Catalytic partial oxidation reforming for syngas processing and products made therefrom

• US 7,932,296 B2
• Filed: 07/18/2008
• Issued: 04/26/2011
• Est. Priority Date: 03/16/2003
• Status: Active Grant

• Current Assignee: Kellogg Brown & Root LLC (KBR Incorporated)
• Original Assignee: Kellogg Brown & Root LLC (KBR Incorporated)
• Inventors: Malhotra, Avinash, Mann, David P.
• Primary Examiner(s): Parsa; Jafar
• Application Number:
  US12/175,749
• Publication Number:
  US 20080275143A1
• Time in Patent Office: 1,012 Days
• Field of Search: 518/700, 518702-705
• US Class Current: 518/700
• CPC Class Codes: B01J 2208/00212 Plates; Jackets; Cylinders
• 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 2208/0053 Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
• CPC Class Codes: B01J 2219/00024 Revamping, retrofitting or modernisation of existing plants
• CPC Class Codes: B01J 8/009 Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
• CPC Class Codes: B01J 8/0453 the beds being superimposed one above the other
• 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 2203/0238 the reforming step being a carbon dioxide 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 2203/025 containing a 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 2203/0405 Purification by membrane separation
• CPC Class Codes: C01B 2203/0415 Purification by absorption in liquids
• CPC Class Codes: C01B 2203/0475 the impurity being carbon dioxide
• CPC Class Codes: C01B 2203/0495 the impurity being water
• 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 2203/0883 : by indirect heat exchange
• CPC Class Codes: C01B 2203/1047 : Group VIII metal catalysts
• CPC Class Codes: C01B 2203/1076 : Copper or zinc-based catalysts
• CPC Class Codes: C01B 2203/1082 : Composition of support materials
• CPC Class Codes: C01B 2203/1235 : Hydrocarbons
• CPC Class Codes: C01B 2203/1241 : Natural gas or methane
• CPC Class Codes: C01B 2203/141 : At least two reforming, decomposition or partial oxidation steps in parallel
• CPC Class Codes: C01B 2203/142 : At least two reforming, decomposition or partial oxidation steps in series
• CPC Class Codes: C01B 2203/143 : Three or more reforming, decomposition or partial oxidation steps in series
• 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 3/48 : followed by reaction of water vapour with carbon monoxide

Abstract

Systems and methods for producing syngas are provided. A first hydrocarbon can be partially oxidized in the presence of an oxidant and one or more first catalysts at conditions sufficient to partially combust a portion of the first hydrocarbon to provide carbon dioxide, non-combusted first hydrocarbon, and heat. The non-combusted first hydrocarbon can be reformed in the presence of the heat generated in the partial oxidation step and the one or more first catalysts to provide a first syngas. Heat can be indirectly exchanged from the first syngas to a second hydrocarbon to reform at least a portion of the second hydrocarbon in the presence of steam and one or more second catalysts to provide a second syngas. A syngas, which can include the at least a portion of the first syngas, at least a portion of the second syngas, or a mixture thereof can be converted to provide one or more Fischer-Tropsch products, methanol, derivatives thereof, or combinations thereof.

Claims

1. A process for producing syngas and one or more hydrocarbon products therefrom, comprising:

partially oxidizing a first hydrocarbon in the presence of an oxidant and one or more first catalysts at conditions sufficient to partially combust a portion of the first hydrocarbon to provide carbon dioxide, non-combusted first hydrocarbon, and heat;

reforming at least a portion of the non-combusted first hydrocarbon in the presence of at least a portion of the heat generated in the partial oxidation step and the one or more first catalysts in a catalytic partial oxidation (CPOX) reactor to provide a first syngas comprising hydrogen, carbon monoxide, and carbon dioxide;

indirectly exchanging heat from the first syngas to a second hydrocarbon to reform at least a portion of the second hydrocarbon in the presence of steam and one or more second catalysts to provide a second syngas comprising hydrogen, carbon monoxide, carbon dioxide, and water; and

reacting the first syngas, the second syngas, or a mixture thereof to provide a tail gas and one or more Fischer-Tropsch products, derivatives thereof, or combinations thereof,

wherein the composition of the first syngas upon exiting the CPOX reactor comprises from about 30% mol dry basis to about 70% mol dry basis hydrogen, from about 5% mol dry basis to about 35% mol dry basis carbon monoxide, and from about 5% mol dry basis to about 25% mol dry basis carbon dioxide.

2. The process of claim 1, further comprising removing at least a portion of the carbon dioxide from the syngas before reacting the syngas to provide the tail gas and the one or more Fischer-Tropsch products, derivatives thereof, or combinations thereof.

3. The process of claim 1, further comprising removing at least a portion of the carbon dioxide and at least a portion of the water from the syngas before reacting the syngas to provide the tail gas and the one or more Fischer-Tropsch products, derivatives thereof, or combinations thereof.

4. The process of claim 1, further comprising at least one of preheating the first hydrocarbon to a temperature of at least 400°

C. prior to partial oxidation and preheating the second hydrocarbon to a temperature of at least 400°

C. prior to reformation.

5. The process of claim 1, further comprising cooling the first syngas by direct heat exchange, indirect heat exchange, or both with a heat transfer medium before indirectly exchanging heat from the first syngas to the second hydrocarbon.

6. The process of claim 1, wherein the one or more first catalysts, second catalysts, or both comprise a mixture of two or more catalysts.

7. The process of claim 1, wherein the first hydrocarbon and the second hydrocarbon are independently one or more C₁—

C₂₀ hydrocarbons.

8. The process of claim 1, wherein the first hydrocarbon and the second hydrocarbon are independently natural gas, de-sulfurized natural gas, methane, de-sulfurized methane, or a mixture thereof.

9. The process of claim 1, wherein the first hydrocarbon and the second hydrocarbon are supplied in a weight ratio of from about 20:

80 to about 80;

20.

10. The process of claim 1, wherein at least a portion of the tail gas is introduced to a methanator to provide a synthetic natural gas.

11. A process for producing syngas >

and hydrocarbon products comprising;

partially oxidizing a first hydrocarbon in the presence of an oxidant and one or more first catalysts at conditions sufficient to partially combust a portion of the first hydrocarbon to provide carbon dioxide, non-combusted first hydrocarbon, and heat;

reforming at least a portion of the non-combusted first hydrocarbon in the presence of at least a portion of the heat generated in the partial oxidation step and the one or more first catalysts in a catalytic partial oxidation (CPOX) reactor to provide a first syngas comprising hydrogen, carbon monoxide, and carbon dioxide;

indirectly exchanging heat from the first syngas to a second hydrocarbon to reform at least a portion of the second hydrocarbon in the presence of steam and one or more second catalysts to provide a second syngas comprising hydrogen, carbon monoxide, carbon dioxide, and water; and

converting at least a portion of the first syngas, at least a portion of the second syngas, or a mixture thereof to methanol, derivatives thereof, or combinations thereof,

wherein the composition of the first syngas upon exiting the CPOX reactor comprises from, about 30% mol dry basis to about 70% mol dry basis hydrogen, from about 5% mol dry basis to about 35% mol dry basis carbon monoxide, and from about 5% mol dry basis to about 25% mol dry basis carbon dioxide.

12. The process of claim 11, further comprising converting at least a portion of the carbon monoxide in the syngas to carbon dioxide before converting at least a portion of the syngas to methanol, derivatives thereof, or combinations thereof.

13. The process of claim 11, further comprising removing at least a portion of the carbon dioxide in the syngas before converting at least a portion of the syngas to methanol, derivatives thereof, or combinations thereof.

14. The process of claim 11, further comprising converting at least a portion of the carbon monoxide in the syngas to carbon dioxide and removing at least a portion of the carbon dioxide from the syngas before converting the syngas to methanol, derivatives thereof, or combinations thereof.

15. The process of claim 11, further comprising cooling the first syngas by direct heat exchange, indirect heat exchange, or both with a heat transfer medium before indirectly exchanging heat from the first syngas to the second hydrocarbon in the presence of steam and the one or more second catalysts.

16. The process of claim 11, wherein the oxidant, comprises oxygen, essentially-oxygen, oxygen-enriched air, nitrogen-free air, essentially nitrogen-free air, or a mixture thereof.

17. The process of claim 11, wherein the second reaction zone comprises one or more tubes, each containing the second catalyst.

18. The process of claim 11, wherein the first hydrocarbon and the second hydrocarbon are independently one or more C₁—

C₂₀ hydrocarbons.

19. The process of claim 11, wherein the first hydrocarbon and the second hydrocarbon are independently natural gas, de-sulfurized natural gas, methane, de-sulfurized methane, or a mixture thereof.