Apparatus for generating hydrogen gas

• US 20020122759A1
• Filed: 02/26/2002
• Published: 09/05/2002
• Est. Priority Date: 03/01/2001
• Status: Active Grant

• Current Assignee: Toyota Jidosha Kabushiki Kaisha (Toyota Motor Corporation)
• Original Assignee: Toyota Jidosha Kabushiki Kaisha (Toyota Motor Corporation)
• Inventors: Hayashi, Takahiro, Sugiyama, Masahiko, Ishikiriyama, Mamoru, Saito, Yasukazu
• Granted Patent: US 7,101,411 B2
• Time in Patent Office: Days
• US Class Current: 422/212
• CPC Class Codes: B01J 16/005 in the presence of catalytically active bodies, e.g. porous plates
• CPC Class Codes: B01J 19/247 Suited for forming thin films
• CPC Class Codes: B01J 19/249 Plate-type reactors
• CPC Class Codes: B01J 19/26 Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
• CPC Class Codes: B01J 19/285 Shaking or vibrating reactors; reactions under the influence of low-frequency vibrations or pulsations for sonic and ultrasonic vibrations B01J19/10
• CPC Class Codes: B01J 2219/00083 Coils
• CPC Class Codes: B01J 2219/00135 Electric resistance heaters
• CPC Class Codes: B01J 2219/00162 controlling the pressure
• CPC Class Codes: B01J 2219/1941 circular or disk-shaped
• CPC Class Codes: B01J 2219/2453 Plates arranged in parallel
• CPC Class Codes: B01J 2219/2458 Flat plates, i.e. plates which are not corrugated or otherwise structured, e.g. plates with cylindrical shape
• CPC Class Codes: B01J 2219/2479 Catalysts coated on the surface of plates or inserts
• CPC Class Codes: B01J 7/02 by wet methods
• CPC Class Codes: C01B 2203/0277 containing a catalytic decomposition step
• CPC Class Codes: C01B 2203/04 containing a purification step for the hydrogen or the synthesis gas
• CPC Class Codes: C01B 2203/0405 Purification by membrane separation
• CPC Class Codes: C01B 2203/0415 Purification by absorption in liquids
• CPC Class Codes: C01B 2203/048 the impurity being an organic compound
• CPC Class Codes: C01B 2203/065 using hydrotreating, e.g. hydrogenation, hydrodesulfurisation
• CPC Class Codes: C01B 2203/066 with fuel cells
• CPC Class Codes: C01B 2203/0811 : by combustion of fuel
• CPC Class Codes: C01B 2203/0822 : the fuel containing hydrogen
• CPC Class Codes: C01B 2203/0827 : at least part of the fuel being a recycle stream
• CPC Class Codes: C01B 2203/085 : by electric heating
• CPC Class Codes: C01B 2203/0866 : by combination of different heating methods
• CPC Class Codes: C01B 2203/0883 : by indirect heat exchange
• CPC Class Codes: C01B 2203/1041 : Composition of the catalyst
• CPC Class Codes: C01B 2203/1052 : Nickel or cobalt catalysts
• CPC Class Codes: C01B 2203/1064 : Platinum group metal catalysts
• CPC Class Codes: C01B 2203/107 : Platinum catalysts
• CPC Class Codes: C01B 2203/1082 : Composition of support materials
• CPC Class Codes: C01B 2203/1247 : Higher hydrocarbons
• CPC Class Codes: C01B 2203/148 : involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
• CPC Class Codes: C01B 2203/1609 : Shutting down the process
• CPC Class Codes: C01B 2203/1619 : Measuring the temperature
• CPC Class Codes: C01B 2203/1633 : Measuring the pressure
• CPC Class Codes: C01B 2203/1647 : Controlling the amount of the product
• CPC Class Codes: C01B 2203/1657 : the product being hydrogen
• CPC Class Codes: C01B 2203/1685 : Control based on demand of downstream process
• CPC Class Codes: C01B 2203/169 : Controlling the feed
• CPC Class Codes: C01B 2203/1695 : Adjusting the feed of the combustion
• CPC Class Codes: C01B 3/26 : using catalysts
• CPC Class Codes: C10G 2/32 : with the use of catalysts
• CPC Class Codes: H01M 8/0606 : with means for production of gaseous reactants
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 20/10 : Process efficiency

Abstract

An apparatus for generating hydrogen gas in which hydrogen gas of a high purity is supplied to a hydrogen-utilizing device by using a decahydronaphthalene/naphthalene reaction. The apparatus includes a storage tank in which decahydronaphthalene is stored as a crude fuel, a reaction tank which has a catalyst and a heater for heating the catalyst and which causes dehydrogenation of decahydronaphthalene supplied from the storage tank to the heated catalyst, and a separation tank in which hydrogen-rich gas is separated out from naphthalene and hydrogen gas supplied from the reaction tank by using a hydrogen separation film and from which the separated hydrogen gas is discharged.

Claims

1. An apparatus for generating hydrogen gas, the apparatus comprising:

a storage tank in which fuel comprised of one of decahydronaphthalene and a substance that includes decahydronaphthalene as a principal component is stored;

supplying means connected to the storage tank for supplying fuel from the storage tank;

a reaction tank which includes a catalyst and a heater for heating the catalyst, the reaction tank being connected to the supplying means for receiving fuel supplied by the supplying means from the storage tank, the supplied fuel forming a liquid-film on the catalyst and being dehydrogenated to generate naphthalene and hydrogen gas; and

a separation tank which includes hydrogen gas separation means, the separation tank being connected to the reaction tank for receiving naphthalene and hydrogen gas, and the hydrogen gas separation means separating hydrogen gas out of received naphthalene and hydrogen gas for discharge of the hydrogen gas.

2. The apparatus of claim 1, further comprising a regeneration tank which includes another catalyst and another heater for heating the other catalyst, the regeneration tank being connected to the separation tank for receiving naphthalene, wherein the regeneration tank receives naphthalene and hydrogen gas, and the naphthalene is hydrogenated on the other catalyst.

3. The apparatus of claim 2, further comprising a hydrogen gas storage tank connected to the separation tank for receiving and storing hydrogen gas discharged from the separation tank.

4. The apparatus of claim 3, wherein the hydrogen gas storage tank is connected to the regeneration tank for supplying hydrogen gas to the regeneration tank.

5. The apparatus of claim 4, wherein hydrogen gas is suppliable into the regeneration tank from an external source.

10. The apparatus of claim 1, further comprising a decahydronaphthalene recovering apparatus which recovers unreacted decahydronaphthalene from the reaction tank.

12. The apparatus of claim 10, wherein the decahydronaphthalene recovering apparatus is connectable to at least one of the storage tank and the separation tank for supplying decahydronaphthalene thereto.

14. The apparatus of claim 1, further comprising:

a hydrogen gas detector connected to the reaction tank for detecting an amount of hydrogen gas generated by dehydrogenation; and

control means connected to the supplying means for controlling amount of fuel on the catalyst in accordance with the amount of hydrogen gas detected by the detector to generate at least a predetermined level of hydrogen gas.

16. The apparatus of claim 1, wherein naphthalene is stored in the separation tank.

18. The apparatus of claim 2, wherein at least one of tetrahydronaphthalene and decahydronaphthalene is generated in the regeneration tank and supplied to the storage tank.

20. The apparatus of claim 1, wherein the hydrogen gas separation means comprises at least one of an adsorption-permeation device which adsorbs naphthalene and decahydronaphthalene and permeates hydrogen gas, a hydrogen gas separation film, and a cooling device which cools naphthalene and hydrogen gas.

22. The apparatus of claim 1, wherein the catalyst comprises at least one of a carbon-supported Pt catalyst, a carbon-supported Pt—

Ir bimetallic catalyst, a carbon-supported Pt—

Re bimetallic catalyst and a carbon-supported Pt—

W bimetallic catalyst.

24. The apparatus of claim 1, wherein the substance that includes decahydronaphthalene as a principal component comprises at least one of a mixed fuel of decahydronaphthalene and tetrahydronaphthalene, and a naphthene-based fuel that includes decahydronaphthalene.

26. The apparatus of claim 1, further comprising a tetrahydronaphthalene storage tank connected to the reaction tank, tetrahydronaphthalene being supplied therefrom to the heated catalyst and dehydrogenated prior to commencing dehydrogenation of the fuel.

6. An apparatus for generating hydrogen gas, the apparatus comprising:

a storage tank in which fuel comprised of one of decahydronaphthalene and a substance that includes decahydronaphthalene as a principal component is stored;

first supplying means connected to the storage tank for supplying fuel from the storage tank;

second supplying means for supplying naphthalene and hydrogen gas;

a reaction-regeneration tank which includes a catalyst and a heater for heating the catalyst, selectively connectable in fluid communication to the first supplying means for receiving fuel supplied by the first supplying means and to the second supplying means for receiving naphthalene and hydrogen gas supplied by the second supplying means, wherein, when fuel is received, the fuel forms a liquid-film on the catalyst and is dehydrogenated to generate naphthalene and hydrogen gas, and when naphthalene and hydrogen gas are received, the naphthalene is hydrogenated on the catalyst; and

a separation tank which includes hydrogen gas separation means, the separation tank being connected to the reaction-regeneration tank for receiving naphthalene and hydrogen gas, and to the second supplying means for supplying naphthalene, the hydrogen gas separation means separating hydrogen gas out of received naphthalene and hydrogen gas for discharge.

7. The apparatus of claim 6, further comprising a hydrogen gas storage tank connected to the separation tank for receiving and storing hydrogen gas discharged from the separation tank.

8. The apparatus of claim 7, wherein the hydrogen gas storage tank is connected to the reaction-regeneration tank for supplying hydrogen gas to the reaction-regeneration tank.

9. The apparatus of claim 6, wherein hydrogen gas is suppliable to the reaction-regeneration tank from an external source.

11. The apparatus of claim 6, further comprising a decahydronaphthalene recovering apparatus which recovers unreacted decahydronaphthalene from the reaction-regeneration tank.

13. The apparatus of claim 11, wherein the decahydronaphthalene recovering apparatus is connectable to at least one of the storage tank and the separation tank for supplying decahydronaphthalene thereto.

15. The apparatus of claim 6, further comprising:

a hydrogen gas detector connected to the reaction-regeneration tank for detecting an amount of hydrogen gas generated by dehydrogenation; and

control means connected to the first supplying means for, when the reaction-regeneration tank is receiving fuel, controlling amount of fuel on the catalyst in accordance with the amount of hydrogen gas detected by the detector to generate at least a predetermined level of hydrogen gas.

17. The apparatus of claim 6, wherein naphthalene is stored in the separation tank.

19. The apparatus of claim 6, wherein at least one of tetrahydronaphthalene and decahydronaphthalene is generated in the regeneration tank and supplied to the storage tank.

21. The apparatus of claim 6, wherein the hydrogen gas separation means comprises at least one of an adsorption-permeation device which adsorbs naphthalene and decahydronaphthalene and permeates hydrogen gas, a hydrogen gas separation film, and a cooling device which cools naphthalene and hydrogen gas.

23. The apparatus of claim 6, wherein the catalyst comprises at least one of a carbon-supported Pt catalyst, a carbon-supported Pt—

Ir bimetallic catalyst, a carbon-supported Pt—

Re bimetallic catalyst and a carbon-supported Pt—

W bimetallic catalyst.

25. The apparatus of claim 6, wherein the substance that includes decahydronaphthalene as a principal component comprises at least one of a mixed fuel of decahydronaphthalene and tetrahydronaphthalene, and a naphthene-based fuel that includes decahydronaphthalene.

27. The apparatus of claim 6, further comprising a tetrahydronaphthalene storage tank connected to the reaction-regeneration tank, tetrahydronaphthalene being supplied therefrom to the heated catalyst and dehydrogenated prior to commencing dehydrogenation of the fuel.