Nickel metal compositions and nickel complexes derived from basic nickel carbonates
Nickel-metal-containing solids for use in manufacturing nickel metal complexes are disclosed. The nickel-metal-containing solids are made by reducing basic nickel carbonates. By varying the molar ratios of carbonates and bicarbonates to nickel salts, the methods provide basic nickel carbonates that produce superior nickel metal-containing solids that react more effectively with phosphorous-containing ligands. The phosphorous containing ligands can be both monodentate and bidentate phosphorous-containing ligands.
1. A method of making a nickel-metal-containing solid, the method comprising:
a. providing or obtaining a starting material nickel composition, wherein said starting material nickel composition is produced by
(i) contacting a precipitant solution with a nickel solution in a precipitation reactor to form a reaction mixture, wherein said nickel solution comprises nickel(II) ions and water and said precipitant solution is formed by a process comprising dissolving in water at least one of (a) a bicarbonate salt, and (b) a bicarbonate salt and a carbonate salt,
wherein a mole ratio of bicarbonate ions to nickel ions in the reaction mixture is about 0.8:1 to about 2:1 and a mole ratio of carbonate ions to nickel ions in the reaction mixture is about 0.8:1 to about 1.6:1; and
(ii) precipitating said starting material nickel composition from said reaction mixture;
b. reducing at least a portion of said starting material nickel composition with a reducing agent to form a nickel-metal-containing solid;
wherein said nickel-metal-containing solid is effective to react with a bidentate phosphorus-containing ligand to form a nickel complex of the phosphorus-containing ligand.
2. The method of claim 1 wherein the contacting (i) comprises adding the precipitant solution to the nickel solution.
3. The method of claim 2 , wherein a source of said nickel(II) ions is selected from the group consisting of NiCl 2 , NiSO 4 , and Ni(NO 3 ) 2 .
4. The method of claim 3 , wherein the source of said nickel(II) ions is NiCl 2 .
5. The method of claim 1 , wherein a source of said nickel(II) ions is selected from the group consisting of NiCl 2 , NiSO 4 , and Ni(NO 3 ) 2 .
6. The method of claim 5 , wherein the source of said nickel(II) ions is NiCl 2 .
7. The method of claim 1 or 2 , wherein the bicarbonate salt is selected from the group consisting of: NaHCO 3 and NH 4 HCO 3 .
8. The method of claim 1 or 2 , wherein the carbonate salt comprises Na 2 CO 3 .
9. The method of claim 1 or 2 further comprising contacting said reaction mixture with carbon dioxide.
10. The method of claim 9 , wherein said contacting is performed while precipitating said starting material nickel composition.
11. The method of one of claims 1 - 4 further comprising digesting the reaction mixture prior to precipitating said starting material nickel composition.
12. The method of claim 11 , wherein said digestion is performed at a temperature from about 50° C. to about 90° C. and a duration from about 0.25 hours to about 24 hours.
13. The method of one of claims 1 - 4 , wherein said precipitating said starting material nickel composition is performed at a temperature of from about 0° C. to about 90° C.
14. The method of claim 13 , wherein said temperature is from about 50° C. to about 90° C.
15. The method of claim 14 , wherein said temperature is from about 65° C. to about 75° C.
16. The method of one of claims 1 - 4 , wherein said mole ratio of bicarbonate ions to nickel ions can be selected from the group consisting of: from about 0.8:1 to about 1.6:1, from about 0.8:1 to about 1.2:1, from about 1.0:1.0 to about 1.9:1, from about 0.8:1 to about 1.4:1, from about 1.0:1 to about 1.8:1, from about 1.0:1 to about 1.6:1, from about 1.0:1 to about 1.4:1, from about 0.8:1 to about 1.4:1, and from about 0.8:1 to about 1.2:1.
17. The method of claim 16 , wherein the bicarbonate salt is selected from the group consisting of: NaHCO 3 and NH 4 HCO 3 .
18. The method of claim 17 , wherein said mole ratio of bicarbonate ions to nickel ions ranges from about 1.0:1 to about 1.8:1.
19. The method of one of claims 1 - 4 , wherein said mole ratio of carbonate ions to nickel ions can be selected from the group consisting of: from about 0.8:1 to about 1.4:1, from about 1.0:1.0 to about 1.2:1, from about 0.8:1 to about 1.4:1, from about 1.0:1 to about 1.6:1, from about 1.0:1 to about 1.6:1, from about 1.0:1 to about 1.4:1, from about 0.8:1 to about 1.4:1, and from about 0.8:1 to about 1.2:1.
20. The method of claim 19 , wherein the carbonate salt comprises Na 2 CO 3 .
21. The method of claim 20 , wherein said mole ratio of carbonate ions to nickel ions ranges from about 0.8:1 to about 1.4:1.
22. The method of one of claims 1 - 4 wherein providing or obtaining the starting material nickel composition further comprises (iii) washing the precipitated product of step (ii) with water, to provide a washed product; and (iv) partially drying the washed product of step (iii), to provide the starting material nickel composition.
23. The method of one of claims 1 - 4 , wherein said reduction of at least a portion of said starting material nickel composition is performed at a temperature range from about 150° C. to about 700° C.
24. The method of claim 23 , wherein said temperature ranges from about 350° C. to about 700° C.
25. The method of claim 24 , wherein said temperature ranges from about 350° C. to about 450° C.
26. The method of one of claims 1 - 4 , wherein said reducing agent is selected from the group consisting of: hydrogen, carbon dioxide, carbon monoxide, methane, ammonia, and hydrogen sulfide.
27. The method of one of claims 1 - 4 , wherein said bidentate phosphorus ligand is selected from the group consisting of:
wherein,
R 41 and R 45 are independently selected from the group consisting of C 1 to C 5 hydrocarbyl, and each of R 42 , R 43 , R 44 , R 46 , R 47 and R 48 and each of R 42 is independently selected from the group consisting of H and C 1 to C 4 hydrocarbyl;
or
R 41 is methyl, ethyl, isopropyl or cyclopentyl;
R 42 is H or methyl;
R 43 is H or a C 1 to C 4 hydrocarbyl;
R 44 is H or methyl;
R 45 is methyl, ethyl or isopropyl; and
R 46 , R 47 and R 48 are independently selected from the group consisting of H and C 1 to C 4 hydrocarbyl;
or
R 41 , R 44 , and R 45 are methyl;
R 42 , R 46 , R 47 and R 48 are H; and
R 43 is a C 1 to C 4 hydrocarbyl;
or
R 41 is isopropyl;
R 42 is H;
R 43 is a C 1 to C 4 hydrocarbyl;
R 44 is H or methyl;
R 45 is methyl or ethyl;
R 46 and R 48 are H or methyl; and
R 47 is H, methyl or tertiary-butyl;
or
R 41 is isopropyl;
R 42 , R 46 , and R 48 are H; and
R 43 , R 44 , R 45 , and R 47 are methyl.
28. A method of making a nickel complex, comprising performing the method of one of claims 1 - 4 to form the nickel-metal-containing solid, further comprising reacting said nickel-metal-containing solid with said bidentate phosphorus-containing ligand to form the nickel complex, wherein the concentration of the nickel-containing solid in the complex is about 820 ppm to about 1460 ppm.
29. The method of claim 28 , wherein said mole ratio of bicarbonate ions to said nickel ions is about 1.2:1 to about 1.9:1.