Process for the conversion of methane to c2+ hydrocarbons

Patent metadata

Field	Value
Publication number	US-2016264497-A1
Application number	US-201415035970-A
Country	US
Kind code	A1
Filing date	Nov 6, 2014
Priority date	Nov 11, 2013
Publication date	Sep 15, 2016
Grant date	—

Abstract

A method of making ethane can comprise: introducing a chlorine stream and a methane stream to a first reaction zone comprising a metal oxide catalyst; converting the metal oxide to metal chloride and reacting the methane to form a product stream comprising the C 2 H 4 ; introducing the metal chloride to a second reaction zone and introducing oxygen to convert the metal chloride to metal oxide and chlorine gas; and directing the metal oxide back to the first reaction zone. Also, a method of making ethane, comprising: introducing only a chlorine stream and a methane stream to a metal oxide catalyst to form the ethane and carbon dioxide, wherein the chlorine stream and the methane stream each comprise less than 1 vol % oxygen, and wherein metal oxide converts to metal chloride; and separately converting the metal chloride back to metal oxide with oxygen from an oxygen source, wherein chlorine gas is produced.

First claim

1 . A method of making C 2+ hydrocarbon, comprising:
introducing a chlorine stream and a methane stream to a first reaction zone comprising a metal oxide catalyst;
converting the metal oxide to metal chloride and reacting the methane to form a product stream comprising the C 2+ hydrocarbon and CO 2 , wherein the C 2+ hydrocarbon comprises at least one of ethane and ethene;
introducing the metal chloride to a second reaction zone;
introducing an oxygen source to the second reaction zone to convert the metal chloride to metal oxide and chlorine gas; and
directing the metal oxide back to the first reaction zone.

2 . The method of claim 1 , wherein less than or equal to 1 vol % O 2 is introduced to the first reaction zone, based upon a total volume of feed introduced to the first reaction zone.

3 . A method of making ethane, comprising:
introducing only a chlorine stream and a methane stream to a metal oxide catalyst to form the ethane and carbon dioxide, wherein the chlorine stream and the methane stream each comprise less than 1 vol % oxygen, and wherein metal oxide converts to metal chloride; and separately converting the metal chloride back to metal oxide with oxygen from an oxygen source, wherein chlorine gas is produced.

4 . The method of claim 1 , wherein the chlorine stream and the methane streams are introduced to the metal oxide catalyst as a mixed stream.

5 . The method of claim 1 , wherein the oxygen source is air.

6 . The method of claim 5 , further comprising separating nitrogen from the chlorine stream.

7 . The method of claim 1 , further comprising recycling the chlorine gas to the first reaction zone.

8 . The method of claim 1 , wherein no oxygen gas is fed to the first reaction zone.

9 . The method of claim 1 , wherein the chlorine stream comprises hydrogen chloride.

10 . The method of claim 1 , further comprising recycling at least a portion of the chlorine gas to the first reaction zone.

11 . The method of claim 1 , wherein the chlorine is fed to the first reaction zone in an amount of 1-5 vol % based upon the total volume of the methane stream and the chlorine stream.

12 . The method of claim 1 , wherein selectivity for ethene is greater than or equal to 70%.

13 . The method of any of claims 1 12 claim 1 , wherein each of the methane stream, the chlorine stream, and any recycled chlorine stream, independently, comprise less than or equal 0.3 vol % O 2 , based upon a total volume of all feed streams.

14 . The method of any of claim 1 , wherein the metal oxide catalyst comprises a metal comprises manganese (Mn), tin (Sn), lead (Pb), copper (Cu), iron (Fe), chromium (Cr), indium (In), germanium (Ge), antimony (Sb), bismuth (Bi), or a combination comprising one or more of the foregoing.

15 . The method of claim 1 , wherein the metal oxide catalyst is modified with an alkali metal comprising sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), or a combination comprising one or more of the foregoing.

16 . A method of making vinyl chloride monomer (VCM), comprising:
forming the ethene and the chlorine gas according to claim 1 ; reacting at least a portion of the chlorine gas and the C 2 H 4 to form the vinyl chloride monomer.

17 . The method of claim 16 , wherein the oxygen source is air, and further comprising, prior to reacting the ethene and chlorine gas, separating N 2 from the chlorine gas.

18 . The method of claim 16 , further comprising, prior to reacting the ethene and chlorine gas, separating the CO 2 from the ethene

19 . The method of claim 16 , wherein each of the methane stream, the chlorine stream, and any recycled chlorine stream, independently, comprise less than or equal 0 . 3 vol % O 2 , based upon a total volume of all feed streams.

20 . The method of claim 3 , wherein each of the methane stream, the chlorine stream, and any recycled chlorine stream, independently, comprise less than or equal 0 . 3 vol % O 2 , based upon a total volume of all feed streams.

Assignees

• Saudi Basic Ind Corp

Inventors

• Mammadov Aghaddin Kh
• West David

Classifications

• B01J38/12

  Treating with free oxygen-containing gas · CPC title

• Y02P20/584

  Recycling of catalysts · CPC title

• C07C2523/72

  Copper · CPC title

• C07C17/10 Primary

  of hydrogen atoms (combined with addition of halogens to unsaturated hydrocarbons C07C17/06) · CPC title

• C07C2523/02

  of the alkali- or alkaline earth metals or beryllium · CPC title