US2782243A - Hydrogenation of esters - Google Patents

Hydrogenation of esters Download PDF

Info

Publication number
US2782243A
US2782243A US419575A US41957554A US2782243A US 2782243 A US2782243 A US 2782243A US 419575 A US419575 A US 419575A US 41957554 A US41957554 A US 41957554A US 2782243 A US2782243 A US 2782243A
Authority
US
United States
Prior art keywords
copper
parts
chromium
catalyst
percent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US419575A
Inventor
Lawrence G Hess
Helmut W Schulz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Union Carbide Corp
Original Assignee
Union Carbide and Carbon Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Union Carbide and Carbon Corp filed Critical Union Carbide and Carbon Corp
Priority to US419575A priority Critical patent/US2782243A/en
Application granted granted Critical
Publication of US2782243A publication Critical patent/US2782243A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases

Definitions

  • This invention relates to the production of lower aliphatic alcohols by the hydrogenation of esters under the influence of a catalyst and more particularly this invention is directed to a process for the production of loweraliphatic monohydric alcohols from esters embodying the same by the hydrogenation of these esters in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and containing from 1 to 5 parts of chromium per 100 parts of copper.
  • One of the significant features of this invention is that now a process is available commercially which will permit the production of ethanol and methanol in substantial yield by the vapor phase hydrogenation of methyl acetate at a temperature above its critical temperature and at an elevated pressure in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and containing from 1 to 5 parts of chromium per 100 parts of copper.
  • alcohols of higher molecular weight may be produced by the catalytic hydrogenation of esters of aliphatic carboxylic acids, utilizing various catalysts such as, for example, copper oxide preferably promoted with an oxide of an alkali or alkaline earth metal; chromium oxide alone or in conjunction with tungstates, vanadates or molybdates; cobalt salts of metal acids deposited on a carrier; reduced copper oxide alone or in conjunction with oxides of zinc, magnesium, manganese and the like. All of these heretofore known processes are essentially liquid phase operations and although vapor phase operations have been proposed they have not been eflicient and the yields of products are low.
  • the process of this invention comprises the reaction of lower aliphatic esters in the presence of hydrogen at. an elevated temperature and pressure in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and con- Theoretically, the reaction calls for two mols of hydrogen per mol of ester but from a practical standpoint the ester is charged to the reaction vessel and reacted in a large excess of hydrogen.
  • the lower aliphatic esters which may be employed in the process of this invention can be esters such as, methyl acetate, ethyl acetate, methyl and ethyl propionate, methyl and ethyl butyrate and the like.
  • the hydrogenolysis conditions which may be advantageously employed in the process of this invention are similar to those conditions of hydrogenation which are generally employed in established hydrogenation techniques and are widely known as involving the use of elevated temperatures and pressures.
  • an elevated temperature which is in the range of 250 C. to 400 C.
  • a detailed example of the preparation of the catalyst in a preferred form involves the addition of approximately 6.6 parts by weight of copper scrap overa three and until the acidity falls below 2.0 percent.
  • a catalyst support should be employed in which case a suitable porous basket containing 0.375 x 0.261 mesh Filtros is immersed for 15 minutes in the impregnating solution having a specific gravity of 1.70- 1.75 at the boiling temperature. After dipping and drainage the impregnated Filtros is roasted in a stream of air for a period of two hours at 350 C.
  • the catalyst is then dipped and roasted until the copper content is 12 percent and the chromium content is 0.3 to 0.4 percent, giving a weight ratio of 2.5-3.5 parts of chromium per parts of copper.
  • the amount of catalyst necessary to promote the hydrogenation of methyl acetate is not a critical feature of this invention.
  • An amount of catalyst suificient to promote the reaction is all that is necessary.
  • a preferred range of catalyst concentration based on copper oxide is an amount equivalent to l to 5 percent, by weight, of the ester charged to the reaction vessel.
  • the catalyst may or may not be supported by an inert carrier and may be charged in a loose form to the reaction vessel or suspended in a porous basket within the reaction vessel; :For continuous reactions the amount of catalyst required depends upon the desired conversion and production rate, the supported catalyst being heated within a high pressure reactor and the vaporized lower aliphatic esters being passed together with hydrogen through the catalyst bed.
  • a rockertype reaction vessel similar to those used in established techniques for laboratory hydrogenations can be utilized although, as indicated above, the process can be operated in a continuous or semi-continuous manner.
  • Methyl acetate, or the other lower aliphatic esters may be hydrogenated in solution with one of the expected alcohols or an inert diluent by passing the reactants over a supported catalyst in the vapor phase.
  • reaction vessel In batchwise experiments the reaction vessel is charged with liquid and solid components and hydrogen is introduced at approximately 500 pounds per square inch pressure and expelled three times to purge the system completely. Hydrogen is then added to the reaction vessel to a pressure calculated to give the desired reaction pressure and the reaction vessel is heated to the desire-d operating temperature, the reaction system being maintained at the desired operating pressure. When the reaction conditions have been maintained for a sufficient period of time, the heating is discontinued and the reaction vessel and its contents cooled. The products are then discharged from the reaction vessel and recovered by any suitable means, such as for example, by fractional distillation.
  • Example I Methyl acetate, as an 82 percent solution with methanol, was reacted in a pressure-resistant reaction vessel with hydrogen at a pressure of 15,000 pounds per square inch for a period of two hours at a temperature of 270 C. using 2 percent by weight, based on contained copper, of the supported catalyst described above. A methyl acetate conversion of 89.5 percent was obtained with an efiiciency to methanol and ethanol of 91.4 percent and 96.4 percent, respectively. The production ratio based on the methanol and ethanol recovered was equivalent to 175 pounds of product per cubic foot of catalyst volume per hour.
  • Example II Methyl acetate, as an 82 percent solution with methanol, was reacted in a pressure-resistant reaction vessel with hydrogen at a pressure of 10,000 pounds per square inch for a period of two hours and at a temperature of 270 C. using 3 percent by weight, based on contained copper, of the supported catalyst described above. A methyl acetate conversion of 81.8 percent was obtained with an efficiency to methanol and ethanol of 82.6 percent and 83.5 percent, respectively. The production ratio based on the combined Weight of methanol and ethanol produced was 90 pounds per cubic foot of supported catalyst per hour.
  • Example III Approximately 350 grams of ethyl propionate were heated to 290 C. in a pressure-resistant vessel in the presence of 125 grams of the supported copper-chrome catalyst described above and under an initial hydrogen pressure of 5300 pounds per square inch. A temperature of 290 C. and a pressure t 15,000 pounds per square inch were maintained for a period of one hour. After the vessel and its contents had been cooled, the crude reaction product was discharged. Distillation and analysis of the fractions showed an ethyl propionate conversion of 80.4 percent and an efficiency to ethanol and npropanol of 82.5 percent and 90.4 percent, respectively, based on the ethyl propionate charged. The production ratio based on the combined weight of ethanol and propanol produced was 125 pounds per cubic foot of supported catalyst per hour.
  • a process for the production of alcohols from esters which comprises reacting a lower aliphatic ester with hydrogen under hydrogenating conditions in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and containing from 1 to 5 parts of chromium per parts of copper.
  • a process for the production of methanol and ethanol which comprises reacting methyl acetate with hydrogen under hydrogenating conditions in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and containing from 1 to 5 parts of chromium per 100 parts of copper.
  • a process for the production of ethanol and propanol which comprises reacting ethyl propionate with hydrogen under hydrogenating conditions in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and containing from 1 to 5 parts of chromium per 100 parts of copper.
  • a process of the production of alcohols from esters which comprises reacting a lower aliphatic ester with hydrogen at a temperature in the range 250 C. to 400 C. and a pressure in the range 5,000 to 15,000 pounds per square inch in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and containing from 1 to 5 parts of chromium per 100 parts of copper.
  • a process for the production of methanol and ethanol which comprises reacting methyl acetate with hydrogen at a temperature in the range 250 C. to 400 C. and a pressure in the range 5,000 to 15,000 pounds per square inch in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and containing from 1 to 5 parts of chromium per 100 parts of copper.
  • a process for the production of ethanol and propanol which comprises reacting ethyl propionate with hydrogen at a temperature in the range 250 C. to 400 C. and a pressure in the range 5,000 to 15,000 pounds per square inch in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and containing from 1 to 5 parts of chromium per 100 parts of copper.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

United States Patent HYDROGENATION 0F ESTERS Lawrence G. Hess and Helmut W. Schulz, Charleston,
W. Va., assignors to Union Carbide and Carbon Corporation, a corporation of New York No Drawing. Application March 29, 1954,
Serial No. 419,575
7 Claims. (Cl. 260-638) This invention relates to the production of lower aliphatic alcohols by the hydrogenation of esters under the influence of a catalyst and more particularly this invention is directed to a process for the production of loweraliphatic monohydric alcohols from esters embodying the same by the hydrogenation of these esters in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and containing from 1 to 5 parts of chromium per 100 parts of copper.
One of the significant features of this invention is that now a process is available commercially which will permit the production of ethanol and methanol in substantial yield by the vapor phase hydrogenation of methyl acetate at a temperature above its critical temperature and at an elevated pressure in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and containing from 1 to 5 parts of chromium per 100 parts of copper.
Heretofore, ethanol and methanol have not been produced by the reaction of hydrogen with methyl acetate, but it is known that alcohols of higher molecular weight may be produced by the catalytic hydrogenation of esters of aliphatic carboxylic acids, utilizing various catalysts such as, for example, copper oxide preferably promoted with an oxide of an alkali or alkaline earth metal; chromium oxide alone or in conjunction with tungstates, vanadates or molybdates; cobalt salts of metal acids deposited on a carrier; reduced copper oxide alone or in conjunction with oxides of zinc, magnesium, manganese and the like. All of these heretofore known processes are essentially liquid phase operations and although vapor phase operations have been proposed they have not been eflicient and the yields of products are low.
While the processes of hydrogenating esters of aliphatic monocarboxylic acids are thoroughly discussed in the literature, the particular processes for hydrogenating methyl acetate to ethanol and methanol are few in number. The reason appears to be that methyl acetate and methanol are subject to gaseous decomposition during the hydrogenation processes utilized by the prior art. Thus, no suitable commercial processes exist for the conversion of methyl acetate to ethanol and methanol.
Therefore, it is one of the purposes of this invention to provide an essentially vapor phase process for the conversion of methyl acetate to ethanol and methanol which is highly efficient and results in substantial yields of products.
The process of this invention, however, in its broader aspects comprises the reaction of lower aliphatic esters in the presence of hydrogen at. an elevated temperature and pressure in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and con- Theoretically, the reaction calls for two mols of hydrogen per mol of ester but from a practical standpoint the ester is charged to the reaction vessel and reacted in a large excess of hydrogen.
The lower aliphatic esters which may be employed in the process of this invention can be esters such as, methyl acetate, ethyl acetate, methyl and ethyl propionate, methyl and ethyl butyrate and the like.
The hydrogenolysis conditions which may be advantageously employed in the process of this invention are similar to those conditions of hydrogenation which are generally employed in established hydrogenation techniques and are widely known as involving the use of elevated temperatures and pressures.
More specifically, though, it is preferred to employ an elevated temperature which is in the range of 250 C. to 400 C.
Pressures above 5,000 pounds per square inch are employed, excellent results being obtained when pressures in the range of 10,000-l5,000 pounds per square inch are utilized.
. it is then roasted to produce a finished catalyst containing from 1 to 5 parts of chromium per 100 parts of copper.
A detailed example of the preparation of the catalyst in a preferred form involves the addition of approximately 6.6 parts by weight of copper scrap overa three and until the acidity falls below 2.0 percent.
taining from 1 to 5 parts of chromium per 100 parts 7 of copper.
The reaction whereby the alcohols are produced in accordance with this invention may be represented, in the case of methyl acetate, by the following equation:
hour period to 100 parts by weight of a 34 percent aqueous nitric acid solution maintained at a temperature of C. When the acidity of the resulting copper nitrate solution is below 20 percent, calculated as nitric acid, 0.45 part of chromium is added as a concentrated aque ous chromium acetate solution. Then 6.5 additional parts of copper scrap are added over a period of three hours. The solution temperature is maintained at 90 C. by cooling or heating as required during all additions The copper-chrome solution is then concentrated by evaporation until a specific gravity of 1.70-1.75 is obtained.
Preferably, a catalyst support should be employed in which case a suitable porous basket containing 0.375 x 0.261 mesh Filtros is immersed for 15 minutes in the impregnating solution having a specific gravity of 1.70- 1.75 at the boiling temperature. After dipping and drainage the impregnated Filtros is roasted in a stream of air for a period of two hours at 350 C.
The catalyst is then dipped and roasted until the copper content is 12 percent and the chromium content is 0.3 to 0.4 percent, giving a weight ratio of 2.5-3.5 parts of chromium per parts of copper.
The amount of catalyst necessary to promote the hydrogenation of methyl acetate is not a critical feature of this invention. An amount of catalyst suificient to promote the reaction is all that is necessary. For batchwise reactions, however, a preferred range of catalyst concentration based on copper oxide is an amount equivalent to l to 5 percent, by weight, of the ester charged to the reaction vessel. The catalyst may or may not be supported by an inert carrier and may be charged in a loose form to the reaction vessel or suspended in a porous basket within the reaction vessel; :For continuous reactions the amount of catalyst required depends upon the desired conversion and production rate, the supported catalyst being heated within a high pressure reactor and the vaporized lower aliphatic esters being passed together with hydrogen through the catalyst bed.
In carrying out the process of this invention, a rockertype reaction vessel similar to those used in established techniques for laboratory hydrogenations can be utilized although, as indicated above, the process can be operated in a continuous or semi-continuous manner. Methyl acetate, or the other lower aliphatic esters, may be hydrogenated in solution with one of the expected alcohols or an inert diluent by passing the reactants over a supported catalyst in the vapor phase.
In batchwise experiments the reaction vessel is charged with liquid and solid components and hydrogen is introduced at approximately 500 pounds per square inch pressure and expelled three times to purge the system completely. Hydrogen is then added to the reaction vessel to a pressure calculated to give the desired reaction pressure and the reaction vessel is heated to the desire-d operating temperature, the reaction system being maintained at the desired operating pressure. When the reaction conditions have been maintained for a sufficient period of time, the heating is discontinued and the reaction vessel and its contents cooled. The products are then discharged from the reaction vessel and recovered by any suitable means, such as for example, by fractional distillation.
The following examples will serve to illustrate the practice of the invention:
Example I Methyl acetate, as an 82 percent solution with methanol, was reacted in a pressure-resistant reaction vessel with hydrogen at a pressure of 15,000 pounds per square inch for a period of two hours at a temperature of 270 C. using 2 percent by weight, based on contained copper, of the supported catalyst described above. A methyl acetate conversion of 89.5 percent was obtained with an efiiciency to methanol and ethanol of 91.4 percent and 96.4 percent, respectively. The production ratio based on the methanol and ethanol recovered was equivalent to 175 pounds of product per cubic foot of catalyst volume per hour.
Example II Methyl acetate, as an 82 percent solution with methanol, was reacted in a pressure-resistant reaction vessel with hydrogen at a pressure of 10,000 pounds per square inch for a period of two hours and at a temperature of 270 C. using 3 percent by weight, based on contained copper, of the supported catalyst described above. A methyl acetate conversion of 81.8 percent was obtained with an efficiency to methanol and ethanol of 82.6 percent and 83.5 percent, respectively. The production ratio based on the combined Weight of methanol and ethanol produced was 90 pounds per cubic foot of supported catalyst per hour.
Example III Approximately 350 grams of ethyl propionate were heated to 290 C. in a pressure-resistant vessel in the presence of 125 grams of the supported copper-chrome catalyst described above and under an initial hydrogen pressure of 5300 pounds per square inch. A temperature of 290 C. and a pressure t 15,000 pounds per square inch were maintained for a period of one hour. After the vessel and its contents had been cooled, the crude reaction product was discharged. Distillation and analysis of the fractions showed an ethyl propionate conversion of 80.4 percent and an efficiency to ethanol and npropanol of 82.5 percent and 90.4 percent, respectively, based on the ethyl propionate charged. The production ratio based on the combined weight of ethanol and propanol produced was 125 pounds per cubic foot of supported catalyst per hour.
What is claimed is: t
1. A process for the production of alcohols from esters which comprises reacting a lower aliphatic ester with hydrogen under hydrogenating conditions in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and containing from 1 to 5 parts of chromium per parts of copper.
2. A process for the production of methanol and ethanol which comprises reacting methyl acetate with hydrogen under hydrogenating conditions in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and containing from 1 to 5 parts of chromium per 100 parts of copper.
3. A process for the production of ethanol and propanol which comprises reacting ethyl propionate with hydrogen under hydrogenating conditions in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and containing from 1 to 5 parts of chromium per 100 parts of copper.
4. A process of the production of alcohols from esters which comprises reacting a lower aliphatic ester with hydrogen at a temperature in the range 250 C. to 400 C. and a pressure in the range 5,000 to 15,000 pounds per square inch in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and containing from 1 to 5 parts of chromium per 100 parts of copper.
5. A process for the production of methanol and ethanol which comprises reacting methyl acetate with hydrogen at a temperature in the range 250 C. to 400 C. and a pressure in the range 5,000 to 15,000 pounds per square inch in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and containing from 1 to 5 parts of chromium per 100 parts of copper.
6. A process for the production of ethanol and propanol which comprises reacting ethyl propionate with hydrogen at a temperature in the range 250 C. to 400 C. and a pressure in the range 5,000 to 15,000 pounds per square inch in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and containing from 1 to 5 parts of chromium per 100 parts of copper.
7. In a process of hydrogenating a lower aliphatic ester to the corresponding alcohol, the improvement which comprises reacting the lower aliphatic ester with hydrogen at an elevated temperature and pressure in the presence of a catalyst consisting of copper oxide promoted with chromium oxide and containing from 1 to 5 parts of chromium per 100 parts of copper.
References Cited in the file of this patent UNITED STATES PATENTS 1,302,011 Christiansen Apr. 29, 1919 1,605,093 Bouvier et al. Nov. 2, 1926 1,977,750 Young Oct. 23, 1934 2,004,135 Rothrock June 11, 1935 2,040,944 Lazier May 9, 1936 2,079,414 Lazier May 4, 1937 2,091,800 Adkins Aug. 31,1937 2,544,771 Young et al. Mar. 13, 1951 2,575,403 Young et al. Nov. 20, 1951 FOREIGN PATENTS 844,891 Germany July 24, 1952 OTHER REFERENCES Adkins et al.: I. A. C. 8., vol. 72 (1950).

Claims (1)

1. A PROCESS FOR THE PRODUCTION OF ALCOHOLS FROM ESTERS WHICH COMPRISES REACTING A LOWER ALIPHATIC ESTER WITH HYDROGEN UNDER HYDROGENATING CONDITIONS IN THE PRESENCE OF A CATALYST CONSISTING OF COPPER OXIDE PROMOTED WITH CHROMIUM OXIDE AND CONTAINING FROM 1 TO 5 PARTS OF CHROMIUM PER 100 PARTS OF COPPER.
US419575A 1954-03-29 1954-03-29 Hydrogenation of esters Expired - Lifetime US2782243A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US419575A US2782243A (en) 1954-03-29 1954-03-29 Hydrogenation of esters

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US419575A US2782243A (en) 1954-03-29 1954-03-29 Hydrogenation of esters

Publications (1)

Publication Number Publication Date
US2782243A true US2782243A (en) 1957-02-19

Family

ID=23662840

Family Applications (1)

Application Number Title Priority Date Filing Date
US419575A Expired - Lifetime US2782243A (en) 1954-03-29 1954-03-29 Hydrogenation of esters

Country Status (1)

Country Link
US (1) US2782243A (en)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2965562A (en) * 1957-12-09 1960-12-20 Phillips Petroleum Co Hydrocracking hydrocarbon oils with a catalyst composite, comprising chromium sesquioxide and reduced cupric oxide
US3180898A (en) * 1961-04-17 1965-04-27 Metallgesellschaft Ag Process for the production of fatty alcohols by catalytic hydrogenation of fatty acids and their derivatives
US4199479A (en) * 1978-02-24 1980-04-22 Chevron Research Company Hydrogenation catalyst
EP0056488A3 (en) * 1981-01-21 1982-08-11 Basf Aktiengesellschaft Continuous process for the production of ethanol
US4398039A (en) * 1981-05-18 1983-08-09 The Standard Oil Company Hydrogenation of carboxylic acids
US4443639A (en) * 1981-05-18 1984-04-17 The Standard Oil Company (Indiana) Hydrogenation of carboxylic acids
US4990682A (en) * 1989-02-02 1991-02-05 Huels Ag Process for the preparation of 5-chloro-2-pentanone
US5134108A (en) * 1991-05-22 1992-07-28 Engelhard Corporation Process for preparing catalyst with copper or zinc and with chromium, molybdenum, tungsten, or vanadium, and product thereof
US5155086A (en) * 1989-09-12 1992-10-13 Engelhard Corporation Hydrogenation catalyst, process for preparing and process of using said catalyst
US5345005A (en) * 1989-09-12 1994-09-06 Engelhard Corporation Hydrogenation catalyst, process for preparing and process of using said catalyst
US20050256337A1 (en) * 2004-01-29 2005-11-17 Zeachem Inc. Recovery of organic acids
US20060019360A1 (en) * 1999-03-11 2006-01-26 Dan Verser Process for producing ethanol
US20080193989A1 (en) * 2007-02-09 2008-08-14 Zeachem, Inc. Energy Efficient Methods to Produce Products
US7507562B2 (en) 1999-03-11 2009-03-24 Zeachem, Inc. Process for producing ethanol from corn dry milling
US20090203098A1 (en) * 2008-02-07 2009-08-13 Zeachem, Inc. Indirect production of butanol and hexanol
US9109174B2 (en) 2011-09-20 2015-08-18 Phillips 66 Company Advanced cellulosic renewable fuels
US10513715B2 (en) 2015-09-24 2019-12-24 Iogen Corporation Wet oxidation of biomass

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1302011A (en) * 1918-12-06 1919-04-29 Jens Anton Christiansen Method of producing methyl alcohol from alkyl formates.
US1605093A (en) * 1923-08-07 1926-11-02 Ste Chim Usines Rhone Process for the reduction of alkyl esters
US1977750A (en) * 1931-12-07 1934-10-23 Carbide & Carbon Chem Corp Process for making acetaldehyde and a catalyst therefor
US2004135A (en) * 1932-12-23 1935-06-11 Du Pont Production of polyhydric alcohols
US2040944A (en) * 1933-09-22 1936-05-19 Du Pont Process for producing polyhydroxy alcohols
US2079414A (en) * 1932-08-20 1937-05-04 Du Pont Process for producing alcohols from esters of nonaromatic carboxylic acids
US2091800A (en) * 1931-09-15 1937-08-31 Rohm & Haas Method of hydrogenating esters
US2544771A (en) * 1943-10-14 1951-03-13 Union Carbide & Carbon Corp Copper-chromium hydrogenation catalyst
US2575403A (en) * 1943-10-14 1951-11-20 Union Carbide & Carbon Corp Catalytic hydrogenation of acetophenone to phenyl methyl carbinol
DE844891C (en) * 1944-07-19 1952-07-24 Basf Ag Process for the preparation of primary alcohols

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1302011A (en) * 1918-12-06 1919-04-29 Jens Anton Christiansen Method of producing methyl alcohol from alkyl formates.
US1605093A (en) * 1923-08-07 1926-11-02 Ste Chim Usines Rhone Process for the reduction of alkyl esters
US2091800A (en) * 1931-09-15 1937-08-31 Rohm & Haas Method of hydrogenating esters
US1977750A (en) * 1931-12-07 1934-10-23 Carbide & Carbon Chem Corp Process for making acetaldehyde and a catalyst therefor
US2079414A (en) * 1932-08-20 1937-05-04 Du Pont Process for producing alcohols from esters of nonaromatic carboxylic acids
US2004135A (en) * 1932-12-23 1935-06-11 Du Pont Production of polyhydric alcohols
US2040944A (en) * 1933-09-22 1936-05-19 Du Pont Process for producing polyhydroxy alcohols
US2544771A (en) * 1943-10-14 1951-03-13 Union Carbide & Carbon Corp Copper-chromium hydrogenation catalyst
US2575403A (en) * 1943-10-14 1951-11-20 Union Carbide & Carbon Corp Catalytic hydrogenation of acetophenone to phenyl methyl carbinol
DE844891C (en) * 1944-07-19 1952-07-24 Basf Ag Process for the preparation of primary alcohols

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2965562A (en) * 1957-12-09 1960-12-20 Phillips Petroleum Co Hydrocracking hydrocarbon oils with a catalyst composite, comprising chromium sesquioxide and reduced cupric oxide
US3180898A (en) * 1961-04-17 1965-04-27 Metallgesellschaft Ag Process for the production of fatty alcohols by catalytic hydrogenation of fatty acids and their derivatives
US4199479A (en) * 1978-02-24 1980-04-22 Chevron Research Company Hydrogenation catalyst
EP0056488A3 (en) * 1981-01-21 1982-08-11 Basf Aktiengesellschaft Continuous process for the production of ethanol
US4454358A (en) * 1981-01-21 1984-06-12 Basf Aktiengesellschaft Continuous production of ethanol and plural stage distillation of the same
US4398039A (en) * 1981-05-18 1983-08-09 The Standard Oil Company Hydrogenation of carboxylic acids
US4443639A (en) * 1981-05-18 1984-04-17 The Standard Oil Company (Indiana) Hydrogenation of carboxylic acids
US4990682A (en) * 1989-02-02 1991-02-05 Huels Ag Process for the preparation of 5-chloro-2-pentanone
US5155086A (en) * 1989-09-12 1992-10-13 Engelhard Corporation Hydrogenation catalyst, process for preparing and process of using said catalyst
US5345005A (en) * 1989-09-12 1994-09-06 Engelhard Corporation Hydrogenation catalyst, process for preparing and process of using said catalyst
US5134108A (en) * 1991-05-22 1992-07-28 Engelhard Corporation Process for preparing catalyst with copper or zinc and with chromium, molybdenum, tungsten, or vanadium, and product thereof
US6054627A (en) * 1991-05-22 2000-04-25 Engelhard Corporation Hydrogenation catalyst, process for preparing and process of using said catalyst
EP2011879A2 (en) 1999-03-11 2009-01-07 Zeachem, Inc. Process for producing ethanol
US8236534B2 (en) 1999-03-11 2012-08-07 Zeachem, Inc. Process for producing ethanol
US7351559B2 (en) 1999-03-11 2008-04-01 Zeachem, Inc. Process for producing ethanol
US20060019360A1 (en) * 1999-03-11 2006-01-26 Dan Verser Process for producing ethanol
US7964379B2 (en) 1999-03-11 2011-06-21 Zeachem, Inc. Process for producing ethanol
US20090023192A1 (en) * 1999-03-11 2009-01-22 Zeachem, Inc. Process for Producing Ethanol
US7507562B2 (en) 1999-03-11 2009-03-24 Zeachem, Inc. Process for producing ethanol from corn dry milling
US20090081749A1 (en) * 1999-03-11 2009-03-26 Verser Dan W Process for producing ethanol from corn dry milling
US7888082B2 (en) 1999-03-11 2011-02-15 Zeachem, Inc. Process for producing ethanol from corn dry milling
US20100273229A1 (en) * 1999-03-11 2010-10-28 Zeachem, Inc. Process for producing ethanol
US7682812B2 (en) 1999-03-11 2010-03-23 Zeachem, Inc. Process for producing ethanol
US20100187472A1 (en) * 2004-01-29 2010-07-29 Zeachem, Inc. Recovery of organic acids
US7601865B2 (en) 2004-01-29 2009-10-13 Zeachem, Inc. Recovery of organic acids
US20050256337A1 (en) * 2004-01-29 2005-11-17 Zeachem Inc. Recovery of organic acids
US8048655B2 (en) 2004-01-29 2011-11-01 Zeachem, Inc. Recovery of organic acids
US20080193989A1 (en) * 2007-02-09 2008-08-14 Zeachem, Inc. Energy Efficient Methods to Produce Products
US8329436B2 (en) 2007-02-09 2012-12-11 Zeachem, Inc. Method of making propanol and ethanol from plant material by biological conversion and gasification
US20090203098A1 (en) * 2008-02-07 2009-08-13 Zeachem, Inc. Indirect production of butanol and hexanol
US8252567B2 (en) 2008-02-07 2012-08-28 Zeachem, Inc. Method for the indirect production of butanol and hexanol
US9109174B2 (en) 2011-09-20 2015-08-18 Phillips 66 Company Advanced cellulosic renewable fuels
US10513715B2 (en) 2015-09-24 2019-12-24 Iogen Corporation Wet oxidation of biomass

Similar Documents

Publication Publication Date Title
US4268695A (en) Process for the continuous preparation of butane-1,4-diol
US2542767A (en) Organic ester synthesis
US2137407A (en) Catalytic hydrogenation process
US2079414A (en) Process for producing alcohols from esters of nonaromatic carboxylic acids
JPS588073A (en) Method for producing 5-alkylbutyrolactone
KR19980703190A (en) Process for preparing 1,4-butanediol and tetrahydrofuran from furan
US3028417A (en) Process of making hydroxy ester compounds
US2105664A (en) Catalytic hydrogenation of hydroaromatic carboxylic acids and their esters
EP0329337A2 (en) The production of formic acid from a nitrogenous base, carbon dioxide and hydrogen
US3344196A (en) Hydrogenation of alkanoic dicarboxylic acids using sintered cobalt catalyst
US2918497A (en) Production of phenoxyacetaldehyde
US3535371A (en) Process for the preparation of acrylic esters
EP0239993B1 (en) A process of reduction of aldehydes and ketones
US2004350A (en) Condensation of alcohols
US2457204A (en) Synthesis of esters
US2617835A (en) Polyhydric alcohol process
US2511467A (en) Ester hydrolysis
US3213145A (en) Catalytic hydrogenation of esters of aromatic monocarboxylic acids to aryl-substituted methanols
US3440276A (en) Process for preparing acrylic esters
US3022338A (en) Process for the production of unsaturated monocarboxylic acid esters
US2920081A (en) Production of 2, 5-dialkoxy-tetrahydrofuran
US2908722A (en) Process for preparing saturated monohydric alcohols
US3313843A (en) Preparation of cinnamate esters
US3141036A (en) Cyclohexane carboxylic acid produced by hydrogenation of molten benzoic acid
US2053845A (en) Production of aldehydes