Methanol homologation using cobalt-ruthenium catalysts

Claim 2

A process for the homogeneous conversion of methanol to acetaldehyde, ethanol or mixtures thereof which comprises contacting methanol with carbon monoxide and hydrogen in a CO:H 2 ratio of from 10:1 to 1:10 at a temperature of from about 100° to 300° C. and a pressure of from about 2 to 100 MPa in the presence of a catalytically effective amount of a catalyst system, said catalyst system consisting essentially of: (a) cobalt-ruthenium complexes selected from the group consisting of HRuCo 3 (CO) 12 , M[RuCo 3 (CO) 12 ], HCoRu 3 (CO) 13 , M[CoRu 3 (CO) 13 ] and C 5 H 5 Ru(Pφ 3 ) 2 Co(CO) 4 where M is a cation; (b) an iodine or iodide promoter; and (c) a phosphorus compound of the formula PR 3 or P(OR) 3 where R is independently a C 1 to C 20 aliphatic radical, C 6 to C 10 aryl, aralkyl having from 1 to 6 carbon atoms in the alkyl or C 3 to C 8 cycloalkyl, with the proviso that if either the ruthenium or cobalt in component (a) bears a PR 3 or P(OR) 3 ligand, component (c) may be omitted.

Claim 3

The process of claim 1 wherein component (a) is C 5 H 5 Ru(Pφ 3 ) 2 Cl plus Co 2 (CO) 8 .

Claim 4

The process of claim 1 wherein component (a) is C 5 H 5 Ru(Pφ 3 ) 2 Co(CO) 4 .

Claim 5

The process of claim 1 wherein the concentration of component (a) is from 0.00001 M to 0.1 M.

Claim 6

The process of claim 1 wherein the temperature is from 140° to 230° C.

Claim 7

The process of claim 1 wherein the pressure is from 15 to 60 MPa.

Claim 8

The process of claim 1 wherein component (b) is at least one of hydrogen iodide, methyl iodide, tetraalkyl ammonium iodide or tetraphenyl phosphonium iodide.

Claim 9

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

Claim 10

A process for the homogeneous conversion of methanol to acetaldehyde, ethanol or mixtures thereof which comprises contacting methanol with carbon monoxide and hydrogen in a CO:H 2 ratio of from 10:1 to 1:10 at a temperature of from about 100° to 300° C. and a pressure of from about 2 to 100 MPa in the presence of a catalytically effective amount of a catalyst system, said catalyst system consisting essentially of: (a) cobalt-ruthenium complexes selected from the group consisting of HRuCo 3 (CO) 12 , M[RuCo 3 (CO) 12 ], HCoRu 3 (CO) 13 , M[CoRu 3 (CO) 13 ] and C 5 H 5 Ru(Pφ 3 ) 2 Co(CO) 4 where M is a cation selected from the group consisting of alkali metal, NR 1 R 2 R 3 R 4 .sup.⊕, PR 1 R 2 R 3 R 4 .sup.⊕ and φ 2 PNPφ 2 where R 1 to R 4 are independently hydrogen C 1 to C 20 alkyl, C 3 to C 8 cycloalkyl, benzyl, phenyl or phenyl substituted by C 1 to C 6 alkyl, C 1 -C 6 alkoxy or halogen; (b) an iodine or iodide promoter; and (c) a phosphorus compound of the formula PR 3 or P(OR) 3 where R is independently a C 1 to C 20 aliphatic radical, C 6 to C 10 aryl, aralkyl having from 1 to 6 carbon atoms in the alkyl, C 3 to C 8 cycloalkyl, with the proviso that if the ruthenium in component (a) bears a PR 3 or P(OR) 3 ligand, component (c) may be omitted.

Claim 11

A process for the homogeneous conversion of methanol to acetaldehyde, ethanol or mixtures thereof which comprises contacting methanol with carbon monoxide and hydrogen in a CO:H 2 ratio of from 10:1 to 1:10 at a temperature of from about 100° to 300° C. and a pressure of from about 2 to 100 MPa in the presence of a catalytically effective amount of a catalyst system, said catalyst system consisting essentially of: (a) cobalt-ruthenium complexes selected from the group consisting of HRuCo 3 (CO) 12 , M[RuCo 3 (CO) 12 ], HCoRu 3 (CO) 13 , M[CoRu 3 (CO) 13 ] and C 5 H 5 Ru(Pφ 3 ) 2 Co(CO) 4 where M is a cation selected from the group consisting of alkali metal, NR 1 R 2 R 3 R 4 .sup.⊕, PR 1 R 2 R 3 R 4 .sup.⊕ and φ 2 PNPφ 2 where R 1 to R 4 are independently hydrogen C 1 to C 20 alkyl, C 3 to C 8 cycloalkyl, benzyl, phenyl or phenyl substituted by C 1 to C 6 alkyl, C 1 -C 6 alkoxy or halogen; (b) an iodine or iodide promoter; and (c) a phosphorus compound of the formula PR 3 or P(OR) 3 where R is independently a C 1 to C 20 aliphatic radical, C 6 to C 10 aryl, aralkyl having from 1 to 6 carbon atoms in the alkyl, C 3 to C 8 cycloalkyl, with the proviso that if the ruthenium in component (a) bears a PR 3 or P(OR) 3 ligand, component (c) may be omitted.

Claim 12

A process for the homogeneous conversion of methanol to acetaldehyde, ethanol or mixtures thereof which comprises contacting methanol with carbon monoxide and hydrogen in a CO:H 2 ratio of from 10:1 to 1:10 at a temperature of from about 100° to 300° C. and a pressure of from about 2 to 100 MPa in the presence of a catalytically effective amount of a catalyst system, said catalyst system consisting essentially of: (a) a soluble ruthenium compound selected from the group consisting of (C 5 H 5 )Ru(Pφ 3 ) 2 Cl, Ru(acetylacetonate) 3 , Ru(acetylacetonate)(CO) 2 , Ru(CO) 3 (Pφ 3 ) 2 and Ru 3 (CO) 12 plus Co 2 CO 8 ; (b) an iodine or iodide promoter; and (c) a phosphorus compound of the formula PR 3 or P(OR) 3 where R is independently a C 1 to C 20 aliphatic radical, C 6 to C 10 aryl, aralkyl having from 1 to 6 carbon atoms in the alkyl, C 3 to C 8 cycloalkyl, with the proviso that if the ruthenium in component (a) bears a PR 3 or P(OR) 3 ligand, component (c) may be omitted.

Claim 13

A process for the homogeneous conversion of methanol to acetaldehyde, ethanol or mixtures thereof which comprises contacting methanol with carbon monoxide and hydrogen in a CO:H 2 ratio of from 10:1 to 1:10 at a temperature of from about 100° to 300° C. and a pressure of from about 2 to 100 MPa in the presence of a catalytically effective amount of a catalyst system, said catalyst system consisting essentially of: (a) a soluble ruthenium compound selected from the group consisting of (C 5 H 5 )Ru(Pφ 3 ) 2 Cl, Ru(acetylacetonate) 3 , Ru(acetylacetonate)(CO) 2 , Ru(CO) 3 (Pφ 3 ) 2 and Ru 3 (CO) 12 plus Co 2 CO 8 ; (b) an iodine or iodide promoter; and (c) a phosphorus compound of the formula PR 3 or P(OR) 3 where R is independently a C 1 to C 20 aliphatic radical, C 6 to C 10 aryl, aralkyl having from 1 to 6 carbon atoms in the alkyl, C 3 to C 8 cycloalkyl, with the proviso that if the ruthenium in component (a) bears a PR 3 or P(OR) 3 ligand, component (c) may be omitted.

Claim 14

A process for the homogeneous conversion of methanol to acetaldehyde, ethanol or mixtures thereof which comprises contacting methanol with carbon monoxide and hydrogen in a CO:H 2 ratio of from 10:1 to 1:10 at a temperature of from about 100° to 300° C. and a pressure of from about 2 to 100 MPa in the presence of a catalytically effective amount of a catalyst system, said catalyst system consisting essentially of: (a) (C 5 H 5-p R 6 p )Ru(L) 2 Co(CO) 4-m where R 6 is C 1 -C 6 alkyl, L is PR 3 , CO or P(OR) 3 where each R is independently C 1 -C 20 aliphatic radical, C 6 -C 10 aryl, aralkyl having from 1 to 6 carbon atoms in the alkyl or C 3 -C 8 cycloalkyl, p is a number from 0 to 5 and m is a number from 0 to 3; (b) an iodine or iodide promoter; and (c) a phosphorus compound of the formula PR 3 or P(OR) 3 , R being defined above, with the proviso that if the ruthenium in component (a) bears a PR 3 or P(OR) 3 ligand, component (c) may be omitted.

Claim 15

A process for the homogeneous conversion of methanol to acetaldehyde, ethanol or mixtures thereof which comprises contacting methanol with carbon monoxide and hydrogen in a CO:H 2 ratio of from 10:1 to 1:10 at a temperature of from about 100° to 300° C. and a pressure of from about 2 to 100 MPa in the presence of a catalytically effective amount of a catalyst system, said catalyst system consisting essentially of: (a) (C 5 H 5-p R 6 p )Ru(L) 2 Co(CO) 4-m where R 6 is C 1 -C 6 alkyl, L is PR 3 , CO or P(OR) 3 where each R is independently C 1 -C 20 aliphatic radical, C 6 -C 10 aryl, aralkyl having from 1 to 6 carbon atoms in the alkyl or C 3 -C 8 cycloalkyl, p is a number from 0 to 5 and m is a number from 0 to 3; (b) an iodine or iodide promoter; and (c) a phosphorus compound of the formula PR 3 or P(OR) 3 , R being defined above, with the proviso that if the ruthenium in component (a) bears a PR 3 or P(OR) 3 ligand, component (c) may be omitted.

Claim 16

The process of claim 11 wherein component (a) is (C 5 H 5 )Ru(Pφ 3 ) 2 Co(CO) 4 .

Claim 17

A process for the homogeneous conversion of methanol to acetaldehyde, ethanol or mixtures thereof which comprises contacting methanol with carbon monoxide and hydrogen in a CO:H 2 ratio of from 10:1 to 1:10 at a temperature of from about 100° to 300° C. and a pressure of from about 2 to 100 MPa in the presence of a catalytically effective amount of a catalyst system, said catalyst system consisting essentially of: (a) C 5 H 5 Ru(Pφ 3 ) 2 Cl plus Co 2 (CO) 8 ; and (b) an iodine or iodide promoter.

Claim 18

A process for the homogeneous conversion of methanol to acetaldehyde, ethanol or mixtures thereof which comprises contacting methanol with carbon monoxide and hydrogen in a CO:H 2 ratio of from 10:1 to 1:10 at a temperature of from about 100° to 300° C. and a pressure of from about 2 to 100 MPa in the presence of a catalytically effective amount of a catalyst system, said catalyst system consisting essentially of: (a) C 5 H 5 Ru(Pφ 3 ) 2 Cl plus Co 2 (CO) 8 ; and (b) an iodine or iodide promoter.

Claim 19

A process for the homogeneous conversion of methanol to acetaldehyde, ethanol or mixtures thereof which comprises contacting methanol with carbon monoxide and hydrogen in a CO:H 2 ratio of from 10:1 to 1:10 at a temperature of from about 100° to 300° C. and a pressure of from about 2 to 100 MPa in the presence of a catalytically effective amount of a catalyst system, said catalyst system consisting essentially of: (a) C 5 H 5 Ru(Pφ 3 ) 2 Co(CO) 4 ; and (b) an iodine or iodide promoter.

Claim 20

A process for the homogeneous conversion of methanol to acetaldehyde, ethanol or mixtures thereof which comprises contacting methanol with carbon monoxide and hydrogen in a CO:H 2 ratio of from 10:1 to 1:10 at a temperature of from about 100° to 300° C. and a pressure of from about 2 to 100 MPa in the presence of a catalytically effective amount of a catalyst system, said catalyst system consisting essentially of: (a) C 5 H 5 Ru(Pφ 3 ) 2 Co(CO) 4 ; and (b) an iodine or iodide promoter.

Claim 21

The process of claims 11 or 14 wherein the temperature is from 140° to 230° C.

Claim 22

The process of claims 10 or 13 wherein the temperature is from 140° to 230° C.