L of region intermediate from temperature distribution of replacing the vertical direction in the tower and the result who replaces the sample of liquid in the tower
ABe 3m, height L from the lower surface of borderline region to the agitating wing of whipping appts
BBe 0.9m, the height L of borderline region is 0.3m.In addition, the TA content C of region intermediate
ABe 7.9 quality %, temperature is 169-185 ℃ (mid-way: 180 ℃), the TA content C of lower region
BBe 33.6 quality %, temperature is 163 ℃.C
BAnd C
APoor (C
B-C
A) be 25.7 quality %, the variable quantity X in the borderline region is 86 quality %/m.
Turn round after 10 hours, analyze M-nitro benzoic acid concentration in the dispersion medium of the magma of importing in displacement tower 1 and the M-nitro benzoic acid concentration in the dispersion medium in the 1st dispersion medium groove (overflow dispersion medium groove) 9, obtain the rate of displacement of dispersion medium.In addition, the displacement slurries are sent to the solid-liquid separation process that uses separating centrifuge or rotary vacuum filter through the partial crystallization operation, and the wet cake of TA is separated with mother liquor, and the biscuit that should wet is dry, obtains the TA crystallization.The result is as shown in table 1.
Table 1
| Elapsed time (h) | Rate of displacement (%) | |
| 4 | 95.6 | |
| 6 | 95.8 | |
| 8 | 95.9 | |
| 10 | 95.7 | 1.20 |
Except in embodiment 1, each is imported flow and take out the flow change following, other and embodiment 1 identical experimentizing.
The importing flow of magma: 14.19t/h
The importing flow of the 2nd dispersion medium: 6.58t/h
The taking-up flow of the 1st dispersion medium: 10.71t/h
The taking-up flow of displacement slurries: 10.06t/h
At this moment, the TA content of magma is 33.5 quality %, and the TA content of displacement slurries is 45.0 quality %, and the riser speed of the dispersion medium of displacement tower inside is 0.66m/h.
Can confirm the height L of region intermediate from temperature distribution of replacing the vertical direction in the tower and the result who replaces the sample of liquid in the tower
ABe 3m, height L from the lower surface of borderline region to the agitating wing of whipping appts
BBe 0.9m, the height L of borderline region is 0.25m.In addition, the TA content C of region intermediate
ABe 7.8 quality %, temperature is 173-185 ℃ (mid-way: 181 ℃), the TA content C of lower region
BBe 45.0 quality %, temperature is 165 ℃.C
BAnd C
APoor (C
B-C
A) be 37.2 quality %, the variable quantity X in the borderline region is 149 quality %/m.
Turn round after 10 hours, analyze M-nitro benzoic acid concentration in the dispersion medium of the magma of importing in displacement tower 1 and the M-nitro benzoic acid concentration in the dispersion medium in the 1st dispersion medium groove (overflow dispersion medium groove) 9, obtain the rate of displacement of dispersion medium.In addition, identical with embodiment 1, obtain the TA crystallization after, measure hue value.The result is as shown in table 2.
Table 2
| Elapsed time (h) | Rate of displacement (%) | |
| 4 | 98.3 | |
| 6 | 98.0 | |
| 8 | 98.2 | |
| 10 | 98.1 | 1.08 |
Except in embodiment 1, each is imported flow and take out the flow change following, other and embodiment 1 identical experimentizing.
The importing flow of magma: 14.00t/h
The importing flow of the 2nd dispersion medium: 20.91t/h
The taking-up flow of the 1st dispersion medium: 10.49t/h
The taking-up flow of displacement slurries: 24.42t/h
At this moment, the TA content of magma is 34.0 quality %, and the TA content of displacement slurries is 18.6 quality %, and the riser speed of the dispersion medium of displacement tower inside is 0.64m/h.
Can confirm the height L of region intermediate from temperature distribution of replacing the vertical direction in the tower and the result who replaces the sample of liquid in the tower
ABe 3m, height L from the lower surface of borderline region to the agitating wing of whipping appts
BBe 0.9m, the height L of borderline region is 0.3m.In addition, the TA content C of region intermediate
ABe 8.0 quality %, temperature is 164-185 ℃ (mid-way: 179 ℃), the TA content C of lower region
BBe 18.6 quality %, temperature is 161 ℃.C
BAnd C
APoor (C
B-C
A) be 10.6 quality %, the variable quantity X in the borderline region is 35 quality %/m.
Turn round after 10 hours, analyze M-nitro benzoic acid concentration in the dispersion medium of the magma of importing in displacement tower 1 and the M-nitro benzoic acid concentration in the dispersion medium in the 1st dispersion medium groove (overflow dispersion medium groove) 9, obtain the rate of displacement of dispersion medium.In addition, identical with embodiment 1, obtain the TA crystallization after, measure hue value.The result is as shown in table 3.
Table 3
| Elapsed time (h) | Rate of displacement (%) | |
| 4 | 94.6 | |
| 6 | 94.9 | |
| 8 | 94.7 | |
| 10 | 94.8 | 1.31 |
Except in embodiment 1, each is imported flow and take out the flow change following, other and embodiment 1 identical experimentizing.
The importing flow of magma: 13.98t/h
The importing flow of the 2nd dispersion medium: 28.23t/h
The taking-up flow of the 1st dispersion medium: 10.49t/h
The taking-up flow of displacement slurries: 31.72t/h
At this moment, the TA content of magma is 33.8 quality %, and the TA content of displacement slurries is 14.2 quality %, and the riser speed of the dispersion medium of displacement tower inside is 0.63m/h.
Can confirm the height L of region intermediate from temperature distribution of replacing the vertical direction in the tower and the result who replaces the sample of liquid in the tower
ABe 3m, height L from the lower surface of borderline region to the agitating wing of whipping appts
BBe 0.9m, the height L of borderline region is 0.35m.In addition, the TA content C of region intermediate
ABe 8.0 quality %, temperature is 164-185 ℃ (mid-way: 179 ℃), the TA content C of lower region
BBe 14.2 quality %, temperature is 161 ℃.C
BAnd C
APoor (C
B-C
A) be 6.2 quality %, the variable quantity X in the borderline region is 18 quality %/m.
Turn round after 10 hours, analyze M-nitro benzoic acid concentration in the dispersion medium of the magma of importing in displacement tower 1 and the M-nitro benzoic acid concentration in the dispersion medium in the 1st dispersion medium groove (overflow dispersion medium groove) 9, obtain the rate of displacement of dispersion medium.In addition, identical with embodiment 1, obtain the TA crystallization after, measure hue value.The result is as shown in table 4.
Table 4
| Elapsed time (h) | Rate of displacement (%) | |
| 4 | 93.6 | |
| 6 | 93.4 | |
| 8 | 93.7 | |
| 10 | 93.8 | 1.42 |
Comparative example 1
Except in embodiment 1, each is imported flow and take out the flow change following, other and embodiment 1 identical experimentizing.
The importing flow of magma: 14.04t/h
The importing flow of the 2nd dispersion medium: 32.18t/h
The taking-up flow of the 1st dispersion medium: 10.53t/h
The taking-up flow of displacement slurries: 35.68t/h
At this moment, the TA content of magma is 33.7 quality %, and the TA content of displacement slurries is 12.6 quality %, and the riser speed of the dispersion medium of displacement tower inside is 0.63m/h.
Can confirm the height L of region intermediate from temperature distribution of replacing the vertical direction in the tower and the result who replaces the sample of liquid in the tower
ABe 3m, height L from the lower surface of borderline region to the agitating wing of whipping appts
BBe 0.9m, the height L of borderline region is 0.35m.In addition, the TA content C of region intermediate
ABe 7.9 quality %, temperature is 161-185 ℃ (mid-way: 177 ℃), the TA content C of lower region
BBe 12.6 quality %, temperature is 160 ℃.C
BAnd C
APoor (C
B-C
A) be 4.7 quality %, the variable quantity X in the borderline region is 13 quality %/m.
Turn round after 10 hours, analyze M-nitro benzoic acid concentration in the dispersion medium of the magma of importing in displacement tower 1 and the M-nitro benzoic acid concentration in the dispersion medium in the 1st dispersion medium groove (overflow dispersion medium groove) 9, obtain the rate of displacement of dispersion medium.In addition, identical with embodiment 1, obtain the TA crystallization after, measure hue value.The result is as shown in table 5.
Table 5
| Elapsed time (h) | Rate of displacement (%) | |
| 4 | 90.8 | |
| 6 | 90.1 | |
| 8 | 89.9 | |
| 10 | 90.4 | 1.75 |
(preparation example 2)
In aqueous acetic acid, with p-Xylol in the presence of the catalyzer that forms by cobalt, manganese and bromine, (temperature of reaction is 200 ℃ to utilize air to carry out liquid phase oxidation reaction, reaction pressure is 16 normal atmosphere), obtain thick TA slurries, with the thick TA slurries partial crystallization that obtains, the solid-liquid separation after drying, obtain thick TA crystallization, the thick TA crystallization heating for dissolving that obtains in water solvent, is carried out catalytic hydrogenation, the magma that obtains is like this imported in the partial crystallization groove that is connected in series, relief pressure successively, be cooled to 160 ℃ after, supply in the former stock tank 8.
Utilize the equipment of Fig. 1, will have the long structure of vertical direction, internal diameter is that the SUS316 system tubular tower of 5m is as displacement tower 1.
To import to the lower region of displacement tower as the water conservancy of the 2nd dispersion medium with the 2nd dispersion medium liquid-feeding pump 14.In this process, utilize heat exchanger 15 100 ℃ of heating down.Make displacement tower 1 for full liquid status,, start whipping appts 13 simultaneously from the 1st dispersion medium conveying end 5 overflow waters.Then, utilize magma liquid-feeding pump 12 to begin to import magma.At this moment, magma is to utilize heat exchanger 17 to import in the displacement tower 1 after the heating down at 160 ℃.After having confirmed to form the high lower region 24 of TA content below the displacement tower 1, begin to take out the displacement slurries.
Each imports flow and takes out flow as follows.
The importing flow of magma: 109.9t/h
The importing flow of the 2nd dispersion medium: 80.6t/h
The taking-up flow of the 1st dispersion medium: 79.4t/h
The taking-up flow of displacement slurries: 111.0t/h
At this moment, the TA content of magma is 32.7 quality %, and the TA content of displacement slurries is 32.1 quality %, and the riser speed of the dispersion medium of displacement tower inside is 0.39m/h.
Can confirm the height L of region intermediate from temperature distribution of replacing the vertical direction in the tower and the result who replaces the sample of liquid in the tower
ABe 5.3m, height L from the lower surface of borderline region to the agitating wing of whipping appts
BBe 2.5m, the height L of borderline region is 0.7m.In addition, the TA content C of region intermediate
ABe 8.0 quality %, temperature is 105-155 ℃ (mid-way: 150 ℃), the TA content C of lower region
BBe 32.1 quality %, temperature is 103 ℃.C
BAnd C
APoor (C
B-C
A) be 24.1 quality %, the variable quantity X in the borderline region is 34 quality %/m.
Turn round after 10 hours, analyze M-nitro benzoic acid concentration in the dispersion medium of the magma of importing in displacement tower 1 and the M-nitro benzoic acid concentration in the dispersion medium in the 1st dispersion medium groove (overflow dispersion medium groove) 9, obtain the rate of displacement of dispersion medium.In addition, identical with embodiment 1, obtain the TA crystallization after, measure hue value.The result is as shown in table 6.
Table 6
| Elapsed time (h) | Rate of displacement (%) | |
| 4 | 96.3 | |
| 6 | 96.7 | |
| 8 | 96.4 | |
| 10 | 96.5 | 0.125 |
Comparative example 2
Except in embodiment 5, each is imported flow and take out the flow change following, other and embodiment 5 identical experimentizing.
The importing flow of magma: 110.0t/h
The importing flow of the 2nd dispersion medium: 130.3t/h
The taking-up flow of the 1st dispersion medium: 79.6t/h
The taking-up flow of displacement slurries: 160.7t/h
At this moment, the TA content of magma is 32.7 quality %, and the TA content of displacement slurries is 22.2 quality %, and the riser speed of the dispersion medium of displacement tower inside is 0.40m/h.
Can confirm the height L of region intermediate from temperature distribution of replacing the vertical direction in the tower and the result who replaces the sample of liquid in the tower
ABe 5.2m, height L from the lower surface of borderline region to the agitating wing of whipping appts
BBe 2.3m, the height L of borderline region is 1.0m.In addition, the TA content C of region intermediate
ABe 8.0 quality %, temperature is 103-155 ℃ (mid-way: 148 ℃), the TA content C of lower region
BBe 22.2 quality %, temperature is 102 ℃.C
BAnd C
APoor (C
B-C
A) be 14.2 quality %, the variable quantity X in the borderline region is 14 quality %/m.
Turn round after 10 hours, analyze M-nitro benzoic acid concentration in the dispersion medium of the magma of importing in displacement tower 1 and the M-nitro benzoic acid concentration in the dispersion medium in the 1st dispersion medium groove (overflow dispersion medium groove) 9, obtain the rate of displacement of dispersion medium.In addition, identical with embodiment 1, obtain the TA crystallization after, measure hue value.The result is as shown in table 7.
Table 7
| Elapsed time (h) | Rate of displacement (%) | |
| 4 | 91.5 | |
| 6 | 90.9 | |
| 8 | 91.6 | |
| 10 | 91.1 | 0.139 |
Except utilizing the equipment of Fig. 4, the magma introducing port is changed to the dispersion ring 30 that is provided with a plurality of slurries introducing ports, stir shaft extends to the tower bottom from tower top, and each is imported flow and take out the flow change following outside, other and embodiment 1 identical experimentizing.
The importing flow of magma: 13.89t/h
The importing flow of the 2nd dispersion medium: 9.89t/h
The taking-up flow of the 1st dispersion medium: 10.39t/h
The taking-up flow of displacement slurries: 13.39t/h
At this moment, the TA content of magma is 33.9 quality %, and the TA content of displacement slurries is 33.5 quality %, and the riser speed of the dispersion medium of displacement tower inside is 0.62m/h.
Can confirm the height L of region intermediate from temperature distribution of replacing the vertical direction in the tower and the result who replaces the sample of liquid in the tower
ABe 3m, the height L of bottom tangent line from the lower surface of borderline region to the displacement tower
BBe 0.9m, the height L of borderline region is 0.3m.In addition, the TA content C of region intermediate
ABe 7.8 quality %, temperature is 169-185 ℃ (mid-way: 179 ℃), the TA content C of lower region
BBe 33.5 quality %, temperature is 163 ℃.C
BAnd C
APoor (C
B-C
A) be 25.7 quality %, the variable quantity X in the borderline region is 86 quality %/m.
Turn round after 10 hours, analyze M-nitro benzoic acid concentration in the dispersion medium of the magma of importing in displacement tower 1 and the M-nitro benzoic acid concentration in the dispersion medium in the 1st dispersion medium groove (overflow dispersion medium groove) 9, obtain the rate of displacement of dispersion medium.In addition, identical with embodiment 1, obtain the TA crystallization after, measure hue value.The result is as shown in table 8.
Table 8
| Elapsed time (h) | Rate of displacement (%) | |
| 4 | 93.5 | |
| 6 | 93.2 | |
| 8 | 93.4 | |
| 10 | 93.8 | 1.44 |
From table 1-4,6,8 as can be seen, the method according to this invention, can be with high displacement efficiency with the 1st dispersion medium with the 2nd replacing dispersion medium, therefore, the terephthalic acid crystalline purity height that finally obtains, hue value is low, can suppress the xanthochromia of terephthalic acid.On the other hand, as can be recognized from Table 5, during the velocity of variation X less than 15 quality %/m of the TA content of borderline region, rate of displacement reduces, and hue value uprises.In addition, by table 7 and table 6 can be confirmed that relatively rate of displacement reduces, hue value uprises.
Claims (7)
1, a kind of preparation method of terephthalic acid, this preparation method will contain the preparation method of the dispersion medium utilization displacement tower metathetical terephthalic acid in the 1st dispersion medium and the terephthalic acid crystalline magma, wherein, the mixed solution of this displacement tower inside comprises upper area, region intermediate, borderline region, and lower region, described upper area is the zone of magma introducing port top, described region intermediate is the zone of the upper surface from the magma introducing port to described borderline region, described borderline region is the zone between described region intermediate and the described lower region, described lower region is the zone of below of the lower surface of described borderline region, and this preparation method satisfies following condition (1)-(3);
Condition (1): the internal diameter of described displacement tower is 1-7m;
Condition (2): the height L of described region intermediate
AFor the 0.3-4 of the internal diameter of displacement tower doubly, and height L
BFor the 0.3-1.5 of the internal diameter of displacement tower doubly, described L
BBe height, perhaps under the situation of not using agitating wing, be height from the lower surface of described borderline region to the bottom tangent line of described displacement tower from the lower surface of described borderline region to the agitating wing of whipping appts;
Condition (3): the height L of described borderline region is 0.1-1m;
This preparation method carries out following operation under following condition (4): import magma from the lower surface of the described upper area of described displacement tower, the 2nd dispersion medium is imported to the described lower region of this displacement tower, mainly take out described the 1st dispersion medium from the described upper area of this displacement tower, the described lower region from this displacement tower takes out the displacement slurries that contain terephthaldehyde's acid crystal and described the 2nd dispersion medium simultaneously;
Condition (4): 15≤X≤500,
In the following formula, X represents the variable quantity (quality %/rice) of terephthaldehyde's acid content of per unit height in the described borderline region, with formula (C
B-C
A)/L represents, described C
ARepresent the terephthaldehyde's acid content (quality %) in the mid-way of described region intermediate, described C
BRepresent the terephthaldehyde's acid content (quality %) in the mid-way of described lower region, L represents the height (rice) of described borderline region.
2, the preparation method of terephthalic acid according to claim 1, wherein, the importing temperature of described magma is 140-240 ℃.
3, the preparation method of terephthalic acid according to claim 1 and 2, wherein, described the 1st dispersion medium is water or aqueous acetic acid, described the 2nd dispersion medium is water or aqueous acetic acid.
4, the preparation method of terephthalic acid according to claim 1 and 2, wherein, described the 1st dispersion medium is an aqueous acetic acid, described the 2nd dispersion medium is a water.
5, according to the preparation method of any described terephthalic acid in the claim 1 to 4, wherein, the temperature in the mid-way of described region intermediate is higher more than 3 ℃ than the temperature in the mid-way of described lower region.
6, according to the preparation method of any described terephthalic acid in the claim 1 to 5, wherein, utilize whipping appts and/or outer loop device to carry out the stirring of described lower region.
7, the preparation method of terephthalic acid according to claim 6 wherein, utilizes whipping appts to carry out the stirring of described lower region, and this whipping appts is arranged to not contact fully with described borderline region.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007049280 | 2007-02-28 | ||
| JP2007049280 | 2007-02-28 | ||
| JP2007-049280 | 2007-02-28 |
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| Publication Number | Publication Date |
|---|---|
| CN101255110A true CN101255110A (en) | 2008-09-03 |
| CN101255110B CN101255110B (en) | 2012-12-05 |
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ID=39890275
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040513A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing aqueous paste of terephthalic acid through solvent displacement |
| TWI719169B (en) * | 2016-03-31 | 2021-02-21 | 日商三菱瓦斯化學股份有限公司 | Method for producing terephthalic acid |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3979505B2 (en) * | 1995-05-17 | 2007-09-19 | 三菱瓦斯化学株式会社 | Method for producing high purity terephthalic acid |
| JPH1045667A (en) * | 1996-07-29 | 1998-02-17 | Mitsubishi Gas Chem Co Inc | Production of high-purity terephthalic acid using dispersion medium exchanger |
-
2008
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040513A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Method for preparing aqueous paste of terephthalic acid through solvent displacement |
| TWI719169B (en) * | 2016-03-31 | 2021-02-21 | 日商三菱瓦斯化學股份有限公司 | Method for producing terephthalic acid |
Also Published As
| Publication number | Publication date |
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| JP5173474B2 (en) | 2013-04-03 |
| JP2008239608A (en) | 2008-10-09 |
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