Compositions and processes for synthesizing borohydride compounds

• US 7,019,105 B2
• Filed: 04/04/2002
• Issued: 03/28/2006
• 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:
  US10/116,767
• Publication Number:
  US 20040191152A1
• Time in Patent Office: 1,454 Days
• Field of Search: 528/394, 528/271, 528/396
• 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 methane with a Y-containing species of formula Y₂O to obtain Y, carbon monoxide and H₂;

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

(C) reacting a boron-containing species of the formula BX₃ with the YH to obtain YHBX₃;

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

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

wherein Y is selected from the group consisting of the alkali metals, pseudo-alkali metals, 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 Y is selected from the group consisting of H, Li, Na, K, Rb, Cs, Fr, NH₄⁺, Tl, 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.

3. The process according to claim 2, wherein Y is selected from the group consisting of Na, Li, and K.

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

5. The process according to claim 1, wherein the steps (D) and (E) are replaced with the following step of reacting YHBX₃ with H₂ to produce YBH₄ and HX.

6. The process according to claim 1, wherein the BX₃ produced in step (B) is recycled for use in steps (C) and (D).

7. The process according to claim 1, wherein the H₂ produced in step (A) is recycled for use in steps (B) and (D).

8. 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 (A);

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

recycling the H₂ for use in steps (B) and (D).

9. The process according to claim 1, wherein the Y-containing species of the formula Y₂O and the boron-containing species of the formula BX₃ are obtained by the process comprising:

(1) reacting a borate of the formula YBO₂ with HX to obtain YX, BX₃, and water;

(2) reacting the YX with water to obtain YOH and HX; and

(3) converting the YOH to Y₂O and H₂O,

wherein Y and X are defined in claim 1.

10. The process according to claim 9, wherein Y is an alkaline earth metal;

and wherein YBO₂ is replaced with Y(BO₂)₂, YX is replaced with YX2, YOH is replaced with Y(OH)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.

11. The process according to claim 9, wherein the BX₃ is 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.

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

13. The process according to claim 9, wherein the BX₃ produced in step (E) is recycled for use in steps (C) and (D).

14. The process according to claim 9, wherein the H₂ produced in step (A) is recycled for use in steps (B) and (D).

15. The process according to claim 9, wherein the HX produced in steps (D) and (2) are recycled for use in step (1).

16. The process according to claim 9, further comprising

reacting methane and water to produce H₂ and carbon monoxide;

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

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

recycling the H₂ for use in steps (B) and (D).

17. The process according to claim 1, wherein the Y-containing species of formula Y₂O and the boron-containing species of the formula BX₃ and obtained by the process comprising:

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

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

(iii) reacting the B₂O₃ with HX to obtain BX₃ and H₂O,

wherein Y and X are defined in claim 1.

18. The process according to claim 17, 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.

19. The process according to claim 17, 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.

20. The process according to claim 17, 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.

21. The process according to claim 17, wherein the X is independently selected to be the same or different in each applicable step.

22. The process according to claim 17, wherein steps (ii) and (A) are substituted with the following steps (ii1) and (A1):

(ii1) converting YHCO₃ to Y₂CO₃, water and carbon dioxide; and

(A1) reacting the Y₂CO₃ with carbon to obtain 2Y and carbon monoxide.

23. The process according to claim 17, wherein the BX₃ produced in step (E) is recycled for use in steps (C) and (D).

24. The process according to claim 17, wherein the H₂ produced in step (A) is recycled for use in steps (B) and (D).

25. The process according to claim 17, wherein the HX produced in step (D) is recycled for use in step (iii).

26. The process according to claim 17, wherein carbon dioxide produced in step (ii) is recycled for use in step (i).

27. The process according to claim 17, further comprising

reacting methane and water to produce H₂ and carbon monoxide;

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

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

recycling the H₂ for use in steps (B) and (D); and

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