Method to produce C4 olefins from natural gas-derived acetylene

Patent metadata

Field	Value
Publication number	US-11530171-B2
Application number	US-202117233907-A
Country	US
Kind code	B2
Filing date	Apr 19, 2021
Priority date	Apr 20, 2020
Publication date	Dec 20, 2022
Grant date	Dec 20, 2022

Abstract

In accordance with the purpose(s) of the present disclosure, as embodied and broadly described herein, the disclosure relates to a method for producing C4 olefins from acetylene using supported metal-based catalysts and metal-based promoters. The method is inexpensive, efficient, and environmentally sound. Additionally, the method is selective for C4 olefins and other value-added products based on changes to reaction parameters including temperature, feed gas composition, and promoter identity. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure.

First claim

What is claimed is:

1. A method for producing C 4 olefins from acetylene, the method comprising:
a. placing a catalyst in a reactor;
b. providing a flow of feed gas through the reactor;
c. reacting the feed gas at a first temperature for a first period of time to produce a product mixture; and
d. collecting the product mixture;
wherein the catalyst comprises a first metal;
wherein the first metal is selected from Cu, Fe, Co, Ni, Pd, Pt, Rh, and combinations thereof; and
wherein the first metal is present in an amount from about 5 wt % to about 15 wt %:

wherein the catalyst comprises a promoter;
wherein the promoter comprises a second metal;
wherein the second metal is selected from Ru, Ga, Ag, and combinations thereof; and
wherein the second metal is present in an amount from about 0.05 wt % to about 10 wt %;

wherein the catalyst further comprises a catalyst support;
wherein the catalyst support is selected from a material comprising SiO 2 , Al 2 O 3 , ZrO 2 , TiO 2 , CeO 2 , a zeolite, ammonium zeolite mordenite, and combinations thereof;

wherein the feed gas comprises acetylene; and
wherein the product mixture comprises at least one C 4 olefin.

2. The method of claim 1 , wherein the first metal comprises Cu.

3. The method of claim 1 , the catalyst support comprises ammonium zeolite mordenite.

4. The method of claim 3 , wherein the ammonium zeolite mordenite comprises SiO 2 and Al 2 O 3 in a mole ratio of from about 10:1 to about 30:1 mole ratio.

5. The method of claim 1 , wherein the first metal comprises copper in an amount of from about 7.5 wt % to about 12.5 wt % of the total weight of the catalyst and the catalyst support.

6. The method of claim 1 , wherein the promoter is present in an amount of from about 0.5 wt % to about 2 wt % of the total weight of the catalyst and the catalyst support.

7. The method of claim 1 , wherein the first metal comprises copper in an amount of 10 wt % of the total weight of the catalyst and the catalyst support, the second metal comprises ruthenium in an amount of from about 0.1 wt % to about 1 wt % of the total weight of the catalyst and the catalyst support, and the catalyst support comprises ammonium zeolite mordenite.

8. The method of claim 1 , wherein the first metal comprises copper in an amount of 10 wt % of the total weight of the catalyst and the catalyst support, the second metal comprises gallium in an amount of 1 wt % of the total weight of the catalyst and the catalyst support, and the catalyst support comprises ammonium zeolite mordenite.

9. The method of claim 1 , wherein the feed gas comprises acetylene and hydrogen.

10. The method of claim 9 , wherein the feed gas comprises from about 5 to about 95 vol % acetylene.

11. The method of claim 9 , wherein the feed gas comprises a molar ratio of hydrogen to acetylene of from about 2:1 to about 8:1.

12. The method of claim 9 , wherein the feed gas comprises a pressure of about 1-200 psig.

13. The method of claim 1 , wherein the first temperature is from about 150° C. to about 300° C.

14. The method of claim 1 , wherein the at least one C 4 olefin comprises 1-butene, cis-2-butene, trans-2-butene, 1,3-butadiene, or a combination thereof.

15. The method of claim 1 , wherein the product mixture comprises at least 80 mol % C 4 olefins.

16. The method of claim 1 , wherein the product mixture further comprises at least one value-added product.

17. The method of claim 16 , wherein the at least one value-added product comprises ethylene, benzene, or a combination thereof.

18. The method of claim 17 , wherein the product mixture comprises from about 3 mol % to about 8 mol % benzene; and wherein the product mixture comprises from about 5 mol % to about 25 mol % ethylene.

19. The method of claim 9 , wherein conversion of acetylene is about 100%.

20. The method of claim 1 , wherein the catalyst support is selected from Al 2 O 3 , a zeolite, ammonium zeolite mordenite, and combinations thereof.

21. A composition comprising a hydrocarbon produced by the method of claim 1 .

22. An article comprising the composition of claim 21 .

Assignees

• Univ West Virginia

Inventors

• Hu Jianli
• Li Qingyuan

Classifications

• C07C2529/46

  Iron group metals or copper · CPC title

• C07C2523/72

  Copper · CPC title

• C07C11/167

  1, 3-Butadiene · CPC title

• C07C2/38 Primary

  of dienes or alkynes · CPC title

• B01J23/72

  Copper · CPC title