WO2010149339A1 - Procédé de préparation d'hydrocarbures - Google Patents

Procédé de préparation d'hydrocarbures Download PDF

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Publication number
WO2010149339A1
WO2010149339A1 PCT/EP2010/003755 EP2010003755W WO2010149339A1 WO 2010149339 A1 WO2010149339 A1 WO 2010149339A1 EP 2010003755 W EP2010003755 W EP 2010003755W WO 2010149339 A1 WO2010149339 A1 WO 2010149339A1
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Prior art keywords
synthesis gas
hydrocarbons
process according
methane
oxygenate
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PCT/EP2010/003755
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English (en)
Inventor
Poul Erik Højlund NIELSEN
Finn Joensen
Esben Lauge Sørensen
Original Assignee
Haldor Topsoe A/S
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Publication of WO2010149339A1 publication Critical patent/WO2010149339A1/fr

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    • C—CHEMISTRY; METALLURGY
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • 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
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0956—Air or oxygen enriched air
    • 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
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
    • 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
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1665—Conversion of synthesis gas to chemicals to alcohols, e.g. methanol or ethanol
    • 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
    • Y02E50/10—Biofuels, e.g. bio-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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the invention relates to a process for the preparation of hydrocarbons from solid and liquid fuels.
  • the invention relates to the preparation of hydrocarbons useful as gasoline compounds from synthesis gas obtained from solid fuel gasification.
  • the synthetic gasoline process is known to take place in two steps: the conversion of synthesis gas to oxygenates and the conversion of oxygenates to gasoline hydrocarbon product. These process steps may either be integrated, producing an oxygenate intermediate, e.g. methanol or methanol dimethyl ether mixtures, which along with unconverted syn- thesis gas is passed in its entirety to a subsequent step for conversion into gasoline or the process may be conducted in two separate steps with intermediate separation of oxygenates, e.g. methanol or raw methanol.
  • an oxygenate intermediate e.g. methanol or methanol dimethyl ether mixtures
  • Useful oxygenates include methanol, dimethyl ether and higher alcohols and ethers thereof, but also oxygenates like ketones, aldehydes and other oxygenates may be applied.
  • conversion of synthesis gas to oxygenates involves heat development in that both the conversion of synthesis gas to oxygenate and the further conversion of oxygenate to gasoline product are exothermic processes.
  • Hydrocarbons and especially as gasoline are prepared by catalytic conversion in two subsequent reactors of a synthesis gas containing hydrogen and carbon oxides and having a mole ratio CO/H2 above 1 and when the conversion commences a mole ratio CO/CO 2 of 5 to 20.
  • Synthesis gas is converted with high ef- ficiency in a first step into an oxygenate intermediate comprising predominantly dimethyl ether (DME) said mixture being converted in a second step into gasoline essentially according to the net reaction scheme
  • (CH 2 ) n represents the wide range of hydrocarbons produced in the gasoline synthesis step.
  • unconverted synthesis gas comprising hydrogen and carbon oxides is recycled to the oxygenate synthesis step after CO 2 is at least partly removed, e.g. in a CO 2 wash.
  • Synthesis gas can be obtained in a variety of manners, for instance by reforming of natural gas or methane or by pre- reforming of higher hydrocarbons to methane, which can be subsequently converted to synthesis gas. Synthesis gas is then converted to gasoline hydrocarbon products.
  • US patent no. 5177114 discloses a process whereby natural gas is converted to synthesis gas, which in turn is converted to liquid hydrocarbon compounds.
  • the liquid hydrocarbon compounds are removed to leave a residual qas stream containing unreacted hydrogen, carbon monoxide and natural gas components.
  • the residual gas stream can be further treated.
  • Combustion of solid renewable fuels such as biomass is associated with difficulty.
  • Gasification of solid fuels provides a means of obtaining a gaseous fuel that is cleaner when burnt, as compared to direct combustion of the solid fuel.
  • the synthesis gas produced by gasification of solid fuel contains a significant amount of undesirable elements which must be removed prior to the synthesis of the hydrocarbon gasoline products.
  • the general objective of the invention is to provide an improved process scheme for the preparation of valuable hydrocarbons, boiling in the gasoline range, from carbon monoxide rich synthesis gas, by an intermediate oxygenate syn- thesis and a gasoline synthesis, whereby inerts and methane present in the process gas do not require removal, but can be converted to valuable power and/or heat.
  • Recycle of unconverted synthesis gas to the oxygenate syn- thesis is optional and removal of carbon dioxide from the intermediate oxygenate synthesis product upstream the gasoline synthesis is not required.
  • step (b) withdrawing from step (a) the entire oxygenate mixture comprising methanol, dimethyl ether and/or higher alcohols, including inerts and methane and transferring the entire oxygenate mixture including inert gases and methane to a catalytic oxygenate conversion step,
  • the synthesis gas is produced by air-blown gasification of a solid fuel.
  • the solid fuel is composed of biomass, bituminous coal, lignite or petroleum coke. In another embodiment the solid fuel is a mixture of bituminous coal, lignite or petroleum coke and biomass.
  • the inert gases in the synthesis gas comprise nitrogen, N2 and argon, Ar.
  • the catalytic conversion to the oxygenate mixture in step (a) is carried out in the presence of a catalyst selected from the group consisting of oxides of Cu, Zn, Al and their mixtures, and combined with a solid acid.
  • the catalytic conversion of methanol, dimethyl ether and/or higher alcohols com- prised in the oxygenate mixture to the liquid phase comprising hydrocarbons in step (c) is carried out in the presence of a zeolite catalyst.
  • the liquid compris- ing hydrocarbons comprises C2-C10 hydrocarbons.
  • the synthesis gas additionally comprises carbon dioxide.
  • Carbon dioxide can be present in amounts of at least 5 vol. %. Typically carbon dioxide is present in amounts of 5 to 15 vol. %.
  • the synthesis gas has a molecular molar ratio between hydrogen and carbon monoxide of less than 1.5 and a molar ratio between carbon monoxide and carbon dioxide of less than 10.
  • the synthesis gas has a molecular molar ratio between hydrogen and carbon monoxide of approximately 1 and a molar ratio between car- bon monoxide and carbon dioxide of approximately 1 to 4 , thereby providing optimal conditions for gasoline synthesis .
  • the process of the invention is particularly suitable for small plants since recycle of unconverted synthesis gas is optional, thereby maintaining a relatively simple process. Furthermore air can be used directly to gasify solid fuel instead of oxygen, leading to production of gasoline hydrocarbon products and an unconverted synthesis gas which in- eludes nitrogen, other inerts and carbon dioxide which are suitable for the co-production of power.
  • the inventive process can accommodate the presence of methane, which is transferred with the inerts, carbon dioxide and nitrogen for production of power.
  • Synthesis gas being useful for the invention is preferably adjusted to a H2/CO ratio of about 1, and is reacted ac- cording to reactions (3), (4) and (5) in presence of an oxygenate catalyst including the known methanol catalysts e.g. catalysts with copper, zinc and/or aluminium oxide or their mixtures combined with a dehydration catalyst com- prising a solid acid such as a zeolite, alumina or silica- alumina.
  • the dehydration catalyst is useful for catalysing the dehydration of methanol to dimethyl ether (DME) according to reaction (5) .
  • the gasoline synthesis is performed at substantially the same pressure as employed in the oxygenate synthesis in the presence of a catalyst being active in the reaction of oxygenates to higher hydrocarbons, preferably C 5+ hydrocarbons.
  • a preferred catalyst for this reaction is the known zeolite H-ZSM-5.
  • the reaction of dimethyl ether to higher hydrocarbons is known to be strongly exothermic and needs either indirect cooling (e.g. boiling water or fluidised bed reactor) or dilution of the reacting gas (e.g. fixed-bed adiabatic re- actor) with an inert gas or the reaction product in order to control the reaction temperature.
  • indirect cooling e.g. boiling water or fluidised bed reactor
  • dilution of the reacting gas e.g. fixed-bed adiabatic re- actor
  • the synthesis gas is produced by air-blown gasification of a solid fuel.
  • the air may, prior to being used in the gasification, be enriched in oxygen, e.g. through membranes or by other means.
  • the solid fuel can be composed of biomass. It can also be composed of bituminous coal, lignite or pe- troleum coke. Furthermore, the solid fuel can be a mixture of bituminous coal, lignite or petroleum coke and biomass.
  • the synthesis gas obtained from air-blown gasification can comprise carbon monoxide, hydrogen and more than 30 mole % of inert gases such as nitrogen, and methane.
  • Gasoline is produced by feeding a syngas having a high inert level to an oxygenate reactor, preferably of the boiling-water type, charged with a catalyst system active in the conversion of synthesis gas into MeOH and DME according to the following reactions:
  • Higher alcohols can be present and they are defined as being C2+ alcohols.
  • the oxygenate synthesis can be carried out at a temperature in the range of 200-300°C.
  • the oxygenate synthesis can be carried out at moderate pressures of approximately 4 MPs, but higher pressures of e.g. 8 to 12 MPa can be applied to increase the synthesis gas conversion and, in turn, the gasoline productivity.
  • Suitable catalysts are alkali promoted oxides of copper, zinc, aluminium and/or their mixtures.
  • Suitable operation pressures are in the range of 2-20 MPa, preferably 4-8 MPa.
  • a boiling water reactor can be used to provide cooling of the exothermic oxygenate synthesis reaction.
  • the reaction effluent from the gasoline reactor contains hydrocarbons in the range from Cl to ClO, water and carbon dioxide and residual amounts of unconverted H 2 , CO and inerts such as nitrogen and argon.
  • a liquid phase of mixed gasoline and light petroleum gas is obtained, referred to as raw gasoline, is separated from a gaseous phase containing inerts, light hydrocarbons such as methane, ethane, etc. and carbon dioxide originating from the synthesis gas and being formed in the upstream processes as described above.
  • the raw gasoline may be further processed by conventional means to obtain a lower- boiling gasoline fraction and a fraction of LPG.
  • a part of the carbon dioxide containing gaseous phase can be recycled to the gasoline synthesis step for temperature control .
  • the process according to the invention does advantageously not require any separate upstream or intermediate carbon dioxide removal.
  • an advantage of the invention is that the amount of CO 2 being present in the synthesis gas feed stream and the amount of CO 2 being produced in the synthesis step may be recovered downstream the gasoline synthesis at essentially the synthesis pressure prevailing in the oxygenate synthesis step.
  • This stream apart from being rich in CO 2 , contains inerts such as N 2 and Ar and also combustible compounds in appreciable amounts of unconverted H 2 and CO as well as uncondensed, primarily light, hydrocarbons and, therefore, represents a significant calorific value.
  • the part of the C0 2 -rich gaseous phase, which is not recycled to the gasoline synthesis, may advantageously be combusted thus providing source for producing power for instance electrical power. If recyle gas to the gasoline reactor is required, the amount of recycle gas is adjusted to provide an oxygenate (MeOH + DME) concentration inlet of the gasoline reactor between 2 and 10% by volume.
  • an oxygenate (MeOH + DME) concentration inlet of the gasoline reactor between 2 and 10% by volume.
  • Conversion to power can be carried out by combustion with air in, e.g., a gas engine, gas turbine or steam boiler to produce electricity and heat.
  • Gasoline is produced by feeding a syngas having a high inert level to an oxygenate reactor, preferably of the boiling-water type, charged with a catalyst system active in the conversion of synthesis gas into MeOH and DME ac- cording to the following reactions:
  • MeOH and DME which, together with unconverted synthesis gas, CO 2 and inerts is passed to the gasoline reactor in which MeOH and DME are converted into predominantly C3-C10 hydrocarbons and water.
  • the gaseous phase containing CO 2 , inerts and combustible compounds such as hydrogen and carbon monoxide and additionally minor amouuL-s of light hydrocarbons like methane, ethane, etc. may thus may advantageously be combusted with air, e.g. in a gas en- gine, gas turbine or steam boiler to produce electricity and heat.
  • Fig. 1 shows an embodiment of the invention.
  • a synthesis gas 1 as obtained by air-blown gasification of a solid fuel is fed to a boiling water oxygenate reactor at a pressure of 4 MPa to produce a reaction MeOH-containing and DME- containing mixture 2 at an exit temperature of 250°C.
  • the effluent from the oxygenate reactor is passed to the gaso- line reactor where MeOH and DME are converted into a stream of C2-C10 hydrocarbons and water 3 and the resulting stream 3 is cooled to 5°C, causing the effluent (stream of C2-C10 hydrocarbons and water 3) to separate into a gaseous phase 4, a liquid phase 5 of raw gasoline and a liquid phase 6 of water.
  • the gaseous phase 4 is combusted with air 7 in the combustor to generate heat and power.
  • Figure 2 represents a process layout similar to that shown in figure 1, the only exception being that a part of the gaseous phase resulting from the separation step is recycled to the gasoline reactor to dilute the oxygenate feed and thereby reduce the exothermicity of the feed gas. This will typically be required in process layouts where the gasoline synthesis takes place in an adiabatic reactor.
  • a synthesis gas 1 as obtained by air-blown gasification of a solid fuel is fed to a boiling water oxygenate reactor at a pressure of 8 MPa to produce a reaction MeOH-containing and DME-containing mixture 2 at an reactor exit temperature of 250°C.
  • the effluent from the oxygenate reactor is mixed with a recycle stream 4' to form stream 2' diluted with respect to MeOH and DME.
  • Stream 2' is fed to the gasoline reactor where MeOH and DME are converted into C 2 -CiO hydrocarbons and water and the resulting stream 3 is cooled to 5°C, causing the effluent to separate into a gaseous phase 4, a liquid phase 5 of raw gasoline and a liquid phase 6 of water.
  • the part of the gaseous phase 4 which is not recycled to the gasoline reactor (4'') is combusted with air 7 in the combustor to generate heat and power.
  • This example demonstrates the effect of conducting the process at a moderate pressure.
  • a synthesis gas as obtained by air-blown gasification of a solid fuel and having the composition according to reference number 1 in Table 1 is fed to a boiling water oxygenate reactor at a pressure of 4 MPa to produce a reaction MeOH-containing and DME-containing mixture 2 at an exit temperature of 250°C.
  • the effluent from the oxygenate reactor is passed to the gasoline reactor where MeOH and DME are converted into C2- ClO hydrocarbons and water and the resulting stream 3 is cooled to 5°C, causing the effluent to separate into a gaseous phase 4, a liquid phase 5 of raw gasoline and a liquid phase 6 of water.
  • the gaseous phase 4 is combusted with air (7) in the combustor to generate heat and power.
  • Example 1 demonstrates that a synthesis gas containing more than one third by volume of inerts (nitrogen and methane) may be partly converted at a modest pressure such as 4 MPa to produce gasoline and leaving a tail gas (gaseous phase) that may be combusted to produce power and heat.
  • inerts nitrogen and methane
  • Example 2 This example demonstrates the effect of conducting the process at a higher pressure: Referring now to Figure 2 and Table 2 a synthesis gas 1 as obtained by air-blown gasification of a solid fuel and having the same composition as in example 1 (composition according to reference number 1 in Table 2) is fed to a boil -ing water oxygenate reactor at a pressure of 8 MPa to produce a reaction MeOH-containing and DME-containing mixture 2 at an reactor exit temperature of 250°C. The effluent from the oxygenate reactor is mixed with a recycle stream 4' (8072 NmVh) to form stream 2' diluted with respect to MeOH and DME.
  • a recycle stream 4' 8072 NmVh
  • Stream 2' is fed to the gasoline reactor where MeOH and DME are converted into C2-C1 0 hydrocarbons and water and the resulting stream 3 is cooled to 5°C, causing the effluent to separate into a gaseous phase 4, a liquid phase 5 of raw gasoline and a liquid phase 6 of wa- ter.
  • the part of the gaseous phase 4 which is not recycled to the gasoline reactor 4'' is combusted with air 7 in the combustor to generate heat and power.
  • Example 2 demonstrates that, by increasing the synthesis pressure, the gasoline productivity may be substantially- increased reaching a lower heating value efficiency of 45%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de préparation d'hydrocarbures à partir d'un gaz de synthèse, en particulier d'un gaz de synthèse obtenu par la gazéification d'une biomasse solide. Le gaz de synthèse contient du monoxyde de carbone, de l'hydrogène et plus de 20 % en mole de gaz inertes et de méthane. Le procédé comprend la conversion catalytique du gaz de synthèse en un mélange de composés oxygénés contenant du méthanol, du diméthyléther et/ou des alcools supérieurs ; le retrait de la totalité du mélange et son transfert vers une étape de conversion catalytique de composés oxygénés ; la conversion catalytique du méthanol, du diméthyléther et/ou des alcools supérieurs pour obtenir une phase liquide contenant des hydrocarbures et une phase gazeuse contenant des gaz inertes et du méthane ; la production d'énergie à partir des gaz inertes et du méthane ; et la transformation de ladite phase liquide contenant des hydrocarbures en essence.
PCT/EP2010/003755 2009-06-26 2010-06-22 Procédé de préparation d'hydrocarbures WO2010149339A1 (fr)

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DKPA200900796 2009-06-26
DKPA200900796 2009-06-26

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013030415A1 (fr) * 2011-09-02 2013-03-07 Guradoor, S.L. Procédé d'obtention d'hydrocarbures à partir d'alcools inférieurs
EP2695946A1 (fr) 2012-08-09 2014-02-12 Methapower Biogas GmbH Procédé et installation destinés à la fabrication de diméthyléther
CN103849421A (zh) * 2014-03-06 2014-06-11 山西潞安矿业(集团)有限责任公司 合成气制汽油一体化工艺及反应器
WO2014124665A1 (fr) 2013-02-13 2014-08-21 Haldor Topsøe A/S Récupération améliorée des huiles à partir d'un réservoir d'hydrocarbures bruts

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WO2007020068A1 (fr) * 2005-08-18 2007-02-22 Haldor Topsøe A/S Procede permettant de convertir des composes oxygenes difficilementconvertibles en essence
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US4263141A (en) * 1978-10-26 1981-04-21 Metallgesellschaft Aktiengesellschaft Process of producing gasoline from synthesis gas
US4476249A (en) * 1982-06-02 1984-10-09 The Johns Hopkins University Low cost method for producing methanol utilizing OTEC plantships
US4481305A (en) 1982-09-07 1984-11-06 Haldor Topsoe A/S Process for the preparation of hydrocarbons
US5177114A (en) 1990-04-11 1993-01-05 Starchem Inc. Process for recovering natural gas in the form of a normally liquid carbon containing compound
WO2007020068A1 (fr) * 2005-08-18 2007-02-22 Haldor Topsøe A/S Procede permettant de convertir des composes oxygenes difficilementconvertibles en essence
WO2009033542A1 (fr) * 2007-09-14 2009-03-19 Haldor Topsøe A/S Production combinée d'hydrocarbures et de puissance électrique

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Publication number Priority date Publication date Assignee Title
WO2013030415A1 (fr) * 2011-09-02 2013-03-07 Guradoor, S.L. Procédé d'obtention d'hydrocarbures à partir d'alcools inférieurs
ES2397451A1 (es) * 2011-09-02 2013-03-07 Guradoor, S.L. Procedimiento para la producción de energía a partir de alcoholes inferiores.
EP2695946A1 (fr) 2012-08-09 2014-02-12 Methapower Biogas GmbH Procédé et installation destinés à la fabrication de diméthyléther
WO2014124665A1 (fr) 2013-02-13 2014-08-21 Haldor Topsøe A/S Récupération améliorée des huiles à partir d'un réservoir d'hydrocarbures bruts
EA032555B1 (ru) * 2013-02-13 2019-06-28 Хальдор Топсёэ А/С Увеличение добычи нефти из месторождения углеводородного сырья
CN103849421A (zh) * 2014-03-06 2014-06-11 山西潞安矿业(集团)有限责任公司 合成气制汽油一体化工艺及反应器

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