Compositions and processes for synthesizing borohydride compounds

• US 6,433,129 B1
• Filed: 11/08/2000
• Issued: 08/13/2002
• Est. Priority Date: 11/08/2000
• Status: Expired due to Fees

• Current Assignee: Millennium Cell Inc.
• Original Assignee: Millennium Cell Inc.
• Inventors: Kelly, Michael T., Amendola, Steven C.
• Primary Examiner(s): Truong, Duc
• Application Number:
  US09/710,041
• Time in Patent Office: 643 Days
• Field of Search: 528/394, 528/396, 528/271
• US Class Current: 528/271
• CPC Class Codes: C01B 2203/0227 containing a catalytic reforming step
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 3/34 by reaction of hydrocarbons with gasifying agents
• CPC Class Codes: C01B 6/21 Preparation of borohydrides of alkali metals, alkaline earth metals, magnesium or beryllium; Addition complexes thereof, e.g. LiBH4.2N2H4, NaB2H7
• CPC Class Codes: Y02P 20/582 Recycling of unreacted starting or intermediate materials

Abstract

The present invention relates to compositions and processes for producing borohydride compounds. In particular, the present invention provides efficient processes and compositions for the large-scale production of borohydride compounds.

Claims

1. A process for producing borohydride compounds, comprising:

(A) reacting a borate of the formula YBO₂ with CO₂ and H₂O to obtain YHCO₃ and B₂O₃;

(B) converting the YHCO₃ to Y₂O, CO₂, and H₂O;

(C) reacting the B₂O₃ with C and X₂ to obtain BX₃ and CO₂;

(D) reacting methane with Y₂O to obtain Y, carbon monoxide and H₂;

(E) reacting the Y with H₂ to obtain YH;

(F) reacting the BX₃ with the YH to obtain YHBX₃;

(G) separately reacting BX₃ with H₂ to obtain B₂H₆ and HX; and

(H) reacting the YHBX₃ with B₂H₆ to obtain YBH₄ and BX₃,

wherein Y is selected from the group consisting of the alkali metals, pseudo-alkali, an ammonium ion, and quaternary amines of formula NR₄⁺, wherein R is independently selected from H and straight or branched C1 to C4 alkyl groups; and

wherein X is selected from the group consisting of halides, alcohols, alkoxides, chalcogens, and chalcogenides.

2. The process according to claim 1, wherein step (C) is replaced with the following step (C2):

reacting the B₂O₃ with methane and X₂ to obtain BX₃, CO₂, and H₂.

3. The process according to claim 1, wherein Y is selected from the group consisting of H, Li, Na, K, Rb, Cs, Fr, NH₄⁺, TI, and quaternary amines of formula NR₄⁺, wherein R is independently selected from H and straight or branched C1 to C4 alkyl groups;

and

wherein X is selected from the group consisting of F, Cl, Br, I, At, —

OH, a C1 to C4 alkoxide, O, S, Se, Te, Po, —

SR, —

SeR, and —

TeR, wherein R is H or a straight or branched C1 to C4 alkyl group.

4. The process according to claim 3, wherein Y is selected from the group consisting of Na, Li, and K.

5. The process according to claim 1, wherein Y is an alkaline earth metal;

and wherein YBO₂ is replaced with Y(BO₂)₂, YHCO₃ is replaced with Y(HCO₃)₂, Y₂O is replaced with YO, YH is replaced with YH₂, YHBX₃ is replaced with Y(HBX₃)₂, and YBH₄ is replaced with Y(BH₄)₂.

6. The process according to claim 1, wherein the BX₃ of step (G) is hydrogenated with an aldehyde selected from the group consisting of formaldehyde, benzaldehyde, acetaldehyde, and mixtures thereof.

7. The process according to claim 1, wherein the BX₃ and YHCO₃ are obtained by the process comprising:

reacting a borate ore of the formula Y₂B₂O₄ with CO₂ and H₂O to obtain YHCO₃ and B(OH)₃; and

reacting the B(OH)₃ with HX to obtain BX₃ and H₂O.

8. The process according to claim 1, wherein the B₂O₃ and YHCO₃ are obtained by the process comprising reacting a borate ore of the formula Y₂B₂O₄ with CO₂ and water to obtain YHCO₃ and B₂O₃.

9. The process according to claim 1, wherein the X is independently selected to be the same or different in each applicable step.

10. The process according to claim 1, wherein steps (B) and (D) are substituted with the following steps (B1) and (D1):

(B1) converting YCO₃ to Y₂CO₃, water and carbon dioxide; and

(D1) reacting the Y₂CO₃ with carbon to obtain 2Y and carbon monoxide.

11. The process according to claim 1, wherein the BX₃ produced in step (H) is recycled for use in steps (F) and (G).

12. The process according to claim 1, wherein the H₂ produced in step (D) is recycled for use in steps (E) and (G).

13. The process according to claim 1, wherein carbon dioxide produced in steps (B) and (C) is recycled for use in step (A).

14. The process according to claim 1, further comprising

reacting methane and water to produce H₂ and carbon monoxide;

combining the carbon monoxide produced in the previous step and in step (D);

reacting the combined carbon monoxide with water to produce additional H₂ and carbon dioxide;

recycling the H₂ for use in steps (E) and (G); and

recycling the carbon dioxide for use in step (A).

15. The process according to claim 1, further comprising reacting the HX produced in step (G) with O₂ and CuX (solid) to produce X₂ and water, and recycling the X₂ for use in step (C).

16. The process according to claim 1, wherein steps (D) to (H) are replaced with the following steps (D2) and (E2):

(D2) reacting the BX₃ with H₂ to obtain B₂H₆ and HX; and

(E2) reacting B₂H₆ with the Y₂O to obtain a YBH₄ and a YBO₂.

17. The process according to claim 16, wherein Y is an alkaline earth metal;

and wherein YBO₂ is replaced with Y(BO₂)₂, YHCO₃ is replaced with Y(HCO₃)₂, and Y₂O is replaced with YO.

18. The process according to claim 16, wherein step (C) is replaced with the following step (C2):

reacting the B₂O₃ with methane and X₂ to obtain BX₃, CO₂, and H₂.

19. The process according to claim 16, wherein the BX3 of step (D2) is hydrogenated with an aldehyde selected from the group consisting of formaldehyde, benzaldehyde, acetaldehyde, and mixtures thereof.

20. The process according to claim 16, wherein the BX₃ and YHCO₃ are obtained by the process comprising:

reacting a borate ore of the formula Y₂B₂O₄ with CO₂ and H₂O to obtain YHCO₃ and B(OH)₃; and

reacting the B(OH)₃ with HX to obtain BX₃ and H₂O.

21. The process according to claim 16, wherein the B₂O₃ and YHCO₃ are obtained by the process comprising reacting a borate ore of the formula Y₂B₂O₄ with CO₂ and water to obtain YHCO₃ and B₂O₃.

22. The process according to claim 16, wherein X is independently selected to be the same or different in each applicable step.

23. The process according to claim 16, wherein the carbon dioxide produced in steps (B) and (C) are recycled for use in step (A).

24. The process according to claim 16, wherein the YBO₂ produced in step (E2) is recycled for use in step (A).

25. The process according to claim 16, further comprising:

reacting methane and water to produce H₂ and carbon monoxide;

reacting the carbon monoxide with water to produce additional H₂ and carbon dioxide;

recycling the H₂ for use in step (D2); and

recycling the carbon dioxide for use in step (A).

26. A borohydride compound obtained by the process according to claim 2.

27. A borohydride compound obtained by the process according to claim 15.

28. A borohydride compound obtained by the process according to claim 15.