EP2473533A1 - Conversion catalytique simultanée de cellulose et de lignine en un combustible liquide dans un liquide ionique - Google Patents

Conversion catalytique simultanée de cellulose et de lignine en un combustible liquide dans un liquide ionique

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Publication number
EP2473533A1
EP2473533A1 EP10766380A EP10766380A EP2473533A1 EP 2473533 A1 EP2473533 A1 EP 2473533A1 EP 10766380 A EP10766380 A EP 10766380A EP 10766380 A EP10766380 A EP 10766380A EP 2473533 A1 EP2473533 A1 EP 2473533A1
Authority
EP
European Patent Office
Prior art keywords
ionic liquid
cellulose
lignin
catalyst
catalysts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10766380A
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German (de)
English (en)
Inventor
Jacobus Johannes Heinerman
Jacob Adriaan Moulijn
Paul O'connor
Jacobus Cornelis Rasser
Armand Eduard Rosheuvel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of EP2473533A1 publication Critical patent/EP2473533A1/fr
Withdrawn legal-status Critical Current

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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
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00—Macromolecular compounds derived from lignocellulosic materials
    • 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
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • 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
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • 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
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • C10G1/045—Separation of insoluble materials
    • 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
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • 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
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • 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
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
    • 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
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • 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
    • C10G2300/1014—Biomass of vegetal origin
    • 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
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
    • 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
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
    • 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
    • C10G2300/1077—Vacuum residues
    • 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
    • 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
    • C10G2400/26—Fuel gas
    • 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 generally to the simultaneous conversion of cellulose and lignin to a liquid fuel, and more particularly to such a conversion process in an Ionic Liquid medium.
  • Another process is the pyrolysis, in particular fast or flash pyrolysis.
  • High liquid yields have been reported, but the pyrolysis liquids have high oxygen content.
  • the liquids are highly acidic and corrosive. They are unstable, due to their propensity to polymerization.
  • the liquids contain large amounts of water, which is difficult to separate from the organic components due to the hydrophilic nature of the organic compounds.
  • the liquids need to be subjected to a separate upgrading to provide usable hydrocarbon products. Upgrading processes reported in the prior art generally comprise two hydrotreatment steps.
  • a first step which is carried out in the presence of the water component of the pyrolysis liquid, the organic compounds are deoxygenated to the point that they become sufficiently hydrophobic to cause phase separation into an aqueous phase and an oil phase.
  • the oil phase is further deoxygenated to form hydrocarbons.
  • the three-step process has a rather poor overall yield.
  • the present invention addresses these problems by providing a process for
  • the present invention relates to a process for catalytically converting a feedstock comprising cellulose and lignin to liquid fuel, said process comprising the steps of:
  • At least part of the lignin present in the Ionic Liquid is converted to a liquid fuel.
  • liquid fuel is insoluble in the Ionic Liquid.
  • the process can comprise the additional step (iii) of removing the liquid fuel from the Ionic Liquid.
  • the process can comprise the additional step of upgrading the liquid fuel.
  • the process comprises the additional step (iv) of
  • This additional regeneration step can comprise removing water from the Ionic Liquid medium.
  • the regeneration step can comprise removing sludge from the Ionic Liquid medium.
  • sludge refers to solid reaction products that are insoluble in the Ionic Liquid medium. The term encompasses such reaction products as coke and certain types of char.
  • the process can be operated such that little or no coke and char are formed.
  • it may be desirable to produce liquid hydrocarbons under conditions that promote cracking.
  • Such reaction conditions can promote the formation of coke and/or char.
  • the operator of the process may well accept a certain amount of coke yield as a price to pay for a high liquid yield, as coke is easily removed from the Ionic Liquid medium.
  • coke removal can be
  • step (ii). accomplished by passing the Ionic Liquid through a suitable filter medium, such as a bed of silica or alumina.
  • the filter medium can be regenerated by burning off the coke and any other components of the sludge. Heat generated during this regeneration process can be used in the conversion process, in particular in step (ii).
  • the removal of water can generally be accomplished by distillation. As will be
  • step (ii) is generally carried out under increased pressure, at temperatures exceeding 100 °C.
  • pressure By releasing the pressure while the temperature of the Ionic Liquid medium is maintained above 100 °C, water is flashed off in a process sometimes referred to as flash-distillation.
  • the Ionic Liquid medium may be recycled to step (i) of the process.
  • Hgnocellulosic material can be used in the process of the invention.
  • Hgnocellulosic biomass materials in particular forestry waste materials (wood chips, saw dust, tree bark, leaves); agricultural waste materials (straw, bagasse, corn stover, and the like); and energy crops (switch grass, coppice, fast-growing trees, such as eucalyptus, willow, poplar).
  • Lignin is insoluble in certain Ionic Liquid media, and partially soluble in others.
  • undissolved lignin is not removed from the process prior to step (ii).
  • Dissolved and undissolved lignin are at least partially converted to hydrocarbon compounds during step (ii).
  • the mixture of hydrocarbon compounds is more complex as a result of the lignin is present in the Ionic Liquid medium during step (ii).
  • This can provide a distinct advantage. For example, if the hydrocarbon products produced by the process are to be used as a gasoline mixing stock, the presence of lignin conversion products tends to increase the octane rating of the mixture.
  • the operator of the process can select an Ionic Liquid medium in which lignin is substantially insoluble.
  • lignin is insoluble in inorganic molten salt hydrates. It has surprisingly been found that nevertheless these materials are capable of dissolving the cellulose component of a lignocellulosic composite material. This makes it possible to unlock the cellulose portion of a lignocellulosic material, without requiring a separate process, such as the Kraft process, which involves the use of aggressive and environmentally undesirable chemicals.
  • lignocellulosic material further contain inorganic materials. To the extent these materials are insoluble in the Ionic Liquid medium they are easily removed from the process prior to step (ii). Inorganic materials that are dissolved in the Ionic Liquid medium can be removed in a regeneration step, for example using solvent extraction.
  • an acid catalyst for example hydrochloric acid (HQ)
  • HQ hydrochloric acid
  • Step (ii) can be carried out in the absence or of a catalyst.
  • Dissolved cellulose in particular when hydrolyzed to sugars, is far more reactive than cellulose in solid form so that suitable conversion yields can be obtained even in the absence of a catalyst.
  • step (ii) it can be advantageous to carry out step (ii) in the presence of a catalyst.
  • a catalyst accelerates the conversion reaction of dissolved cellulose, which reduces the reaction time; or permits the reaction to be carried out at a lower temperature than the uncatalyzed reaction; or a combination of these two advantages.
  • use of a catalyst generally results in a more selective hydrogenation reaction.
  • suitable catalysts include catalysts selected from the group consisting of hydrotreatment catalysts, hydrogenation catalysts, hydrocracking catalysts, and combinations thereof.
  • the catalyst comprises a hydrotreatment catalyst.
  • the hydrotreatment catalyst is in a sulfided form.
  • the catalyst may be converted to the sulfided form by contacting it with a feedstock that has been spiked with a sulfur-containing compound.
  • the practice of sulfiding hydrotreatment catalysts is well known in the world of oil refining, and will not be further disclosed here.
  • hydrotreatment catalysts are more active when in a sulfided form, as compared to an oxide form.
  • the use of sulfur results in consumption of hydrogen for the formation of ELS. This is undesirable from a perspective of a loss of valuable hydrogen, as well as from the resulting need to remove I3 ⁇ 4S from the reaction mixture.
  • lignocellulosic feedstocks typically contain little or no sulfur, it is necessary to spike the feedstock with sulfur in order to keep the catalyst in its sulfided form.
  • hydrotreatment catalyst as the lower catalyst activity is more than outweighed by the advantage of being able to operate sulfur-free.
  • the catalyst comprises a hydrogenation catalyst.
  • examples include catalysts containing Ni, Fe, or a metal from the Pt group in its metallic form. Particularly preferred are the noble transition metals.
  • the catalyst comprises a hydrocracking catalyst.
  • hydrocracking catalyst refers to catalysts containing both a hydrogenation functionality and a cracking functionality.
  • the hydrogenation functionality is generally provided by one or more of the typical hydrogenation metals (Ni, Fe, noble transition metals).
  • the cracking functionality is generally provided by acidic sites in the catalyst material.
  • a hydrogenation metal on a solid acid support such as an acidic zeolite, is typically a very effective hydrocracking catalyst.
  • Ionic Liquids are strong Lewis acids, and can act as acidic catalysts.
  • the combination of a hydrogenation catalyst in an Ionic Liquid medium that is a strong Lewis acid can show strong hydrocracking properties.
  • the Ionic Liquid medium can comprise an organic anion.
  • dicationic organic Ionic Liquids are excellent solvents for cellulose and hemicellulose.
  • Organic Ionic Liquids also have major disadvantages, the most important ones being high cost, and limited temperature resistance. Many have the additional disadvantage that they are poor solvents for cellulose when contaminated with water.
  • Preferred Ionic Liquids are inorganic Ionic Liquids, in particular inorganic molten salt hydrates. As compared to organic Ionic Liquids, inorganic Ionic Liquids are more temperature stable, and have a lower cost. In addition, in particular the inorganic molten salt hydrates are effective solvents for cellulose even in the presence of water. In fact, as their name indicates, a certain amount of water needs to be present for these materials to function as Ionic Liquid media.
  • Inorganic Ionic Liquids have an inorganic anion.
  • the anion can contain a halogen atom. Examples include halides, oxyhalides and hydroxyhalides, in particular chloride, oxychlorides, and hydroxychlorides.
  • the anion can also be hydroxide; for example, the hydroxide of the Cu/ammonia complex is a suitable Ionic Liquid medium for use in the process of the present invention.
  • the molten salt hydrate further comprises a cation, in particular Zn, Ba, Ca, Li, Al, Cr, Fe, or Cu.
  • Mixtures of inorganic salts can also be used, in particular eutectic mixtures.
  • any salt or salt hydrate that is liquid at a temperature of 200 °C or below, and is capable of dissolving cellulose, is suitable as the Ionic Liquid medium in the process of the present invention.
  • step (ii) comprises reaction with hydrogen (hydrogenation, hydrotreatment or
  • this step is preferably carried out at a hydrogen partial pressure in the range of from 1 to 200 bar, more preferably from 5 to 60 bar.
  • the temperature used in step (iii) to obtain the desired conversion of cellulose and/or sugars to hydrocarbons will depend on the amount and type of catalyst used, and on the contact time between the reactants and the catalyst. In general reaction temperatures in the range of from 150 °C to 400 °C are suitable, temperatures in the range of from 180 °C to 350 °C being preferred.
  • step (ii) is carried out in the substantial absence of hydrogen (pyrolysis, thermal cracking, catalytic cracking), this step is generally carried out at a temperature in the range of from 200 °C to 600 °C, preferably from 200 °C to 450 °C.
  • step (ii) Even when step (ii) is carried out in the presence of hydrogen, the reaction products obtained in step (ii) can still contain residual oxygen.
  • the main objective of step (ii) is to convert cellulose, hemicellulose and their hydrolysis products (C 6 and C 5 sugars, respectively) to reaction products that do not dissolve in the Ionic Liquid medium.
  • reaction products are a Ce and C5 hydrocarbon mixture that is oxygen-free, or has an oxygen content low enough for the mixture to be used as a blending stock for gasoline.
  • step (ii) is operated such that the reaction products have oxygen content just low enough for them to be insoluble in the Ionic Liquid medium, and miscible with a refinery feedstock.
  • the reaction products can be easily recovered from the Ionic Liquid medium, due to their insolubility therein.
  • the reaction products can also easily be co-processed with a refinery stream, due to their miscibility therewith.
  • step (ii) is operated to produce primarily dry gas, in

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Abstract

L'invention porte sur un procédé permettant de convertir une matière lignocellulosique en combustibles liquides. Dans le procédé, la cellulose est dissoute dans un milieu liquide ionique. Le procédé de conversion peut comprendre une pyrolyse, un craquage thermique, un hydrocraquage, un craquage catalytique, un hydrotraitement ou une combinaison de ceux-ci. La réaction de conversion est réalisée en présence de lignine. La lignine est au moins partiellement convertie dans le procédé. Le milieu liquide ionique est, de préférence, un hydrate d'un sel fondu inorganique.
EP10766380A 2009-09-01 2010-09-01 Conversion catalytique simultanée de cellulose et de lignine en un combustible liquide dans un liquide ionique Withdrawn EP2473533A1 (fr)

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US8652261B2 (en) 2009-09-01 2014-02-18 Kior, Inc. Process for dissolving cellulose-containing biomass material in an ionic liquid medium
US8882924B2 (en) 2009-09-01 2014-11-11 Kior, Inc. Pretreatment of solid biomass material comprising cellulose with ionic liquid medium
TWI462778B (zh) 2011-12-06 2014-12-01 Ind Tech Res Inst 生質物的液化方法與有機銨鹽溶液用於將生質物液化的用途
US9309471B2 (en) * 2012-06-29 2016-04-12 Uop Llc Decontamination of deoxygenated biomass-derived pyrolysis oil using ionic liquids
MX2016012430A (es) * 2014-03-28 2017-04-27 Reliance Ind Ltd Conversion hidrotermica de la biomasa en biocombustible crudo asistida por catalizadores.
EP3741828A1 (fr) * 2019-05-23 2020-11-25 Vertoro B.V. Procédé de craquage catalytique fluide d'huile de lignine brute (clo)

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US20070161095A1 (en) * 2005-01-18 2007-07-12 Gurin Michael H Biomass Fuel Synthesis Methods for Increased Energy Efficiency
WO2008098036A1 (fr) * 2007-02-06 2008-08-14 North Carolina State University Préparation et récupération d'un produit issu de la thermolyse de matières lignocellulosiques dans des liquides ioniques
AU2008226825B2 (en) * 2007-03-14 2013-02-21 Suganit Systems, Inc. Biomass pretreatment

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