Hydrocarbon and oxygenate conversion by high severity pyrolysis to make acetylene and ethylene

Patent metadata

Field	Value
Publication number	US-9815751-B2
Application number	US-201113993211-A
Country	US
Kind code	B2
Filing date	Dec 20, 2011
Priority date	Jan 19, 2011
Publication date	Nov 14, 2017
Grant date	Nov 14, 2017

Abstract

The invention relates to hydrocarbon conversion processes, e.g., to processes for producing acetylene from hydrocarbon and then hydrogenating at least a portion of the acetylene. The invention also relates to polymerizing one or more products derived from the acetylene saturation, and to equipment useful for these processes.

First claim

The invention claimed is:

1. A hydrocarbon conversion process, comprising:
(a) providing a first mixture comprising hydrocarbon and ≧10 wt. % of CO 2 based on the weight of the first mixture;
(b) exposing the first mixture to high severity thermal pyrolysis conditions including a temperature in the range of from 1.45×10 3 ° C. to 2.20×10 3 ° C., a total pressure in the range of from 2 bar (absolute) to 10 bar (absolute), and a residence time ≦5.0×10 −3 second, in a first region to form a second mixture, the second mixture having a CO:acetylene molar ratio in the range of 2.5×10 −3 to 3.0, a CO 2 :acetylene molar ratio ≦0.01, and comprising ≧1.0 wt. % C 2 unsaturates based on the weight of the second mixture;
(c) transferring at least a portion of the second mixture, as a transferred mixture, to at least one acetylene converter; and
(d) catalytically converting at least a portion of the transferred mixture in the acetylene convertor to produce a product;
wherein,
the transferred mixture has a CO:acetylene molar ratio in the range of 0.01-1.5 and comprises A 2 wt % acetylene and A 3 wt % ethylene based on the weight of the transferred mixture,
the catalytic converting is carried out in the presence of an a catalyst comprising ≧0.1 wt. % of one or more of Pt, Pd, and Ni, and
the product comprises A 5 wt. % of acetylene and A 6 wt. % of ethylene based on the weight of the product wherein A 6 ≧A 3 , A 5 <A 2 , and (A 6 −A 3 )/(A 2 −A 5 )≧0.50.

2. The process of claim 1 , wherein the catalytic acetylene conversion is conducted at least partially in the vapor or liquid phase and wherein (A 6 −A 3 )/(A 2 −A 5 )≧0.70.

3. The process of claim 1 , wherein
(i) the first mixture further comprises molecular hydrogen, and
(ii) the hydrocarbon of the first mixture comprises methane.

4. The process of claim 1 , further comprising exothermically reacting a fourth mixture in a second region to produce a fifth mixture, the first and second regions being at least partially coextensive, and conducting the fifth mixture away from the second region; wherein
(i) the fourth mixture comprises (i) hydrocarbon and/or hydrogen and (ii) oxidant,
(ii) the fifth mixture comprises water and/or carbon dioxide, and
(iii) the exposing of the first mixture and the reacting of the fourth mixture occur at substantially different times.

5. The process of claim 4 , wherein
(i) the hydrocarbon conversion process is continuous or semi-continuous,
(ii) at least a portion of the fifth mixture is conducted away from the second region before the exposing of the first mixture in the first region, and
(iii) the exposure temperature in the first region results at least in part from the heat generated during the reacting of the fourth mixture in the second region.

6. The process of claim 4 , further comprising at least one of:
(i) separating from the fifth mixture a byproduct comprising oxygenate and utilizing least a portion of the separated byproduct to produce the first and/or fourth mixtures or
(ii) separating from the second mixture a second byproduct comprising hydrocarbon and hydrogen and utilizing at least a portion of the separated second byproduct to produce at least one of the first, third, or fourth mixtures.

7. The process of claim 1 , wherein the transferred mixture comprises a third mixture, the process further comprising exposing at least a portion of the second mixture to a temperature <100.0° C.; and separating from the second mixture, prior to transferring the at least a portion of the second mixture, one or more of coke, heteroatom species, or saturated hydrocarbons to form the third mixture.

8. The process of claim 1 , wherein the acetylene conversion catalyst is a selectivated acetylene conversion catalyst, the catalyst being selectivated by at least a portion of the transferred mixture's carbon monoxide.

9. The process of claim 1 , wherein (i) the first mixture has a hydrogen content in the range of 6.0 wt. % to 25.0 wt. % and/or (ii) the first mixture further comprises ≧15.0 wt. % molecular hydrogen based on the weight of the first mixture.

10. The process of claim 1 , further comprising compressing the second mixture.

11. The process of claim 1 , further comprising contacting the second mixture with a fluid having a pH >7.0.

12. The process of claim 1 , further comprising separating ethylene from the product and enriching at least a portion of the transferred mixture with separated ethylene to produce a third mixture.

13. The process of claim 1 , wherein (i) the second mixture comprises 5.0×10 2 ppmm to 1.0×10 4 ppmm of carbon monoxide per mole of the second mixture and/or (ii) the second mixture has a carbon monoxide to acetylene molar ratio in the range of 2.5×10 −3 to 1.0.

14. The process of claim 1 , wherein the transferred mixture has a carbon monoxide:acetylene molar ratio in the range of 0.04 to 0.50 and a molecular hydrogen:acetylene molar ratio in the range of 1.0 to 50.0, the transferred mixture comprising (i) ≧2.0 wt. % C 2 unsaturates based on the weight of the third mixture and (ii) 1.0×10 3 ppmm to 2.5×10 4 ppmm of carbon monoxide per mole of the third mixture.

15. The process of claim 1 , wherein the transferred mixture has a carbon monoxide:acetylene molar ratio in the range of 3.5×10 −3 to 0.20 and comprises 2.0×10 2 ppmm to 1.0×10 4 ppmm of carbon monoxide per mole of the second mixture.

16. The process of claim 1 , wherein the second mixture has a carbon monoxide:acetylene molar ratio in the range of 0.005 to 0.050.

17. The process of claim 1 , further comprising polymerizing at least a portion of the ethylene in the product.

18. The process of claim 17 , further comprising separating at least a portion of the carbon monoxide in the product before the polymerizing.

19. The polymer product of claim 17 .

20. A hydrocarbon conversion process, comprising:
(a) mixing hydrocarbon and CO 2 to provide a first mixture wherein the first mixture comprises ≧1 wt. % CO 2 based on the weight of the first mixture;
(b) exposing the first mixture to high severity thermal pyrolysis conditions including a temperature in the range of from 1.45×10 3 ° C. to 2.20×10 3 ° C., a total pressure in the range of from 2 bar (absolute) to 10 bar (absolute), and a residence time ≦5.0×10 −3 second, to form a second mixture having a CO:acetylene molar ratio in the range of 0.04 to 0.50 and a CO 2 :acetylene molar ratio ≦0.01; and
(c) catalytically converting at least a portion of the second mixture in the presence of an acetylene conversion catalyst to form a product;
wherein,
the second mixture comprises ≧1.0 wt. % C 2 unsaturates, A 1 wt. % of saturated hydrocarbon, A 2 wt. % of acetylene, and A 3 wt. % of ethylene based on the weight of the second mixture,
the acetylene conversion catalyst comprises ≧0.1 wt. % of one or more of Pt, Pd, and Ni,
the product comprises A 4 wt. % of saturated hydrocarbon, A 5 wt. % of acetylene, and A 6 wt. % of ethylene based on the weight of the product, wherein (i) A 6 ≧A 3 , (ii) A 5 <A 2 , (iii) (A 6 −A 3 )/(A 2 −A 5 )≧0.70, and
the conversion catalyst is selectivated by at least a portion of the second mixture's carbon monoxide.

21. A hydrocarbon conversion process, comprising:
(a) mixing hydrocarbon and CO 2 to provide a first mixture comprising ≧10 wt. % CO 2 based on the weight of the first mixture;
(b) exposing the first mixture to high severity thermal pyrolysis conditions including a temperature in the range of from 1.45×10 3 ° C. to

Assignees

• Keusenkothen Paul F
• Hershkowitz Frank
• Exxonmobil Chemical Patents Inc

Inventors

• Keusenkothen Paul F
• Hershkowitz Frank

Classifications

• Y02P30/20

  using bio-feedstock · CPC title

• C07C2/84

  catalytic · CPC title

• C10G57/00

  Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process · CPC title

• C07C5/05 Primary

  Partial hydrogenation · CPC title

• C10G9/00

  Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils · CPC title