Classifications

• • 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
  • 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
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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
  • 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
  • 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
  • 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
  • C10G1/086—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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
  • C10G3/55—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds
  • C10G3/57—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds according to the fluidised bed technique
• • 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
• • 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
• • 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
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/16—Clays or other mineral silicates
• • 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/007—Mixed salts
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
  • B01J29/084—Y-type faujasite
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• • 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
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/4006—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
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/44—Solvents
• • 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
  • 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 conversion of lignocellulosic biomass, and more particularly to such a conversion process comprising use of an Ionic Liquid medium.
• One such process comprises gasification of cellulose to synthesis gas ("syngas", a mixture of carbon monoxide and hydrogen), and conversion of the syngas in a Fischer-Tropsch reaction to hydrocarbons.
• syngas gasification of cellulose to synthesis gas
• This process is inherently inefficient, because long-chain polymeric materials are first broken down to small molecules, which are subsequently built back up to larger molecules. It is inefficient also because the oxygen content is first increased (syngas has higher oxygen content than cellulose), and subsequently reduced or eliminated.
• 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
• the three-step process has a rather poor overall yield.
• the present invention addresses these problems by providing a process for converting Hgnocellulosic biomass material to a liquid fuel, said process comprising the steps of:
• the present invention relates to a process for converting Hgnocellulosic biomass material to a liquid fuel, said process comprising the steps of:
• 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. It is an essential part of the process that undissolved lignin is removed from the Ionic Liquid in step (ii). Dissolved lignin is at least partially converted to hydrocarbon compounds during step (iii). The mixture of hydrocarbon compounds is more complex as a result when lignin is present in the Ionic Liquid medium during step (iii). 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. Accordingly, the process of the present invention permits separate processing of the cellulose (and hemicellulose) components of a lignocellulosic biomass material, on the one hand, and the lignin component on the other.
• 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 (iii). Inorganic materials that are dissolved in the Ionic Liquid medium can be removed in a regeneration step, for example using solvent extraction.
• An important aspect of the process of the present invention is that the (hemi-)cellulose and cellulose component of the lignocellulosic biomass material are converted at one temperature, Ti, whereas the lignin component is converted at a different temperature, T 2 .
• the (hemi-)cellulose conversion is carried out at a lower temperature than the lignin conversion. In other words, Ti ⁇ T 2 .
• T2 is at least 50 °C higher than Ti, more preferably at least 100 °C; most preferably at least 200 °C.
• the conversion of the (hemi-)cellulose component takes place in solution, which permits the use of low conversion temperatures.
• Ti is less than 200 °C.
• the conversion of solid lignin generally requires a temperature greater than 200 °C, preferably in the range of from 300°C to 600 °C.
• Step (iii) 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 (iii) it can be advantageous to carry out step (iii) 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.
• examples include catalysts comprising one or more of the elements from the group consisting of Ni, Co, Mo, and W. Preferred are catalysts comprising Mo. More preferred are catalysts comprising Mo and Ni or Co.
• the hydrotreatment catalyst is in a sulfided form.
• catalyst may be converted to the sulfided form by contacting it with a feedstock that has been spiked with a sulfur-containing compound.
• 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 I3 ⁇ 4S. 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 have been reported in the literature as being capable of
• 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.
• Step (iv) can, for example, be carried out in a cyclone reactor, a fixed fluidized bed reactor, or a transported fluidized bed reactor.
• the process of step (iv) can be carried out in the absence of a catalyst, for example a pyro lytic conversion or a thermal cracking process.
• step (iv) is carried out in the presence of a catalyst, for example a
• the catalyst can be used as a heat transfer medium to apply heat to the endothermic conversion reaction.
• the catalyst in step (iv) comprises a solid acid.
• suitable solid acids include acidic zeolites, such as zeolite-Y, ZSM-5 (in particular HZSM-5), and combinations thereof.
• the catalyst comprises a solid base.
• suitable solid base materials include hydrotalcite; hydrotalcite-like
• the catalyst can comprise alumina.
• the catalyst can be mixed with an inert heat transfer medium, such as silica sand.
• 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.
• hydrates of ZnC in particular ZnCl 2 .4H 2 0.
• 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 to 400 °C are suitable, temperatures in the range of from 180 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 (C6 and C5 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
• 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 (v) 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 (vi) 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.
• 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 (iii) is generally carried out under increased pressure, at temperatures exceeding 100 °C. 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.
• steps (iii) and (iv) can be conducted independent from each other.
• lignin recovered from step (ii) can be transported to a separate location for conversion in step (iv).
• steps (iii) and (iv) are carried out at the same location, they can be carried out at different points in time.
• step (iii) can be carried out immediately after step (ii), while lignin from step (ii) can be stockpiled for conversion in step (iv) at a later time.
• excess heat as may be generated during a catalyst regeneration step of (iv) can be used to fuel the reaction of step (iii).

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• 2010
  • 2010-09-01 EP EP10766381A patent/EP2473534A1/de not_active Withdrawn
  • 2010-09-01 WO PCT/US2010/047507 patent/WO2011028788A1/en active Application Filing
  • 2010-09-01 US US13/391,720 patent/US20120304529A1/en not_active Abandoned

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