System and process for producing synthetic liquid hydrocarbon

• US 8,444,725 B2
• Filed: 09/11/2007
• Issued: 05/21/2013
• Est. Priority Date: 09/11/2006
• Status: Active Grant

• Current Assignee: Purdue Research Foundation (Purdue University)
• Original Assignee: Purdue Research Foundation (Purdue University)
• Inventors: Agrawal, Rakesh, Singh, Navneet R.
• Primary Examiner(s): MERKLING, MATTHEW J
• Application Number:
  US11/853,484
• Publication Number:
  US 20080115415A1
• Time in Patent Office: 2,079 Days
• Field of Search: 48/61, 481/97.R, 482/10, 481/97.A, 482/02, 423/644
• US Class Current: 48/210
• CPC Class Codes: C01B 32/50 Carbon dioxide
• CPC Class Codes: C10G 2/32 with the use of catalysts
• CPC Class Codes: C10J 2300/0916 Biomass
• CPC Class Codes: C10J 2300/0956 Air or oxygen enriched air
• CPC Class Codes: C10J 2300/0959 Oxygen
• CPC Class Codes: C10J 2300/0966 Hydrogen
• CPC Class Codes: C10J 2300/0973 Water
• CPC Class Codes: C10J 2300/1284 by renewable energy, e.g. solar energy, photovoltaic cells, wind
• CPC Class Codes: C10J 2300/1618 Modification of synthesis gas composition, e.g. to meet some criteria
• CPC Class Codes: C10J 2300/1659 to liquid hydrocarbons
• CPC Class Codes: C10J 2300/1681 with biological plants, e.g. involving bacteria, algae, fungi
• CPC Class Codes: C10J 2300/1815 for carbon dioxide
• CPC Class Codes: C10J 3/02 Fixed-bed gasification of lump fuel
• CPC Class Codes: C10J 3/06 Continuous processes
• CPC Class Codes: C10J 3/463 in stationary fluidised beds
• CPC Class Codes: C10J 3/466 Entrained flow processes
• CPC Class Codes: C10K 3/026 Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]
• CPC Class Codes: Y02P 20/00 Technologies relating to chemical industry
• CPC Class Codes: Y02P 20/145 the feedstock being materials of biological origin

Abstract

Production of synthetic liquid hydrocarbon fuel from carbon containing moieties such as biomass, coal, methane, naphtha as a carbon source and hydrogen from a carbon-free energy source is disclosed. The biomass can be fed to a gasifier along with hydrogen, oxygen, steam and recycled carbon dioxide. The synthesis gas from the gasifier exhaust is sent to a liquid hydrocarbon conversion reactor to form liquid hydrocarbon molecules. Unreacted CO & H₂ can be recycled to the gasifier along with CO₂ from the liquid hydrocarbon conversion reactor system. Hydrogen can be obtained from electrolysis of water, thermo-chemical cycles or directly by using energy from carbon-free energy sources.

Claims

1. A process for converting a carbon-containing moiety to a liquid hydrocarbon fuel, comprising:

gasifying with a predetermined energy source at least a portion of the carbon-containing moiety to produce a syngas stream comprising carbon monoxide and hydrogen, wherein the carbon-containing moiety is selected from the group consisting of biomass, coal, pet coke, methane, naphtha, and combinations thereof, at least a portion of the predetermined energy source being from a carbon-free energy source;

reacting the syngas stream to form liquid hydrocarbon fuel;

wherein the syngas stream is reacted in a hydrocarbon conversion reactor system to form liquid hydrocarbon fuel and carbon dioxide, wherein the liquid hydrocarbon fuel is a material comprising carbon and hydrogen that can exist in a closed container at normal temperature and pressure of 20°

C. and 1 atmospheric pressure in a liquid state, and wherein the carbon dioxide from the hydrocarbon conversion reactor system is recycled to the gasifier;

wherein the gasifying comprises introducing hydrogen derived from a carbon-free energy source into a gasifier, wherein the carbon-free energy source is selected from the group consisting of solar, wind, hydro and nuclear energy, wherein hydrogen includes excess hydrogen in excess of the amount of hydrogen reacting with the carbon-containing moiety,

dividing a given biomass into a first fraction that can be directly converted by micro organisms to a liquid hydrocarbon and a second fraction that is not readily converted by micro organisms to liquid hydrocarbons;

feeding the first fraction to a direct conversion unit containing microorganisms and recovering a liquid hydrocarbon product stream, a CO₂ containing stream, and optionally an unreacted biomass stream;

feeding the second fraction of the biomass to the gasifier, and

reacting excess hydrogen with carbon dioxide to decrease the concentration of carbon dioxide.

2. The process of claim 1 wherein the liquid hydrocarbon fuel is selected from the group consisting of methanol, ethanol, long chain alcohols, alkanes, alkenes, aromatics, and substituted aromatics compounds thereof.

3. The process of claim 1 wherein the biomass comprises a plant or tree.

4. The process of claim 1 wherein the biomass is selected from the group consisting of switch grass, sugar cane, corn, wood, and any cellulosic mass.

5. The process of claim 1 wherein the coal is any suitable coal or coal-derived material.

6. The process of claim 1 wherein the coal is selected from the group consisting of peat, lignite, sub-bituminous, bituminous, anthracite, and combinations thereof.

7. The process of claim 1 wherein the syngas stream is reacted in a hydrocarbon conversion reactor system to form liquid hydrocarbon fuel and CO₂, and wherein energy from the carbon-free energy source is additionally supplied as heat to the gasifier.

8. The process of claim 7 wherein any CO₂ separated prior to the reacting is recycled to the gasifier.

9. The process of claim 7 wherein a low molecular weight hydrocarbon from the hydrocarbon conversion reactor system is recycled to the gasifier.

10. The process of claim 1 wherein the syngas stream is reacted in a hydrocarbon conversion reactor system to form liquid hydrocarbon fuel and CO₂, such that a processing temperature at a point in the gasifier at which the hydrogen is supplied is higher than about 350°

C.

11. The process of claim 10 wherein any CO₂ separated prior to the reacting is recycled to the gasifier.

12. The process of claim 10 wherein a low molecular weight hydrocarbon from the hydrocarbon conversion reactor system is recycled to the gasifier.

13. The process of claim 1 wherein the syngas stream is reacted in a hydrocarbon conversion reactor system to form liquid hydrocarbon fuel and CO₂, and wherein the hydrogen derived from the carbon-free energy source is fed to a predetermined location in the gasifier.

14. The process of claim 13 wherein any CO₂ separated prior to the reacting is recycled to the predetermined location in the gasifier.

15. The process of claim 1 wherein any CO₂ collected prior to the reacting or generated by the reacting is fed to a predetermined location in the gasifier.

16. The process of claim 1 wherein the syngas stream is reacted in a hydrocarbon conversion reactor system to form liquid hydrocarbon fuel and CO₂, and wherein a combined gaseous stream containing CO₂ and unreacted CO and H₂ from the hydrocarbon conversion reactor system is recycled to a predetermined location in the gasifier.

17. The process of claim 1 wherein energy from the carbon-free energy source is used to dry the biomass prior to feeding the biomass to the gasifier.

18. The process of claim 1 wherein the syngas stream is reacted in a hydrocarbon conversion reactor system to form liquid hydrocarbon fuel and CO₂, and wherein reaction heat from the reacting is used to dry the biomass prior to feeding the biomass to the gasifier.

19. The process of claim 1 wherein the unreacted biomass stream from feeding the first fraction is fed to the gasifier.

20. The process of claim 1 wherein the CO₂ containing stream from feeding the first fraction is fed to the gasifier.

21. The process of claim 20 wherein a specific feed point in the gasifying is positioned in a suitable location in the gasifier.

22. The process of claim 1 wherein the syngas stream is reacted in a hydrocarbon conversion reactor system to form liquid hydrocarbon fuel and CO₂, and wherein heat available from one of the gasifying and the reacting is used to supply process heat for the direct conversion unit.

23. The process of claim 22 wherein the process heat is used in the fermentation.

24. The process of claim 22 wherein the process heat is used in separation of the liquid hydrocarbon.

25. The process of claim 1 wherein excess hydrogen includes an amount of hydrogen exceeding an about two to one ratio of hydrogen gas and carbon monoxide.

26. The process of claim 1 wherein the supply of the predetermined energy source including excess hydrogen is sufficient to reduce the concentration of carbon dioxide through the reverse water gas shift reaction.

27. The process of claim 26 wherein the reduction of carbon dioxide is sufficient to increase the yield of liquid hydrocarbon fuel.

28. The process of claim 26 wherein the excess hydrogen ensures that there is no significant carbon dioxide release from the process.

29. The process of claim 1 wherein reacting excess hydrogen with carbon dioxide decreases the amount of carbon dioxide.