CN109096089A - The preparation method and its device of terephthalic acid (TPA) - Google Patents
The preparation method and its device of terephthalic acid (TPA) Download PDFInfo
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- CN109096089A CN109096089A CN201810985261.1A CN201810985261A CN109096089A CN 109096089 A CN109096089 A CN 109096089A CN 201810985261 A CN201810985261 A CN 201810985261A CN 109096089 A CN109096089 A CN 109096089A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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Abstract
The preparation method and its device of terephthalic acid (TPA) of the present invention, it is related to 1, the preparation of 4- benzene dicarboxylic acid, the mixed liquor constituted using paraxylene, acetic acid solvent and catalyst, using reaction rectification technique, utilizes the heat for reacting itself releasing as raw material, the water of solvent acetic acid and reaction production is separated during the reaction, the moisture in reaction system is successfully removed, constant, the obtained terephthalic acid (TPA) of acetate concentration in reaction system is maintained；Equipment therefor is the reactive distillation column being made of reactive distillation column stripping section, circulating pump, middle section steam generator, reactive distillation column rectifying section, air preheater, overhead vapours generator, water cooler, return tank and reflux pump.The present invention overcomes cannot effectively remove the moisture generated in reaction existing for prior art processes method, it cannot be guaranteed that solvent acetic acid constant concentration and equipment and complex process, the defect of high production cost.
Description
Technical field
Technical solution of the present invention is related to the preparation of Isosorbide-5-Nitrae-benzene dicarboxylic acid, the specifically preparation method of terephthalic acid (TPA)
And its device.
Background technique
Terephthalic acid (TPA) is important bulk chemical, is to be produced by paraxylene (abbreviation PX) by air oxidation
It arrives.In the prior art, the process of preparing of terephthalic acid (TPA) be raw material in stirred autoclave using acetic acid as solvent, with cobalt manganese
Bromine is catalyst, contacts with the oxygen in air and oxidation reaction occurs, and paraxylene is oxidized production terephthalic acid (TPA).This process
For oxidation heat liberation process, steam generator and water cooler is arranged in tower top, to take out the heat that reaction is released, and by condensation reflux liquid
It flows back into reaction kettle, tail gas is discharged to tail gas clean-up workshop section from liquid separation tank.The reaction product obtained in reaction kettle is rich in benzene
The slurry of dicarboxylic acid crystals, slurry are sent to oxidizing and crystallizing workshop section and go production p-phthalic acid (abbreviation PTA), this preparation process
Method is in the presence of cannot effectively remove the moisture produced in reaction, it cannot be guaranteed that the defect of solvent acetic acid constant concentration.
CN1257146C discloses the production method and device of terephthalic acid (TPA): the device consists of three parts: bubbling column reactor, slurry
Material processing device, exhaust gas processing device；The Integral Thought of method is: being realized using the bubbling column reactor with gas fallaway section
The liquid phase catalytic oxidation of paraxylene；Slurry treatment device recycles solid terephthaldehyde using multistage evaporation, filtering, drying steps
Acid；Exhaust gas processing device recycles reaction heat using multi-stage condensing byproduct steam, using azeotropic distillation method recycling design.
There are equipment and complex process for technology disclosed in CN1257146C, cannot remove the water that reaction generates in time, it is flat to influence reaction
Weighing apparatus and reaction conversion ratio, the defect of high production cost.
Summary of the invention
The technical problems to be solved by the present invention are: the preparation method and its device of terephthalic acid (TPA), using reactive distillation
Technology is during the reaction separated the water of solvent acetic acid and reaction production using the heat itself released is reacted, at
Function removes the moisture in reaction system, maintains the constant of acetate concentration in reaction system, overcomes prior art processes
The moisture generated in reaction cannot be effectively removed existing for method, it cannot be guaranteed that solvent acetic acid constant concentration and equipment and technique
Complexity, the defect of high production cost.
The present invention solves technical solution used by the technical problem: the preparation method of terephthalic acid (TPA), specific steps
It is as follows:
The first step, p xylene oxidation generate terephthalic acid (TPA):
It is in mass ratio paraxylene by raw material paraxylene, acetic acid solvent and catalyst: acetic acid: catalyst=1: 3~5
: 0.001~0.003 mixed liquor constituted, from reactive distillation column stripping section the top, column plate enters in tower, using air preheat
Air after device preheating enters in tower from reactive distillation column stripping section bottommost, in the effect of reactive distillation column stripping section column plate
Under, air and above-mentioned mixed liquor come into full contact on reactive distillation column stripping section column plate, under the effect of the catalyst in air
Dioxygen oxidation paraxylene, thus complete p xylene oxidation and generate terephthalic acid (TPA), generated terephthalic acid (TPA) is not with having
There is the acetic acid solvent of volatilization to flow back into reactive distillation column stripping section tower bottom and forms the slurry reaction liquid for being rich in terephthalic acid (TPA)；
The rectifying of second step, solvent acetic acid and water separates:
The terephthalic acid (TPA) that the above-mentioned first step generates is dissolved in acetic acid solvent, is flowed back as circulation fluid with acetic acid solvent
To reactive distillation column tower reactor, the reaction solution slurry containing acetic acid, catalyst and terephthalic acid (TPA) is obtained, the reaction solution slurry is anti-
What is generated after answering rectifying column stripping section to react mainly enters reactive distillation column rectifying section by the tail gas of nitrogen, acetic acid and water constituted
Bottom one layer of column plate goes rectifying, under the action of the overhead reflux liquid of reactive distillation column, completes in reactive distillation column rectifying section
The rectifying separation process of acetic acid and water, obtaining mass percent purity in the bottom of reactive distillation column rectifying section is 95% or more
Acetic acid；
Third step, solvent acetic acid recycle:
It is equipped with circulating pump in the bottom of reactive distillation column rectifying section, the circulation fluid of above-mentioned second step is in reactive distillation column
After section steam generator takes heat, a part in circulation fluid is flowed back on the column plate of reactive distillation column rectifying section with control reaction essence
The bottom temp of tower rectifying section is evaporated, another part acetic acid in circulation fluid is sent to above reactive distillation column stripping section by circulating pump
First layer column plate, continues as reaction dissolvent；
4th step, gas-liquid separation:
It is equipped with overhead gas three-level cooling system at the top of reactive distillation column rectifying section, the first order is air preheater,
The second level is overhead vapours generator, and the third level is water cooler, using circulating water, reactive distillation column rectifying section top gaseous phase
After three-level is cooling, moisture and acetic acid in gas are condensed, and gas-liquid separation is realized in return tank, are contained
Phegma is flowed back into first layer column plate at the top of reactive distillation column rectifying section by reflux pump by the lime set of acetate in minute, and containing micro-
The tail gas for measuring acetic acid is discharged from return tank, into exhaust gas purification system, is vented after purification；
5th step, the acquisition of terephthalic acid (TPA):
It obtains the slurry containing terephthalic acid (TPA) in the tower bottom of reactive distillation column to be discharged from tower bottom, the slurry is by drop
After temperature, crystallization, filtering, crude terephthalic acid is obtained.
The preparation method of above-mentioned terephthalic acid (TPA), the catalyst are that cobalt acetate, manganese acetate and hydrobromic acid are used in mixed way, three
The mass ratio of person's mixing is cobalt acetate: manganese acetate: hydrobromic acid=1: 1: 2.
The preparation method of above-mentioned terephthalic acid (TPA), used in raw material, reagent and equipment pass through known approach and obtain,
Operating method is that those skilled in the art will appreciate that.
The preparation facilities of above-mentioned terephthalic acid (TPA), be by reactive distillation column stripping section, circulating pump, middle section steam generator,
The reaction essence that reactive distillation column rectifying section, air preheater, overhead vapours generator, water cooler, return tank and reflux pump are constituted
Evaporate tower, the connection type of above-mentioned component is: the top of reactive distillation column is reactive distillation column rectifying section, the lower part of reactive distillation column
For reactive distillation column stripping section, the bottom of circulating pump setting reactive distillation column rectifying section is simultaneously connect with middle section steam generator, in
At the top of section steam generator access reactive distillation column rectifying pars infrasegmentalis and stripping section, overhead vapours generator side and air preheat
Device connection, the overhead vapours generator other side are connect with water cooler side, and the water cooler other side is connect with return tank top again, are returned
It is connect below stream tank with reflux pump, thus constitutes the preparation facilities of terephthalic acid (TPA).
The preparation facilities of above-mentioned terephthalic acid (TPA), wherein the operating condition of the reactive distillation column stripping section are as follows: reaction essence
The tower diameter for evaporating tower stripping section is 1.6~6.5m, is equipped with 30 layers of column plate, 1.3~5.0MPa of operating pressure, operation temperature 190~300
DEG C, operating reflux ratio is 0.1~1.0, and operating gas velocity is 0.06~0.36m/s, reactive distillation in reactive distillation column stripping section tower
The liquid air speed of tower stripping section is 2.0~5.00h-1, the tower top temperature of reactive distillation column stripping section is 190~200 DEG C, tower bottom temperature
Degree is 200~300 DEG C；The operating condition of the reactive distillation column rectifying section are as follows: the tower diameter of reactive distillation column rectifying section be 1.4~
6.2m is equipped with 70 layers of column plate, 1.25~4.95MPa of top pressure, operating gas flow velocity in reactive distillation column rectifying section tower
0.08~1.5m/s, 168~178 DEG C of reactive distillation column rectifying section tower top temperature, 175~199 DEG C of column bottom temperature, in overhead reflux
Than being 0.2~0.3, i.e. 284~14t/h.
The preparation facilities of above-mentioned terephthalic acid (TPA) the, wherein reflux ratio, that is, regurgitant volume/inlet amount.
The beneficial effects of the present invention are: compared with prior art, the present invention have following substantive distinguishing features outstanding and
Marked improvement:
(1) reaction rectification technique is used, using the heat itself released is reacted, during the reaction by solvent acetic acid and instead
The water that should be generated is separated, and the moisture in reaction system is successfully removed, and maintains acetate concentration in reaction system
Constant, the moisture generated in reaction cannot effectively be removed by overcoming existing for prior art processes method, it cannot be guaranteed that solvent vinegar
Acid concentration is constant and equipment and complex process, the defect of high production cost.
(2) compared with CN1257146C, the present invention is consisted of three parts for its device of CN1257146C: bubble tower reaction
Device, slurry treatment device, exhaust gas processing device three parts structure carried out innovative innovation and creation, the present invention is only with one
Platform reactive distillation column is achieved that the reaction of bubbling column reactor, exhaust gas processing device multi-stage condensing byproduct steam recycling reaction heat
With the function using azeotropic distillation method recycling design, equipment is greatly simplified, and production cost is greatly reduced, and is conducive to environment guarantor
Shield.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is the device and its technique stream in the prior art that terephthalic acid (TPA) is prepared by raw material p xylene oxidation technique
Journey schematic diagram.
Fig. 2 is of the invention to prepare the device of terephthalic acid (TPA) by raw material p xylene oxidation technique and its process flow is shown
It is intended to.
In figure, 101. solvents in the prior art, 102. catalyst in the prior art, 103. raw materials in the prior art
Paraxylene, 104. stirred autoclaves in the prior art, 105. steam generators in the prior art, 106. in the prior art
Cooler, 107. tail gas in the prior art, 108. liquid separation tanks in the prior art, 109. air in the prior art；
110. slurry in the prior art, 111. condensation reflux liquids in the prior art, 201. acetic acid solvents, 202. raw materials are to diformazan
Benzene, 203. catalyst, 204. reactive distillation column stripping sections, 205. circulating pumps, 206. middle section steam generators, 207. reactive distillations
Tower rectifying section, 208. air, 209. air preheaters, 210. overhead vapours generators, 211. water coolers, 212. return tanks,
213. tail gas, 214. reflux pumps, 215. waste water, 216. phegmas, 217. slurries.
Specific embodiment
Fig. 1 shows the equipment and its work in the prior art that terephthalic acid (TPA) is prepared by raw material p xylene oxidation technique
Skill process is: with acetic acid being existing in the stirred autoclave 104 of raw material paraxylene 103 in the prior art in the prior art
Solvent 101 in technology is that oxygen connects in catalyst 102 in the prior art, with air 109 in the prior art with cobalt manganese bromine
Raw oxidation reaction is triggered, paraxylene is oxidized production terephthalic acid (TPA).This process is oxidation heat liberation process, and tower top setting is existing
Steam generator 105 and water cooler in the prior art 106 in technology, to take out the heat that reaction is released, and by existing skill
Condensation reflux liquid 111 in art flows back into stirred autoclave 104 in the prior art, and tail gas 107 in the prior art is from now
There is the liquid separation tank 108 in technology to be discharged to tail gas clean-up workshop section.The reaction obtained in stirred autoclave 104 in the prior art produces
Object is rich in the slurry in the prior art 110 of terephthalic acid crystals, and the slurry 110 in the prior art is sent to oxidizing and crystallizing
Workshop section goes production p-phthalic acid.
Embodiment illustrated in fig. 2 shows the device of the invention that terephthalic acid (TPA) is prepared by raw material p xylene oxidation technique
It is a kind of reactive distillation column, by reactive distillation column stripping section 204, circulating pump 205, middle section steam generator 206, reactive distillation column
Rectifying section 207, air preheater 209, overhead vapours generator 210, water cooler 211, return tank 212 and reflux pump 214 are constituted,
The connection type of above-mentioned component is: the top of reactive distillation column is reactive distillation column rectifying section 207, and the lower part of reactive distillation column is
Reactive distillation column stripping section 204, circulating pump 205 be arranged reactive distillation column rectifying section 207 bottom and with middle section steam generator
206 connections, middle section steam generator 206 access 207 top of reactive distillation column rectifying section, and air preheater 209 connects anti-simultaneously
The top and lower part of rectifying column are answered, 210 side of overhead vapours generator is connect with air preheater 209, overhead vapours generator
210 other sides are connect with 211 side of water cooler, 211 other side of water cooler again with connected above return tank 212, under return tank 212
Side is connect with reflux pump 214, thus constitutes the preparation facilities of terephthalic acid (TPA).
Embodiment illustrated in fig. 2 is also shown that the work of the invention that terephthalic acid (TPA) is prepared by raw material p xylene oxidation technique
Skill process is: raw material paraxylene 202, acetic acid solvent 201 and the mixed reaction solution slurry of catalyst 203 are mentioned from reactive distillation column
It evaporates 204 the top column plate of section to enter in reactive distillation column tower, the air 208 after preheating using air preheater 209 is smart from reaction
204 bottommost of tower stripping section is evaporated to enter in reactive distillation column tower, under the action of reaction tower 204 column plate of stripping section, 208 He of air
Above-mentioned reaction solution slurry comes into full contact on 204 column plate of reaction tower stripping section, under the action of catalyst 203 in air 208
Oxygen completes the oxidation process of paraxylene, and the terephthalic acid (TPA) of generation is dissolved in acetic acid solvent 201, with acetic acid solvent
201 flow back into the tower reactor of reactive distillation column, the reaction solution slurry 217 containing acetic acid, catalyst and terephthalic acid (TPA) are obtained, anti-
The tail gas that mainly nitrogen, acetic acid and water are constituted after answering rectifying column stripping section 204 to react enters reactive distillation column rectifying section 207
Rectifying is gone, under the action of overhead reflux liquid 216, was separated in the rectifying that reactive distillation column rectifying section 207 completes acetic acid and water
Journey, 207 bottom of reactive distillation column rectifying section obtain the acetic acid of 95% or more purity, and 207 bottom of reactive distillation column rectifying section is equipped with
Circulating pump 205, for circulation fluid after middle section steam generator 206 takes heat, a part in circulation fluid flows back into reaction tower rectifying section
To control 207 bottom temp of reaction tower rectifying section on 207 column plates, another part acetic acid in circulation fluid is sent to reactive distillation column
204 upper first layer column plate of stripping section, continues as reaction dissolvent, and tower overhead gas is equipped at the top of reactive distillation column rectifying section 207
Body three-level cooling system, the first order are air preheater 209, and the second level is overhead vapours generator 210, and the third level is water cooler
211, after three-level is cooling, moisture and acetic acid in gas are condensed recirculated cooling water, and real in return tank 212
Gas-liquid separation is showed, phegma 216 is flowed back into reactive distillation column rectifying section by reflux pump 214 by the lime set containing acetate in minute
207 top first layer column plates, and the tail gas 213 containing acetate in minute enters exhaust gas purification system, is vented after purification, it is obtained
Slurry 217 containing terephthalic acid (TPA) is discharged from the tower bottom of reactive distillation column, which obtains after cooling, crystallization, filtering
To crude terephthalic acid.
Prior art Fig. 1 and the comparative illustration of the technology of the present invention Fig. 2 are as follows:
The prior art is prepared present in the equipment and its process flow of terephthalic acid (TPA) as raw material p xylene oxidation technique
Defect be: the process flow is long, and process is more, and energy consumption is high, cannot remove the water that reaction generates, influence reaction conversion ratio and product
Yield.
Compared with the prior art shown in Fig. 1, the technology of the present invention prepares terephthalic acid (TPA) by raw material p xylene oxidation technique
Device and its advantages of process flow be: process is short, and low energy consumption；The water that reaction generates is removed in time, improves reaction conversion
Rate and product yield.
The preparation facilities and process for the terephthalic acid (TPA) that following all examples uses are above-mentioned embodiment illustrated in fig. 2
Description.
Embodiment 1
The present embodiment is the terephthalic acid (TPA) for producing 1,200,000 tons/year, 150t/h year.
The first step, p xylene oxidation generate terephthalic acid (TPA):
It is in mass ratio ortho-xylene: acetic acid by raw material paraxylene 202, acetic acid solvent 201 and catalyst 203: catalysis
Agent=1: 3: 0.001 mixed liquors constituted, with the dosage of 98.25t/h raw material paraxylene 202 from reactive distillation column stripping section
204 the top column plates enter in tower, and air preheater 209 is used to be preheated to the sky after 150 DEG C of preheating with 470t/h air
Gas enters in tower from 204 bottommost of reactive distillation column stripping section, under the action of reactive distillation column 204 column plate of stripping section, air
208 and above-mentioned mixed liquor come into full contact on 30 layers of column plate of reactive distillation column stripping section 204, in the effect of catalyst 203
Thus dioxygen oxidation ortho-xylene 202 in lower air 208 completes the oxidation of ortho-xylene 202 and generates terephthalic acid (TPA), generated
Terephthalic acid (TPA) is formed as the acetic acid solvent 201 not volatilized flows back into 204 tower bottom of reactive distillation column stripping section rich in benzene
217 reaction solution of slurry of dioctyl phthalate, above-mentioned catalyst 203 are that cobalt acetate, manganese acetate and hydrobromic acid are used in mixed way, three's mixing
Mass ratio is cobalt acetate: manganese acetate: hydrobromic acid=1: 1: 2；
The rectifying of second step, solvent acetic acid and water separates:
The terephthalic acid (TPA) that the above-mentioned first step generates is dissolved in acetic acid solvent 201, as circulation fluid with acetic acid solvent
201 flow back into reactive distillation column tower reactor, obtain the reaction solution slurry containing acetic acid, catalyst and terephthalic acid (TPA), the reaction solution
The tail gas 1900t/h of the composition of nitrogen, acetic acid and water that slurry generates after the reaction of reactive distillation column stripping section 204 enters reaction
The bottom one layer of column plate of rectifying column rectifying section 207 goes rectifying, under the action of overhead reflux liquid 216 of reactive distillation column, anti-
The rectifying separation process that acetic acid and water are completed under the centrifugation of 70 layers of column plate of rectifying column rectifying section 207 is answered, in reactive distillation
The bottom of tower rectifying section 207 obtains the acetic acid that mass percent purity is 95% or more；
Third step, solvent acetic acid recycle:
It is equipped with circulating pump 205 in the bottom of reactive distillation column rectifying section 207, the circulation fluid of above-mentioned second step is in reactive distillation
After the middle section steam generator 206 of tower takes heat, steam, acetic acid occur in middle section steam generator 206 for the acetic acid in circulation fluid
170 DEG C are cooled to, to control column bottom temperature as 185 DEG C, a part in circulation fluid flows back into reactive distillation column rectifying section 207
Column plate on to control the bottom temp of reactive distillation column rectifying section, circulating pump 205 is by another part acetic acid quilt in circulation fluid
It is sent to 207 upper first layer column plate of reactive distillation column stripping section, is continued as reaction dissolvent；
4th step, gas-liquid separation:
It is equipped with overhead gas three-level cooling system at the top of reactive distillation column rectifying section 207, the first order is air preheat
Device 209, the second level are overhead vapours generator 210, and the third level is water cooler 211, using circulating water, reactive distillation column essence
207 top gaseous phase of section is evaporated by after the heat exchange of air 208, is cooled to 165 DEG C from 170 DEG C, and air 208 is heated to 150 DEG C,
165 DEG C of overhead gas is cooled to 140 DEG C in overhead vapours generator 210, is finally cooled to 40 in water cooler 211
℃；After three-level is cooling, moisture and acetic acid in gas are condensed recirculated cooling water used, and are in pressure
Gas-liquid separation is realized in the return tank 212 of 1.45MPa, the lime set containing acetate in minute flows back into phegma by reflux pump
207 top first layer column plate of reactive distillation column rectifying section, and the tail gas containing acetate in minute is discharged from return tank 201, into tail
Gas purification system is vented after purification；
5th step, the acquisition of terephthalic acid (TPA):
It obtains the slurry 217 containing terephthalic acid (TPA) in the tower bottom of reactive distillation column to be discharged from tower bottom, the slurry 217 warp
After crossing cooling, crystallization, filtering, crude terephthalic acid is obtained.
In the preparation method of the terephthalic acid (TPA) of the present embodiment and its device, wherein the reactive distillation column stripping section
204 operating condition are as follows: 204 tower diameter of reactive distillation column stripping section is 6.5m, is equipped with 30 layers of column plate, operating pressure 1.6MPa, behaviour
Making temperature is 190 DEG C, operating reflux ratio 0.1, and operating gas velocity is 0.36m/s, reaction essence in 204 tower of reactive distillation column stripping section
The liquid air speed for evaporating tower stripping section 204 is 2.0h-1, the tower top temperature of reactive distillation column stripping section 204 is 190 DEG C, column bottom temperature
It is 200 DEG C, the operating condition of the reactive distillation column rectifying section 207 are as follows: 207 tower diameter 6.2m of reactive distillation column rectifying section is equipped with
70 layers of column plate, top pressure 1.55MPa, operating gas flow velocity 1.16m/s in 207 tower of reactive distillation column rectifying section, reaction essence
170 DEG C of 207 tower top temperature of tower rectifying section is evaporated, 185 DEG C of column bottom temperature, be 0.2 in overhead reflux ratio, i.e. 284t/h.
Embodiment 2
The present embodiment is the terephthalic acid (TPA) for producing 600,000 tons/year, 75t/h year.
The first step, p xylene oxidation generate terephthalic acid (TPA):
It is in mass ratio ortho-xylene: acetic acid by raw material paraxylene 202, acetic acid solvent 201 and catalyst 203: catalysis
Agent=1: 4: 0.002 mixed liquors constituted, with the dosage of 49.125t/h raw material paraxylene 202 from reactive distillation column stripping
204 the top column plates of section enter in tower, after using air preheater 209 to be preheated to 151 DEG C of preheating with 235t/h air
Air enters in tower from 204 bottommost of reactive distillation column stripping section, empty under the action of reactive distillation column 204 column plate of stripping section
Gas 208 and above-mentioned mixed liquor come into full contact on 30 layers of column plate of reactive distillation column stripping section 204, in the work of catalyst 203
With the dioxygen oxidation ortho-xylene 202 in lower air 208, thus completes the oxidation of ortho-xylene 202 and generate terephthalic acid (TPA), give birth to
At terephthalic acid (TPA) with the acetic acid solvent 201 not volatilized flow back into 204 tower bottom of reactive distillation column stripping section formed rich in pair
217 reaction solution of slurry of phthalic acid, above-mentioned catalyst 203 are that cobalt acetate, manganese acetate and hydrobromic acid are used in mixed way, three's mixing
Mass ratio be cobalt acetate: manganese acetate: hydrobromic acid=1: 1: 2；
The rectifying of second step, solvent acetic acid and water separates:
The terephthalic acid (TPA) that the above-mentioned first step generates is dissolved in acetic acid solvent 201, as circulation fluid with acetic acid solvent
201 flow back into reactive distillation column tower reactor, obtain the reaction solution slurry containing acetic acid, catalyst and terephthalic acid (TPA), the reaction solution
The tail gas 950t/h of the composition of nitrogen, acetic acid and water that slurry generates after the reaction of reactive distillation column stripping section 204 enters reaction
The bottom one layer of column plate of rectifying column rectifying section 207 goes rectifying, under the action of overhead reflux liquid 216 of reactive distillation column, anti-
The rectifying separation process that acetic acid and water are completed under the centrifugation of 70 layers of column plate of rectifying column rectifying section 207 is answered, in reactive distillation
The bottom of tower rectifying section 207 obtains the acetic acid that mass percent purity is 95% or more；
Third step, solvent acetic acid recycle:
It is equipped with circulating pump 205 in the bottom of reactive distillation column rectifying section 207, the circulation fluid of above-mentioned second step is in reactive distillation
After the middle section steam generator 206 of tower takes heat, steam, acetic acid occur in middle section steam generator 206 for the acetic acid in circulation fluid
160 DEG C are cooled to, to control column bottom temperature as 175 DEG C, a part in circulation fluid flows back into reactive distillation column rectifying section 207
Column plate on to control the bottom temp of reactive distillation column rectifying section, circulating pump 205 is by another part acetic acid quilt in circulation fluid
It is sent to 207 upper first layer column plate of reactive distillation column stripping section, is continued as reaction dissolvent；
4th step, gas-liquid separation:
It is equipped with overhead gas three-level cooling system at the top of reactive distillation column rectifying section 207, the first order is air preheat
Device 209, the second level are overhead vapours generator 210, and the third level is water cooler 211, using circulating water, reactive distillation column essence
207 top gaseous phase of section is evaporated by after the heat exchange of air 208, is cooled to 163 DEG C from 168 DEG C, and air 208 is heated to 151 DEG C,
168 DEG C of overhead gas is cooled to 140 DEG C in overhead vapours generator 210, is finally cooled to 40 in water cooler 211
℃；After three-level is cooling, moisture and acetic acid in gas are condensed recirculated cooling water used, and are in pressure
Gas-liquid separation is realized in the return tank 212 of 1.20MPa, the lime set containing acetate in minute flows back into phegma by reflux pump
207 top first layer column plate of reactive distillation column rectifying section, and the tail gas containing acetate in minute is discharged from return tank 201, into tail
Gas purification system is vented after purification；
5th step, the acquisition of terephthalic acid (TPA):
It obtains the slurry 217 containing terephthalic acid (TPA) in the tower bottom of reactive distillation column to be discharged from tower bottom, the slurry 217 warp
After crossing cooling, crystallization, filtering, crude terephthalic acid is obtained.
In the preparation method of the terephthalic acid (TPA) of the present embodiment and its device, wherein the reactive distillation column stripping section
204 operating condition are as follows: 204 tower diameter of reactive distillation column stripping section is 4.8m, is equipped with 30 layers of column plate, operating pressure 1.3MPa, behaviour
Making temperature is 250 DEG C, operating reflux ratio 0.5, and operating gas velocity is 0.32m/s, reaction essence in 204 tower of reactive distillation column stripping section
The liquid air speed for evaporating tower stripping section 204 is 2.16h-1, the tower top temperature of reactive distillation column stripping section 204 is 191 DEG C, column bottom temperature
It is 201 DEG C；The operating condition of the reactive distillation column rectifying section 207 are as follows: 207 tower diameter 4.6m of reactive distillation column rectifying section is equipped with
70 layers of column plate, top pressure 1.25MPa, operating gas flow velocity 1.5m/s in tower, 207 tower top temperature of reactive distillation column rectifying section
168 DEG C, 175 DEG C of column bottom temperature, be 0.25 in overhead reflux ratio, i.e. 142t/h.
Embodiment 3
The present embodiment is the terephthalic acid (TPA) for producing 6.5 ten thousand tons/year, 7.7t/h year.
The first step, p xylene oxidation generate terephthalic acid (TPA):
It is in mass ratio ortho-xylene: acetic acid by raw material paraxylene 202, acetic acid solvent 201 and catalyst 203: catalysis
Agent=1: 5: 0.003 mixed liquors constituted, with the dosage of 5t/h raw material paraxylene 202 from reactive distillation column stripping section 204
The top column plate enters in tower, the air after using air preheater 209 to be preheated to 161 DEG C of preheating with 24t/h air from
204 bottommost of reactive distillation column stripping section enters in tower, under the action of reactive distillation column 204 column plate of stripping section, 208 He of air
Above-mentioned mixed liquor comes into full contact on 30 layers of column plate of reactive distillation column stripping section 204, air under the action of catalyst 203
Thus dioxygen oxidation ortho-xylene 202 in 208 completes the oxidation of ortho-xylene 202 and generates terephthalic acid (TPA), generates to benzene two
Formic acid is formed as the acetic acid solvent 201 not volatilized flows back into 204 tower bottom of reactive distillation column stripping section rich in terephthalic acid (TPA)
217 reaction solution of slurry, above-mentioned catalyst 203 be cobalt acetate, manganese acetate and hydrobromic acid be used in mixed way, three mixing mass ratio
For cobalt acetate: manganese acetate: hydrobromic acid=1: 1: 2；
The rectifying of second step, solvent acetic acid and water separates:
The terephthalic acid (TPA) that the above-mentioned first step generates is dissolved in acetic acid solvent 201, as circulation fluid with acetic acid solvent
201 flow back into reactive distillation column tower reactor, obtain the reaction solution slurry containing acetic acid, catalyst and terephthalic acid (TPA), the reaction solution
The tail gas 95t/h of the composition of nitrogen, acetic acid and water that slurry generates after the reaction of reactive distillation column stripping section 204 enters reaction essence
It evaporates the bottom one layer of column plate of tower rectifying section 207 and goes rectifying, under the action of overhead reflux liquid 216 of reactive distillation column, reacting
The rectifying separation process that acetic acid and water are completed under the centrifugation of 70 layers of column plate of rectifying column rectifying section 207, in reactive distillation column
The bottom of rectifying section 207 obtains the acetic acid that mass percent purity is 95% or more；
Third step, solvent acetic acid recycle:
It is equipped with circulating pump 205 in the bottom of reactive distillation column rectifying section 207, the circulation fluid of above-mentioned second step is in reactive distillation
After the middle section steam generator 206 of tower takes heat, steam, acetic acid occur in middle section steam generator 206 for the acetic acid in circulation fluid
180 DEG C are cooled to, to control column bottom temperature as 199 DEG C, a part in circulation fluid flows back into reactive distillation column rectifying section 207
Column plate on to control the bottom temp of reactive distillation column rectifying section, circulating pump 205 is by another part acetic acid quilt in circulation fluid
It is sent to 207 upper first layer column plate of reactive distillation column stripping section, is continued as reaction dissolvent；
4th step, gas-liquid separation:
It is equipped with overhead gas three-level cooling system at the top of reactive distillation column rectifying section 207, the first order is air preheat
Device 209, the second level are overhead vapours generator 210, and the third level is water cooler 211, using circulating water, reactive distillation column essence
207 top gaseous phase of section is evaporated by after the heat exchange of air 208, is cooled to 173 DEG C from 178 DEG C, and air 208 is heated to 161 DEG C,
168 DEG C of overhead gas is cooled to 140 DEG C in overhead vapours generator 210, is finally cooled to 40 in water cooler 211
℃；After three-level is cooling, moisture and acetic acid in gas are condensed recirculated cooling water used, and are in pressure
Gas-liquid separation is realized in the return tank 212 of 4.9MPa, the lime set containing acetate in minute flows back into phegma by reflux pump
207 top first layer column plate of reactive distillation column rectifying section, and the tail gas containing acetate in minute is discharged from return tank 201, into tail
Gas purification system is vented after purification；
5th step, the acquisition of terephthalic acid (TPA):
It obtains the slurry 217 containing terephthalic acid (TPA) in the tower bottom of reactive distillation column to be discharged from tower bottom, the slurry 217 warp
After crossing cooling, crystallization, filtering, crude terephthalic acid is obtained.
In the preparation method of the terephthalic acid (TPA) of the present embodiment and its device, wherein the reactive distillation column stripping section
Operating condition are as follows: 204 tower diameter of reactive distillation column stripping section be 1.6m, be equipped with 30 layers of column plate, operating pressure 5.0MPa, operation temperature
Degree is 300 DEG C, operating reflux ratio 1.0, and operating gas velocity is 0.06m/s, reactive distillation column in 204 tower of reactive distillation column stripping section
The liquid air speed of stripping section 204 is 5.0h-1, the tower top temperature of reactive distillation column stripping section 204 is 200 DEG C, column bottom temperature 300
℃；The operating condition of the reactive distillation column rectifying section 207 are as follows: 207 tower diameter 1.4m of reactive distillation column rectifying section is equipped with 70 layers of tower
Plate, top pressure 4.95MPa, operating gas flow velocity 0.08m/s in tower, 207 tower top temperature 178 of reactive distillation column rectifying section
DEG C, 199 DEG C of column bottom temperature, be 0.3 in overhead reflux ratio, i.e. 14t/h.
In above-described embodiment, raw material used, reagent and equipment pass through known approach and obtain, and operating method is this field
Technical staff will appreciate that.
Claims (4)
1. the preparation method of terephthalic acid (TPA), it is characterised in that specific step is as follows:
The first step, p xylene oxidation generate terephthalic acid (TPA):
It is in mass ratio paraxylene by raw material paraxylene, acetic acid solvent and catalyst: acetic acid: catalyst=1: 3 ~ 5: 0.001
~ 0.003 mixed liquor constituted, from reactive distillation column stripping section the top, column plate enters in tower, is preheated using air preheater
Air afterwards enters in tower from reactive distillation column stripping section bottommost, under the action of reactive distillation column stripping section column plate, air
It is come into full contact on reactive distillation column stripping section column plate with above-mentioned mixed liquor, under the effect of the catalyst the oxygen oxygen in air
Change paraxylene, thus complete p xylene oxidation and generate terephthalic acid (TPA), generated terephthalic acid (TPA) is not with volatilizing
Acetic acid solvent flows back into reactive distillation column stripping section tower bottom and forms the slurry reaction liquid for being rich in terephthalic acid (TPA)；
The rectifying of second step, solvent acetic acid and water separates:
The terephthalic acid (TPA) that the above-mentioned first step generates is dissolved in acetic acid solvent, is flowed back into instead as circulation fluid with acetic acid solvent
Tower bottom of rectifying tower is answered, the reaction solution slurry containing acetic acid, catalyst and terephthalic acid (TPA) is obtained, the reaction solution slurry is in reaction essence
Evaporate generate after the reaction of tower stripping section mainly to enter reactive distillation column rectifying section by the tail gas of nitrogen, acetic acid and water constituted most lower
One layer of face column plate goes rectifying, under the action of the overhead reflux liquid of reactive distillation column, completes acetic acid in reactive distillation column rectifying section
With the rectifying separation process of water, the acetic acid that mass percent purity is 95% or more is obtained in the bottom of reactive distillation column rectifying section；
Third step, solvent acetic acid recycle:
It is equipped with circulating pump in the bottom of reactive distillation column rectifying section, the circulation fluid of above-mentioned second step steams in the middle section of reactive distillation column
After vapour generator takes heat, a part in circulation fluid is flowed back on the column plate of reactive distillation column rectifying section to control reactive distillation column
Another part acetic acid in circulation fluid is sent to first above reactive distillation column stripping section by the bottom temp of rectifying section, circulating pump
Layer column plate, continues as reaction dissolvent；
4th step, gas-liquid separation:
It is equipped with overhead gas three-level cooling system at the top of reactive distillation column rectifying section, the first order is air preheater, second
Grade is overhead vapours generator, and the third level is water cooler, and using circulating water, reactive distillation column rectifying section top gaseous phase passes through
After three-level is cooling, moisture and acetic acid in gas are condensed, and gas-liquid separation is realized in return tank, containing micro
Phegma is flowed back into first layer column plate at the top of reactive distillation column rectifying section by reflux pump by the lime set of acetic acid, and contains micro vinegar
The tail gas of acid is discharged from return tank, into exhaust gas purification system, is vented after purification；
5th step, the acquisition of terephthalic acid (TPA):
It obtains the slurry containing terephthalic acid (TPA) in the tower bottom of reactive distillation column to be discharged from tower bottom, the slurry is by cooling, knot
After brilliant, filtering, crude terephthalic acid is obtained.
2. the preparation method of terephthalic acid (TPA) according to claim 1, it is characterised in that: the catalyst is cobalt acetate, vinegar
Sour manganese and hydrobromic acid are used in mixed way, and the mass ratio of three's mixing is cobalt acetate: manganese acetate: hydrobromic acid=1: 1: 2.
3. the preparation facilities of above-mentioned terephthalic acid (TPA), it is characterised in that: steamed by reactive distillation column stripping section, circulating pump, middle section
Vapour generator, reactive distillation column rectifying section, air preheater, overhead vapours generator, water cooler, return tank and reflux pump are constituted
Reactive distillation column, the connection type of above-mentioned component is: the top of reactive distillation column be reactive distillation column rectifying section, reactive distillation
The lower part of tower be reactive distillation column stripping section, circulating pump be arranged reactive distillation column rectifying section bottom and with middle section steam generator
Connection, middle section steam generator access at the top of reactive distillation column rectifying pars infrasegmentalis and stripping section, overhead vapours generator side with
Air preheater connection, the overhead vapours generator other side are connect with water cooler side, and the water cooler other side is again and on return tank
Side's connection, return tank lower section are connect with reflux pump, thus constitute the preparation facilities of terephthalic acid (TPA).
4. the preparation facilities of terephthalic acid (TPA) according to claim 3, it is characterised in that: wherein, the reactive distillation column mentions
Evaporate the operating condition of section are as follows: the tower diameter of reactive distillation column stripping section be 1.6~6.5m, be equipped with 30 layers of column plate, operating pressure 1.3~
5.0MPa, 190~300 DEG C of operation temperature, operating reflux ratio is 0.1~1.0, and operating gas velocity is in reactive distillation column stripping section tower
0.06~0.36m/s, the liquid air speed of reactive distillation column stripping section are 2.0~5.00h-1, the tower top of reactive distillation column stripping section
Temperature is 190~200 DEG C, and column bottom temperature is 200~300 DEG C；The operating condition of the reactive distillation column rectifying section are as follows: reaction essence
The tower diameter for evaporating tower rectifying section is 1.4~6.2m, is equipped with 70 layers of column plate, 1.25~4.95MPa of top pressure, reactive distillation column
0.08~1.5m/s of operating gas flow velocity in rectifying section tower, 168~178 DEG C of reactive distillation column rectifying section tower top temperature, tower bottom temperature
175~199 DEG C of degree is 0.2~0.3 in overhead reflux ratio, i.e. 284~14t/h.
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