Methanol homologation using iron-cobalt carbonyl cluster catalyst

Claim 2

A process for the homogeneous catalytic conversion of methanol to ethanol, acetaldehyde or mixtures thereof which comprises: (a) contacting methanol with carbon monoxide and hydrogen at a hydrogen to carbon monoxide mole ratio of from 1:10 to 10:1 in the presence of a catalytically effective amount of an iron-cobalt carbonyl cluster complex and an effective amount of an iodide promoter; and (b) heating the mixture of step (a) to a temperature of about 100° to 250° C. at a pressure of from 5 to 100 MPa.

Claim 3

The process of claim 1 wherein the iron-cobalt carbonyl cluster complex has the formula M[FeCo.sub.3 (CO).sub.12 ] or M[CoFe.sub.3 (CO).sub.13 ] wherein M is hydrogen, alkali metal cation, (C 6 H 5 ) 3 PNP(C 6 H 5 ) 3 .sup.⊕, salts of C 3 to C 9 heterocyclic ring compounds containing nitrogen, R 1 R 2 R 3 R 4 N.sup.⊕, R 1 R 2 R 3 R 4 P.sup.⊕ or R 1 R 2 R 3 R 4 As.sup.⊕ wherein R 1 to R 4 are each hydrogen, C 1 to C 20 alkyl, C 3 to C 8 cycloalkyl, benzyl, phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen.

Claim 4

The process of claim 1 wherein the iron-cobalt carbonyl complex is (C 4 H 9 ) 4 N[FeCo 3 (CO) 12 ].

Claim 5

The process of claim 1 wherein the concentration of iron-cobalt carbonyl complex is from 0.0001 M to 0.1 M.

Claim 6

The process of claim 1 wherein the temperature is from 140° to 220° C.

Claim 7

The process of claim 1 wherein the promoter is at least one of alkyl iodide, hydrogen iodide, tetraalkylammonium iodide, tetraalkyl phosphonium iodide, tetraphenyl phosphonium iodide, tetraalkyl arsonium iodide or tetraphenyl arsonium iodide.

Claim 8

The process of claim 1 wherein the ratio of moles of iodide to gram atoms of iron plus cobalt is from 0.5:1 to 100:1.

Claim 9

The process of claim 1 wherein the reaction is heated from 0.1 to 24 hours.

Claim 10

The process of claim 1 wherein the ethanol is the product and the mole ratio of hydrogen to carbon monoxide is from 1.5:1 to 3:1.

Claim 11

The process of claim 9 wherein the temperature is from about 200° to 220° C.

Claim 12

The process of claim 9 wherein the mixture is heated for from 3 to 6 hours.

Claim 13

The process of claim 1 wherein the product is acetaldehyde and the hydrogen to carbon monoxide ratio is from 0.5:1 to 1:1.

Claim 14

The process of claim 12 wherein the temperature is from about 140° to 200° C.

Claim 15

The process of claim 12 wherein the mixture is heated for from 1 to 3 hours.

Claim 16

The process of claim 2 wherein the iron-cobalt carbonyl complex is generated in situ from iron and cobalt compounds capable of forming the iron-cobalt carbonyl complex in the presence of an M cation.

Claim 17

A process for the homogeneous catalytic conversion of methanol to ethanol, acetaldehyde or mixtures thereof which comprises: (a) contacting methanol with carbon monoxide and hydrogen at a hydrogen to carbon monoxide mole ratio of from 1:10 to 10:1 in the presence of a catalytically effective amount of an iron-cobalt carbonyl cluster complex of the formula M[FeCo.sub.3 (CO).sub.12 ] wherein M is alkali metal cation, (C 6 H 5 ) 3 PNP(C 6 H 5 ) 3 .sup.⊕, salts of C 3 to C 9 heterocyclic ring compounds containing nitrogen R 1 R 2 R 3 R 4 N.sup.⊕, R 1 R 2 R 3 R 4 P.sup.⊕ or R 1 R 2 R 3 R 4 As.sup.⊕ where R 1 to R 4 are each hydrogen, C 1 to C 20 alkyl, C 3 to C 8 cycloalkyl, benzyl, phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen and an effective amount of an iodide promoter; and (b) heating the mixture of step (a) to a temperature of about 100° to 250° C. at a pressure of from 5 to 100 MPa.

Claim 18

A process for the homogeneous catalytic conversion of methanol to ethanol, acetaldehyde or mixtures thereof which comprises: (a) contacting methanol with carbon monoxide and hydrogen at a hydrogen to carbon monoxide mole ratio of from 1:10 to 10:1 in the presence of a catalytically effective amount of an iron-cobalt carbonyl cluster complex of the formula M[FeCo.sub.3 (CO).sub.12 ] wherein M is alkali metal cation, (C 6 H 5 ) 3 PNP(C 6 H 5 ) 3 .sup.⊕, salts of C 3 to C 9 heterocyclic ring compounds containing nitrogen R 1 R 2 R 3 R 4 N.sup.⊕, R 1 R 2 R 3 R 4 P.sup.⊕ or R 1 R 2 R 3 R 4 As.sup.⊕ where R 1 to R 4 are each hydrogen, C 1 to C 20 alkyl, C 3 to C 8 cycloalkyl, benzyl, phenyl or phenyl substituted by lower alkyl, lower alkoxy or halogen and an effective amount of an iodide promoter; and (b) heating the mixture of step (a) to a temperature of about 100° to 250° C. at a pressure of from 5 to 100 MPa.

Claim 19

A process for the homogeneous catalytic conversion of methanol to ethanol, acetaldehyde or mixtures thereof which comprises: (a) contacting methanol with carbon monoxide and hydrogen at a hydrogen to carbon monoxide mole ratio of from 1:10 to 10:1 in the presence of a catalytically effective amount of (C 4 H 9 ) 4 N[FeCo 3 (CO) 12 ] and an effective amount of an iodide promoter; and (b) heating the mixture of step (a) to a temperature of about 100° to 250° C. at a pressure of from 5 to 100 MPa.

Claim 20

A process for the homogeneous catalytic conversion of methanol to ethanol, acetaldehyde or mixtures thereof which comprises: (a) contacting methanol with carbon monoxide and hydrogen at a hydrogen to carbon monoxide mole ratio of from 1:10 to 10:1 in the presence of a catalytically effective amount of (C 4 H 9 ) 4 N[FeCo 3 (CO) 12 ] and an effective amount of an iodide promoter; and (b) heating the mixture of step (a) to a temperature of about 100° to 250° C. at a pressure of from 5 to 100 MPa.