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WO2010050186A1 - Procédé et appareil pour la fabrication de carburant biodiesel, et catalyseur de décomposition pour la décarboxylation de graisses utilisé dans le procédé - Google Patents

Procédé et appareil pour la fabrication de carburant biodiesel, et catalyseur de décomposition pour la décarboxylation de graisses utilisé dans le procédé Download PDF

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Publication number
WO2010050186A1
WO2010050186A1 PCT/JP2009/005669 JP2009005669W WO2010050186A1 WO 2010050186 A1 WO2010050186 A1 WO 2010050186A1 JP 2009005669 W JP2009005669 W JP 2009005669W WO 2010050186 A1 WO2010050186 A1 WO 2010050186A1
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WIPO (PCT)
Prior art keywords
catalyst
oil
fat
decarboxylation
biodiesel fuel
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Ceased
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PCT/JP2009/005669
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English (en)
Japanese (ja)
Inventor
藤元薫
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Kitakyushu Foundation for Advancement of Industry Science and Technology
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Kitakyushu Foundation for Advancement of Industry Science and Technology
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Application filed by Kitakyushu Foundation for Advancement of Industry Science and Technology filed Critical Kitakyushu Foundation for Advancement of Industry Science and Technology
Priority to KR1020117011091A priority Critical patent/KR101391221B1/ko
Priority to CN200980143059.3A priority patent/CN102203218B/zh
Priority to JP2010535661A priority patent/JP5353893B2/ja
Publication of WO2010050186A1 publication Critical patent/WO2010050186A1/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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/14—Silica and magnesia
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 efficiently producing a high-quality biodiesel fuel from fats and oils and a raw material for oil extraction, and a production apparatus therefor.
  • the present invention also relates to an oil and fat decarboxylation catalyst having excellent efficiency used in the production method and production apparatus.
  • Biodiesel fuel is an extremely important technology for reducing the emissions of greenhouse gases and air pollutants and for building an energy recycling society.
  • a fatty acid methyl ester (FAME) method has been widely introduced.
  • a diesel engine fuel is obtained by a transesterification reaction between a raw oil and fat and a lower alcohol (subsidiary raw material) (Non-patent Document 1).
  • Patent Document 1 discloses “a method for producing a fatty acid alkyl ester by reacting oil and fat with a lower alcohol in the presence of a calcium-based solid catalyst”. Yes.
  • Patent Document 2 states that “in the process A and the process A in which the raw oil and fat are reacted with alcohol in the presence of a solid acid catalyst, and the free fatty acid present in the raw oil and fat is converted into a fatty acid alkyl ester.
  • Step B for removing moisture from the obtained reaction mixture, and the liquid obtained in Step B and the alcohol are reacted in the presence of a solid base catalyst to transesterify triacylglyceride, which is the main component of the raw oil and fat.
  • a process C for converting it into a fatty acid alkyl ester, and a method for producing a biodiesel oil.
  • Non-patent Document 1 As another method for producing biodiesel fuel, a hydrotreatment method described in (Non-patent Document 1) is known.
  • the hydrotreating method is a method that applies the hydrotreating technology that is a conventional petroleum refining process, and by hydrotreating under high pressure such as 10 MPa, oxygen in the raw material fat is mainly removed as water and lightened. A unsaturated oil-derived unsaturated bond is saturated to obtain a hydrocarbon oil having a boiling point range of light oil.
  • Patent Document 3 states that “a fluidized catalytic cracking apparatus having a reaction zone, a separation zone, a stripping zone and a regeneration zone is used, and a feedstock containing biomass is added in a reaction zone having an outlet temperature of 480 to 540 ° C.
  • Patent Document 4 states that “a solid acid catalyst is heated to a temperature range of 350 to 450 ° C. in a reaction vessel, and liquid oil is contacted with the solid acid catalyst to remove oxygen-containing components from the oil. And a method for catalytic cracking of fats and oils that synthesizes a hydrocarbon mixture mainly composed of olefins and paraffins having 9 to 24 carbon atoms.
  • Non-Patent Document 1 Patent Document 1
  • Patent Document 2 requires a large amount of lower alcohol, and thus has a problem of requiring high running costs.
  • impurities such as dienes, hydroxyl groups, peroxides, etc.
  • impurities in the raw oil and fat are likely to remain in the product oil, so that the product oil is unstable to air and has a problem of lacking storage stability. It was.
  • a process of adsorbing impurities such as peroxide by using an adsorbent such as activated clay and removing it from the produced oil is required, which has a problem that the processing process becomes complicated.
  • Patent Document 2 discloses a technique for removing free fatty acids from raw material fats and oils by treating the free fatty acids in the presence of a solid acid catalyst as a previous step. Is disclosed. The technique disclosed in Patent Document 2 requires a plurality of steps in order to treat a free fatty acid in the presence of a solid acid catalyst in Step A and then react the alcohol in the presence of a solid base catalyst in Step C. The problem is that the processing steps become complicated. (5) The hydrotreating method described in Non-Patent Document 1 has a problem that the resulting hydrocarbon oil has a high freezing point of + 20 ° C. and poor fluidity.
  • Patent Document 3 is a technique for obtaining a gasoline base material or the like from fats and oils using a fluid catalytic cracking apparatus having a reaction zone, a separation zone, a stripping zone and a regeneration zone. In this technology, it is necessary to transport the collected raw material fats and oils to a site where a large-scale fluid catalytic cracking apparatus is present for processing.
  • plant-based biomass which is a raw material for fats and oils
  • plant-based biomass which is a raw material for fats and oils
  • a fluid catalytic cracking device because it is a distributed production resource based on a vast land.
  • constructing a large-scale fluid catalytic cracker at the plant biomass production base simply for the purpose of producing biodiesel fuel has problems such as increased running costs. Had.
  • Patent Document 4 is a fuel for a diesel engine mainly comprising an olefin having a carbon number of 9 to 24 and paraffin as a main component from oil and fat by contacting the heated solid acid catalyst with oil and fat by catalytic cracking. This is a technique for obtaining a hydrocarbon mixture. Although a solid acid catalyst is used, the reaction temperature is lower by using a reaction temperature lower than that of Patent Document 3, and the carbon-to-carbon cleavage ratio of the alkyl group is low.
  • the present invention solves the above-mentioned conventional problems, does not require alcohol (subsidiary raw material), does not by-produce glycerin, and is a product of impurities such as dienes, hydroxyl groups, and peroxides in the raw oil and fat Residual in the interior, low coke production, low pour point, and impurities such as carboxylic acids (free fatty acids) are hardly produced as a by-product.
  • impurities such as dienes, hydroxyl groups, and peroxides in the raw oil and fat Residual in the interior, low coke production, low pour point, and impurities such as carboxylic acids (free fatty acids) are hardly produced as a by-product.
  • an oil and fat decarboxylation catalyst used in a method for producing biodiesel fuel that can efficiently obtain a good quality biodiesel fuel from fat and oil by advancing the decarboxylation decomposition reaction while suppressing the breakage of the double bond of the oil and fat. For the purpose.
  • the biodiesel fuel production method of the present invention has the following configuration.
  • the oil / fatty acid decarboxylation / decomposition catalyst is brought into contact with the oil / fatty acid decarboxylation / decomposition catalyst in the reaction vessel at 350 ° C. to 475 ° C. ) To produce mainly C 8 -C 24 hydrocarbons.
  • the reaction apparatus can be constructed at a low cost at a plant biomass production base or a required place, and a distributed energy supply system that supplies necessary energy at a required place can be constructed.
  • the fat is liquid and hardly evaporates. Therefore, only the product is led out as gas from the reaction vessel.
  • fats and oils hardly thermally decompose.
  • oils and fats include rapeseed oil, palm oil, palm kernel oil, olive oil, soybean oil, sesame oil, castor oil, jatropha oil, corn oil and other vegetable oils, terpenes, fish oil, pork fat, and beef tallow Oils and fats collected from certain types of algae such as animal fats and the like, and mixtures thereof can be used.
  • waste cooking oils such as tempura oil, can also be used. Oils and fats such as lard and beef tallow that solidify at room temperature are melted and liquefied by a heated catalyst or preheating, so that the oils and fats can be either liquid or solid. The fats and oils can be reacted by bringing one or more kinds of mixtures into contact with the catalyst.
  • oil / fat can be preheated at a temperature of 475 ° C. or lower before being brought into contact with the catalyst. The reason is to increase the decomposition efficiency by heating quickly after contact with the catalyst.
  • Oils and fats are triacylglycerols (three acyl groups esterified to glycerin), but phospholipids, glycolipids, fatty acids, and the like can also be used as the raw material of the present invention.
  • the oil and fat decarboxylation catalyst is preferably weakly alkaline, neutral, or weakly acidic.
  • at least one of solid catalyst silica, activated carbon, solid base, clay mineral, and alkali-poisoned solid acid is used.
  • the activated carbon include carbides such as granular powder and fiber processed at a high temperature of about 1000 ° C. Many ceramics can also be used as catalysts. More specifically, activated carbon (particularly activated at a high temperature of 500 ° C.
  • alkaline earth metal oxides such as MgO, CaO, SrO, BaO, La 2 O 3 , Th 2 Lanthanoids such as O 3 , oxides of actinides, metal oxides such as ZrO 2 and TiO 2 , metal carbonates such as alkaline earth metals, composite oxides such as SiO 2 —MgO and SiO 2 —CaO, Rb and Cs Zeolite exchanged with alkali metal ions such as alkali metal ions and alkaline earth metal ions, FCC catalyst and FCC waste catalyst partially or completely poisoned by addition of alkali metal compounds and alkaline earth metal compounds, alkalis such as Na and K Na / MgO the metal is deposited, the metal deposited metal oxides, such as K / MgO, KF / Al 2 O 3, LiCO 3 / SiO 2 or the like alkali metal salts of It can be used.
  • alkali metal ions such as MgO, CaO, SrO, BaO, La
  • a mixture or a support (for example, a support in which a solid base is supported on silica, coke, or the like) can also be used.
  • a mineral such as dolomite that becomes a mixture of MgO and CaO when heated can be suitably used.
  • the temperature rise and desorption temperature of ammonia is 50 to 250 ° C. for alumina, 30 to 200 ° C. for silica gel, 200 to 600 ° C. for zeolite, and 0 to 100 ° C. for activated carbon.
  • the FCC catalyst poisoned with Na is 30 to 200 ° C
  • the silicon oxide supporting magnesium oxide is 0 to 60 ° C
  • the activated carbon supporting magnesium oxide is 0 to 70 ° C.
  • Ammonia temperature rise and desorption temperature is higher than 400 ° C, which is a very strong acid catalyst, and it is easy to reduce the molecular weight of the product by cleaving the carbon-carbon bond of the alkyl group in the oil and fat, and attacking the carbon-carbon double bond.
  • the production of coke increases because more aromatics are produced.
  • the yield of the product oil is lowered, and further, the increased coke accelerates the decrease in the activity of the catalyst, the decarboxylation ability is lowered, the production of carboxylic acid is increased, and the quality of the product oil is lowered.
  • a catalyst with a temperature rising / leaving temperature of ammonia of 100 ° C. or less such as activated carbon and activated coke
  • a mixture of fats and oils and mineral oil can be used as a raw material.
  • catalysts such as activated carbon and activated coke hardly reduce the molecular weight of mineral oil.
  • Mineral oil includes atmospheric residual oil obtained by distilling crude oil, vacuum gas oil obtained by further distillation of atmospheric residue under reduced pressure, vacuum residue, hydrotreated oil, or pyrolysis oil, and Of the mixture.
  • generated by decarboxylation decomposition of fats and oils can also be used. These mineral oils can function as an extractant for the oils and fats remaining in the residue and can further increase efficiency.
  • the heating temperature of the oil and fat decarbonation decomposition catalyst is lower than 350 ° C.
  • the progress of the decarbonation decomposition reaction is slowed, and the fats and oils are polymerized and solidified, and the hydrocarbon productivity tends to decrease.
  • the temperature is higher than 475 ° C.
  • the production amount of light gas and coke having 4 or less carbon atoms increases, and the production amount of products mainly composed of olefins and paraffins having 8 to 24 carbon atoms tends to decrease. Therefore, neither is preferable.
  • reaction apparatus for producing biodiesel fuel for example, an apparatus equipped with a reaction vessel in which an oil decarboxylation catalyst is accommodated and a heating device for heating the oil decarboxylation decomposition catalyst in the reaction vessel is used.
  • a reaction vessel a fixed bed method, a fluidized bed method, a rotary kiln method, a stirring method, or the like can be used. Of these, the stirring method is preferable.
  • decomposition products aromatic compounds, etc.
  • decomposition products such as fats and oils polymerize and adhere to the surface of the fat decarbonization decomposition catalyst, and a plurality of fat decarbonization decomposition catalysts are combined by the polymer.
  • the agglomeration in the reaction vessel may result in the inability to operate, but the agglomeration can be prevented mechanically by stirring to prevent agglomeration.
  • the decarbonation process when the fat and oil decarbonization catalyst is heated and the catalyst reaches the reaction temperature, the raw material and fat are introduced into the reaction vessel by spraying, spraying, dripping, spraying, etc., and contacted with the fat and decarbonization catalyst. Let Processing can be performed continuously or batchwise. Oils and fats are decomposed in contact with a heated oil and fat decarboxylation decomposition catalyst, and have a vapor pressure as a combustible gas.
  • the generated combustible gas can be discharged out of the system.
  • the discharged combustible gas is cooled to become biodiesel fuel oil.
  • a water-soluble component can be dissolved in water vapor to obtain a cleaning effect of combustible gas.
  • a catalyst such as CaO
  • the deactivated fat decarboxylation catalyst can also be regenerated as needed in the reaction vessel or after being extracted from the reaction vessel.
  • MgO catalyst
  • MgO after decarboxylation repeatedly contributes to the decomposition of fats and oils.
  • CaO combines with CO 2 of fats and oils in the presence of moisture to decompose the fats and oils to become calcium hydrogen carbonate. Since calcium carbonate is decomposed and decarboxylated at around 300 ° C., CaO after decarboxylation repeatedly contributes to the decomposition of fats and oils.
  • the pressure in the reaction vessel is preferably maintained at atmospheric pressure or positive pressure.
  • Combustible gases such as light oil and kerosene are generated by decarboxylation and decomposition of fats and oils, so if the pressure is negative, air may be introduced into the reaction vessel, and the generated combustible gas may ignite and explode. Because.
  • the liquid space velocity indicating the input amount (volume) per hour with respect to the fat and oil decarboxylation decomposition catalyst (volume) is 0.05 / h to 2.0 / h, preferably 0.8. 3 / h to 1.0 / h is preferably used. If the liquid space velocity is less than 0.05 / h, the treatment efficiency is low, and the product oil becomes light gas due to secondary decomposition, and the yield of lamp / light oil decreases, which is not preferable. On the other hand, if it exceeds 2.0 / h, the contact time between the catalyst and the oil and fat is shortened and the oil decomposition rate is lowered, which is not preferable.
  • Invention of Claim 2 of this invention is a manufacturing method of the biodiesel fuel of Claim 1, Comprising: Either one or both of the said fats and oils decarboxylation decomposition catalyst and the said fats and oils contacts and desorbs. It has a configuration in which it is heated to 350 ° C. to 475 ° C. prior to the carbonic acid reaction. With this configuration, in addition to the operation obtained in the first aspect, the following operation can be obtained.
  • Invention of Claim 3 of this invention is a manufacturing method of the biodiesel fuel of Claim 1 or 2, Comprising: It has the structure by which an oil extraction raw material is used instead of the said fats and oils. With this configuration, in addition to the operation obtained in the first or second aspect, the following operation can be obtained. (1) When the oiled raw material comes into contact with the fat and oil decarboxylation and decomposition catalyst at 350 ° C.
  • cellulose such as shells in the oiled raw material is carbonized, and the oil and fat component of the oiled raw material is eluted and the oil and fat decarbonation and decomposition catalyst
  • the ester bond portion of the oil / fat component is cleaved by contact with the gas, and de-CO 2 or de-CO shown in (Chemical Formula 1) occurs, and a cracked gas (hydrocarbon chain) serving as a biodiesel fuel can be obtained.
  • de-CO 2 or de-CO shown in (Chemical Formula 1) occurs, and a cracked gas (hydrocarbon chain) serving as a biodiesel fuel can be obtained.
  • the raw materials for oil extraction include oil palm pulp and seeds, coconut endosperm, rapeseed, olive fruits, seeds such as sesame seeds and castor sesame seeds, and berries and seeds of plants before oil extraction, such as seeds of oilseed burdock (Yatrofa) and kohjiju Etc.
  • oilseed burdock Yatrofa
  • kohjiju Etc kohjiju Etc.
  • certain types of algae are known to store oils and fats in cells, and the algae obtained by dehydrating and concentrating the algae can also be used. It is preferable to use the raw material for oil extraction after drying. This is to remove moisture and increase heating efficiency.
  • the fat and oil decarboxylation decomposition catalyst it is preferable to use a material that has a large surface area by pulverization or crushing.
  • An oil raw material after being oiled by pressing or the like can also be used. It is known that many oils and fats still remain after oil extraction.
  • cellulose such as a shell of the raw material for oil extraction, is carbonized and remains in the reaction vessel, the remaining carbide may be extracted from the reaction vessel as necessary.
  • a raw material for extraction after thermally extracting with a mineral oil such as hexane can be used. It is known that many oils and fats still remain after oil extraction.
  • alkaline oil candy, fish bream, and livestock shark (internal organs) discharged from the oil refining process are rich in oil and fat and can be used as raw materials.
  • the fat and oil decarboxylation catalyst can be regenerated by heating to 500 ° C. to 600 ° C. and exposing to an atmosphere containing oxygen.
  • the coke adhering to the surface of the fat decarboxylation catalyst is burned out and regenerated simply by aeration while heating the fat decarbonation decomposition catalyst whose activity has been lowered due to adhesion of coke, etc., and is excellent in resource saving.
  • the reaction vessel can be used as it is for the regeneration of the fat and oil decarboxylation catalyst.
  • the heating temperature for regeneration is preferably 500 ° C. to 600 ° C. If it is less than 500 ° C., regeneration takes time and it is not practical. If the temperature exceeds 600 ° C., the structure of the ceramics may be changed and the fat decarboxylation / decomposition catalyst may be modified and the activity may be lowered.
  • the organic acid contained in the raw oil and fat or the raw material for oil extraction has a problem that it becomes a catalyst poison and lowers the activity of the catalyst, but the organic acid is easily decomposed into hydrocarbons and carbon dioxide by the fat and oil decarboxylation decomposition catalyst.
  • the problem that the activity of the catalyst decreases is unlikely to occur. For this reason, it is not necessary to use a large amount of catalyst in anticipation of a decrease in activity, and there is no increase in running cost or productivity due to incidental work such as treatment or reactivation of the used catalyst. .
  • Invention of Claim 4 of this invention is a manufacturing method of the biodiesel fuel of Claim 3, Comprising:
  • disassembly catalyst is carbon dioxide derived from the oil extraction raw material remaining after manufacture of biodiesel fuel. In the atmosphere, it has the structure containing what was made into the activated carbon by heating in the said reaction container. With this configuration, in addition to the operation obtained in the third aspect, the following operation can be obtained. (1) By heating in an oxygen atmosphere, the coke accumulated on the surface of the fat and oil decarboxylation catalyst in the reaction vessel is burned, and the fat and oil decarboxylation decomposition catalyst is regenerated.
  • the reaction vessel can be used as it is for the activation of the carbide derived from the oil extraction raw material.
  • the heating temperature for regeneration is preferably 500 ° C. to 600 ° C. Below 500 ° C., it takes time to regenerate the catalyst and activate carbon, which is not practical. If the temperature exceeds 600 ° C., the structure of the ceramics may be changed and the fat decarboxylation / decomposition catalyst may be modified and the activity may be lowered.
  • Invention of Claim 5 of this invention is a manufacturing method of the biodiesel fuel of any one of Claims 1 thru
  • a method for producing biodiesel fuel according to claim 6 of the present invention is the method for producing biodiesel fuel according to any one of claims 1 to 5, wherein the molar ratio in the decarboxylation reaction is 1 /. 10 to 10/1 (H 2 O / oil and fat) water vapor coexists.
  • the following actions are obtained. (1) Since steam promotes hydrolysis of ester bonds, the decomposition efficiency of fats and oils is improved.
  • a biodiesel fuel production apparatus is a biodiesel fuel production apparatus used in the biodiesel fuel production method according to any one of the first to sixth aspects, wherein the fats and oils are used.
  • a first reaction vessel having a decarboxylation decomposition catalyst therein, a heating unit for heating the fat decarboxylation decomposition catalyst or the fat or oiled raw material, and an input unit for charging the oiled raw material or fat into the first reaction vessel; And a first gas deriving unit for deriving the generated gas mixture from the first reaction vessel.
  • the first reaction vessel can be provided with a stirring device.
  • a stirring device when using an oil-extracted raw material, it is preferable to provide a stirring device so that the catalyst in the reaction vessel and the oil-extracted raw material can sufficiently come into contact with each other.
  • the raw material and fat are put into the reaction vessel by spraying, spraying, dripping, spraying, etc., and contacted with the fat and decarboxylation catalyst. Let The fats and oil extraction raw materials can be charged continuously or batchwise.
  • Oils and fats are decomposed in contact with a heated oil and fat decarboxylation decomposition catalyst, and have a vapor pressure as a combustible gas.
  • an inert gas such as nitrogen gas or helium gas or a flow gas such as water vapor continuously or intermittently, the generated combustible gas can be discharged out of the system.
  • the discharged combustible gas is cooled to become biodiesel fuel oil.
  • the amount of the oil and fat decarboxylation catalyst is preferably 5% by volume or more, more preferably 20% by volume or more. If the amount of the fat decarboxylation catalyst is less than 5% by volume, the ratio of fats and oils that can come into contact with the catalyst is reduced, and the ratio of fats and oils that are thermally decomposed by heating is increased. Absent. In addition, when the oil extraction raw material is added, if it exceeds 60% by volume, it is not preferable because the raw material to be heated without increasing contact with the catalyst increases when the raw material having a large volume such as the oil extraction raw material is supplied and the discharge frequency of the residue increases. . More preferably, the amount of the oil / fatty acid decarboxylation / decomposition catalyst is 50% by volume or less when the raw material is input.
  • oiling raw materials and fats When oiling raw materials and fats are heated and decomposed, when they reach the reaction temperature, the oiling raw materials and fats are put into the reaction vessel by spraying, jetting, dripping, spraying, etc., and brought into contact with the fat decarboxylation and decomposition catalyst . Since the catalyst is heated by the heated oil and fat, continuous processing can be performed. When processing in a batch system, it is preferable to heat the oil extraction raw material and fats or oils in consideration of the amount of heat necessary for heating the catalyst, or to preheat the catalyst.
  • the invention according to claim 8 of the present invention is the biodiesel fuel production apparatus according to claim 7, wherein the second reaction is connected to the first gas lead-out part and filled with the fat decarboxylation catalyst.
  • a container, a gas introduction part for introducing the product gas mixture of the first reaction vessel into the second reaction vessel, and a gas mixture decarboxylated and decomposed by the oil decarboxylation catalyst of the second reaction vessel The second gas deriving unit is provided.
  • the fat decarboxylation catalyst used in the first reaction vessel and the second reaction vessel is not necessarily the same. Further, since the gas mixture led out from the first reaction vessel and introduced into the second reaction vessel is at a high temperature, it is not always necessary to warm the fat decarboxylation decomposition catalyst in the second reaction vessel. However, when the temperature of the fat and oil decarboxylation decomposition catalyst in the second reaction vessel during operation is lower than 350 ° C., a heating device for heating the fat and oil decarboxylation decomposition catalyst in the second reaction vessel is required. As the second reaction vessel, a single tube or a packed bed reactor such as a radial flow type is used.
  • the oil and fat decarboxylation decomposition catalyst according to claim 9 of the present invention is the method for producing biodiesel fuel according to any one of claims 1 to 6, or the biodiesel fuel according to claim 7 or 8.
  • An oil / fat decarbonation decomposition catalyst used in a production apparatus has a configuration including a solid acid catalyst in which acid sites are poisoned by one or more of an alkali metal and an alkaline earth metal. With this configuration, the following effects can be obtained. (1) Since the acid point has been weakened, the cleavage of the double bond portion in the fat and oil is suppressed, and decarboxylation decomposition occurs efficiently. Moreover, the production
  • 50% or more is used for poisoning of acid sites, more preferably 90% or more. If the acid point poisoning is less than 50%, the production of coke and light gas increases, which is not preferable. As the acid sites are poisoned, the temperature rise and desorption temperature of ammonia decreases.
  • the ammonia temperature rise and desorption temperature is preferably less than 400 ° C, more preferably less than 200 ° C, and even more preferably less than 100 ° C due to poisoning.
  • the temperature is 400 ° C. or higher, the product tends to have a low molecular weight, and a large amount of aromatics is formed to become coke, and the catalytic activity tends to decrease. When the temperature is lower than 100 ° C., the carbon-carbon bond is hardly broken, so that it can be used for raw materials in which mineral oil or the like is mixed.
  • the invention described in claim 10 of the present invention is the oil decarboxylation cracking catalyst according to claim 9, wherein the solid acid catalyst includes an FCC catalyst.
  • the following operation can be obtained. (1) Since an FCC catalyst widely used in fluid catalytic cracking of petroleum can be used, it is easy to obtain a catalyst.
  • the FCC catalyst is a synthetic zeolitic solid acid catalyst that is used in a fluid catalytic cracking process of petroleum and is formed into a granular powder of 40 to 80 ⁇ m.
  • Various methods can be used for poisoning the FCC catalyst with an alkali metal.
  • a method in which the FCC catalyst is poisoned by immersing the FCC catalyst in an aqueous alkali metal salt solution can be used.
  • the FCC waste catalyst currently processed as industrial waste can also be used as an FCC catalyst.
  • the FCC waste catalyst is discharged from the fluid catalytic cracking process of petroleum. In the fluid catalytic cracking process of petroleum, coke accumulates on the catalyst surface and the catalytic activity gradually decreases.
  • the fluid catalytic cracking process of petroleum has a step of regenerating the catalyst by heating and incinerating the coke, it has a step of adding a new catalyst and a step of extracting the old catalyst in order to keep the catalyst activity constant.
  • This extracted old catalyst is an FCC waste catalyst, and many are treated as industrial waste.
  • the FCC waste catalyst still has sufficient catalytic activity and can be obtained at a very low cost.
  • the invention according to claim 11 of the present invention is used in the method for producing biodiesel fuel according to any one of claims 1 to 6 or the apparatus for producing biodiesel fuel according to claim 7 or 8.
  • An oil and fat decarboxylation catalyst comprising activated carbon coated with a weak alkaline compound consisting of one or more of magnesium hydroxide, oxide and carbonate, activated coke, alumina, silica and alkali It has a structure containing any one or more of a modified non-acidic zeolite, a clay mineral, and a mixture thereof. With this configuration, the following effects can be obtained.
  • Non-acidic zeolite modified with activated carbon, activated coke, alumina, silica, or alkali coated with a weak alkaline compound consisting of one or more of magnesium hydroxide, oxide and carbonate , Clay minerals, and mixtures of these composites hardly reduce the molecular weight of mineral oil, so using a mixture of fats and oiled raw materials and mineral oil as raw materials increases the extraction efficiency of fats and oils and yields of decomposed oils Can be raised.
  • the method for producing biodiesel fuel of the present invention the following advantageous effects can be obtained.
  • the invention of claim 1 (1) Unlike the conventional FAME method, since no secondary raw material alcohol is required, the running cost can be greatly reduced, and impurities such as dienes and hydroxyl groups in the raw oil and fat hardly remain in the product. Since the amount of coke produced is small and impurities such as carboxylic acids (free fatty acids) are hardly produced as a by-product, it is stable against air and has excellent storage stability with no blackening or off-flavor, and has a freezing point of around -20 ° C.
  • biodiesel fuel from which a biodiesel fuel excellent in fluidity can be obtained.
  • glycerin is not produced as a by-product, so it is not necessary to establish glycerin processing technology or processing man-hours, and to adsorb and remove impurities such as peroxide using an adsorbent.
  • Production of biodiesel fuel that eliminates the need for a process and that does not cause problems such as reduced catalyst activity due to coke depositing on the surface of the catalyst and that the catalyst binds and agglomerates, enabling stable operation at a high yield. Can provide a method.
  • biodiesel fuel that can be used as a raw material simply by drying organic matter containing a large amount of oil and fat.
  • oil extraction raw material generates water vapor when heated and decomposed, it is suitable when using an oil decarboxylation and decomposition catalyst that functions well in the presence of moisture such as CaO.
  • a method for producing biodiesel fuel with higher efficiency using raw materials can be provided.
  • Activated carbon, activated coke, alumina, silica, magnesium oxide, non-acidic zeolite modified with alkali, and mixed oxides of these composites are rarely made of low molecular weight mineral oil.
  • mineral oil works as an oil and fat extractant and can provide a highly efficient method for producing biodiesel fuel.
  • Biodiesel fuel with low yield of coke, high thermal efficiency, and good yield because decarbonation and decomposition reactions proceed simultaneously with the oil and fat decarboxylation cracking catalyst at 350 ° C to 475 ° C.
  • Manufacturing equipment can be provided.
  • a second reaction vessel for introducing the gas mixture produced from the first reaction is filled with the oil / fatty acid decarboxylation catalyst, and the organic acid in the gas produced from the first reaction vessel is subjected to the second reaction. Since it is decarboxylated and decomposed by the fat and oil decarboxylation catalyst in the container, it is possible to provide an apparatus for producing biodiesel fuel in which the acid in the product is further reduced and the quality of the product oil is good. (2) Even if the organic acid generated in the first reaction vessel or the organic acid contained in the raw oil / fat is led out together with the gas generated in the first reactor without touching the catalyst through the upper part of the first reactor.
  • the widely used FCC catalyst can be used with a simple operation, and therefore it is easy to implement.
  • the FCC catalyst can be easily regenerated even if the catalytic function is lowered, a large regenerator is not required.
  • the processing method is established even if it processes without reproducing
  • the FCC waste catalyst currently processed as waste can also be utilized, the oil-and-fat decarboxylation decomposition catalyst which becomes very cheap in operating cost can be provided.
  • Non-acidic zeolite modified with activated carbon, activated coke, alumina, silica, or alkali coated with a weak alkaline compound consisting of one or more of magnesium hydroxide, oxide and carbonate , Clay minerals, and mixed oxides of these composites hardly reduce the molecular weight of mineral oil, so the use of a mixture of fats and oiled raw materials and mineral oil as raw materials increases the extraction efficiency of fats and oils and yields of decomposed oils High fat and oil decarboxylation catalyst.
  • Configuration diagram of the reactor according to Embodiment 1 Configuration diagram of reactor of embodiment 2
  • Configuration diagram of reactor of embodiment 3 The figure which shows carbon number distribution of the cracked oil obtained in Example 2
  • the figure which shows carbon number distribution of the cracked oil obtained in Example 7 The figure which shows carbon number distribution of the cracked oil obtained in Example 8
  • the figure which shows carbon number distribution of the cracked oil obtained in Example 9 The figure which shows carbon number distribution of the cracked oil obtained in Example 10
  • FIG. 1 is a configuration diagram of the reactor according to the first embodiment.
  • 1 is the reaction apparatus of Embodiment 1 used in the examples of the present invention
  • 2 is a reaction vessel
  • 3 is granular silica contained in the reaction vessel 2
  • activated carbon solid base
  • Fat decarbonation cracking catalyst such as poisoned FCC catalyst
  • 4 is a heater for heating the catalyst 3 contained in the reaction vessel 2 to 350 to 475 ° C
  • 5 is spraying, dripping and spraying the fat and oil raw material to the reaction vessel 2
  • the raw material input unit 6 is supplied by, for example, a flow gas introduction unit 6 for introducing an inert gas such as nitrogen gas or a flow gas such as water vapor into the reaction vessel 2
  • 7 is a stirring device for stirring the catalyst 3
  • 8 is the reaction vessel 2.
  • a first outlet pipe for letting out the product generated in the flow gas to the outside of the reaction vessel 2 and 9 is connected to the first outlet pipe 8 and has a boiling point of 0 ° C. to the temperature of the reaction vessel.
  • a cracked oil reservoir for storing a cracked product (hereinafter referred to as cracked oil) of 0 is a discharge pipe whose one end is connected to the cracked oil reservoir 9, 11 is a cooling pipe which is disposed in the discharge pipe 10 and cools the discharge pipe 10 to 0 ° C.
  • a discharge pipe 10 is connected to the other end of the cooling trap device for storing a liquefied decomposition product (hereinafter referred to as light oil) having a boiling point of ⁇ 80 to 0 ° C. It is a connected gas exhaust pipe.
  • FIG. 2 is a configuration diagram of the reactor according to the second embodiment.
  • 21 is the reaction apparatus of the second embodiment. Portions common to those in FIG. 1 are denoted by the same reference numerals and description thereof is omitted.
  • Reference numeral 22 denotes a heating unit that heats the raw oil and fat and the raw material for oil extraction.
  • Reference numeral 23 denotes an auxiliary heating unit for heating when the temperature of the catalyst 3 is low, such as at the start of operation.
  • FIG. 3 is a block diagram of the reactor according to the third embodiment.
  • reference numeral 31 denotes a reactor according to the third embodiment. Portions common to those in FIG. 1 are denoted by the same reference numerals and description thereof is omitted.
  • Reference numeral 32 denotes a first reaction vessel according to Embodiment 3, which corresponds to the reaction vessel 2 of FIG. 33 is an oil and fat decarboxylation catalyst A such as granular silica contained in the first reaction vessel 32, and 8 is a product produced in the first reaction vessel 32 accompanied by a flow gas to the outside of the first reaction vessel 32.
  • 1 is a first outlet pipe
  • 34 is a second reaction vessel
  • 35 is an oil decarboxylation cracking catalyst B such as granular silica, activated carbon, solid base, etc. accommodated in the second reaction vessel 34
  • Reference numeral 38 denotes a second outlet pipe for leading the gas decarboxylated and decomposed in the second reaction vessel 34.
  • the oil and fat decarboxylation / decomposition catalyst (hereinafter abbreviated as catalyst) 3 uses silica for catalyst (manufactured by Fuji Silysia Chemical Co., Ltd., trade name: Caractect Q-15, particle size: 1.18 to 2.36 mm). 50 mL of the catalyst was accommodated in the reaction container 2 having an internal volume of 150 mL, and heated to 420 ° C. while being stirred by the stirring device 7 (50 rpm). The heating temperature of the catalyst 3 was measured by bringing a thermocouple (not shown) placed in the reaction vessel 2 into contact with the catalyst 3.
  • a thermocouple not shown
  • palm oil oil and fat
  • the amount of oil and fat charged was 0.25 mL / min, and the amount of flow gas (nitrogen gas) introduced from the flow gas inlet 6 was 50 mL / min.
  • a product was obtained by adding a total of 75 g of fats and oils.
  • Component analysis of the cracked oil stored in the cracked oil storage unit 9 and the gas substances (carbon monoxide, carbon dioxide, and light hydrocarbon gas) discharged from the gas discharge pipe 13 was performed. Analysis of cracked oil was performed using GC-MS. Among gas substances, analysis of carbon monoxide and carbon dioxide was performed using GC-TCD, and analysis of light hydrocarbon gas was performed using GC-FID. . Further, the catalyst after the experiment was analyzed by TG-DTA.
  • Example 2 The same procedure as in Example 1 was performed except that a catalyst in which MgO was supported on the catalyst silica used in Example 1 was used and the reaction temperature was 410 ° C.
  • the catalyst in which MgO is supported on silica is magnesium nitrate (Mg (NO 3 ) 2 ⁇ 6H 2 O) in an amount corresponding to 10% by mass as metal magnesium with respect to the catalyst silica used in Example 1.
  • the aqueous solution was impregnated in silica by the Incipient Wetness method, dried at 120 ° C. after the impregnation, and then calcined in the air at 500 ° C. for 3 hours.
  • Example 2 The same procedure as in Example 1 was carried out except that active coke (manufactured by Mitsui Mining Co., Ltd., particle size after crushing: 1.18 to 2.36 mm) was used as the fat and oil decarboxylation decomposition catalyst, and the reaction temperature was 400 ° C.
  • active coke manufactured by Mitsui Mining Co., Ltd., particle size after crushing: 1.18 to 2.36 mm
  • Example 3 The same procedure as in Example 1 was performed except that a catalyst in which MgO was supported on the active coke used in Example 3 was used and the reaction temperature was 400 ° C.
  • the catalyst in which MgO is supported on active coke is magnesium nitrate (Mg (NO 3 ) 2 ⁇ 6H 2 O) in an amount corresponding to 10% by mass as metal magnesium with respect to the active coke used in Example 3.
  • the aqueous solution was impregnated into activated coke by the Incipient Wetness method, dried at 120 ° C. after impregnation, and then calcined at 350 ° C. for 3 hours in a nitrogen atmosphere.
  • Example 1 The same procedure as in Example 1 was conducted, except that an FCC waste catalyst was used as the catalyst and the reaction temperature was 420 ° C.
  • the FCC waste catalyst is a regeneration of a synthetic zeolite-based solid acid catalyst that has been granulated into 40-80 ⁇ m granules used in a fluid catalytic cracking (FCC) process of petroleum.
  • Table 1 shows the amount of product and the yield of cracked oil in Examples 1 to 4 and Comparative Example 1.
  • Examples 1-4 It was found that about 50-60% of paraffins and about 30-40% of olefins were present in the cracked oil, but there were almost no aromatic compounds. From this result, it was surmised that the residue was mainly coke, and the coke was a polymer of an olefin-derived aromatic compound produced by the acid point of the catalyst (FCC waste catalyst). In Examples 1 to 4, since neutral silica or a solid base was used as a catalyst, almost no aromatic compound was produced, and it was assumed that the production of coke was small and the amount of residue produced was small. It was.
  • Comparative Example 1 a small amount of alcohol and fatty acid were detected as oxygen-containing substances in the cracked oil, but in Examples 1 to 4, they were not detected, and ketones were mainly produced.
  • the cracked oil of Comparative Example 1 had a bad odor and turned black so that it could be visually confirmed when left for about a week.
  • the cracked oils of Examples 1 to 4 did not turn black or have a bad odor and were stored. It was found to be excellent in stability. This cause was presumed to be the influence of impurities such as carboxylic acid (fatty acid) contained in the cracked oil of Comparative Example 1.
  • FIG. 4 is a graph showing the carbon number distribution of the cracked oil obtained in Example 2.
  • the fatty acid composition of the fats and oils (palm oil) used in the experiment is as follows: lauric acid (C12) 0.2%, myristic acid (C14) 1.1%, palmitic acid (C16) 44.0%, stearic acid (C18) ) 4.5%, oleic acid (C18: 1) 39.2%, linoleic acid (C18: 2) 10.1%, linolenic acid (C18: 3) 0.4%. From FIG. 2, it was found that in Example 2, paraffins or olefins having a carbon number corresponding to the fatty acid contained in the oil were mainly produced. The other examples had the same tendency.
  • the pour point of the obtained cracked oil was measured based on JIS K2269 (pour point of crude oil and petroleum product and cloud point test method of petroleum product) and found to be -12.5 ° C. Since the pour point of commercially available general light oil is -7 ° C, it was found that cracked oil having a pour point as low as that of general light oil can be produced.
  • Table 2 shows amounts of carbon monoxide and carbon dioxide generated in Examples 1 to 4 and Comparative Example 1. When the amount of carbon dioxide was compared, it was found that the amount increased in the order of Comparative Example 1, Example 1, and Examples 2 to 4.
  • the catalyst of Comparative Example 1 is a solid acid
  • the catalyst of Example 1 is silica (neutral)
  • the catalysts of Examples 2 to 4 are solid bases
  • the silica or solid base is catalyzed as in Examples 1 to 4.
  • CO 2 can be selectively recovered.
  • the oil and fat decomposition mechanism is inferred as follows. Glycerin is removed from the oil contacted with the heated oil decarboxylation decomposition catalyst, and fatty acid is produced. In the produced fatty acid, the carboxyl group portion is removed as CO 2 and the remaining carbon chain is recovered as cracked oil.
  • the glycerin group is recovered as a light hydrocarbon gas such as propane.
  • a waste edible oil (75 g of soybean oil and rapeseed oil) actually used for one week in a university cafeteria is reacted under atmospheric pressure.
  • the procedure was the same as in Example 1 except that it was dropped into the container (0.25 mL / min) and He gas (50 mL / min) was used as the flow gas.
  • Example 2 Using rice bran discharged from a rice mill as raw oil and fat, an experiment was carried out to produce cracked oil from the raw material. Except for using a catalyst in which MgO is supported on silica for catalyst (the same catalyst as in Example 2), the reaction temperature was set to 410 ° C., and rice bran (500 g) was added little by little with a micro feeder into a reaction vessel under atmospheric pressure. Was the same as in Example 1.
  • Jatropha oil fat was dropped from the raw material charging unit 5 into the reaction vessel 2 under atmospheric pressure.
  • the amount of oil and fat charged was 1.0 mL / min, and the amount of flow gas (nitrogen gas) introduced from the flow gas inlet 6 was 50 mL / min.
  • a product was obtained by adding a total of 75 g of fats and oils.
  • Example 4 was the same as Example 4 except that pork fat (500 g) discharged from the meat processing plant as raw oil was heated to 80 ° C. and used in a liquid state.
  • Example 4 The same procedure as in Example 4 was conducted except that beef fat (500 g) discharged from a meat processing plant as raw material fat was heated to 80 ° C. and used in a liquid state.
  • Table 3 shows the amount of product and the yield of cracked oil in Example 5, Example 6, and Example 8.
  • oily components, aqueous components, precipitates, and suspended matters were mixed in the cracked oil. It is considered that the raw material for oil extraction contains abundant components other than fats and oils. Therefore, the cracked oil yield of Example 6 was converted from the ratio of the oily component to the input amount, unlike Examples 1 to 5, in order to exclude the influence of precipitates and the like.
  • the gas substance was not analyzed. This is because the influence of components other than fats and oils is great.
  • the aqueous content increases in the cracked oil produced as in Example 6. Therefore, in order to use it as a fuel, the water is removed from the raw material or from the cracked oil. A process of removing is necessary.
  • Example 5 it was confirmed that cracked oil was obtained from waste edible oil in a yield of 60% or more. This is almost the same result as in Examples 1 to 4 in which palm oil is used as the raw material fat. Although it is considered that waste cooking oil has a higher degree of oxidation than palm oil, it was revealed that cracked oil was obtained in a high yield according to this example. Moreover, as shown in Example 6, it was confirmed that an oil component was obtained with a yield of 5.7% from the raw material for oil extraction (soybean). Since it is said that the content of fats and oils in domestic soybeans is about 10 wt%, the oil component yield of 5.7 wt% can be said to be a considerably high yield.
  • FIG. 5 shows the carbon number distribution of the cracked oil obtained from rice bran in Example 7. Production of hydrocarbons with a wide range of carbon numbers from C5 to C34 was observed. In particular, it contained a large amount of C10-C20 lamps and light oil. The cracked oil contained about 20% of C6-C13 aromatic hydrocarbons. Rice bran is rich in lipase and free fatty acids, but has an oxidation degree of 0.35 mg KOH / g and an oxidation stability of 24 h or more, and can be used as a biodiesel fuel.
  • Table 3 shows the results obtained from Jatropha oil in Example 8. Jatropha oil is unsaturated with palmitic acid (C16) 14.9%, stearic acid (C18) 6.9%, oleic acid (C18: 1) 41.8%, linoleic acid (C18: 2) 34.8% Although the yield of the pyrolysis method was low due to the high fatty acid ratio, the method of the present invention showed a high cracked oil recovery rate of 63.1%.
  • FIG. 6 shows the carbon number distribution of hydrocarbons in the cracked oil obtained. It was shown that the number of carbons is distributed over a wide range but the double bonds are conserved.
  • Jatropha oil has a high phosphoric acid content, and when it is converted into fuel by the conventional method, it remains in the fuel oil and damages the engine and the like.
  • the phosphoric acid concentration of the cracked oil of Example 8 and the Jatropha oil used as the raw material fat was measured by IPC, it was about 10 mg / L for the raw fat and oil, and 0.9 mg / L for the cracked oil. It was shown that the phosphoric acid in the raw material fats and oils does not migrate to the cracked oil, and a cracked oil with a low phosphoric acid content can be obtained.
  • FIG. 7 shows the carbon number distribution of hydrocarbons in cracked oil obtained from pork fat in Example 9
  • FIG. 8 shows the carbon number distribution of hydrocarbons in cracked oil obtained from beef tallow in Example 10.
  • Hydrocarbons with a wide range of carbon numbers from C5 to C34 from tallow and from C5 to C31 from tallow were produced. Both the kerosene and light oil components in the cracked oil were approximately 65%.
  • biodiesel fuel production method of the present invention is extremely useful because it does not require alcohol (a secondary raw material) and does not by-produce glycerin.
  • the same procedure as in Comparative Example 1 was performed except that a catalyst obtained by poisoning the FCC waste catalyst used in Comparative Example 1 with NaCl was used.
  • the catalyst obtained by poisoning the FCC waste catalyst with NaCl was prepared by adding 1.0 L of 50 g / L NaCl aqueous solution to 50 g FCC waste catalyst and treating at 50 ° C. ⁇ 5 ° C. for 1 hour.
  • the acid point of the catalyst obtained by this method was poisoned by approximately 90%.
  • the acid point of the catalyst obtained by this method was evaluated by the ammonia temperature rising desorption method, about 90% of the acid point was poisoned.
  • Comparative Example 2 The same procedure as in Comparative Example 1 was performed except that silica, which is a solid acid catalyst, was used as the catalyst.
  • Comparative Example 1 was the same as that of Comparative Example 1 except that the catalyst used in Comparative Example 2 was poisoned with an aqueous magnesium nitrate solution.
  • the catalyst in which silica was poisoned with an aqueous magnesium nitrate solution was prepared by adding 1.0 L of 50 g / L Mg (NO 3 ) 2 aqueous solution to 50 g of silica and treating it at 50 ° C. ⁇ 5 ° C. for 1 hour.
  • the acid point of the catalyst obtained by this method was evaluated by the ammonia temperature rising desorption method, about 90% of the acid point was poisoned.
  • Example 2 The same procedure as in Comparative Example 1 was conducted except that the FCC waste catalyst used in Example 1 was poisoned with Mg and a catalyst carrying magnesium oxide was used.
  • the catalyst in which the FCC waste catalyst was poisoned with Mg and magnesium oxide was supported was added 50 g / L of Mg (NO 3 ) 2 aqueous solution 1.0 L to 50 g of FCC waste catalyst 50 ° C. ⁇ 5 ° C. And processed for 1 hour.
  • the term “supported” refers to a state in which magnesium oxide is contained in the catalyst in excess of the acid point poisoning.
  • Table 4 shows the results when the acid sites are poisoned.
  • the upper part of the table shows the amount of product and the yield of cracked oil in Comparative Example 1, Example 11, Comparative Example 2, Example 12 and Example 13.
  • Alkaline poisoning of the solid acid catalyst increases the production of CO 2 and increases the yield of cracked oil. Furthermore, by supporting magnesium oxide, the production of CO 2 increases and the yield of cracked oil increases. The yield increases and the amount of residue decreases. The breakdown of the residue is shown at the bottom of Table 4. It is thought that the amount of coke produced as a by-product was significantly reduced compared with Comparative Examples 1 and 2 and the yield of cracked oil was increased because the cleavage of double bond parts in fats and oils was reduced by alkaline poisoning of the fixed acid catalyst. It is done.
  • Example 2 The same procedure as in Example 2 was performed except that the reaction temperature was 350 ° C.
  • Example 2 was repeated except that the reaction temperature was 475 ° C. (Comparative Example 3) Example 2 was repeated except that the reaction temperature was 300 ° C. (Comparative Example 4) Example 2 was repeated except that the reaction temperature was 550 ° C.
  • Table 5 is a table showing the effect on the yield of cracked oil at each temperature.
  • the amount of product and the yield of cracked oil in Comparative Example 3, Example 14, Example 2, Example 15, and Comparative Example 4 are shown. It is shown. From this, it was shown that the reaction temperature range is preferably 350 ° C. to 475 ° C. At 300 ° C. (Comparative Example 3), the reaction is slow and impractical. Moreover, it is considered that the residue amount increased due to the polymerization and solidification of fats and oils, and the productivity of hydrocarbons decreased. At 550 ° C. (Comparative Example 4), the yield of cracked oil is low, and the amount of residue is large. Therefore, it is considered that pyrolysis occurred and the amount of gas and coke produced increased.
  • Example 5 If the reaction is repeated many times, the activity of the catalyst gradually decreases. The same procedure as in Example 2 was performed, except that a catalyst with reduced activity was used. The carbon content of the catalyst with reduced activity was measured as a weight loss after heating at 800 ° C. for 1 hour in an air atmosphere and found to be 45% by weight.
  • the catalyst was heated and held at 500 ° C. ⁇ 20 ° C. for 6 hours while flowing a mixed gas of 50% air + 50% nitrogen gas at 200 ml / min into the reaction vessel containing the catalyst used in Comparative Example 5. Thereafter, the carbon content was measured in the same manner as in Comparative Example 5. During the regeneration, the stirring blade was rotated at 10 times / min and slowly stirred. Next, the same procedure as in Example 2 was performed except that the regenerated catalyst was used.
  • Example 16 The same operation as in Example 16 was performed except that the holding temperature during regeneration was 550 ° C. ⁇ 20 ° C.
  • Example 16 The same operation as in Example 16 was performed except that the holding temperature at the time of regeneration was 600 ° C. ⁇ 20 ° C. (Comparative Example 6) The same procedure as in Example 16 was performed except that the heating and holding temperature of the catalyst during regeneration was 450 ° C. ⁇ 20 ° C. (Comparative Example 7) The same operation as in Example 12 was conducted except that the heating and holding temperature of the catalyst during regeneration was 650 ° C. ⁇ 20 ° C.
  • Table 6 is a table showing the effects of catalyst regeneration and regeneration temperature, and shows the results of Example 2, Comparative Examples 5 to 7, and Examples 16 to 18. From this, it was shown that the catalyst can be regenerated by maintaining at 500 ° C. to 600 ° C. in an atmosphere containing oxygen. At 450 ° C. (Comparative Example 5), regeneration was slow, carbon remained, and activity was low. In addition, the activity decreased at 650 ° C., which was not preferable. The regenerated one (Examples 16-18) showed a higher recovery of cracked oil than the new catalyst (Example 2). .
  • Example 2 The procedure was the same as Example 2 except that the liquid space velocity was 0.05 / h.
  • Example 2 The procedure was the same as Example 2 except that the liquid space velocity was 2.0 / h.
  • Comparative Example 8 The procedure was the same as Example 2 except that the liquid space velocity was 0.05 / h.
  • Comparative Example 9 The same as Example 2 except that the liquid space velocity was 4.0 / h.
  • Table 7 is a table showing the effect of liquid space velocity on cracked oil yield, showing the amount of product and cracked oil yield in Comparative Example 8, Example 19, Example 20 and Comparative Example 9. Is. From this, it was shown that the range of the liquid space velocity is preferably 0.05 / h to 2.0 / h. 0.02 / h (Comparative Example 8) is not preferable because the processing speed is slow, the processing efficiency is low, and the product oil is gasified by secondary decomposition, resulting in a decrease in yield. In 4.0 / h (Comparative Example 9), the yield of cracked oil is low, and the amount of residue is large. Therefore, the contact time between the catalyst and the fat / oil is shortened, and the fat / oil decomposition rate is considered to be decreased.
  • Table 8 shows the results of Example 21 and Comparative Example 5.
  • the oxidation, iodine value, and oxidation stability were measured according to the BDF standard draft of the Agency for Natural Resources and Energy. The installation of the second reactor reduces the acid in the product.
  • the present invention does not require alcohol (subsidiary raw material) from fats and oiled raw materials, does not by-produce glycerin, and impurities such as dienes and hydroxyl groups in the raw fats and oils hardly remain in the product, Since the amount of coke produced is small, the pour point of the produced oil is low, and impurities such as carboxylic acids (free fatty acids) are hardly produced as a by-product, so it is stable against air, etc.
  • a method for producing biodiesel fuel can be provided.
  • pretreatment and the like for removing free fatty acids from raw oils and fats are not necessary, and the reaction can be performed under normal pressure, so that the manufacturing process and the reaction apparatus can be simplified, and at the necessary place.
  • biodiesel fuel production apparatus capable of constructing a distributed energy supply system that supplies necessary energy. Furthermore, it is difficult to cause a problem that the activity of the catalyst is reduced due to the free fatty acid produced as a by-product, so that the running cost increases or the productivity decreases due to incidental work such as treatment or reactivation of the used catalyst.
  • the decarboxylation decomposition catalyst used for the manufacturing method of the biodiesel fuel which is excellent in production efficiency and productivity can be provided.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Liquid Carbonaceous Fuels (AREA)
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Abstract

La présente invention concerne un procédé pour la fabrication de carburant biodiesel, permettant la construction d'un système d'alimentation d'énergie distribué qui fournit l'énergie requise à des emplacements nécessitant l'énergie. Le système se caractérise par une excellent stabilité au stockage, de sorte que l'alcool (en tant que matière première subsidiaire) n'est pas nécessaire, que du glycérol n'est pas produit sous forme de dérivé, et qu'il est improbable que des impuretés telles que des dioléfines subsistent dans le produit, que la quantité de coke générée est faible, que le point d'écoulement est bas, et que le noircissement et des odeurs anormales se produisent rarement grâce à la stabilité contre l'air. Le système se caractérise également par une excellente efficacité de production et une productivité qui empêchent l'accroissement des frais d'exploitation et la réduction de la productivité entraînés par les tâches secondaires telles que le traitement ou la réactivation de catalyseurs épuisés. Le système se caractérise en outre en permettant un procédé de fabrication simplifié et un réacteur simplifié ne nécessitant aucun prétraitement pour éliminer des acides gras libres à partir des graisses constituant les matières premières. Au cours du procédé, à une température comprise entre 350°C et 475°C, un catalyseur de décomposition pour la décarboxylation de graisses et des graisses sont mis en contact, et une partie de liaison ester est clivée dans la réaction de décarboxylation sous l'action d'un catalyseur de décomposition pour la décarboxylation des graisses, et du carburant biodiesel formé majoritairement d'hydrocarbures C8 à C24 est obtenu.
PCT/JP2009/005669 2008-10-31 2009-10-27 Procédé et appareil pour la fabrication de carburant biodiesel, et catalyseur de décomposition pour la décarboxylation de graisses utilisé dans le procédé Ceased WO2010050186A1 (fr)

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CN200980143059.3A CN102203218B (zh) 2008-10-31 2009-10-27 生物柴油燃料的制备方法及其制备装置、用于该方法的油脂脱羧分解催化剂
JP2010535661A JP5353893B2 (ja) 2008-10-31 2009-10-27 バイオディーゼル燃料の製造方法及びその製造装置、その方法に用いる油脂脱炭酸分解触媒

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JP2012077131A (ja) * 2010-09-30 2012-04-19 Hidenori Kanetsuna バイオ石油燃料製造方法と、それに使用する触媒および製造システム
JP2012162649A (ja) * 2011-02-07 2012-08-30 Takuma Co Ltd ディーゼル燃料製造システムおよびディーゼル燃料製造方法
JP2012188577A (ja) * 2011-03-11 2012-10-04 Takuma Co Ltd ディーゼル燃料製造用精製器および精製方法、これを用いたディーゼル燃料製造システムおよび製造方法
WO2013069737A1 (fr) * 2011-11-08 2013-05-16 公益財団法人北九州産業学術推進機構 Catalyseur de craquage, son procédé de production et carburant de type biodiesel obtenu au moyen de celui-ci
JP2016074852A (ja) * 2014-10-08 2016-05-12 公益財団法人北九州産業学術推進機構 炭化水素油の精製方法
CN110041978A (zh) * 2019-04-30 2019-07-23 蔡国宇 一种透气型高燃烧效率生物质颗粒的制备方法
WO2019221287A1 (fr) * 2018-05-18 2019-11-21 一般社団法人 ＨｉＢＤ研究所 Procédé de production de carburéacteur biologique
WO2025068057A1 (fr) 2023-09-25 2025-04-03 Basell Poliolefine Italia S.R.L. Installation de vapocraqueur pour la conversion de déchets plastiques en oléfines
JP7788604B1 (ja) 2024-12-13 2025-12-19 横井 明 バイオディーゼル燃料の製造方法

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012077131A (ja) * 2010-09-30 2012-04-19 Hidenori Kanetsuna バイオ石油燃料製造方法と、それに使用する触媒および製造システム
JP2012162649A (ja) * 2011-02-07 2012-08-30 Takuma Co Ltd ディーゼル燃料製造システムおよびディーゼル燃料製造方法
JP2012188577A (ja) * 2011-03-11 2012-10-04 Takuma Co Ltd ディーゼル燃料製造用精製器および精製方法、これを用いたディーゼル燃料製造システムおよび製造方法
WO2013069737A1 (fr) * 2011-11-08 2013-05-16 公益財団法人北九州産業学術推進機構 Catalyseur de craquage, son procédé de production et carburant de type biodiesel obtenu au moyen de celui-ci
JPWO2013069737A1 (ja) * 2011-11-08 2015-04-02 公益財団法人北九州産業学術推進機構 接触分解触媒及びそれを用いて得られたバイオディーゼル燃料
JP2016074852A (ja) * 2014-10-08 2016-05-12 公益財団法人北九州産業学術推進機構 炭化水素油の精製方法
WO2019221287A1 (fr) * 2018-05-18 2019-11-21 一般社団法人 ＨｉＢＤ研究所 Procédé de production de carburéacteur biologique
JP6635362B1 (ja) * 2018-05-18 2020-01-22 一般社団法人ＨｉＢＤ研究所 バイオジェット燃料の製造方法
US11603501B2 (en) 2018-05-18 2023-03-14 Hibd Laboratory Association Method for producing bio-jet fuel
CN110041978A (zh) * 2019-04-30 2019-07-23 蔡国宇 一种透气型高燃烧效率生物质颗粒的制备方法
WO2025068057A1 (fr) 2023-09-25 2025-04-03 Basell Poliolefine Italia S.R.L. Installation de vapocraqueur pour la conversion de déchets plastiques en oléfines
JP7788604B1 (ja) 2024-12-13 2025-12-19 横井 明 バイオディーゼル燃料の製造方法

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CN102203218A (zh) 2011-09-28
JP5353893B2 (ja) 2013-11-27
MY155384A (en) 2015-10-15
CN102203218B (zh) 2015-03-25
JP5721152B2 (ja) 2015-05-20

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