Hydrogenation and ethynylation catalysts

Patent metadata

Field	Value
Publication number	US-10399062-B2
Application number	US-201615557578-A
Country	US
Kind code	B2
Filing date	Mar 30, 2016
Priority date	Mar 31, 2015
Publication date	Sep 3, 2019
Grant date	Sep 3, 2019

Abstract

A process for preparing a catalyst includes impregnating a metal oxide carrier with an aqueous solution to form an impregnated carrier; drying the impregnated carrier to form a dried, impregnated carrier; and heat-treating the dried, impregnated carrier in air to form the catalyst; wherein: the aqueous solution includes a copper salt; and from about 3 wt % to about 15 wt % of a C3-C6 multifunctional carboxylic acid; and the catalyst includes from about 5 wt % to about 50 wt % copper oxide.

First claim

What is claimed is:

1. A process for forming a catalyst for hydrogenation, dehydrogenation, hydrogenolysis, or ethynylation, the process comprising:
impregnating a metal oxide carrier with an aqueous solution to form an impregnated carrier;
drying the impregnated carrier to form a dried, impregnated carrier; and
heat-treating the dried, impregnated carrier to form the catalyst;
wherein:
the aqueous solution comprises:
a copper salt; and
from about 1 wt % to about 15 wt % of a C 3 -C 6 multifunctional carboxylic acid; and

the catalyst consists of about 5 wt % to about 50 wt % copper oxide and optionally a bismuth salt.

2. The process of claim 1 , wherein the copper salt comprises copper nitrate, copper sulfate, copper acetate, copper chloride, or copper citrate.

3. The process of claim 1 , wherein the catalyst is an ethynylation catalyst and the aqueous solution further comprises the bismuth salt and the catalyst comprises up to about 5 wt % Bi 2 O 3.

4. The process of claim 3 , wherein the bismuth salt comprises bismuth nitrate, bismuth sulfate, bismuth acetate, bismuth chloride, or bismuth citrate.

5. The process of claim 1 , wherein the multifunctional carboxylic acid is a C 3 -C 5 multi-carboxylic acid.

6. The process of claim 1 , wherein the catalyst is a hydrogenation, dehydrogenation, or hydrogenolysis catalyst and the aqueous solution consists essentially of the copper salt, from about 1 wt % to about 15 wt % of a C 3 -C 6 multifunctional carboxylic acid, and, optionally, a precipitation agent.

7. The process of claim 1 , wherein the aqueous solution comprises from about 2.5 wt % to about 7 wt % of the C 3 -C 6 multifunctional carboxylic acid.

8. The process of claim 1 , wherein the drying is carried out at a temperature from about 100° C. to about 125° C. for a period of time sufficient to remove substantially all free water present in the impregnated carrier, and the impregnating is carried out at a temperature of about 10° C. to about 90° C.

9. The process of claim 1 , wherein the heat-treating comprises calcining in air.

10. The process of claim 1 , wherein the heat-treating comprises pyrolyzing in an atmosphere substantially free of oxygen at a temperature from about 250° C. to about 750° C.

11. The process of claim 10 , wherein the heat-treating comprises calcination in an oxygen-limited atmosphere has less than 21 vol % oxygen.

12. The process of claim 1 , wherein the metal oxide carrier is a siliceous oxide comprising silica or silica and gamma-alumina.

13. The process of claim 1 , wherein the ethynylation catalyst comprises from about 5 wt % to about 50 wt % CuO.

14. The process of claim 1 , wherein a pore volume the metal oxide carrier is from about 0.3 ml/g to about 2.5 ml/g.

15. The process of claim 1 , wherein a molar ratio of copper:multifunctional carboxylic acid is from about 1 to 15 when calcined in air.

16. The process of claim 1 , wherein the catalyst is a hydrogenation catalyst and the process further comprises activating the hydrogenation catalyst by forming Cu(0) metal.

17. The process of claim 1 , wherein the catalyst is an ethynylation catalyst and the process further comprises activating the ethynylation catalyst by forming Cu(I)acetylide.

18. A process for forming a catalyst for ethynylation, the process comprising:
impregnating a metal oxide carrier with an aqueous solution to form an impregnated carrier;
drying the impregnated carrier to form a dried, impregnated carrier;
heat-treating the dried, impregnated carrier to form the catalyst; and
activating the ethynylation catalyst by forming Cu(I)acetylide;
wherein:
the aqueous solution comprises:
a copper salt; and
from about 1 wt% to about 15 wt% of a C 3 -C 6 multifunctional carboxylic acid; and

the catalyst comprises from about 5 wt% to about 50 wt% copper oxide.

19. The process of claim 1 , wherein the copper salt comprises copper nitrate, copper sulfate, copper acetate, copper chloride, or copper citrate.

20. The process of claim 1 , wherein the catalyst is an ethynylation catalyst and the aqueous solution further comprises a bismuth salt and the catalyst comprises up to about 5 wt% Bi 2 O 3 .

Assignees

• Basf Corp

Inventors

• Deutsch Keenan Lee
• Madon Rostam J

Classifications

• C07C29/44

  increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond (C07C29/16 takes precedence) · CPC title

• C07C29/154

  containing copper, silver, gold, or compounds thereof · CPC title

• B01J37/086

  Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid · CPC title

• B01J37/0018

  Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat) · CPC title

• B01J23/72

  Copper · CPC title