CN102060686B - 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 improving one's methods for methylarenes liquid phase catalytic oxidation production aromatic carboxylic acid.Take aliphatic carboxylic acid as solvent, and employing air or oxygen is oxygen source, and 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 aromatic carboxylic acid product.As arene oxidizing promotor nitrogen heterocyclic ring, comprise: 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, since catalyzed oxidation methylarenes liquid phase is produced the appearance of aromatic carboxylic acid, the method is widely used industrial.It is solvent that the method generally adopts acetic acid, and temperature of reaction is 100～320 ℃, keeps reaction pressure to make aliphatic carboxylic acid kind solvent in liquid state.The product that application the method is commercially produced has a lot, as phenylformic acid, terephthalic acid, m-phthalic acid, phthalic acid, Tetra hydro Phthalic anhydride, equal (partially) benzenetricarboxylic acid, pyromellitic acid dianhydride etc., wherein industrial scale maximum is terephthalic acid.Aromatic carboxylic acid is the important source material of producing trevira and resin, with the aromatic carboxylic acid that cobalt/manganese/bromine three-element catalytic is produced, accounts for the more than 80% of all aromatic carboxylic acid ultimate productions.
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 costs; The selectivity of improving catalytic process is also 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 costs, improves the quality of products.
In methylarenes liquid phase catalytic oxidation process, to cobalt/manganese/bromine three-way catalyst system, be added with organic compounds to reach the existing many cases of object of strengthening reaction, 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 is mainly the nitrogenous class organic bases with rock steady structure, as multiamino 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 there is N=O base, the ad hoc structure such as N-hydroxyl, N-acyloxy containing 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, to cobalt/manganese/bromine three-way catalyst system, add the 4th kind of metal catalyst to reach the existing many cases of object of strengthening reaction, the metal component of interpolation is mainly 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 the transition metal such as nickel, molybdenum, chromium, tungsten, zirconium, hafnium in former catalyst system, main reaction activity is had to raising in various degree, reaction process is accelerated.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 also there are some problems in application, as obvious not enough to the acceleration effect of reaction, the burning reaction that also makes having increases, and what have is expensive, what have has the follow-up refining step of certain residual impact etc. at solid phase prod, has therefore affected the practicality of above-mentioned technology.
Patent US-6194607 proposes the method for adding alkalimetal ion and alkaline-earth metal ions in cobalt/manganese/bromine three-way catalyst system, proposes at CO simultaneously
2in the situation that coexists, p-Xylol liquid phase oxidation reaction speed is accelerated, 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 to higher synergy and utilize CO
2the 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 main reaction active, reaction process is accelerated, 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 is produced aromatic carboxylic acid's method basis, and it is:
A, take aliphatic carboxylic acid as solvent, adopt the gas oxidation methyl aromatic hydrocarbon of oxygen-containing molecules or the product in the middle of its partial oxidation directly to obtain aromatic carboxylic acid product;
B, employing catalyst system are cobalt/manganese/bromine/nitrogen-containing heterocycle compound quaternary compound system, in existing cobalt/manganese/bromine three-element catalytic system, add nitrogen-containing heterocycle compound as oxidation promotor;
Above-mentioned catalyst system can also add other appropriate rare earth metals, transition metal, alkali and alkaline earth metal ions ion except cobalt and manganese.
The nitrogen-containing heterocycle compound class oxidation promotor using in 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 solvent system, with the form being dissolved in solvent, uses.The nitrogen-containing heterocycle compound class oxidation promotor adding and the mol ratio of Co-Mn metal total ion concentration are approximately 0.05～20, or preferably 1～5.
The present invention uses oxidation promotor to be selected from the 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., preferably the mixture of 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 that air, oxygen-rich air, oxygen and rare gas element, as the gaseous mixture of nitrogen and pure oxygen, are preferably air.
Oxidation initiator methylarenes of the present invention refers 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-tolualdehyde, p-tolyl aldehyde, a carboxyl benzaldehyde, 2-carboxybenzaldehyde, to carboxyl benzaldehyde.
The oxidation target product the present invention relates to is 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, alkali and alkaline earth metal ions ion selected from cerium, europium, samarium, zirconium, hafnium, molybdenum, chromium, nickel, vanadium, potassium, sodium and calcium.
Basic catalyst system in 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, preferably 0.2～20; The mol ratio of Br/ (Co+Mn) is 0.1～10, preferably 0.5～2.The concentration of cobalt is 50～10000ppm of weight of solvent, preferably 100～2000ppm.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 containing 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 applicable temperature of reaction of the present invention is 100～255 ℃, and preferably 155～205 ℃, reaction pressure determines by temperature of reaction, and reaction pressure is about 0.5～1.5MPa conventionally, or selects 1.0～1.4MPa.
It is solvent that aliphatic carboxylic acid (as acetic acid) is take in the present invention, find first and apply nitrogen-containing heterocycle compound compounds 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 to 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 PX oxidation reaction condition, rapidly and Co, Mn combination, generate the active component that promotes, arene oxidizing reaction is accelerated significantly, under the identical reaction times, for given transformation efficiency, the reaction conditions gentleer (lower catalyst concn or lower temperature of reaction) that the present invention needs, can significantly reduce side reaction simultaneously, improve the selectivity of reaction process, therefore 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 significantly reduce the consumption of bromine component, the discharge of minimizing poisonous fume, the corrosion of reduction equipment.
Embodiment
Take p xylene oxidation reaction as example: in the autoclave of 500 milliliters, 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, under stirring, be heated to 190 ℃, with the airway in insertion reaction liquid, pass into continuously air, air pressure 1.5Mpa, flow is 12 liters/min, tail gas is discharged from serpentine condenser, react 45 minutes, take out 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 selectivity of transformation efficiency and the terephthalic acid of p-Xylol.
In specific implementation process, the experiment condition of arene oxidizing, p-methylbenzoic acid in oxidation products (PT acid), to the data such as concentration of carboxyl benzaldehyde (4-CBA) in Table 1.Result shows, adds the quaternary composite catalyst system after nitrogen-containing heterocycle compound, can be effective.Carry out by the following examples specifically to set forth the facilitation effect of additive to PX oxidation, and after using additive, the effect that cobalt, manganese and hydrobromic usage quantity reduce.
Embodiment 1:
In the autoclave of 500 milliliters, 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, lower same), the aminopyridine of 70ppm (by molecule, lower same), is heated to 195 ℃ under stirring, with the airway in insertion reaction liquid, pass into continuously air, air pressure 1.5Mpa, flow is 12 liters/min, tail gas is discharged from serpentine condenser, fixes 1 hour and finishes reaction.
Embodiment 2
In the autoclave of 500 milliliters, drop into 60 milliliters of p-Xylol, 300 milliliters of acetic acid, the Cobaltous diacetate of 250ppm, the Hydrogen bromide of the manganese acetate of 350ppm, 800ppm, the 2-carboxyl pyridine of 70ppm, is heated to 195 ℃ under stirring, with the airway in insertion reaction liquid, pass into continuously air, air pressure 1.5Mpa, flow is 12 liters/min, tail gas is discharged from serpentine condenser, fixes 1 hour and finishes reaction.
Embodiment 3
In the autoclave of 500 milliliters, drop into 60 milliliters of p-Xylol, 300 milliliters of acetic acid, the Cobaltous diacetate of 250ppm, the Hydrogen bromide of the manganese acetate of 350ppm, 800ppm, the 2-pyrazine carboxylic acid of 70ppm, is heated to 195 ℃ under stirring, with the airway in insertion reaction liquid, pass into continuously air, air pressure 1.5Mpa, flow is 12 liters/min, tail gas is discharged from serpentine condenser, fixes 1 hour and finishes reaction.
Embodiment 4
In the autoclave of 500 milliliters, drop into 60 milliliters of p-Xylol, 300 milliliters of acetic acid, the Cobaltous diacetate of 250ppm, the Hydrogen bromide of the manganese acetate of 350ppm, 800ppm, the pyrimidine of 70ppm, is heated to 195 ℃ under stirring, with the airway in insertion reaction liquid, pass into continuously air, air pressure 1.5Mpa, flow is 12 liters/min, tail gas is discharged from serpentine condenser, fixes 1 hour and finishes reaction.
Embodiment 5
In the autoclave of 500 milliliters, drop into 60 milliliters of p-Xylol, 300 milliliters of acetic acid, the Cobaltous diacetate of 250ppm, the Hydrogen bromide of the manganese acetate of 350ppm, 800ppm, the pyridine of 70ppm, is heated to 195 ℃ under stirring, with the airway in insertion reaction liquid, pass into continuously air, air pressure 1.5Mpa, flow is 12 liters/min, tail gas is discharged from serpentine condenser, fixes 1 hour and finishes reaction.
Embodiment 6
In the autoclave of 500 milliliters, drop into 60 milliliters of p-Xylol, 300 milliliters of acetic acid, the Cobaltous diacetate of 250ppm, the Hydrogen bromide of the manganese acetate of 350ppm, 800ppm, the imidazoles of 70ppm, is heated to 195 ℃ under stirring, with the airway in insertion reaction liquid, pass into continuously air, air pressure 1.5Mpa, flow is 12 liters/min, tail gas is discharged from serpentine condenser, fixes 1 hour and finishes reaction.
Comparative example 1
In the autoclave of 500 milliliters, drop into 60 milliliters of p-Xylol, 300 milliliters of acetic acid, the Cobaltous diacetate of 250ppm are, the Hydrogen bromide of the manganese acetate of 350ppm, 1600ppm, under stirring, be heated to 195 ℃, the airway with in insertion reaction liquid, passes into air continuously, air pressure 1.5Mpa, flow is 12 liters/min, and tail gas is discharged from serpentine condenser, fixes 1 hour and finishes reaction.
Comparative example 2
In the autoclave of 500 milliliters, drop into 60 milliliters of p-Xylol, 300 milliliters of acetic acid, the Cobaltous diacetate of 250ppm are, the Hydrogen bromide of the manganese acetate of 350ppm, 800ppm, under stirring, be heated to 195 ℃, the airway with in insertion reaction liquid, passes into air continuously, air pressure 1.5Mpa, flow is 12 liters/min, 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
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | Comparative example 1 | Comparative example 2 |
| Cobaltous diacetate (ppm) | 250 | 250 | 250 | 250 | 250 | 250 | 250 | 250 |
| Manganese acetate (ppm) | 350 | 350 | 350 | 350 | 350 | 350 | 350 | 350 |
| Hydrogen bromide (ppm) | 800 | 800 | 800 | 800 | 800 | 800 | 1600 | 800 |
| Additive (70ppm) | Aminopyridine | 2-Pyridinecarboxylic Acid | 2-pyrazine carboxylic acid | Pyrimidine | Pyridine | Imidazoles | 0 | 0 |
| PX transformation efficiency (%) | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| PT acid residual content (%) | 1.2 | 5.2 | 3.1 | 6.2 | 5.5 | 4.2 | 2.7 | 5.8 |
| 4-CBA residual content (%) | 2.5 | 6.1 | 4.2 | 8.5 | 6.1 | 7.1 | 4.3 | 7.8 |
Table 1 result shows, interpolation along with nitrogenous organic heterocyclic compounds, same reaction is in the time, product analysis shows, in reaction solution, the content of PT acid and 4-CBA all decreases, show that itrogenous organic substance promotes the process of p xylene oxidation to have stronger promoter action to cobalt/manganese/bromine three-way catalyst, effectively accelerates PX oxidation reaction process
Comparing embodiment 1-6 can find out, the PX oxidising process reactive behavior of adding aminopyridine is the highest, and selectivity is best.So in heterocyclic compound more preferably aminopyridine as oxidation promotor.
Embodiment 7-10: illustrate that by embodiment 7-10 the aminopyridine of different concns is as the catalytic activity of oxidation promotor, to select the interpolation concentration of suitable aminopyridine industrial application, the results are shown in table 2.The mode identical with embodiment 1 carried out the oxidizing reaction of p-Xylol, and the concentration of the aminopyridine of just adding in embodiment 7,8,9 and 10 is changed into respectively 100ppm, 300ppm, 500ppm, 900ppm.All experimental results are summarized in table 2.
PX oxidation results under the different aminopyridine activator of 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 result shows, increase along with the addition of aminopyridine, same reaction is in the time, product analysis shows, in reaction solution, the content of PT acid and 4-CBA all reduces, show that aminopyridine has stronger promoter action to the process of cobalt/manganese/bromine three-element catalytic p xylene oxidation, but, when aminopyridine addition surpasses when a certain amount of, to the impact effect of reaction system, can become more and more not obvious, as when aminopyridine concentration is increased to 90ppm from 50ppm, the residual content of PT acid just reduces by 0.5, 4-CBA reduces by 0.9, so 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, the aliphatic carboxylic acid that contains 1-6 carbon atom of take 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 one or more to ad hoc structure is simultaneously added in this catalyst system to optimize oxidising process.The method can be used in oxidation or purifying methyl aromatic hydrocarbon comes in the various industrial application processes of production aromatic acid product, and carries out condition optimizing for different reaction process.
The present invention finds and discloses application five yuan or hexa-atomic organic nitrogen-containing heterogeneous ring compound first as methylarenes liquid-phase oxidation promotor.The particularly important is, compare with common liquid-phase oxidation technology, the present invention has more feature: (a) can strengthen the reactive behavior of catalyst system, thereby accelerated oxidation process reaches the object of strengthening reaction; (b) can reduce the burning reaction of reaction system, thereby the selectivity of increase oxidising process reaches the object that reduces material consumption; (c) under identical temperature of reaction and pressure condition, add a small amount of aminopyridine, can adopt lower bromine concentration just to obtain the reaction throughput identical with general MC method, thereby reduced the corrodibility of brominated toxic gas discharge and reactive system.
The invention is not restricted to these disclosed embodiments, the present invention is the scope covering described in patent claims, and the various modification of claim scope and equivalence change.
Claims (7)
1. the nitrogen-containing heterocycle compound of usining is produced the method for aromatic carboxylic acid as oxidation promotor, it is characterized in that:
The described reaction system for the production of aromatic carboxylic acid is, take aliphatic carboxylic acid as solvent, 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 aromatic carboxylic acid product;
The catalyst system adopting is cobalt/manganese/bromine/nitrogen-containing heterocycle compound quaternary compound system, in existing cobalt/manganese/bromine three-element catalytic system, adds nitrogen-containing heterocycle compound as arene oxidizing promotor; 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;
Described nitrogen-containing heterocycle compound is aminopyridine, 2-carboxyl pyridine, 2-pyrazine carboxylic acid, imidazoles, pyridine, pyrimidine.
2. method according to claim 1, is characterized in that: in catalyst system, be also added with one or more in transition metal, rare earth metal, basic metal, alkaline-earth metal ions.
3. method according to claim 1 and 2, is characterized in that: in described catalyst system, be also added with one or more in cerium, europium, samarium, zirconium, hafnium, molybdenum, chromium, nickel, vanadium, potassium, sodium, calcium.
4. method according to claim 1, is characterized in that: described solvent is the aliphatic carboxylic acid that contains 1～6 carbon atom or contains 2～25% quality than the aliphatic carboxylic acid solution of water.
5. 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, hexamethyl-benzene.
6. 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-tolualdehyde, p-tolyl aldehyde, a carboxyl benzaldehyde, 2-carboxybenzaldehyde, to one or more in carboxyl benzaldehyde.
7. 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, benzene hexacarboxylic acid.
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| CN102941121B (en) * | 2012-11-22 | 2015-02-18 | 中山大学 | Aryl alkane oxidation reaction catalytic system and application thereof |
| CN104418748B (en) * | 2013-08-22 | 2016-03-23 | 中国科学院大连化学物理研究所 | A kind of o-Xylene Oxidation in Liquid Phase is coupled with esterification and prepares the method for Bisphthalate |
| CN106187750B (en) * | 2015-05-06 | 2019-07-12 | 中国科学院大连化学物理研究所 | A kind of method that dimethylbenzene liquid phase catalytic oxidation prepares phthalic 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 |
| 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 |
| 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 |
| CN107774316B (en) * | 2016-08-29 | 2020-05-01 | 中国石油化工股份有限公司 | Liquid phase oxidation synthesis aromatic polycarboxylic acid catalyst |
| 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 |
| 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 |
| 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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