CN102060686A - Method for producing aromatic carboxylic acid by using nitrogen heterocyclic ring compound as oxidation accelerator - Google Patents
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Abstract
The invention provides a method for producing aromatic carboxylic acid by using a nitrogen heterocyclic ring compound as an oxidation accelerator. In a reaction system, aliphatic series carboxylic acid is used as a solvent, air, oxygen-enriched air or oxygen is used as an oxygen source, methyl arene is oxidized or an intermediate product is partially oxidized to directly obtain the aromatic carboxylic acid; and a Co/Mn/Br/ nitrogen heterocyclic ring compound quaternary composite system is used as a catalysis system. Compared with a Co/Mn/Br ternary catalytic oxidation process, a nitrogen heterocyclic ring compound is added as the oxidation accelerator to ensure that the oxidation reaction of the methyl arene is remarkably accelerated and the process of converting the methyl arene into the aromatic carboxylic acid is promoted. According to the method, the concentration of bromine in the reaction system can be properly reduced through adding a proper amount of nitrogen heterocyclic ring compound, thus the corrosion to equipment by the reaction system and the emission of bromine-containing toxic gases are reduced.
Description
Technical field
The invention discloses a kind of methylarenes liquid phase catalytic oxidation that is used for and produce improving one's methods of aromatic carboxylic acid.With the aliphatic carboxylic acid is solvent, and the employing air or oxygen is an oxygen source, and the employing catalyst system is cobalt/manganese/bromine/nitrogen-containing heterocycle compound quaternary compound system, and direct oxidation methyl aromatic hydrocarbon or its intermediate oxidation product obtain the aromatic carboxylic acid product.Comprise as arene oxidizing promotor nitrogen heterocyclic ring: imidazoles, pyrazoles, pyridine, carboxyl pyridine, aminopyridine, pyrazine, carboxyl pyrazine, pyrimidine etc. and amino or carboxyl substituted thing.
Background technology
From adopting cobalt/manganese/bromine ternary combination, catalyzed oxidation methylarenes liquid phase has been produced since the appearance of aromatic carboxylic acid, and this method is extensive use of industrial.It is solvent that this method generally adopts acetic acid, and temperature of reaction is 100～320 ℃, keeps reaction pressure to make the aliphatic carboxylic acid kind solvent be in liquid state.Using the product that this method commercially produces has a lot, and as phenylformic acid, terephthalic acid, m-phthalic acid, phthalic acid, Tetra hydro Phthalic anhydride, all (partially) benzenetricarboxylic acid, pyromellitic acid dianhydride etc., wherein the industrial scale maximum is terephthalic acid.Aromatic carboxylic acid is the important source material of producing trevira and resin, accounts for more than 80% of all aromatic carboxylic acid ultimate productions with the aromatic carboxylic acid of cobalt/manganese/bromine three-element catalytic production.
In the production process of aromatic carboxylic acid, it is very important improving reaction efficiency, by accelerated reaction is reduced in the reaction times, can boost productivity, and reduces cost; The selectivity of improving catalytic process also is to improve the important directions of product competitiveness, and the selectivity that improves catalyst system can reduce the burning consumption of methylarenes and solvent, thereby reduces cost, improves the quality of products.
In methylarenes liquid phase catalytic oxidation process, be added with organic compounds to reach the existing many cases of the purpose of strengthening reaction to cobalt/manganese/bromine three-way catalyst system, CN1974521, CN1974520 propose stable organic compound and also can be used as effective the 4th activator of cobalt/manganese/bromine three-element catalytic system.The organic compound component of adding mainly is the nitrogenous class organic bases with rock steady structure, as polyamino compound, guanidine compound, the corrodibility CN1865214 that the interpolation of these compounds can increase cobalt/manganese/bromine system catalytic activity, improve the selectivity of reaction and reduce system disclose have the N=O base, ad hoc structures such as N-hydroxyl, N-acyloxy contain oxynitrides as oxidation promotor, to improve the performance of existing cobalt/manganese/bromine three-way catalyst.
In addition, in methylarenes liquid phase catalytic oxidation process, add the 4th kind of metal catalyst to reach the existing many cases of the purpose of strengthening reaction to cobalt/manganese/bromine three-way catalyst system, the metal component of interpolation mainly is the related salts of transition metal, rare earth metal and alkaline-earth metal.
US-47867530, US-4992580, US-5110984 and US-6153790 disclose the method for adding the soluble salts compound of transition metal such as nickel, molybdenum, chromium, tungsten, zirconium, hafnium in former catalyst system, the main reaction activity all there is in various degree raising, makes reaction process obtain quickening.Although above-mentioned metallic additions can improve the synergistic effect of catalyst system as the 4th catalyst component, improve oxidizing reaction rate, improve quality product.But on using, also there are some problems, as obvious not enough to the acceleration effect of reaction, the burning reaction that also makes that has increases, and what have costs an arm and a leg, what have has the follow-up refining step of certain residual influence etc. at solid phase prod, has therefore influenced the practicality of above-mentioned technology.
Patent US-6194607 proposes to add the method for alkalimetal ion and alkaline-earth metal ions in cobalt/manganese/bromine three-way catalyst system, propose at CO simultaneously
2P-Xylol liquid phase oxidation reaction speed is accelerated under the coexistence situation, and transformation efficiency and terephthalic acid selectivity increase.Its major cause is Co or Mn oxidation part and CO
2Reaction generates the higher peroxidation carbonate material of oxidation activity.Further research also shows CO when Ni coexists
2Reaction is had higher synergy utilize CO
2This method also can improve TA yield and quality product significantly.
Summary of the invention
The oxidation promotor that the present invention adopts is constitutionally stable organic compound, in former cobalt/manganese/bromine three-element catalytic system, add five yuan or hexa-atomic nitrogen-containing heterocycle compound, accelerate the main reaction activity, make reaction process obtain quickening, reduce the usage quantity of bromine and cobalt manganese simultaneously, reduce burning reaction, weaken the novel method of corrosive liquid phase catalytic oxidation production aromatic carboxylic acid of reaction system.
The present invention carries out improvedly on existing liquid phase catalytic oxidation production aromatic carboxylic acid's method basis, and it is:
A, be solvent, adopt gas cyaniding methyl aromatic hydrocarbon or its partial oxidation intermediary product of oxygen-containing molecules directly to obtain the aromatic carboxylic acid product with the aliphatic carboxylic acid;
B, employing catalyst system are cobalt/manganese/bromine/nitrogen-containing heterocycle compound quaternary compound system, promptly add nitrogen-containing heterocycle compound as oxidation promotor in existing cobalt/manganese/bromine three-element catalytic system;
Above-mentioned catalyst system can also add an amount of other rare earth metals, transition metal, basic metal and alkaline-earth metal ions except that cobalt and manganese.
The nitrogen-containing heterocycle compound class oxidation promotor that uses among the present invention can be that one or more five yuan or hexa-atomic nitrogen heterocyclic ring are as arene oxidizing promotor.
This nitrogen-containing heterocycle compound class oxidation promotor must be the compound that this process adopts solubility in the solvent system, uses with the form that is dissolved in the solvent.The nitrogen-containing heterocycle compound class oxidation promotor that adds and the mol ratio of Co-Mn metal total ion concentration approximately are 0.05～20, or preferred 1～5.
The present invention uses oxidation promotor to be selected from compounds such as imidazoles, pyrazoles, pyridine, carboxyl pyridine, aminopyridine, pyrazine, carboxyl pyrazine, pyrimidine and amino thereof, carboxyl substituted thing.
The solvent that the present invention uses can adopt C
2～C
6Aliphatic carboxylic acid, as acetic acid, propionic acid, butanic acid, valeric acid, caproic acid, trimethylacetic acid etc., the mixture of preferred acetic acid or acetic acid and water is generally the vinegar stock that contains 2～25% quality water.The mass ratio of aromatic hydrocarbons reactant and solvent is generally 1～10.
The gas of oxygen-containing molecules of the present invention comprises the gaseous mixture and the pure oxygen of air, oxygen-rich air, oxygen and rare gas element such as nitrogen, is preferably air.
Oxidation initiator methylarenes of the present invention is meant to have one or more substituent methyl benzene, naphthalene and other derivative, comprises toluene, dimethylbenzene, trimethylbenzene, durene, pentamethylbenzene, hexamethyl-benzene.
The methyl aromatic hydrocarbon intermediate oxidation product of partial oxidation of the present invention is selected from phenyl aldehyde, m-methyl benzoic acid, o-toluic acid, p-methylbenzoic acid, a tolyl aldehyde, o-methyl-benzene formaldehyde, p-tolyl aldehyde, a carboxyl benzaldehyde, 2-carboxybenzaldehyde, to carboxyl benzaldehyde.
The oxidation target product that the present invention relates to is an aromatic carboxylic acid, selected is to have the compound that one or more replace benzene, naphthalene or the class quasi-aromatic compound of carboxyl, phenylformic acid, terephthalic acid, m-phthalic acid, phthalic acid, Tetra hydro Phthalic anhydride, trimesic acid, trimellitic acid, pyromellitic acid dianhydride, benzene pentacarbonic acid, benzene hexacarboxylic acid etc.
Described rare earth metal, transition metal, basic metal and alkaline-earth metal ions are selected from cerium, europium, samarium, zirconium, hafnium, molybdenum, chromium, nickel, vanadium, potassium, sodium and calcium.
Basic catalyst system among the present invention is cobalt/manganese/bromine three-element catalytic system, also can add other transition metal or rare earth metal component.In basic catalyst system, the mol ratio of Co/Mn is 0.1～100, preferred 0.2～20; The mol ratio of Br/ (Co+Mn) is 0.1～10, preferred 0.5～2.The concentration of cobalt is 50～10000ppm of weight of solvent, preferred 100～2000ppm.The bromine source can be taken from bromine-containing compound, as hydrogen bromide, Potassium Bromide, tetrabromoethane etc.; As for manganese and cobalt source, can be dissolved in solvent contain manganese and cobalt compound all can, as acetate, carbonate, oxalate, acetate tetrahydrate, bromide etc.Preferred cobalt, manganese, bromine source are respectively Co (OAc)
24H
2O, Mn (OAc)
24H
2O and hydrogen bromide.
The temperature of reaction that the present invention is suitable for is 100～255 ℃, and preferred 155～205 ℃, reaction pressure is determined that by temperature of reaction reaction pressure is about 0.5～1.5MPa usually, or selects 1.0～1.4MPa.
The present invention is a solvent with aliphatic carboxylic acid (as acetic acid), find and use the nitrogen-containing heterocycle compound compounds first as methylarenes liquid-phase oxidation oxidation promotor, adopt cobalt/manganese/bromine/nitrogen-containing heterocycle compound quaternary composite catalyst system, aroamtic hydrocarbon raw material is carried out liquid phase oxidation reaction with the gas that contains oxygen molecule.Compare with existing cobalt/manganese/bromine three-element catalytic method for oxidation, the interpolation of nitrogen-containing heterocycle compound, under the PX oxidation reaction condition, rapidly and Co, the Mn combination, generate the active component that promotes, the arene oxidizing reaction is quickened significantly, under the identical reaction times, for given transformation efficiency, the reaction conditions that the present invention needs is gentle (lower catalyst concn or lower temperature of reaction), simultaneously can significantly reduce side reaction, improve the selectivity of reaction process, so the present invention not only can improve the productivity of aromatic carboxylic acid, can also reduce material consumption, improve the quality of products, reduce production costs.And because cobalt/manganese/bromine/nitrogen-containing heterocycle compound quaternary composite catalyst system is a kind of eco-friendly catalyzer, so the present invention can reduce the consumption of bromine component, the discharging of minimizing poisonous fume, the corrosion of reduction equipment significantly.
Embodiment
With the p xylene oxidation reaction is example: in 500 milliliters autoclave, drop into 60 milliliters of p-Xylol, 300 milliliters of acetic acid, a certain amount of Cobaltous diacetate, manganese acetate, Hydrogen bromide and oxidation additive, stir down heat temperature raising to 190 ℃, with the airway in the insertion reaction liquid, continuous bubbling air, air pressure 1.5Mpa, flow is 12 liters/minute, tail gas is discharged from serpentine condenser, reacted 45 minutes, take out the reaction solution solid mixture, isolate solid product and analyze wherein p-Xylol (PX) with HPLC, p-methylbenzoic acid (PT acid), to carboxyl benzaldehyde (4-CBA), the content of terephthalic acid (TA), and calculate the transformation efficiency of p-Xylol and the selectivity of terephthalic acid.
In specific implementation process, the experiment condition of arene oxidizing, sees Table 1 to the data such as concentration of carboxyl benzaldehyde (4-CBA) at p-methylbenzoic acid in the oxidation products (PT acid).The result shows that the quaternary composite catalyst system behind the interpolation nitrogen-containing heterocycle compound can be effective.Come specifically to set forth the facilitation effect of additive by the following examples, and use after the additive effect that cobalt, manganese and hydrobromic usage quantity reduce the PX oxidation.
Embodiment 1:
In 500 milliliters autoclave, drop into 60 milliliters of p-Xylol, the Cobaltous diacetate of 300 milliliters of acetic acid, 250ppm is (by molecule, down together), the manganese acetate of 350ppm is (by molecule, down together), the Hydrogen bromide of 800ppm is (by molecule, down together), the aminopyridine of 70ppm (by molecule, down with) stirs down heat temperature raising to 195 ℃, with the airway in the insertion reaction liquid, continuous bubbling air, air pressure 1.5Mpa, flow are 12 liters/minute, tail gas is discharged from serpentine condenser, fixes 1 hour and finishes reaction.
Embodiment 2
In 500 milliliters autoclave, drop into 60 milliliters of p-Xylol, 300 milliliters of acetic acid, the Cobaltous diacetate of 250ppm, the manganese acetate of 350ppm, the Hydrogen bromide of 800ppm, the 2-carboxyl pyridine of 70ppm stirs down heat temperature raising to 195 ℃, with the airway in the insertion reaction liquid, continuous bubbling air, air pressure 1.5Mpa, flow are 12 liters/minute, tail gas is discharged from serpentine condenser, fixes 1 hour and finishes reaction.
Embodiment 3
In 500 milliliters autoclave, drop into 60 milliliters of p-Xylol, 300 milliliters of acetic acid, the Cobaltous diacetate of 250ppm, the manganese acetate of 350ppm, the Hydrogen bromide of 800ppm, the 2-pyrazine carboxylic acid of 70ppm stirs down heat temperature raising to 195 ℃, with the airway in the insertion reaction liquid, continuous bubbling air, air pressure 1.5Mpa, flow are 12 liters/minute, tail gas is discharged from serpentine condenser, fixes 1 hour and finishes reaction.
Embodiment 4
In 500 milliliters autoclave, drop into 60 milliliters of p-Xylol, 300 milliliters of acetic acid, the Cobaltous diacetate of 250ppm, the manganese acetate of 350ppm, the Hydrogen bromide of 800ppm, the pyrimidine of 70ppm stirs down heat temperature raising to 195 ℃, with the airway in the insertion reaction liquid, continuous bubbling air, air pressure 1.5Mpa, flow are 12 liters/minute, tail gas is discharged from serpentine condenser, fixes 1 hour and finishes reaction.
Embodiment 5
In 500 milliliters autoclave, drop into 60 milliliters of p-Xylol, 300 milliliters of acetic acid, the Cobaltous diacetate of 250ppm, the manganese acetate of 350ppm, the Hydrogen bromide of 800ppm, the pyridine of 70ppm stirs down heat temperature raising to 195 ℃, with the airway in the insertion reaction liquid, continuous bubbling air, air pressure 1.5Mpa, flow are 12 liters/minute, tail gas is discharged from serpentine condenser, fixes 1 hour and finishes reaction.
Embodiment 6
In 500 milliliters autoclave, drop into 60 milliliters of p-Xylol, 300 milliliters of acetic acid, the Cobaltous diacetate of 250ppm, the manganese acetate of 350ppm, the Hydrogen bromide of 800ppm, the imidazoles of 70ppm stirs down heat temperature raising to 195 ℃, with the airway in the insertion reaction liquid, continuous bubbling air, air pressure 1.5Mpa, flow are 12 liters/minute, tail gas is discharged from serpentine condenser, fixes 1 hour and finishes reaction.
The comparative example 1
In 500 milliliters autoclave, drop into 60 milliliters of p-Xylol, 300 milliliters of acetic acid, the Cobaltous diacetate of 250ppm, the manganese acetate of 350ppm, the Hydrogen bromide of 1600ppm, stir down heat temperature raising to 195 ℃, with the airway in the insertion reaction liquid, bubbling air continuously, air pressure 1.5Mpa, flow is 12 liters/minute, and tail gas is discharged from serpentine condenser, fixes 1 hour and finishes reaction.
The comparative example 2
In 500 milliliters autoclave, drop into 60 milliliters of p-Xylol, 300 milliliters of acetic acid, the Cobaltous diacetate of 250ppm, the manganese acetate of 350ppm, the Hydrogen bromide of 800ppm, stir down heat temperature raising to 195 ℃, with the airway in the insertion reaction liquid, bubbling air continuously, air pressure 1.5Mpa, flow is 12 liters/minute, and tail gas is discharged from serpentine condenser, fixes 1 hour and finishes reaction.
PX oxidation results under compound activated dose of condition of the different nitrogen heterocyclic rings of table 1
Table 1 is the result show, interpolation along with nitrogenous organic heterocyclic compounds, same reaction is in the time, product analysis shows, the content of PT acid and 4-CBA all decreases in the reaction solution, show that itrogenous organic substance promotes the process of p xylene oxidation that stronger promoter action is arranged to cobalt/manganese/bromine three-way catalyst, effectively quickens the PX oxidation reaction process
Comparing embodiment 1-6 as can be seen, the PX oxidising process reactive behavior of adding aminopyridine is the highest, selectivity is best.So in the heterocyclic compound more preferably aminopyridine as oxidation promotor.
Embodiment 7-10: by embodiment 7-10 the catalytic activity of the aminopyridine of different concns as oxidation promotor is described,, the results are shown in table 2 to select the interpolation concentration of suitable aminopyridine industrial application.The mode identical with embodiment 1 carried out the oxidizing reaction of p-Xylol, and just the concentration of the aminopyridine of being added in embodiment 7,8,9 and 10 is changed into 100ppm respectively, 300ppm, 500ppm, 900ppm.All experimental results are summarized in table 2.
PX oxidation results under the different aminopyridine activator of the table 2 addition condition
| Embodiment | 7 | 8 | 9 | 1 | 10 |
| Cobaltous diacetate (ppm) | 250 | 250 | 250 | 250 | 250 |
| Manganese acetate (ppm) | 350 | 350 | 350 | 350 | 350 |
| Hydrogen bromide (ppm) | 800 | 800 | 800 | 800 | 800 |
| Additive (ppm) | 10 | 30 | 50 | 70 | 90 |
| PX transformation efficiency (%) | 100 | 100 | 100 | 100 | 100 |
| PT acid residual content (%) | 5.4 | 3.2 | 1.5 | 1.2 | 1.0 |
| 4-CBA residual content (%) | 7.1 | 4.6 | 2.8 | 2.5 | 1.9 |
Table 2 is the result show, increase along with the addition of aminopyridine, same reaction is in the time, product analysis shows, the content of PT acid and 4-CBA all reduces in the reaction solution, show that aminopyridine has stronger promoter action to the process of cobalt/manganese/bromine three-element catalytic p xylene oxidation, but, when the aminopyridine addition surpasses when a certain amount of, impact effect to reaction system can become more and more not obvious, as when aminopyridine concentration when 50ppm is increased to 90ppm, the residual content of PT acid just reduces by 0.5,4-CBA reduces by 0.9, so the preferred 500ppm of the addition of aminopyridine.
In a word, the present invention discloses improving one's methods of a kind of aromatics family's carboxylic acid production, with the aliphatic carboxylic acid that contains 1-6 carbon atom is solvent, methylarenes adopts the gas that contains oxygen molecule to carry out oxidizing reaction in bromine/manganese/bromine catalyst system, and the nitrogen-containing heterocycle compound component that simultaneously one or more is had ad hoc structure is added in this catalyst system to optimize oxidising process.This method can be used in oxidation or the purifying methyl aromatic hydrocarbon comes in the various industrial application processes of production aromatic acid product, and carries out condition optimizing at different reaction process.
The present invention finds first and discloses and uses five yuan or hexa-atomic organic nitrogen-containing heterogeneous ring compound as methylarenes liquid-phase oxidation promotor.The particularly important is, compare with common liquid-phase oxidation technology, the present invention has more characteristics: (a) can strengthen the reactive behavior of catalyst system, thereby the promote the oxidation process reaches the purpose of strengthening reaction; (b) can reduce the burning reaction of reaction system, thereby the selectivity that increases oxidising process reaches the purpose that reduces material consumption; (c) under identical temperature of reaction and pressure condition, add a spot of aminopyridine, can adopt lower bromine concentration just to obtain and the general identical reaction throughput of MC method, thereby reduced the corrodibility of brominated toxic gas discharging and reactive system.
The invention is not restricted to these disclosed embodiments, the present invention will cover the scope described in the patent claims, and the various modification of claim scope and equivalence variation.
Claims (10)
1. with the method for nitrogen-containing heterocycle compound, it is characterized in that as oxidation promotor production aromatic carboxylic acid:
The described reaction system that is used to produce aromatic carboxylic acid is, is solvent with the aliphatic carboxylic acid, and adopting air, oxygen-rich air or oxygen is oxygen source, and the intermediate product of oxidation methyl aromatic hydrocarbon or its partial oxidation directly obtains the aromatic carboxylic acid product;
The catalyst system that adopts is cobalt/manganese/bromine/nitrogen-containing heterocycle compound quaternary compound system, promptly adds nitrogen-containing heterocycle compound as arene oxidizing promotor in existing cobalt/manganese/bromine three-element catalytic system; In the reaction system of producing aromatic carboxylic acid, the concentration of cobalt ion is 50-500ppm, and the concentration of mn ion is 50-700ppm, and the concentration of bromide anion is 100-1000ppm; The concentration of nitrogen-containing heterocycle compound is 20-500ppm.
2. method according to claim 1 is characterized in that: also be added with in transition metal, rare earth metal, basic metal, the alkaline-earth metal ions one or more in the catalyst system.
3. method according to claim 1 and 2 is characterized in that: also be added with in cerium, europium, samarium, zirconium, hafnium, molybdenum, chromium, nickel, vanadium, potassium, sodium, the calcium one or more in the described catalyst system.
4. method according to claim 1 is characterized in that: described nitrogen-containing heterocycle compound be have rock steady structure, in 5-member heterocyclic ring containing nitrogen or six-ring nitrogen-containing heterocycle compound and the derivative thereof one or more.
5. according to claim 1 or 4 described methods, it is characterized in that: described nitrogen-containing heterocycle compound be imidazoles, pyrazoles, pyridine, pyrazine, pyrimidine, triazine, and their derivatives in one or more.
6. method according to claim 4 is characterized in that: described nitrogen-containing heterocycle compound is a kind of or two kinds of five yuan or the hexa-atomic nitrogen-containing heterocycle compounds that organic group replaces in amino, the carboxyl.
7. method according to claim 1 is characterized in that: described solvent is to contain the aliphatic carboxylic acid of 1～6 carbon atom or contain the aliphatic carboxylic acid solution of 2～25% quality than water.
8. method according to claim 1 is characterized in that: described methyl aromatic hydrocarbon is selected from one or more in toluene, dimethylbenzene, trimethylbenzene, durene, pentamethylbenzene, the hexamethyl-benzene.
9. method according to claim 1 is characterized in that: the methyl aromatic hydrocarbon intermediate oxidation product of described partial oxidation is selected from phenyl aldehyde, m-methyl benzoic acid, o-toluic acid, p-methylbenzoic acid, a tolyl aldehyde, o-methyl-benzene formaldehyde, p-tolyl aldehyde, a carboxyl benzaldehyde, 2-carboxybenzaldehyde, in the carboxyl benzaldehyde one or more.
10. method according to claim 1 is characterized in that: described aromatic carboxylic acid is selected from one or more in phenylformic acid, m-phthalic acid, phthalic acid, terephthalic acid, Tetra hydro Phthalic anhydride, trimesic acid, trimellitic acid, pyromellitic acid dianhydride, benzene pentacarbonic acid, the benzene hexacarboxylic acid.
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| CN107282103A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic multi-carboxy acid |
| CN107282103B (en) * | 2016-04-12 | 2020-02-04 | 中国石油化工股份有限公司 | Catalyst for producing aromatic polycarboxylic acids |
| CN107442167A (en) * | 2016-05-30 | 2017-12-08 | 中国石油化工股份有限公司 | Liquid phase oxidation prepares the catalyst used in polycarboxylic aromatic acids |
| CN107442167B (en) * | 2016-05-30 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic polycarboxylic acid by liquid phase oxidation |
| CN107698445A (en) * | 2016-08-09 | 2018-02-16 | 朱翠英 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
| CN107698438A (en) * | 2016-08-09 | 2018-02-16 | 朱翠英 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
| CN107698437A (en) * | 2016-08-09 | 2018-02-16 | 朱翠英 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
| CN107698436A (en) * | 2016-08-09 | 2018-02-16 | 朱翠英 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
| CN107759460A (en) * | 2016-08-15 | 2018-03-06 | 朱翠英 | A kind of method for preparing the more acid monomers of polyphenyls |
| CN107790179A (en) * | 2016-08-29 | 2018-03-13 | 中国石油化工股份有限公司 | Liquid phase oxidation produces the catalyst of polycarboxylic aromatic acids |
| CN107790179B (en) * | 2016-08-29 | 2020-04-17 | 中国石油化工股份有限公司 | Catalyst for producing aromatic polycarboxylic acid by liquid phase oxidation |
| CN107774316A (en) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | Liquid phase oxidation synthesizes polycarboxylic aromatic acids catalyst |
| CN112441910A (en) * | 2019-09-04 | 2021-03-05 | 中国石油化工股份有限公司 | Method for synthesizing aromatic polycarboxylic acid by liquid-phase oxidation |
| CN114181075A (en) * | 2020-09-14 | 2022-03-15 | 中国石油化工股份有限公司 | Method for producing isophthalic acid by oxidizing m-xylene |
| CN114181075B (en) * | 2020-09-14 | 2024-01-05 | 中国石油化工股份有限公司 | Method for producing isophthalic acid by oxidizing meta-xylene |
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