Catalytic steam reforming of hydrocarbons

• US 4,337,170 A
• Filed: 01/23/1980
• Issued: 06/29/1982
• Est. Priority Date: 01/23/1980
• Status: Expired due to Term

• Current Assignee: UOP Des Plaines IL A NY General Partnership
• Original Assignee: Union Carbide Corporation (Dow, Inc.)
• Inventors: Fuderer, Andrija
• Primary Examiner(s): MARS, HOWARD
• Application Number:
  US06/114,566
• Time in Patent Office: 888 Days
• Field of Search: 252/373, 48/214 R, 48/214 A, 48/197 R
• US Class Current: 252/373
• CPC Class Codes: B01J 8/062 being installed in a furnace
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/043 Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
• CPC Class Codes: C01B 2203/0811 by combustion of fuel
• CPC Class Codes: C01B 2203/0816 Heating by flames
• 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 2203/1011 Packed bed of catalytic structures, e.g. particles, packing elements
• CPC Class Codes: C01B 2203/1041 Composition of the catalyst
• CPC Class Codes: C01B 2203/1052 Nickel or cobalt catalysts
• CPC Class Codes: C01B 2203/1241 Natural gas or methane
• CPC Class Codes: C01B 2203/1247 Higher hydrocarbons
• CPC Class Codes: C01B 2203/127 Catalytic desulfurisation
• 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 3/384 the catalyst being continuously externally heated
• CPC Class Codes: Y02P 20/129 Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Abstract

The hot effluent from the catalytic steam reforming of a major portion of a fluid hydrocarbon feed stream in the reformer tubes of a primary reformer, or said effluent after secondary reforming thereof, is mixed with the hot effluent from the catalytic steam reforming of the remaining portion of the feed discharged from the reformer tubes of a primary reformer-exchanger. The combined gas steam is passed on the shell side of the reformer-exchanger countercurrently to the passage of feed in the reformer tubes thereof, thus supplying the heat for the reforming of the portion of the feed passed through the reformer tubes of the reformer-exchanger. At least about 2/3 of the hydrocarbon feed stream is passed to the reformer tubes of said primary reformer, heated by radiant heat transfer and/or by contact with combustion gases, at a steam/hydrocarbon mole ratio of about 2-4/1. The remainder of said feed stream is passed to the reformer tubes of said reformer-exchanger at a steam/hydrocarbon mole ratio of about 3-6/1. The reformer shell of the reformer-exchanger is internally insulated by a refractory lining or by use of a double shell with passage of water or a portion of the feed material between the inner and outer shells. There is no significant difference between the pressure inside and outside of the reformer tubes of said primary reformer-exchanger.

Claims

1. An improved process for the catalytic stream reforming of fluid hydrocarbons comprising:

(a) catalytically reacting a major portion of a fluid hydrocarbon feed stream with steam in catalyst-containing reformer tubes positioned within a first primary reforming zone maintained at an elevated temperature by radiant heat transfer and/or by contact with combustion gases, the hot reformer tube effluent comprising a first reformed gas mixture which is passed directly to the hot discharge end of the reformer tubes in the second primary reforming zone;

(b) catalytically reacting the remaining portion of said hydrocarbon feed stream with steam at an elevated temperature in a second primary reforming zone having catalyst-containing reformer tubes positioned therein, the hot effluent from said tubes comprising a second reformed gas mixture;

(c) combining the first and second reformed gas mixtures at the hot discharge end of the reformer tubes of said second primary reforming zone, thus forming a hot combined reformer gas stream within said second primary reforming zone at the hot discharge end of the reformer tubes therein;

(d) passing the hot combined reformer gas stream countercurrently on the shell side of said second primary reaction zone, thereby supplying heat to maintain said second primary reforming zone at an elevated temperature; and

(e) withdrawing the thus-partially cooled combined reformer effluent stream, comprising a combination of said first and second reformed gas mixtures, from said second primary reaction zone, whereby the desired overall steam reforming is accomplished at a substantial reduction in hydrocarbon fuel consumption.

2. The process of claim 1 in which said major portion of the fluid hydrocarbon feed stream comprises at least about two-thirds of said stream.

3. The process of claim 2 in which said major portion comprises from about 70% to about 80% by volume of said fluid feed stream.

4. The process of claim 1 in which said hydrocarbon feed comprises a natural gas stream.

5. The process of claim 1 in which said hydrocarbon feed comprises light naphtha.

6. The process of claim 1 in which said hydrocarbon feed comprises propane and butane.

7. The process of claim 3 in which the mole ratio of steam to hydrocarbon feed in the first primary reforming zone is from about 2/1 to about 4/1, and said mole ratio in the second primary reforming zone is from about 3/1 to about 6/1.

8. The process of claim 7 in which said hot reformer tube effluent of the first primary reforming zone is at a temperature of from about 800°

C. to about 900°

C., said effluent from the second primary reforming zone is at a temperature between 700°

C. and about 860°

C., and the partially cooled combined reformer gas stream is withdrawn from the second primary reaction zone.

9. The process of claim 1 in which the partially cooled combined reformer effluent stream is passed to a waste heat recovery zone for the generation of steam therein.

10. The process of claim 9 in which steam generated in said waste heat recovery is employed as said steam used in said catalytic steam reforming operations.

11. The process of claim 9 and including passing said partially cooled combined reformer effluent stream to a carbon monoxide shift reactor zone.

12. The process of claim 10 in which import steam is employed for said catalytic steam reforming operations in addition to the steam generated in said waste heat recovery zone.