Auto-oxidation and internal heating type reforming method and apparatus for hydrogen production

• US 6,506,359 B1
• Filed: 10/13/2000
• Issued: 01/14/2003
• Est. Priority Date: 10/20/1999
• Status: Expired due to Fees

• Current Assignee: Nippon Chemical Plant Consultant Co., Ltd.
• Original Assignee: Nippon Chemical Plant Consultant Co., Ltd.
• Inventors: Maruko, Saburo
• Primary Examiner(s): Langel, Wayne A.
• Application Number:
  US09/688,752
• Time in Patent Office: 823 Days
• Field of Search: 423/648.1, 423/652, 423/656
• US Class Current: 423/648.1
• CPC Class Codes: B01J 2208/00309 with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
• CPC Class Codes: B01J 8/0484 the beds being placed next to each other
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/0244 the reforming step being an autothermal reforming step, e.g. secondary reforming processes
• CPC Class Codes: C01B 2203/0405 Purification by membrane separation
• CPC Class Codes: C01B 2203/047 the impurity being carbon monoxide
• CPC Class Codes: C01B 2203/0811 by combustion of fuel
• CPC Class Codes: C01B 2203/0844 the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
• 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 2203/0894 Generation of steam
• CPC Class Codes: C01B 2203/1041 Composition of the catalyst
• CPC Class Codes: C01B 2203/1047 Group VIII metal catalysts
• CPC Class Codes: C01B 2203/1052 Nickel or cobalt catalysts
• CPC Class Codes: C01B 2203/1064 Platinum group metal catalysts
• CPC Class Codes: C01B 2203/1082 Composition of support materials
• CPC Class Codes: C01B 2203/1217 Alcohols
• CPC Class Codes: C01B 2203/1235 Hydrocarbons
• CPC Class Codes: C01B 2203/1276 Mixing of different feed components
• CPC Class Codes: C01B 2203/1294 Evaporation by heat exchange with hot process stream
• CPC Class Codes: C01B 2203/141 : At least two reforming, decomposition or partial oxidation steps in parallel
• CPC Class Codes: C01B 2203/143 : Three or more reforming, decomposition or partial oxidation steps in series
• CPC Class Codes: C01B 2203/80 : Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
• CPC Class Codes: C01B 2203/82 : Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
• CPC Class Codes: C01B 3/323 : Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
• CPC Class Codes: C01B 3/38 : using catalysts
• CPC Class Codes: C01B 3/384 : the catalyst being continuously externally heated
• CPC Class Codes: C01B 3/48 : followed by reaction of water vapour with carbon monoxide

Abstract

An auto-oxidation and internal heating type reforming method and apparatus for hydrogen production are disclosed for use in a process in which a gaseous mixture of a hydrocarbon or an aliphatic alcohol with water vapor is fed into contact with a mass of a reforming catalyst to bring about a reforming reaction of the gaseous mixture to produce hydrogen, wherein a small amount of an oxidizing catalyst is admixed with the reforming catalyst in that mass; and a small amount of oxygen is admixed with the gaseous mixture, whereby a portion of the hydrocarbon or aliphatic alcohol is exothermally oxidized to generate a quantity of heat required to reform the gaseous mixture of the hydrocarbon or aliphatic alcohol with water vapor.

Claims

1. An auto-oxidation and internal heating type reforming method for hydrogen production for use in a process which comprises contacting (i) a gaseous mixture of a hydrocarbon or an aliphatic alcohol and water vapor with (ii) a mass of a reforming catalyst to bring about a reforming reaction of the gaseous mixture to produce hydrogen, the method comprising the steps of:

distributively admixing an oxidizing catalyst with said reforming catalyst in said mass, said oxidizing catalyst being in an amount ranging between 1 and 10% of said reforming catalyst; and

admixing oxygen with the gaseous mixture of said hydrocarbon or aliphatic alcohol with water vapor, after the gaseous mixture comes into contact with said mass and the gaseous mixture is thereby in part reformed,

whereby a portion of said hydrocarbon or aliphatic alcohol is exothermally oxidized to generate an amount of heat required to reform said gaseous mixture of said hydrocarbon or aliphatic alcohol with water vapor.

2. The reforming method as set forth in claim 1, which further comprises the steps of:

using a reforming reaction catalyst loaded bed, a reforming reaction catalyst and oxidizing catalyst mixture loaded bed and a shift catalyst loaded bed partitioned by wall surfaces; and

transferring heat generated by (i) an oxidation in said reforming reaction catalyst and oxidizing catalyst mixture loaded bed and (ii) a shift reaction in said shift catalyst bed, into said reforming reaction catalyst loaded bed.

3. The reforming method as set forth in claim 1, wherein the reforming reaction is carried out at a pressure of 6 to 8 kg/cm².

4. The reforming method as set forth in claim 2, wherein the reforming reaction is carried out at a pressure of 6 to 8 kg/cm².

5. The reforming method as set forth in claim 1, wherein the gaseous mixture includes a hydrocarbon.

6. The reforming method as set forth in claim 5, wherein the reforming reaction is carried out at a space velocity of 1,500 to 8,000.

7. The reforming method of claim 6, wherein the hydrocarbon is selected from the group consisting of methane, ethane, propane, kerosene and gasoline.

8. The reforming method of claim 7, wherein the reforming reaction is carried out at a temperature of 750 to 800°

C.

9. The reforming method of claim 8, wherein the proportion of water vapor to hydrocarbon is 2.5 to 3.5.

10. The reforming method of claim 9, wherein the hydrocarbon is methane.

11. The reforming method as set forth in claim 1, wherein the gaseous mixture includes an aliphatic alcohol.

12. The reforming method as set forth in claim 11, wherein the amount of the oxidizing catalyst is 1 to 5% of the reforming catalyst.

13. The reforming method as set forth in claim 11, wherein the aliphatic alcohol is methanol and the amount of the oxidizing catalyst is 1 to 3% of the reforming catalyst.

14. The reforming method as set forth in claim 11, wherein the reforming reaction is carried out at a space velocity of 2,000 to 8,000.

15. The reforming method as set forth in claim 14, wherein the proportion of water vapor to aliphatic alcohol is 2 to 3.

16. The reforming method as set forth in claim 1, wherein the reforming catalyst is selected from the group consisting of NiS.SiO₂.Al₂O₃, WS₂—

SiO₂.Al₂O₃ and NiS—

WS₂. SiO₂.Al₂O₃.

17. The reforming method as set forth in claim 16, wherein the oxidizing catalyst is selected from the group consisting of platinum and palladium.