WO2013072391A1 - Procédé de transformation de matière cellulosique - Google Patents

Procédé de transformation de matière cellulosique Download PDF

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Publication number
WO2013072391A1
WO2013072391A1 PCT/EP2012/072656 EP2012072656W WO2013072391A1 WO 2013072391 A1 WO2013072391 A1 WO 2013072391A1 EP 2012072656 W EP2012072656 W EP 2012072656W WO 2013072391 A1 WO2013072391 A1 WO 2013072391A1
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WO
WIPO (PCT)
Prior art keywords
equal
catalyst
catalytic cracking
organic solvent
feed
Prior art date
Application number
PCT/EP2012/072656
Other languages
English (en)
Inventor
Andries Quirin Maria Boon
Leticia ESPINOSA ALONSO
Johan Willem Gosselink
John William Harris
Andries Hendrik Janssen
Jean-Paul Lange
Colin John Schaverien
Nicolaas Wilhelmus Joseph Way
Original Assignee
Shell Internationale Research Maatschappij B.V.
Shell Oil Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij B.V., Shell Oil Company filed Critical Shell Internationale Research Maatschappij B.V.
Priority to IN3435DEN2014 priority Critical patent/IN2014DN03435A/en
Priority to CN201280061527.4A priority patent/CN104011177A/zh
Priority to AU2012338868A priority patent/AU2012338868A1/en
Priority to CA2855584A priority patent/CA2855584A1/fr
Priority to EP12788186.0A priority patent/EP2780433A1/fr
Priority to BR112014011506A priority patent/BR112014011506A2/pt
Publication of WO2013072391A1 publication Critical patent/WO2013072391A1/fr

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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
    • C10G1/006—Combinations of processes provided in groups C10G1/02 - C10G1/08
    • 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
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • 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
    • C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
    • C10G1/042—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction by the use of hydrogen-donor 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts 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
    • 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
    • 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 conversion of a cellulosic material and use of the products produced in such a process.
  • renewable energy sources With the diminishing supply of crude mineral oil, use of renewable energy sources is becoming increasingly important for the production of liquid fuels. These fuels from renewable energy sources are often referred to as biofuels .
  • Biofuels derived from non-edible renewable energy sources are preferred as these do not compete with food production. These biofuels are also referred to as second generation, or advanced, biofuels. Most of these non-edible cellulosic materials, however, are solid materials that are cumbersome to convert into biofuels.
  • WO2010/135734 describes a method for co-processing a biomass feedstock and a refinery feedstock in a refinery unit comprising catalytically cracking the biomass feedstock and the refinery feedstock in a refinery unit comprising a fluidized reactor, wherein hydrogen is transferred from the refinery feedstock to carbon and oxygen of the biomass feedstock.
  • the biomass feedstock comprises a plurality of solid biomass particles having an average size between 50 and 1000 microns.
  • solid biomass particles can be pre-processed to increase brittleness, susceptibility to catalytic conversion (e.g. by roasting, toasting, and/or torrefication) and/or susceptibility to mixing with a petrochemical feedstock.
  • WO2010/135734 is that proper handling of the biomass feedstock comprising the solid biomass particles is critical to avoid instability of the feedstock, clogging of feed lines to a fluidized catalytic cracking unit and/or coking in a fluidized catalytic cracking unit .
  • the present invention provides a process for conversion of a cellulosic material comprising
  • a catalytic cracking step comprising contacting at least part of the final liquefied product with a
  • fluidized catalytic cracking catalyst at a temperature of equal to or more than 400°C, to produce one or more cracked products.
  • the final liquefied product allows for a more stable feedstock to a fluidized catalytic cracking process than any pyrolysis oil and/or any solid biomass particles.
  • the process according to the invention therefore provides a less critical process for conversion of a cellulosic material.
  • the one or more cracked products may advantageously be fractionated to produce one or more product fractions and optionally hydrotreated to produce one or more hydrotreated product fractions. These one or more product fractions and/or one or more hydrotreated product
  • the present invention therefore further provides a process for the production of a biofuel comprising blending such biofuel components with one or more other components to produce a biofuel.
  • the produced biofuel may
  • a cellulosic material is contacted with a liquid solvent to produce a final liquefied product.
  • This step may also be referred to herein as a liquefaction or liquefying of the cellulosic material.
  • the liquefaction or liquefying may be carried out by means of a liquefaction or liquefying reaction.
  • liquefying is herein understood the conversion of a solid material, such as cellulosic material, into one or more liquefied products.
  • a liquefied product is herein understood a product that is liquid at a temperature of 20 °C and a pressure of 1 bar absolute (0.1 MegaPascal) and/or a product that can be converted into a liquid by melting (for example by applying heat) or dissolving in a solvent.
  • the liquefied product is a liquefied product that is liquid at a temperature of 80 °C and a pressure of 1 bar absolute (0.1 MegaPascal) .
  • liquefied product may vary widely in its viscosity and may be more or less viscous.
  • Liquefaction of a cellulosic material can comprise cleavage of covalent linkages in that cellulosic
  • liquefaction of lignocellulosic material can comprise cleavage of covalent linkages in cellulose, hemicellulose and/or lignin present and/or cleavage of covalent linkages between lignin,
  • cellulosic material refers to material containing cellulose.
  • the cellulosic material is a lignocellulosic material.
  • a lignocellulosic material comprises lignin, cellulose and optionally hemicellulose .
  • the liquefaction step makes it possible to liquefy not only the cellulose but also the lignin and hemicelluloses .
  • any suitable cellulose-containing material may be used as cellulosic material in the process according to the present invention.
  • the cellulosic material for use according to the invention may be obtained from a variety of plants and plant materials including agricultural wastes, forestry wastes, sugar processing residues and/or mixtures thereof.
  • suitable cellulose- containing materials include agricultural wastes such as corn stover, soybean stover, corn cobs, rice straw, rice hulls, oat hulls, corn fibre, cereal straws such as wheat, barley, rye and oat straw; grasses; forestry products such as wood and wood-related materials such as sawdust; waste paper; sugar processing residues such as bagasse and beet pulp; or mixtures thereof.
  • Step a) may further comprise drying, torrefaction, steam explosion, particle size reduction, densification and/or pelletization of the cellulosic material before the cellulosic material is contacted with the liquid solvent.
  • pelletization of the cellulosic material may
  • the cellulosic material is preferably processed into small particles in order to facilitate liquefaction.
  • the cellulosic material is processed into particles having a particle size distribution with an average particle size of equal to or more than 0.05 millimeter, more preferably equal to or more than 0.1 millimeter, most preferably equal to or more than 0.5 millimeter and preferably equal to or less than 20 centimeters, more preferably equal to or less than 10 centimeters and most preferably equal to or less than 3 centimeters.
  • the particle size in the centimeter and millimeter range can be determined by sieving .
  • the cellulosic material is a lignocellulosic material it may also have been subjected to a pre- treatment to remove and/or degrade lignin and/or
  • hemicelluloses examples include fractionation, pulping and torrefaction processes.
  • liquid solvent is herein preferably understood a solvent that is liquid at a pressure of 1 bar
  • a liquid solvent is herein understood to be a solvent that is liquid at the temperature and pressure at which the liquefaction step is carried out.
  • liquid solvent comprises or is water.
  • the liquid solvent comprises or is an organic solvent.
  • an organic solvent is herein understood a solvent comprising one or more hydrocarbon compounds.
  • a hydrocarbon compound is herein understood a compound that contains at least one hydrogen atom and at least one carbon atom, more
  • a hydrocarbon compound is herein understood to contain at least one hydrogen atom and at least one carbon atom bonded to eachother via at least one covalent bond .
  • hydrocarbon compound may contain for example heteroatoms such as sulphur, oxygen and/or nitrogen.
  • heteroatoms such as sulphur, oxygen and/or nitrogen.
  • hydrocarbon compounds that may preferably be present in the organic solvent include acetic acid, formic acid, levulinic acid and gamma-valerolactone and/or mixtures thereof.
  • the organic solvent may comprise polar and/or non- polar hydrocarbon compounds.
  • the organic solvent comprises at least one or more polar hydrocarbon compounds.
  • the organic solvent comprises more than one, more preferably more than two, more preferably more than three different polar
  • a measure of the polarity of a polar hydrocarbon compound is its log P value, where P is defined as the partition coefficient of a compound in a two phase octanol-water system.
  • the log P value can be determined experimentally or calculated according to standard procedures as discussed in Handbook of Chemistry and Physics, 83 rd Edition, pages 16-43 to 16-47, CRC Press (2002) .
  • the organic solvent may preferably comprise one or more polar hydrocarbon compound (s), which one or more polar hydrocarbon compound (s) preferably is/are a hydrocarbon compound having a polarity of log P less than +3, more preferably less than +1.
  • the polar hydrocarbon compound is a
  • the polar hydrocarbon compound is a hydrocarbon compound having a polarity of log P less than 0.
  • the organic solvent may preferably comprise one or more non-polar hydrocarbon compounds (s) , which one or more non-polar hydrocarbon compound (s) preferably is/are a hydrocarbon compound having a polarity of log P in the range from +5 to +10, more preferably in the range from +7 to +8.
  • the organic solvent comprises one or more carboxylic acids.
  • a carboxylic acid is herein understood a hydrocarbon compound
  • carboxylic acids can be polar hydrocarbon compounds as herein described above. More preferably the organic solvent comprises equal to or more than 5 wt% carboxylic acids, more preferably equal to or more than 10 wt% carboxylic acids, most preferably equal to or more than
  • the organic solvent may comprise equal to or less than 90wt%, more preferably equal to or less than 80wt% of carboxylic acids, based on the total weight of organic solvent.
  • the organic solvent comprises at least acetic acid, levulinic acid and/or pentanoic acid. Especially acetic acid may be useful as it can be
  • the organic solvent comprises paraffinic compounds, naphthenic compounds, olefinic compounds and/or aromatic compounds. Such compounds may be present in refinery streams such as gasoil, fuel oil and/or residue oil. These refinery streams may therefore also be suitable as organic solvent in the liquefaction step. This is explained in more detail below.
  • the organic solvent comprises at least a part of a liquefied product.
  • part of the liquefied product (for example part of a final liquefied product and/or part of an intermediate liquefied product as described herein below) is therefore recycled to the liquefaction step to be used as organic solvent.
  • part of the liquefied product for example part of a final liquefied product and/or part of an intermediate liquefied product as described herein below
  • organic solvent in a preferred embodiment equal to or more than 10 wt%, more preferably equal to or more than 20 wt% of the organic solvent is obtained from an
  • any recycle of liquefied product (s) comprises a weight amount of liquefied
  • At least part of the organic solvent is derived from cellulosic, and
  • lignocellulosic, material preferably lignocellulosic, material.
  • the organic solvent may be generated in-situ during liquefaction of the cellulosic material. More preferably at least part of the organic solvent is obtained by acid hydrolysis of
  • cellulosic, and preferably lignocellulosic, material examples include acetic acid, formic acid and levulinic acid.
  • Hydrocarbon compounds which are obtainable from such acid hydrolysis products by hydrogenation thereof may also suitably be used. Examples of such hydrogenated
  • hydrocarbon compounds include gamma-valerolactone which is obtainable from levulinic acid by hydrogenation, tetrahydrofufuryl and tetrahydropyranyl components which are derived from furfural or hydroxymethylfurfural , mono- and di- alcohols and ketones which are derived from sugars, and guaiacol and syringol components which are derived from lignin.
  • the organic solvent may comprise one, two or more of such hydrocarbon compounds.
  • the above compounds may also become part of the final liquefied product.
  • the final liquefied product or part thereof may comprise one, two or more of the above listed, optionally
  • hydroxymethylfurfural mono- and/or di- alcohols and/or mono- and/or di-ketones, which can be derived from sugars; and/or guaiacol and/or syringol components, which can be derived from lignin.
  • the hydrocarbon compound (s) may for example be generated in-situ and/or recycled and/or used as a make-up organic solvent, affording significant economic and processing advantages .
  • At least part of the organic solvent in the liquefaction step is not generated in situ by conversion of the cellulosic material.
  • Such an ex-situ provided organic solvent may co-exist with an in-situ formed organic solvent.
  • Such a solvent that is not generated in-situ but is ex-situ provided may therefore herein also be referred to as "co-solvent”.
  • the organic solvent comprises at least one or more hydrocarbon compound (s) that are at least partly obtained and/or derived from a source other than the cellulosic material used as a feedstock in the liquefaction step, for example a
  • hydrocarbon compounds (s) may for example be mixed with the cellulosic material before starting the liquefaction or may be added to the reaction mixture during the liquefaction.
  • the organic solvent in the liquefaction step comprises one or more hydrocarbon compounds that also may be suitable to act as a fluid hydrocarbon co-feed in the catalytic cracking step.
  • the organic solvent used in the liquefaction step contains one or more hydrocarbon compounds obtained from a
  • conventional crude oil also sometimes referred to as a petroleum oil or mineral oil
  • unconventional crude oil that is, oil produced or extracted using techniques other than the traditional oil well method
  • a renewable source such as for example a vegetable oil
  • the organic solvent used in the liquefaction step comprises or consists of a fraction of a petroleum oil or renewable oil.
  • the organic solvent comprises or consists of a straight run (atmospheric) gas oils, flashed
  • VGO vacuum gas oils
  • light cycle oil heavy cycle oil
  • hydrowax coker gas oils
  • coker gas oils diesel
  • gasoline gasoline
  • kerosene naphtha
  • liquefied petroleum gases atmospheric residue
  • long residue vacuum residue
  • vacuum residue vacuum residue
  • the organic solvent comprises or consists of a long residue.
  • the co-solvent as mentioned above is an organic solvent that comprises or consists of a petroleum oil or a fraction thereof.
  • the advantage of using a petroleum oil or a fraction thereof as an organic solvent or organic co-solvent is that this organic solvent or co-solvent may also be a suitable feed to the catalytic cracking step.
  • the organic solvent or organic co-solvent comprises or is a petroleum oil or a fraction thereof, this may lead to a more efficient and cheaper operation and hardware as no separation of such a organic solvent or organic co-solvent may be needed.
  • the present invention therefore also provides a process for conversion of a cellulosic material comprising
  • a) a liquefaction step comprising contacting a
  • a catalytic cracking step comprising contacting a mixture of at least part of the final liquefied product and the fraction of a petroleum oil with a fluidized catalytic cracking catalyst in a fluidized catalytic cracking reactor at a temperature of equal to or more than 400°C, to produce one or more cracked products.
  • a fluidized catalytic cracking catalyst in a fluidized catalytic cracking reactor at a temperature of equal to or more than 400°C, to produce one or more cracked products.
  • the liquefied product in step b) may suitably be the final liquefied product or any part thereof.
  • the fraction of a petroleum oil is preferably chosen from the group consisting of straight run (atmospheric) gas oils, flashed distillate, vacuum gas oils (VGO) , light cycle oil, heavy cycle oil, hydrowax, coker gas oils, diesel, gasoline, kerosene, naphtha, liquefied petroleum gases, atmospheric residue ("long residue”) and vacuum residue ("short residue”) and/or mixtures thereof as indicated above. At least part of this fraction of a petroleum oil or the whole of this fraction of a
  • petroleum oil may be contacted with the fluidized
  • the organic solvent is partly derived from cellulosic, preferably lignocellulosic, material and partly derived from a petroleum source.
  • the organic solvent comprises a mixture of i) a fraction of a petroleum oil and ii) one or more hydrocarbon compounds that may be obtained by acid hydrolysis of cellulosic, preferably
  • the organic solvent comprises at least one or more carboxylic acids, such as for example acidic acid, levulinic acid and/or pentanoic acid, which carboxylic acid(s) are preferably present before beginning the liquefaction reaction, that is, which carboxylic acid(s) are preferably not in-situ obtained and/or derived from the cellulosic material during the reaction.
  • carboxylic acids such as for example acidic acid, levulinic acid and/or pentanoic acid
  • the organic solvent may be water- miscible at the reaction temperature of the liquefaction step.
  • the liquefaction step comprises contacting the cellulosic material with a solvent mixture comprising the organic solvent and water.
  • the liquid solvent may comprise a solvent mixture containing water and an organic solvent.
  • the water in the solvent mixture may for example be generated in-situ during the liquefaction step.
  • the organic solvent is preferably present in an amount of less than or equal to 95% by weight, more preferably less than or equal to 90% by weight and most preferably less than or equal to 80% by weight, based on the total weight of water and organic solvent. Further the organic solvent is preferably present in an amount of more than or equal to 5% by weight, more preferably more than or equal to 10% by weight, and most preferably more than or equal to 20% by weight, based on the total weight of water and organic solvent. The organic solvent is preferably present in an amount of from 20% to 60% by weight, based on the total weight of the water and organic solvent.
  • Preferably water is present in an amount of less than or equal to 95% by weight, more preferably an amount of less than or equal to 90% by weight, and most
  • a solvent mixture contains the organic solvent and water in a weight ratio of organic solvent to water of less than or equal to 9:1, more preferably less than or equal to 8:2. Further a solvent mixture preferably contains the organic solvent and water in a weight ratio of organic solvent to water of more than or equal to 1:9 more preferably more than or equal to 2:8.
  • the cellulosic material and the organic solvent or - if a solvent mixture containing water and organic solvent is present - the solvent mixture are preferably mixed in a solvent mixture or organic solvent-to-cellulosic material ratio of 2:1 to 20:1 by weight, more preferably in a solvent mixture or organic solvent-to-cellulosic material ratio of 3:1 to 15:1 by weight and most
  • the liquefaction step may be carried out in the presence or absence of a catalyst.
  • a catalyst advantageously allows one to lower the reaction
  • the liquefaction step may comprise contacting a cellulosic material with an organic solvent, optionally in the essential absence of an externally provided acid catalyst, at a temperature of equal to or more than 200°C, more preferably equal to or more than 250°C, still more preferably a temperature of equal to or more than 300 °C and preferably a temperature equal to or less than 450°C.
  • the liquefaction step may comprise contacting a cellulosic material with an organic solvent in the presence of a, preferably acid, catalyst at a temperature of equal to or more than 100 °C, more preferably a temperature of equal to or more than 150°C , still more preferably a temperature of equal to or more than 200°C and preferably a temperature of equal to or less than 450°C, more preferably a temperature of equal to or less than 350°C.
  • a, preferably acid, catalyst at a temperature of equal to or more than 100 °C, more preferably a temperature of equal to or more than 150°C , still more preferably a temperature of equal to or more than 200°C and preferably a temperature of equal to or less than 450°C, more preferably a temperature of equal to or less than 350°C.
  • the catalyst is an acid catalyst.
  • the acid catalyst for use in liquefaction step to the
  • the invention may be any acid catalyst known in the art to be suitable for liquefying of cellulosic material.
  • the acid catalyst may be a Bronsted acid or a Lewis acid.
  • the acid catalyst may be a
  • the acid catalyst is a homogeneous or finely dispersed heterogeneous catalyst, most preferably the acid catalyst is a homogeneous catalyst.
  • the acid catalyst remains liquid and stable under the
  • the acid catalyst is a Bronsted acid and more preferably the acid catalyst is a mineral or organic acid, preferably a mineral or organic acid having a pKa value below 5.0, more preferably below 4.25, still more preferably below 3.75, even more preferably below 3.0, and most preferably below 2.5.
  • mineral acids examples include sulphuric acid, para toluene sulphonic acid, nitric acid,
  • the acid catalyst used in the liquefaction step is sulphuric acid or phosphoric acid.
  • suitable organic acids which may be used in the liquefaction step include levulinic acid, acetic acid, oxalic acid, formic acid, lactic acid, citric acid, trichloracetic acid and mixtures thereof.
  • the acid catalyst is an organic acid, it may suitably be an organic acid that is generated in-situ or ex-situ (i.e. provided externally) .
  • an in-situ generated organic acid is herein understood an organic catalyst that is generated in-situ during liquefaction of the cellulosic material.
  • An example of such an in-situ generated organic acid may be acetic acid or formic acid.
  • the acid catalyst is preferably present in an amount of less than or equal to 35% by weight, more preferably less than or equal to 20% by weight, even more preferably less than or equal to 10% by weight and still more preferably less than or equal to 5% by weight, and most preferably less than or equal to 1% by weight, based on the total weight of organic solvent or - if applicable - solvent mixture and acid catalyst. Further the acid catalyst is preferably present in an amount of more than or equal to 0.01% by weight, more preferably more than or equal to 0.1% by weight and most preferably more than or equal to 0.2% by weight, based on the total weight of organic solvent or - if applicable - solvent mixture and acid catalyst.
  • the amount of acid required will depend on the strength of the acid.
  • the acid catalyst is present in an amount of from 1% to 10% by weight, preferably from 2% to 5% by weight, based on the weight of organic solvent or - if applicable - solvent mixture and acid catalyst.
  • At least part of the liquefied product obtained after liquefaction of the cellulosic material is hydrogenated .
  • Liquefaction and hydrogenation may be carried out simultaneously or hydrogenation may be carried out subsequent to the liquefaction .
  • the liquefaction step comprises contacting the cellulosic material with the organic solvent in the presence of an acid catalyst at a
  • hydrotreating the intermediate liquefied product with a source of hydrogen in the presence of a hydrotreatment catalyst to produce a final liquefied product.
  • hydrotreating of the intermediate liquefied product comprises hydrogenating of the intermediate liquefied product and preferably the hydrotreatment catalyst is a hydrogenation catalyst.
  • the liquefaction step can advantageously comprise the
  • hydrogenation of the cellulosic material can be effected as any hydrolysis product can be in-situ hydrogenated .
  • the hydrogenation catalyst is preferably a
  • the hydrogenation catalyst can comprise a heterogeneous and/or homogeneous catalyst.
  • the hydrogenation catalyst is a homogeneous catalyst.
  • the hydrogenation catalyst is a heterogeneous catalyst.
  • the hydrogenation catalyst preferably comprises a
  • hydrogenation reactions such as for example iron, molybdenum, cobalt, nickel, copper, ruthenium, rhodium, palladium, iridium, platinum and gold, or mixtures thereof.
  • the hydrogenation catalyst comprising such a hydrogenation metal may be sulfided.
  • Molybdenum sulfide potentionally including Cobalt and/or Nickel as a promotor.
  • the catalyst preferably comprises a
  • Suitable carriers include for example carbon, alumina, titanium dioxide, zirconium dioxide, silicon dioxide and mixtures thereof. Examples of preferred heterogeneous
  • hydrogenation catalysts include ruthenium, platinum or palladium supported on a carbon carrier.
  • Other preferred examples of heterogeneous hydrogenation catalysts include ruthenium supported on titanium dioxide (Ti02), platina supported on titanium dioxide and ruthenium supported on zirconium dioxide ( Zr02 ) .
  • the heterogeneous catalyst and/or carrier may have any suitable form including the form of a mesoporous powder, granules or extrudates or a megaporous structure such as a foam, honeycomb, mesh or cloth.
  • the heterogeneous catalyst may be present in a liquefaction reactor comprised in a fixed bed or
  • the heterogeneous catalyst is present in a liquefaction reactor as a fixed bed.
  • the hydrogenation catalyst is a homogeneous hydrogenation catalyst
  • the catalyst preferably comprises an organic or inorganic salt of the hydrogenation metal, such as for example the acetate-, acetylacetonate- , nitrate-, sulphate- or chloride- salt of ruthenium, platinum or palladium.
  • the homogeneous hydrogenation metal such as for example the acetate-, acetylacetonate- , nitrate-, sulphate- or chloride- salt of ruthenium, platinum or palladium.
  • the homogeneous hydrogenation metal such as for example the acetate-, acetylacetonate- , nitrate-, sulphate- or chloride- salt of ruthenium, platinum or palladium.
  • the homogeneous hydrogenation metal such as for example the acetate-, acetylacetonate-
  • catalyst is an organic or inorganic acid salt of the hydrogenation metal, wherein the acid is an acid which is already present in the process as acid catalyst or product.
  • the source of hydrogen may be any source of hydrogen known to be suitable for hydrogenation purposes. It may for example include hydrogen gas, but also an hydrogen- donor such as for example formic acid.
  • the source of hydrogen is a hydrogen gas.
  • a hydrogen gas can be applied in the process of the invention at a partial hydrogen pressure that preferably lies in the range from 2 to 200 bar absolute (0.1 to 20 MegaPascal) , more preferably in the range from 10 to 170 bar absolute (1 to 17 MegaPascal), and most preferably in the range from 30 to 150 bar absolute (3 to 15 MegaPascal) .
  • a hydrogen gas can be supplied to a liquefaction reactor co-currently, cross-currently or counter-currently to the cellulosic material.
  • a hydrogen gas is
  • the liquefaction step can be carried out at any total pressure known to be suitable for liquefaction processes.
  • the process can be carried out under a total pressure that preferably lies in the range from 2 to 200 bar absolute (0.1 to 20 MegaPascal), more preferably in the range from 10 to 170 bar absolute (1 to 17
  • the liquefaction process according to the invention can be carried out batch-wise, semi-batch wise and continuously .
  • the cellulosic material is liquefied, i.e. the cellulosic material is converted into one or more liquefied products, to produce a final liquefied product.
  • a final liquefied product is herein preferably understood a liquefied product which is ready to be forwarded to the catalytic cracking step.
  • the final liquefied product may have been hydrogenated (as
  • the final liquefied product may have been separated from the reaction effluent or not.
  • the final liquefied product has been hydrogenated and/or is obtained after one or more separations as described herein below.
  • the reaction effluent produced in the liquefaction step may include so-called humins, the liquefied
  • step a) may further comprise separating a final liquefied product from a reaction effluent produced in the liquefaction step.
  • humins is understood the solid insoluble material remaining after liquefaction. It is sometimes also referred to as char.
  • the liquefied product (s) may comprise monomeric and/or oligomeric compounds and optionally excess water produced during the liquefaction process. From the liquefied product a product containing monomeric and oligomeric compounds may be separated. Also part of the liquefied product may be separated for recycling to the liquefaction step as organic solvent.
  • reaction effluent is preferably forwarded to a separation section.
  • separation section insoluble humins, monomeric and/or oligomeric compounds and/or water, co-solvent and/or acid catalyst can be separated off from the reaction effluent.
  • the humins may be separated from the reaction effluent in a manner known to be suitable for this purpose. Preferably such humins are separated off via filtration or settling. Any humins formed in the liquefaction step can be converted to diesel, kerosene and gasoline fraction in the catalytic cracking step of the process according to the invention or in another conventional refinery step.
  • the liquefied products and/or any co-solvent are separated from the reaction effluent in a manner known to be suitable for this purpose.
  • liquid/liquid separation techniques such as phase separation, (solvent) extraction and/or membrane filtration or (vacuum) distillation.
  • the monomeric products and oligomeric products may be conveniently separated from eachother using one or more membranes.
  • monomeric compounds and/or optionally water can be separated from any C9-C20 oligomeric compounds and C20+ oligomeric compounds by a ceramic membrane (for example a T1O 2 membrane) or a polymeric membrane (for example a Koch MPF 34 (flatsheet) or a Koch MPS-34 (spiral wound) membrane) .
  • the C9-C20 oligomers and the C20+ oligomers can be any suitable oligomers.
  • excess water produced during the liquefaction step is removed by distillation, pervaporation and/or reversed osmosis.
  • this recycle stream also contains at least part of any monomeric compounds and/or oligomeric
  • any excess of water, co-solvent, acid catalyst , hydrogenation catalysts and/or monomeric compounds is preferably purged via a purge stream.
  • a purge stream preferably more than or equal to 50% by weight, more preferably more than or equal to 60% by weight and most preferably more than or equal to 70% by weight of the cellulosic material may advantageously be liquefied into liquefied product, preferably in less than 3 hours.
  • the co-solvent is an organic co-solvent such as a petroleum oil or a fraction of a petroleum oil
  • the liquefaction step comprises hydrogenating of the one or more liquefied products, the petroleum oil or a fraction of the
  • petroleum oil may suitably also be hydrogenated . This may be advantageous during the catalytic cracking step.
  • the catalytic cracking step comprises contacting at least part of the final liquefied product with a
  • the final liquefied product or part thereof may comprises one, two or more compounds chosen from the group consisting of gamma-valerolactone and/or levulinic acid; tetrahydrofufuryl and/or
  • tetrahydropyranyl furfural and/or hydroxymethylfurfural ; mono- and/or di- alcohols and/or mono- and/or di-ketones; and/or guaiacol and/or syringol components.
  • the final liquefied product or part thereof is a fraction of the reaction effluent obtained from the liquefaction step which comprises or essentially consists of one or more, preferably
  • the final liquefied product in this embodiment comprises one or more compounds
  • such a final liquefied product includes hydrocarbon compounds and/or oxygenates, such as for example alcohols.
  • a final liquefied product may comprise or may consist of mono- and/or di- alcohols and/or mono-and/or di-ketones which are derived from sugars.
  • More preferably such final liquefied product is a final liquefied product containing butanone, butanol and/or furfural.
  • the final liquefied product or part thereof is a fraction of the reaction effluent obtained from the liquefaction step which comprises or essentially consists of one or more, preferably
  • the final liquefied product in this embodiment comprises one or more compounds containing equal to or more than 9 carbon atoms,
  • the final liquefied product or part thereof can be produced as described above.
  • the final liquefied product or any part thereof to be contacted with the fluidized catalytic cracking catalyst can optionally be obtained after a separation step as described above.
  • the final liquefied product or any part thereof can be fed to a fluidized catalytic cracking reactor in an essentially liquid state, in an essentially gaseous state or in a partially liquid-partially gaseous state.
  • the catalytic cracking step comprises contacting at least part of the final liquefied product and a fluid hydrocarbon co-feed with the fluidized catalytic cracking catalyst, preferably in a fluidized catalytic cracking reactor, at a temperature of equal to or more than 400°C, to produce the one or more cracked products. That is, in a preferred embodiment also a fluid hydrocarbon co-feed other than the at least part of the final liquefied product may be added into a fluidized catalytic cracking reactor.
  • a hydrocarbon co-feed is herein understood a co- feed that contains one or more hydrocarbon compounds .
  • a fluid hydrocarbon co-feed is herein understood a hydrocarbon feed that is not in a solid state.
  • the fluid hydrocarbon co-feed is preferably a liquid hydrocarbon co-feed, a gaseous hydrocarbon co-feed, or a mixture thereof.
  • the fluid hydrocarbon co-feed can be fed to a catalytic cracking reactor in an essentially liquid state, in an essentially gaseous state or in a partially liquid-partially gaseous state.
  • the fluid hydrocarbon co-feed in an essentially or partially liquid state, the fluid hydrocarbon co-feed preferably vaporizes upon entry and preferably is contacted in the gaseous state with the fluidized catalytic cracking catalyst.
  • the fluid hydrocarbon co-feed can be any non-solid hydrocarbon co-feed known to the skilled person to be suitable as a co-feed for a catalytic cracking unit.
  • the fluid hydrocarbon co-feed can for example be obtained from a conventional crude oil (also sometimes referred to as a petroleum oil or mineral oil) , an unconventional crude oil (that is, oil produced or extracted using techniques other than the traditional oil well method) or a Fisher Tropsch oil and/or a mixture thereof.
  • the fluid hydrocarbon co-feed may even be a fluid hydrocarbon co-feed from a renewable source, such as for example a vegetable oil.
  • a renewable source such as for example a vegetable oil.
  • the fluid hydrocarbon co-feed is derived from a, preferably conventional, crude oil.
  • Examples of conventional crude oils include West Texas Intermediate crude oil, Brent crude oil, Caribbean-Oman crude oil, Arabian Light crude oil, Midway Sunset crude oil or
  • the fluid hydrocarbon co-feed comprises a fraction of a, preferably conventional, crude oil or renewable oil.
  • Preferred fluid hydrocarbon co- feeds include straight run (atmospheric) gas oils, flashed distillate, vacuum gas oils (VGO) , light cycle oil, heavy cycle oil, hydrowax, coker gas oils, diesel, gasoline, kerosene, naphtha, liquefied petroleum gases, atmospheric residue ("long residue”) and vacuum residue (“short residue”) and/or mixtures thereof.
  • the fluid hydrocarbon co-feed comprises a long residue .
  • the composition of the fluid hydrocarbon co-feed may vary widely.
  • the fluid hydrocarbon co-feed may for example contain paraffins, olefins and aromatics.
  • the fluid hydrocarbon co-feed comprises equal to or more than 1 wt% paraffins, more preferably equal to or more than 5 wt% paraffins, and most
  • wt% paraffins preferably equal to or more than 10 wt% paraffins, and preferably equal to or less than 100 wt% paraffins, more preferably equal to or less than 90 wt% paraffins, and most preferably equal to or less than 30 wt% paraffins, based on the total fluid hydrocarbon co-feed.
  • paraffins both normal-, cyclo- and branched-paraffins are understood.
  • a paraffinic fluid hydrocarbon co-feed is herein understood a fluid hydrocarbon co-feed comprising at least 50 wt% of paraffins, preferably at least 70 wt% of paraffins, based on the total weight of the fluid hydrocarbon co-feed.
  • the paraffin content of all fluid hydrocarbon co-feeds having an initial boiling point of at least 260°C can be
  • paraffinic fluid hydrocarbon co-feeds examples include so-called Fischer-Tropsch derived hydrocarbon streams such as described in WO2007/090884 and herein incorporated by reference, or a hydrogen rich feed like hydrotreater product or hydrowax.
  • Fischer-Tropsch derived hydrocarbon streams such as described in WO2007/090884 and herein incorporated by reference, or a hydrogen rich feed like hydrotreater product or hydrowax.
  • hydrocracking processes which may yield a bottoms fraction that can be used as fluid hydrocarbon co-feed, are described in EP-A-699225, EP-A-649896, WO-A- 97/18278, EP-A-705321, EP-A-994173 and US-A-4851109 and herein incorporated by reference.
  • the fluid hydrocarbon co- feed comprises equal to or more than 8 wt% elemental hydrogen, more preferably more than 12 wt% elemental hydrogen (i.e. hydrogen atoms), based on the total fluid hydrocarbon co-feed on a dry basis (i.e. water-free basis) .
  • a high content of elemental hydrogen such as a content of equal to or more than 8 wt%, allows the hydrocarbon feed to act as a cheap hydrogen donor in the catalytic cracking process.
  • a particularly preferred fluid hydrocarbon co-feed having an elemental hydrogen content of equal to or more than 8 wt% is Fischer-Tropsch derived waxy raffinate. Such Fischer-Tropsch derived waxy raffinate may for example comprise about 85 wt% of elemental carbon and 15 wt% of elemental hydrogen.
  • the weight ratio of fluid hydrocarbon co-feed to liquefied product (s) (or part thereof) is preferably equal to or more than 50 to 50 (5:5), more preferably equal to or more than 70 to 30 (7:3), still more preferably equal to or more than 80 to 20 (8:2), even still more preferably equal to or more than 90 to 10 (9:1) .
  • the weight ratio of fluid hydrocarbon co-feed to liquefied product (s) (or part thereof) is preferably equal to or less than 99.9 to 0.1 (99.9:0.1), more preferably equal to or less than 95 to 5 (95:5) .
  • the fluid hydrocarbon co-feed and the final liquefied product (or part thereof) are preferably being fed to a fluidized catalytic cracking reactor in a weight ratio within the above ranges.
  • hydrocarbon co-feed supplied to a fluidized catalytic cracking reactor is preferably equal to or less than 50 wt%, more preferably equal to or less than 30 wt%, most preferably equal to or less than 20 wt% and even more preferably equal to or less than 10 wt%.
  • amount of liquefied product (s) present based on the total weight of liquefied product (s) and fluid hydrocarbon co-feed supplied to a fluidized
  • catalytic cracking reactor is preferably equal to or more than 0.1 wt%, more preferably equal to or more than 1 wt%.
  • the catalytic cracking step is preferably carried out in a fluidized catalytic cracking reactor.
  • the fluidized catalytic cracking reactor can be any fluidized catalytic cracking reactor known in the art to be
  • the fluidized dense bed reactor or a riser reactor Most preferably the catalytic cracking step is carried out in a riser reactor. Preferably this fluidized catalytic cracking reactor is part of a fluidized catalytic
  • FCC cracking
  • the organic solvent in the liquefaction step comprises one or more hydrocarbon compounds that also may suitable act as a fluid
  • hydrocarbon co-feed preferably a mixture of the
  • liquefied product (s) and any organic solvent may be supplied to the fluidized catalytic cracking reactor.
  • the fluid hydrocarbon co-feed as described herein may comprise or consist of such a co-solvent.
  • the organic solvent used in the liquefaction step is chosen from the fluid hydrocarbon co-feeds described above.
  • Preferences for the fluid hydrocarbon co-feed are as described herein above.
  • the fluidized catalytic cracking reactor is a riser reactor and the fluid hydrocarbon co-feed is supplied to a riser reactor at a location downstream of the location where the liquefied product (s) is/are supplied to a riser reactor.
  • a mixture of the liquefied product (s) and a first hydrocarbon co-feed (which may for example be the organic solvent when the organic solvent is chosen from the described fluid hydrocarbon co-feeds) is supplied to a riser reactor at a first location and a second fluid hydrocarbon co-feed is supplied to the riser reactor at a second location downstream of the first location.
  • a first hydrocarbon co-feed which may for example be the organic solvent when the organic solvent is chosen from the described fluid hydrocarbon co-feeds
  • a riser reactor is herein understood an elongated essentially tube-shaped reactor suitable for carrying out catalytic cracking reactions.
  • the elongated essentially tube-shaped reactor is preferably oriented in an
  • the riser reactor may be a so-called internal riser reactor or a so-called external riser reactor as
  • the internal riser reactor is an essentially vertical essentially tube-shaped reactor, that may have an essentially vertical upstream end located outside a vessel and an essentially vertical downstream end located inside the vessel.
  • the vessel is suitably a reaction vessel suitable for catalytic
  • the internal riser reactor may be especially advantageous in the catalytic cracking step as it may be less prone to plugging, thereby increasing safety and hardware
  • the length of the riser reactor may vary widely.
  • the riser reactor preferably has a length in the range from equal to or more than 10 meters, more preferably equal to or more than 15 meters and most preferably equal to or more than 20 meters, to equal to or less than 65 meters, more preferably equal to or less than 55 meters and most preferably equal to or less than 45 meters.
  • the liquefied product (s) produced in the liquefaction step are supplied to a riser reactor, at the bottom of this riser reactor.
  • This may advantageously result in in-situ water formation at the bottom of the reactor.
  • the in-situ water formation may lower the hydrocarbon partial pressure and reduce second order hydrogen transfer reactions, thereby resulting in higher olefin yields.
  • the hydrocarbon partial pressure is lowered to a pressure in the range from 0.7 to 2.8 bar absolute (0.07 to 0.28 MegaPascal) , more
  • a lift gas at the bottom of the riser reactor.
  • a liftgas examples include steam, vaporized oil and/or oil fractions, and mixtures thereof. Steam is most preferred as a lift gas from a practical perspective.
  • a vaporized oil and/or oil fraction preferably vaporized liquefied petroleum gas, gasoline, diesel, kerosene or naphtha
  • a liftgas may have the advantage that the liftgas can simultaneously act as a hydrogen donor and may prevent or reduce coke formation.
  • a fluid hydrocarbon co-feed is used as an organic solvent in the liquefaction step, also vaporized organic solvent may be used as a liftgas.
  • the fluidized catalytic cracking catalyst can be any catalyst known to the skilled person to be suitable for use in a cracking process.
  • the fluidized catalytic cracking catalyst comprises a zeolitic
  • the fluidized catalytic cracking catalyst can contain an amorphous binder compound and/or a filler.
  • the amorphous binder component include silica, alumina, titania, zirconia and magnesium oxide, or combinations of two or more of them.
  • fillers include clays (such as kaolin) .
  • the zeolite is preferably a large pore zeolite.
  • the large pore zeolite includes a zeolite comprising a porous, crystalline aluminosilicate structure having a porous internal cell structure on which the major axis of the pores is in the range of 0.62 nanometer to
  • zeolites include FAU or faujasite, preferably synthetic faujasite, for example, zeolite Y or
  • USY ultra-stable zeolite Y
  • REY Rare Earth zeolite Y
  • REUSY Rare Earth USY
  • the fluidized catalytic cracking catalyst can also comprise a medium pore zeolite.
  • the medium pore zeolite that can be used according to the present invention is a zeolite comprising a porous, crystalline aluminosilicate structure having a porous internal cell structure on which the major axis of the pores is in the range of 0.45 nanometer to 0.62 nanometer.
  • Examples of such medium pore zeolites are of the MFI structural type, for example, ZSM-5; the MTW type, for example, ZSM-12; the TON
  • ZSM-5 is preferably used as the medium pore zeolite.
  • a blend of large pore and medium pore zeolites may be used.
  • the ratio of the large pore zeolite to the medium pore size zeolite in the cracking catalyst is preferably in the range of 99:1 to 70:30, more preferably in the range of 98:2 to 85:15.
  • cracking catalyst is preferably in the range of 5 wt% to 40 wt%, more preferably in the range of 10 wt% to 30 wt%, and even more preferably in the range of 10 wt% to 25 wt% relative to the total mass of the fluidized catalytic cracking catalyst.
  • the liquefied product (s) and any fluid hydrocarbon feed flow co-currently in the same direction.
  • the fluidized catalytic cracking catalyst can be
  • the catalytic cracking catalyst is contacted in a cocurrent flow configuration with a cocurrent flow of the liquefied product (s) and optionally the fluid hydrocarbon feed.
  • the catalytic cracking step comprises: a fluidized catalytic cracking step comprising contacting at least part of the final liquefied product with a fluidized catalytic cracking catalyst at a temperature of equal to or more than 400°C, to produce one or more cracked products and a spent fluidized catalytic cracking catalyst ;
  • a separation step comprising separating the one or more cracked products from the spent fluidized catalytic cracking catalyst
  • a regeneration step comprising regenerating spent
  • a recycle step comprising recycling the regenerated fluidized catalytic cracking catalyst to the fluidized catalytic cracking step.
  • the fluidized catalytic cracking step is preferably carried out as described herein before.
  • the separation step is preferably carried out with the help of one or more cyclone separators and/or one or more swirl tubes. Suitable ways of carrying out the separation step are for example described in the Handbook titled "Fluid Catalytic Cracking; Design, Operation, and Troubleshooting of FCC Facilities" by Reza Sadeghbeigi, published by Gulf Publishing Company, Houston Texas
  • the separation step may further comprise a stripping step.
  • a stripping step the spent fluidized catalytic cracking catalyst may be stripped to recover the products absorbed on the spent fluidized catalytic cracking catalyst before the regeneration step. These products may be recycled and added to a stream comprising one or more cracked products obtained from the catalytic cracking step.
  • the regeneration step preferably comprises
  • regeneration coke that can be deposited on the catalyst as a result of the fluidized catalytic cracking reaction, is burned off to restore the catalyst activity.
  • the oxygen containing gas may be any oxygen
  • oxygen containing gas may be air or oxygen-enriched air.
  • oxygen enriched air is herein understood air comprising more than 21 vol. % oxygen (0 2 ) , more preferably air comprising equal to or more than 22 vol. % oxygen, based on the total volume of air.
  • the heat produced in the exothermic regeneration step is preferably employed to provide energy for the endothermic catalytic cracking step.
  • the heat produced can be used to heat water and/or generate steam.
  • the steam may be used elsewhere in the refinery, for example as a liftgas in a riser reactor.
  • catalyst is regenerated at a temperature in the range from equal to or more than 575 °C, more preferably from equal to or more than 600 °C, to equal to or less than 950 °C, more preferably to equal to or less than 850 °C.
  • the spent fluidized catalytic cracking is regenerated at a temperature in the range from equal to or more than 575 °C, more preferably from equal to or more than 600 °C, to equal to or less than 950 °C, more preferably to equal to or less than 850 °C.
  • catalyst is regenerated at a pressure in the range from equal to or more than 0.5 bar absolute to equal to or less than 10 bar absolute (0.05 MegaPascal to
  • a side stream of make-up fluidized catalytic cracking catalyst is added to the recycle stream to make-up for loss of fluidized catalytic cracking catalyst in the reaction zone and regenerator.
  • one or more cracked products are produced.
  • this/these one or more cracked products is/are subsequently fractionated to produce one or more product fractions.
  • Fractionation may be carried out in any manner known to the skilled person in the art to be suitable for fractionation of products from a catalytic cracking unit.
  • the fractionation may be carried out as described in the Handbook titled "Fluid Catalytic
  • At least one of the one or more product fractions obtained by fractionation are subsequently hydrotreated with a source of hydrogen, preferably in the presence of a hydrotreatment catalyst to produce a hydrotreated product fraction.
  • the hydrotreatment step may for example comprise hydrodeoxygenation,
  • the one or more product fractions and/or the one or more hydrotreated product fractions and/or any fractions derived therefrom can conveniently be used as a biofuel component.
  • a biofuel component may conveniently be blended with one or more other components to produce a biofuel.
  • examples of such one or more other components include anti-oxidants , corrosion inhibitors, ashless detergents, dehazers, dyes, lubricity improvers and/or mineral fuel components, but also conventional petroleum derived gasoline, diesel and/or kerosene fractions.
  • a biofuel is herein understood a fuel that is at least party derived from a renewable energy source.
  • the biofuel may advantageously be used in the engine of a transportation vehicle.
  • sulphuric acid (0.86 g) was injected.
  • the autoclave was pressurised with hydrogen (3 ⁇ 4) to 4 MegaPascal (40 bar) and subsequently heated in 70 min to 200 °C.
  • Reactor pressure was subsequently increased to 8 MegaPascal (80 bar) by adding 3 ⁇ 4 .
  • the reaction was continued for 60 min, occasionally 3 ⁇ 4 was added to maintain the pressure at 8 MegaPascal.
  • the reaction was stopped by rapid cooling to room temperature (20°C), subsequently 3 ⁇ 4 was vented and 143.2 g of a first total product (including liquid, tar, insoluble humins and catalyst) was collected.
  • a second total product 143.7 g
  • the first and second total product were combined.
  • methyl-tetrahydrofuran m- THF, 400 grams
  • the mixture of methyl- tetrahydrofuran and total products was stirred for 10 minutes at room temperature (20 °C) and subsequently filtered over a P3 glass filter to produce a filtrate and a filter cake.
  • the filtrate was stored overnight (about 12 hours) to facilitate phase separation and produce a top organic layer and a bottom aqueous layer.
  • the top organic layer was collected.
  • the filter cake on the P3 filter were washed with m- THF (300 g) to produce a m-THF solution.
  • the m-THF solution was combined with the top organic layer.
  • THF was removed from the combination of top organic layer and m-THF solution by vacuum distillation at 80°C, 20 mbar (2 KiloPascal) to produce 25.1 grams of a liquefied product.
  • 80°C, 20 mbar 2 KiloPascal
  • the m-THF was again removed by vacuum distillation at 80°C, 20 mbar (2
  • the brownish black coloured viscous liquefied product was characterized by SEC (RI/UV) (size exclusion chromatography with UV and refractive index detectors) , Gas Chromatography and 13 C-Nuclear Magnetic Resonance ( 13 C-NMR) . Elemental analysis of carbon, hydrogen and oxygen resulted in C: 63.5 w% ( ⁇ 0.3), H: 7.89 w% ( ⁇ 0.1), 0 (by calculating the balance) : 27.3 w% ( ⁇ 0.5) .
  • the brownish black coloured viscous liquefied product had a H/Ceff of 0.85.
  • Total acid number (TAN) was determined to be ( ⁇ 5) mg KOH/g.
  • the above brownish black coloured viscous liquefied product was used as a final liquefied product.
  • a heavy feed mixture comprising long residue was used as a fluid hydrocarbon co-feed.
  • the final liquefied product was blended with the fluid hydrocarbon co-feed to prepare a feed mixture containing a weight percentage of 20 wt% of the final liquefied product based on the total weight of final liquefied product and the fluid
  • the feed mixture was injected into the fluidized catalyst bed of a MAT-5000 fluidized catalytic cracking unit.
  • the fluidized catalyst bed contained 10 grams of FCC equilibrium catalyst containing ultra stable zeolite Y.
  • the fluidized catalyst bed was kept at 520 °C and about 1 bar absolute (about 0.1
  • the run included 7 experiments with 7 catalyst to feed weight ratios, namely catalyst/feed weight ratios of 3, 4, 5, 6, 6.5, 7 and 8.
  • the feed mixture of final liquefied product and fluid hydrocarbon co-feed is more reactive.
  • the feed mixture of final liquefied product and fluid hydrocarbon co-feed shows a similar yield of valuable products (gasoline, light cycle oil and LPG) and a similar coke yield when compared to the reference feed.
  • Table 1 The feed mixture of final liquefied product and fluid hydrocarbon co-feed shows a similar yield of valuable products (gasoline, light cycle oil and LPG) and a similar coke yield when compared to the reference feed.
  • Conversion is subsequently defined as the weight in grams of drygas + LPG + gasoline + coke divided by the corrected weight in grams of the total feed.
  • product yield [weight X] / [weight of the total feed - (weight of oxygen in feed - weight of oxygen in CO and C0 2 ) *18/16] *100%
  • FHCF F1 uid Hydrocarbon Co-Feed
  • LCO Light Cycle Oil
  • HCO heavy Cycle Oil
  • LPG liquefied Petroleum Gas.
  • Furfural respectively furfuryl alcohol was used as an artificial representative of a final liquefied product.
  • a heavy feed mixture having a composition as illustrated in tables 2a and 2b was used as a fluid hydrocarbon co-feed.
  • Table 2a Boiling range distribution of the fluid hydrocarbon feed as determined by gas chromatography according to ASTM D2887-06a.
  • the furfural respectively furfuryl alcohol was blended with the fluid hydrocarbon co-feed to prepare a feed mixture containing a weight percentage of 20 wt% of furfural respectively furfuryl alcohol based on the total weight of the feed mixture.
  • the feed mixture was
  • the fluidized catalyst bed contained 10 grams of FCC equilibrium catalyst containing ultra stable zeolite Y.
  • the fluidized catalyst bed was kept at 520 °C and about 1 bar absolute (about 0.1 MegaPascal) .
  • the catalyst/feed weight ratio was 3.
  • the effective molar ratio of hydrogen to carbon (H/C eff ) of furfural respectively furfuryl alcohol is 0.0
  • H/C eff hydrogen to carbon
  • the feed mixture comprising furfural respectively
  • furfuryl alcohol shows a slight decrease of valuable products (gasoline, light cycle oil and LPG) and a slight increase in coke yield when compared to the reference feed.
  • table 2c The below results in table 2c have been normalized and calculated on a dry basis , i.e. without 3 ⁇ 40.
  • a corrected weight of the total feed is calculated by subtracting the weight of one water molecule for each oxygen atom that has not been converted into CO or C02 from the feed. Subsequently the product yield is defined as the weight in grams of the specific product divided by the corrected weight in grams of the total feed. In other words, the product yield distribution is on hydrocarbon basis.
  • product yield for product X [weight X] / [weight of the total feed - (weight of oxygen in feed - weight of oxygen in CO and C0 2 ) *18/16] *100%
  • FHCF F1 uid Hydrocarbon Co-Feed
  • LCO Light Cycle Oil
  • HCO heavy Cycle Oil
  • LPG liquefied Petroleum Gas.
  • Example 2 further shows the advantage of co-feeding a complete final liquefied product, which is a mixture of several components, to the FCC unit, rather than a feed containing only furfural or furfuryl alcohol.
  • Respectively tetrahydrofuran (THF) , butanone and 2- butanol were used as an artificial representative of a final liquefied product.
  • a vacuum gas oil (VGO) was used as a fluid hydrocarbon co-feed.
  • the feed mixture was injected into the fluidized catalyst bed of a MAT-5000 fluidized catalytic cracking unit.
  • the fluidized catalyst bed contained 10 grams of FCC equilibrium catalyst containing ultra stable zeolite Y.
  • the fluidized catalyst bed was kept at 550 °C and about 1 bar absolute (about 0.1 MegaPascal) .
  • the catalyst/feed weight ratio was 3.
  • the feed mixture comprising respectively tetrahydrofuran
  • hydrocarbon co-feed (at a constant cat/oil ratio of 3.0 and a temperature of 550°C)
  • a corrected weight of the total feed is calculated by subtracting the weight of one water molecule for each oxygen atom that has not been converted into CO or C02 from the feed. Subsequently the product yield is defined as the weight in grams of the specific product divided by the corrected weight in grams of the total feed. In other words, the product yield distribution is on hydrocarbon basis.
  • product yield for product X [weight X] / [weight of the total feed - (weight of oxygen in feed - weight of oxygen in CO and C0 2 ) *18/16] *100%

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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne un procédé de transformation de matière cellulosique comprenant une étape de liquéfaction, consistant à mettre une matière cellulosique en contact avec un solvant liquide à une température d'au moins 200 °C ; ou à mettre une matière cellulosique en contact avec un solvant liquide à une température d'au moins 100 °C en présence d'un catalyseur, pour produire un produit final liquéfié ; une étape de craquage catalytique, consistant à mettre au moins une partie du produit final liquéfié en contact avec un catalyseur de craquage catalytique sur lit fluidisé à une température d'au moins 400 °C, pour produire un ou plusieurs produits de craquage.
PCT/EP2012/072656 2011-11-14 2012-11-14 Procédé de transformation de matière cellulosique WO2013072391A1 (fr)

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IN3435DEN2014 IN2014DN03435A (fr) 2011-11-14 2012-11-14
CN201280061527.4A CN104011177A (zh) 2011-11-14 2012-11-14 转化纤维素材料的方法
AU2012338868A AU2012338868A1 (en) 2011-11-14 2012-11-14 Process for conversion of a cellulosic material
CA2855584A CA2855584A1 (fr) 2011-11-14 2012-11-14 Procede de transformation de matiere cellulosique
EP12788186.0A EP2780433A1 (fr) 2011-11-14 2012-11-14 Procédé de transformation de matière cellulosique
BR112014011506A BR112014011506A2 (pt) 2011-11-14 2012-11-14 processo para a conversão de um material celulósico, uso, e, processo para a produção de um biocombustível

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EP11189049.7 2011-11-14
EP11189049 2011-11-14
EP12190054.2 2012-10-25
EP12190054 2012-10-25

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AU (1) AU2012338868A1 (fr)
BR (1) BR112014011506A2 (fr)
CA (1) CA2855584A1 (fr)
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EP2886628A1 (fr) 2013-12-18 2015-06-24 Shell International Research Maatschappij B.V. Procédé de lavage d'une charge dérivée biologiquement
SE2051093A1 (en) * 2020-09-18 2022-03-19 Rise Res Institutes Of Sweden Ab Process for one-step conversion of lignocellulosic material to hydrocarbon products and catalyst for use in said process
SE544501C2 (en) * 2020-09-18 2022-06-21 Rise Res Institutes Of Sweden Ab Process for one-step conversion of lignocellulosic material to hydrocarbon products and catalyst for use in said process

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CN104011177A (zh) 2014-08-27
US20130118059A1 (en) 2013-05-16
AU2012338868A1 (en) 2014-05-01
BR112014011506A2 (pt) 2017-05-09
IN2014DN03435A (fr) 2015-06-05
CA2855584A1 (fr) 2013-05-23
EP2780433A1 (fr) 2014-09-24

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