Catalytic Partial Oxidation Reforming

• US 20090064582A1
• Filed: 07/18/2008
• Published: 03/12/2009
• 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.
• Granted Patent: US 8,273,139 B2
• Time in Patent Office: Days
• US Class Current: 48/85
• CPC Class Codes: B01J 2208/00274 involving reactant vapours
• 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 2219/00006 Large-scale industrial plants
• CPC Class Codes: B01J 2219/00024 Revamping, retrofitting or modernisation of existing plants
• 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 2203/0288 containing two CO-shift steps
• 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 2203/068 Ammonia synthesis
• 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 2203/1047 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 3/025 : Preparation or purification of gas mixtures for ammonia synthesis
• 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
• CPC Class Codes: C01C 1/0405 : from N2 and H2 in presence of a catalyst
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts

Abstract

Systems and processes 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. At least a portion of the non-combusted first hydrocarbon can be reformed in the presence of at least a portion of the heat generated in the partial oxidation step and the one or more first catalysts to provide a first syngas. The first syngas can comprise hydrogen, carbon monoxide, and carbon dioxide. 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. The second syngas can comprise hydrogen, carbon monoxide, and carbon dioxide.

Claims

1. ) A process for producing syngas, 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 to provide a first syngas comprising hydrogen, carbon monoxide, and carbon dioxide; and

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, and carbon dioxide.

2. ) 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 in the presence of steam and the one or more second catalysts.

3. ) The process of claim 1, further comprising mixing at least a portion of the first syngas and at least a portion of the second syngas to provide a syngas product.

4. ) The process of claim 1, further comprising:

reacting at least a portion of the carbon monoxide in the first syngas, the second syngas, or a mixture thereof to carbon dioxide to provide a converted syngas comprising 5% mol dry basis or less carbon monoxide; and

separating at least a portion of the hydrogen from the converted syngas gas to provide a hydrogen product.

5. ) The process of claim 4, further comprising reacting at least a portion of the hydrogen product with nitrogen in the presence of one or more third catalysts to provide an ammonia product.

6. ) The process of claim 5, further comprising reacting at least a portion of the ammonia product with one or more reactants to provide one or more ammonia derivatives.

7. ) The process of claim 1, further comprising:

reacting at least a portion of the carbon monoxide in the first syngas, the second syngas, or a mixture thereof to carbon dioxide to provide a converted syngas comprising 5% mol dry basis or less carbon monoxide;

separating at least a portion of the carbon dioxide from the converted syngas to provide a first hydrogen product, comprising hydrogen, carbon monoxide, and carbon dioxide;

reacting at least a portion of carbon monoxide and carbon dioxide in the first hydrogen product to provide a second hydrogen product comprising hydrogen, methane, and water; and

reacting at least a portion of the second hydrogen product with nitrogen in the presence of one or more third catalysts to provide an ammonia product.

8. ) The process of claim 7, further comprising reacting at least a portion of the ammonia product with one or more reactants to provide one or more ammonia derivatives.

9. ) The process of claim 1, further comprising:

reacting at least a portion of the carbon monoxide in at least a portion of the first syngas, the second syngas, or a mixture thereof to carbon dioxide to provide a converted syngas comprising 5% mol dry basis or less carbon monoxide;

separating at least a portion of the carbon dioxide from the converted syngas to provide a first hydrogen product, comprising hydrogen, carbon monoxide, and carbon dioxide;

reacting at least a portion of the carbon monoxide and the carbon dioxide in the first hydrogen product to provide a second hydrogen product comprising hydrogen, methane, and water;

separating at least a portion of the water from the second hydrogen product to provide a dried hydrogen product; and

reacting at least a portion of the dried hydrogen product with nitrogen in the presence of one or more third catalysts to provide an ammonia product.

10. ) The process of claim 9, further comprising reacting at least a portion of the ammonia product with one or more reactants to provide one or more ammonia derivatives.

11. ) The process of claim 1, further comprising:

reacting at least a portion of the carbon monoxide in the first syngas, the second syngas, or a mixture thereof to carbon dioxide to provide a converted syngas comprising 5% mol dry basis or less carbon monoxide;

separating at least a portion of the carbon dioxide from the converted syngas to provide a first hydrogen product, comprising hydrogen, carbon monoxide, and carbon dioxide;

reacting at least a portion of carbon monoxide and carbon dioxide in the first hydrogen product to provide a second hydrogen product comprising hydrogen, methane, and water;

separating at least a portion of the water from the second hydrogen product to provide a dried hydrogen product; and

purifying at least a portion of the dried hydrogen product to provide a fourth hydrogen product comprising hydrogen, wherein the purifying comprises separating at least a portion of any residual gases, wherein the residual gases comprise one or more of carbon monoxide, carbon dioxide, water, and inerts.

12. ) The process of claim 1, further comprising:

reacting at least a portion of the carbon monoxide in the first syngas, the second syngas, or a mixture thereof to carbon dioxide to provide a converted syngas comprising 5% mol dry basis or less carbon monoxide;

separating at least a portion of the carbon dioxide from the converted syngas to provide a first hydrogen product, comprising hydrogen, carbon monoxide, and carbon dioxide;

reacting at least a portion of carbon monoxide and carbon dioxide in the first hydrogen product to provide a second hydrogen product comprising hydrogen, methane, and water;

separating at least a portion of the methane and water from the second hydrogen product to provide a dried hydrogen product; and

purifying at least a portion of the dried hydrogen product to provide a purified hydrogen product comprising hydrogen and nitrogen in a molar ratio of from about 2.7 to about 3.3, wherein the purifying comprises separating at least a portion of any residual gases and excess nitrogen, wherein the residual gases comprise one or more of carbon monoxide, carbon dioxide, water, and inerts, wherein the oxidant comprises air, excess air, nitrogen enriched air, or mixtures thereof.

13. ) The process of claim 1, wherein the one or more first catalysts, second catalysts, or both comprise two or more catalysts.

14. ) The process of claim 1, wherein the first hydrocarbon and the second hydrocarbon comprise one or more C₁-C₂₀ hydrocarbons.

15. ) The process of claim 1, wherein the first hydrocarbon and the second hydrocarbon comprise natural gas, de-sulfurized natural gas, methane, de-sulfurized methane, or a mixture thereof.

16. ) The process of claim 1, wherein the first hydrocarbon and the second hydrocarbon are different.

17. ) A process for producing syngas, comprising:

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

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

indirectly exchanging heat from the first syngas to a second hydrocarbon in a second reaction zone 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, and carbon dioxide.

18. ) The process of claim 17, 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.

19. ) The process of claim 17, wherein the one or more first catalysts, second catalysts, or both comprises two or more catalysts.

20. ) The process of claim 17, wherein the first reaction zone, the second reaction zone, or both comprises two or more catalyst-containing beds.

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

22. ) A system for producing syngas, comprising:

a first reactor adapted to partially oxidize a first hydrocarbon in the presence of an oxidant at conditions sufficient to partially combust at least a portion of the first hydrocarbon to provide carbon dioxide, non-combusted hydrocarbon, and heat, and adapted to at least partially reform the non-combusted hydrocarbon in the presence of the heat generated in the partial oxidation step and one or more first catalysts to provide a first syngas comprising carbon monoxide, carbon dioxide, and hydrogen; and

a second reactor adapted to indirectly exchange 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 carbon monoxide, carbon dioxide, and hydrogen.

23. ) The system of claim 22, further comprising a mixing zone adapted to mix at least a portion of the first syngas and the second syngas to provide a syngas.

24. ) The system of claim 22, further comprising one or more converters adapted to convert at least a portion of the carbon monoxide in the first syngas, second syngas, or a mixture of the first syngas and the second syngas to carbon dioxide to provide a syngas comprising less than 2% mol dry basis carbon monoxide.

25. ) The system of claim 22, further comprising one or more carbon dioxide removal systems adapted to remove at least a portion of the carbon dioxide in the syngas to provide a carbon dioxide lean syngas and a carbon dioxide waste product.

26. ) The system of claim 22, wherein the one or more first catalysts, second catalysts or both comprises two or more catalysts.