Hydrogen generation system using stabilized borohydrides for hydrogen storage

• US 6,811,764 B2
• Filed: 09/12/2002
• Issued: 11/02/2004
• Est. Priority Date: 09/12/2002
• Status: Expired due to Fees

• Current Assignee: GM Global Technology Operations LLC (General Motors Company)
• Original Assignee: General Motors Corporation (Motors Liquidation Co. GUC Trust)
• Inventors: Jorgensen, Scott Willis, Perry, Belinda K.
• Primary Examiner(s): Bos, Steven
• Assistant Examiner(s): Medina, Maribel
• Application Number:
  US10/242,183
• Publication Number:
  US 20040052722A1
• Time in Patent Office: 782 Days
• Field of Search: 423/648.1, 423/658.2, 429/17
• US Class Current: 423/658.2
• CPC Class Codes: B01J 7/02 by wet methods
• CPC Class Codes: B01J 8/10 moved by stirrers or by rotary drums or rotary receptacles or endless belts
• CPC Class Codes: C01B 3/065 from a hydride
• CPC Class Codes: F17C 11/005 for hydrogen
• CPC Class Codes: H01M 8/04216 characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
• CPC Class Codes: H01M 8/065 by dissolution of metals or alloys; by dehydriding metallic substances
• CPC Class Codes: Y02E 60/32 Hydrogen storage
• CPC Class Codes: Y02E 60/36 Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

A method is provided that generates hydrogen to power a hydrogen consuming device. Hydrogen is stored on-board a motorized vehicle, or the like, in a stabilized slurry of alkali metal borohydride particles and water. Upon demand from the hydrogen consuming device, such as a fuel cell, a portion of the slurry is conveyed to a reactor where borohydride particles are heated so that they hydrolyze to produce hydrogen gas and solid-phase by-products. The reactor includes a mixing element therein where the slurry is mixed and ground to expose unreacted borohydride particles from the solid reaction products. A separate grinding mechanism can be used to further crush and grind by-product particles for reaction efficiency and product transport. The solid-phase by-products are then stored in a by-products storage vessel whereas hydrogen gas is delivered to either a hydrogen buffer container for temporary storage or to the hydrogen consuming device.

Claims

1. A method of generating hydrogen in a fuel supply system combined with a hydrogen consuming device, said method comprising the steps of:

storing a slurry of lithium and/or sodium borohydride particles in water in a fuel supply storage vessel, said water containing sufficient dissolved hydroxide ion to inhibit chemical reaction with said borohydride at ambient storage temperatures of said slurry, said slurry comprising, by weight, about 1.6 to 2.5 parts of water per 1 part of lithium borohydride, or 1 to 1.5 parts of water per 1 part of sodium borohydride;

conveying a portion of said slurry to the inlet of an axial flow-through reactor upon demand for hydrogen from said hydrogen consuming device, said reactor having a reaction zone;

reacting said borohydride particles and water in said reaction zone at a temperature above approximately 90°

C. to produce reaction products comprising hydrogen gas and solid by-products while mixing said borohydride particles and solid by-products in said reaction zone to expose unreacted borohydride particle surfaces for reaction with said water, and conveying the mixed materials through said reaction zone, said mixing and conveying using two rotating augers, the rate of conveying of said slurry to said reactor being controlled so as to retain a hydrogen gas volume in said reaction zone;

removing said reaction products from said reactor; and

conveying said hydrogen gas to said hydrogen consuming device or to a hydrogen buffer container for said device.

2. A method as recited in claim 1, comprising pre-heating said slurry before it enters said reactor.

3. A method as recited in claim 1, comprising reacting said borohydride particles at temperatures of at least 120°

C.

4. A method as recited in claim 1, comprising grinding said solid by-products and conveying them to an unheated by-products storage vessel.

5. A method as recited in claim 1, further comprising conveying said hydrogen gas from said reactor to said fuel supply storage vessel before conveying said hydrogen to said hydrogen consuming device or buffer.

6. A method as recited in claim 1, comprising conveying said reaction products from said reactor to a grinding mechanism for comminution of said solid by-product.

7. A method as recited in claim 6, further comprising conveying said hydrogen gas, water vapor and said solid by-products from said grinding operation to a by-products storage vessel.

8. A method as recited in claim 7, further comprising conveying said hydrogen gas and any vaporized water from said by-products storage vessel to said slurry in said fuel supply vessel to condense at least a portion of said water vapor.

9. A method as recited in claim 1, comprising separately storing said by-products and said slurry in said fuel supply storage vessel.

10. A method of generating hydrogen in a fuel supply system combined with a hydrogen consuming device, said method comprising the steps of:

storing a slurry of lithium and/or sodium borohydride particles in water in a fuel supply storage vessel, said water containing sufficient dissolved hydroxide ion to inhibit chemical reaction with said borohydride at ambient storage temperatures of said slurry, said slurry comprising, by weight, about 1.6 to 2.5 parts of water per 1 part of lithium borohydride, or 1 to 1.5 parts of water per 1 part of sodium borohydride;

conveying a portion of said slurry to the inlet of an axial flow-through reactor upon demand for hydrogen from said hydrogen consuming device, said reactor having a reaction zone and a grinding zone downstream from said reaction zone;

reacting said borohydride particles and water in said reaction zone at a temperature above approximately 90°

C. to produce reaction products comprising hydrogen gas and solid by-products while mixing said borohydride particles and solid by-products in said reaction zone to expose unreacted borohydride particle surfaces for reaction with said water, and conveying the mixed materials through said reaction zone, said mixing and conveying using two rotating augers, the rate of conveying of said slurry to said reactor being controlled so as to retain a gas volume in said reaction zone at least as large as the volume of said mixed materials in said reactor;

grinding said solid by-products to a storable particle size in said grinding zone, and conveying them to a by-products storage vessel; and

conveying said hydrogen gas to said hydrogen consuming device or to a hydrogen buffer container for said device.

11. A method as recited in claim 10, comprising pre-heating said slurry before entering said reactor.

12. A method as recited in claim 10, comprising reacting said borohydride particles at temperatures of at least 120°

C.

13. A method as recited in claim 10, comprising conveying said hydrogen gas and any vaporized water from said by-products storage vessel to said slurry in said fuel supply vessel to condense at least a portion of said water vapor.

14. A method as recited in claim 10, comprising separately storing said by-products and said slurry in said fuel supply vessel.

15. A method of generating hydrogen in a fuel supply system combined with a hydrogen consuming device, said method comprising the steps of:

storing a slurry of lithium and/or sodium borohydride particles in water in a fuel supply storage vessel, said water containing sufficient dissolved hydroxide ion to inhibit chemical reaction with said borohydride at ambient storage temperatures of said slurry, said slurry comprising, by weight, about 1.6 to 2.5 parts of water per 1 part of lithium borohydride, or 1 to 1.5 parts of water per 1 part of sodium borohydride;

conveying a portion of said slurry to an axial flow-through reactor upon demand for hydrogen from said hydrogen consuming device, said reactor having a reaction zone and a gas separation zone;

reacting said borohydride particles and water in said reaction zone at a temperature above approximately 90°

C. to produce reaction products comprising hydrogen gas and solid by-products while mixing said borohydride particles and solid by-products in said reaction zone to expose unreacted borohydride particle surfaces for reaction with said water, and conveying the mixed materials through said reaction zone, said mixing and conveying using two rotating augers, the rate of conveying of said slurry to said reactor being controlled so as to retain a gas volume in said reaction zone at least as large as the volume of said mixed materials in said reactor;

separating said hydrogen from said solid by-products in said separation zone and conveying said hydrogen gas from said separation zone to said slurry stored in said fuel supply storage vessel to condense any water vapor in said gas; and

conveying said hydrogen gas from said fuel supply storage vessel to said hydrogen consuming device or to a hydrogen buffer container for said device.

16. A method as recited in claim 15, comprising conveying said by-products to a by-products storage vessel.

17. A method as recited in claim 15, comprising reacting said borohydride particles at temperatures of at least 120°

C.

18. A method as recited in claim 15, comprising separately storing said by-products and said slurry in said fuel supply vessel.