IE970418A1 - Process for production of aromatic tricarboxylic acids - Google Patents
Process for production of aromatic tricarboxylic acidsInfo
- Publication number
- IE970418A1 IE970418A1 IE970418A IE970418A IE970418A1 IE 970418 A1 IE970418 A1 IE 970418A1 IE 970418 A IE970418 A IE 970418A IE 970418 A IE970418 A IE 970418A IE 970418 A1 IE970418 A1 IE 970418A1
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- Prior art keywords
- reactor
- oxidation
- reaction
- oxygen
- catalyst
- Prior art date
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The production of aromatic tricarboxylic acids, as trimellitic acid, is enhanced by conducting an improved catalytic liquid phase oxidation of a trimethyl substituted aromatic hydrocarbon, as pseudocumene, continuously in at least three stages of reaction in series. The use as promoter of a ketene or an aldehyde at the first stage of reaction and of bromine at the following stages, in combination with the use of oxygen as oxidizing medium, allows to reduce substantially the global consumption of metal catalysts (co, Mn, Zr, Ce) and to achieve high values of conversion and of selectivity.
Description
Process for production of aromatic tricarboxylic acids
The production of aromatic tricarboxylic acids, as trimellitic acid, is enhanced by conducting an improved catalytic liquid phase oxidation of a trimethyl substituted aromatic hydrocarbon, as pseudocumene, continuously in at least three stages of reaction in series. The use as promoter of a ketene or an aldehyde at the first stage of reaction and of bromine at the following stages, in combination with the use of Oxygen as oxidizing medium, allows to reduce substantially the global consumption of metal catalysts (CO, Mn, Zr, Ce) and to achieve high values of conversion and of selectivity.
TRUE COPY AS
LODGED rROUND OF THE INVENTION
APPUCATIOWNo.
The process described herein relates to the production of aromatic tricarboxylic acid having only two vicinal carboxylic acid groups and more particularly pertains to an .improved technique for catalytic liquid phase oxidation of a trimethyl substituted aromatic hydrocarbon having only two methyl substituents on vicinal ring carbons such as pseudocumene to an aromatic tricarboxylic acid having only two carboxylic acid group substituents on vicinal ring carbons and having the third carboxyl group as a substituent on a non-vicinal ring carbon, such as trimellitic acid.
The conversion of trimethyl substituted aromatic hydrocarbons by catalytic liquid phase oxidation in the presence of heavy metal oxidation catalysts and side chain oxidation initiators or promoters to aromatic tricarboxylic acids is described in the technical literature. In general, the use different catalyst systems are proposed. All employ heavy metals of the class of those having atomic weight from about 50 to about 200, desirably those in this class which are variable valence or transition metals, and show a preference for using cobalt, alone or in combination with manganese. These oxidation metal catalysts are usually introduced in a form soluble in the hydrocarbon to be oxidized and/or an oxidation solvent medium, which preferably is acetic acid. The catalyst systems are provided by the use in combination with said heavy metals of one promoter or initiator of side chain oxidation, which is tipically a compound containing bromine.
Any form of bromine supplying ionic bromine in the rection system, i.e. hydrogen bromide or combined bromine as in organic bromides, can be used. The discovery of the system of catalysis provided by heavy metal oxidation catalysts and bromine for the rapid, high conversion od di-, tri- and other polysubstituted aromatic with air in a liquid system on a once through basis is described in U.S. Patent No. 2,833,816. Later patents teach applications of said unique system of catalysis to various means for exploiting that oxidation method, for the commercial production of benzene tricarboxylic acids. As described in U.S. Patent No 3.920.735, it has been found that zirconium is unique among the Group IV B metals to substantially enhancing the activity of the bromine-cobalt or ****·*·»* the bromine cobalt-manganese systems of catalysis.
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The use of cerium in association with cobalt or cobalt-manganese as transition metal catalyst is described in US Pat. No 3491144 and US Pat. No 3683016.
In general the aforementioned catalytic liquid phase oxidations using air as a source of molecular oxygen are conducted at 150°C to 250°C and at a pressure adequate to maintain a liquid phase of alkyl substituted aromatic hydrocarbons. Commercial developments utilizing the foregoing systems of catalysis employ controlled reaction temperature within a narrow range; staged reaction temperatures such as starting at a low or initiation temperatures, increasing reaction temperature, to obtain maximum oxidation or substantial completion of the oxidation to oxidize small amounts of partial oxidation co-products such as methylol benzoic acids, formylbenzoic acid, and the like. Staged oxidations have been applied to time staged intermitent batchwise or semicontinuous mode of operation.
It has been found that certain polymethyl substituted aromatics, when oxidized in the foregoing catalytic liquid oxidation systems, appear to produce oxidation co-products which provide undersired autoinhibition of oxidation. That is, there are formed partial oxidation products which prevent substantial completion of the oxidation of the polymethyl substituted aromatic hydrocarbon feeds to the desired aromatic polycarboxylic acids. This autoinhibition is most pronounced in the oxidation of aromatics having two methyl substituents on vicinal ring carbons, like 1, 2, 4trimethylbenzene (pseudo cumene). In the catalytic liquid phase oxidation of pseudocumene the autoinhibition has the effect of limiting trimellitic acid yields to the range of 65 to 75 mole per cent. The effect of autoinhibition appears to be to prevent the oxidation of methyl substituted phthalic acids to trimellitic acid and the oxidation of reducible partial oxidation products such as formyl phthalic acids and methylol phthalic acids to trimellitic acid. Trimellitic acid appears to have an autoinhibiting effect on the oxidation of pseudocumene rather than an auto-oxidative effect. Some free radical mechanisms are believed to adversely effect the oxidation of methyl phthalic acids and the reducible partial oxidation products. The same or similar autoinhibition occurs in the catalytic liquid phase oxidation of other trimethyl substituted aromatics having only two methyls on vicinal ring carbons.
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It has been found that a higher thermal driving force, higher reaction temperature or a selected stage of use of higher reaction temperature in batch operation, effectively results in higher trimellitic acid yields.
However, reaction temperatures above 230-240°C induce decarboxylation of trimellitic acid to the phthalic acids and the ultimate result is a lover rather than a higher trimellitic acid yield.
The preparation of trimellitic acid by oxidation of pseudocumene in the presence of lower alkanoic acid reaction solvent presents a problem of its own. Trimellitic acid is substantially soluble in the reaction solvent media to make recovery of more than about 65 to 70% of trimellitic acid commercially not feasible by the crystallization thereof from the liquid reaction mixture. Thus the lower the oxidation yield of trimellitic acid the lower will be the recovery of the desired product from a crystallization technique. Trimellitic acid recovery can be increased by removing a substantial portion or all of the acidic reaction solvent. However, when there also present large amounts of such by products as benzoic acid (two COOH groups being lost by decarboxylation), the three phthalic acid isomers; methylphthalic acids, reducible partial oxidation products such as formyl phthalic acids and methylol phthalic acids and the like, there are too many closely related acid impurities in admixture with trimellitic acid to make* commercially feasible recovery of it in a suitable pure form. A recovery system wherein the total liquid reaction mixture is distilled, trimellitic acid is dehydrated to its intramolecular anhydride and this anhydride is distilled off and recovered becomes feasible commercial recovery system provided a high yield of trimellitic acid and lower yield of methylphthalic acids and reducible partial oxidation products is obtainable.
It has been discovered, and described in the literature, that the prior oxidation problems which came from the autoinhibitions during pseudocumene oxidation in a catalytic liquid phase system was provided, in general, by having too active a catalyst system in the beginning and during about 2/3 of the oxidation and a system not sufficiently active in the last of the oxidation. By oxidation rate studies applied to the oxidation of the second and the third methyl group it has been learned how the catalytic liquid phase oxidation of pseudocumene could be conducted in order to achieve higher yields of conversion.
The oxidation rate studies have shown that the yields of liquid phase oxidations of trimethyl substituted aromatic hydrocarbons, such as pseudocumene, can be improved
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MIX.
using, during the initial stage of the oxidation of pseudocumene, a combination of side chain initiator bromine with heavy metal catalysts having the oxidation potential at least equal to that of cobalt and manganese.
In the following stages of reaction, the temperature is increased while additional catalyst consisting of manganese, alone or in association with zirconium and/or cerium, is added with additional bromine promoter.
The staged batch mode of operation of the reaction, as described in the U.S. Pat. No 3920715 and in other patents, although providing a more efficient system of reaction compared with the previous status of the technology of oxidation of trimethyl substituted aromatic hydrocarbons, presents still several disadvantages.
The consumption of metal catalysts contributes substantially to the cost of production of trimellitic anhydride.
Recycle of catalyst is mentioned in the literature, but requires rather complex and expensive procedures for freeing the metals from the contaminants.
Furthermore batch oxidations have disadvantages because the concentration of the hydrocarbon to be oxidized is high at the start of the reaction and its rate of oxidation is difficult to control. This leads to a low concentration of dissolved oxygen and to an increased amount of radical reaction producing high boiling by products which reduce the yield. Thermally induced destruction of methyl groups occur, leading to the formation of xylenes, which become oxidized to dicarboxylic acids, contributing to yield losses.
Finally the batch mode of operation requires additional operating costs and presents higher safety hazards due to the risk of forming explosive mixtures particularly at the transient conditions of the reaction (i.e.: start and end of the batch).
The above mentioned disadvantages are to a large extent reduced by the improved process object of the present invention mcarb.
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DESCRIPTION OF THE INVENTION
It is an object of the present invention an improved process for production of tricarboxylic acids having only two carboxylic acid group substituents on vicinal ring carbons, such as trimellitic acid, by means of catalytic liquid phase oxidation of trimethyl substituted aromatic hydrocarbons having only two methyl substituents on vicinal ring carbons, such as pseudocumene.
As described in the backgrounds, the liquid phase oxidation reaction, as applied to pseudocumene, is very difficult and has been practiced industrially as a batch process because the reaction product, trimellitic acid, is a poison for the catalyst.
The present invention provides an improved method for a continuous liquid phase oxidation of pseudocumene with an oxygen containing gas, in the presence of suitable oxidation catalysts.
More particularly, it is an object of the present invention to provide an improved method for effecting the mentioned oxidation process to produce trimellitic acid to be converted to trimellitic anhydride, with improved selectivity and yield.
It is a related object of the present invention to provide an improved method for effecting the aforesaid oxidation process continuously.
It is a further object of the present invention to provide and improved method for effecting the aforesaid oxidation process using reduced amounts of metal catalysts.
These objects are achieved by an improved method of a staged continuous liquid phase oxidation of a trimethyl aromatic feedstock, such as pseudocumene, to produce an aromatic tricarboxylic acid such as trimellitic acid, comprising:
a) providing at least three stages of reaction in series consisting of one initial reactor, one or more than one intermediate reactor, one final reactor
b) introducing into the initial reactor an oxygen contaning gas, the aromatic feedstock, a solvent, preferably acetic acid, and a primary catalyst provided by transition or variable valence metals, such as cobalt and/or manganese. The catalysis is promoted by the use of a ketone such as methylethylketone or an aldehyde such as, and preferably, acetaldehyde.
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The temperature at the initial reactor is from 90°C to 140°C, preferably from 120°C to 130°C.
c) introducing into the intermediate reactor(s) an oxygen containing gas, the effluent from the first reactor and a secondary catalyst consisting of heavy metal oxidation catalysts such cerium and zirconium. In the intermediate^) reactor the catalysts is provided by the addition of bromine, in the form of organic or inorganic compound, such as hydrogen bromide.
The temperature at the intermediate reactor(s) is from 130 to 190°C preferably from 160 to 180°C.
d) introducing into the final reactor an oxygen containing gas, the effluent from the intermediate reactor(s) and a stream of mother liquor, containing catalyst, recovered from the product separation section, reactivated by the addition of bromine. The temperature at the final reactor is from 170°C to 220°C preferably from 180 to 210°C.
e) operating the reaction system at a pressure not inferior to the minimum pressure necessary to maintain the liquid phase of the solvent.
f) using, as oxidizing medium, oxygen being dissolved in a recycling stream of reaction gas effluents, consisting mostly of carbon dioxide, carbon monoxide, water, solvent and organic vapors.
g) adjusting the content of oxygen in each stage of reaction in order to assure an adequate rate of oxidation, assuring at same time that, for safety purposes, the oxygen concentration in the exhaust gas does not exceed 8% by volume.
-6tricarb.
o.toiu. ix · 03 \E 970448
The use of a ketone, such as methylethylketone, or of an aldehydre, such as acetaldehydre as promoter of the catalysis provided by transition or variable valence metals in liquid phase oxidations for the preparation of benzene carboxylic acids has been described in US Pat. No 2.245.528 and practiced in the industry for the production of terephthalic acid and isophthalic acid.
However, such aldehyde or ketone promoted catalysis was found not suitable in the oxidation of trimethylbenzene being capable only for converting the trimethylbenzene to its benzene mono and dicarboxylic derivatives.
It has now been found that the use of a ketone or of an aldehyde, preferably acetaldehyde, in the initial stage of a reaction system comprising at least 3 stages of reaction in series, eliminates the risk of autoinhibition, reduces the amount of metal catalysts and of bromine activator and allows to recycle to the final stage of reaction a fraction of the mother liquor, containing metal catalyst, recovered after crystallization and filtration of the reactor effluent, allowing a substantial reduction of the global consumption of metal catalysts.
The performances of this novel process of catalytic oxidation of pseudocumene to trimellitic acid, are enhanced by the use of oxygen as oxidizing medium.
Optimum overall performances can be achieved by optimizing, at each stage of reaction, the major operating parameters such as the temperature, the partial pressure of oxygen in the oxidizing medium, the concentration of a primary and secondary metal catalysts rhe concentration of the promoter (aldehyde or ketone in the initial stage, bromine in the intermediate and final stages), the amount of mother liquor containing catalyst being recycled to the final stage of reaction.
The embodiments of the process object of the present invention can be illustrated by the following examples:
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EXAMPLE (BASE1
BASE experiments were carried out in three 5 liters fully equipped autoclaves connected in series.
Oxygen was used as oxidizing medium, dissolved in a recycling offgas stream.
A feedstock misture was continuous introduced in the first autoclave consisting of480 gr of pseudocumene, 960 gr of acetic acid containing 4% of water, 50 gr of acetaldehyde and a primary with catalyst consisting of 360 mg of cobalt, supplied in the form of cobalt acetate, and of 240 mg of manganese, supplied in the form of manganese acetate.
The mixture was oxidized at a temperature of about 125°C. The oxidizing medium was oxygen with 16% vol concentration in a gaseous stream consisting of carbon dioxide, carbon monoxide, water and acetic acid vapors plus minor amounts of inerts.
The effluent from the first autoclave was continuously transfered to the intermediate autoclave where was added an additional stream of catalytic components (secondary catalyst) consisting of 5 mg of zirconium, supplied in the form of zirconium octanoate, of 20 mg of cerium, supplied in the form of cerium chloride, and of 400 mg of bromine supplied in the form of hydrogen bromide.
In the intermediate autoclave the oxidation was continued at a temperature of about 170°C. The oxidizing medium was oxygen with 19% by vol. concentration in the gaseous stream of the above mentioned composition.
The effluent from the intermediate autoclave was continuously transfered to the third autoclave where was added an additional stream consisting of recycling mother liquor containing about 150 mg of metals (Co-Mn-Ce-Zr) catalysts, added with 250 mg of fresh hydrogen bromide.
In the third autoclave the oxidation was completed at a temperature of about 195°C.
The oxidizing medium was oxygen with 21% by vol. concentration in a gaseous steam of the above mentioned composition.
The overall performances of the reaction resulted as follows;
Yield to trimellitic acid To by products:
To CO+CO2:
92,8% mol 3,4% mol 3,8% mol
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Following the crystallization, a crude solid stream of trimellitic acid was separated by filtration and a fraction of mother liquor, containing about 150 mg of metals (Co, Mn, Ce, Zr.) was recycled to the third autoclave.
The pressure in the reaction system was about 24 Bar.
COMPARATIVE EXAMPLE A
The BASE experiment was repeated, replacing the acetaldehyde fed to the first autoclave with 250 mg of bromine and operating the first autoclave at a temperature of 160°C instead of 125°C.
The performance of the reaction resulted as follows:
Yield to trimellitic acid: To by products:
To CO+CO2:
82,7% mol 12,2% mol 5,1% mol
COMPARATIVE EXAMPLE B
The experiment described in COMPARATIVE EXAMPLE A was repeated without recycling to the third autoclave the mother liquor containing metal catalysts.
The performances of the reaction resulted as follows:
Yield to trimellitic acid: To by products:
To CO+CO2:
84,2% mol 10,9% mol 4,9% mol
-9tricaib.
COMPARATIVE EXAMPLE C
The experiment described in COMPARATIVE EXAMPLE B was repeated doubling the amount of metal catalyst and of bromine fed to each reactor.
The performances of the reaction resulted as follows:
Yield to trimellitic acid: 89,9% mol To by products: To CO+CO2: 5,2% mol 4,9% mol COMPARATIVE EXAMPLE D
The BASE experiment was repeated in identical conditions using air instead of oxygen. The performances of the reaction resulted as follows:
Yield to trimellitic acid: 90,2% mol To by products: To CO+CO2: 4,9% mol 4,9% mol
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Claims (10)
1. A process for production of aromatic tricarboxylic acids, as trimellitic acid, by continuous liquid phase oxidation of a trimethyl aromatic feedstock, as pseudocumene, comprising: a) providing at least three stages of reaction in series consisting of one initial reactor, one or more than one intermediate reactor, one final reactor b) introducing into the initial reactor an oxygen contaning gas, the aromatic feedstock, a solvent, preferably acetic acid, and a primary catalyst provided by transition or variable valence metals, such as cobalt and/or manganese. The catalysis is promoted by the use of a ketone such as methylethylketone or an aldehyde such as, and preferably, acetaldehyde. The temperature at the initial reactor is from 90°C to 140°C, preferably from 120°C to 130°C, c) introducing into the intermediate reactor(s) an oxygen containing gas, the effluent from the first reactor and a secondaiy catalyst consisting of heavy metal oxidation catalysts such cerium and zirconium. In the intermediate(s) reactor the catalysts is provided by the addition of bromine, in the form of organic or inorganic compound, such as hydrogen bromide. The temperature at the intermediate(s) reactor is from 130 to 190°C preferably from 160 to 180°C. d) introducing into the final reactor an oxygen containing gas, the effluent from the intermediate reactor(s) and a stream of mother liquor, containing catalyst, recovered from the product separation section, reactivated by the addition of bromine. The temperature at the final reactor is from 170°C to 220°C preferably from 180 to 210°C. -11tricarb. O.LjIU. 1Ι·<+Χ e) operating the reaction system at a pressure not inferior to the minimum pressure necessary to maintain the liquid phase of the solvent. f) using, as oxidizing medium, oxygen being dissolved in a recycling stream of reaction gas effluents, consisting mostly of carbon dioxide, carbon monoxide, water, solvent and organic vapors. g) adjusting the content of oxygen in each stage of reaction in order to assure an adequate rate of oxidation, assuring at same time that for safety purposes, the oxygen concentration in the exhaust gas does not exceed 8% by volume.
2. A process as defined in claim 1 where the ketone or aldehyde promoter, preferably acetaldehyde, fed to the first reactor vary from 5 to 20% wt, preferably from S to 12% wt relative to trimethylbenzene.
3. A process as defined in claims 1 and 2 where the concentration of metal components, cobalt and manganese, to the first reactor (primary catalyst) vary between 0.1 and 0.3% by weight, preferably from 0.1 to 0.2% wt, relative to the trimethylbenzene feed.
4. A process as defined in claim 3 where the concentration of manganese in the primary catalyst is between 25 to 50% wt preferably from 35 to 45% wt, referred to the total weight of primary catalyst.
5. A process as defined in claim 1,2,3 where the concentration of cerium plus zirconium metal components fed to the intermediate reactor (s) (secondary catalyst) very between 0,002 and 0,01% wt, preferably from 0,004 to 0,006% by weight, relative to the trimethylbenzene feed. -12tri carb. J. Giu. Ι'ό'^ί' il Wo? Ό
6. A process as defined in claim 5 where the concentration of zirconium in the secondary catalyst is between 10 to 40%, preferably from 15 to 25% wt, referred to the total of secondary catalyst.
7. A process as defined in claim 1, 2, 3, 5 where the concentration of bromine fed to the intermediate reactor(s) vary between 0.06 and 0.15%, wt preferably from 0.08 to 0.12% wt, relative to the trimethylbenzene feed.
8. A process as defined in claims 1, 2, 3, 5, 7, 8 where a fraction of the mother liquor stream recovered after the separation of trimellitic acid, is recycled to the final reactor, containing from 10 to 40%, preferably from 20 to 30%, referred to the total of fresh metal catalysts (Cobalt, Manganese, Zirconium, Cerium) fed to the reaction system.
9. A process as defined in claims 1, 2, 3, 5, 7 where the concentration of bromine fed to the final reactor vary between 0.02 to 0.1% wt, preferably from 0.04 to 0.08% wt, relative to the trimethyl benzene feed. »
10. A process as defined in claims 1 to 9 for the preparation of trimellitic anhydride of high purity.
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IE970418A IE970418A1 (en) | 1997-06-04 | 1997-06-04 | Process for production of aromatic tricarboxylic acids |
BR9806036A BR9806036A (en) | 1997-06-04 | 1998-06-02 | Process for the production of aromatic tricarboxylic acids |
CA002260846A CA2260846A1 (en) | 1997-06-04 | 1998-06-02 | Process for production of aromatic tricarboxylic acids |
AU87272/98A AU731622B2 (en) | 1997-06-04 | 1998-06-02 | Process for production of aromatic tricarboxylic acids |
RU99104145/04A RU99104145A (en) | 1997-06-04 | 1998-06-02 | METHOD FOR PRODUCING AROMATIC Tricarboxylic Acids |
PCT/EP1998/003291 WO1998055441A1 (en) | 1997-06-04 | 1998-06-02 | Process for production of aromatic tricarboxylic acids |
KR1019997000946A KR20000068053A (en) | 1997-06-04 | 1998-06-02 | Process for production of aromatic tricarboxylic acids |
EP98938600A EP0914314A1 (en) | 1997-06-04 | 1998-06-02 | Process for production of aromatic tricarboxylic acids |
CN98800761A CN1228077A (en) | 1997-06-04 | 1998-06-02 | Process for producing aromatic tricarboxylic acids |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IE970418A IE970418A1 (en) | 1997-06-04 | 1997-06-04 | Process for production of aromatic tricarboxylic acids |
Publications (1)
Publication Number | Publication Date |
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IE970418A1 true IE970418A1 (en) | 1998-12-16 |
Family
ID=11041503
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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IE970418A IE970418A1 (en) | 1997-06-04 | 1997-06-04 | Process for production of aromatic tricarboxylic acids |
Country Status (9)
Country | Link |
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EP (1) | EP0914314A1 (en) |
KR (1) | KR20000068053A (en) |
CN (1) | CN1228077A (en) |
AU (1) | AU731622B2 (en) |
BR (1) | BR9806036A (en) |
CA (1) | CA2260846A1 (en) |
IE (1) | IE970418A1 (en) |
RU (1) | RU99104145A (en) |
WO (1) | WO1998055441A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1052239B1 (en) * | 1999-05-10 | 2004-04-14 | Mitsubishi Gas Chemical Company, Inc. | Process for producing pyromellitic acid |
US20020151745A1 (en) | 1999-05-10 | 2002-10-17 | Kazuo Tanaka | Process for producing pyromellitic acid |
JP4678081B2 (en) * | 2000-06-09 | 2011-04-27 | 三菱瓦斯化学株式会社 | Method for producing trimellitic acid |
MY123568A (en) * | 2000-06-09 | 2006-05-31 | Mitsubishi Gas Chemical Co | Process for producing trimellitec anhydride |
SG103937A1 (en) * | 2002-09-11 | 2004-05-26 | Mitsubishi Gas Chemical Co | Process for producing trimellitic acid |
KR102055750B1 (en) * | 2018-02-21 | 2019-12-13 | 포항공과대학교 산학협력단 | Manufacturing method of porous metal-organic frameworks with heterogeneous pores using decarboxylation |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3562318A (en) * | 1966-11-10 | 1971-02-09 | Petro Tex Chem Corp | Catalytic oxidation process of mono-aryl compounds |
US3683016A (en) * | 1970-04-24 | 1972-08-08 | Standard Oil Co | Staged catalyst addition for catalytic liquid phase oxidation of pseudocumene to trimellitic acid |
BE788349A (en) * | 1971-09-17 | 1973-01-02 | Labofina Sa | LIQUID PHASE OXIDATION PROCESS OF METHYLAROMATIC COMPOUNDS IN POLYCARBOXYLIC ACIDS |
US3920735A (en) * | 1973-05-21 | 1975-11-18 | Standard Oil Co | Zirconium enhanced activity of transition metal-bromine catalysis of di- and trimethyl benzene oxidation in liquid phase |
JPS6366149A (en) * | 1986-09-09 | 1988-03-24 | Idemitsu Petrochem Co Ltd | Production of trimellitic acid |
-
1997
- 1997-06-04 IE IE970418A patent/IE970418A1/en unknown
-
1998
- 1998-06-02 RU RU99104145/04A patent/RU99104145A/en not_active Application Discontinuation
- 1998-06-02 CA CA002260846A patent/CA2260846A1/en not_active Abandoned
- 1998-06-02 AU AU87272/98A patent/AU731622B2/en not_active Ceased
- 1998-06-02 EP EP98938600A patent/EP0914314A1/en not_active Withdrawn
- 1998-06-02 KR KR1019997000946A patent/KR20000068053A/en not_active Application Discontinuation
- 1998-06-02 BR BR9806036A patent/BR9806036A/en not_active Application Discontinuation
- 1998-06-02 CN CN98800761A patent/CN1228077A/en active Pending
- 1998-06-02 WO PCT/EP1998/003291 patent/WO1998055441A1/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
CN1228077A (en) | 1999-09-08 |
RU99104145A (en) | 2000-12-27 |
EP0914314A1 (en) | 1999-05-12 |
BR9806036A (en) | 1999-08-24 |
KR20000068053A (en) | 2000-11-25 |
CA2260846A1 (en) | 1998-12-10 |
AU731622B2 (en) | 2001-04-05 |
AU8727298A (en) | 1998-12-21 |
WO1998055441A1 (en) | 1998-12-10 |
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