CA2797878A1 - Method of producing a hydrocarbon composition - Google Patents

Method of producing a hydrocarbon composition Download PDF

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Publication number
CA2797878A1
CA2797878A1 CA2797878A CA2797878A CA2797878A1 CA 2797878 A1 CA2797878 A1 CA 2797878A1 CA 2797878 A CA2797878 A CA 2797878A CA 2797878 A CA2797878 A CA 2797878A CA 2797878 A1 CA2797878 A1 CA 2797878A1
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CA
Canada
Prior art keywords
hydrogen
gas
carbon monoxide
fischer
tropsch reactor
Prior art date
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Abandoned
Application number
CA2797878A
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French (fr)
Inventor
Jukka Koskinen
Jan Wahlstroem
Isto Eilos
Sebastian Johansson
Sami Toppinen
Marianne Pettersson
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Neste Oyj
Original Assignee
Neste Oyj
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Publication of CA2797878A1 publication Critical patent/CA2797878A1/en
Abandoned legal-status Critical Current

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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
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    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/001—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by thermal treatment
    • C10K3/003—Reducing the tar content
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    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/023—Reducing the tar content
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    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
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    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
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    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
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    • C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
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    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
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    • C01B2203/0415—Purification by absorption in liquids
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    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
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    • C01B2203/0465—Composition of the impurity
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    • C01B2203/14—Details of the flowsheet
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    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
    • Y02T50/678—Aviation using fuels of non-fossil origin

Abstract

Method of producing a hydrocarbon composition. The method comprises providing a biomass raw-material; gasifying the raw-material in the presence of oxygen to produce a gas containing carbon monoxide, carbon dioxide, hydrogen and hydrocarbons possibly together with inert components; separately increasing the hydrogen-to-carbon monoxide ratio of the gas to a value of about 2; feeding the gas to a Fischer-Tropsch reactor; converting in the Fischer-Tropsch reactor at least a significant part of the carbon monoxide and hydrogen contained in the gas into a hydrocarbon composition containing C4-C90 hydrocarbons; and recovering the hydrocarbon composition. According to the invention, fresh external hydrogen is introduced into the gas before feeding into the Fischer-Tropsch reactor. By using external hydrogen feed, the capacity of a biomass gasification process can be increased and the need for a conventional Water Gas Shift for producing hydrogen from carbon monoxide and steam can be eliminated.

Claims (25)

1. Method of producing a hydrocarbon composition, comprising the steps of - providing a biomass raw-material;
- gasifying the raw-material in the presence of oxygen to produce a gas containing carbon monoxide, carbon dioxide, hydrogen and hydrocarbons possibly together with inert components;
- separately increasing the hydrogen-to-carbon monoxide ratio of the gas to a value of about 2;
- feeding the gas to a Fischer-Tropsch reactor;
- converting in the Fischer-Tropsch reactor at least a significant part of the carbon monoxide and hydrogen contained in the gas into a hydrocarbon composition containing C4-C90 hydrocarbons; and - recovering the hydrocarbon composition, characterized by - introducing fresh hydrogen derived from an external source of hydrogen into the gas before the gas is fed into the Fischer-Tropsch reactor, the hydrogen being derived from a source selected from natural gas and other sources of light hydrocarbons, in particular methane, hydrogen produced by bioelectricity and methane hydrate.
2. The method according to claim 1, wherein fresh hydrogen is introduced at a point immediately before the Fischer-Tropsch reactor in order to raise the hydrogen-to carbon monoxide ratio of the gas to about 2.
3. The method according to claim 1, wherein hydrogen is produced from natural gas or another source of methane and other light hydrocarbons by catalytic reforming.
4. The method according to claim 3, wherein hydrogen is produced from natural gas or another source of methane and other light hydrocarbons in a cascade formed by at least one unit for catalytic reforming and one unit for a water gas shift reaction.
5. The method according to any of claims 1 to 4, comprising the steps of - gasifying the raw-material in the presence of oxygen to produce a gas containing carbon monoxide, carbon dioxide, hydrogen and hydrocarbons possibly together with inert components;
- feeding the gas obtained by gasification of the raw-material into a reformer;
- reforming the gas in the presence of oxygen in order to increase the ratio of hydrogen to carbon monoxide in a gaseous effluent of the reformer to a value in the range of 0.5 to 1.5;
- withdrawing the gaseous effluent from an outlet of the reformer; and - further increasing the hydrogen-to-carbon monoxide ratio of the gaseous effluent to a value of about 2 by introducing fresh hydrogen therein.
6. The method according to claim 5, wherein gasification is carried out at a first temperature and reforming at a second temperature, said second temperature being essentially higher than the first temperature.
7. The method according to claim 5 or 6, wherein reforming is carried out in catalyst bed reformer at a temperature in excess of 850 °C, preferably about 900 -1200 °C.
8. The method according to any of claims 1 to 4, comprising the steps of - gasifying the raw-material in the presence of oxygen at a temperature in excess of 1000 °C to produce a gas containing carbon monoxide, carbon dioxide, hydrogen and hydrocarbons possibly together with inert components; and - further increasing the hydrogen-to-carbon monoxide ratio of the gas effluent to a value of about 2 by introducing fresh hydrogen into the gas.
9. The method according to any of claims 1 to 8, wherein carbon dioxide is withdrawn from the gas before it is fed into the Fischer-Tropsch reactor and used for forming carbon monoxide by a reversed water gas shift.
10. The method according to claim 9, wherein carbon dioxide is withdrawn from the gas downstream any gas washing process arranged before the Fischer-Tropsch reactor.
11. The method according to claim 9 or 10, wherein carbon dioxide is separated from the gas by membrane filtration, by pressure swing absorption or by washing with a liquid capable of absorbing carbon dioxide.
12. The method according to any of claims 9 to 11, wherein significantly all of the carbon dioxide contained in the gas is removed before it is fed into the Fischer-Tropsch reactor and used for forming carbon monoxide by a reversed water gas shift reaction by use of external hydrogen.
13. The method according to any of claims 9 to 11, wherein only a part of the carbon dioxide contained in the gas is removed and used for forming carbon monoxide by a reversed water gas shift reaction by use of external hydrogen.
14. The method according to claim 13, wherein external hydrogen is both fed into the gas in order to increase hydrogen-to-carbon monoxide ratio and used for forming carbon monoxide by reversed water gas shift reaction.
15. The method according to claim 14, wherein the molar ratio between hydrogen and CO2 fed into the gas and used for forming carbon monoxide, respectively, is in the range of 0.5:1-6:1 in particular 0.9:1- 4:1.
16. The method according to any of claims 9 to 15, comprising the steps of - feeding the carbon dioxide together with fresh hydrogen into the gaseous effluent of a reformer or a high temperature gasifier in order to produce a modified gaseous effluent; and - feeding the modified gaseous effluent into a reaction zone for a reversed water gas shift reaction.
17. The method according to any of claims 12 to 16, wherein the reversed water gas shift reaction is carried out at a temperature in the range of about 500 to 1000 °C, in particular about 700 to 850 °C.
18. The method according to any of the preceding claims, wherein less than 20 mole-%, preferably less than 10 mole-%, in particular less than 5 mole-% of the carbon monoxide produced from the biomass raw-material is used for producing hydrogen gas for use in the Fischer-Tropsch reactor.
19. The method according to claim 18, wherein essentially none of the carbon monoxide produced from the biomass raw-material is used for producing hydrogen gas for use in the Fischer-Tropsch reactor.
20. The method according to any of the preceding claims, wherein the molar ratio of the fresh hydrogen fed into the gaseous effluent to the carbon monoxide produced by gasification of the biomass raw-material amounts from 0.55 to 2.4.
21. The method according to any of the preceding claims, wherein the recovered hydrocarbon composition is further treated to produce a fuel or lubricant for combustion engines.
22. The method according to claim 21, comprising producing hydrocarbon compositions suitable for fuel applications having distillation cut points in the range of about 150 to 300 °C, in particular 180 to 240 °C.
23. The method according to claim 21, comprising producing hydrocarbon compositions suitable for lubricant applications, said compositions having carbon numbers in the range of 30 to 40.
24. The method according to any of the preceding claims, wherein the external hydrogen is fed directly into a reformer or into a reversed water gas shift reactor or into both.
25. The use of a method according to any of the preceding claims for decreasing CO2 emissions of a Fischer-Tropsch process wherein hydrocarbons are produced from syngas obtained by gasification of a biomass raw-material.
CA2797878A 2010-05-10 2011-05-10 Method of producing a hydrocarbon composition Abandoned CA2797878A1 (en)

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FI20105503A FI20105503A (en) 2010-05-10 2010-05-10 A process for producing a hydrocarbon composition
PCT/FI2011/050430 WO2011141635A1 (en) 2010-05-10 2011-05-10 Method of producing a hydrocarbon composition

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CA (1) CA2797878A1 (en)
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US20130072583A1 (en) 2013-03-21
FI20105503A0 (en) 2010-05-10
EA201291188A1 (en) 2013-06-28
CN102918136A (en) 2013-02-06
FI20105503A (en) 2011-11-11
WO2011141635A1 (en) 2011-11-17
EP2569397A1 (en) 2013-03-20

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