Process and apparatus for the production of synthesis gas

• US 7,670,586 B2
• Filed: 02/24/2003
• Issued: 03/02/2010
• Est. Priority Date: 02/25/2002
• Status: Active Grant

• Current Assignee: NiQuan Energy LLC
• Original Assignee: GTLpetrol LLC
• Inventors: Repasky, John, Wang, Shoou-I, Peng, Xiang-Dong, Nataraj, Shankar
• Primary Examiner(s): Mayes; Melvin C
• Assistant Examiner(s): Gregorio; Guinever S
• Application Number:
  US10/518,038
• Publication Number:
  US 20060128818A1
• Time in Patent Office: 2,563 Days
• Field of Search: None
• US Class Current: 423/650
• CPC Class Codes: B01J 2208/00256 in a heat exchanger for the heat exchange medium separate from the reactor
• CPC Class Codes: B01J 2208/00504 by means of a burner
• CPC Class Codes: B01J 2208/0053 Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
• CPC Class Codes: B01J 2219/00006 Large-scale industrial plants
• CPC Class Codes: B01J 8/0285 Heating or cooling the reactor for tubular reactors in furnaces B01J8/062
• CPC Class Codes: B01J 8/0488 the beds being placed in separate reactors
• CPC Class Codes: B01J 8/067 Heating or cooling the reactor B01J8/062 takes precedence
• 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 2203/0255 containing a non-catalytic partial oxidation step
• CPC Class Codes: C01B 2203/0261 containing a catalytic partial oxidation step [CPO]
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/06 Integration with other chemical processes
• CPC Class Codes: C01B 2203/061 Methanol production
• CPC Class Codes: C01B 2203/062 Hydrocarbon production, e.g. Fischer-Tropsch process
• CPC Class Codes: C01B 2203/0838 by heat exchange with exothermic reactions, other than 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 2203/0877 by direct injection of fluid
• CPC Class Codes: C01B 2203/1241 Natural gas or methane
• CPC Class Codes: C01B 2203/127 Catalytic desulfurisation
• 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 3/26 : using catalysts
• CPC Class Codes: C01B 3/36 : using oxygen or mixtures containing oxygen as gasifying agents
• CPC Class Codes: C01B 3/382 : Multi-step processes
• CPC Class Codes: C01B 3/384 : the catalyst being continuously externally heated
• CPC Class Codes: C01B 3/386 : Catalytic partial combustion
• CPC Class Codes: C10J 2300/094 : Char
• CPC Class Codes: C10J 2300/0976 : as steam
• CPC Class Codes: C10J 2300/0986 : Catalysts
• CPC Class Codes: C10J 3/02 : Fixed-bed gasification of lump fuel
• CPC Class Codes: C10J 3/20 : Apparatus; Plants
• CPC Class Codes: C10K 3/026 : Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]
• CPC Class Codes: Y02E 60/32 : Hydrogen storage
• CPC Class Codes: Y02P 20/129 : Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts

Abstract

Reactive diluent fluid (22) is introduced into a stream of synthesis gas (or “syngas”) produced in a heat-generating unit such as a partial oxidation (“POX”) reactor (12) to cool the syngas and form a mixture of cooled syngas and reactive diluent fluid. Carbon dioxide and/or carbon components and/or hydrogen in the mixture of cooled syngas and reactive diluent fluid is reacted (26) with at least a portion of the reactive diluent fluid in the mixture to produce carbon monoxide-enriched and/or solid carbon depleted syngas which is fed into a secondary reformer unit (30) such as an enhanced heat transfer reformer in a heat exchange reformer process. An advantage of the invention is that problems with the mechanical integrity of the secondary unit arising from the high temperature of the syngas from the heat-generating unit are avoided.

Claims

1. A process for the production of synthesis gas (“

syngas”

) comprising carbon monoxide and molecular hydrogen, said process comprising;

exothermically reacting hydrocarbon-containing fuel with an oxidant gas comprising molecular oxygen in a first reactor to produce an exothermically-generated syngas product, the exothermically-generated syngas product includes solid-carbon components;

combining a stream of reactive diluent fluid with a stream of said exothermically-generated syngas product to produce a reactive mixture, the reactive diluent fluid is recycled from downstream processing;

gasifying at least a portion of the solid-carbon components in the exothermically-generated syngas product using the reactive diluent fluid;

reacting said reactive mixture in a catalytic second reactor to produce a reacted syngas product; and

endothermically reforming hydrocarbon-containing fuel gas with steam over a catalyst in a heat exchange reformer to produce a heat exchange-reformed syngas product,

wherein at least a portion of the heat required in the generation of said heat exchange-reformed syngas product is obtained by recovering heat from said reacted syngas product thereby cooling said reacted syngas.

2. The process as claimed in claim 1 wherein said heat exchange-reformed syngas product is combined with said reacted syngas product prior to heat recovery.

3. The process as claimed in claim 1 wherein the reactive diluent fluid controls the temperature of the exothermically-generated syngas product.

4. The process as claimed in claim 1, wherein the oxidant gas consists of molecular oxygen.

5. The process as claimed in claim 1, wherein the hydrocarbon fuel is reacted with the oxidant gas in the presence of water.

6. The process as claimed in claim 1, wherein the reactive mixture comprises carbon dioxide, at least a portion of which is reacted together with at least a portion of the molecular hydrogen in said reactive mixture over a catalyst in a reverse water gas shift reaction zone in the second reactor to produce a carbon monoxide-enriched syngas product.

7. The process as claimed in claim 1, wherein the reactive mixture comprises solid carbon particles, at least a portion of which is gasified by reaction with at least one other component of the reactive mixture in a gasification zone in the second reactor to produce a solid carbon-depleted syngas product.

8. The process as claimed in claim 1, wherein the reactive diluent fluid is a gas thereby cooling the exothermically-generated syngas product via sensible heat exchange.

9. The process as claimed in claim 1, wherein the reactive diluent fluid is a liquid thereby cooling the exothermically-generated syngas product via vaporisation and sensible heat exchange.

10. The process as claimed in any of claim 1, wherein the reactive diluent fluid is recovered and recycled from downstream processing of syngas.

11. The process as claimed in any of claim 1, wherein the reactive diluent fluid comprises carbon dioxide.

12. The process as claimed in claim 11 wherein the reactive diluent fluid comprises carbon dioxide separated and recycled from downstream syngas.

13. The process as claimed in claim 11 wherein the reactive diluent fluid comprises the products of a combustion process.

14. The process as claimed in claim 13 wherein the combustion products are selected from the group consisting of combustion furnace flue gases and gas turbine exhaust gas.

15. The process as claimed in claim 11 wherein the reactive diluent fluid comprises carbon dioxide imported from an external source.

16. The process as claimed in claim 1, wherein the reactive diluent fluid further comprises a component selected from the group consisting of methane and other hydrocarbon(s).

17. The process as claimed in claim 1, wherein the reactive diluent fluid comprises molecular hydrogen.

18. The process as claimed in claim 1, wherein the reactive diluent fluid comprises water.

19. The process as claimed in claim 18 wherein the water is in the form of liquid water.

20. The process as claimed in claim 18 wherein at least a portion of the water is in the form of steam.

21. The process as claimed in claim 1 wherein the heat exchange-reformed syngas product or a syngas mixture derived therefrom is used in a downstream conversion process to produce conversion products selected from the group consisting of hydrocarbon liquid fuels, methanol, DME and oxo-alcohols.

22. The process as claimed in claim 1 further comprising combining a second diluent fluid with a syngas stream between the point at which the reactive diluent fluid is combined with said exothermically-generated syngas product and the point at which heat is recovered from the reacted syngas product to adjust the temperature and/or change the composition of relevant syngas stream.

23. The process as claimed in claim 22 wherein the second diluent fluid is combined with the reactive mixture in any section of the second reactor.

24. The process as claimed in claim 22 wherein the second diluent fluid is combined with the reacted syngas product at any point between the second reactor and the heat exchange reformer or, where the heat exchange reformer is a shell and tube style reformer in which the endothermic reforming reaction occurs within the tubes and the reacted syngas product is introduced to the shell-side, in any section of the shell-side of the heat exchange reformer.

25. The process as claimed in claim 24 comprising combining molecular hydrogen as the second diluent fluid with the reacted syngas product to enhance the heat exchange efficiency inside the heat exchange reformer.

26. The process as claimed in claim 24 comprising combining water and/or steam as the second diluent fluid with the reacted syngas product to reduce the amount of metal dusting inside the heat exchange reformer and/or to adjust the temperature of the reacted syngas product.

27. The process as claimed in claim 22 wherein the second diluent fluid is inert.

28. The process as claimed in claim 22 wherein the second diluent fluid is selected from the group consisting of water vapour, steam, liquid water, molecular hydrogen, carbon dioxide, methane, other hydrocarbons, off-gas from downstream processes, combustion furnace flue gases and gas turbine exhaust gas.