Claims
- 1. A process for the production of ethanol which process comprises reacting, at elevated temperature and pressure, methanol with hydrogen and carbon monoxide in the presence of an aryl halide, a thiophene, or a silicone oil inert liquid which is deliberately charged to the reaction system, and a catalyst comprising cobalt, an iodide or a bromide and a compound having the formula ##STR3## wherein X is nitrogen or phosphorus and A, B, and C are individually monovalent organic radicals, or X is phosphorus and any two of A, B, and C together form an organic divalent cyclic ring system bonded to the X atom, or X is nitrogen and all of A, B and C together form an organic trivalent cyclic ring system bonded to the X atom.
- 2. A process according to claim 1 wherein the elevated temperature is in the range 150.degree. to 250.degree. C., the elevated pressure is greater than 100 bars, the residence time is up to 8 hours, the molar ratio of carbon monoxide to hydrogen is in the range 2:1 to 1:3, the molar ratio of methanol to inert liquid is in the range from 30:1 to 1:10, the molar ratio of methanol to synthesis gas is in the range from 10:1 to 1:20, the molar ratio of cobalt to iodine or bromine in the catalyst is in the range from 1:3 to 10:1, the molar ratio of cobalt to the compound of formula (I) in the catalyst is in the range from 2:1 to 1:10, the molar ratio of iodine or bromine to the compound of formula (I) in the catalyst is in the range from 2:1 to 1:10 and the molar ratio of cobalt to methanol is in the range from 1:10 to 1:1000.
- 3. A process according to claim 1 wherein the elevated temperature is in the range from 180.degree. to 230.degree. C., the elevated pressure is in the range 140 to 300 bars, the residence time is from 10 to 180 minutes, the molar ratio of carbon monoxide to hydrogen is in the range 2:1 to 1:3, the molar ratio of methanol to inert liquid is in the range from 25:1 to 1:2, the molar ratio of methanol to synthesis gas is in the range from 2:1 to 1:5, the molar ratio of cobalt to iodine in the catalyst is in the range from 1:1 to 5:1, the molar ratio of cobalt to the compound of formula (I) in the catalyst is in the range from 1:1 to 1:5, the molar ratio of iodine or bromine to the compound of formula (I) in the catalyst is in the range from 1:1 to 1:8 and the molar ratio of cobalt to methanol is in the range from 1:40 to 1:800.
- 4. A process according to claim 1 wherein the molar ratio of carbon monoxide to hydrogen is in the range 1:1 to 1:2.
- 5. A process according to claim 1 wherein the compound having the formula (I) is a phosphine having the general formula:
- R.sub.3 P (II)
- wherein R independently is a hydrocarbyl group containing from 1 to 20 carbon atoms selected from unsubstituted saturated aliphatic, unsubstituted saturated cycloaliphatic and unsubstituted aromatic groups.
- 6. A process according to claim 5 wherein the phosphine of formula (II) is triethyl phosphine, tributyl phosphine, tri-t-butyl phosphine or triphenylphosphine.
- 7. A process according to claim 1 wherein the compound of formula (I) is pyridine or diphenylamine.
- 8. A process according to claim 1 wherein, in addition to the inert liquid, there is added a nonpolar solvent selected from alkanes, benzene and alkyl-substituted benzenes.
- 9. A process according to claim 1 wherein, in addition to the inert liquid, there is added an acid and/or an acid derivative thereof having the formula: ##STR4## wherein the substituent R is a hydrocarbyl group or an oxygen-containing hydrocarbyl group and the substituent X is the group --OR.sup.1 in which R.sup.1 is independently a hydrogen atom, a hydrocarbyl group or an oxygen-containing hydrocarbyl group or X is the group --O--CO--R.sup.2 in which R.sup.2 is independently a hydrocarbyl group or an oxygen-containing hydrocarbyl group.
- 10. A process according to claim 1 when operated in a continuous manner.
- 11. A process as defined in claim 1 wherein said inert liquid is a chlorobenzene, tetrahydrothiophene, a polydimethyl siloxane fluid or a methyl phenyl silicone fluid.
Priority Claims (1)
Number |
Date |
Country |
Kind |
46329/77 |
Nov 1977 |
GBX |
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Parent Case Info
This is a continuation of application Ser. No. 957,700, filed Nov. 6, 1978, now abandoned.
US Referenced Citations (3)
Number |
Name |
Date |
Kind |
3248432 |
Riley et al. |
Apr 1966 |
|
4045492 |
Kniese et al. |
Aug 1977 |
|
4133966 |
Pretzer et al. |
Jan 1979 |
|
Continuations (1)
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Number |
Date |
Country |
Parent |
957700 |
Nov 1978 |
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