EP2699644A1 - Process for converting a solid biomass material - Google Patents

Process for converting a solid biomass material

Info

Publication number
EP2699644A1
EP2699644A1 EP12716019.0A EP12716019A EP2699644A1 EP 2699644 A1 EP2699644 A1 EP 2699644A1 EP 12716019 A EP12716019 A EP 12716019A EP 2699644 A1 EP2699644 A1 EP 2699644A1
Authority
EP
European Patent Office
Prior art keywords
equal
solid biomass
biomass material
feed
catalytic cracking
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12716019.0A
Other languages
German (de)
English (en)
French (fr)
Inventor
Andries Quirin Maria Boon
Johan Willem Gosselink
John William Harris
Andries Hendrik Janssen
Sander Van Paasen
Colin John Schaverien
Nicolaas Wilhelmus Joseph Way
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
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 BV filed Critical Shell Internationale Research Maatschappij BV
Priority to EP12716019.0A priority Critical patent/EP2699644A1/en
Publication of EP2699644A1 publication Critical patent/EP2699644A1/en
Withdrawn legal-status Critical Current

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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
    • C10G1/08—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
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/16—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form
    • C10B49/20—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form in dispersed form
    • C10B49/22—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form in dispersed form according to the "fluidised bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/02—Multi-step carbonising or coking processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
    • 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
    • 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
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
    • C10L9/083—Torrefaction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1077—Vacuum residues
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the invention relates to a process for converting a solid biomass material, products thereof and a process for producing a biofuel and/or biochemical and products thereof.
  • 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 biofuels, renewable or advanced biofuels. Most non-edible renewable energy sources, however, are solid biomass materials that are cumbersome to convert into liquid fuels.
  • the process described in WO 2010/062611 for converting solid biomass to hydrocarbons requires three catalytic conversion steps.
  • First the solid biomass is contacted with a catalyst in a first riser operated at a temperature in the range of from about 50 to about 200°C to produce a first biomass-catalyst mixture and a first product comprising hydrocarbons (referred to as pretreatment ) .
  • first biomass-catalyst mixture is charged to a second riser operated at a temperature in the range of from about 200° to about 400°C to thereby produce a second biomass-catalyst mixture and a second product comprising hydrocarbons
  • WO 2010/062611 mentions the possibility of preparing the biomass for co-processing in conventional petroleum refinery units. The process of WO 2010/062611, however, is cumbersome in that three steps are needed, each step requiring its own specific catalyst.
  • 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.
  • oxygen-containing-hydrocarbons concentration of oxygen-containing-hydrocarbons than the product obtained by catalytic cracking of a conventional feed.
  • oxygen-containing hydrocarbons such as for example ethers, esters, acids and/or alcohols may have several disadvantages when present in a biofuel and/or biochemical.
  • oxygen containing compounds such as ethers may under certain circumstances lead to peroxide formation when contacted with air, which
  • Acids present in the product may lead to corrosion downstream of the reactor or, if such acids are included in a biofuel, corrosion in the engines of the cars of the end-users. Alcohols like phenols present in the product may be toxic for
  • any ethers or esters present may be undesirable for the downstream waste water cleaning units as they may lead to groundwater contamination in case of a spill.
  • the present invention provides a process for converting a solid biomass material comprising a) contacting the solid biomass material and a fluid hydrocarbon feed with a catalytic cracking catalyst at a temperature of more than 400°C in a catalytic cracking reactor to produce one or more cracked products;
  • step b) fractionating one or more cracked product (s) produced in step a) to produce one or more product fractions;
  • step b) hydrodeoxygenating one or more product fractions (s) produced in step b) to produce one or more
  • hydrodeoxygenated products Some of these hydrodeoxygenated products are novel and inventive in itself.
  • the present invention therefore also provides a hydrodeoxygenated product composition comprising
  • composition comprises in the range from equal to or more than 0.02 wt% to equal to or less than 50 wt% of bio-carbon, based on the total weight of carbon present in the composition.
  • the one or more hydrodeoxygenated products can conveniently be used as a biofuel component and/or a biochemical component or can be converted into a biofuel component and/or a biochemical component.
  • the invention further also provides a process for the preparation of a biofuel respectively a biochemical comprising a biofuel component respectively a biochemical component wherein the biofuel component respectively the biochemical component comprises one or more
  • biochemical component is derived from one or more hydrodeoxygenated products obtained in a process as described above.
  • biofuels and/or biochemicals are novel and inventive in itself.
  • the present invention therefore also provides a biofuel composition comprising
  • a biofuel component comprising
  • biofuel component comprises in the range from equal to or more than 0.02 wt% to equal to or less than 50 wt% of bio-carbon, based on the total weight of carbon present in the composition.
  • the process according to the invention allows one to prepare a biofuel and/or biochemical component via catalytic cracking of a solid biomass material, wherein the biofuel and/or biochemical component has a minimal concentration of oxygen-containing hydrocarbons.
  • the fluid hydrocarbon co-feed provides hydrogen, which hydrogen can advantageously be used in the removal of oxygen by hydrogen transfer during the catalytic cracking reaction and/or in the hydrodeoxygenation of one or more of the product fraction (s) of step b) .
  • hydrogen can advantageously be used in the removal of oxygen by hydrogen transfer during the catalytic cracking reaction and/or in the hydrodeoxygenation of one or more of the product fraction (s) of step b) .
  • the fluid hydrocarbon co-feed therefore assists in minimization of the formation of oxygen-containing hydrocarbons .
  • the process according to the invention can be simple and may require a minimum of processing steps to convert a solid biomass material to a biofuel component or biochemical component that is low in oxygen content.
  • biofuel component may be fully fungible.
  • the process according to the invention may not need any complicated actions, for example it may not need a pre-mixed composition of the solid biomass material and the catalyst.
  • the process according to the invention therefore also provides a more direct route via catalytic cracking of solid biomass material to second generation, renewable or advanced, biofuels and/or biochemicals .
  • Figure 1 shows a schematic diagram of a first process according to the invention.
  • Figure 2 shows a schematic diagram of a second process according to the invention.
  • step a) of the process a solid biomass material and a fluid hydrocarbon feed are contacted with a
  • catalytic cracking catalyst at a temperature of more than 400°C in a catalytic cracking reactor to produce one or more cracked products.
  • a solid biomass material is herein understood a solid material obtained from a renewable source.
  • a renewable source is herein understood a composition of matter of biological origin as opposed to a composition of matter obtained or derived from petroleum, natural gas or coal. Without wishing to be bound by any kind of theory it is believed that such material obtained from a renewable source may contain carbon-14 isotope in an abundance of about 0.0000000001 %, based on total moles of carbon.
  • the renewable source is a composition of matter of cellulosic or lignocellulosic origin.
  • Any solid biomass material may be used in the process of the invention.
  • the solid biomass material is not a material used for food production.
  • Examples of preferred solid biomass materials include aquatic plants and algae, agricultural waste and/or forestry waste and/or paper waste and/or plant material obtained from domestic waste.
  • the solid biomass material contains cellulose and/or lignocellulose .
  • suitable cellulose- and/or lignocellulose- 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 and/or forestry residues such as wood and wood-related materials such as sawdust; waste paper; sugar processing residues such as bagasse and beet pulp; or mixtures thereof. More
  • the solid biomass material is selected from the group consisting of wood, sawdust, straw, grass, bagasse, corn stover and/or mixtures thereof.
  • the solid biomass material may have undergone drying, torrefaction, steam explosion, particle size reduction, densification and/or pelletization before being contacted with the catalyst, to allow for improved process operability and economics.
  • the solid biomass material in step a) is a torrefied solid biomass material.
  • step a) comprises a step of torrefying the solid biomass material at a temperature of more than 200°C to obtain a torrefied solid biomass material that can be contacted with the catalytic cracking catalyst in step a) .
  • torrefying and torrefaction are used interchangeable herein .
  • torrefying or torrefaction is herein understood the treatment of the solid biomass material at a
  • an oxygen-poor atmosphere an atmosphere containing equal to or less than 15 vol.% oxygen, preferably equal to or less than 10 vol% oxygen and more preferably equal to or less than 5 vol% oxygen.
  • an oxygen-free atmosphere is understood that the torrefaction is carried out in the essential absence of oxygen.
  • a temperature of more than 200°C more preferably at a temperature equal to or more than 210°C, still more preferably at a temperature equal to or more than 220°C, yet more preferably at a
  • torrefying of the solid biomass material is preferably carried out at a temperature less than 350°C, more preferably at a temperature equal to or less than 330°C, still more preferably at a temperature equal to or less than 310 °C, yet more preferably at a temperature equal to or less than 300°C.
  • Torrefaction of the solid biomass material is preferably carried out in the essential absence of oxygen.
  • the torrefaction is carried under an inert atmosphere, containing for example inert gases such as nitrogen, carbon dioxide and/or steam; and/or under a reducing atmosphere in the presence of a reducing gas such as hydrogen, gaseous hydrocarbons such as methane and ethane or carbon monoxide.
  • inert gases such as nitrogen, carbon dioxide and/or steam
  • reducing atmosphere in the presence of a reducing gas such as hydrogen, gaseous hydrocarbons such as methane and ethane or carbon monoxide.
  • the torrefying step may be carried out at a wide range of pressures. Preferably, however, the torrefying step is carried out at atmospheric pressure (about 1 bar, corresponding to about 0.1 MegaPascal) .
  • the torrefying step may be carried out batchwise or continuously. If operated batchwise, a torrefaction reactor may be filled with solid biomass material, whereafter the solid biomass material in the torrefaction reactor may be heated at the torrefaction temperature for a time period in the range from 1 minute to 12 hours, more preferably for a period in the range from 30 minutes to 8 hours and most preferably for a period in the range from 1 to 6 hours.
  • the torrefaction reactor may be cooled down and emptied to start a new cycle.
  • the TORSPYD (trademark) process of Thermya may be used, wherein a flow of solid biomass material flows from top to bottom in a reactor column, counter-currently to a flow of gas flowing from bottom to top of the reactor column.
  • the temperature of the reactor column gradually increases from top to bottom.
  • Residence time for the solid biomass material in the torrefaction reactor may lie in the range from equal to or more than 0.5 minute, more preferably equal to or more than 5 minutes and most preferably equal to or more than 15 minutes to equal to or less than 2 hours, more preferably equal to or less than 1 hour and most preferably equal to or less than 45 minutes.
  • the torrefied solid biomass material has a higher energy density, a higher mass density and greater
  • the torrefied solid biomass material has an oxygen content in the range from equal to or more than 10 wt%, more preferably equal to or more than 20 wt% and most preferably equal to or more than 30wt% oxygen, to equal to or less than 60 wt%, more preferably equal to or less than 50 wt%, based on total weight of dry matter.
  • torrefaction gases can be produced.
  • These torrefaction gases can contain carbon monoxide and carbon dioxide but also volatile fuels such as for example methane, ethane, ethene and/or methanol.
  • volatile fuels such as for example methane, ethane, ethene and/or methanol.
  • these volatile fuels are retrieved from the torrefaction gases and recycled to the process as a fuel to provide at least part of the heat for the torrefaction and/or the cracking in step (a) .
  • carbon monoxide and/or carbon dioxide may be retrieved from the torrefaction gases and recycled to provide the inert or reducing atmosphere for torrefaction .
  • any torrefying or torrefaction step further comprises drying the solid biomass material before such solid biomass material is torrefied.
  • the solid biomass material is preferably dried until the solid biomass material has a moisture content in the range of equal to or more than 0.1 wt% to equal to or less than 25 wt%, more preferably in the range of equal to or more than 5 wt% to equal to or less than 20 wt%, and most preferably in the range of equal to or more than 5 wt% to equal to or less than 15wt%.
  • moisture content can be determined via ASTM E1756-01 Standard Test method for Determination of Total solids in Biomass. In this method the loss of weight during drying is a measure for the original moisture content.
  • the solid biomass material in step a) is a micronized solid biomass material.
  • a micronized solid biomass material is herein understood a solid biomass material that has a particle size distribution with a mean particle size in the range from equal to or more than 5 micrometer to equal to or less than 5000 micrometer, as measured with a laser scattering particle size distribution analyzer.
  • the process according to the invention comprises a step of reducing the particle size of the solid biomass material, optionally before or after such solid biomass material is torrefied.
  • Such a particle size reduction step may for example be especially advantageous when the solid biomass material comprises wood or torrefied wood.
  • the particle size of the, optionally torrefied, solid biomass material can be reduced in any manner known to the skilled person to be suitable for this purpose. Suitable methods for particle size reduction include crushing, grinding and/or milling. The particle size reduction may for example be achieved by means of a ball mill, hammer mill, (knife) shredder, chipper, knife grid, or cutter.
  • the solid biomass material has a particle size distribution where the mean particle size lies in the range from equal to or more than 5 micrometer
  • micron (micron) , more preferably equal to or more than 10 micrometer, even more preferably equal to or more than 20 micrometer, and most preferably equal to or more than 100 micrometer to equal to or less than 5000 micrometer, more preferably equal to or less than 1000 micrometer and most preferably equal to or less than 500 micrometer.
  • the solid biomass material has a particle size distribution where the mean particle size is equal to or more than 100 micrometer to avoid blocking of pipelines and/or nozzles. Most preferably the solid biomass material has a particle size distribution where the mean particle size is equal to or less than 3000 micrometer to allow easy injection into the riser reactor.
  • the solid biomass material has a particle size distribution where the mean particle size is equal to or more than 2000 micrometer, more preferably equal to or more than 2500 micrometer, most preferably equal to or more than 3000 micrometer.
  • the process according to the invention can be carried out such that a longer residence time in the catalytic cracking reactor is obtained for the solid biomass material. Such longer residence times in turn allow one to advantageously use solid biomass material with larger particles.
  • the solid biomass material in this case has a particle size
  • mean particle size is equal to or less than 2 cm, more preferably equal to or less than 1 cm, most preferably equal to or less than 5000
  • the process of this embodiment may be novel and inventive of its own and therefore the present invention further provides a process for converting a solid biomass material comprising contacting the solid biomass material and a fluid hydrocarbon feed with a catalytic cracking catalyst at a temperature of more than 400°C in a catalytic cracking reactor to produce one or more cracked products, wherein the solid biomass material has a particle size distribution with a mean particle size of equal to or more than 2000 micrometer.
  • Particle Size Distribution Analyzer preferably a Horiba LA950, according to the ISO 13320 method titled "Particle size analysis - Laser diffraction methods”.
  • the process of the invention comprises a step of reducing the particle size of the solid biomass material, optionally before and/or after torrefaction, to generate a particle size distribution having a mean particle size in the range from equal to or more than 5, more preferably equal to or more than 10 micron, and most preferably equal to or more than 20 micron, to equal to or less than 2 cm, more preferably to equal to or less than 5000 micrometer (micron) , more preferably equal to or less than 1000 micrometer and most preferably equal to or less than 500 micrometer to produce a micronized, optionally torrefied, solid biomass material .
  • such a suspension of solid biomass particles in a hydrocarbon-containing liquid is prepared by a process comprising a first particle size reduction step wherein the particle size of a solid biomass
  • first particulate product comprising solid biomass particles
  • mixing step wherein the first particulate product is suspended in a hydrocarbon-containing liquid to produce a suspended first particulate product comprising solid biomass particles suspended in the hydrocarbon-containing liquid
  • second particle size reduction step wherein the particle size of the suspended first particulate product is further reduced to produce a suspended second
  • particulate product comprising solid biomass particles suspended in the hydrocarbon-containing liquid.
  • At least 80wt% of the first particulate product has a particle size of equal to or less than 300 micrometer and at least 80 wt% of the second particulate product has a particle size of equal to or less than 100 micrometer .
  • the hydrocarbon-containing liquid Preferably the hydrocarbon-containing liquid
  • VGO vacuum gas oils
  • coker gas oils gasoline, naphtha, diesel, kerosene, atmospheric residue
  • the hydrocarbon- containing liquid comprises gasoline, naphtha, diesel, kerosene, and/or mixtures thereof.
  • the fluid hydrocarbon co-feed as described herein below is used as hydrocarbon-containing liquid .
  • the, optionally micronized and optionally torrefied, solid biomass material is dried before being supplied to the riser reactor.
  • the solid biomass material may be dried before and/or after torrefaction .
  • the solid biomass material is preferably dried at a temperature in the range from equal to or more than 50°C to equal to or less than
  • The, optionally micronized and/or torrefied, solid biomass material is preferably dried for a period in the range from equal to or more than 30 minutes to equal to or less than 2 days, more preferably for a period in the range from equal to or more than 2 hours to equal to or less than 24 hours.
  • a fluid hydrocarbon feed (herein also referred to as fluid hydrocarbon co-feed) is contacted with the catalytic cracking catalyst in the catalytic cracking reactor.
  • hydrocarbon feed a feed that contains one or more hydrocarbon compounds .
  • hydrocarbon compounds are herein understood compounds that contain or preferably consist of both hydrogen and carbon.
  • a fluid hydrocarbon 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 (preferably a riser reactor) in an essentially liquid state, in an
  • the fluid hydrocarbon co-feed When entering the catalytic cracking reactor 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 catalytic cracking catalyst and/or the solid biomass material.
  • the fluid hydrocarbon feed can be any non-solid hydrocarbon feed known to the skilled person to be suitable as a feed for a catalytic cracking reactor.
  • the fluid hydrocarbon 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
  • renewable oil that is, oil derived from a renewable source, such as pyrolysis oil, vegetable oil or the products of a biomass liquefaction process
  • Fisher Tropsch oil sometimes also referred to as a synthetic oil
  • the fluid hydrocarbon feed is derived from a, preferably conventional, crude oil.
  • Examples of conventional crude oils include West Texas Intermediate crude oil, Brent crude oil, Dubai-Oman crude oil, Arabian Light crude oil, Midway Sunset crude oil or Tapis crude oil.
  • the fluid hydrocarbon feed comprises a fraction of a, preferably conventional, crude oil or renewable oil.
  • Preferred fluid hydrocarbon feeds include straight run (atmospheric) gas oils, flashed distillate, vacuum gas oils (VGO) , coker gas oils, diesel, gasoline, kerosene, naphtha, liquefied petroleum gases, atmospheric residue ("long residue”) and vacuum residue ("short residue”) and/or mixtures thereof.
  • VGO vacuum gas oils
  • coker gas oils diesel
  • gasoline gasoline
  • kerosene kerosene
  • naphtha liquefied petroleum gases
  • atmospheric residue long residue
  • vacuum residue vacuum residue
  • the fluid hydrocarbon feed comprises a long residue, a vacuum gas oil or a mixture thereof.
  • the fluid hydrocarbon feed preferably has a 5 wt% boiling point, as measured by means of distillation based on ASTM D86 titled “Standard Test Method for Distillation of Petroleum Products at Atmospheric Pressure", respectively as measured by ASTM D1160 titled “ Standard Test Method for Distillation of Petroleum Products at Reduced Pressure", at a pressure of
  • An example of such a fluid hydrocarbon feed is long residue.
  • equal to or more than 70 wt%, preferably equal to or more than 80 wt%, more preferably equal to or more than 90 wt% and still more preferably equal to or more than 95 wt% of the fluid hydrocarbon feed boils in the range from equal to or more than 150°C to equal to or less than 600°C, as measured by means of a distillation by ASTM D86 titled "Standard Test Method for Distillation of Petroleum Products at
  • Atmospheric Pressure respectively as measured by ASTM D1160 titled “ Standard Test Method for Distillation of Petroleum Products at Reduced Pressure", at a pressure of 1 bar absolute (0.1 MegaPascal) .
  • the composition of the fluid hydrocarbon feed may vary widely.
  • the fluid hydrocarbon feed may for example contain paraffins, naphthenes, olefins and/or aromatics.
  • the fluid hydrocarbon feed comprises in the range from equal to or more than 50wt ⁇ 6 , more
  • the fluid hydrocarbon feed comprises equal to or more than 1 wt% paraffins, more preferably equal to or more than 5 wt% paraffins, and most
  • paraffins both normal-, cyclo- and branched-paraffins are 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 feed.
  • paraffins both normal-, cyclo- and branched-paraffins are
  • the fluid hydrocarbon feed comprises or consists of a paraffinic fluid hydrocarbon feed.
  • a paraffinic fluid hydrocarbon feed is herein understood a fluid hydrocarbon feed comprising in the range from at least 50 wt% of paraffins, preferably at least 70 wt% of paraffins, and most preferably at least 90 wt% paraffins, up to and including 100 wt% paraffins, based on the total weight of the fluid hydrocarbon feed.
  • paraffin content of all fluid hydrocarbon feeds having an initial boiling point of at least 260°C can be measured by means of ASTM method D2007-03 titled "Standard test method for characteristic groups in rubber extender and processing oils and other petroleum-derived oils by clay-gel absorption
  • the paraffin content of the fluid hydrocarbon feed can be measured by means of comprehensive multi-dimensional gas chromatography
  • 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.
  • Hydrowax is understood the bottoms fraction of a hydrocracker .
  • Examples of 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.
  • Fischer-Tropsch derived hydrocarbon stream is meant that the hydrocarbon stream is a product from a
  • Fischer-Tropsch hydrocarbon synthesis process or derived from such product by a hydroprocessing step, i.e.
  • the Fischer-Tropsch reaction converts carbon
  • n(CO + 2H 2 ) (-CH 2 -) n + nH 2 0 + heat, in the presence of an appropriate catalyst and preferably at elevated temperature, for example 125 to 300 ° C, preferably 175 to 250 ° C, and elevated pressure, for example 5 to 100 bar (0.5 to 10 MegaPascal) , preferably 12 to 80 bar (1.2 to 8.0 MegaPascal).
  • the carbon monoxide and hydrogen is typically derived from a hydrocarbonaceous feedstock by partial oxidation.
  • Suitable hydrocarbonaceous feedstocks for such partial oxidation include gaseous hydrocarbons such as natural gas or methane, coal, biomass, or residual fractions from crude oil distillation.
  • the Fischer-Tropsch derived hydrocarbon stream may suitably be a so-called syncrude as described in for example GB-A-2386607 , GB-A-2371807 or EP-A-0321305.
  • Other suitable Fischer-Tropsch hydrocarbon streams may be hydrocarbon fractions boiling in the naphtha, kerosene, gas oil, or wax range, as obtained from the Fischer- Tropsch hydrocarbon synthesis process, optionally
  • the Fischer-Tropsch hydrocarbon stream product has been obtained by hydroisomerisation of hydrocarbons directly obtained in the Fischer-Tropsch hydrocarbon synthesis reaction.
  • the use of a hydro- isomerised hydrocarbon fraction is advantageous because it contributes to a high yield in gasoline due to the high content of iso-paraffins in said fraction.
  • a hydro- isomerised fraction boiling in the kerosene or gas oil range may suitable be used as the Fischer-Tropsch derived hydrocarbon stream.
  • a higher boiling hydro-isomerised fraction is used.
  • a particularly suitable hydro-isomerised hydrocarbon fraction is a fraction which has a T10wt% boiling point of between 350 and 450 °C and a T90 wt% of between 450 and 600 °C and a wax content of between 5 and 60 wt%.
  • Such fraction is typically referred to as waxy raffinate.
  • the wax content is between 5 and 30 wt%.
  • the wax content is measured by solvent dewaxing at -27 °C in a 50/50 vol. /vol. mixture of methyl ethyl ketone and toluene.
  • Examples of such a hydrocarbon streams are the commercially available Waxy Raffinate product as is marketed by Shell MDS (Malaysia) and the waxy raffinate product as obtained by the process described in WO-A- 02/070630 or in EP-B-0668342.
  • the weight ratio of the solid biomass material to fluid hydrocarbon co-feed may vary widely.
  • the weight ratio of fluid hydrocarbon co-feed to solid biomass material 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 solid biomass material 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 solid biomass material are preferably being fed to a catalytic cracking reactor in a weight ratio within the above ranges.
  • hydrocarbon co-feed present in a feed to a catalytic cracking reactor is preferably equal to or less than 30 wt%, more preferably equal to or less than 20 wt%, most preferably equal to or less than 10 wt% and even more preferably equal to or less than 5 wt%.
  • the amount of solid biomass material present, based on the total weight of solid biomass material and fluid hydrocarbon co-feed present in a feed to a catalytic cracking reactor is preferably equal to or more than 0.1 wt%, more preferably equal to or more than 1 wt%.
  • the total feed to step (a) comprises:
  • the fluid hydrocarbon co- feed comprises equal to or more than 8 wt% elemental hydrogen, more preferably more than 12 wt% elemental hydrogen, based on the total fluid hydrocarbon co-feed on a dry basis (i.e. on a water-free basis) .
  • a high content of elemental hydrogen such as a content of equal to or more than 8 wt%, allows the hydrocarbon co-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.
  • Fischer-Tropsch derived waxy raffinate may for example comprise about 85 wt% of elemental carbon and 15 wt% of elemental hydrogen.
  • step (a) is carried out in a catalytic cracking unit, more preferably in a fluidized catalytic cracking (FCC) unit.
  • the catalytic cracking unit comprises at least a catalytic cracking reactor and a catalyst regenerator.
  • the catalytic cracking reactor used in step (a) can be any catalytic cracking reactor known in the art to be suitable for the purpose, including for example a
  • the fluidized bed reactor or a riser reactor is a riser reactor.
  • the catalytic cracking reactor is a riser reactor.
  • the fluid hydrocarbon co-feed and the, optionally micronized and/or optionally torrefied, solid biomass material can be mixed prior to entry into a catalytic cracking reactor or they can be added separately, at the same location or at different locations to the catalytic cracking reactor.
  • the fluid hydrocarbon co-feed and the, optionally micronized and/or torrefied, solid biomass material are not mixed together prior to entry into a catalytic cracking reactor.
  • the fluid hydrocarbon co-feed and the solid biomass material may be fed simultaneously (that is at one location) to the catalytic cracking reactor, and optionally mixed upon entry of the catalytic cracking reactor; or,
  • the fluid hydrocarbon co-feed and the solid biomass material may be added separately (at different locations) to the catalytic cracking reactor.
  • reactors can have multiple feed inlet nozzles.
  • the solid biomass material and the fluid hydrocarbon co-feed can therefore be processed in the catalytic cracking reactor even if both components are not miscible by feeding each component through a separate feed inlet nozzle.
  • fluid hydrocarbon co-feed and the solid biomass material are mixed together prior to entry into a catalytic cracking reactor to provide a feed mixture comprising the fluid hydrocarbon co-feed and the solid biomass material.
  • the solid biomass material is preferably a torrefied and micronized biomass material as described herein before.
  • the fluid hydrocarbon co-feed and the, optionally micronized and/or torrefied, solid biomass material may be mixed in any manner known to a skilled person to be suitable for mixing a viscous liquid and a solid.
  • the fluid hydrocarbon co-feed and the, optionally micronized and/or torrefied, solid biomass material are mixed by means of shaking, stirring and/or extruding.
  • the feed mixture may be prepared just before entry to a catalytic cracking reactor or it may optionally be held in a stirred feed vessel before being forwarded to a catalytic cracking reactor.
  • the catalytic cracking reactor is preferably a riser reactor.
  • a riser reactor is a riser reactor suitable for fluidized
  • catalytic cracking More preferably such a riser reactor is part of a catalytic cracking unit, more preferably of a fluidized catalytic cracking (FCC) unit.
  • FCC fluidized catalytic cracking
  • a suspension of solid biomass material suspended in a fluid hydrocarbon feed is supplied to a riser reactor. Preferences for the fluid hydrocarbon feed are as described herein above.
  • the catalytic cracking reactor is a riser reactor and the solid biomass material is supplied to the riser reactor at a location downstream of a location where a fluid hydrocarbon feed is supplied to the riser reactor.
  • a fluid hydrocarbon feed is supplied to the riser reactor.
  • the catalytic cracking reactor is a riser reactor and the solid biomass material is supplied to the riser reactor at a location upstream of a location where a fluid hydrocarbon feed is supplied to the riser reactor.
  • a fluid hydrocarbon feed is supplied to the riser reactor.
  • supplying the solid biomass material upstream of the fluid hydrocarbon feed may lead to in-situ water production in the upstream part of the riser reactor, leading to lower partial hydrocarbon pressures in the upstream part of the riser reactor and higher olefins yields. Further supplying the solid biomass material upstream of the fluid hydrocarbon feed allows for longer residence times for the solid biomass material, making it possible to use a solid biomass material with a particle size distribution having a particle size of equal to or more than 2000 micrometer.
  • a suspension of solid biomass material suspended in a first fluid hydrocarbon feed is supplied to the riser reactor at a first location and a second fluid hydrocarbon feed is supplied to the riser reactor at a second location downstream of the first location.
  • Preferences for the first and second fluid hydrocarbon feed are as described for the fluid hydrocarbon feed herein above.
  • elongated, preferably essentially tube-shaped, reactor suitable for carrying out catalytic cracking reactions.
  • a fluidized catalytic cracking catalyst flows in the riser reactor from the upstream end to the downstream end of the reactor.
  • the elongated, preferably essentially tube-shaped, reactor is preferably oriented in an
  • a fluidized catalytic cracking catalyst flows from the bottom of the riser reactor upwards to the top of the riser reactor.
  • the riser reactor may be a so-called internal riser reactor or a so-called external riser reactor as described therein.
  • an internal riser reactor is herein preferably understood an essentially vertical, preferably
  • 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 cracking reactions and/or a vessel that comprises one or more cyclone separators and/or swirl tubes.
  • the internal riser reactor is especially advantageous because in the process according to the invention, the solid biomass material may be converted into an intermediate oil product (also sometimes referred to as pyrolysis oil) . Without wishing to be bound to any kind of theory it is believed that this intermediate oil product or pyrolysis oil may be more prone to
  • intermediate oil product may be more corrosive than conventional oils due to oxygen-containing hydrocarbons that may be present.
  • the internal riser reactor may be less sensitive to erosion by any unconverted particles of solid biomass material. The use of an internal riser reactor allows one to reduce the risk of plugging due to polymerization and/or to reduce the risk of corrosion and/or erosion, thereby increasing safety and hardware integrity.
  • an external riser reactor is herein preferably understood a riser reactor that is located outside a vessel.
  • the external riser reactor can suitably be connected via a so-called crossover to a vessel.
  • the external riser reactor comprises a, preferably essentially vertical, riser reactor pipe.
  • a riser reactor pipe is located outside a vessel.
  • the riser reactor pipe may suitably be connected via a, preferably essentially horizontal, downstream crossover pipe to a vessel.
  • the downstream crossover pipe is a, preferably essentially horizontal, downstream crossover pipe.
  • the vessel may suitably be a reaction vessel suitable for catalytic cracking reactions and/or a vessel that comprises one or more cyclone separators and/or swirl separators.
  • an external riser reactor it may be advantageous to use an external riser reactor with a curve or low velocity zone at its upper end as for example illustrated in the Handbook titled "Fluid
  • the curve and/or low velocity zone may for example connect the riser reactor pipe and the so-called crossover pipe.
  • a low velocity zone is herein preferably
  • the low velocity zone may for example comprise an accumulation space located at the most downstream end of the upstream riser reactor pipe as described above, extending such riser reactor pipe beyond the connection with the
  • a part of the catalytic cracking catalyst may deposit in the curve or low velocity zone, thereby forming a protective layer against corrosion and/or erosion by the catalytic cracking catalyst and/or any residual solid particles and against corrosion by any oxygen-containing hydrocarbons.
  • the solid biomass material is supplied to the riser reactor in the most upstream half, more preferably in the most upstream quarter, and even more preferably at the most upstream tenth of the riser reactor.
  • Most preferably solid biomass material is supplied to the riser reactor at the bottom of this reactor. Addition of the solid biomass material in the upstream part, preferably the bottom, of the reactor may advantageously result in in-situ water formation at the upstream part, preferably the bottom, of the reactor. The in-situ water formation may lower the hydrocarbon partial pressure and reduce second order hydrogen transfer
  • 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 preferably 1.2 to 2.8 bar absolute (0.12 to 0.28 MegaPascal).
  • 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
  • the use of a vaporized oil and/or oil fraction as a liftgas may have the advantage that the liftgas can simultaneously act as a hydrogen donor and may prevent or reduce coke formation.
  • both steam as well as vaporized oil and/or a vaporized oil fraction are used as a liftgas.
  • a vaporized oil fraction preferably liquefied petroleum gas, vaporized gasoline, diesel, kerosene or naphtha
  • the liftgas consists of steam.
  • the solid biomass material is supplied at the bottom of the riser reactor, is may optionally be mixed with such a lift gas before entry in the riser reactor.
  • the solid biomass material may be fed simultaneously with the liftgas (at one and the same location) to the riser reactor, and optionally mixed upon entry of the riser reactor; or it may be fed separately from any liftgas (at different locations) to the riser reactor .
  • the riser reactor comprises a riser reactor pipe and a bottom section, which bottom section has a larger diameter than the riser reactor pipe, and wherein the solid biomass material is supplied to the riser reactor in the bottom section.
  • a diameter is herein preferably understood to refer to the inner diameter, as for example the inner (i.e. internal) diameter of the bottom section or riser reactor pipe.
  • the maximum inner diameter of the bottom section of the riser reactor is larger than the maximum inner diameter of the riser reactor pipe.
  • the bottom section having the larger diameter may for example have the form of a lift pot.
  • the bottom section having the larger diameter is therefore also herein referred to as liftpot or enlarged bottom section.
  • Such a enlarged bottom section preferably has a diameter larger than the diameter of the riser reactor pipe, more preferably a diameter in the range from equal to or more than 0.4 to equal to or less than 5 meters, most preferably a diameter in the range from equal to or more than 1 to equal to or less than 2 meters.
  • the height of the enlarged bottom section or liftpot preferably lies in the range from equal to or more than 1 meter to equal to or less than 5 meter.
  • the increase of diameter may be intermittent, resulting in two or more sections of the riser reactor having a fixed diameter, wherein each preceding section has a smaller diameter than the subsequent section, when going in a downstream direction; the increase of diameter may be gradual, resulting in a gradual increase of the riser reactor diameter in a downstream direction; or the increase in diameter may be a mixture of gradual and intermittent increases.
  • 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 temperature in the catalytic cracking reactor ranges from equal to or more than 450°C, more preferably from equal to or more than 480°C, to equal to or less than 800°C, more
  • the temperature at the location where the solid biomass material is supplied lies in the range from equal to or more than 500°C, more preferably equal to or more than 550°C, and most preferably equal to or more than 600°C, to equal to or less than 800°C, more
  • the solid biomass material can be advantageous to supply the solid biomass material to a location in a riser reactor where the temperature is slightly higher, for example where the temperature lies in the range from equal to or more than 700°C, more preferably equal to or more than 720 °C, even more preferably equal to or more than 732°C to equal to or less than 800°C, more
  • the pressure in the catalytic cracking reactor ranges from equal to or more than 0.5 bar absolute to equal to or less than 10 bar absolute (0.05 MegaPascal to 1.0 MegaPascal) , more preferably from equal to or more than 1.0 bar absolute to equal to or less than 6 bar absolute (0.1 MegaPascal to
  • the total average residence time of the solid biomass material lies in the range from equal to or more than 1 second, more preferably equal to or more than 1.5 seconds and even more preferably equal to or more than 2 seconds to equal to or less than 10 seconds, preferably equal to or less than 5 seconds and more preferably equal to or less than 4 seconds .
  • residence time includes not only the residence time of a specified feed (such as the solid biomass material) but also the residence time of its conversion products.
  • the total average residence time of the solid biomass material most preferably lies in the range from equal to or more than 1 seconds, preferably to equal to or less than 2.5 seconds.
  • the total average residence time of the solid biomass material most preferably lies in the range from equal to or more than 0.1 to equal to or less than 1 seconds.
  • the weight ratio of catalyst to feed (that is the total feed of solid biomass material and the fluid hydrocarbon feed)- herein also referred to as catalyst: feed ratio- preferably lies in the range from equal to or more than 1:1, more preferably from equal to or more than
  • the weight ratio of catalyst to solid biomass material (catalyst : solid biomass material ratio) at the location where the solid biomass material is supplied to the riser reactor preferably lies in the range from equal to or more than 1:1, more preferably from equal to or more than 2 : 1 and most preferably from equal to or more than 3:1 to equal to or less than 150:1, more preferably to equal to or less than 100:1, even more preferably to equal to or less than 50:1, most preferably to equal to or less than 20:1.
  • the fluid hydrocarbon feed may preferably be introduced to the catalytic cracking reactor at a location where the solid biomass material already had a residence time in the range from equal to or more than 0.01 seconds, more preferably from equal to or more than 0.05 seconds, and most preferably from equal to or more than 0.1 seconds to equal to or less than 2 seconds, more preferably to equal to or less than 1 seconds, and most preferably to equal to or less than 0.5 seconds.
  • the temperature at the location in a riser reactor where the fluid hydrocarbon feed is
  • the solid biomass material is introduced to a riser reactor at a location with
  • Tl and T2 are equal to or more than 400°C, more preferably equal to or more than 450°C.
  • the catalytic cracking catalyst can be any catalyst known to the skilled person to be suitable for use in a cracking process.
  • the catalytic cracking catalyst comprises a zeolitic component.
  • the catalytic cracking catalyst can contain an amorphous binder compound and/or a filler. Examples of 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
  • USY is preferably used as the large pore zeolite.
  • the 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
  • 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 catalytic cracking catalyst .
  • the catalytic cracking catalyst is contacted in a cocurrent flow configuration with a cocurrent flow of the, preferably solid, biomass material and optionally fluid hydrocarbon feed.
  • Catalytic cracking of a biomass material with a catalytic cracking catalyst as described herein is preferably carried out in a catalytic cracking unit, preferably a fluidized catalytic cracking unit.
  • step a) comprises a catalytic cracking process comprising:
  • a catalytic cracking step comprising contacting the solid biomass material and the fluid hydrocarbon feed with a catalytic cracking catalyst at a temperature of more than 400°C in a catalytic cracking reactor to produce one or more cracked products and a spent catalytic cracking catalyst ;
  • a separation step comprising separating the one or more cracked products from the spent catalytic cracking catalyst ;
  • a regeneration step comprising regenerating spent
  • catalytic cracking catalyst to produce a regenerated catalytic cracking catalyst, heat and carbon dioxide; and a recycle step comprising recycling the regenerated catalytic cracking catalyst to the catalytic cracking step .
  • the 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 cyclone separators are preferably operated at a velocity in the range from 18 to 80 meters/second, more preferably at a velocity in the range from 25 to 55 meters/second.
  • the separation step may further comprise a stripping step.
  • a stripping step the spent catalyst may be stripped to recover the products absorbed on the spent catalyst before the regeneration step. These products may be recycled and added to the cracked product stream obtained from the catalytic cracking step.
  • the regeneration step preferably comprises
  • 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 the riser reactor.
  • the spent catalytic cracking 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 catalytic cracking 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 1.0 MegaPascal) , more preferably from equal to or more than 1.0 bar absolute to equal to or less than
  • the regenerated catalytic cracking catalyst can be recycled to the catalytic cracking step.
  • a side stream of make-up catalyst is added to the recycle stream to make-up for loss of catalyst in the reaction zone and regenerator.
  • one or more cracked products are produced. At least one of the one or more cracked products is
  • step b subsequently fractionated in step b) to obtain one or more product fractions.
  • oxygen-containing- hydrocarbons examples include ethers, esters, ketones, acids and alcohols.
  • oxygen-containing- hydrocarbons include ethers, esters, ketones, acids and alcohols.
  • the one or more cracked products may contain phenols.
  • the one or more cracked product (s) produced in step (a) and fractionated in step (b) have an elemental oxygen content in the range from equal to or more than 0.01 wt%, more preferably equal to or more than
  • 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 reactor.
  • the fractionation may be carried out as described in the Handbook titled "Fluid Catalytic Cracking technology and operations", by Joseph W. Wilson, published by PennWell Publishing Company (1997), chapter
  • the one or more cracked products are preferably obtained as gaseous cracked products from step (a) . These gaseous cracked products can subsequently be separated into various gas and liquid products in one or more fractionation units.
  • step (a) It has been found that the use of a solid biomass material as part of the feed in step (a) may lead to additional coke formation in conduits that transport the one or more cracked products from the catalytic cracking reactor. It has therefore been found advantageous to use insulated pipelines in step (b) to transfer the one or more cracked products from the catalytic cracking reactor into one or more subsequent fractionation units. Most preferably so called cold-wall pipelines are used which comprise an insulation on the inside pipeline surface.
  • a main fractionator is used to cool the gaseous cracked products obtained from step (a) and to condense any heavy liquid products.
  • the main fractionator preferably comprises a distillation tower comprising a bottom section (sometimes referred to as flash zone) at the bottom of the tower; a heavy cycle oil (HCO) section, a light cycle oil (LCO) section and a top section.
  • HCO heavy cycle oil
  • LCO light cycle oil
  • the cracked products are preferably cooled via contact with a circulating stream of fractionator bottoms product, sometimes also referred to as a bottoms pump-around.
  • a circulating stream of fractionator bottoms product sometimes also referred to as a bottoms pump-around.
  • the circulating liquid In addition to cooling gaseous cracked products, the circulating liquid
  • fractionator bottoms product can advantageously also be used to wash out any residual solid biomass particles.
  • the bottom section is preferably also fitted with one or more baffle plates, grid packing and/or one or more solid biomass particle catchers. Residual solid biomass particles accumulated in these catchers may advantageously be recycled to step a) .
  • the product obtained from the bottom section at the bottom of the tower is sometimes also referred to as slurry oil.
  • slurry oil is herein preferably understood a fraction of the cracked products of which at least 80wt ⁇ 6 , more preferably at least 90wt% boils at or above 425°C (at 0.1
  • the slurry oil may still contain solid biomass particles that were not converted in the
  • Such solid biomass particles can be separated from the slurry oil by means of
  • step a) settling, filtration and/or electrostatic filtration and advantageously recycled to step a) .
  • heavy cycle oil In the heavy cycle oil (HCO) section so called heavy cycle oil may be withdrawn from the distillation tower.
  • HCO heavy cycle oil
  • heavy cycle oil is herein preferably understood a fraction of the cracked products of which at least 80wt%, more preferably at least 90wt% boils in the range from equal to or more than 370°C to less 425°C (at 0.1
  • this heavy cycle oil is advantageously recycled and used as a fluid hydrocarbon co-feed in step a) .
  • the heat of the one or more cracked products can be retrieved and advantageously used to preheat the feed in step a) .
  • one or more of the feed streams for step a) can be used to cool the circulating liquid fractionator bottoms product.
  • At least part of the heavy cycle oil and/or at least part of the slurry oil may be used as a fuel to provide the heat for an optional torrefaction step as described herein before.
  • LCO light cycle oil
  • light cycle oil is herein preferably understood a fraction of the cracked products of which at least 80wt%, more preferably at least 90wt% boils in the range from equal to or more than 221°C to less than 370°C (at 0.1 MegaPascal) .
  • This light cycle oil or parts thereof can advantageously be hydrodeoxygenated in step (c) to prepare the one or more hydrodeoxygenated product (s) as described in more detail below.
  • at least part of the light cycle oil may also be withdrawn and directly used as a biofuel component and/or a biochemical component .
  • naphtha products In the top section of the distillation tower, naphtha products and so-called dry gas can be withdrawn.
  • naphtha products is herein preferably understood a fraction of the cracked products of which at least
  • the dry gas may comprise for example methane, ethane, ethene, carbon-monoxide, carbon- dioxide, hydrogen and nitrogen.
  • the naphtha products may comprise fractions that may be useful as a biofuel component for gasoline compositions and/or diesel
  • the dry gas is separated from the naphtha products by means of one or more gas/liquid separator (s) and/or one or more absorber (s) .
  • the naphtha products may be debutanized and/or
  • naphtha products may be advantageously hydrodeoxygenated in step (c) to prepare one or more hydrodeoxygenated products as described in more detail below.
  • at least part of the naphtha products may also be withdrawn and directly used as a biofuel component and/or a biochemical component .
  • optionally debutanized and/or depentanized, naphtha products are forwarded to one or more further distillation column (s) .
  • the, optionally debutanized and/or depentanized, naphtha products may be split up into a light-light-cycle oil (LLCO, sometimes also referred to as heavycat-cracked gasoline (HCCG) ) ; a cat-cracked gasoline (CCG, sometimes also referred to as heart cut CCG) ; and a light cat- cracked gasoline (LCCG, sometimes also referred to as cat-cracked tops) .
  • LLCO light-light-cycle oil
  • CCG cat-cracked gasoline
  • LCCG light cat- cracked gasoline
  • light cat-cracked gasoline is herein preferably understood a fraction of the naphtha products of which at least 80 wt%, more preferably at least 90 wt% boils in the range from equal to or more than 35°C to less than 125°C (at 0.1 MegaPascal) .
  • each of the light-light cycle oil, heavy cat cracked gasoline and/or light cat-cracked gasoline may independently be hydrodeoxygenated as described herein below for step c) .
  • fractionation of at least one of the one or more cracked products in step (b) results in one or more product fractions.
  • At least one of the one or more product fractions obtained in step (b) is
  • step (c) subsequently hydrodeoxygenated in step (c) to produce one or more hydrodeoxygenated products.
  • Examples of product fractions that can be obtained from step (b) and can be hydrodeoxygenated in step (c) include naphtha products, such as gasoline or diesel fractions; light cycle oils (LCO) ; heavy cycle oil (HCO) ; slurry oil; fractions thereof and/or mixtures thereof.
  • naphtha products such as gasoline or diesel fractions; light cycle oils (LCO) ; heavy cycle oil (HCO) ; slurry oil; fractions thereof and/or mixtures thereof.
  • step (b) the one or more product fractions obtained in step (b) and subsequently
  • hydrodeoxygenated in step (c) contain naphtha products; naphtha product fractions (such as for example heavy cat cracked gasoline) ; light cycle oils (LCO) ; LCO
  • step (b) obtained in step (b) and subsequently hydrodeoxygenated in step (c) consists of a fraction of the cracked
  • step (c) subsequently hydrodeoxygenated in step (c) consists of a fraction of the cracked products of which at least 70 wt%, more preferably at least 80 wt%, most preferably at least 90 wt% boils in the range from equal to or more than 30°C to less than 221°C (at 0.1 MegaPascal) .
  • the one or more product fractions obtained in step (b) and subsequently hydrodeoxygenated in step (c) may contain one or more oxygen-containing-hydrocarbons .
  • oxygen-containing-hydrocarbons examples include ethers, esters, ketones, acids and alcohols.
  • one or more product fractions may contain phenols and/or substituted phenols.
  • the one or more product fraction (s) produced in step (b) and hydrodeoxygenated in step (c) have an elemental oxygen content in the range from equal to or more than 0.01 wt%, more preferably equal to or more than 0.1 wt%, even more preferably equal to or more than 0.2 wt% and most preferably equal to or more than 0.3 wt% oxygen, to equal to or less than 20 wt ⁇ 6 , more preferably equal to or less than 10 wt%, and most
  • hydrodeoxygenation is herein understood reducing the concentration of oxygen-containing hydrocarbons in one or more product fraction (s) containing oxygen- containing hydrocarbons by contacting the one or more product fraction (s) with hydrogen in the presence of a hydrodeoxygenation catalyst.
  • hydrocarbons that can be removed include acids, ethers, esters, ketones, aldehydes, alcohols (such as phenols) and other oxygen-containing compounds.
  • the hydrodeoxygenation preferably comprises
  • catalyst at a temperature in the range from equal to or more than 200°C, preferably equal to or more than 250°C, to equal to or less than 450°C, preferably equal to or less than 400°C; at a total pressure in the range of equal to or more than 10 bar absolute (1.0 MegaPascal) to equal to or less than 350 bar absolute (35 MegaPascal) ; and at a partial hydrogen pressure in the range of equal to or more than 2 bar absolute (0.2 MegaPascal) to equal to or less than 350 bar absolute (35 MegaPascal) .
  • a total pressure in the range of equal to or more than 30 bar absolute (3.0 MegaPascal) and most preferably equal to or more than 50 bar absolute (5.0 MegaPascal) to equal to or less than 350 bar
  • MegaPascal more preferably equal to or less than 300 bar absolute (30 MegaPascal) .
  • hydrodeoxygenation is more preferably carried out at a total pressure in the range of equal to or more than 10 bar absolute (1.0 MegaPascal) and most preferably equal to or more than 20 bar absolute (2.0 MegaPascal) to equal to or less than 100 bar absolute (10 MegaPascal), more preferably equal to or less than 60 bar absolute (6.0 MegaPascal); and at a partial hydrogen pressure in the range of equal to or more than 5 bar absolute (0.5 MegaPascal) and most preferably equal to or more than 10 bar absolute (1.0 MegaPascal) to equal to or less than 100 bar absolute (10 MegaPascal) , more preferably equal to or less than 60 bar absolute (6.0 MegaPascal) .
  • the hydrodeoxygenation catalyst can be any type of hydrodeoxygenation catalyst known by the person skilled in the art to be suitable for this purpose.
  • the hydrodeoxygenation catalyst preferably comprises one or more hydrodeoxygenation metal (s) , preferably supported on a catalyst support.
  • the catalyst support is preferably inert as a hydrodeoxygenation catalyst at the hydrodeoxygenation conditions.
  • the one or more hydrodeoxygenation metal (s) are preferably chosen from Group VIII and/or Group VIB of the Periodic Table of Elements.
  • the hydrodeoxygenation metal may for example be present as a mixture, alloy or organometallic compound.
  • the one or more hydrodeoxygenation metal (s) is chosen from the group consisting of
  • Nickel (Ni) Chromium (Cr) , Molybdenum (Mo) , Tungsten (W) , Cobalt (Co), Platinum (Pt) , Palladium (Pd) , Rhodium (Rh) , Ruthenium (Ru) , Iridium (Ir), Osmium (Os) , Copper
  • the one or more metal (s) may be present in elementary form; in the form of alloys or mixtures; and/or in the form of oxides, sulfides or other metal-organic compounds.
  • the hydrodeoxygenation catalyst in step (c) is a catalyst comprising Tungsten, Ruthenium,
  • Rhenium Cobalt, Nickel, Copper, Molybdenum, alloys thereof and/or mixtures thereof.
  • the hydrodeoxygenation catalyst is chosen from the group consisting of Rhodium-Cobalt catalysts, Nickel-Tungsten catalysts, Nickel-Copper catalysts, Cobalt-Molybdenum catalysts and Nickel- Molybdenum catalyst.
  • Rhodium-Cobalt catalysts are chosen from the group consisting of Rhodium-Cobalt catalysts, Nickel-Tungsten catalysts, Nickel-Copper catalysts, Cobalt-Molybdenum catalysts and Nickel- Molybdenum catalyst.
  • Nickel-Tungsten catalysts Nickel-Copper catalysts
  • catalysts may contain such metals supported on an inert catalyst support as described above.
  • the hydrodeoxygenation catalyst comprises a catalyst support
  • such catalyst support may be shaped in the form of balls, rings or otherwise shaped extrudates.
  • the catalyst support may comprise a refractory oxide or mixtures thereof, preferably alumina, amorphous silica- alumina, titania, silica, ceria, zirconia; or it may comprise an inert component such as carbon or silicon carbide. Preferred are for example Zr02, Ce02, Ce02 and/or mixtures thereof.
  • the catalyst support may further comprise a zeolitic compound such as for example zeolite
  • Y zeolite beta, ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-48, SAPO-11, SAPO-41, and ferrierite.
  • Suitable catalysts include Rh/Si02;
  • Rh/Ce0 2 Ni/Si0 2 ; Ni/Cr 2 0 3 ; Ni/Al 2 0 3 ; Ni/Zr0 2 ; Ni-Cu/Al 2 0 3 ;
  • the catalyst is chosen from the group consisting of Rh/Al 2 0 3 , RhCo/Al 2 0 3 ; Rh/Zr0 2 ; Rh/Ce0 2 ; Ni/Cr 2 0 3 ; Ni/Al 2 0 3 ; Ni/Zr0 2 ; Ni-Cu/Al 2 0 3;
  • Ni-Mo/Zr0 2 Co-Mo/Al 2 0 3 ; Co-Mo/Zr0 2 and/or mixtures thereof .
  • hydrodeoxygenation catalysts comprising Rhodium on alumina (Rh/Al 2 0 3 ) , Rhodium-Cobalt on alumina (RhCo/Al 2 0 3 ) , Nickel-Copper on
  • NiCu/Al 2 0 3 Nickel-Tungsten on alumina
  • NiW/ AI 2 O3 Nickel-Tungsten on alumina
  • Cobalt-Molybdenum on alumina CoMo/Al 2 0 3 or
  • Nickel-Molybdenum on alumina NiMo/Al 2 0 3
  • the one or more product fractions also contain one or more sulphur-containing hydrocarbons it may be advantageous to use a sulphided hydrodeoxygenation catalyst.
  • the hydrodeoxygenation catalyst is sulphided the catalyst may be sulphided in-situ or ex-situ.
  • Such in-situ or ex-situ sulphiding can be carried out in any manner known by the skilled person to be suitable for in- situ or ex-situ sulphiding.
  • a sulfur source usually hydrogen sulphide or a hydrogen sulphide precursor
  • a sulfur source is preferably supplied to the hydrodeoxygenation catalyst before operation of the process in a hydrodeoxygenation reactor.
  • step (c) may comprise further steps, if so desired or necessary.
  • step (c) may further comprise hydrodesulphurization, hydrodenitrogenation,
  • Hydrodesulphurization may reduce the concentration of any sulphur-containing hydrocarbons.
  • Hydrodenitrogenation may reduce the concentration of any nitrogen-containing hydrocarbons.
  • Hydroisomerization may increase the concentration of branched hydrocarbons.
  • Hydrocracking may further crack the product in smaller compounds .
  • hydrodesulphurization, hydrodenitrogenation, hydrocracking and/or hydroisomerization may be carried out before, after and/or simultaneously with the
  • the hydrodeoxygenation can be carried out in any type of reactor known by the skilled person in the art to be suitable for a hydrodeoxygenation process.
  • a fixed bed reactor, trickle flow reactor, ebullated bed reactor or fluidized bed reactor is used.
  • a weight hourly space velocity is used that is equal to or more than 0.2 and equal to or less than 4.0 kg/litre hour.
  • one or more hydrodeoxygenated product (s) may be obtained.
  • These one or more hydrodeoxygenated product (s) can be used as biofuel component (s) and/or a biochemical component (s) .
  • a biofuel component is herein understood a component that can be useful in the preparation of a biofuel.
  • a biochemical component is herein understood a component that can be useful in the preparation of a biochemical.
  • product (s) has an elemental oxygen content of equal to or less than 0.03 wt% (300 ppmw) , more preferably equal to or less than 0.01 wt%. Most preferably the the one or more hydrodeoxygenated product (s) is essentially free of oxygen-containing hydrocarbons and/or contains
  • hydrodeoxygenated product (s) produced in step (c) can be blended with one or more other components to produce a biofuel and/or a biochemical. Examples of one or more other components with which the one or more
  • hydrodeoxygenated product (s) may be blended include anti ⁇ oxidants, corrosion inhibitors, ashless detergents, dehazers, dyes, lubricity improvers and/or mineral fuel components.
  • the one or more hydrodeoxygenated product (s) can be used in the preparation of a biofuel component and/or a biochemical component.
  • the biofuel component and/or biochemical component prepared from the one or more hydrodeoxygenated product may be subsequently blended with one or more other components (as listed above) to prepare a biofuel and/or a biochemical.
  • a biofuel a biochemical is herein understood a fuel or a chemical that is at least party derived from a renewable energy source.
  • figure 1 one embodiment according to the
  • wood parts (102) are fed into a torrefaction unit (104), wherein the wood is torrefied to produce torrefied wood (108) and gaseous products (106) are obtained from the top.
  • the torrefied wood (108) is forwarded to a micronizer (110), wherein the torrefied wood is micronized into micronized
  • the micronized torrefied wood (112) is subsequently forwarded to a mixer or extruder (114) where it is mixed with a mixture of vacuum gas oil and long residue as a fluid hydrocarbon co-feed (116) to produce a feed mixture (118) which is fed into the bottom of an FCC reactor riser (120) .
  • the feed mixture (118) is contacted with new and regenerated catalytic cracking catalyst (122) at a catalytic cracking temperature.
  • a mixture of spent catalytic cracking catalyst (128) and produced cracked products (124) is separated in a separator (126) .
  • the spent catalytic cracking catalyst (128) is forwarded to regenerator (130), where it is regenerated and recycled to the bottom of the riser reactor as part of the
  • the cracked products (124) are forwarded to a fractionator (132) .
  • the cracked products (124) are fractionated into several product fractions, such as for example a slurry oil containing fraction (134), a heavy cycle oil containing fraction (136), a light cycle oil containing fraction (138) and a naphtha containing fraction (140) . At least part of the naphtha containing fraction (140) is forwarded to a slurry oil containing fraction (134), a heavy cycle oil containing fraction (136), a light cycle oil containing fraction (138) and a naphtha containing fraction (140) . At least part of the naphtha containing fraction (140) is forwarded to a
  • hydrodeoxygenated product 144
  • the hydrodeoxygenated product can be blended with one or more other components to produce a biofuel suitable for use in automotive engines.
  • FIG 2 another embodiment according to the invention is illustrated.
  • wood parts (202) are fed into a torrefaction unit (204), wherein the wood is torrefied to produce torrefied wood (208) and gaseous products (206) are obtained from the top.
  • the torrefied wood (208) is forwarded to a micronizer (210), wherein the torrefied wood is micronized into micronized
  • torrefied wood (212) The micronized torrefied wood (212) is fed directly into the bottom of an FCC reactor riser
  • a long residue (216) is fed to the bottom of the FCC reactor riser (220) at a position located downstream of the entry of the micronized
  • torrefied wood (212) torrefied wood (212) .
  • the micronized torrefied wood (212) is contacted with new and regenerated catalytic cracking catalyst (222) in the presence of the long residue as a fluid hydrocarbon co- feed (216) at a catalytic cracking temperature.
  • a mixture of spent catalytic cracking catalyst (228) and produced cracked products (224) is separated in a separator (226) .
  • the spent catalytic cracking catalyst (228) is forwarded to regenerator (230), where it is regenerated and
  • the cracked products (124) are forwarded to a fractionator (232) .
  • the cracked products (224) are fractionated into several product fractions, such as for example a slurry oil containing fraction
  • hydrodeoxygenated over a Nickel-Molybdenum on alumina catalyst to produce a hydrodeoxygenated product (244).
  • the hydrodeoxygenated product can be blended with one or more other components to produce a biofuel suitable for use in automotive engines.
  • Eurovector EA3000 apparatus commercially available from Eurovector
  • Vario Cube apparatus of Elementar GmbH unless indicated otherwise
  • elemental sulphur analysis is carried out by ASTM D5453 combustion by UV-fluorescence detection on an Antek 9000 apparatus, unless indicated otherwise.
  • Gas Chromatography and oxygen content of the feed were determined with ASTM D5599-95 unless indicated otherwise .
  • Example 1- preparation of a mixture of milled torrefied poplar wood with fluid hydrocarbon feed.
  • Chips of poplar wood were torrefied at 250 °C for 6 hours. These were finely milled using a Retch PM 400 ball mill for 4 hours and at 400 rpm to produce a micronized torrefied wood material.
  • the milled torrefied poplar wood had an apparent Bulk Density of 0.42 g/mL and a mean particle size distribution of 36 micrometer (as measured at a Horiba LA950, Laser Scattering Particle Size Distribution Analyzer) .
  • the milled torrefied poplar wood was dried during 1 day at 105 °C. Subsequently the milled torrefied poplar wood (MTPW) was added to a fluid hydrocarbon feed (HF) in weight ratios as indicated below :
  • Table 1 Boiling range distribution of the fluid hydrocarbon feed as determined by gas chromatography according to ASTM D2887-06a.
  • Table 2 Element analyses of fluid hydrocarbon feed and milled torrefied poplar wood.
  • Each mixture was tested in a separate run.
  • Each run included 7 experiments with 7 catalyst to feed weight ratios, namely catalyst to feed (Cat/feed) weight ratios of 3, 4, 5, 6, 6.5, 7 and 8.
  • FCC equilibrium catalyst i.e. the catalytic cracking catalyst
  • ultra stable zeolite Y with a composition as listed in table 3
  • the fluidized catalyst bed was kept at 520 °C .
  • the liquid products also referred to as total liquid product (TLP)
  • TLP total liquid product
  • the catalytic cracking catalyst was stripped with nitrogen. The gas produced during such stripping was weighted and analyzed online with a gas chromatograph (GC) .
  • the catalytic cracking catalyst was regenerated in-situ at 650 °C in the presence of air. During such regeneration the coke was converted to CO 2 , which was quantified by on-line infrared measurement. After regeneration the reactor was cooled to the cracking temperature and a new injection was started. One cycle including all catalyst to oil ratios took approximately 16 hours. The 7 experiments were used to generate extrapolated results for each catalyst to feed weight ratio and each conversion. From these extrapolated results the yields for the different products fractions are listed in table 4 were determined. The elemental analysis of the total liquid product is listed in table 5.
  • Table 3 properties of the catalytic cracking catalyst.
  • Table 5 Element analyses of Total Liquid Product obtained after catalytic cracking of mixtures of milled torrefied poplar wood and fluid hydrocarbon feed.
  • Example 3 Determination of the bio-carbon content in the Total Liquid Product.
  • a feed mixture containing 18 wt% milled torrefied poplar wood and 82 wt% fluid hydrocarbon feed with properties as listed in tables 1 and 2 was catalytically cracked at 520°C with a catalyst to feed weight ratio of 3 in a MAT-5000 fluidized catalytic cracking unit and with a catalytic cracking catalyst as described in example 2 to produce a Total Liquid Product (TLP) .
  • TLP Total Liquid Product
  • the concentration of oxygen was below the detection limit so it was calculated by measuring carbon, hydrogen, nitrogen and sulphur and subtracting from 100 wt%.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Processing Of Solid Wastes (AREA)
EP12716019.0A 2011-04-21 2012-04-23 Process for converting a solid biomass material Withdrawn EP2699644A1 (en)

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CN103582691B (zh) 2016-11-16
JP2014514411A (ja) 2014-06-19
AU2012245142A1 (en) 2013-10-31
CN103582691A (zh) 2014-02-12

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