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WO2018147281A1 - Procédé de production d'hydrocarbures, appareil et système de production associés, et procédé de production de bio-brut - Google Patents

Procédé de production d'hydrocarbures, appareil et système de production associés, et procédé de production de bio-brut Download PDF

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Publication number
WO2018147281A1
WO2018147281A1 PCT/JP2018/004023 JP2018004023W WO2018147281A1 WO 2018147281 A1 WO2018147281 A1 WO 2018147281A1 JP 2018004023 W JP2018004023 W JP 2018004023W WO 2018147281 A1 WO2018147281 A1 WO 2018147281A1
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WIPO (PCT)
Prior art keywords
biocrude
biomass
catalytic cracking
hydrocarbon
fluid catalytic
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
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PCT/JP2018/004023
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English (en)
Japanese (ja)
Inventor
五百里 嶋田
晴久 太田
鈴木　健吾
透 高塚
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.)
Shinshu University NUC
Euglena Co Ltd
Chiyoda Corp
Original Assignee
Shinshu University NUC
Euglena Co Ltd
Chiyoda Corp
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Application filed by Shinshu University NUC, Euglena Co Ltd, Chiyoda Corp filed Critical Shinshu University NUC
Priority to JP2018567441A priority Critical patent/JPWO2018147281A1/ja
Publication of WO2018147281A1 publication Critical patent/WO2018147281A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • 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
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
    • C10G47/30—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles according to the "fluidised-bed" technique
    • 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 present invention relates to a method for producing hydrocarbon, an apparatus for producing the same, a system for producing the same, and a method for producing a biocrude.
  • Patent Document 1 As a synthesis method of fuel replacing petroleum, a method of producing liquid fuel using biomass such as plants as a raw material has been researched and developed (see, for example, Patent Document 1).
  • woody biomass and an organic solvent are mixed and subjected to a liquefaction process by thermal decomposition at 250 ° C. to 400 ° C., and this decomposition product is separated to obtain a liquid fuel It is what you get.
  • An object of the present invention is to provide a manufacturing system and a method of manufacturing a biocrude.
  • the method for producing a hydrocarbon according to the present invention comprises a pretreatment step of obtaining biocrude by mixing at least biomass and a solvent containing an oxygen-containing aromatic compound and performing solvolysis, and the pretreatment step obtained by the pretreatment step. And a fluid catalytic cracking step of performing fluid catalytic cracking using the biocrude and the hydrogen donor as raw materials.
  • the solvent in the pretreatment step preferably contains an organic acid.
  • the biomass may be woody biomass, and the solvent in the pretreatment step may contain the biocrude.
  • the biocrude and the hydrogen donor may be separately supplied in the fluid catalytic cracking step.
  • the method for producing a biocrude according to the present invention is characterized in that the biocrude is obtained by mixing at least biomass and a solvent containing an oxygen-containing aromatic compound and subjecting them to solvolysis.
  • An apparatus for producing a hydrocarbon according to the present invention is an apparatus for producing a hydrocarbon used in the fluid catalytic cracking step of the process for producing a hydrocarbon according to the present invention, the reactor in which the fluid catalytic cracking is performed; A raw material supply means for supplying the raw material to the reactor, wherein the raw material supply means supplies a biocrude supply unit for supplying the biocrude; and a hydrogen donor supply unit for supplying the hydrogen donor. It is characterized by having separately.
  • the system for producing hydrocarbon according to the present invention uses the method for producing hydrocarbon according to the present invention, wherein the pretreatment step and the fluid catalytic cracking step are performed at places separated from each other, The biocrude obtained by the treatment process is transported and supplied to the fluid catalytic cracking process.
  • the biomass may be woody biomass
  • the pretreatment step may be performed at a raw wood core of the woody biomass material.
  • biomass is pretreated by solvolysis from thermal decomposition, subcritical water treatment or supercritical water treatment which is a conventional pretreatment method. Also, when biomass is liquefied at a low temperature and it is catalytically cracked with a hydrogen donor in the subsequent fluid catalytic cracking step, deoxygenation is performed by hydrodeoxygenation to remove much oxygen as water, The production of carbon monoxide and carbon dioxide is suppressed, and the loss of carbon resources can be reduced. Thereby, hydrocarbons can be efficiently produced from biomass.
  • biocrude and the hydrogen donor may result in part of the biomass being precipitated as a solid.
  • the biocrude and the hydrogen donor are supplied to the reactor by separate feeding units, the biocrude and the hydrogen donor are not mixed in the feeding unit. It can prevent the precipitation of biomass.
  • the pretreatment step and the fluid catalytic cracking step are performed at locations separated from each other, and the biocrude obtained by the pretreatment step is transported to the fluid catalytic cracking step. From the supply, transporting the biocrude to a facility that performs a fluid catalytic cracking process can lower the cost of transportation compared to transporting solid, bulky biomass than liquid biocrude.
  • the method for producing a hydrocarbon according to the present invention comprises a pretreatment step of obtaining a biocrude by mixing at least biomass and a solvent containing an oxygen-containing aromatic compound and performing solvolysis, and a bio obtained by the pretreatment step.
  • the method is characterized by comprising a fluid catalytic cracking step of performing fluid catalytic cracking using crude and hydrogen donors as raw materials.
  • the method for producing biocrude according to the present invention is characterized in that the biocrude is obtained by mixing at least biomass and a solvent containing an oxygen-containing aromatic compound and performing solvolysis.
  • biocrude refers to a liquid product obtained by solvolysis in the pretreatment step.
  • the biocrude obtained by subjecting woody biomass to the pretreatment step includes methoxyphenols derived from lignin, alkylphenols such as alkylphenol, and oxygen-containing aromatic compounds such as furan derived from cellulose or hemicellulose, About 80) copolymerized high molecular compounds etc. are included.
  • hydrocarbon in the present invention for example, an oxygen-free Drop-in fuel (a fuel which can use an existing engine or infrastructure), an aromatic compound such as benzene, toluene or xylene, ethylene, propylene or butadiene etc. So-called petrochemical products such as olefins are mentioned.
  • hydrocarbons in the present invention are not limited to these.
  • Biomass is an organic source of biological origin excluding fossil resources.
  • forest resources such as woody biomass, agricultural products processing residues and the like can be used.
  • woody biomass can be suitably used.
  • biomass and a solvent are mixed to perform solvolysis.
  • solvolysis is allowed to proceed for a predetermined time.
  • the liquid product is recovered and made biocrude.
  • the resulting biocrude is subjected to a fluid catalytic cracking step.
  • any apparatus may be used as long as it can heat the mixture of biomass and solvent at the set temperature and time to perform solvolysis.
  • an autoclave or a tubular reactor may be used. Can.
  • the pretreatment step in order to suppress the vaporization of the liquid during the reaction, it is preferable to pressurize and make the reaction.
  • the biomass and the solvent in order to suppress the vaporization of the liquid during the reaction, it is preferable to pressurize and make the reaction.
  • the biomass and the solvent in order to suppress the vaporization of the liquid during the reaction, it is preferable to pressurize and make the reaction.
  • the biomass and the solvent in order to suppress the vaporization of the liquid during the reaction, it is preferable to pressurize and make the reaction.
  • the biomass and the solvent can be mixed to form a mixture, and then the mixture can be supplied into the reactor.
  • the solvent in the pretreatment step promotes the solvolysis reaction of biomass, and contains an oxygen-containing aromatic compound.
  • the oxygen-containing aromatic compounds used for the solvent are substances soluble in cellulose, hemicellulose, lignin and their decomposition products, and specifically, methoxyphenols such as guaiacol (2-methoxyphenol), alkylphenols , Vegetable oil or fat and the like can be used.
  • the solvent in the pretreatment step preferably further contains an organic acid.
  • the organic acid used for the solvent is an organic acid which exhibits acidity in an aqueous solution, such as a carboxylic acid, an organic acid having 1 to 6 carbon atoms, etc.
  • formic acid, acetic acid, propionic acid or butyric acid may be used. it can.
  • woody biomass what is by-produced in a pretreatment process is preferred, and especially acetic acid can be used conveniently.
  • the solvent contains an oxygen-containing aromatic compound or an organic acid
  • the solvolysis of the biomass is promoted, so the biomass is decomposed even at a lower temperature than thermal decomposition, subcritical water treatment or supercritical water treatment, and it is liquefied Is possible.
  • the biomass and the decomposition product thereof can be dissolved with high solubility in the solvent, so that the radical is diluted and dispersed in the solvent to suppress repolymerization,
  • the liquefaction reaction (solvolysis) can be promoted.
  • an organic acid when an organic acid is contained in the solvent, it acts as an acid catalyst on solvolysis, so that the liquefaction reaction of biomass can be further promoted.
  • biocrude obtained by the pretreatment step can be used in addition to or instead of the oxygen-containing aromatic compound or the organic acid. That is, a part of the biocrude obtained by the pretreatment process may be stored and then used as a solvent when the biomass-derived material is subjected to the pretreatment process. In addition, even when biocrude is added to a solvent and the pretreatment step is performed, the obtained biocrude can be added to the solvent and used in the next pretreatment step.
  • the biocrude obtained by the pretreatment step of the present invention contains, as an oxygen-containing aromatic compound, methoxyphenols such as guaiacol, alkylphenols, and organic acids such as acetic acid. It is done. Thereby, even if it does not add an oxygen-containing aromatic compound and an organic acid separately, a biocrude can be added and a liquefaction reaction of biomass can be promoted.
  • FIG. 1 is a figure which shows an example of the process flow of a pre-processing process in the case of collect
  • the biomass, if necessary, water, an organic acid, or a solvent an oxygen-containing aromatic compound and an organic acid
  • the reaction product is supplied to a distillation column, and it is fractionated into gas and water, a solvent (oxygen-containing aromatic compound and organic acid), and biocrude, and the solvent is subjected again to the solvolysis reaction.
  • the oxygen-containing aromatic compound and the organic acid may be recovered from the reaction product by distillation and used again as the solvent in the pretreatment step.
  • a substance that accelerates the solvolysis reaction can be used again as a solvent, and the solvolysis reaction can be advanced more efficiently, and more substances serving as hydrocarbon raw materials can be used in the fluid catalytic decomposition step.
  • gas, light oil and water may be recovered and used for other applications. Thereby, resources contained in biomass can be used more effectively.
  • the water content of the reaction system can be adjusted to an appropriate amount.
  • the hydrolysis reaction can be advanced by the water contained in the biomass without adding water to the reaction system, so in the pretreatment process of the present invention, at least the biomass and the solvent And solvolysis, and may not add water. That is, in the pretreatment process of the present invention, the solvolysis reaction can be advanced without requiring a large amount of water.
  • water it is preferable that 5% or more is contained in the reaction system. By containing water of 5% or more in the reaction system, the liquefaction reaction of biomass can be efficiently advanced in the pretreatment step.
  • the dissociation of the acid catalyst proceeds to accelerate the solvolysis reaction, and depending on the raw material, the effect can be enjoyed.
  • biocrude is repeatedly used in addition to or in place of the oxygen-containing aromatic compound or organic acid, there is no water accumulated in the reaction system at the start of the operation, the type of biomass, Water may be added to the solvent of the pretreatment step depending on the condition and the like. By containing water, it is possible to advance the hydrolysis of the biomass and to promote the acid dissociation of the organic acid.
  • water may not be added to the solvent of the pretreatment process.
  • the oxygen-containing aromatic compound itself can be used as a solvent.
  • the pretreatment step is preferably performed at 160 ° C. or higher. If the temperature is too low, the solvolysis reaction may not proceed and the carbon yield of the liquid product (biocrude) may be low. Moreover, it is preferable to perform a pre-processing process at 290 degrees C or less. If the temperature is too high, the thermal decomposition reaction proceeds to form carbon monoxide (CO) and carbon dioxide (CO 2 ), and coking also proceeds, which may cause loss of carbon as a gas or solid. From this, by appropriately setting the temperature conditions of the pretreatment process, the solvolysis reaction can be advanced, and the formation of carbon monoxide and carbon dioxide can be suppressed.
  • CO carbon monoxide
  • CO 2 carbon dioxide
  • the biomass to be subjected to the pretreatment step is preferably pre-crushed. Since the specific surface area of the solid particles is increased by being crushed, the solvolysis reaction proceeds more efficiently even in the same treatment time in the pretreatment step, and the yield of the biocrude obtained by the pretreatment step is improved. be able to.
  • the degree of pulverization may be appropriately set in consideration of the cost of pulverization and the cost of solvolysis.
  • hydrocarbon is produced by performing fluid catalytic cracking using biocrude and a hydrogen donor as raw materials.
  • the hydrogen donor in the fluid catalytic cracking process of the present invention includes substances capable of donating hydrogen in the fluid catalytic cracking process, and such materials.
  • Organic hydrogen donors have high H / C (the ratio of hydrogen to carbon in the compound), and the decomposition reaction proceeds easily in the fluid catalytic cracking reaction, and an organic that can donate hydrogen due to the progressing hydrogen transfer reaction at the same time It is a compound and, for example, heavy oil represented by vacuum gas oil and atmospheric residual oil can be used.
  • a linear alkane substituent is developed in a polycyclic aromatic such as alkyl tetralin or alkyl naphthalene (for example, the following compound 1), or a linear alkane structure represented by hexadecane or eicosane (for example, Of the compound 2), and includes such substances, and those substances.
  • a polycyclic aromatic such as alkyl tetralin or alkyl naphthalene (for example, the following compound 1)
  • a linear alkane structure represented by hexadecane or eicosane for example, Of the compound 2
  • a zeolite or amorphous silica-alumina having appropriate acid properties can be used as a catalyst, and in the case of zeolite, particularly large pores among zeolites in consideration of the molecular size of the raw material
  • the FAU type zeolite which has is preferably used.
  • hydrogen contained in a hydrogen donor is hydroxyl group (-OH), ether bond (-O-), or carboxyl group (Bio-crude). It is delivered to an oxygen-containing component having a structure such as —COOH), and hydrodeoxygenation proceeds to produce water.
  • the hydrocarbon production apparatus 100 is used in a fluid catalytic cracking process, and comprises a raw material storage tank 10 for storing raw materials, and a raw material supply pipe 20 serving as a raw material supply means for supplying raw materials to a riser reaction pipe 30 described later. , Distillation of the hydrocarbon obtained in the riser reaction tube 30, which is a reactor in which fluid catalytic cracking is performed, the regeneration tower 40 for regenerating the catalyst to which coke is attached, and the riser reaction tube 30, and fractionated to each component And a distillation column 50.
  • a valve 21 for adjusting the supply amount of the raw material is provided between the raw material supply pipe 20 and the riser reaction pipe 30.
  • the raw material biocrude and the hydrogen donor are mixed in advance and stored in the raw material storage tank 10 as a raw material slurry.
  • Fluid catalytic cracking is one of the petroleum refining techniques, and is also referred to as a FCC (Fluid Catalytic Cracking) process.
  • the fluid catalytic cracking reaction is roughly divided into a reaction system (cracking of raw materials and catalyst regeneration) and a separation and purification system of cracked products.
  • the reaction system the raw material and the vapor are supplied to the riser reaction tube 30, and the raw material is made into fine powder of zeolite or amorphous silica-alumina having an appropriate acid property at a temperature of about 450 ° C. to 650 ° C. It is decomposed in contact with a finely powdered solid acid catalyst (indicated by white circles (() in FIG. 2).
  • a heavy oil which is a hydrogen donor is decomposed at an acid point which is an active point dispersed in micropores or mesopores of a solid acid catalyst, and an olefin is produced via an intermediate carbenium ion. Furthermore, as a cyclization reaction or a hydrogen transfer reaction proceeds, the oxygen in the compound contained in the biocrude is removed as water and the decomposition proceeds. Since coke is formed on the catalyst in the decomposition reaction of the raw material, the catalyst on which coke has adhered after the reaction (indicated by black circles ( ⁇ ) in FIG. 2, the caulking catalyst) is 600 ° C. to 800 ° C. in the regenerator 40.
  • the catalyst is burned at a high temperature to remove coke and is regenerated and supplied again to the riser reaction tube 30 as a regenerated catalyst (indicated by white circles (() in FIG. 2).
  • a regenerated catalyst indicated by white circles (() in FIG. 2).
  • air is sent from the lower part of the regeneration tower 40, and carbon monoxide, carbon dioxide and water are released from the upper part of the regeneration tower 40 along with the combustion of coke.
  • part of the regenerated catalyst is withdrawn and fresh catalyst is replenished.
  • the reaction system of the fluid catalytic cracking reaction proceeds.
  • the reactant obtained in the riser reaction tube 30 is sent to the distillation column 50 and fractionated for each component.
  • Light fraction such as propylene, butene or gasoline from the top of distillation column 50, light cycle oil (LCO) from middle, middle fraction such as light oil from middle, heavy cycle oil (HCO) from bottom, or Heavy fractions such as slurry oil (CSO) are obtained.
  • LCO light cycle oil
  • HCO heavy cycle oil
  • CSO slurry oil
  • the deoxygenation reaction and the cracking reaction of the biocrude proceed by redistribution of hydrogen in the raw material, and a high energy fuel can be obtained.
  • the fluid catalytic cracking process is not a reaction process in a fixed bed but a reaction process composed of a dilute fluidized bed, even if a small amount of solid remains in the pretreatment process, the reactor is clogged, etc. The operation can be continued without causing any defect.
  • the hydrocarbon manufacturing apparatus 200 includes a raw material storage tank 210 for storing raw materials, a raw material supply pipe 220 serving as a raw material supply means for supplying raw materials to a riser reaction pipe 30 described later, and a riser reaction pipe 30 for performing fluid catalytic cracking. And a regeneration tower 40 for regenerating the catalyst to which coke has been attached, and a distillation tower 50 for distilling the hydrocarbon obtained in the riser reaction tube 30 and fractionating the components into components.
  • the raw material storage tank 210 is configured to have a biocrude storage tank 211 and a hydrogen donor storage tank 212.
  • the biocrude and the hydrogen donor are combined. Are stored in separate storage tanks.
  • the raw material supply pipe 220 includes a biocrude supply pipe 222 connected to the biocrude storage tank 211, a hydrogen donor supply pipe 223 connected to the hydrogen donor storage tank 212, a biocrude supply pipe 222, and hydrogen donating.
  • a mixed supply pipe 224 joined to the body supply pipe 223 and connected to the riser reaction pipe 30. That is, in the hydrocarbon production apparatus 200 of the present embodiment, the biocrude and the hydrogen donor are separately stored, mixed in the feed pipe, and supplied to the riser reaction pipe 30.
  • a valve 221 is provided between the mixing supply pipe 224 and the riser reaction pipe 30 to adjust the supply amount of the raw material.
  • the biocrude storage tank 211 is provided upstream of the hydrogen donor storage tank 212, but the hydrogen donor storage tank 212 may be provided upstream.
  • the hydrocarbon manufacturing apparatus 300 is a reactor in which fluid catalytic cracking is performed, and a raw material storage tank 310 for storing raw materials, a raw material supply pipe 320 which is a raw material supply means for supplying raw materials to a riser reaction pipe 30 described later.
  • the raw material storage tank 310 is configured to include a biocrude storage tank 311 and a hydrogen donor storage tank 312.
  • the biocrude and the hydrogen donor are combined.
  • the raw material supply pipe 320 is a biocrude supply pipe 322 (biocrude supply part) connected to the biocrude storage tank 311, and a hydrogen donor supply pipe 323 (hydrogen donor connected to the hydrogen donor storage tank 312).
  • a supply unit that is, in the hydrocarbon production apparatus 300 of the present embodiment, the biocrude and the hydrogen donor are separately stored, and are supplied to the riser reaction pipe 30 by the separate supply pipes.
  • a valve 321 a for adjusting the supply amount of biocrude is provided between the biocrude supply pipe 322 and the riser reaction pipe 30, and hydrogen is provided between the hydrogen donor supply pipe 323 and the riser reaction pipe 30.
  • a valve 321 b is provided to adjust the amount of donor supply.
  • biocrude and hydrogen donor may be separately supplied.
  • the production apparatus used in the fluid catalytic cracking step of the present invention separately has a biocrude supply unit for supplying biocrude and a hydrogen donor supply unit for supplying a hydrogen donor as raw material supply means. It may be
  • the biomass is stabilized in the hydrogen donor slurry.
  • it can be configured as the hydrocarbon production apparatus 100 of the first embodiment or the hydrocarbon production apparatus 200 of the second embodiment. That is, as in the hydrocarbon production apparatus 100 shown in FIG. 2, the raw material slurry obtained by mixing the biocrude and the hydrogen donor is supplied to the lower part of the riser reaction tube 30 where the fluid catalytic cracking reaction is performed.
  • the biocrude and the hydrogen donor are stored in separate tanks and mixed in the raw material supply pipe 220 (mixing supply pipe 224). The raw material can be configured to be supplied to the riser reaction tube 30.
  • the solvent in the biocrude in which the biomass is dispersed may be back-extracted to the hydrogen donor to precipitate the biomass.
  • the supply nozzle may be clogged.
  • the biocrude and the hydrogen donor are stored in separate tanks, and separate supply pipes up to the riser reaction pipe 30 (biocrude (biocrude) It is preferable to be configured to be supplied through the supply pipe 322 and the hydrogen donor supply pipe 323).
  • the biomass can be prevented from being precipitated since the biocrude and the hydrogen donor are not mixed in the supply pipe. Thereby, the clogging of the raw material supply pipe and the supply nozzle can be prevented.
  • the catalyst which is solid particles, flows at a high flow rate, and clogging does not occur.
  • how to configure a hydrocarbon production apparatus can be selected according to the properties of the raw material crude crude and the hydrogen donor.
  • the biomass is pretreated by solvolysis at a lower temperature than thermal decomposition, subcritical water treatment or supercritical water treatment.
  • decomposition reaction proceeds, when it is catalytically decomposed with a hydrogen donor in the subsequent fluid catalytic cracking step, deoxygenation is carried out by hydrodeoxygenation reaction, and a large amount of oxygen is removed as water, so that monooxidation The formation of carbon and carbon dioxide is suppressed, and the loss of carbon resources can be reduced.
  • hydrocarbons can be efficiently produced from biomass.
  • a monocyclic aromatic compound is produced by hydrogenolysis of a polycyclic aromatic compound that constitutes biomass.
  • part of the biomass may be precipitated as a solid.
  • the hydrocarbon production apparatus of the present invention since the biocrude and the hydrogen donor are separately supplied, the deposition of the biomass is prevented without the biocrude and the hydrogen donor being mixed in the feed pipe. be able to.
  • the hydrocarbon production system of the present invention uses the above-mentioned hydrocarbon production method, and may be carried out in a place where the pretreatment step and the fluid catalytic cracking step are in proximity, or each other
  • the biocrude obtained by the pretreatment step may be transported at a remote place and supplied to the fluid catalytic cracking step.
  • Whether the pretreatment step and the fluid catalytic cracking step are performed in close proximity to each other or in locations separated from each other can be appropriately selected depending on the biomass production site, the location conditions of equipment, and the like.
  • the equipment used for the fluid catalytic cracking process is provided in the forest area, and the pretreatment process and the fluid catalytic cracking process Can be done at a distance from each other.
  • the biocrude obtained in the pretreatment process can be transported by a tank lorry, a truck or the like.
  • the biocrude may be transported by a transport pipe. The transport of the biocrude may be performed not only by the vehicle transport but also by other transport means in consideration of the transport cost.
  • a place separated from each other refers to a batch such as a tank lorry or a truck instead of transporting the reactant by directly connecting the facility used in the pretreatment process and the facility used in the fluid catalytic cracking process with piping or the like. It indicates that they are separated to the extent of being transported via transport. If the equipment used for the pretreatment process is provided in a place where tank lorries, trucks, etc. can not pass, as described above, transport the reactant through transport pipes etc. to the passable place, The reactants may then be transported by batch transport to the site where equipment is used for the fluid catalytic cracking process.
  • transporting the biocrude to a facility that performs the fluid catalytic cracking step is more than transporting the bulkier biomass than the biocrude. Transportation costs can be reduced.
  • the pretreatment step may be performed at the biomass production site.
  • the operation of the pretreatment process may be performed at a site near mountain where a raw wood as a material of the woody biomass is present.
  • woody biomass is bulkier than biocrude
  • transportation of woody biomass from a production area to a hydrocarbon production facility increases transportation costs.
  • woody biomass that is bulkier than biocrude becomes liquid biocrude, and can be transported by a tank lorry or the like. From this, the transportation cost can be lower than that for transporting woody biomass that is bulkier than biocrude as it is.
  • a ratio shows a mass ratio unless there is particular notice.
  • simulated cedar was examined as a model material of cedar.
  • the “simulated cedar” in the present example is a composition in which cellulose and lignin are mixed in a ratio of 6: 4 to simulate the composition of cedar.
  • the composition of lignin is about 30% in general cedar (Harokuchi, et al. (1993) “Chemistry of wood” by Bunneijido), but it is easy to understand the decomposition of lignin in fluid catalytic decomposition.
  • the composition was increased to 40%.
  • cellulose and hemicellulose do not differ greatly in decomposition characteristics structurally (cellulose + hemicellulose)
  • the composition was replaced with cellulose to make 60%.
  • thermogravimetric analysis was performed. Sugi chip and simulated Japanese cedar were used as materials. For measurement, the temperature was raised from room temperature to 800 ° C. at 10 K / min under a nitrogen atmosphere (50 ml / min) using a thermogravimetric analyzer (manufactured by Shimadzu Corporation, TGA-51). The results of thermogravimetric analysis are shown in FIG. The ordinate represents the residual ratio (%, a value obtained by calculating the weight ratio of the residue to the weight of the sample subjected to thermogravimetric analysis), and the abscissa represents the temperature. The broken line in the figure indicates the cedar chip, and the solid line indicates the analysis result of simulated cedar.
  • the cedar chips used in Example 1 were ground beforehand using cedar chips having an average particle diameter of 100 ⁇ m or more using a planetary ball mill (Fritchu Japan, model number P-7), and then sieved to 75 ⁇ m and 106 ⁇ m. It is a Sugi chip which entered between the sieves. That is, a cedar chip having an average particle diameter of about 80 ⁇ m was used as a raw material. The same sieving was performed on the simulated Japanese cedar used in Example 2, and the simulated Japanese cedar inserted between 75 ⁇ m and 106 ⁇ m sieves was used as the valve amount.
  • the above materials were mixed and subjected to an autoclave (MM Labotech, MMJ-500, internal volume 430 ml).
  • the reaction conditions were 200 ° C., 1 hour, and then natural cooling.
  • the generated gas product (gas) was collected by a gas bag and analyzed using gas chromatography (manufactured by Shimadzu Corporation, GC-8A). The detection was performed by a thermal conductivity detector.
  • liquid products and solid products are described in no. Separation by vacuum filtration using 5 C filter paper. After filtration, the liquid product remaining in the solid product or in the reaction vessel was washed with acetone and extracted. The acetone extract was evaporated at a temperature of 60 ° C. to evaporate acetone, and the residue also became a liquid product. Further, the solid product after acetone washing was subjected to vacuum drying at room temperature overnight using a desiccator and an aspirator (manufactured by Tokyo Rika Kikai, model number A-3S), and then the mass was measured. The carbon fraction in the dried solid product was measured using an NC analyzer (manufactured by Sumika Analysis Center, SUMIGRAPH NC-1000).
  • the carbon mass in Japanese cedar or simulated Japanese cedar was measured by an NC analyzer (manufactured by Sumika Analysis Center, model number SUMIGRAPH NC-1000).
  • NC analyzer manufactured by Sumika Analysis Center, model number SUMIGRAPH NC-1000.
  • carbon contained in the produced gas and carbon in the solid were all derived from cedar or simulated cedar. Therefore, the carbon mass in the gaseous product with respect to the carbon mass in the raw material cedar or simulated cedar as the gaseous carbon yield, and the carbon mass in the solid product with respect to the carbon mass in the raw cedar or simulated cedar as the solid carbon yield Calculated.
  • the liquid carbon yield was calculated by subtracting the gaseous carbon yield and the solid carbon yield from 100%.
  • the gaseous carbon yield, liquid carbon yield, and solid carbon yield shown below are based on carbon in the raw material cedar or simulated cedar, and the conversion from solvents (guaiacol, water, acetic acid) is low.
  • the conversion from the solvent is not considered because it is considered that the carbon yield is not greatly affected.
  • Example 3 The following were used as materials. Sugi chip 10% Guaiacol 85% Water 5% The same operation as in Example 1 was performed except that acetic acid was changed to 0% (no addition).
  • Examples 4 to 6 The following were used as materials. Simulated cedar 10% Guaial 75-85% Water 5% Acetic acid 0-10% Acetic acid is respectively 0% (Example 4, no addition), 5% (Example 5), 10% (Example 6), and guaiacol is 85% (Example 4), 80% (Example 5), respectively. The same operation as in Example 2 was performed except that 75% (Example 6) was used.
  • Example 7 The following were used as materials. Simulated cedar 10% Guaiacol 85% Water 5% In addition, the same operation as in Example 2 was performed except that the reaction temperature was 150 ° C. (Example 7), 250 ° C. (Example 8), and 300 ° C. (Example 9) as the reaction conditions.
  • Example 10 The following were used as materials. Simulated cedar 10% Guaia call 74 to 89% Water 0 to 15% Acetic acid 1% Using simulated Japanese cedar as the material, the moisture content is made 0% (Example 10, no addition), 10% (Example 11), 15% (Example 12), 89% (Example 10), 79% of guaiacol (Example 11) The same operation as in Example 2 was performed except that 74% (Example 12) was used.
  • Example 13 Using the liquid product (biocrude) obtained in Example 2 as a solvent, a second pretreatment step was performed under the same conditions as in Example 2 with the following composition. Simulated cedar 10% Liquid product obtained in the pretreatment reaction of Example 2 84% Water 5% Acetic acid 1%
  • the liquid product obtained in the above second pre-treatment step is used as a solvent, and the above composition (10% simulated cedar, 84% liquid product obtained in the second pre-treatment step, 5% water, acetic acid 1
  • the third pretreatment step was performed under the same conditions as in Example 2 in%). Furthermore, the liquid product obtained in the third pretreatment step is used as a solvent, and the above composition (10% simulated cedar, 84% liquid product obtained in the third pretreatment step, 5% water, acetic acid 1
  • the fourth pretreatment step was performed under the same conditions as in Example 2 in%). The liquid, gas and solid after the fourth pretreatment step were recovered by the same method as in Example 2 to calculate the carbon yield.
  • Example 14 The same operation as in Example 1 was carried out except that the cedar chips of the material were not crushed by a planetary ball mill.
  • Example 1 The conditions were the same as in Example 1 except that 10% of cedar chip was used as the material, guaiacol was 0% (no addition), acetic acid was 1%, and water was 89%. As a result, a large amount of solid remained, and almost no liquid product was obtained. From this, it is difficult to obtain sufficient biocrude under the condition that no solvent containing oxygenated aromatic compound is added, and the obtained product contains a large amount of solid matter, and therefore fluid contact It has been shown to be difficult to provide for the degradation step.
  • Example 1 using Sugi and Example 2 using simulated Sugi the carbon yields of the liquid product, the gas product, and the solid product were almost the same. . From the results of thermogravimetric analysis and the results of Examples 1 and 2, it was shown that simulated cedar is useful as a model substance of cedar.
  • the reaction temperature of 200 ° C. (Example 2) has a higher carbon yield of the liquid product and the higher temperature than the reaction temperature of 150 ° C. (Example 7).
  • the carbon yield of the liquid product decreased.
  • the carbon yield of the liquid product was the highest. Comparing the carbon yields of non-liquid products, the carbon yield of solid products is the highest at a reaction temperature of 150 ° C, and the carbon yield of gaseous products is that of reaction temperatures of 250 ° C and 300 ° C. It got higher.
  • the carbon yield of the liquid product is higher when the added amount of water is 5% (Example 2) than when no water is added (Example 10), and the added amount of water is 10% Also in (Example 11) and 15% (Example 12), the carbon yield of the liquid product was almost the same and showed a high value. That is, it was confirmed that the carbon yield in the liquid product is higher when water is added to the reaction system. This is considered to be because the addition of water to the reaction system facilitates the progress of the hydrolysis reaction. Further, it was also confirmed from Examples 2 and 10 to 12 that a small amount of water of about 15% or less is sufficient for the reaction system. Generally, considering the amount of water contained in biomass, when using about 10% of the reaction system as the material of the pretreatment process, the water contained in the reaction system will be about 5% or more. Was considered to proceed even if water was not further added to the reaction system.
  • the carbon yield in the liquid product (Biocrude) became a high value of 91.5% in Example 2 where the liquid product (biocrude) was repeatedly subjected to the pretreatment step of Example 2 and the liquid product being reused as a solvent. . From this, it was shown that carbon can be efficiently recovered to the solvolysis liquid product of biomass even if the liquid product is added as a solvent.
  • Example 14 From the results of Example 1 and Example 14, it was confirmed that most of carbon was recovered as a liquid product under both conditions. Furthermore, since the carbon yield of the liquid product was higher in Example 1 in which the sugi chip was crushed than in Example 14 in which the sugi chip was not crushed, the biomass was finely ground to form a liquid even at the same treatment time. It has been shown that carbon can be efficiently recovered by waste.
  • Example 15 composition analysis of the biocrude obtained by the pretreatment process was performed. The following materials were used. In addition, the mass ratio shown below shall show preparation density
  • the liquid product was also subjected to GC-MS analysis to confirm the compounds contained in the liquid product.
  • GC-MS analysis was performed with Rxi-1 ms (Restec), a vaporization chamber temperature of 300 ° C., an interface temperature of 330 ° C., and a column temperature of 35-330 ° C.
  • Example 16 The same operation as in Example 15 was performed except that acetic acid was 0% (no addition) and guaiacol was 65%. The results of the GPC measurement are shown in FIG. In FIG. 6, the result of Example 16 is indicated by a broken line.
  • the liquid products of Examples 15 and 16 mainly contain guaiacol as a single ring oxygen-containing aromatic compound, and in addition, catechol, cresol, dimethylphenol, methoxyphenol And benzenediol, etc., and the content of the single ring oxygen-containing aromatic compound was 63% by mass.
  • biomass can be decomposed in the pretreatment step of the present invention to efficiently recover a carbon product as a liquid product, ie, a biocrude.
  • Example 17 The biocrude obtained in Example 1 was subjected to a fluid catalytic cracking step.
  • Industrial RFCC equilibrium catalyst (UCS value (unit lattice constant) 24.27 ⁇ (2.427 nm) containing FAU type zeolite as a catalyst, using a fixed bed flow reactor according to ASTM D3907-92 as the reactor.
  • the experimental method was as follows. It was carried out according to the method defined in ASTM D 5154-10 In Example 17, eicosane was used as a hydrogen donor.
  • the resulting product was analyzed as follows.
  • the reaction products passed through the catalyst bath were cooled in an ice bath and separated after gas-liquid separation. Gas recovery was carried out by water replacement.
  • Hydrogen, carbon monoxide and carbon dioxide contained in the gaseous product are analyzed by gas chromatography with thermal conductivity detector (GC-8A, manufactured by Shimadzu Corporation), and hydrocarbon is with hydrogen flame ionization detector.
  • Gas chromatography (manufactured by Shimadzu Corporation, GC-2014) was analyzed.
  • Hydrocarbons and oxygenated compounds in the liquid product can be detected using a gas chromatography with hydrogen flame ionization detector (GC-2014, manufactured by Shimadzu Corporation) and a gas chromatograph mass spectrometer (GCMS-QP2010 Plus, manufactured by Shimadzu Corporation) analyzed.
  • the amount of coke produced was determined from the weight change of the catalyst tank before and after the reaction, and the components were analyzed using an NC analyzer (Sumigraph NC-1000, manufactured by Sumika Chemical Analysis Center).
  • NC analyzer Sudigraph NC-1000, manufactured by Sumika Chemical Analysis Center
  • Example 18 The same operation as in Example 17 was performed except that a catalyst having a different UCS value from the industrial RFCC equilibrium catalyst of Example 17 was used.
  • the catalyst had a UCS value of 24.30 ⁇ (2.430 nm, Example 18), 24.35 ⁇ (2.435 nm, Example 19), 24.40 ⁇ (2.440 nm, Example 20).
  • Example 2 The same procedure as in Example 17 was performed, except that no hydrogen donor was added, that is, only biocrude was subjected to fluid catalytic cracking. As a result, the tube was clogged, and a large amount of coke was formed to precipitate carbon, and a small amount of hydrocarbon was formed. In addition, since only a biocrude does not form carbenium ions and there is no hydrogen donor, hydrodeoxygenation reaction and hydrogenolysis do not proceed by hydrogen transfer reaction, and therefore, almost no hydrocarbons are formed. it is conceivable that.
  • the reaction products (Examples 17 to 20) in the fluid catalytic cracking step contain gaseous hydrocarbons, and paraffins, olefins, aromatic hydrocarbons as liquid hydrocarbons, and contain oxygen As a compound, methylphenols were included. Therefore, it has been confirmed that hydrocarbons can be produced by subjecting a cedar-derived biocrude and a hydrogen donor, eicosane, to fluid catalytic cracking. In addition, the higher the UCS value, that is, the higher the catalytic activity, the higher the amount of hydrocarbons produced. However, in Example 20, which has the highest catalytic activity, not only the hydrocarbons but also the amount of coke are high. It was confirmed that
  • oxygen contained in the biocrude subjected to the fluid catalytic cracking step is contained in the reaction product as an oxygen-containing compound, carbon monoxide (CO), carbon dioxide (CO 2 ), or water.
  • an oxygen-containing compound carbon monoxide (CO), carbon dioxide (CO 2 ), or water.
  • CO carbon monoxide
  • CO 2 carbon dioxide
  • water water
  • the hydrodeoxygenation reaction proceeds in which hydrogen is transferred from the hydrogen donor, eicosane, to the oxygen-containing compound contained in the biocrude to form water. Therefore, it is presumed that the production of hydrocarbons by subjecting the biocrude and the hydrogen donor to the fluid catalytic cracking step is due to the hydrodeoxygenation reaction of the oxygen-containing compound contained in the biocrude.
  • Examples 1 to 20 which is an exemplary embodiment of the present invention, most of carbon resources are recovered from biomass into biocrude, and loss of carbon resources is reduced, and fluid catalytic cracking is performed. It has been shown that hydrocarbons can be produced.

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Abstract

Le problème abordé par la présente invention est de pourvoir à : un procédé de production d'hydrocarbures qui permet de produire efficacement un hydrocarbure à l'aide d'une biomasse, supprimant ainsi un gaspillage des ressources carbonées ; un appareil et un système de production associés ; et un procédé de production de bio-brut. La solution selon la présente invention est caractérisée en ce qu'elle comprend : une étape de prétraitement pour obtenir un bio-brut par mise en œuvre d'une solvolyse par mélange d'au moins une biomasse et d'un solvant ; et une étape de craquage catalytique de fluide pour effectuer un craquage catalytique de fluide en utilisant le bio-brut obtenu à l'étape de prétraitement et un donneur d'hydrogène à titre de matériaux de départ.
PCT/JP2018/004023 2017-02-07 2018-02-06 Procédé de production d'hydrocarbures, appareil et système de production associés, et procédé de production de bio-brut Ceased WO2018147281A1 (fr)

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WO2020026883A1 (fr) * 2018-08-03 2020-02-06 国立大学法人信州大学 Procédé de production d'hydrocarbure et procédé de production de biobrut
EP3741828A1 (fr) * 2019-05-23 2020-11-25 Vertoro B.V. Procédé de craquage catalytique fluide d'huile de lignine brute (clo)

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JP2006063310A (ja) * 2004-07-27 2006-03-09 Univ Nihon 木質バイオマス由来の液体燃料の製造方法及び製造装置
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JPS61225280A (ja) * 1985-03-30 1986-10-07 Agency Of Ind Science & Technol セルロ−ス含有バイオマスの液化方法
JPH11279563A (ja) * 1998-03-30 1999-10-12 Hisaka Works Ltd 液化方法
JP2006063310A (ja) * 2004-07-27 2006-03-09 Univ Nihon 木質バイオマス由来の液体燃料の製造方法及び製造装置
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020026883A1 (fr) * 2018-08-03 2020-02-06 国立大学法人信州大学 Procédé de production d'hydrocarbure et procédé de production de biobrut
EP3741828A1 (fr) * 2019-05-23 2020-11-25 Vertoro B.V. Procédé de craquage catalytique fluide d'huile de lignine brute (clo)
WO2020234369A1 (fr) * 2019-05-23 2020-11-26 Vertoro B.V. Procédé de craquage catalytique à lit fluidisé de pétrole brut de lignine (clo)
CN113874474A (zh) * 2019-05-23 2021-12-31 沃特罗有限公司 粗木质素油（clo）的流化催化裂化工艺
CN113874474B (zh) * 2019-05-23 2022-08-26 沃特罗有限公司 粗木质素油（clo）的流化催化裂化工艺
US11518946B2 (en) 2019-05-23 2022-12-06 Vertoro B.V. Fluid catalytic cracking process of crude lignin oil (CLO)

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