CN1594302A - Process for continuous preparation of trimellitic anhydride by step catalytic oxidation process - Google Patents
Process for continuous preparation of trimellitic anhydride by step catalytic oxidation process Download PDFInfo
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Abstract
The invention provides a process for continuous preparation of trimellitic anhydride by step catalytic oxidation process by using pseudocumene as raw material, fatty group carboxylic acid as dissolvent, cobalt, manganese and bromine as catalyst, the preparing process comprises the steps of, (1) stepwise continuous catalysis oxidizing process, (2) crystallization and liquid-solid separation, (3) anhydride forming procedure, (4) subtractive process, and (5) solvent reclamation.
Description
Technical field
The present invention relates to a kind of continuous processing method of oxidizing process production trimellitic acid 1,2-anhydride step by step.This method is raw material with the unsym-trimethyl benzene, and lower aliphatic carboxylic acid (as acetic acid) is a solvent, adopts cobalt, manganese, bromine catalyst system, and unsym-trimethyl benzene is carried out liquid phase oxidation reaction with the gas that contains oxygen molecule.Behind the oxidation certain phase,, carry out trimellitic acid production by carrying out the adding of catalyzer once more.Compare with domestic original batch production technology, oxidation production method step by step makes the yield of product reach 90 (mol) % continuously, and the security of simultaneous oxidation reactive system improves, constant product quality, service life of equipment increases, and is easy to use in large-scale industrial production.
Background technology
Be a kind of important organic chemical industry's intermediate to benzenetricarboxylic anhydride (TMA) partially, the solidifying agent of heat-resisting softening agent, water soluble alkyd resin coating and the epoxy resin of Chang Zuowei production polyvinyl chloride etc. are widely used in the Chemicals production.In recent years, along with the development of household electrical appliance such as televisor, video recorder, combination audio, the demand of TMA is in rising trend.
China TMA suitability for industrialized production mainly adopts liquid phase air oxidation technology, promptly at 170 ℃~230 ℃, under 18~23atm condition, at first, with Co-Mn-Br is catalyzer, and in acetate solvate, unsym-trimethyl benzene and air carry out oxidizing reaction, oxidation generates trimellitic acid, prepares trimellitic acid 1,2-anhydride through being dehydrated into anhydridization process then.In the batch production process, at first drop into air in a small amount, treat that oxidizing reaction temperature begins to rise, strengthen the air consumption one by one, temperature of reaction begins to rise to maximum, behind the reaction certain hour, reduces the air consumption more one by one, stops test after tail oxygen concentration reaches 18%.The oxidizing reaction material is transported to decrease temperature and pressure in the kettle, sloughs solvent (acetic acid and water mixture) earlier, at high temperature carries out certain embodiments then, finally obtains thick trimellitic acid 1,2-anhydride.In the batch fractionating treating process, slightly trimellitic acid 1,2-anhydride is disposable enters in first rectifying still, carries out rectification under vacuum, and the product that steams enters second rectifying still, carries out secondary rectifying, finally obtains highly purified trimellitic acid anhydride product.Adopt this method, producing materials is intermittently, after reaction material is heated to temperature of reaction, could drop into air and react, discharging then, the oxygenated products of generation is a still one still, reactor need carry out buck process repeatedly, and it is big not only to operate labour intensity, and equipment is tired easily.Temperature fluctuation is big in the operation, strengthened equipment corrosion speed.The periodical operation gas flow changes in time, causes in the oxidation reactor gas distribution inhomogeneous, has influenced quality product.At present, domestic batch production handicraft product yield (mole) is 50~60% (with the unsym-trimethyl benzene calculating that feeds intake).
Summary of the invention
The present invention is exactly the improvement on intermittence liquid phase air oxidation basis, by provide a kind of continuously, catalysed oxidation processes step by step, solved the problems in the batch production, improved the yield and the acid number of trimellitic acid.
The catalyzed oxidation method of producing the trimellitic acid anhydride process step by step continuously,, with the unsym-trimethyl benzene is raw material, acetic acid is solvent, Cobaltous diacetate, manganese acetate, tetrabromoethane or hydrogen bromide are catalyzer, feed pressurized air line by line continuously step by step oxidizing reaction make trimellitic acid, trimellitic acid pass through into anhydride process make trimellitic anhydride, thick trimellitic acid 1,2-anhydride is removed impurity through treating process, must smart trimellitic acid 1,2-anhydride finished product.Pass through to adopt crystallization, filtration and purification apparatus in the production process, the abundant separation and the process for refining high-recovery of solid-liquid have been realized, simultaneously, produce the middle and high concentration acetic acid and the aqueous solution through reclaiming separation system, improved acetate concentration in the solution, thereby it can be reused, and concrete art production process is as follows:
Technical solution of the present invention is as follows:
A kind of method of the continuous production of catalyzed oxidation step by step trimellitic acid 1,2-anhydride may further comprise the steps:
1, unsym-trimethyl benzene and lower fatty acid solvent are sent in the raw material mixing tank, add an amount of Cobaltous diacetate, tetrabromoethane or hydrogen bromide, its optimum solvent is generally 1~10 than (unsym-trimethyl benzene and solvent quality ratio), is heated to about 20--100 ℃, stirs.
2, said mixture is sent in the reactor, when 100~300 ℃ of temperature, pressure is to feed pressurized air under 0.6~5.4MPa condition continuously to carry out oxidizing reaction, generates the stair oxidation reaction product, for keeping process stabilization continuous, oxygen level is at 0.1~19% (volume) in the control reaction end gas.
3, the stair oxidation reaction product is imported the secondary oxidation reactor continuously, at 100~300 ℃ of temperature, pressure is under the condition of 0.1~0.3MPa, add Mn catalyst, feed oxygen-containing gas simultaneously and carry out the secondary oxidation reaction continuously, generate the oxidizing reaction final product, oxygen level is at 0.1~12% (volume) in the control reaction end gas.
4, the oxidizing reaction final product is imported in the multi-stage mold continuously, 100~300 ℃ of temperature, pressure is under 0.01~1.0MPa condition, and solid phase is separated out, and centrifugal solid-liquid separates, and makes the wet cake of thick trimellitic acid.
5, the wet cake of thick trimellitic acid is sent into be dehydrated into acid anhydride in the kettle, become the acid anhydride temperature at 60~400 ℃, pressure (absolute pressure) is at 0.01~0.8Mpa.
6, the thick trimellitic acid 1,2-anhydride that obtains in the kettle is sent in the refining system, 150~350 ℃ of temperature, pressure (absolute pressure) carries out rectifying less than under the 0.008MPa condition, sloughs impurity and obtains the trimellitic acid 1,2-anhydride liquid end product.
Optimum solvent of the present invention is for containing the acetic acid of 2~25% (WT) water, unsym-trimethyl benzene is (0.5: 1~1: 10) with the weight of solvent ratio, based on the metal catalyst total amount of solvent is 0.05~1.50% (wt) or more preferably 0.02~1.0% (wt), and cobalt accounts for total metal catalyst total amount 35~90% (wt), or more preferably 40~85%, manganese accounts for metal catalyst total amount at least 1.0%, or preferable range is at 1.5~15% (wt).Bromine accounts for 50~90% (wt) of metal catalyst total amount or preferred 55~85%, and the bromine source can be taken from and contain bromide as hydrogen bromide, tetrabromoethane, Potassium Bromide etc.The compound that contains cobalt and manganese that can be dissolved in solvent all can, as acetate, carbonate, bromide etc., being more preferably respectively is Co (OAC) as cobalt, manganese, bromine source
24H2O, Mn (OAC)
24H2O and tetrabromoethane.
Liberated heat in the first order reaction process is taken away by the multi-stage condensing device, and cooled condensed fluid turns back in the reactor in proportion, and unnecessary phlegma is retracted to dehydration tower further to be separated, and separates back acetic acid Returning reactor raw material mixing tank.
Heat is removed by the solvent evaporates form in the second order reaction process, and part is extracted out in condensation reflux liquid simultaneously, and the extraction amount is total feed 1~30% (wt), control tail oxygen level 3~8% (vol) in the two-stage reaction process.More excellent Tc is 150~250 ℃ in the above-mentioned steps, and pressure is 0.05~0.5Mpa.
Becoming the preferred temperature of acid anhydride in the above-mentioned steps is 100~300 ℃, pressure (absolute pressure) 0.05~0.6Mpa,
The acetic acid that oxidising process produces in the above-mentioned steps and the mixture of water are sent into the acetic acid recovery system and are carried out rectifying and dewatering, reclaim acetate solvate.
Continuous production processes among the present invention, make the production process security, stability improves, energy consumption reduces, service life of equipment increases simultaneously, and adopt second stage manganese addition technology that the trimellitic acid product yield of acquisition is improved, simultaneously owing to side reaction degree in the oxidising process decreases, impurity concentration reduces in the reaction, also separate out the condition that provides for more solid phase products in the process, this is because the product that the side reaction process generates, help trimellitic acid and dissolve in acetic acid, thereby pollute final oxygenated products on the one hand, it is very difficult simultaneously oxygenated products to be separated from acetate solvate.
Description of drawings
Fig. 1 is catalyzed oxidation continuous production trimellitic acid 1,2-anhydride process flow sheet step by step
1,2-material-compound tank 3 air compressor machine 4-5 oxidation reactor 6-8 crystallizers 9 whizzer 10-11 kettles 12 dehydration towers 13 rectifying tower 14 storage tanks 15 finished product jars
The invention will be described further in conjunction with schema
The trimellitic acid 1,2-anhydride production process is to be raw material with the unsym-trimethyl benzene among the present invention, produce by the liquid phase air oxidation method, the catalyst system that this method is used is a cobalt, manganese, bromine, acetic acid is as the reaction system solvent, comprise that specifically following technical process (1) raw material mixes (2) one-level catalyzed oxidation system trimellitic acid slurries (3) secondary catalyzed oxidation system trimellitic acid slurries (4) trimellitic acid slurry crystallization continuously continuously, centrifugally liquid-solidly separate to such an extent that the wet cake of wet cake (5) trimellitic acid of trimellitic acid becomes the thick trimellitic acid 1,2-anhydride of acid anhydride (6) further refining, obtain smart trimellitic acid anhydride product.
The catalytic amount control unsym-trimethyl benzene that continuously first step adds in the oxidizing reaction step by step among the present invention can only partial oxidation, reduce the side reaction amount simultaneously, and secondary adding Mn catalyst further is converted into the purpose product with the intermediate product that generates, to avoid poisoning of catalyst.The material that oxidation generates by the liquid-solid separation of crystallization, and then is carried out to the acid anhydride treating process.
When carrying out serialization production, with unsym-trimethyl benzene, acetic acid is delivered to continuously in the batching still by transferpump respectively from storage tank 1 and 2 and is added Cobaltous diacetate, manganese acetate and tetrabromoethane catalyzer, stir, maintain the temperature at about 50~80 ℃, send in the reactor continuously by transferpump, after material is heated to 100~350 ℃, drive air compressor, in reactor, feed pressurized air continuously, keep reactor pressure at 1.0~5.4Mpa, carrying out oxidizing reaction causes, through causing the material feeding process, realize producing and carry out continuously, controlling reactor tail oxygen level is between 0.1~10%, make reaction safety, stable carrying out, the product pump that oxidation reactor comes out is delivered in the secondary oxidation reactor, join continuously in the secondary oxidation reactor containing Mn catalyst in the catalyst mix jar simultaneously, in reactor, inject air, carry out the secondary oxidation reaction, the heat that produces in oxidation reaction process passes through solvent evaporates, remove heat on reactor top through the multi-stage condensing device, reach the suitable speed of response purpose of maintenance by water extraction amount in the dehydration tower of controlling reactor top, the slurry that comes out in the reactor enters in the multi-stage mold, finishes trimellitic acid crystal grain and separates out, process of growth, 100~300 ℃ of Tcs, pressure are 150~250 ℃ of 0.01~1.0Mpa or more excellent Tcs, and pressure is 0.05~0.5Mpa.Multistep crystallizer pressure distribution is 0.05~1.0Mpa, or 0.15~1.0Mpa more preferably, crystalline particle grows into to be sent material into whizzer after the suitable size and carries out separating of solid phase and liquid phase, separate the back mother liquor and deliver to the acetic acid recovery tower, wet cake material is sent to kettle continuously and is dehydrated into acid anhydride, become the acid anhydride temperature at 60~400 ℃, pressure (absolute pressure) is at 0.01~0.8Mpa.Or more preferably temperature is 100~300 ℃, pressure (absolute pressure) 0.05~0.6Mpa, the thick trimellitic acid 1,2-anhydride that generates in the kettle is sent in the rectifying tower, obtains the trimellitic acid 1,2-anhydride liquid product, in order to keep operational stability by rectifying, rectification temperature is at 150~350 ℃, pressure (absolute pressure) is in 0.005Mpa~0.01Mpa, or 200~320 ℃ of more excellent temperature, and pressure (absolute pressure) is in 0.008Mpa, discharging will be isolated waste residue and will be discharged in the outside storage tank by pump simultaneously continuously.
In the continuous production method of the present invention, the slurry that comes out from crystallizer is by liquid-solid separation, make and to be dissolved in that the catalyzer major part enters in the recovery tower with separating mother liquor in the solution, thereby reduced catalyst content in the wet biscuit, improved catalyst utilization on the one hand, simultaneously, the wet cake of low catalyst levels is carried out to charing phenomenon and the reduction of polyreaction degree in the acid anhydride rectifying, has improved smart trimellitic acid 1,2-anhydride yield.
Embodiment
Embodiment 1. is with unsym-trimethyl benzene 1500kg, acetic acid 15000kg, join in the batching still 1 with the conveying and metering pump, add Cobaltous diacetate 8kg then, tetrabromoethane 7kg, stir, temperature is 80 ℃ in the maintenance batching still, simultaneously, acetic acid 250kg and manganese acetate 1kg is joined in the material-compound tank 2, stir, temperature is 80 ℃ in the still that keeps preparing burden.By reacting charge pump with 3m
3/ h flow is reinforced in oxidizing reactor 4, after adding about 30 minutes, stop charging, use the nitrogen sealing gland, the reacting by heating material feeds pressurized air by air compressor 3 then and carries out initiation reaction, when temperature of reaction presents ascendant trend to temperature of reaction, and when tail gas content begins to rise in the reactor 4, with 5m
3The feed rate of/h adds fresh material continuously in reactor 4, adjust pressurized air air inlet total amount, about 3~5% (vol), keep reaction pressure 2.2Mpa with oxygen level in the controlling reactor tail gas, 210 ℃ of temperature, make system reach homeostasis gradually, along with material accumulates in reactor 4, the liquid level of reactor 4 increases thereupon, when liquid level reaches reactor total height 70~75%, open the outlet regulating valve, reactor 4 dischargings enter oxidizing reactor 5, simultaneously with 1m
3/ h adds jar 2 manganese acetate catalysts to oxidizing reactor 5.Adjust the flow of bubbling air, keep reactor pressure 2.2Mpa, 210 ℃ of temperature of reaction, tail oxygen level 3~5% (vol) in the control reaction end gas, when liquid level reaches reactor total height 70~75%, open the reacting material outlet valve, enter and carry out further oxidation in the oxidation reactor 6.Enter crystallization in 7,8 crystallization kettles then, crystallization kettle pressure at different levels will be 0.5~1.0Mpa, slurry after the crystallization enters whizzer 9-centrifugation continuously, wet cake after will separating is then sent into kettle 10,11-is dehydrated into acid anhydride, kettle is 0.02Mpa at pressure, temperature is that dehydration generates thick trimellitic acid 1,2-anhydride finished product under 120 ℃ of conditions, thick trimellitic acid 1,2-anhydride is sent in the rectifying still 12,200 ℃ of temperature, pressure (absolute pressure) is less than under the 0.001Mpa condition, and rectifying obtains pure trimellitic acid anhydride product, sends into continuously in the finished product jar and deposits.Acetic acid steam enters recovery tower in the one-tenth acid anhydride, purifies and utilizes.Can obtain the trimellitic acid of 2150Kg like this, its product yield (mol) is 90%.
Embodiment 2. unsym-trimethyl benzene raw material 1000Kg, acetic acid 1500Kg adds Cobaltous diacetate 3kg then, tetrabromoethane 8kg, stir, temperature is 80 ℃ in the still that keeps preparing burden, simultaneously, acetic acid 150kg and manganese acetate 0.8kg are joined in the material-compound tank 2, stir, temperature is 80 ℃ in the still that keeps preparing burden.By reacting charge pump with 2m
3/ h flow is reinforced in oxidizing reactor 4, after adding about 15 minutes, stop charging, use the nitrogen sealing gland, the reacting by heating material feeds pressurized air by air compressor 3 then and carries out initiation reaction, when temperature of reaction presents ascendant trend to temperature of reaction, and when tail gas content begins to rise in the reactor, with 3m
3The feed rate of/h adds fresh material continuously in reactor, adjust pressurized air air inlet total amount, about 3~5% (vol), keep reaction pressure 2.2Mpa with oxygen level in the controlling reactor tail gas, 210 ℃ of temperature, make system reach homeostasis gradually, along with material accumulates in reactor 4, the liquid level of reactor 4 increases thereupon, when liquid level reaches reactor total height 70~75%, open the outlet regulating valve, reactor 4 dischargings enter oxidizing reactor 5, simultaneously with 0.8m
3/ h adds manganese acetate catalyst in the jar 2 to oxidizing reactor 5.Adjust the flow of bubbling air, keep reactor pressure 2.2Mpa, 210 ℃ of temperature of reaction, tail oxygen level 3~5% (vol) in the control reaction end gas, when liquid level reaches reactor total height 70~75%, open the reacting material outlet valve, enter and carry out further oxidation in the oxidation reactor 6.Enter crystallization in 7,8 crystallization kettles then, crystallization kettle pressure at different levels will be 0.5~1.0Mpa, slurry after the crystallization enters whizzer 9-centrifugation continuously, wet cake after will separating is then sent into kettle 10,11-is dehydrated into acid anhydride, kettle is 0.02Mpa at pressure, temperature is that dehydration generates thick trimellitic acid 1,2-anhydride finished product under 120 ℃ of conditions, thick trimellitic acid 1,2-anhydride is sent in the rectifying still 12,200 ℃ of temperature, pressure (absolute pressure) is less than under the 0.001Mpa condition, and rectifying obtains pure trimellitic acid anhydride product, sends into continuously in the finished product jar and deposits.Acetic acid steam enters recovery tower in the one-tenth acid anhydride, purifies and utilizes.Can obtain the trimellitic acid of 1280Kg like this, its product yield (mol) is 80%.
The present invention adopts continuously, the trimellitic acid 1,2-anhydride of liquid phase air oxidation explained hereafter step by step, compares with domestic existing interrupter method, and economic target is relatively under the same materials:
Two kinds of technology comparative results of table 1
Project | Method | |
Continuous oxidation process step by step | Intermittent oxidation technology | |
Quality index | ||
Acid anhydride content (wt%) | ????99.7 | ????95.5 |
Fusing point ℃ | ????168 | ????164 |
Consume | ||
Unsym-trimethyl benzene (ton/ton product) | ????0.80 | ????0.98 |
Acetic acid (ton/ton product) | ????0.10 | ????0.30 |
Cobaltous diacetate (Kg/ ton product) | ????4.0 | ????8 |
Manganese acetate (Kg/ ton product) | ????3.5 | ????8 |
Tetrabromoethane (Kg/ ton product) | ????6.0 | ????8 |
Electricity (degree/ton) | ????1300 | ????2200 |
Coal (degree/ton product) | ????2.0 | ????4 |
Trimellitic acid 1,2-anhydride yield % (mol unsym-trimethyl benzene) | ????85-90 | ????55-65 |
Claims (12)
1. method of catalyzed oxidation continuous production trimellitic acid 1,2-anhydride step by step may further comprise the steps:
A, unsym-trimethyl benzene and acetic acid are sent in the raw material mixing tank, add an amount of Cobaltous diacetate, tetrabromoethane or hydrogen bromide, be heated to 20~100 ℃, stir;
B, a certain amount of said mixture is sent in the reactor, when 100~300 ℃ of temperature, pressure is to feed pressurized air under 0.6~5.4MPa condition continuously to carry out oxidizing reaction, generate the stair oxidation reaction product, for keeping process stabilization continuous, oxygen level is at 0.1~19% (VOL) in the control reaction end gas;
C, the stair oxidation reaction product is imported the secondary oxidation reactor continuously, at 100~300 ℃ of pressure of temperature is under the condition of 0.1~0.3MPa, add Mn catalyst, feed oxygen-containing gas simultaneously and carry out the secondary oxidation reaction continuously, generate the oxidizing reaction final product, oxygen level is at 0.1~12% (vol) in the control reaction end gas;
D, the oxidizing reaction final product is imported in the multi-stage mold continuously, 100~300 ℃ of temperature, pressure is under 0.01~1.0MPa condition, and solid-phase crystallization is separated out, and centrifugal solid-liquid separates, and makes the wet cake of thick trimellitic acid;
E, the wet cake of thick trimellitic acid sent into be dehydrated into thick trimellitic acid 1,2-anhydride in the kettle, become the acid anhydride temperature at 60~400 ℃, pressure (absolute pressure) is at 0.01~0.8Mpa;
Unsym-trimethyl benzene and acetic acid weight ratio are 0.5: 1~1: 10, metal catalyst total amount based on acetic acid is 0.05~1.50% (wt), cobalt accounts for total metal catalyst total amount 35~90% (wt), and manganese accounts for metal catalyst total amount at least 1.0%, and bromine accounts for 50~90% (wt) of metal catalyst total amount.
2, method according to claim 1 also comprises treating process, and the thick trimellitic acid 1,2-anhydride that is about to obtain is sent in the refining system, 150~350 ℃ of temperature, pressure (absolute pressure) carries out rectifying less than under the 0.008MPa condition, sloughs impurity and obtains the trimellitic acid 1,2-anhydride liquid end product.
3, method according to claim 1, wherein acetic acid preferably contains the acetic acid of 2~25% (WT) water.
4, method according to claim 1 is wherein based on preferred 0.02~1.0% (wt) of the metal catalyst total amount of acetic acid.
5, method according to claim 1, wherein cobalt accounts for preferred 40~85% (wt) of total metal catalyst total amount.
6, method according to claim 1, wherein manganese accounts for preferred 1.5~15% (wt) of metal catalyst total amount.
7, method according to claim 1, wherein bromine accounts for metal catalyst total amount preferred 55~85%.
8, method according to claim 1,150~250 ℃ of wherein more excellent Tcs, pressure is 0.05~0.5Mpa.
9, method according to claim 1, wherein more excellent one-tenth acid anhydride temperature is 100~300 ℃, pressure (absolute pressure) 0.05~0.6Mpa.
10, method according to claim 1, wherein C, the water of D step generation and the mixture of acetic acid carry out rectifying and dewatering by the acetic acid recovery system, and the acetate solvate that reclaims is reused for reactive system.
11, method according to claim 1 is characterized in that: the Control for Oxygen Content in the oxidizing reaction tail gas is between 3~8% (VOL).
12, method according to claim 1 is characterized in that: the evaporable solvent only partly turns back in the reactor by cooled condensed fluid in the oxidation reaction process, and the extraction amount is charging total amount 1~30% (wt).
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CN110560110A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Catalyst for synthesizing meta-anhydride by oxidizing meta-trimethylbenzene |
CN110560109A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Catalyst for producing trimellitic anhydride |
CN110560112A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Catalyst for preparing trimellitic anhydride |
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CN110560114A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Catalyst for improving yield of trimellitic anhydride |
CN110560111A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Catalyst for synthesizing meta-anhydride from pseudocumene |
CN110560112B (en) * | 2018-06-05 | 2021-11-30 | 中国石油化工股份有限公司 | Catalyst for preparing trimellitic anhydride |
CN110560116B (en) * | 2018-06-05 | 2021-11-30 | 中国石油化工股份有限公司 | Catalyst for oxidation of pseudocumene to prepare meta-anhydride |
CN110560116A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Catalyst for oxidation of pseudocumene to prepare meta-anhydride |
CN110560113B (en) * | 2018-06-05 | 2021-11-30 | 中国石油化工股份有限公司 | Catalyst for pseudocumene catalytic oxidation |
CN110560114B (en) * | 2018-06-05 | 2021-11-30 | 中国石油化工股份有限公司 | Catalyst for improving yield of trimellitic anhydride |
CN110560109B (en) * | 2018-06-05 | 2021-11-30 | 中国石油化工股份有限公司 | Catalyst for producing trimellitic anhydride |
CN110560115B (en) * | 2018-06-05 | 2021-11-30 | 中国石油化工股份有限公司 | Catalyst for synthesizing trimellitic anhydride |
CN108892653A (en) * | 2018-08-14 | 2018-11-27 | 南通百川新材料有限公司 | A kind of method that pseudocumene aoxidizes trimellitic anhydride processed |
CN108892653B (en) * | 2018-08-14 | 2022-03-29 | 南通百川新材料有限公司 | Method for preparing trimellitic anhydride by oxidizing pseudocumene |
CN110448932A (en) * | 2019-09-04 | 2019-11-15 | 江苏正丹化学工业股份有限公司 | A kind of trimellitic acid continuous crystallisation is centrifuged into acid anhydride equipment |
CN110448932B (en) * | 2019-09-04 | 2024-05-28 | 江苏正丹化学工业股份有限公司 | Trimellitic acid continuous crystallization centrifugation becomes anhydride equipment |
CN112694396A (en) * | 2019-10-23 | 2021-04-23 | 中国石化扬子石油化工有限公司 | Preparation method and application of trimellitic acid or trimesic acid |
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