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WO2014064007A1 - Process for converting a solid biomass material - Google Patents

Process for converting a solid biomass material Download PDF

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Publication number
WO2014064007A1
WO2014064007A1 PCT/EP2013/071852 EP2013071852W WO2014064007A1 WO 2014064007 A1 WO2014064007 A1 WO 2014064007A1 EP 2013071852 W EP2013071852 W EP 2013071852W WO 2014064007 A1 WO2014064007 A1 WO 2014064007A1
Authority
WO
WIPO (PCT)
Prior art keywords
pneumatic
catalytic cracking
fluid
biomass material
reactor
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.)
Ceased
Application number
PCT/EP2013/071852
Other languages
French (fr)
Inventor
Robert Alexander LUDOLPH
Colin John Schaverien
Johannes VEERMAN
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
Shell USA Inc
Original Assignee
Shell Internationale Research Maatschappij BV
Shell Oil Co
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, Shell Oil Co filed Critical Shell Internationale Research Maatschappij BV
Publication of WO2014064007A1 publication Critical patent/WO2014064007A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/1802Organic compounds containing oxygen natural products, e.g. waxes, extracts, fatty oils
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/083Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1011Biomass
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the invention relates to a process for converting a solid biomass material.
  • the invention further relates to a process for producing a biofuel and/or biochemical.
  • renewable energy sources With the diminishing supply of crude petroleum 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, renewable or advanced, biofuels. Most non-edible renewable energy sources, however, are solid materials that are cumbersome to convert into liquid fuels.
  • US2012/0160741 describes a method of upgrading biomass to fuel products comprising: mixing a biomass feed stream with a solvent to produce a mixed feed stream; transporting the mixed feed stream through a slurry pump, mixer, or mixer and slurry pump to a riser; combining the mixed feed stream with a conventional FCC feed stream and regenerated catalyst in the riser;
  • 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.
  • WO2010/135734 describes that the biomass material may be particulated by mechanical processing.
  • mechanical processing may include particulating the biomass material by conveying biomass material in a stream of gas, and forcing the stream, with the biomass material, to collide with a surface, or with particles, of greater hardness than the biomass material. This appears to be referred to in
  • Non-prepublished international patent application no. PCT/EP2012/ 057415 describes a process for converting a solid biomass material, comprising contacting the solid biomass material with a catalytic cracking catalyst at a temperature of more than 400°C in a riser reactor to produce one or more cracked products.
  • the process may comprise feeding the solid biomass material to the riser reactor as a mixture of solid biomass material and a gas.
  • the gas may be selected from the group consisting of steam, vaporized liquefied petroleum gas, gasoline, diesel, kerosene, naphtha and mixtures thereof.
  • the patent application explains that solid biomass material may be supplied to the riser reactor with the help of a screw feeder, or if the solid biomass material is
  • the present invention provides a process for converting a solid biomass material, comprising a) providing a pneumatic fluid;
  • pneumatic fluid to prepare a pneumatic dispersion and transporting the pneumatic dispersion to a reactor;
  • particles of solid biomass material may be more sticky and tend to clog up equipment more easily.
  • Supplying the solid biomass material to a reactor as a dispersion of solid biomass material in a pneumatic fluid via a pneumatic transport may be advantageous over the use of a screw feeder or slurry pump, as the risk of plugging may be reduced.
  • the reactor is a fluid
  • the pneumatic fluid allows one to immediately fluidize the solid biomass material upon entering of the catalytic cracking reactor.
  • a solid biomass material is herein understood a solid material containing biomass.
  • the solid biomass material is a solid material consisting of biomass.
  • biomass 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 biomass may contain carbon-14 isotope in an abundance of about 0.0000000001 %, based on total moles of carbon.
  • any solid biomass material may be used in the process of the invention.
  • the solid biomass material is not a material used for food
  • solid biomass material examples include aquatic plants and algae, agricultural waste and/or forestry waste and/or paper waste and/or plant material obtained from domestic waste.
  • Other examples of a solid biomass material can include animal fat and/or used cooking oil, with the proviso that such animal fat and/or used cooking oil must be supplied at a temperature wherein they are in a solid state.
  • the solid biomass material contains cellulose and/or lignocellulose .
  • cellulose and/or lignocellulose are preferred.
  • cellulose respectively "lignocellulose” is herein also referred to as a "cellulosic” , respectively "lignocellulosic” material.
  • a cellulosic material is herein understood a material containing cellulose and optionally also lignin and/or hemicellulose .
  • lignocellulosic material is herein understood a material containing cellulose and lignin and optionally
  • 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.
  • the solid biomass material is selected from the group consisting of wood, sawdust, straw, grass, bagasse, corn stover and/or mixtures thereof. When the solid biomass material is wood, both hard as well as soft wood may be used.
  • the solid biomass material may have undergone drying, demineralization, torrefaction, steam explosion, particle size reduction, densification and/or pelletization before being dispersed into the pneumatic fluid, to allow for improved process operability and economics.
  • the solid biomass material is a torrefied solid biomass material.
  • the process according to the invention comprises a step of torrefying the solid biomass material at a temperature of more than 200°C to produce a torrefied solid biomass material that may be dispersed into the pneumatic fluid.
  • torrefying and torrefaction are used
  • 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
  • thermoforming 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.
  • 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 absolute, corresponding to about 0.1 MegaPascal).
  • the torrefying step may be carried out batchwise or continuously.
  • a continuous torrefaction process is preferred as this allows a continuous combination of any torrefaction with the transporting according to the invention .
  • the torrefied solid biomass material has a higher energy density, a higher mass density and greater
  • 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 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
  • 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.
  • 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 preferably 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, even more preferably equal to or more than 100 micrometer, and most preferably equal to or more than 200 micrometer, to equal to or less than 5000 micrometer, more preferably equal to or less than 3000 micrometer, even 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 a reactor.
  • the particle size distribution and mean particle size of the solid biomass material can be determined with a Laser Scattering Particle Size
  • 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 micrometer (micron) , more preferably equal to or more than 10 micrometer, even more preferably equal to or more than 20 micrometer, even more preferably equal to or more than 100 micrometer, and most preferably equal to or more than 200 micrometer, to equal to or less than 5000 micrometer, more preferably equal to or less than 3000 micrometer, even 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.
  • micron micrometer
  • a pneumatic fluid is provided.
  • the pneumatic fluid may be a pneumatic liquid; a pneumatic gas; or a combination thereof where the fluid is partially liquid partially gaseous.
  • the pneumatic fluid is a pneumatic gas.
  • pneumatic is herein preferably understood creating movement solely by applying a pressure difference causing a flow from one location to another location. That is, no mechanical forces are used to create the movement.
  • pneumatic fluid is a gas
  • pneumatic may be understood to refer to moving or working by gas pressure.
  • pneumatic fluids examples include water, steam, nitrogen, oils and/or oil fractions, or mixtures thereof.
  • the pneumatic fluid is an oil or oil fraction.
  • oil fractions that may be suitable as a pneumatic fluid include liquefied petroleum gas, gasoline, diesel, kerosene or naphtha.
  • the pneumatic fluid is a vaporized oil or oil fraction. More preferably the pneumatic fluid is selected from the group consisting of vaporized liquefied petroleum gas, - - vaporized gasoline, vaporized diesel, vaporized kerosene, vaporized naphtha and/or mixtures thereof.
  • the pneumatic fluid is a vaporized liquefied petroleum gas, a liquid or vaporized naphtha fraction or a mixture thereof.
  • a naphtha fraction is herein preferably understood an oil fraction of which at least 80 wt%, more preferably at least 90 wt% boils in the range from equal to or more than 30°C to less than 221°C as determined at 0.1
  • a liquefied petroleum gas is herein preferably understood an oil fraction of which at least 80 wt%, more preferably at least 90 wt% boils in the range from equal to or more than -65°C to less than 88°C at 0.1
  • the advantage of using a liquid- or vaporized oil; or a liquid- or vaporized oil fraction as a pneumatic fluid; may be that oil or oil fraction may have a higher
  • the pneumatic fluid is pressurized to a specific pressure, herein further also referred to as pneumatic pressure.
  • the pneumatic pressure may be less than 0.1 MegaPascal.
  • the pneumatic fluid is pressurized to a pressure in the range from equal to or more than 0.0001 MegaPascal (0.001 bar absolute), preferably equal to or more than 0.001 MegaPascal (0.01 bar absolute) to less than 0.1
  • the pneumatic fluid may be provided by a so- called vacuum system.
  • the pneumatic pressure may be more than 0.1 MegaPascal.
  • the pneumatic fluid is pressurized to a pressure in the range from more than 0.10 MegaPascal (1 bar absolute) to equal to or less than 1.00 MegaPascal (10 bar absolute), more preferably in the range from equal to or more than 0.15 MegaPascal (1.5 bar absolute) to equal to or less than 0.80 MegaPascal (8 bar absolute) and most preferably in the range from equal to or more than 0.20 MegPascal (2 bar absolute) to equal to or less than 0.60 MegaPascal (6 bar absolute) .
  • the pneumatic fluid may be provided by a so-called pressure system.
  • a combination may be used, where the pneumatic fluid may be provided by a so-called pressure-vacuum system.
  • step b) the solid biomass material is dispersed into the pneumatic fluid to prepare a pneumatic
  • the solid biomass material 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, more preferably a particle size distribution with a mean particle size in the range from equal to or more than 100 micrometer to equal to or less than 5000 micrometer, and the solid biomass material is dispersed in a pneumatic fluid that is pressurized to a pressure in the range from more than 0.10 MegaPascal (1 bar absolute) to equal to or less than
  • pneumatic fluid preferably has a flow rate in the range from equal to or more than 1.0 kg/minute to equal to or less than 150 kg/minute.
  • the pneumatic fluid in this embodiment is a gas. More preferably such a gaseous pneumatic fluid is provided by a so-called positive-displacement blower or a compressor.
  • This embodiment may also be referred to as a pressurized system as indicated above.
  • This embodiment is very advantageous in the process of the invention as the solid biomass material does not need to be conveyed through any pump or compressor. That is, there are no compressors or pumps that may clog up with the solid biomass particles.
  • a vacuum can be used to induce a solid biomass material having a mean particle size in the range from equal to or more than 5 micrometer to equal to or less than 5000 micrometer, more preferably 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 500 micrometer, into a conveyer and move the solid biomass material over a distance to a separator; in the separator the pneumatic gas can be passed through a filter and into the suction side of a positive-displacement blower or compressor; subsequently the feed of solid biomass material may be fed by a rotary feeder into the conveyer positive pressure air system.
  • This embodiment may also be referred to as a pressure- vacuum system as indicated above.
  • the pneumatic dispersion preferably has a density in the range from equal to or more than 10 kilogram per cubic meter (m 3 ) to equal to or less than 4000 kilogram per cubic meter (m 3 ) .
  • the pneumatic dispersion is subsequently transported to a reactor.
  • Such transport may involve transport through a pipeline, preferably through a so- called feedline.
  • the pneumatic dispersion is transported to the reactor via one or more reactor inlets.
  • the one or more reactor inlets may for example comprise one or more bottom entry reactor inlets and/or one or more side entry reactor inlets.
  • Such a reactor inlet may have the form of a feed nozzle.
  • the pneumatic dispersion may be transported to the reactor via one or more feed nozzles.
  • the one or more feed nozzles may comprise one or more bottom entry feed nozzles and/or one or more side entry feed nozzles.
  • a bottom entry feed nozzle is herein preferably understood a feed nozzle protruding the reactor from the bottom.
  • a side entry feed nozzle is herein preferably understood a feed nozzle protruding the reactor via a side wall.
  • step c) the pneumatic dispersion is contacted with a catalyst in the reactor to produce a product stream comprising one or more conversion products.
  • the pneumatic dispersion is contacted in step c) with a catalyst at a temperature of equal to or more than 300°C, more preferably equal to or more than 350°C, and most preferably at a temperature of equal to or more than 400°C.
  • the pneumatic dispersion is further preferably contacted in step c) with a catalyst at a temperature of equal to or less than 800°C, more - - preferably equal to or less than 700°C, and most
  • the reactor is a fluid catalytic cracking reactor as described herein below, the pneumatic
  • dispersion is preferably contacted in step c) with a fluid catalytic cracking catalyst at a temperature of equal to or more than 450°C to equal to or less than 650°C.
  • the reactor may be any type of reactor known to the skilled person to be suitable for contacting such a pneumatic dispersion with a catalyst.
  • the catalyst is a hydrocracking catalyst and the reactor is a hydrocracker reactor.
  • the reactor is a hydrocracker reactor.
  • the catalyst is a catalytic cracking catalyst and the reactor is a catalytic cracking reactor.
  • the catalyst is a fluid catalytic
  • the reactor is a fluid catalytic cracking reactor.
  • the reactor is a so-called riser reactor.
  • a riser reactor is the type of reactor most preferred for use as a fluid catalytic cracking reactor in a fluid catalytic cracking process. Examples of suitable riser reactors are described in the Handbook titled "Fluid Catalytic Cracking technology and operations", by Joseph W. Wilson, published by PennWell Publishing Company (1997), chapter 3, especially pages
  • a riser reactor comprises a liftpot and a riser reactor standpipe, where such liftpot may suitably be fluidly connected to such riser reactor standpipe. Further, the liftpot may suitably be located upstream of the riser reactor standpipe, such that a fluid catalytic cracking catalyst may flow in a direction from the liftpot to the riser reactor standpipe.
  • the - - riser reactor, the liftpot and/or the riser reactor standpipe comprise metal as a construction material.
  • the weight of a riser reactor standpipe is generally carried higher up in a unit. During heating of the riser reactor, any metal that is used as a construction material may expand.
  • the riser reactor, the liftpot and/or the riser reactor standpipe may move into a downward direction.
  • the necessity to compensate for any upward or downward movement of the riser reactor and/or liftpot may compromise the
  • a pneumatic feeding system as described herein does not have that disadvantage.
  • the present invention therefore further provides a fluid catalytic cracking process for converting a solid biomass material comprising contacting the solid biomass material with a fluid catalytic cracking catalyst at a temperature of equal to or more than 400°C in a fluid catalytic cracking reactor to produce a product stream comprising one or more conversion products, wherein the solid biomass material is transported into the fluid catalytic cracking reactor with the help of a pneumatic fluid and/or a pneumatic transport system.
  • a pneumatic transport system is herein understood a feed system that makes use of a pneumatic fluid as described herein before.
  • a system may be a vacuum system, pressure system or combination thereof as
  • the fluid catalytic cracking reactor is preferably a riser reactor. Further - - preferences, for example for the pneumatic fluid, are as describe above.
  • the pneumatic fluid and/or pneumatic transport system may be combined with an screw feeder and/or slurry pump. This may especially be advantageous when a torrefied solid biomass material is used and/or when the solid biomass material needs to be reduced in size .
  • the process according to the invention is a fluid catalytic cracking process;
  • the pneumatic fluid is an oil or oil fraction as described herein above;
  • the catalyst is a fluid catalytic cracking catalyst and the reactor is a fluid catalytic cracking reactor, preferably a riser reactor.
  • the pneumatic fluid is a vaporized oil and/or a vaporized oil fraction as exemplified herein above.
  • the process according to the invention has the further advantage that such vaporized oil and/or vaporized oil fraction may conveniently be simultaneously used as a co-feed in a fluid catalytic cracking process.
  • a vaporized oil and/or a vaporized oil fraction may conveniently allow one to fluidize the solid biomass material without the use of steam or nitrogen. This is advantageous as the use of steam in fluid catalytic cracking of a solid biomass material may result in products being formed that may be troublesome in the normal work-up section of a refinery.
  • the process of the invention is a fluid catalytic cracking process for converting a solid biomass material, comprising
  • pneumatic fluid comprises or consists of an oil, one or more oil fractions and/or a mixture thereof;
  • preferably comprises or consists of a vaporized oil, one or more vaporized oil fractions and/or a mixture thereof, and most preferably comprises or consists of a vaporized liquefied petroleum gas, a vaporized naphtha fraction and/or a combination thereof.
  • step c) or step vi) comprises
  • a separation step comprising separating the one or more cracked products from the spent fluid catalytic cracking catalyst
  • a regeneration step comprising regenerating spent fluid catalytic cracking catalyst to produce a
  • a recycle step comprising recycling the regenerated fluid catalytic cracking catalyst to the catalytic cracking step.
  • step c) of the process according to the invention may be carried out in the presence of an additional hydrocarbon feed.
  • a - - hydrocarbon feed is herein understood a feed that
  • hydrocarbon compounds contains one or more hydrocarbon compounds.
  • hydrocarbon compounds include paraffins (including
  • the additional hydrocarbon feed can for example be derived from a conventional crude oil (also sometimes referred to as a petroleum oil or mineral oil), an unconventional crude oil (that is, oil produced or extracted using techniques other than the traditional oil well method) or a Fisher Tropsch oil (sometimes also referred to as a synthetic oil) and/or a mixture of any of these.
  • 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
  • Fisher Tropsch oil sometimes also referred to as a synthetic oil
  • the additional hydrocarbon feed is a hydrocarbon feed that is partly or wholly derived from a petroleum crude oil. More preferably the hydrocarbon feed is an essentially completely petroleum-derived
  • hydrocarbon feed as opposed to a biomass-derived
  • hydrocarbon feed examples of conventional crude oils (also called petroleum oils) include West Texas
  • the hydrocarbon feed comprises a fraction of a petroleum crude oil, unconventional crude oil or synthetic crude oil.
  • Preferred fractions 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 hydrocarbon feed comprises an atmospheric residue, vacuum residue and/or a vacuum gas oil.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

A process for converting a solid biomass material, comprising providing a pneumatic fluid; dispersing the solid biomass material into the pneumatic fluid to prepare a pneumatic dispersion and transporting the pneumatic dispersion to a reactor; contacting the pneumatic dispersion with a catalyst in the reactor to produce a product stream comprising one or more conversion products.

Description

PROCESS FOR CONVERTING A SOLID BIOMASS MATERIAL
FIELD OF THE INVENTION
The invention relates to a process for converting a solid biomass material. The invention further relates to a process for producing a biofuel and/or biochemical. BACKGROUND TO THE INVENTION
With the diminishing supply of crude petroleum 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, such as cellulosic materials, are preferred as these do not compete with food production. These biofuels are also referred to as second generation, renewable or advanced, biofuels. Most non-edible renewable energy sources, however, are solid materials that are cumbersome to convert into liquid fuels.
US2012/0160741 describes a method of upgrading biomass to fuel products comprising: mixing a biomass feed stream with a solvent to produce a mixed feed stream; transporting the mixed feed stream through a slurry pump, mixer, or mixer and slurry pump to a riser; combining the mixed feed stream with a conventional FCC feed stream and regenerated catalyst in the riser;
cracking and upgrading the biomass feed to upgraded fuel products in the riser; separating upgraded fuel products from deactivated catalyst in reactor/stripper ;
regenerating the deactivated FCC catalyst in the
regenerator; and recycling the regenerated FCC catalyst to the FCC riser, wherein long chain petroleum compounds - - and biomass are upgraded to fuel products in the FCC riser .
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. In one of the
embodiments WO2010/135734 describes that the biomass material may be particulated by mechanical processing. In an alternative embodiment, mechanical processing may include particulating the biomass material by conveying biomass material in a stream of gas, and forcing the stream, with the biomass material, to collide with a surface, or with particles, of greater hardness than the biomass material. This appears to be referred to in
WO2010/135734 as "pneumatic conveyance".
Non-prepublished international patent application no. PCT/EP2012/ 057415 describes a process for converting a solid biomass material, comprising contacting the solid biomass material with a catalytic cracking catalyst at a temperature of more than 400°C in a riser reactor to produce one or more cracked products. The process may comprise feeding the solid biomass material to the riser reactor as a mixture of solid biomass material and a gas. The gas may be selected from the group consisting of steam, vaporized liquefied petroleum gas, gasoline, diesel, kerosene, naphtha and mixtures thereof. The patent application explains that solid biomass material may be supplied to the riser reactor with the help of a screw feeder, or if the solid biomass material is
supplied to the riser reactor as a suspension of solid - - biomass particles in a hydrocarbon-containing liquid, with the help of a slurry pump.
It would be an advancement in the art to improve the above process further.
SUMMARY OF THE INVENTION
Such an improvement has now been achieved with the process according to the invention.
Accordingly the present invention provides a process for converting a solid biomass material, comprising a) providing a pneumatic fluid;
b) dispersing the solid biomass material into the
pneumatic fluid to prepare a pneumatic dispersion and transporting the pneumatic dispersion to a reactor;
c) contacting the pneumatic dispersion with a catalyst in the reactor to produce a product stream comprising one or more conversion products.
Contrary to for example catalyst particles, particles of solid biomass material may be more sticky and tend to clog up equipment more easily. Supplying the solid biomass material to a reactor as a dispersion of solid biomass material in a pneumatic fluid via a pneumatic transport may be advantageous over the use of a screw feeder or slurry pump, as the risk of plugging may be reduced. In addition, when the reactor is a fluid
catalytic cracking reactor, the pneumatic fluid allows one to immediately fluidize the solid biomass material upon entering of the catalytic cracking reactor.
DETAILED DESCRIPTION OF THE INVENTION
By a solid biomass material is herein understood a solid material containing biomass. Preferably the solid biomass material is a solid material consisting of biomass. By biomass 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 biomass may contain carbon-14 isotope in an abundance of about 0.0000000001 %, based on total moles of carbon.
Any solid biomass material may be used in the process of the invention. In a preferred embodiment the solid biomass material is not a material used for food
production .
Examples of solid biomass material include aquatic plants and algae, agricultural waste and/or forestry waste and/or paper waste and/or plant material obtained from domestic waste. Other examples of a solid biomass material can include animal fat and/or used cooking oil, with the proviso that such animal fat and/or used cooking oil must be supplied at a temperature wherein they are in a solid state.
Preferably the solid biomass material contains cellulose and/or lignocellulose . Such a material
containing "cellulose" respectively "lignocellulose" is herein also referred to as a "cellulosic" , respectively "lignocellulosic" material. By a cellulosic material is herein understood a material containing cellulose and optionally also lignin and/or hemicellulose . By a
lignocellulosic material is herein understood a material containing cellulose and lignin and optionally
hemicellulose .
Examples of 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 preferably the solid biomass material is selected from the group consisting of wood, sawdust, straw, grass, bagasse, corn stover and/or mixtures thereof. When the solid biomass material is wood, both hard as well as soft wood may be used.
The solid biomass material may have undergone drying, demineralization, torrefaction, steam explosion, particle size reduction, densification and/or pelletization before being dispersed into the pneumatic fluid, to allow for improved process operability and economics.
Preferably the solid biomass material is a torrefied solid biomass material. In a preferred embodiment the process according to the invention comprises a step of torrefying the solid biomass material at a temperature of more than 200°C to produce a torrefied solid biomass material that may be dispersed into the pneumatic fluid. The words torrefying and torrefaction are used
interchangeable herein.
By torrefying or torrefaction is herein understood the treatment of the solid biomass material at a
temperature in the range from equal to or more than 200 °C to equal to or less than 350°C in the essential absence of a catalyst and in an oxygen-poor, preferably an oxygen-free, atmosphere. By an oxygen-poor atmosphere is understood 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. By an oxygen-free atmosphere is understood that the torrefaction is carried out in the essential absence of oxygen. - -
Torrefying of the solid biomass material is
preferably carried out at 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
temperature equal to or more than 230 °C. In addition 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. More preferably 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.
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 absolute, corresponding to about 0.1 MegaPascal).
The torrefying step may be carried out batchwise or continuously. A continuous torrefaction process is preferred as this allows a continuous combination of any torrefaction with the transporting according to the invention .
The torrefied solid biomass material has a higher energy density, a higher mass density and greater
flowability, making it easier to transport, pelletize - - and/or store. Being more brittle, it can be easier reduced into smaller particles.
In a further preferred embodiment, any torrefying or torrefaction step further comprises drying the solid biomass material before such solid biomass material is torrefied. In such a drying step, 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%. For practical purposes 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.
Preferably the solid biomass material is a micronized solid biomass material. By 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. In a preferred embodiment 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 preferably be achieved by means of a ball mill, hammer mill, (knife) shredder, chipper, knife grid, or cutter.
Preferably 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) , more preferably equal to or more than 10 micrometer, even more preferably equal to or more than 20 micrometer, even more preferably equal to or more than 100 micrometer, and most preferably equal to or more than 200 micrometer, to equal to or less than 5000 micrometer, more preferably equal to or less than 3000 micrometer, even more preferably equal to or less than 1000
micrometer and most preferably equal to or less than 500 micrometer .
Most preferably 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 a reactor.
For practical purposes the particle size distribution and mean particle size of the solid biomass material can be determined with a Laser Scattering Particle Size
Distribution Analyzer, preferably a Horiba LA950,
according to the ISO 13320 method titled "Particle size analysis - Laser diffraction methods".
Hence, preferably 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 micrometer (micron) , more preferably equal to or more than 10 micrometer, even more preferably equal to or more than 20 micrometer, even more preferably equal to or more than 100 micrometer, and most preferably equal to or more than 200 micrometer, to equal to or less than 5000 micrometer, more preferably equal to or less than 3000 micrometer, even 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.
In step a) of the process according to the invention a pneumatic fluid is provided. The pneumatic fluid may be a pneumatic liquid; a pneumatic gas; or a combination thereof where the fluid is partially liquid partially gaseous. In a preferred embodiment the pneumatic fluid is a pneumatic gas.
By pneumatic is herein preferably understood creating movement solely by applying a pressure difference causing a flow from one location to another location. That is, no mechanical forces are used to create the movement. When the pneumatic fluid is a gas, pneumatic may be understood to refer to moving or working by gas pressure.
Examples of pneumatic fluids include water, steam, nitrogen, oils and/or oil fractions, or mixtures thereof. In one preferred embodiment the pneumatic fluid is an oil or oil fraction. Examples of oil fractions that may be suitable as a pneumatic fluid include liquefied petroleum gas, gasoline, diesel, kerosene or naphtha. Preferably the pneumatic fluid is a vaporized oil or oil fraction. More preferably the pneumatic fluid is selected from the group consisting of vaporized liquefied petroleum gas, - - vaporized gasoline, vaporized diesel, vaporized kerosene, vaporized naphtha and/or mixtures thereof.
In an especially preferred embodiment the pneumatic fluid is a vaporized liquefied petroleum gas, a liquid or vaporized naphtha fraction or a mixture thereof.
By a naphtha fraction is herein preferably understood an oil fraction of which at least 80 wt%, more preferably at least 90 wt% boils in the range from equal to or more than 30°C to less than 221°C as determined at 0.1
MegaPascal by ASTM D86 titled "Standard Test Method for
Distillation of Petroleum Products at Atmospheric
Pressure"
By a liquefied petroleum gas is herein preferably understood an oil fraction of which at least 80 wt%, more preferably at least 90 wt% boils in the range from equal to or more than -65°C to less than 88°C at 0.1
MegaPascal .
The advantage of using a liquid- or vaporized oil; or a liquid- or vaporized oil fraction as a pneumatic fluid; may be that oil or oil fraction may have a higher
density, allowing for a better transport of the solid biomass material.
The pneumatic fluid is pressurized to a specific pressure, herein further also referred to as pneumatic pressure. In one embodiment the pneumatic pressure may be less than 0.1 MegaPascal. In this embodiment preferably the pneumatic fluid is pressurized to a pressure in the range from equal to or more than 0.0001 MegaPascal (0.001 bar absolute), preferably equal to or more than 0.001 MegaPascal (0.01 bar absolute) to less than 0.1
MegaPascal (1 bar absolute) preferably equal to or less than 0.01 MegaPascal (0.1 bar absolute) . In this - - embodiment the pneumatic fluid may be provided by a so- called vacuum system.
In another embodiment the pneumatic pressure may be more than 0.1 MegaPascal. In this embodiment, preferably the pneumatic fluid is pressurized to a pressure in the range from more than 0.10 MegaPascal (1 bar absolute) to equal to or less than 1.00 MegaPascal (10 bar absolute), more preferably in the range from equal to or more than 0.15 MegaPascal (1.5 bar absolute) to equal to or less than 0.80 MegaPascal (8 bar absolute) and most preferably in the range from equal to or more than 0.20 MegPascal (2 bar absolute) to equal to or less than 0.60 MegaPascal (6 bar absolute) . In that case the pneumatic fluid may be provided by a so-called pressure system.
In a still further embodiment a combination may be used, where the pneumatic fluid may be provided by a so- called pressure-vacuum system.
In step b) the solid biomass material is dispersed into the pneumatic fluid to prepare a pneumatic
dispersion.
In a preferred embodiment the solid biomass material 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, more preferably a particle size distribution with a mean particle size in the range from equal to or more than 100 micrometer to equal to or less than 5000 micrometer, and the solid biomass material is dispersed in a pneumatic fluid that is pressurized to a pressure in the range from more than 0.10 MegaPascal (1 bar absolute) to equal to or less than
1.00 MegaPascal (10 bar absolute), more preferably in the range from equal to or more than 0.15 MegaPascal (1.5 bar absolute) to equal to or less than 0.80 MegaPascal (8 bar - - absolute) and most preferably in the range from equal to or more than 0.20 MegPascal (2 bar absolute) to equal to or less than 0.60 MegaPascal (6 bar absolute), to prepare the pneumatic dispersion. In this embodiment the
pneumatic fluid preferably has a flow rate in the range from equal to or more than 1.0 kg/minute to equal to or less than 150 kg/minute. Preferably the pneumatic fluid in this embodiment is a gas. More preferably such a gaseous pneumatic fluid is provided by a so-called positive-displacement blower or a compressor. This embodiment may also be referred to as a pressurized system as indicated above. This embodiment is very advantageous in the process of the invention as the solid biomass material does not need to be conveyed through any pump or compressor. That is, there are no compressors or pumps that may clog up with the solid biomass particles.
In another embodiment a vacuum can be used to induce a solid biomass material having a mean particle size in the range from equal to or more than 5 micrometer to equal to or less than 5000 micrometer, more preferably 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 500 micrometer, into a conveyer and move the solid biomass material over a distance to a separator; in the separator the pneumatic gas can be passed through a filter and into the suction side of a positive-displacement blower or compressor; subsequently the feed of solid biomass material may be fed by a rotary feeder into the conveyer positive pressure air system. This embodiment may also be referred to as a pressure- vacuum system as indicated above. Although this
embodiment may be useful, it is less preferred in the - - process of the invention as the rotary feeder may become clogged with sticky particles of solid biomass material.
The pneumatic dispersion preferably has a density in the range from equal to or more than 10 kilogram per cubic meter (m3) to equal to or less than 4000 kilogram per cubic meter (m3) .
In step b) the pneumatic dispersion is subsequently transported to a reactor. Such transport may involve transport through a pipeline, preferably through a so- called feedline. Preferably the pneumatic dispersion is transported to the reactor via one or more reactor inlets. The one or more reactor inlets may for example comprise one or more bottom entry reactor inlets and/or one or more side entry reactor inlets. Such a reactor inlet may have the form of a feed nozzle. For example the pneumatic dispersion may be transported to the reactor via one or more feed nozzles. The one or more feed nozzles may comprise one or more bottom entry feed nozzles and/or one or more side entry feed nozzles. By a bottom entry feed nozzle is herein preferably understood a feed nozzle protruding the reactor from the bottom. By a side entry feed nozzle is herein preferably understood a feed nozzle protruding the reactor via a side wall.
In step c) the pneumatic dispersion is contacted with a catalyst in the reactor to produce a product stream comprising one or more conversion products.
Preferably the pneumatic dispersion is contacted in step c) with a catalyst at a temperature of equal to or more than 300°C, more preferably equal to or more than 350°C, and most preferably at a temperature of equal to or more than 400°C. The pneumatic dispersion is further preferably contacted in step c) with a catalyst at a temperature of equal to or less than 800°C, more - - preferably equal to or less than 700°C, and most
preferably at a temperature of equal to or less than 650°C. When the reactor is a fluid catalytic cracking reactor as described herein below, the pneumatic
dispersion is preferably contacted in step c) with a fluid catalytic cracking catalyst at a temperature of equal to or more than 450°C to equal to or less than 650°C.
The reactor may be any type of reactor known to the skilled person to be suitable for contacting such a pneumatic dispersion with a catalyst. In one preferred embodiment the catalyst is a hydrocracking catalyst and the reactor is a hydrocracker reactor. In another
preferred embodiment the catalyst is a catalytic cracking catalyst and the reactor is a catalytic cracking reactor.
More preferably the catalyst is a fluid catalytic
cracking catalyst and the reactor is a fluid catalytic cracking reactor. Most preferably the reactor is a so- called riser reactor. Such a riser reactor is the type of reactor most preferred for use as a fluid catalytic cracking reactor in a fluid catalytic cracking process. Examples of suitable riser reactors are described in the Handbook titled "Fluid Catalytic Cracking technology and operations", by Joseph W. Wilson, published by PennWell Publishing Company (1997), chapter 3, especially pages
101 to 112, herein incorporated by reference.
Preferably a riser reactor comprises a liftpot and a riser reactor standpipe, where such liftpot may suitably be fluidly connected to such riser reactor standpipe. Further, the liftpot may suitably be located upstream of the riser reactor standpipe, such that a fluid catalytic cracking catalyst may flow in a direction from the liftpot to the riser reactor standpipe. Suitably the - - riser reactor, the liftpot and/or the riser reactor standpipe comprise metal as a construction material. The weight of a riser reactor standpipe is generally carried higher up in a unit. During heating of the riser reactor, any metal that is used as a construction material may expand. As a result of the thermal expansion of such metal, the riser reactor, the liftpot and/or the riser reactor standpipe may move into a downward direction. When feeding a solid biomass material into a riser reactor and/or liftpot via a direct connection with a heavy weight screw feeder or slurry pump, the necessity to compensate for any upward or downward movement of the riser reactor and/or liftpot, may compromise the
mechanical integrity and therewith the reliability and safety of a process. A pneumatic feeding system as described herein does not have that disadvantage.
The present invention therefore further provides a fluid catalytic cracking process for converting a solid biomass material comprising contacting the solid biomass material with a fluid catalytic cracking catalyst at a temperature of equal to or more than 400°C in a fluid catalytic cracking reactor to produce a product stream comprising one or more conversion products, wherein the solid biomass material is transported into the fluid catalytic cracking reactor with the help of a pneumatic fluid and/or a pneumatic transport system.
By a pneumatic transport system is herein understood a feed system that makes use of a pneumatic fluid as described herein before. Such a system may be a vacuum system, pressure system or combination thereof as
described herein above. The fluid catalytic cracking reactor is preferably a riser reactor. Further - - preferences, for example for the pneumatic fluid, are as describe above.
If so desired, the pneumatic fluid and/or pneumatic transport system may be combined with an screw feeder and/or slurry pump. This may especially be advantageous when a torrefied solid biomass material is used and/or when the solid biomass material needs to be reduced in size .
In an especially preferred embodiment the present invention further provides a fluid catalytic cracking process for converting a solid biomass material
comprising
i) torrefying the solid biomass material to produce a torrefied solid biomass material;
ii) reducing the particle size of the torrefied solid biomass material to produce a torrefied, micronized solid biomass material;
iii) transporting the torrefied, micronized solid biomass material with the help of an screw feeder and/or slurry pump to a pneumatic transport system;
iv) providing a pneumatic fluid and dispersing the torrefied, micronized solid biomass material into the pneumatic fluid in the pneumatic transport system to prepare a pneumatic dispersion;
v) transporting the pneumatic dispersion to a fluid catalytic cracking reactor; and
vi) contacting the pneumatic dispersion with a fluid catalytic cracking catalyst at a temperature of equal to or more than 400°C in a fluid catalytic cracking reactor to produce a product stream comprising one or more conversion products.
Also for this embodiment, preferences are as
described herein above. - -
In an especially advantageous embodiment the process according to the invention is a fluid catalytic cracking process; the pneumatic fluid is an oil or oil fraction as described herein above; the catalyst is a fluid catalytic cracking catalyst and the reactor is a fluid catalytic cracking reactor, preferably a riser reactor. More preferably the pneumatic fluid is a vaporized oil and/or a vaporized oil fraction as exemplified herein above. When a vaporized oil and/or a vaporized oil fraction is used as a pneumatic fluid, the process according to the invention has the further advantage that such vaporized oil and/or vaporized oil fraction may conveniently be simultaneously used as a co-feed in a fluid catalytic cracking process. Further the use of a vaporized oil and/or a vaporized oil fraction may conveniently allow one to fluidize the solid biomass material without the use of steam or nitrogen. This is advantageous as the use of steam in fluid catalytic cracking of a solid biomass material may result in products being formed that may be troublesome in the normal work-up section of a refinery.
Further the use of nitrogen is less commercially
desirable, as it is a less available and expensive gas for use in a catalytic cracking process. Hence in a preferred embodiment the process of the invention is a fluid catalytic cracking process for converting a solid biomass material, comprising
a) providing a pneumatic fluid, wherein such
pneumatic fluid comprises or consists of an oil, one or more oil fractions and/or a mixture thereof;
b) dispersing the solid biomass material into the pneumatic fluid to prepare a pneumatic dispersion and transporting the pneumatic dispersion to a fluid
catalytic cracking reactor; - - c) contacting the pneumatic dispersion with a fluid catalytic cracking catalyst at a temperature of equal to or more than 400°C in the fluid catalytic cracking reactor to produce a product stream comprising one or more cracked products.
In this embodiment the pneumatic fluid more
preferably comprises or consists of a vaporized oil, one or more vaporized oil fractions and/or a mixture thereof, and most preferably comprises or consists of a vaporized liquefied petroleum gas, a vaporized naphtha fraction and/or a combination thereof.
In a further preferred embodiment step c) or step vi) comprises
- a fluid catalytic cracking step comprising
contacting the pneumatic dispersion, and optionally any additional hydrocarbon feed, with the fluid catalytic cracking catalyst at a temperature of equal to or more than 400°C in a riser reactor to produce a product stream comprising one or more cracked products and a spent fluid catalytic cracking catalyst;
- a separation step comprising separating the one or more cracked products from the spent fluid catalytic cracking catalyst;
- a regeneration step comprising regenerating spent fluid catalytic cracking catalyst to produce a
regenerated fluid catalytic cracking catalyst, heat and carbon dioxide; and
- a recycle step comprising recycling the regenerated fluid catalytic cracking catalyst to the catalytic cracking step.
As mentioned herein before step c) of the process according to the invention may be carried out in the presence of an additional hydrocarbon feed. By a - - hydrocarbon feed is herein understood a feed that
contains one or more hydrocarbon compounds. Examples of hydrocarbon compounds include paraffins ( including
naphthenes), olefins and aromatics.
The additional hydrocarbon feed can for example be derived from a conventional crude oil (also sometimes referred to as a petroleum oil or mineral oil), an unconventional crude oil (that is, oil produced or extracted using techniques other than the traditional oil well method) or a Fisher Tropsch oil (sometimes also referred to as a synthetic oil) and/or a mixture of any of these.
Preferably the additional hydrocarbon feed is a hydrocarbon feed that is partly or wholly derived from a petroleum crude oil. More preferably the hydrocarbon feed is an essentially completely petroleum-derived
hydrocarbon feed, as opposed to a biomass-derived
hydrocarbon feed. Examples of conventional crude oils (also called petroleum 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.
More preferably the hydrocarbon feed comprises a fraction of a petroleum crude oil, unconventional crude oil or synthetic crude oil. Preferred fractions 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. Most preferably the hydrocarbon feed comprises an atmospheric residue, vacuum residue and/or a vacuum gas oil.

Claims

2 P Q ~WO 2014/064007 PCT/EP2013/071852 - 20 - C L A I M S
1. A process for converting a solid biomass material, comprising
a) providing a pneumatic fluid;
b) dispersing the solid biomass material into the
pneumatic fluid to prepare a pneumatic dispersion and transporting the pneumatic dispersion to a reactor;
c) contacting the pneumatic dispersion with a catalyst in the reactor to produce a product stream comprising one or more conversion products.
2. The process according to claim 1, wherein the pneumatic fluid is an oil or oil fraction.
3. The process according to anyone of the preceding claims, wherein the pneumatic fluid is selected from the group consisting of vaporized liquefied petroleum gas, vaporized gasoline, vaporized diesel, vaporized kerosene, vaporized naphtha and/or mixtures thereof.
4. The process according to anyone of the preceding claims, wherein the solid biomass material has a particle size distribution with a mean particle size in the range from equal to or more than 100 micrometer to equal to or less than 5000 micrometer and the solid biomass material is dispersed in a pneumatic fluid that is pressurized to a pressure in the range from more than 0.10 MegaPascal to equal to or less than 1.00 MegaPascal, to prepare the pneumatic dispersion.
5. The process according to anyone of the preceding claims, wherein the pneumatic dispersion has a density in the range from equal to or more than 10 kilogram per cubic meter (m3) to equal to or less than 4000 kilogram per cubic meter (m3) .
6. The process according to anyone of the preceding claims, wherein the catalyst is a hydrocracking catalyst or a catalytic cracking catalyst and the reactor is a hydrocracker reactor or a catalytic cracking reactor.
7. The process according to anyone of the preceding claims, wherein the process is a fluid catalytic cracking process for converting a solid biomass material,
comprising
a) providing a pneumatic fluid, wherein such pneumatic fluid comprises or consists of an oil, one or more oil fractions and/or a mixture thereof;
b) dispersing the solid biomass material into the
pneumatic fluid to prepare a pneumatic dispersion and transporting the pneumatic dispersion to a fluid
catalytic cracking reactor;
c) contacting the pneumatic dispersion with a fluid catalytic cracking catalyst in the fluid catalytic cracking reactor to produce a product stream comprising one or more conversion products.
8. The process according to claim 7, wherein the pneumatic fluid comprises or consists of a vaporized oil, one or more vaporized oil fractions and/or a mixture thereof .
9. The process according to claim 7 or 8, wherein step c) comprises a fluid catalytic cracking step comprising contacting the pneumatic dispersion, and optionally any additional hydrocarbon feed, with the fluid catalytic cracking catalyst at a temperature of at least 400°C in a riser reactor to produce a product stream comprising one or more cracked products and a spent fluid catalytic cracking catalyst.
10. The process according to claim 9, further
comprising - a separation step comprising separating the one or more cracked products from the spent fluid catalytic cracking catalyst ;
- a regeneration step comprising regenerating spent fluid catalytic cracking catalyst to produce a regenerated fluid catalytic cracking catalyst, heat and carbon dioxide; and
- a recycle step comprising recycling the regenerated fluid catalytic cracking catalyst to the catalytic cracking step.
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