PROCESSES FOR FORMING TITANIUM CATECHOL COMPLEXES

• US 20180029965A1
• Filed: 07/26/2016
• Published: 02/01/2018
• Est. Priority Date: 07/26/2016
• Status: Active Grant

• Current Assignee: Lockheed Martin Corporation (Martin Marietta Corporation)
• Original Assignee: Lockheed Martin Advanced Energy Storage, LLC (Martin Marietta Corporation)
• Inventors: MILLARD, Matthew
• Granted Patent: US 10,343,964 B2
• Time in Patent Office: Days
• CPC Class Codes: C07C 303/22 from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
• CPC Class Codes: C07C 309/42 having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
• CPC Class Codes: C07C 37/66 by conversion of hydroxy groups to O-metal groups
• CPC Class Codes: C07C 39/235 Metal derivatives of a hydroxy group bound to a six-membered aromatic ring
• CPC Class Codes: C07F 7/28 Titanium compounds
• CPC Class Codes: H01M 2300/0002 Aqueous electrolytes
• CPC Class Codes: H01M 2300/0014 Alkaline electrolytes
• CPC Class Codes: H01M 8/08 Fuel cells with aqueous electrolytes
• CPC Class Codes: H01M 8/083 Alkaline fuel cells
• CPC Class Codes: H01M 8/188 by recharging of redox couples containing fluids; Redox flow type batteries
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

Titanium complexes containing catecholate ligands can be desirable active materials for flow batteries and other electrochemical energy storage systems. Such complexes can be formed, potentially on very large scales, through reacting a catechol compound in an organic solvent with titanium tetrachloride, and then obtaining an aqueous phase containing an alkali metal salt form of the titanium catechol complex. More specifically, the methods can include: forming a catechol solution and heating, adding titanium tetrachloride to the catechol solution, reacting the titanium tetrachloride with a catechol compound to evolve HCl gas and to form an intermediate titanium catechol complex, and adding an alkaline aqueous solution to the intermediate titanium catechol complex to form an alkali metal salt form titanium catechol complex that is at least partially dissolved in an aqueous phase. The aqueous phase can be separated from an organic phase. The resulting complexes can be substantially free of alkali metal halide salts.

Claims

1. A method comprising:

forming a catechol solution comprising a catechol compound and an organic solvent;

heating the catechol solution;

adding titanium tetrachloride to the catechol solution to form a reaction mixture;

reacting the titanium tetrachloride with the catechol compound to evolve HCl gas from the reaction mixture and to form an intermediate titanium catechol complex; and

adding an alkaline aqueous solution to the intermediate titanium catechol complex, the alkaline aqueous solution comprising an alkali metal base;

wherein the alkali metal base converts the intermediate titanium catechol complex into an alkali metal salt form titanium catechol complex that is at least partially dissolved in an aqueous phase.

2. The method of claim 1, wherein the catechol compound is 1,2-dihydroxybenzene.

3. The method of claim 1, wherein the catechol compound comprises at least one substituted catechol compound.

4. The method of claim 3, wherein the at least one substituted catechol compound comprises 3,4-dihydroxybenzenesulfonic acid.

5. The method of claim 1, wherein the alkali metal base comprises an alkali metal hydroxide selected from the group consisting of sodium hydroxide, potassium hydroxide, and any combination thereof.

6. The method of claim 1, wherein the alkali metal base comprises a mixture of sodium hydroxide and potassium hydroxide.

7. The method of claim 1, wherein the HCl gas is substantially removed from the reaction mixture before adding the alkaline aqueous solution to the intermediate titanium catechol complex.

8. The method of claim 7, wherein the reaction mixture is maintained at a reduced pressure before adding the alkaline aqueous solution thereto.

9. The method of claim 7, wherein a flowing inert gas contacts the reaction mixture while evolving the HCl gas therefrom.

10. The method of claim 1, wherein the intermediate titanium catechol complex is insoluble in the reaction mixture.

11. The method of claim 1, wherein the intermediate titanium catechol complex is not isolated from the reaction mixture before adding the alkaline aqueous solution thereto.

12. The method of claim 1, wherein the organic solvent comprises a water-immiscible organic solvent.

13. The method of claim 12, wherein the water-immiscible organic solvent is selected from the group consisting of toluene, xylenes, cyclohexane, dichloromethane, dichloroethane, and any combination thereof.

14. The method of claim 1, wherein an amount of the alkali metal base in the alkaline aqueous solution is such that the aqueous phase containing the alkali metal salt form titanium catechol complex has a pH of about 6 to about 8.

15. The method of claim 14, further comprising:

adding an additional quantity of the alkaline aqueous solution or a different alkaline aqueous solution to the aqueous phase to adjust the pH of the aqueous phase to a range of about 9 to about 10.

16. The method of claim 1, wherein the alkali metal salt form titanium catechol complex has a formula of

D₂Ti(L)₃;

wherein D is an alkali metal ion or a mixture of alkali metal ions, and L is a substituted catecholate ligand, an unsubstituted catecholate ligand, or any combination thereof.

17. The method of claim 1, wherein the intermediate titanium catechol complex and the alkali metal salt form titanium catechol complex are formed consecutively in a single reaction vessel.

18. A method comprising:

providing a catechol solution comprising a catechol compound and an organic solvent, the organic solvent being water-immiscible;

while heating the catechol solution, adding titanium tetrachloride thereto to evolve HCl gas and to form a reaction mixture comprising an intermediate titanium catechol complex;

wherein the intermediate titanium catechol complex is insoluble in the reaction mixture;

without isolating the intermediate titanium catechol complex from the reaction mixture, adding an alkaline aqueous solution to the intermediate titanium catechol complex;

wherein the alkaline aqueous solution comprises an alkali metal base;

reacting the alkali metal base with the intermediate titanium catechol complex to form an alkali metal salt form titanium catechol complex that is at least partially dissolved in an aqueous phase; and

separating the aqueous phase and an organic phase from one another.

19. The method of claim 18, wherein the alkali metal base comprises a mixture of sodium hydroxide and potassium hydroxide.

20. The method of claim 18, wherein heating is continued after adding the alkaline aqueous solution to the reaction mixture.

21. The method of claim 18, wherein the HCl gas is substantially removed from the reaction mixture before adding the alkaline aqueous solution thereto.

22. The method of claim 21, wherein the reaction mixture is maintained at a reduced pressure before adding the alkaline aqueous solution thereto.

23. The method of claim 21, wherein a flowing inert gas contacts the reaction mixture while evolving the HCl gas therefrom.

24. The method of claim 18, wherein an amount of the alkali metal base in the alkaline aqueous solution is such that the aqueous phase containing the alkali metal salt form titanium catechol complex has a pH of about 6 to about 8.

25. The method of claim 24, further comprising:

adding an additional quantity of the alkaline aqueous solution or a different alkaline aqueous solution to the aqueous phase to adjust the pH of the aqueous phase to a range of about 9 to about 10.

26. A composition comprising:

an aqueous phase; and

an alkali metal salt form titanium catechol complex dissolved in the aqueous phase;

wherein the composition comprises about 0.01 molar equivalents or less of alkali metal halide salts relative to the alkali metal salt form titanium catechol complex.

27. A flow battery comprising an electrolyte solution comprising the composition of claim 26.