WO2001096859A1 - The rapid evaluation method of hydropurification catalyst - Google Patents
The rapid evaluation method of hydropurification catalyst Download PDFInfo
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- WO2001096859A1 WO2001096859A1 PCT/KR2001/001022 KR0101022W WO0196859A1 WO 2001096859 A1 WO2001096859 A1 WO 2001096859A1 KR 0101022 W KR0101022 W KR 0101022W WO 0196859 A1 WO0196859 A1 WO 0196859A1
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- WIPO (PCT)
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- catalyst
- hydropurification
- impurities
- purified
- carboxybenzaldehyde
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/10—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using catalysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2550/00—Monitoring or diagnosing the deterioration of exhaust systems
- F01N2550/20—Monitoring artificially aged exhaust systems
Definitions
- the present invention is related to the rapid aging method of catalyst compositions on the base of NIH group metals for the hydropurification of organic material including aromatic carboxylic acid.
- the invention is also related to the evaluation of hydropurification catalyst utilizing the rapid aging method.
- the method of the present invention is based on the contact of a hydropurification catalyst with impurities, to be removed by hydrogenation, and similar materials in the presence of reducing agent such as hydrogen.
- a hydropurification catalyst can be aged very fast, and the life and performance of catalyst can be estimated very easily.
- NHI group metals such as palladium and platinum on a support such as carbon, silica and alumina have been used as catalysts in various hydrogenation and hydropurification.
- palladium supported on carbon US Patent, ⁇ os. 3,584,039, 4,260,817, 4,467,110, PCT Publication No. WO94/20,447 has been utilized in the hydropurification of crude aromatic carboxylic acid to manufacture purified terephthalic acid (PTA) and isophthalic acid (IP A).
- Puskas US Patent No. 4,394,299
- Puskas could evaluate a catalyst via a "simulated aging" and purification afterward.
- the simulated aging was composed of aging a catalyst in the presence of hydrogen and water in high temperature.
- Schroeder (US Patent No. 4,629,715) could evaluate a catalyst after aging for 72 hr in high temperature in the presence of hydrogen, water and terephthalic acid.
- the present invention relates to a method of aging an hydropurification catalyst for such material as aromatic carboxylic acid etc.
- the present invention relates to a method of evaluation of a hydropurification catalyst for such material as aromatic carboxylic acid etc.
- the present invention solves the problem of slow aging of a hydropurification catalyst in laboratory with the utilization of impurities to be removed in aging with hydrogenation agent such as hydrogen at high temperature.
- the catalyst that can be applied in the present invention is a metal catalyst supported on a solid support, more preferably is one or more of NIH group metal and/or one or more of transition metal supported on carbon, silica, alumina, silica-alumina and titania.
- a metal catalyst supported on a solid support more preferably is one or more of NIH group metal and/or one or more of transition metal supported on carbon, silica, alumina, silica-alumina and titania.
- One or more of palladium, platinum, ruthenium, nickel and rhodium supported on carbon such as Pt/C, Pd/C, Ru/C, Pd-Ru/C, Pd- Pt/C are preferably applied.
- the impurities to be applied in the present invention can be any organic compounds that react with hydrogen, more preferably are reaction intermediates(from incomplete oxidation of alkyl aromatics) in a crude aromatic carboxylic acid, most preferably are aromatic compounds with aldehyde or hydroxy alkyl groups in a crude aromatic carboxylic acid such as 4- carboxybenzaldehyde (4-CBA), 3- carboxybenzaldehyde (3-CBA) or 2- formyl-6-naphthoic acid.
- the mixtures such as terephthalic acid and 4-CBA, isophthalic acid and 3-CBA, 2,6-naphthalenedicarboxylic acid and 2-formyl-6- naphthoic acid can be applied.
- the hydrogenation to be applied in the present invention can be any reaction with hydrogen, more preferably is hydropurification, even more preferably is hydropurification of crude aromatic carboxylic acid, most preferably is the hydropurification of crude aromatic carboxylic acids containing impurities such as 4-CBA, 3-CBA and 2-formyl-6-naphthoic acid.
- the present fast aging method can be executed by hydrogenation of impurities to be removed with a catalyst in the solvent such as water in the presence of hydrogen.
- This aging can be executed in a batch or continuous manner with the partial pressure(at room temperature, 1 atm) of hydrogen is 15 ⁇ lOOOpsi, more preferably is 100 ⁇ 500psi.
- the aging temperature and pressure may be any value to make a part of reaction mixture liquid, more preferably are 0-350 °C and 0 ⁇ 1500psi.
- Aging time can be lhr ⁇ 10days, more preferably be 2 ⁇ 72hr.
- the catalysts used in the present invention were manufactuted with the following methods. Three catalysts such as Pd/active carbon, Pd/Sibunit, and Pd- Ru/Sibunit were manufactured, and denoted as catalyst A, B and C, respectively.
- Catalyst A(0.5%Pd/active carbon) Aqueus solution of Na 2 PdCl 4 was sprayed over active carbon, and reduced with hydrogen similar to the example 1 of European patent No. 0879641 Al.
- Catalyst B(0.5%Pd/Sibunit) and C(0.3%Pd-0.2 Ru/Sibunit) Catalysts B and C were manufactured by the way of example 1 and 3, respectively, in the Korean patent application No.1020000001712, "The catalyst for purification of terephthalic acid", 2000. 1. 14) . In other words, aqueous solutions of PdCl 2 and RuOHCl were sprayed over carbon support Sibunit, and reduced with flowing hydrogen.
- each catalyst A, B and C were loaded in a separate chamber of Hastelloy high pressure reactor, and 250g of distilled water and 25g of 4-CBA were added to the reactor.
- the hydrogen was charged, after the air was replaced with hydrogen, in the reactor to the pressure of 200psi.
- the reactor was heated to 250 °C, and as soon as this temperature was reached the reactor was agitated with speed of 400rpm. The aging was continued for 44 hr while the used hydrogen was supplied a check valve.
- the catalysts were separated from organic materials after cooling, and recovered and reserved in distilled water with blanket of nitrogen to evaluate the residual activities.
- the activity of aged catalyst A was determined with the hydropurification of 25g of terephthalic acid containg 3% of 4-CBA in 250g of distilled water at 250 °C for 30 min.
- the partial pressure of hydrogen was 200 psi(at room temperature and latm), and the reactor was agitated with the speed of 800rpm.
- the purified terephthalic acid was recovered after cooling and was analyzed (after dissolution in alkaline solution) with HPLC(for 4-CBA, p-toluic acid, benzoic acid) and UN spectrometer(for alkaline transmittance at 340 and 400nm).
- Aged catalysts B and C were also used in hydropurification in similar manner.
- the activities and performances of aged catalysts A, B and C were very low as compared with the catalysts aged in the condition of Comparative Example 1 and with the catalyst without aging(comparative example 2). Especially the performance of catalysts can be differentiated as C>B>A.
- the sintering of metals can occur with the reaction.
- the obtained metal size of catalyst A, B and C after aging, 29.4, 21.5 and 14.8nm, respectively, also confirms the stability as C>B>A.
- the catalyst can be aged fast and can be evaluated very efficiently.
- Catalysts were aged similar to the method of example 1, except the aging material was changed from 25g of 4-CBA to 25g of terephthalic acid containing 30% of 4-CBA.
- the activities of the catalyst were determined by the method of example 1.
- the residual activities of aged catalysts were low as compared with those of comparative examples 1 and 2.
- the performance of hydropurification catalyst can be analyzed via aging of example 2 because the remained activity is C ⁇ B>A. But the aging speed was lower than that of example 1.
- Catalysts were aged similar to the method of example 1, except the aging material was changed from 25g of 4-CBA to 25g of terephthalic acid.
- the activities of the catalyst were determined by the method of example 1.
- the activities of the catalysts were determined by the method of example 1 without any aging.
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- Analytical Chemistry (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
An efficient and fast evaluation method of hydropurification catalyst comprising: (a) aging of the catalyst with impurities to be purified with the catalyst; and (b) evaluating the residual performance of the above aged catalyst via hydropurification reaction or measurement of metal size.
Description
The rapid evaluation method of hydropurification catalyst
TECHNICAL FIELD
The present invention is related to the rapid aging method of catalyst compositions on the base of NIH group metals for the hydropurification of organic material including aromatic carboxylic acid. The invention is also related to the evaluation of hydropurification catalyst utilizing the rapid aging method.
The method of the present invention is based on the contact of a hydropurification catalyst with impurities, to be removed by hydrogenation, and similar materials in the presence of reducing agent such as hydrogen.
With the present invention, a hydropurification catalyst can be aged very fast, and the life and performance of catalyst can be estimated very easily.
BACKGROUND ART
Supported NHI group metals such as palladium and platinum on a support such as carbon, silica and alumina have been used as catalysts in various hydrogenation and hydropurification. Especially, palladium supported on carbon (US Patent, Νos. 3,584,039, 4,260,817, 4,467,110, PCT Publication No. WO94/20,447) has been utilized in the hydropurification of crude aromatic carboxylic acid to manufacture purified terephthalic acid (PTA) and isophthalic acid (IP A).
It is very difficult to estimate, especially in a laboratory scale, the performances of a metal supported catalyst. The performance of a catalyst can be analyzed only by application in an actual reactor for years because the lifetime of the catalyst is quite long for years. But the reliable and easy estimation of a catalyst from the view point of lifetime and performance is extremely important because a good catalyst can improve productivity and decrease the cost of catalyst production. Therefore, a performance test for a catalyst in a short time in
laboratory is very important. But a test usually needs much time and efforts and has a problem of reliability.
Some test methods for the performances of Pd/C used for the hydropurification of crude terephthalic acid have been reported. Puskas (US Patent No. 4,394,299) could evaluate a catalyst via a "simulated aging" and purification afterward. The simulated aging was composed of aging a catalyst in the presence of hydrogen and water in high temperature. Similarly,
Schroeder (US Patent No. 4,629,715) could evaluate a catalyst after aging for 72 hr in high temperature in the presence of hydrogen, water and terephthalic acid.
But above methods had drawback of low aging speed. With these methods, only the fresh, non-steady state activity of a catalyst could be removed in a short period, and the real performances could not be analyzed easily and fast.
Therefore, it is very important to develop an estimation method via rapid aging of a catalyst in a laboratory.
DISCLOSURE OF INVENTION As a result of research for resolving the above problems of aging, the inventors herein contacted a catalyst with an impurity to be removed or similar materials in the presence of hydrogen at high temperature. The inventors found that a decline in activity is very fast and reliable with this aging. Based on such findings, the present invention has been perfected.
In view of the foregoing, the present invention relates to a method of aging an hydropurification catalyst for such material as aromatic carboxylic acid etc.
In another aspect, the present invention relates to a method of evaluation of a hydropurification catalyst for such material as aromatic carboxylic acid etc.
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention solves the problem of slow aging of a hydropurification catalyst in laboratory with the utilization of impurities to be removed in aging with hydrogenation agent such as hydrogen at high temperature.
The catalyst that can be applied in the present invention is a metal catalyst supported on a solid support, more preferably is one or more of NIH group metal and/or one or more of transition metal supported on carbon, silica, alumina, silica-alumina and titania. One or more of palladium, platinum, ruthenium, nickel and rhodium supported on carbon such as Pt/C, Pd/C, Ru/C, Pd-Ru/C, Pd- Pt/C are preferably applied.
The impurities to be applied in the present invention can be any organic compounds that react with hydrogen, more preferably are reaction intermediates(from incomplete oxidation of alkyl aromatics) in a crude aromatic carboxylic acid, most preferably are aromatic compounds with aldehyde or hydroxy alkyl groups in a crude aromatic carboxylic acid such as 4- carboxybenzaldehyde (4-CBA), 3- carboxybenzaldehyde (3-CBA) or 2- formyl-6-naphthoic acid. The mixtures such as terephthalic acid and 4-CBA, isophthalic acid and 3-CBA, 2,6-naphthalenedicarboxylic acid and 2-formyl-6- naphthoic acid can be applied.
The hydrogenation to be applied in the present invention can be any reaction with hydrogen, more preferably is hydropurification, even more preferably is hydropurification of crude aromatic carboxylic acid, most preferably is the hydropurification of crude aromatic carboxylic acids containing impurities such as 4-CBA, 3-CBA and 2-formyl-6-naphthoic acid.
The present fast aging method can be executed by hydrogenation of impurities to be removed with a catalyst in the solvent such as water in the presence of hydrogen. This aging can be executed in a batch or continuous manner with the
partial pressure(at room temperature, 1 atm) of hydrogen is 15 ~ lOOOpsi, more preferably is 100~500psi. The aging temperature and pressure may be any value to make a part of reaction mixture liquid, more preferably are 0-350 °C and 0~1500psi. Aging time can be lhr ~10days, more preferably be 2 ~ 72hr.
The present invention is explained in detail by examples below. Nevertheless, the examples are illustrative only and should not be deemed to limit the present invention.
Examples
The catalysts used in the present invention were manufactuted with the following methods. Three catalysts such as Pd/active carbon, Pd/Sibunit, and Pd- Ru/Sibunit were manufactured, and denoted as catalyst A, B and C, respectively.
Catalyst A(0.5%Pd/active carbon) : Aqueus solution of Na2PdCl4 was sprayed over active carbon, and reduced with hydrogen similar to the example 1 of European patent No. 0879641 Al.
Catalyst B(0.5%Pd/Sibunit) and C(0.3%Pd-0.2 Ru/Sibunit) : Catalysts B and C were manufactured by the way of example 1 and 3, respectively, in the Korean patent application No.1020000001712, "The catalyst for purification of terephthalic acid", 2000. 1. 14) . In other words, aqueous solutions of PdCl2 and RuOHCl were sprayed over carbon support Sibunit, and reduced with flowing hydrogen.
Example 1
0.28g of each catalyst A, B and C were loaded in a separate chamber of Hastelloy high pressure reactor, and 250g of distilled water and 25g of 4-CBA were added to the reactor. The hydrogen was charged, after the air was replaced with hydrogen, in the reactor to the pressure of 200psi. The reactor was heated to
250 °C, and as soon as this temperature was reached the reactor was agitated with speed of 400rpm. The aging was continued for 44 hr while the used hydrogen was supplied a check valve. The catalysts were separated from organic materials after cooling, and recovered and reserved in distilled water with blanket of nitrogen to evaluate the residual activities.
The activity of aged catalyst A was determined with the hydropurification of 25g of terephthalic acid containg 3% of 4-CBA in 250g of distilled water at 250 °C for 30 min. The partial pressure of hydrogen was 200 psi(at room temperature and latm), and the reactor was agitated with the speed of 800rpm. The purified terephthalic acid was recovered after cooling and was analyzed (after dissolution in alkaline solution) with HPLC(for 4-CBA, p-toluic acid, benzoic acid) and UN spectrometer(for alkaline transmittance at 340 and 400nm). Aged catalysts B and C were also used in hydropurification in similar manner.
The activities and performances of aged catalysts A, B and C were very low as compared with the catalysts aged in the condition of Comparative Example 1 and with the catalyst without aging(comparative example 2). Especially the performance of catalysts can be differentiated as C>B>A. The sintering of metals can occur with the reaction. The obtained metal size of catalyst A, B and C after aging, 29.4, 21.5 and 14.8nm, respectively, also confirms the stability as C>B>A.
With the present invention, the catalyst can be aged fast and can be evaluated very efficiently.
The detailed data including the contents of 4-CBA remained after purification and alkali transmittance are given in table 1.
Example 2
Catalysts were aged similar to the method of example 1, except the aging
material was changed from 25g of 4-CBA to 25g of terephthalic acid containing 30% of 4-CBA. The activities of the catalyst were determined by the method of example 1.
The residual activities of aged catalysts were low as compared with those of comparative examples 1 and 2. The performance of hydropurification catalyst can be analyzed via aging of example 2 because the remained activity is C≥ B>A. But the aging speed was lower than that of example 1.
The detailed data including the contents of 4-CBA remained after purification and alkali transmittance are given in table 1.
Comparative example 1
Catalysts were aged similar to the method of example 1, except the aging material was changed from 25g of 4-CBA to 25g of terephthalic acid. The activities of the catalyst were determined by the method of example 1.
It was nearly impossible to differentiate the performance of catalysts because the aged catalysts produced terephthalic acid with simiar 4-CBA and color property.
The detailed data including the contents of 4-CBA remained after purification and alkali transmittance are given in table 1.
Comparative example 2
The activities of the catalysts were determined by the method of example 1 without any aging.
It was nearly impossible to differentiate the performance of catalysts because the fresh catalysts produced terephthalic acid with simiar 4-CBA and color property. The activities of catalysts were higher than catalysts aged by any methods of
example 1 and 2 and comparative example 1.
The detailed data including the contents of 4-CBA remained after purification and alkali transmittance are given in table 1.
<Table 1> 4-CBA and alkali transmittance of terephthalic acid purified with a catalyst aged with different conditions and metal size of catalyst determined by CO chemisorption.
* Residual 4-CBA from 3% in terephthalic acid purified with aged catalyst.
** Alkaline transmittance at 340nm of terephthalic acid purified with aged catalyst and dissolved in aqueous KOH.
Claims
1. A method of evaluation of hydropurification catalyst, which comprises (a) aging of a hydropurification catalyst by contacting with impurities to be purified with the catalyst in the presence of hydrogen; and (b) evaluating the residual performance of the above aged catalyst .
2. The method according to Claim 1, wherein said hydropurification catalyst is one or more of N-π group metals supported on a solid support.
3. The method according to Claim 2, wherein said solid support is selected from the group consisting of carbon, silica, alumina, silica-alumina and titania.
4. The method according to Claim 2, wherein one or more of NHI group metal is selected from the group consisting of platinum, palladium, ruthenium, palladium-ruthenium, palladium-platinum.
5. The method according to Claim 1, wherein said impurities to be purified with hydropurification are reaction intermediates produced by insufficient oxidation of alkyl aromatic compounds.
6. The method according to Claim 5, wherein said impurities to be purified with hydropurification are aromatic aldehydes, aromatic ketones and hydroxyalkyl aromatic compounds.
7. The method according to Claim 5, wherein said impurities to be purified with hydropurification are 4-carboxybenzaldehyde, 3-carboxybenzaldehyde and 2-formyl-6-naphthoic acid.
8. The method according to Claim 1, wherein said hydropurification catalyst is one of Pd/C or Pd-Ru/C, and said impurities to be purified with hydropurification are 4-carboxybenzaldehyde, 3- carboxybenzaldehyde and 2-formyl-6-naphthoic acid.
9. The method according to Claim 1, wherein said hydropurification catalyst is one of Pd/C or Pd-Ru/C, and said impurities to be purified with hydropurification are a mixture of 4-carboxybenzaldehyde and terephthalic acid, a mixture of 3-carboxybenzaldehyde and isophthalic acid, and a mixture of 2-formyl-6-naphthoic acid and 2,6-naphthalenedicarboxylic acid.
10. The method according to claim 1, wherein said evaluation of residual performance is carried out by hydropurification reaction or measurement of metal size.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2001264381A AU2001264381A1 (en) | 2000-06-14 | 2001-06-14 | The rapid evaluation method of hydropurification catalyst |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020000032736A KR100642133B1 (en) | 2000-06-14 | 2000-06-14 | An improved test method for the performance of the hydropurification catalyst |
| KR2000/32736 | 2000-06-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2001096859A1 true WO2001096859A1 (en) | 2001-12-20 |
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ID=19671910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2001/001022 WO2001096859A1 (en) | 2000-06-14 | 2001-06-14 | The rapid evaluation method of hydropurification catalyst |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100642133B1 (en) |
| AU (1) | AU2001264381A1 (en) |
| WO (1) | WO2001096859A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1205241A1 (en) * | 1999-07-29 | 2002-05-15 | Institut Kataliza Imeni G.K. Boreskova Sibirskogo Otdelenia Rossiiskoi Akademii Nauk | Catalytic composition, method for manufacturing thereof and method for the purification of terephthalic acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4394299A (en) * | 1981-10-29 | 1983-07-19 | Standard Oil Company (Indiana) | Palladium-rhodium catalyst for purification of crude terephthalic acid |
| US4476242A (en) * | 1981-10-29 | 1984-10-09 | Standard Oil Company (Indiana) | Process for preparing palladium on carbon catalysts for purification of crude terephthalic acid |
| US4629715A (en) * | 1985-10-07 | 1986-12-16 | Amoco Corporation | Purification of terephthalic acid to relatively low levels of 4-carboxybenzaldehyde and catalyst therefor |
| US5396794A (en) * | 1993-04-05 | 1995-03-14 | Applied Computer Engineering, Inc. | Engine catalyst aging system and method for aging catalyst |
-
2000
- 2000-06-14 KR KR1020000032736A patent/KR100642133B1/en not_active IP Right Cessation
-
2001
- 2001-06-14 WO PCT/KR2001/001022 patent/WO2001096859A1/en active Application Filing
- 2001-06-14 AU AU2001264381A patent/AU2001264381A1/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4394299A (en) * | 1981-10-29 | 1983-07-19 | Standard Oil Company (Indiana) | Palladium-rhodium catalyst for purification of crude terephthalic acid |
| US4476242A (en) * | 1981-10-29 | 1984-10-09 | Standard Oil Company (Indiana) | Process for preparing palladium on carbon catalysts for purification of crude terephthalic acid |
| US4629715A (en) * | 1985-10-07 | 1986-12-16 | Amoco Corporation | Purification of terephthalic acid to relatively low levels of 4-carboxybenzaldehyde and catalyst therefor |
| US5396794A (en) * | 1993-04-05 | 1995-03-14 | Applied Computer Engineering, Inc. | Engine catalyst aging system and method for aging catalyst |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1205241A1 (en) * | 1999-07-29 | 2002-05-15 | Institut Kataliza Imeni G.K. Boreskova Sibirskogo Otdelenia Rossiiskoi Akademii Nauk | Catalytic composition, method for manufacturing thereof and method for the purification of terephthalic acid |
| EP1205241A4 (en) * | 1999-07-29 | 2003-08-27 | Boreskova Inst Kataliza Sibir | Catalytic composition, method for manufacturing thereof and method for the purification of terephthalic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100642133B1 (en) | 2006-11-13 |
| KR20010111952A (en) | 2001-12-20 |
| AU2001264381A1 (en) | 2001-12-24 |
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