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US2776323A - Higher fatty alcohols - Google Patents

Higher fatty alcohols Download PDF

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US2776323A
US2776323A US2776323DA US2776323A US 2776323 A US2776323 A US 2776323A US 2776323D A US2776323D A US 2776323DA US 2776323 A US2776323 A US 2776323A
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higher fatty
hydrogenation
ester
catalyst
fat
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C27/00Processes involving the simultaneous production of more than one class of oxygen-containing compounds
    • C07C27/04Processes involving the simultaneous production of more than one class of oxygen-containing compounds by reduction of oxygen-containing compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132Preparation 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
    • C07C29/136Preparation 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
    • C07C29/147Preparation 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
    • C07C29/149Preparation 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02Monohydroxylic acyclic alcohols
    • C07C31/125Monohydroxylic acyclic alcohols containing five to twenty-two carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/03Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/22Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/24Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with monohydroxylic compounds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom

Definitions

  • Patent 1,839,974 such metals as cadmium, silver, tin and their oxides, as well as the oxides of zinc, chromium, magnesium and manganese; and the ruthenium-containing hydrogenation catalysts as described in U. S. Patent 2,607,807.
  • Hydrogenation can be effected at a temperature within about the range of 400 to 700 F. and pressures within about the range of 500 to 5000 pounds, for a period of time varying from a few minutes and longer, e. g., 60 minutes, with about /2% to of catalyst based on the ester, the catalyst being suspended in the ester or employed in fixed bed over which the ester is passed.
  • the fat e. g., tallow containing the ester interchange catalyst, e. g., litharge
  • the higher fatty alcohol e. g., tallow alcohol produced in a subsequent step of the process, hereinafter to be shown, near the bottom.
  • the ester interchange reaction occurs with the tallow alcohol distilling up the column forming glycerine and the tallow acid-tallow alcohol ester.
  • reaction temperature e' g., 400 F.
  • glycerine, and excess tallow alcohol are distilled into a separator where two easily separable phases of tallow alcohol and glycerine are formed, hydrogen gas being circulated through the reactor to maintain the partial pressure necessary to distill the alcohol and glycerine at the reaction temperature.
  • the tallow acid-tallow alcohol ester collects at the base I interchange zone, and the ester passed into the hydrogenation zone.
  • Catalyst e. g., copper chromite
  • Catalyst is contacted with incoming ester and hydrogen introduced near the bottom of the hydrogenation zone, and the tallow acid-tallow alcohol ester hydrogenated under the conditions hereinabove given.
  • catalyst is removed from the hydrogenation products and returned to the hydrogenation zone with any catalyst makeup.
  • the hydrogenation products containing higher fatty alcohol are conducted to the ester interchange zone for use in the ester interchange reaction earlier described.
  • Process for the production of higher fatty alcohols which comprises contacting a fat with a higher fatty alcohol under transesterifying conditions in a distillation zone, withdrawing an overhead fraction comprising fatty alcohol and glycerine and a bottoms fraction comprising a higher fatty alcohol ester of a fatty acid from the distillation zone, contacting the bottoms fraction with hydrogen in the presence of a hydrogenation catalyst under hydrogenating conditions in a hydrogenation zone and passing the hydrogenation reaction product into the distillation zone together with further quantities of fat.
  • Process for the production of higher fatty alcohols which comprises heating a fat with a stoichiometric excess of a higher fatty alcohol in a distillation zone at a temperature between about 300 and 600 F. under reduced pressure in the presence of an ester interchange catalyst, withdrawing an overhead fraction comprising fatty alcohol and glycerine and a bottoms fraction comprising a higher fatty alcohol ester of a fatty acid from the distillation zone, contacting the bottoms fraction with a hydrogenation catalyst at elevated temperatures and pressures to produce a hydrogenation product containing the higher fatty alcohols, and passing said hydrogenation product into the distillation zone together with further quantities of fat.
  • Process for the production of higher fatty alcohols which comprises contacting a fat with a higher fatty alcohol under transesterifying conditions, fractionally distilling the transesterification reaction product to separate glycerine and fatty alcohol overhead and to produce a bottoms fraction rich in fatty alcohol ester of fatty acid, contacting the bottoms fraction with hydrogen in the presence of a hydrogenation catalyst under hydrogenating conditions and then contacting at least a major proportion of the hydrogenation reaction product with further quantities of fat under transesterifying conditions.

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

Description

Jan. 1, 1957 w. e. TOLAND ET AL 2,776,323
HIGHER FATTY ALCOHOLS Filed July 5, 1955 ALCOHOL HYDROGEN SEPARATOR FAT w 3 z I. CC I CATALYST 3 5 ESTER 0 INTERCHANGE J SEPARATOR U D Q g CATALYST RECYCLE Z 0 p CATALYST Z U O O (I 2 CATALYST z: HYDROGENATION HYDROGEN ,5 SEPARATOR i INVENTORS WILL/AM G. TOLAND IRVING E. LEV/NE ATTORNEYS for example in U. S. Patent 1,839,974; such metals as cadmium, silver, tin and their oxides, as well as the oxides of zinc, chromium, magnesium and manganese; and the ruthenium-containing hydrogenation catalysts as described in U. S. Patent 2,607,807.
Hydrogenation can be effected at a temperature within about the range of 400 to 700 F. and pressures within about the range of 500 to 5000 pounds, for a period of time varying from a few minutes and longer, e. g., 60 minutes, with about /2% to of catalyst based on the ester, the catalyst being suspended in the ester or employed in fixed bed over which the ester is passed.
In order to illustrate the practice of the invention reference is made to the accompanying drawing which is a schematic block diagram showing the zones of ester interchange, hydrogenation, separation and recycle of hydrogenation products and catalyst.
Referring now to the drawing, the fat, e. g., tallow containing the ester interchange catalyst, e. g., litharge, is fed to the top of the ester interchange zone, and the higher fatty alcohol, e. g., tallow alcohol produced in a subsequent step of the process, hereinafter to be shown, near the bottom. As the fat travels down the ester interchange zone, under interchange conditions hereinabove described, the ester interchange reaction occurs with the tallow alcohol distilling up the column forming glycerine and the tallow acid-tallow alcohol ester. At the reaction temperature, e' g., 400 F., glycerine, and excess tallow alcohol are distilled into a separator where two easily separable phases of tallow alcohol and glycerine are formed, hydrogen gas being circulated through the reactor to maintain the partial pressure necessary to distill the alcohol and glycerine at the reaction temperature.
The tallow acid-tallow alcohol ester collects at the base I interchange zone, and the ester passed into the hydrogenation zone. Catalyst, e. g., copper chromite, is contacted with incoming ester and hydrogen introduced near the bottom of the hydrogenation zone, and the tallow acid-tallow alcohol ester hydrogenated under the conditions hereinabove given. Following hydrogenation, catalyst is removed from the hydrogenation products and returned to the hydrogenation zone with any catalyst makeup. The hydrogenation products containing higher fatty alcohol are conducted to the ester interchange zone for use in the ester interchange reaction earlier described.
Obviously many modifications and variations of the invention, as hereinbefore set forth, may be made without departing from the spirit and scope thereof and, therefore, only such limitations should be imposed as are indicated in the appended claims.
We claim:
1. Process for the production of higher fatty alcohols which comprises contacting a fat with a higher fatty alcohol under transesterifying conditions in a distillation zone, withdrawing an overhead fraction comprising fatty alcohol and glycerine and a bottoms fraction comprising a higher fatty alcohol ester of a fatty acid from the distillation zone, contacting the bottoms fraction with hydrogen in the presence of a hydrogenation catalyst under hydrogenating conditions in a hydrogenation zone and passing the hydrogenation reaction product into the distillation zone together with further quantities of fat.
2. Process according to claim 1 wherein the hydrogenation catalyst is a copper chromite.
3. Process for the production of higher fatty alcohols which comprises heating a fat with a stoichiometric excess of a higher fatty alcohol in a distillation zone at a temperature between about 300 and 600 F. under reduced pressure in the presence of an ester interchange catalyst, withdrawing an overhead fraction comprising fatty alcohol and glycerine and a bottoms fraction comprising a higher fatty alcohol ester of a fatty acid from the distillation zone, contacting the bottoms fraction with a hydrogenation catalyst at elevated temperatures and pressures to produce a hydrogenation product containing the higher fatty alcohols, and passing said hydrogenation product into the distillation zone together with further quantities of fat.
4. Process according to claim 3 wherein the bottoms fraction is contacted with a hydrogenation catalyst at a temperature within the range of 400 F. to 700 F. and at pressure within about the range of 500 to 5000 pounds.
5. Process according to claim 4 wherein the ester interchange catalyst is litharge.
6. Process according to claim 3 wherein the hydrogenation catalyst is a copper chromite.
7. Process according to claim 6 wherein the fat is tallow.
8. Process according to claim 7 wherein the fatty alcohol and fat is introduced into the interchange zone in a mole ratio of from greater than 3 to 1 up to 7 to l.
9. Process for the production of higher fatty alcohols which comprises contacting a fat with a higher fatty alcohol under transesterifying conditions, fractionally distilling the transesterification reaction product to separate glycerine and fatty alcohol overhead and to produce a bottoms fraction rich in fatty alcohol ester of fatty acid, contacting the bottoms fraction with hydrogen in the presence of a hydrogenation catalyst under hydrogenating conditions and then contacting at least a major proportion of the hydrogenation reaction product with further quantities of fat under transesterifying conditions.
No references cited.

Claims (1)

1. PROCESS FOR THE PRODUCTION OF HIGHER FATTY ALCOHOLS WHICH COMPRISES CONTACTING A FAT WITH A HIGHER FATTY ALCOHOL UNDER TRANSESTERIFYING CONDITIONS IN A DISTILLATION ZONE, WITHDRAWING AN OVERHEAD FRACTION COMPRISING FATTY ALCOHOL AND GLYCERINE AND A BOTTOMS FRACTION COMPRISING A HIGHER FATTY ALCOHOL ESTER OF A FATTY ACID FROM THE DISTILLATION ZONE, CONTACATING THE BOTTOMS FRACTION WITH HYDROGEN IN THE PRESENCE OF A HYDROGENATION CATALYST UNDER HYDROGENATING CONDITIONS IS A HYDROGERNATION ZONE AND PASSING THE HYDROGENATION REACTAION PRODUCT INTO THE DISTILLATION ZONE TOGETHER WITH FURTHER QUANTITIES OF FAT.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3180881A (en) * 1959-09-11 1965-04-27 Ziegler Karl Transalkylation of aluminum and boron alkyl compounds
US3859368A (en) * 1971-09-08 1975-01-07 Halcon International Inc Method of producing polyhydric compounds such as ethylene glycol by disproportionation of its monoacetate
US3949007A (en) * 1969-08-01 1976-04-06 Bayer Aktiengesellschaft Process for the production of primary alkenols
US3968175A (en) * 1971-09-08 1976-07-06 Halcon International, Inc. Method of producing polyhydric compounds
US3968174A (en) * 1971-09-08 1976-07-06 Halcon International, Inc. Method of producing polyhydric compounds
US5266716A (en) * 1991-12-19 1993-11-30 Bayer Aktiengesellschaft Process for the splitting of polycarbonates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3180881A (en) * 1959-09-11 1965-04-27 Ziegler Karl Transalkylation of aluminum and boron alkyl compounds
US3949007A (en) * 1969-08-01 1976-04-06 Bayer Aktiengesellschaft Process for the production of primary alkenols
US3859368A (en) * 1971-09-08 1975-01-07 Halcon International Inc Method of producing polyhydric compounds such as ethylene glycol by disproportionation of its monoacetate
US3968175A (en) * 1971-09-08 1976-07-06 Halcon International, Inc. Method of producing polyhydric compounds
US3968174A (en) * 1971-09-08 1976-07-06 Halcon International, Inc. Method of producing polyhydric compounds
US5266716A (en) * 1991-12-19 1993-11-30 Bayer Aktiengesellschaft Process for the splitting of polycarbonates
EP0547479A3 (en) * 1991-12-19 1994-10-19 Bayer Ag Process for cracking polycarbonates

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