Nickel form for preparation of catalytic nickel-ligand complexes

Patent metadata

Field	Value
Publication number	US-9687836-B2
Application number	US-201514669121-A
Country	US
Kind code	B2
Filing date	Mar 26, 2015
Priority date	Jun 10, 2011
Publication date	Jun 27, 2017
Grant date	Jun 27, 2017

Abstract

A novel nickel particulate form is provided that efficiently forms a zero-valent nickel complex with a phosphorus-containing ligands in an organic liquid to form a hydrocyanation catalyst. Particles in the nickel particulate form comprise nickel crystallites. For example, the nickel particulate form can have a BET Specific Surface Area of at least about 1 m 2 /gm; an average crystallite size less than about 20-25 nm, the nickel particulate form can have at least 10% of the crystallites in the nickel form can have can have a diameter (C10) of less than about 10 nm, and/or there are on average at least about 10 15 surface crystallites per gram nickel. A ratio of BET SSA to C50 for the nickel particulate form can be at least about 0.1×10 9 m/gm and preferably at least about 0.4×10 9 m/gm. Methods of preparation and use are also provided.

First claim

What is claimed:

1. A method for hydrocyanating a compound having at least one C═C bond comprising:
contacting the compound with HC≡N in the presence of a catalyst comprising a complex comprising one or more phosphorus-containing ligands and nickel atoms from a nickel particulate form comprising nickel crystallites, wherein the nickel particulate form has a BET Specific Surface Area of at least about 1 m 2 /gm; at least 10% of the nickel crystallites have a size (C10) that is less than about 20 nm; the nickel crystallites have an average crystallite size of no greater than about 100 nm; and the nickel crystallite size distribution span is greater than about 1.0.

2. The method of claim 1 , wherein one or more phosphorus-containing ligands comprises a phosphite ligand.

3. The method of claim 1 , wherein one or more phosphorus-containing ligands comprises a bidentate phosphite ligand.

4. The method of claim 1 , wherein the one or more of the phosphorus ligands is a ligand of Formula (III):

wherein:
X 11 , X 12 , X 13 , X 21 , X 22 and X 23 independently represent oxygen or a single direct bond;
R 11 and R 12 independently represent identical or different, single or bridged organic radicals; and
R 21 and R 22 independently represent identical or different, single or bridged organic radicals; and
Y represents a bridging group.

5. The method of claim 1 , wherein one or more of the phosphorus containing ligand is Ligand (V):

6. The method of claim 1 , wherein the contacting of the compound with the HC≡N in the presence of the catalyst comprising the complex is carried out in an organic liquid, wherein the organic liquid solution further comprises about 0.001 wt % to about 15 wt % sulfur, wherein the sulfur weight percentage is relative to the total weight of nickel in the solution.

7. The method of claim 1 , wherein the contacting of the compound with the HC≡N in the presence of the catalyst occurs in an organic liquid solution comprising the one or more phosphorus-containing ligands and the nickel particulate form.

8. The method of claim 7 , wherein the nickel particulate form is suspended in the solution.

9. The method of claim 7 , wherein the solution further comprises one or more pentenenitriles.

10. The method of claim 7 , wherein the solution comprises one or more pentenenitriles as a solvent.

11. The method of claim 7 , wherein the solution further comprises a Lewis acid.

12. The method of claim 11 , wherein the Lewis acid is zinc chloride, ferrous chloride, or a combination thereof.

13. The method of claim 7 , further comprising forming the complex between the one or more phosphorus-containing ligands and the nickel atoms from the nickel particulate form.

14. The method of claim 1 , further comprising forming the complex having catalytic activity, comprising mixing an organic liquid solution comprising the one or more phosphorus-containing ligands and the nickel particulate form comprising nickel crystallites.

15. The method of claim 14 , wherein the organic liquid solution further comprises a Lewis acid.

16. The method of claim 15 , wherein the Lewis acid is zinc chloride, ferrous chloride, or a combination thereof.

17. The method of claim 14 , wherein the organic liquid solution further comprises the compound having at least one C═C bond.

18. The method of claim 17 , wherein the compound having the at least one C═C bond is a mononitrile.

19. The method of claim 14 , wherein the organic liquid solution comprises one or more pentenenitriles.

20. The method of claim 14 , wherein the organic liquid solution comprises one or more pentenenitriles as a solvent.

21. The method of claim 14 , wherein the complex forms between one or more bidentate phosphorus-containing ligands and nickel atoms from the nickel particulate form.

22. The method of claim 14 , wherein an equilibrium of complex formation between Ligand (V) and nickel atoms from the nickel particulate form is reached within about 2 hours when about 4 to 5 wt % of the nickel particulate form is mixed with 3-pentenenitrile containing approximately 5.25 wt % Ligand (V) and approximately 6300 ppm ZnCl 2 ; and wherein Ligand (V) has the following formula:

Assignees

• Invista North America Sarl

Inventors

• Fraga-Dubreuil Joan
• Medhekar Vinay
• Micka Thomas A
• Whiston Keith

Classifications

• B01J31/2409

  with more than one complexing phosphine-P atom · CPC title

• B01J2531/007

  Promoter-type Additives · CPC title

• B01J2231/322

  Hydrocyanation · CPC title

• B01J31/22 Primary

  Organic complexes · CPC title

• B01J2531/847

  Nickel · CPC title