Ethynylation catalyst and method of making same

Patent metadata

Field	Value
Publication number	US-9308522-B2
Application number	US-201514645594-A
Country	US
Kind code	B2
Filing date	Mar 12, 2015
Priority date	Mar 15, 2013
Publication date	Apr 12, 2016
Grant date	Apr 12, 2016

Abstract

A novel catalyst useful in the ethynylation of formaldehyde to butynediol is formed by precipitating copper and bismuth from a salt solution of such metals, utilizing an alkali metal hydroxide as the precipitating agent to deposit copper and bismuth hydroxide as a coating around a siliceous carrier particle.

First claim

The invention claimed is:

1. A method of preparing a catalyst for the ethynylation of formaldehyde, the method comprising:
depositing by precipitation a mixture of copper and bismuth hydroxides, via the reaction of an acidic copper and bismuth salt solution with an alkaline metal hydroxide, on a particulate siliceous carrier to form a treated carrier; and
calcining the treated carrier to yield a copper and bismuth oxide coating around said carrier particulate siliceous carrier.

2. The method of claim 1 , wherein said acidic solution comprises a mixture of copper nitrate and bismuth nitrate.

3. The method of claim 1 , wherein said alkali metal hydroxide comprises sodium hydroxide.

4. The method of claim 3 , wherein the sodium hydroxide is provided in a separate vessel from the acidic solution, and the siliceous carrier particles in water in a precipitation vessel separate from the sodium hydroxide and acidic solution.

5. The method of claim 3 , wherein said acidic solution and said sodium hydroxide are added simultaneously to the precipitation vessel.

6. The method of claim 4 , wherein said precipitation is carried out at a constant pH of about 6 to about 10.

7. The method of claim 4 , wherein said precipitation is carried out at a constant pH from 7.5 to 9.5.

8. The method of claim 4 , wherein said precipitation is carried out at a temperature of about 40° C. to 90° C.

9. The method of claim 8 , wherein said temperature is 45° C. to 65° C.

10. The method of claim 1 , wherein said precipitate is filtered, washed and dried and the dried material calcined in air at a temperature of about 250° C. to about 550° C.

11. The method of claim 1 , wherein said siliceous carrier particles comprise silica.

12. The method of claim 1 , wherein said siliceous carrier particles comprise a metal silicate.

13. The method of claim 1 , wherein said siliceous carrier particles comprise a magnesium silicate.

14. A novel ethynylation catalyst comprising the product formed by the process of claim 1 .

15. The catalyst of claim 14 , comprising 30 to about 60 wt. % cupric oxide and from about 1.0 to about 5 wt. % bismuth oxide.

16. The catalyst of claim 14 , comprising 40 to about 50 wt. % cupric oxide and from 2 to 4 wt. % bismuth oxide.

17. The catalyst of claim 14 , wherein said carrier comprises magnesium silicate.

18. The catalyst of claim 17 , wherein said magnesium silicate has an average diameter of about 5 to 60 microns.

19. The catalyst of claim 17 , wherein said magnesium silicate has a particle size of about 10 to 30 microns.

20. The catalytic ethynylation of formaldehyde with acetylene, the Reppe reaction, conducted in the presence of said catalyst of claim 14 .

Assignees

• Basf Corp

Inventors

• Madon Rostam
• Nagel Peter
• Hedrick Scott
• Thakur Deepak

Classifications

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J35/50

  characterised by their shape or configuration · CPC title

• B01J35/40

  characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77) · CPC title

• B01J2523/00

  Constitutive chemical elements of heterogeneous catalysts · CPC title