WO1993017787A1 - Catalyst and method for production of alkyl pyrrolidones - Google Patents
Catalyst and method for production of alkyl pyrrolidones Download PDFInfo
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- WO1993017787A1 WO1993017787A1 PCT/US1993/001397 US9301397W WO9317787A1 WO 1993017787 A1 WO1993017787 A1 WO 1993017787A1 US 9301397 W US9301397 W US 9301397W WO 9317787 A1 WO9317787 A1 WO 9317787A1
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- catalyst
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- pyrrolidone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/02—Preparation of lactams
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D211/74—Oxygen atoms
- C07D211/76—Oxygen atoms attached in position 2 or 6
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D223/08—Oxygen atoms
- C07D223/10—Oxygen atoms attached in position 2
Definitions
- This invention relates to catalysts and more particularly to catalysts for producing alkyl substituted pyrrolidones from alcohols and 2-pyrrolidone.
- N-substituted 2-pyrrolidones are produced by the reaction of butyrolactone with the corresponding amine.
- amines are more costly than corresponding alcohols since they are prepared from the alcohols, requiring an extra processing step.
- the amines are produced in less than quantitative yields due to the formation of secondary and tertiary amines. Consequently, it would be economically desirable- to prepare N-substituted pyrrolidones directly from alcohols and 2- pyrrolidone, providing the yields are sufficiently high.
- a method which utilizes copper catalysts in a hydrogen atmosphere at temperatures of 180 to 450°C to react various alcohols with 2-pyrrolidone.
- the catalysts discussed are copper, copper-chromium, copper- rhenium, copper-silver, copper-nickel, copper-molybdenum, copper-manganese, copper-tungsten, and a copper-chromium- manganese catalyst. These were found to provide satisfactory selectivity relative to alcohol and pyrrolidone, however the yields were fairly low.
- a catalyst for converting various alcohols and cyclic lactams to N-substituted cyclic lactams in a hydrogen environment comprises from 10 to 15% cooper, 0.01 to 0.15% palladium disposed on a carrier. Utilizing a copper-palladium catalyst produces noticeable improvements in yield and selectively over other catalysts, including those disclosed in the Japanese Application, particularly in the production of N-octyl 2- pyrrolidone. DETAILED DESCRIPTION OF THE INVENTION
- the active catalytic components according 'to the present invention are copper and palladium deposited on a substrate support material. While various substrates could be used, a manganese silicate support substrate is preferred.
- the active catalytic material copper and palladium
- the active catalytic material are deposited on the substrate material by any conventional method.
- metal salts are dissolved in either aqueous or organic solvents and dried on a substrate and then treated with hydrogen to form metal crystallites. While metal deposition from the nitrates is preferred, any acceptable route to form the metal crystallites on the substrate material may be used, such as hydrogen reduction of the salt to form the metal crystallites or oxidation of the salt in air followed by reduction in hydrogen.
- the amounts of copper and palladium used may vary somewhat but are generally used in amounts based on catalyst plus support materials of 10 to 15% by weight copper, 0.01 to 0.15% palladium. Preferably, 10 to 12% copper and 0.09 to 0.13% palladium are used.
- the catalyst is usable at temperatures of from about 150° to 400°C.
- the inventive catalyst provides improved conversion and selectively in the conversion of alcohols and cyclic lactams of the Formula I to produce N-substituted lactams of the Formula II:
- n is an integer from 2 to 20.
- 2-pyrrolidone of Formula III is used, to produce the N-substituted pyrrolidones of Formula IV:
- R', R" and R 1 are H or lower alkyl
- R IV is
- n 2 to 20.
- the reactions described in the example can be varied to alter the characteristics of the catalyst. Longer reaction times and higher temperatures may produce catalysts which have an increase in effectiveness as it was found that during the initial reaction with copper nitrate, the longer reaction times, higher temperatures and higher acid levels may result in the production of a catalyst which has copper disposed deeper in the substrate. This tends to induce a stronger interaction of the copper with the substrate which increases the efficiency of the catalyst when used in the reaction of the invention.
- a reaction was also carried out as described in example 2 using copper chromite and ruthenium catalysts as described in Table II which follows. Conditions such as pressure, temperature and time were also varied. The best results were obtained at a hydrogen pressure of 1,000 psi where the selectively was 50% and the yield was 39.7%. In addition, Raney copper, and copper-bismuth were also utilized, none of which were as effective as even the copper chromite catalyst.
- inventive catalyst economic conversion of alcohols and 2-pyrrolidone or cyclic lactams to corresponding alkyl pyrrolidones and alkyl substituted lactams are achieved.
- inventive process processing costs are reduced through the reduction in cost of raw materials for producing the finished product. For example, octylamine sells for approximately $2.50/pound while octyl alcohol sells for approximately $.83/pound.
- the invention offers significant improvements over the prior art processes for producing N-substituted pyrrolidones. While preferred embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes and modifications could be made without varying from the scope of the present invention.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Pyrrole Compounds (AREA)
Abstract
A catalyst and method for producing N-substituted pyrrolidones utilizes a copper-palladium catalyst disposed on a support and mixed with a desired alcohol and 2-pyrrolidone. A reaction is undertaken under a hydrogen atmosphere, preferably at 50 to 1000 psig, and at a temperature ranging up to 400 °C. Utilizing a copper-palladium catalyst provides superior results in selectivity and yield over previous catalysts.
Description
CATALYST AND METHOD FOR PRODUCTION OF ALKYL PYRROLIDONES
TECHNICAL FIELD
This invention relates to catalysts and more particularly to catalysts for producing alkyl substituted pyrrolidones from alcohols and 2-pyrrolidone.
BACKGROUND OF THE INVENTION
Presently, N-substituted 2-pyrrolidones are produced by the reaction of butyrolactone with the corresponding amine. However, amines are more costly than corresponding alcohols since they are prepared from the alcohols, requiring an extra processing step. Also, the amines are produced in less than quantitative yields due to the formation of secondary and tertiary amines. Consequently, it would be economically desirable- to prepare N-substituted pyrrolidones directly from alcohols and 2- pyrrolidone, providing the yields are sufficiently high.
In Japanese unexamined Patent Application No. 117,459, a method is disclosed which utilizes copper catalysts in a hydrogen atmosphere at temperatures of 180 to 450°C to react various alcohols with 2-pyrrolidone. The catalysts discussed are copper, copper-chromium, copper- rhenium, copper-silver, copper-nickel, copper-molybdenum, copper-manganese, copper-tungsten, and a copper-chromium- manganese catalyst. These were found to provide
satisfactory selectivity relative to alcohol and pyrrolidone, however the yields were fairly low.
In a Journal of Molecular Catalysis article, 55(1989) p. 241 to 246, a catalyst for the n-alkylation of amides and lactams using alcohols is discussed with the catalyst being homogenous ruthenium. However r ruthenium is quite expensive and difficult to recover. Also, it appears that tri-substituted phosphine is needed to carry out the reaction, thus making the process even more expensive.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a novel catalyst for producing N-substituted 2- pyrrolidones from alcohols and 2-pyrrolidone. It is a further object to provide a novel catalyst of relatively low cost and high selectivity which produces the N-substituted pyrrolidones in economic yields.
These and other objects of the present invention are achieved by providing a catalyst for converting various alcohols and cyclic lactams to N-substituted cyclic lactams in a hydrogen environment. The catalyst comprises from 10 to 15% cooper, 0.01 to 0.15% palladium disposed on a carrier. Utilizing a copper-palladium catalyst produces noticeable improvements in yield and selectively over other catalysts, including those disclosed in the Japanese Application, particularly in the production of N-octyl 2- pyrrolidone.
DETAILED DESCRIPTION OF THE INVENTION
The active catalytic components according 'to the present invention are copper and palladium deposited on a substrate support material. While various substrates could be used, a manganese silicate support substrate is preferred.
The active catalytic material, copper and palladium, are deposited on the substrate material by any conventional method. Generally, metal salts are dissolved in either aqueous or organic solvents and dried on a substrate and then treated with hydrogen to form metal crystallites. While metal deposition from the nitrates is preferred, any acceptable route to form the metal crystallites on the substrate material may be used, such as hydrogen reduction of the salt to form the metal crystallites or oxidation of the salt in air followed by reduction in hydrogen. The amounts of copper and palladium used may vary somewhat but are generally used in amounts based on catalyst plus support materials of 10 to 15% by weight copper, 0.01 to 0.15% palladium. Preferably, 10 to 12% copper and 0.09 to 0.13% palladium are used. The catalyst is usable at temperatures of from about 150° to 400°C.
The inventive catalyst provides improved conversion and selectively in the conversion of alcohols and cyclic lactams of the Formula I to produce N-substituted lactams of the Formula II:
where m is an integer from 2 to 5 and n is an integer from 2 to 20.
Preferably 2-pyrrolidone of Formula III is used, to produce the N-substituted pyrrolidones of Formula IV:
R' ' R
where R', R" and R1" are H or lower alkyl, RIV is
H, alkyl, alkoxyl, cycloalkyl or aralkyl, and n is 2 to 20.
EXAMPLE 1
800 millimeters of water and 3.25 grams of concentrated nitric acid were combined and then 65 grams of copper nitrate hemipentahydrate was dissolved in the mixture which was combined with 130 grams of manganese silicate (SILPREC) with heating at 50°C for about an hour. 52 grams of sodium carbonate dissolved in 200 milliliters of water was then added slowly to the mixture to neutralize the acid. After stirring for another hour, the solution was filtered and the filter cake washed 3 times with distilled water. The filter cake was then dried at 200°C and then calcined overnight at 450°C. The calcined powder was broken up and combined with a solution of palladium nitrate which comprised 0.375 grams in 200 milliliters of water. After mixing, the material was dried at 200°C and
again calcined overnight at 450°C. The dry powder was then passed through a No. 30 sieve.
The reactions described in the example can be varied to alter the characteristics of the catalyst. Longer reaction times and higher temperatures may produce catalysts which have an increase in effectiveness as it was found that during the initial reaction with copper nitrate, the longer reaction times, higher temperatures and higher acid levels may result in the production of a catalyst which has copper disposed deeper in the substrate. This tends to induce a stronger interaction of the copper with the substrate which increases the efficiency of the catalyst when used in the reaction of the invention.
EXAMPLE 2
170 grams (2 moles) of 2-pyrrolidonef 195 grams
(1.5 moles) of 1-octanol and 18 grams (5% by weight) of the catalyst of example 1 were added to a 1 liter autoclave.
After purging the reactor with nitrogen to remove air, the nitrogen pressure was lowered to atmospheric pressure and 100 psig of hydrogen gas was introduced. The reactor was then sealed and heated to 275°C and held for 10 hours while temperature and pressure readings were recorded. The mixture was then cooled, discharged and filtered to remove the catalyst. The remaining material was analyzed by gas chro atography. Calculations were made to determine the selectivity, conversion and yield of the reaction based
upon the recovered weight of product and 1 octanol. 1- octanol was the limiting material, and thus the selectively and yield are based on 1-octanol rather than on conversion of the 2-pyrrolidone. Yield was calculated as the amount of product formed relative to the maximum amount of product possible based on reaction stoichiometry assuming a complete reaction. For a mole ratio of 2 moles of 2- pyrrolidone to 1.5 moles of 1-octanol, the following equations apply:
Yield = % octyl pyrrolidone formed x 100
81.0
% Selectively — 66 x (% octyl pyrrolidone) x 100 53.43 - (% 1-octanol remaining)
% Conversion = n-(% 1-octanol remaining)] x 100
53.43 For example, in the reaction of Example 2, the amount of 2-pyrrolidone in excess was 0.5 moles or 42.5 grams. The maximum amount of water that can be formed in the reaction was 1.5 moles or 27 grams for a total of 69.5 grams. Since the total weight introduced is 195 grams of 1-octanol and 170 grams of 2-pyrrolidone, the total weight exclusive of catalyst is 365 grams. The proportion of 2- pyrrolidone in excess plus the amount of water in the material that adds weight to the crude product but which could not be product. These constitute 19% [(69.5/365) x 100] of the weight, leaving 81% of the crude product which could be the desired octyl pyrrolidone. Consequently, the yield is given by the equation which includes division by
81. The equations for selectivity and conversion are derived in a similar fashion from these definitions*. The results are shown in Table II. Table I shows the reaction using the catalyst of Example 1 at 100 psi of hydrogen pressure producing average results of 68.8% yield and selectivity of 82.8%.
COMPARATIVE EXAMPLE 1
A reaction was also carried out as described in example 2 using copper chromite and ruthenium catalysts as described in Table II which follows. Conditions such as pressure, temperature and time were also varied. The best results were obtained at a hydrogen pressure of 1,000 psi
where the selectively was 50% and the yield was 39.7%. In addition, Raney copper, and copper-bismuth were also utilized, none of which were as effective as even the copper chromite catalyst.
Various branched and unbranched C2-C2o alcohols were tested to determine whether these would also be reactive with the inventive catalyst and 2-pyrrolidone to produce various alkyl pyrrolidones. For example, 1 butanol was reacted with 2-pyrrolidone and the copper-palladium catalyst of the invention to produce butylpyrrolidone with a yield estimated at 60% and selectivity at greater than 80%. Similarly, branched and cyclic alcohols such as 2 ethylhexanol and cyclohexanol were converted into the corresponding pyrrolidones, N-2-ethylhexyl pyrrolidone and
N-cyclohexyl pyrrolidone. The reaction was also under taken between 1-octanol and caprolactam to produce N-octyl- caprolactam.
Utilizing the inventive catalyst, economic conversion of alcohols and 2-pyrrolidone or cyclic lactams to corresponding alkyl pyrrolidones and alkyl substituted lactams are achieved. With the inventive process, processing costs are reduced through the reduction in cost of raw materials for producing the finished product. For example, octylamine sells for approximately $2.50/pound while octyl alcohol sells for approximately $.83/pound. Thus, the invention offers significant improvements over the prior art processes for producing N-substituted pyrrolidones. While preferred embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes and modifications could be made without varying from the scope of the present invention.
Claims
1. A catalyst for producing N-substituted cyclic lactam from alcohol and cyclic lactam comprising: 10 to 15% copper and 0.01 to 0.15% palladium disposed on a support.
2. The catalyst of claim 1 wherein from 10 to 12% copper is used.
3. The catalyst of claim 1 wherein from 0.09 to 0.13% palladium is used.
4. The catalyst of claim 1 wherein 13% copper is used.
5. The catalyst of claim 1 wherein 0.11% palladium is used.
6. The catalyst of claim 1 wherein the support is a manganese silicate support.
7. A method for producing N-substituted cyclic lactams from a reaction of an alcohol and a cyclic lactam comprising: providing a catalyst containing 0.01 to 0.15% palladium, 10 to 15% copper, disposed on a support, mixing the catalyst with the cyclic lactam and the alcohol, heating the mixture to a temperature of 150° to 400°C in a hydrogen atmosphere, holding the mixture at that temperature for a time sufficient to promote conversion of the alcohol and cyclic lactam to the N-substituted cyclic lactam, cooling the mixture, removing the catalyst after reaction completion, and separating the N-substituted cyclic lactam from the mixture.
8. The method of claim 7 wherein the reaction is conducted under a hydrogen pressure of 50 to 1000 psig.
9. The method of claim 7 wherein a 10 to 50% excess of alcohol is present in the mixture.
10. The method of claim 7 wherein the alcohol is from the group consisting of branched and unbranched alcohols.
11. The method of claim 7 wherein the alcohol is a C2-C20 unbranched alcohol.
12. The method of claim 7 wherein the alcohol is 2-ethylhexyl alcohol.
13. The method of claim 7 wherein the cyclic lactam is of the following formula I:
where m= 2, 3 or 4, or 5
14. The method of claim 7 wherein the cyclic lactam is a pyrrolidone of the following formula III:
R1 ' R' ' '
where R1 , R" and RMI are H or lower alkyl, RIV is H, alkyl, alkoxyl, cycloalkyl or aralkyl, and n is 2 to 20.
15. The method of claim 7 wherein the cyclic lactam is pyrrolidone, piperidone or caprolactam.
16. The method of claim 7 wherein the alcohol is from the group consisting of ethanol, hexanol, octanol and dodecanol.
17. A method for producing N-substituted pyrrolidones from alcohol and 2-pyrrolidone comprising: providing a catalyst containing 0.01 to 0.15% palladium, 10 to 15% copper, disposed on a support, mixing the catalyst with 2-pyrrolidone and an alkyl alcohol, heating the mixture to a temperature of 150° to 400°C in a hydrogen atmosphere, holding the mixture at that temperature for a time sufficient to promote conversion of alcohol and 2-pyrrolidone to the N-substituted pyrrolidone, cooling the mixture, removing the catalyst after reaction completion, and separating the N-substituted pyrrolidone from the reaction mixture.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US84713592A | 1992-03-06 | 1992-03-06 | |
| US847,135 | 1992-03-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1993017787A1 true WO1993017787A1 (en) | 1993-09-16 |
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ID=25299855
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1993/001397 WO1993017787A1 (en) | 1992-03-06 | 1993-02-18 | Catalyst and method for production of alkyl pyrrolidones |
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| WO (1) | WO1993017787A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0794176A1 (en) * | 1996-03-05 | 1997-09-10 | Nippon Shokubai Co., Ltd. | Process for production of tertiary amine compound |
| EP1067114A1 (en) * | 1999-07-05 | 2001-01-10 | Atanor S.A. | Method of preparing amino-, imino- and nitrilocarbonxylic acids and silver-promoted copper catalyst for use in said method |
| WO2015158794A1 (en) | 2014-04-15 | 2015-10-22 | Byk-Chemie Gmbh | Storage-stable urea preparations which are suitable as rheology control agents |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU264249A1 (en) * | CATALYST FOR WATER GAS CONVERSION | |||
| US2674602A (en) * | 1954-04-06 | Production of n-alkyl lactams | ||
| US3767644A (en) * | 1970-12-30 | 1973-10-23 | Asahi Chemical Ind | Process for the preparation of n-alkyl substituted lactams |
| US3865814A (en) * | 1972-07-28 | 1975-02-11 | Inventa Ag | Process for preparing n-substituted lactams |
| WO1980002023A1 (en) * | 1979-03-28 | 1980-10-02 | Gallaher Ltd | Catalytic processes and catalysts |
| US4845065A (en) * | 1986-03-27 | 1989-07-04 | Topy Industries, Ltd. And Japan Tobacco, Inc. | Carbon monoxide oxidizing catalyst |
-
1993
- 1993-02-18 WO PCT/US1993/001397 patent/WO1993017787A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU264249A1 (en) * | CATALYST FOR WATER GAS CONVERSION | |||
| US2674602A (en) * | 1954-04-06 | Production of n-alkyl lactams | ||
| US3767644A (en) * | 1970-12-30 | 1973-10-23 | Asahi Chemical Ind | Process for the preparation of n-alkyl substituted lactams |
| US3865814A (en) * | 1972-07-28 | 1975-02-11 | Inventa Ag | Process for preparing n-substituted lactams |
| WO1980002023A1 (en) * | 1979-03-28 | 1980-10-02 | Gallaher Ltd | Catalytic processes and catalysts |
| US4845065A (en) * | 1986-03-27 | 1989-07-04 | Topy Industries, Ltd. And Japan Tobacco, Inc. | Carbon monoxide oxidizing catalyst |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0794176A1 (en) * | 1996-03-05 | 1997-09-10 | Nippon Shokubai Co., Ltd. | Process for production of tertiary amine compound |
| US5847213A (en) * | 1996-03-05 | 1998-12-08 | Nippon Shokubai Co., Ltd. | Process for production of tertiary amine compound |
| EP1067114A1 (en) * | 1999-07-05 | 2001-01-10 | Atanor S.A. | Method of preparing amino-, imino- and nitrilocarbonxylic acids and silver-promoted copper catalyst for use in said method |
| WO2015158794A1 (en) | 2014-04-15 | 2015-10-22 | Byk-Chemie Gmbh | Storage-stable urea preparations which are suitable as rheology control agents |
| US9796860B2 (en) | 2014-04-15 | 2017-10-24 | Byk-Chemie Gmbh | Storage-stable urea preparations which are suitable as rheology control agents |
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