Processes for synthesizing alkali metal borohydride compounds

• US 6,586,563 B1
• Filed: 12/18/2001
• Issued: 07/01/2003
• Est. Priority Date: 12/18/2001
• Status: Expired due to Fees

• Current Assignee: Millennium Cell Inc.
• Original Assignee: Millennium Cell Inc.
• Inventors: Ortega, Jeffrey V., Kelly, Michael T., Amendola, Steven C., Wu, Ying
• Primary Examiner(s): Boykin, Terressa M.
• Application Number:
  US10/022,077
• Publication Number:
  US 20030114632A1
• Time in Patent Office: 560 Days
• Field of Search: 528/271, 528/394, 528/396
• US Class Current: 528/394
• 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: C01B 6/23 Preparation of borohydrides of other metals, e.g. aluminium borohydride; Addition complexes thereof, e.g. Li[Al(BH4)3H]

Abstract

Processes for synthesizing borohydride compounds with reduced energy requirements and high efficiency are disclosed. The processes include the reaction of a base with a borane complex or diborane to produce a borohydride compound of formula YBH₄, where Y is a monovalent cationic moiety.

Claims

1. A process for producing borohydride compounds, wherein the process comprises reacting a borane complex in a solution comprising a non-aqueous aprotic solvent or a non-aqueous polar solvent with a base, thereby providing a borohydride compound of formula YBH₄, wherein Y is a monovalent cationic moiety and the base is selected from the group consisting of a hydroxide of formula YOH and a carbonate of formula Y₂CO₃.

2. The process according to claim 1, wherein Y is selected from the group consisting of alkali metals, pseudo-alkali metals, and a quaternary ammonium ion of formula NR₄⁺ wherein R is a straight chain C₁ to C₄ alkyl group, a branched chain C₁ to C₄ alkyl group, or a mixture thereof.

3. The process according to claim 1, wherein Y is selected from the group consisting of Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Fr⁺, Tl⁺, and a quaternary ammonium ion of formula NR₄⁺, wherein R is a straight chain C₁ to C₄ alkyl group or a branched chain 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 the borane complex is in solution in a non-aqueous aprotic solvent, and said solvent is an organic glyme.

6. The process according to claim 1, wherein the borane complex and the base are reacted at a temperature between about −

5 and about 30°

C.

7. The process according to claim 1, wherein the borane complex and the base are reacted for a time period between 2 and 70 hours.

8. The process according to claim 1, wherein the borane complex is selected from the group consisting of borane-tetrahydrofuran, borane-morpholine, borane-ammonia, borane-triethylamine, borane-trimethylamine, borane-N,N-diethylaniline, borane-dimethylamine, borane-dimethylsulfide, borane-tert-butylamine, borane-diethylamine, borane-iso-propylamine and borane-pyridine.

9. The process according to claim 8, wherein the borane complex is selected from the group consisting of borane-tetrahydrofuran and borane-triethylamine.

10. A process for producing borohydride compounds, comprising,

(a) reacting gaseous diborane with a carbonate of formula Y₂CO₃ in the solid phase the absence of solvent, thereby providing a borohydride of formula YBH₄, a borate of formula YBO₂, and unreacted solid carbonate, where Y is sodium;

(b) isolating the borohydride;

(c) adding an alcohol, wherein the borate is substantially soluble in the alcohol and the unreacted solid sodium carbonate is substantially insoluble in the alcohol; and

(d) isolating the unreacted sodium solid carbonate.

11. A process for producing borohydride compounds, comprising:

(a) reacting gaseous diborane with a carbonate of formula Y₂CO₃ suspended in a non-aqueous aprotic solvent or a non-aqueous polar solvent, thereby providing a borohydride of formula YBH₄, a borate of formula YBO₂, and unreacted solid carbonate, where Y is sodium;

(b) isolating the borohydride;

(c) adding an alcohol, wherein the borate is substantially soluble in the alcohol and the unreacted solid sodium carbonate is substantially insoluble in the alcohol; and

(d) isolating the unreacted solid sodium carbonate.

12. A process for producing borohydride compounds, comprising:

(a) reacting a borane complex in a solution comprising a non-aqueous polar solvent with a carbonate of formula Y₂CO₃ suspended therein, thereby providing a borohydride of formula YBH₄, a borate of formula YBO₂, and unreacted solid carbonate, where Y is sodium;

(b) isolating the borohydride;

(c) adding an alcohol to the borate and the unreacted solid carbonate, wherein the borate is substantially soluble in the alcohol and the unreacted solid sodium carbonate is substantially insoluble in the alcohol; and

(d) isolating the unreacted solid sodium carbonate.