Gas phase production of alkyl alkanoates

Patent metadata

Field	Value
Publication number	US-10144697-B2
Application number	US-201615558287-A
Country	US
Kind code	B2
Filing date	Mar 22, 2016
Priority date	Mar 26, 2015
Publication date	Dec 4, 2018
Grant date	Dec 4, 2018

Abstract

An alkane-containing stream is reacted to produce an alkene, which is carbonylated to produce an alkyl alkanoate, e.g., methyl propanoate, by a gas phase process comprising the step of contacting under carbonylation conditions the alkene, e.g., ethylene, carbon monoxide, an alkanol, e.g., methanol, and a solid sulfide-based metal catalyst.

First claim

What is claimed is:

1. A process comprising: (a) providing a gas feed stream comprising >1 mol % of an alkane; (b) at least partially converting the alkane to produce a gaseous first intermediate stream comprising water, unreacted alkane, and >1 mol % of an alkene; (c) removing the majority of the water from the gaseous first intermediate stream to produce a gaseous second intermediate stream comprising at least one alkene; and (d) contacting under gas phase carbonylation conditions the gaseous second intermediate stream, carbon monoxide gas, an alkanol gas and a solid sulfide-based metal catalyst to produce an alkyl alkanoate, wherein the carbonylation conditions include a temperature from 200° C. to 400° C. and a pressure from 0.1 MPa to 10 MPa.

2. The process of claim 1 comprising: (a) providing a gas feed stream comprising >1 mol % of an alkane; (b) at least partially converting the alkane to produce a gaseous first intermediate stream comprising water, other hydrocarbons, H 2 , CO, CO 2 , unreacted alkane, and >1 mol % of an alkene; (c) removing the majority of the water from the gaseous first intermediate stream to produce a gaseous second intermediate stream comprising at least one alkene, other hydrocarbons, H 2 , CO, CO 2 and unreacted alkane; and (d) contacting under gas phase carbonylation conditions the gaseous second intermediate stream, carbon monoxide gas, an alkanol gas and a solid sulfide-based metal catalyst to produce an alkyl alkanoate.

3. The process of claim 1 wherein the alkene is of the formula Call, in which n is from 2 to 12, and the alkanol comprises from 1 to 30 carbon atoms.

4. The process of claim 1 wherein the alkane is methane and the alkene is ethylene.

5. The process of claim 1 wherein the solid, sulfide-based metal catalyst comprises one or more of iron, cobalt, rhodium, and nickel.

6. The process of claim 1 wherein the catalyst is supported.

7. The process of claim 1 wherein the carbonylation conditions are halogen-free.

8. The process of claim 1 in which the alkanol comprises 1-30 carbon atoms.

9. The process of claim 1 in which the alkanol is methanol.

10. The process of claim 1 wherein the alkane is methane, and step (b) comprises OCM.

11. The process of claim 1 wherein the alkyl alkanoate is methyl propanoate.

12. The process of claim 1 further comprising: (e) contacting under condensation conditions the alkyl alkanoate with an aldehyde to produce an alkyl ester of an aliphatic carboxylic acid, and wherein the alkyl alkanoate is methyl propanoate, the aldehyde is formaldehyde, and the product is methyl methacrylate.

13. The process of claim 1 comprising: (a) providing a gas feed stream comprising >1% of methane; (b) at least partially converting the methane via an OCM process to produce a gaseous first intermediate stream comprising water, other hydrocarbons, H 2 , CO, CO 2 , unreacted methane, and >1% of ethylene; (c) removing the majority of the water from the gaseous first intermediate stream to produce a gaseous second intermediate stream comprising ethylene, other hydrocarbons, H 2 , CO, CO 2 and unreacted methane; and (d) contacting under carbonylation conditions the gaseous second intermediate stream, carbon monoxide gas, gaseous methanol and a solid sulfide-based metal catalyst to produce methyl propanoate.

14. The process of claim 1 , wherein the solid, sulfide-based metal catalyst comprises cobalt.

Assignees

• Dow Global Technologies Llc

Inventors

• Budroni Gerolamo
• Corthals Steven L F

Classifications

• C07C67/343

  by increase in the number of carbon atoms · CPC title

• C07C11/04

  Ethene · CPC title

• C07C67/38 Primary

  by addition to an unsaturated carbon-to-carbon bond · CPC title

• C07C69/24

  esterified with monohydroxylic compounds · CPC title

• C07C2/82

  oxidative coupling · CPC title