Hydrocyanation of pentenenitriles and/or 2-methyl-3-butenenitrile using promoters obtained from the chlorination of titanium-rich ores

1. A process for hydrocyanation of at least one substrate selected from the group consisting of 2-pentenenitrile, 3-pentenenitrile, 4-pentenenitrile, and 2-methyl-3-butenenitrile comprising contacting the substrate with hydrogen cyanide in the presence of a zero-valent nickel hydrocyanation catalyst and a promoter, wherein said promoter is a byproduct of a method for producing titanium tetrachloride from titanium ore, said method comprising the steps of contacting a titanium-containing ore with chlorine under reducing conditions to obtain a gaseous reaction product, recovering titanium tetrachloride from the reaction product, thereby leaving behind a residue, and condensing the residue to obtain said byproduct, and wherein said byproduct consists essentially of iron (II) chloride, manganese (II) chloride, sand, and coke.

2. A process comprising:

a) chlorinating a titanium-containing material, wherein the titanium-containing material contains iron oxide in an amount of about 0.5 to 50 percent by weight, to produce a mixture of metal chlorides comprising titanium tetrachloride and other iron-based chlorides;

b) separating the titanium tetrachloride;

c) obtaining a byproduct material consisting essentially of iron (II) chloride, manganese (II) chloride, sand, and coke;

d) using the byproduct material as a promoter in a process for hydrocyanation, said hydrocyanation process comprising contacting at least one substrate selected from the group consisting of 2-pentenenitrile, 3-pentenenitrile, 4-pentenenitrile, and 2-methyl-3-butenenitrile with hydrogen cyanide in the presence of a zero-valent nickel hydrocyanation catalyst and the promoter.

3. The process of claim 2 , wherein the substrate is 2-pentenenitrile.

4. The process of claim 2 , wherein the substrate is 3-pentenenitrile.

5. The process of claim 2 , wherein the substrate is 4-pentenenitrile.

6. The process of claim 2 , wherein the substrate is 2-methyl-3-butenenitrile.

7. The process of claim 2 , wherein chlorinating a titanium-containing material is performed in a fluidized bed reactor.

8. The process of claim 2 , wherein the byproduct material is used in a process for hydrocyanation without prior purification or separation.

9. The process of claim 2 , wherein the nickel hydrocyanation catalyst comprises a bidentate phosphite ligand.

10. The process of claim 1 , wherein the nickel hydrocyanation catalyst comprises the bidentate phosphite ligand having the formula.

11. A process comprising:

reacting 2-methyl-3-butenenitrile with hydrogen cyanide to produce 2-methylglutaronitrile in the presence of a zero-valent nickel catalyst and a promoter obtained as a byproduct from a titanium ore chlorination process, wherein said byproduct consists essentially of iron (II) chloride, manganese (II) chloride, sand, and coke.

12. A process comprising:

reacting a mixture of pentenenitriles with hydrogen cyanide to produce both adiponitrile and 2-methyglutaronitrile in the presence of a zero-valent nickel catalyst and a promoter obtained as a byproduct from a titanium ore chlorination process, wherein said byproduct consists essentially of iron (II) chloride, manganese (II) chloride, sand, and coke.

13. The process of claim 2 , wherein the titanium-containing material is rutile ore; ilmenite ore; anatase ore; beneficiates of rutile, ilmenite, or anatase ore; titanium containing by-products or slags; and mixtures thereof.

14. The process of claim 2 , wherein in step d) the byproduct material is added to the hydrocyanation reaction mixture directly as a solid, or as a slurry in either a hydrocyanation solvent or a mixture of nitriles, or as a homogeneous solution after filtration from materials which are not dissolved in the mixture of substrate nitriles or solvent.