WO2007132857A1 - Procédé d'hydroraffinage - Google Patents

Procédé d'hydroraffinage Download PDF

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Publication number
WO2007132857A1
WO2007132857A1 PCT/JP2007/059972 JP2007059972W WO2007132857A1 WO 2007132857 A1 WO2007132857 A1 WO 2007132857A1 JP 2007059972 W JP2007059972 W JP 2007059972W WO 2007132857 A1 WO2007132857 A1 WO 2007132857A1
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WIPO (PCT)
Prior art keywords
oil
mass
catalyst
oxygen
hydrogen
Prior art date
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PCT/JP2007/059972
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English (en)
Japanese (ja)
Inventor
Hideshi Iki
Akira Koyama
Yasutoshi Iguchi
Yuko Aoki
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Nippon Oil Corporation
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Filing date
Publication date
Priority claimed from JP2006138297A external-priority patent/JP5189740B2/ja
Priority claimed from JP2006138296A external-priority patent/JP2007308564A/ja
Application filed by Nippon Oil Corporation filed Critical Nippon Oil Corporation
Priority to KR1020087030783A priority Critical patent/KR101362950B1/ko
Priority to CNA2007800178680A priority patent/CN101448918A/zh
Publication of WO2007132857A1 publication Critical patent/WO2007132857A1/fr

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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
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • 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
    • B01J21/02—Boron or aluminium; 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
    • B01J21/12—Silica and alumina
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B01J29/068—Noble metals
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B01J29/072—Iron group metals or copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/10—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing platinum group metals or compounds thereof
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
    • 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 hydrorefining method.
  • biomass energy derived from plants does not lead to an increase in carbon dioxide in the atmosphere from the viewpoint of life cycle because hydrocarbons converted from carbon dioxide by photosynthesis can be used effectively in the growth process of plants. In other words, it has a carbon-eutral nature.
  • Fatty acid methyl ester oil (Fatty Acid Methyl Ester) is known as a diesel fuel using animal and vegetable oils.
  • Fatty acid methyl ester oils are produced by transesterification with methanol using alkali or the like for the triglyceride structure, which is a general structure of animal and vegetable oils.
  • Patent Document 1 it is necessary to treat glycerin produced as a by-product, washing the produced oil, etc.
  • Patent Document 1 Japanese Patent Laid-Open No. 2005-154647
  • the present invention provides a hydrorefining method capable of obtaining a hydrorefined oil having a sufficiently reduced oxygen content when an oil to be treated containing an oxygen-containing hydrocarbon compound is used.
  • the purpose is to provide.
  • the present invention is selected from an oil to be treated containing an oxygen-containing hydrocarbon compound, aluminum, silicon, zirconium, boron, titanium, and magnesium force in the presence of hydrogen.
  • a support containing a porous inorganic oxide containing at least one element and containing at least one metal selected from Group 6A and Group 8 elements of the periodic table supported on the support Hydrogenation purification process in which the catalyst to be contacted under the conditions of hydrogen pressure 2 to 13 MPa, liquid space velocity 0.1 to 3.
  • Oh " 1 hydrogen oil ratio 150 to 1500 NLZL, reaction temperature 150 to 380 ° C
  • a hydrorefining method characterized in that a refined oil is obtained.
  • a hydrorefined oil having a sufficiently reduced oxygen content can be obtained by bringing the oil to be treated containing an oxygen-containing hydrocarbon compound into contact with the specific catalyst. It can be obtained very effectively economically.
  • the carrier preferably contains a crystalline molecular sieve.
  • a hydrorefined oil having a sufficiently reduced oxygen content and a sufficiently practical low-temperature performance can be obtained extremely effectively economically.
  • the fatty acids that make up animal and vegetable fats and oils have straight-chain paraffin or straight-chain olefins as hydrocarbon skeletons, but in the case of conventional hydrorefining methods that do not have this structure, the norafine content obtained is Low temperature performance such as cloud point may not be practical enough.
  • the oxygen content is preferably 0.1 to 15% by mass based on the total amount of oil to be treated.
  • the oil to be treated contains a sulfur content, and it is preferable that the content is sufficiently low even if it is contained, and the sulfur content is based on the total amount of the oil to be treated.
  • the amount is preferably 50 mass ppm or less Yes.
  • the oxygen-containing hydrocarbon compound is an oil and fat component derived from animal and vegetable oils from the viewpoint of effective use of biomass energy.
  • the proportion of the compound having a triglyceride structure in the oxygen-containing hydrocarbon compound is preferably 90 mol% or more.
  • the ratio of isoparaffin to normal paraffin in the paraffin contained in the fraction of 150 to 350 ° C of the refined oil obtained from the oil to be treated It is preferable to carry out the hydrorefining step so that the mass of isoparaffin (the mass of Z normal paraffin) is 0.2 or more. As a result, it is possible to sufficiently improve the low-temperature performance as a fuel typified by the cloud point of refined oil.
  • the crystalline molecular sieve constituting the catalyst contains zeolite containing caustic, and the zeolite contains a key element for constituent elements excluding oxygen and kale. It is preferable that the ratio of the number of atoms (the number of atoms Z, the number of atoms of elements other than oxygen and key) is 3 or more. As a result, excessive decomposition reaction can be suppressed, and efficient fuel production and improvement of low-temperature performance can be achieved more sufficiently.
  • the metal constituting the catalyst contains one or more elements selected from Pd, Pt, Rh, Ir, Au, Ni, and Mo. Good. As a result, the hydrodeoxygenation reaction is promoted, and the improvement in low-temperature performance such as hydroisomerization reaction and paraffin decomposition / removal reaction can be achieved more sufficiently.
  • the carbon monoxide adsorption amount per lg of the catalyst in which the metal is in a reduced state is preferably in the range of 0.003 to 0.005 mmol.
  • the hydrotreating step includes the treatment object.
  • a first hydrogenation step in which 70% by mass or more of the initial oxygen content contained in the oil is removed to obtain a first refined oil, and 95% by mass or more of the initial oxygen content is removed.
  • the ratio of isoparaffin to normal paraffin mass of isoparaffin Z mass of normal paraffin
  • an oil to be treated containing an oxygen-containing hydrocarbon compound is used.
  • the oxygen-containing hydrocarbon compound oil and fat components derived from animal and vegetable oils are suitable.
  • the oil and fat component in the present invention includes animal and vegetable oils and fats and animal and vegetable oil components and Z or natural or artificially produced and produced components, and components produced and produced from these fats and oils and fat products. Ingredients added for the purpose of maintaining and improving the performance are included.
  • Examples of fat components derived from animal and vegetable oils include beef tallow, rapeseed oil, soybean oil, palm oil and the like.
  • any oil and fat may be used as the oil and fat component derived from animal and vegetable oils, and waste oil after using these oils and fats may be used.
  • rapeseed oil, soybean oil, and palm oil are more preferable from the viewpoint of carbon-eutral, from the viewpoint of the number of fatty acid alkyl chain carbons preferred by vegetable oils and their reactivity.
  • the above fats and oils may be used alone or in combination of two or more.
  • Oils and fats derived from animal and vegetable oils generally have a fatty acid triglyceride structure, but may contain other oils and fats processed into esters such as fatty acids and fatty acid methyl esters. However, fatty acids and fatty acid esters are produced from vegetable oils and fats.
  • a component having a triglyceride structure is mainly used as vegetable oil from the viewpoint of reducing emission of diacid carbon.
  • the proportion of the compound having a triglyceride structure in the oxygen-containing hydrocarbon compound contained in the oil to be treated is preferably 90 mol% or more, more preferably 92 mol% or more. More preferably, it is at least mol%.
  • the oil to be treated may contain carbon monoxide as an oxygen-containing hydrocarbon compound, in addition to the oil and fat components derived from the above-mentioned animal and vegetable oils, and compounds derived from chemicals such as plastics and solvents. Including synthetic oil obtained via a Fischer-Tropsch reaction using a synthetic gas composed of hydrogen and hydrogen as a raw material.
  • the oil to be treated may contain a petroleum hydrocarbon fraction.
  • a petroleum hydrocarbon fraction a fraction obtained in a general petroleum refining process can be used.
  • a distillation corresponding to a predetermined boiling range obtained by atmospheric distillation equipment or vacuum distillation equipment, or hydrodesulfurization equipment, hydrocracking equipment, residual oil direct desulfurization equipment, fluid catalytic cracking equipment, etc.
  • Fractions corresponding to a predetermined boiling range may be used.
  • the fractions that can also obtain the above-described apparatus forces may be used alone or in combination of two or more.
  • the mixing amount of these fractions can be arbitrarily set as long as the oxygen content and sulfur content in the oil to be treated satisfy the predetermined concentration range.
  • these fractions may be mixed together with the above-mentioned chemical-derived compounds and synthetic oils obtained via the Fischer-Tropsch reaction.
  • the oxygen content in the oil to be treated is preferably 0.1 to 15% by mass, more preferably 1 to 15% by mass, and still more preferably 3 to 14% by mass, based on the total amount of the oil to be treated. Particularly preferred is 5 to 13% by mass.
  • the oxygen content is less than 0.1% by mass, it tends to be difficult to stably maintain the deoxidation activity and the desulfurization activity.
  • the oxygen content exceeds 15% by mass, equipment required for treatment of by-product water is required, and the interaction between water and the catalyst carrier becomes excessive, resulting in a decrease in activity and a decrease in catalyst strength.
  • the oxygen content can be measured with a general elemental analyzer.
  • the oil to be treated may optionally contain a sulfur-containing hydrocarbon compound.
  • the sulfur-containing yellow hydrocarbon compound is not particularly limited, and specific examples include sulfur, disulfide, polysulfide, thiol, thiophene, benzothiophene, dibenzothiophene, and derivatives thereof.
  • the sulfur-containing hydrocarbon compound contained in the oil to be treated may be a single compound or a mixture of two or more.
  • a petroleum hydrocarbon fraction containing a sulfur content may be mixed with the oil to be treated.
  • the content of sulfur in the oil to be treated is preferably 50 mass ppm or less, more preferably 20 mass ppm or less, still more preferably 10 mass ppm or less, based on the total amount of the oil to be treated. . If the sulfur content exceeds 50 ppm by mass, it tends to be difficult to stably maintain the deoxygenation activity, and the sulfur content in the hydrorefined oil tends to increase. When used as a fuel for diesel engines, etc., there are concerns about adverse effects on engine exhaust gas purification equipment.
  • the sulfur content in the present invention means the mass content of the sulfur content measured according to the method described in JIS K 2541 “Sulfur content test method” or ASTM-5453.
  • the sulfur-containing hydrocarbon compound When the sulfur-containing hydrocarbon compound is contained in the oil to be treated, the sulfur-containing hydrocarbon compound may be mixed with the oil to be treated in advance and the mixture may be introduced into the reactor of the hydrorefining apparatus. When introducing the oil to be treated into the reactor, the oil to be treated may be supplied before the reactor.
  • the oil to be treated used in the present invention preferably contains a fraction having a boiling point of 300 ° C or higher, and preferably does not contain a heavy fraction having a boiling point of 700 ° C or higher. Do not contain a fraction with a boiling point of 300 ° C or higher! If the oil to be treated is used, it tends to be difficult to obtain a sufficient yield by excessive decomposition. On the other hand, when the oil to be treated contains a heavy fraction having a boiling point exceeding 700 ° C., the heavy component promotes carbon deposition in the catalyst, and the activity tends to decrease.
  • the boiling point in the present invention is a value measured according to the method described in JIS K 2254 “Distillation test method” or ASTM-D86.
  • a carrier containing a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium carbonate. And elements of Groups 6A and 8 of the periodic table carried on the carrier A catalyst containing one or more metals selected from elemental materials is used.
  • the catalyst carrier used in the present invention includes two or more kinds selected from aluminum, silicon, zirconium, boron, titanium, and magnesium catalyst.
  • Inorganic acids are used.
  • the porous inorganic oxide to be produced it is preferable to use at least two kinds selected from aluminum, silicon, zirconium, boron, titanium, and magnesium strength from the viewpoint that the deoxygenation activity and desulfurization activity can be further improved. More preferred are inorganic oxides containing aluminum and other elements (a composite oxide of aluminum oxide and other oxides).
  • the carrier contained in the catalyst used in the present invention preferably contains a crystalline molecular sieve.
  • the crystalline molecular sieve preferably contains at least silicon in order to impart sufficient hydrodeoxygenation activity and hydroisomerization activity.
  • the crystalline molecular sieve preferably contains at least one of aluminum, zirconium, fluorine, titanium, gallium, zinc, and phosphorus as a constituent element other than silicon. More preferably, it contains at least one of sulfur, zirconium, boron, titanium and phosphorus. Crystalline Molecular Sibuca S By containing these elements, hydrodeoxygenation reaction and skeletal isomerization reaction of hydrocarbon can be promoted at the same time, and the low temperature performance improvement of refined oil can be achieved more fully. .
  • zeolite containing a zeolite preferred by zeolite and aluminum that is, an aluminosilicate is more preferable.
  • the ratio of caustic to the constituent elements excluding oxygen and kae is It is preferably 3 or more, more preferably 10 or more, and even more preferably 30 or more. When this ratio is less than 3, the decomposition reaction of paraffin is promoted, and there is a possibility that the activity is reduced by coking.
  • the pore diameter of the crystalline molecular sieve is preferably 0.8 nm or less, more preferably 0.65 nm or less. When the pore diameter is larger than 0.8 nm, there is a concern that the decomposition reaction of paraffin occurs.
  • the crystal structure of the crystalline molecular sieve is not particularly limited, but is a structure defined by the International Zeolite Society, FAU, A EL, MFI, MMW, TON, MTW, * BEA, MOR, etc.
  • the method for synthesizing the crystalline molecular sieve that constitutes the catalyst used in the present invention is not particularly limited, and is generally known.
  • Water is a water component containing a component raw material and an amine compound as a structure indicator.
  • a thermal synthesis method or the like can be used.
  • constituent raw materials include sodium silicate, colloidal silica, and alkoxide in the case of a key compound containing silicon, and aluminum hydroxide and sodium aluminate in the case of aluminum. It is done.
  • the structure directing agent include tetrapropyl ammonium salt.
  • the crystalline molecular sieve may be subjected to hydrothermal treatment with steam or the like, immersion treatment with an alkaline or acidic aqueous solution, ion exchange, surface treatment with a basic or acidic gas such as chlorine gas or ammonia, if necessary.
  • the physical properties can be adjusted by applying a single process or a combination of a plurality of processes.
  • examples of constituents other than the crystalline molecular sieve include inorganic oxides containing elements of which aluminum, silicon, zirconium, boron, titanium, and magnesium power are also selected. These inorganic oxides are used as a bonding agent for forming crystalline molecular sieves, and also function as active ingredients for promoting hydrodeoxygenation and hydroisomerization. Zirconium, fluorine, titanium, and magnesium power It is preferable that it contains two or more elements selected.
  • the content of the crystalline molecular sieve in the total catalyst is preferably 2 to 90% by mass, more preferably 5 to 85% by mass, based on the total amount of the catalyst, and 10 to 80% by mass. More preferably.
  • this content is less than 2% by mass, the hydrodeoxygenation activity and hydroisomerization activity as a catalyst tend to decrease.
  • it exceeds 90% by mass the catalyst moldability decreases, There is a risk of hindrance to industrial production.
  • the method of introducing constituent elements other than aluminum, ie, silicon, zirconium, boron, titanium, and magnesium is not particularly limited.
  • a solution containing these elements may be used as a raw material.
  • silicon, caustic acid, water glass, silica Boron, boric acid for boron, phosphorous for phosphoric acid and alkali metal salts of phosphoric acid, titanium for titanium sulfate, tetra-salt titanium and various alkoxide salts, zirconium for zirconium sulfate And various alkoxide salts can be used.
  • the raw materials of the carrier constituents other than aluminum oxide are added in the step prior to the firing of the carrier.
  • the above raw materials are added to a prepared hydroxy aluminum gel that may be prepared from a hydroxyaluminum gel containing these components. May be.
  • the above raw materials may be added.
  • the carrier containing the crystalline molecular sieve carries one or more metals selected from elemental forces of Group 6A and Group 8 of the periodic table.
  • metals selected from elemental forces of Group 6A and Group 8 of the periodic table.
  • Suitable combinations include, for example, Pd—Pt, Pd—Ir, Pd—Rh, Pd—Au, Pd—Ni, Pt—Rh, Pt—Ir, Pt—Au, Pt—Ni ⁇ Rh—Ir, Rh—Au, Rh—Ni ⁇ Ir Au ⁇ IrNi ⁇ Au—Ni ⁇ Ni—Mo, Pd—Pt—Rh, Pd—Pt—Ir, Pd—Pt—Ni, and the like.
  • Pd—Pt, Pd—Ni, Pt—Ni, Pd—Ir, Pt—Rh, Pt—Ir, Rh—Ir, Pd—Pt—Rh, Pd—Pt—Ir, Pt—Pd—Ni Combinations of Pd—Pt, Pd—Ni, Pt—Ni, Pd—Ir, Pt—Ir, Pd—Pt—Ir, and Pt—Pd—Ni are more preferred.
  • the total content of the active metal based on the catalyst mass is preferably 0.1 to 2 mass% of the force S as the metal, more preferably 0.2 to 1.5 mass%. More preferably 3% by weight. If the total supported amount of metals is less than 0.1% by mass, the active sites tend to decrease and sufficient activity cannot be obtained. On the other hand, if it exceeds 2% by mass, the metal is not effectively dispersed and There is a tendency that sufficient activity cannot be obtained.
  • the method of incorporating these active metals into the catalyst is not particularly limited, and a known method applied when producing a normal desulfurization catalyst can be used.
  • a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed.
  • an equilibrium adsorption method, a pore filling method, an incipient-wetness method and the like are preferably employed.
  • the pore filling method is a method in which the pore volume of a support is measured in advance and impregnated with a metal salt solution having the same volume.
  • the impregnation method is not particularly limited, and it can be impregnated by an appropriate method depending on the amount of metal supported and the physical properties of the catalyst carrier.
  • the catalyst used in the present invention is preferably subjected to reduction treatment of the active metal contained in the catalyst before being subjected to the reaction.
  • a reduction process is not specifically limited, it reduces by processing at the temperature of 200-400 degreeC under hydrogen stream. Further, this reduction treatment is preferably performed in the range of 240 to 380 ° C. If the reduction temperature is less than 200 ° C, the reduction of the active metal does not proceed sufficiently, and the hydrodeoxygenation and hydroisomerization activity may not be fully exhibited. Further, when the reduction temperature exceeds 400 ° C, the aggregation of the active metal proceeds, and there is a possibility that the activity cannot be sufficiently exhibited.
  • the power of carbon monoxide adsorption capacity s 0.003 to 0.05 mmol per lg of catalyst S is preferable, 0.005 to More preferably, it is 0.04 mmol, more preferably 0.009 to 0.03 mmol.
  • the amount of adsorption is less than 0.003 mmol, the active site tends to decrease because the metal is aggregated.
  • the adsorbed amount exceeds 0.05 mmol the decrease in activity tends to be promoted as the reaction time elapses.
  • a general measurement method used for a catalyst carrying a reduced metal can be applied. Specifically, after a certain amount of catalyst is reduced at 350 ° C under a hydrogen stream, it is cooled to 50 ° C, and the pulse method can be obtained by the constant volume method.
  • the scale component that flows along with the oil to be treated is trapped, or the hydrotreating is performed at the separation part of the catalyst bed.
  • a guard catalyst, a metal removal catalyst, or an inert packing may be used. In addition, these can be used individually or in combination.
  • the conditions for contacting the oil to be treated with the catalyst in the presence of hydrogen are as follows: hydrogen pressure 2 to 13 MPa, liquid space velocity (LHSV) O. 1 to 3.
  • hydrogen oil ratio (hydrogen Z oil ratio) 150 to 150 ONLZL preferably hydrogen pressure 2 to 13 MPa, liquid hourly space velocity (LHSV) 0.1 to 3.
  • Hydrogen oil ratio is 300 to 1200 NLZL, more preferably, hydrogen pressure is 3 to 8 MPa, space velocity is 0.8 to 1.8 h " ⁇ hydrogen oil ratio is 350 to 1000 NLZL.
  • the temperature condition for bringing the oil to be treated into contact with the catalyst in the presence of hydrogen is 150 to 380 ° C.
  • the temperature is preferably 170 to 360 ° C, more preferably 220 to 350 ° C. If the temperature is less than 150 ° C, the deoxygenation activity tends to be insufficient. On the other hand, if the temperature exceeds 380 ° C, the oil to be treated is excessively decomposed and is a useful fraction for the production of liquid fuel. The yield of (for example, a fraction having a boiling point in the range of 250 to 350 ° C.) tends to decrease.
  • the reactor type a fixed bed system can be adopted.
  • hydrogen can adopt either a countercurrent or a cocurrent flow with respect to the oil to be treated.
  • it is good also as a form which combined countercurrent and parallel flow using several reactors.
  • As a general format it is a down flow, and a gas-liquid twin parallel flow format can be adopted.
  • the reactor may adopt a structure in which a single reactor or a combination of a plurality of reactors is divided into a plurality of catalyst beds.
  • the hydrorefined oil hydrorefined in the reactor is fractionated into a hydrorefined oil containing a predetermined fraction through a gas-liquid separation step, a rectification step, and the like.
  • a light oil fraction is fractionated into a residual fraction.
  • gas, naphtha fraction, and kerosene fraction may be fractionated as necessary.
  • Hydrogen can be produced by reforming a part of the light hydrocarbon fraction produced in a steam reformer. Since the hydrogen produced in this way is a biomass-derived hydrocarbon as a raw material used for steam reforming, it has a feature of carbon-eutal and can reduce the burden on the environment. Water, carbon monoxide, carbon dioxide, hydrogen sulfide, etc.
  • the gas component from which the by-product gas has been removed by the by-product gas removing device may be mixed with the oil to be treated and recycled for use. It can also be used after the purity of hydrogen contained in the gas is increased by a membrane separator or pressure swing adsorption device before mixing with the oil to be treated.
  • the concentration of carbon monoxide contained in the gas to be recycled is preferably 0.5% by volume or less, more preferably 0.1% by volume or less, from the viewpoint of maintaining catalytic activity.
  • Hydrogen gas is generally introduced at the initial reactor inlet force along with the oil to be treated before or after passing through the heating furnace. Separately, the temperature inside the reactor is controlled. In addition, hydrogen gas may be introduced between the catalyst beds or between the reactors in order to maintain the hydrogen pressure throughout the reactor.
  • the hydrogen introduced in this way is generally called Taenti hydrogen.
  • the ratio of Taenthi hydrogen to the hydrogen gas introduced along with the oil to be treated is preferably 10 to 60% by volume, more preferably 15 to 50% by volume. If the proportion of Taenti hydrogen is less than 10 volumes, the reaction at the subsequent reaction site tends not to proceed sufficiently. If the proportion of Taenti hydrogen exceeds 60% by volume, the reaction near the reactor inlet proceeds sufficiently. There is a tendency not to.
  • the hydrorefined oil produced according to the present invention contains at least a fraction having a boiling point of 260 to 300 ° C and a sulfur content of 10 mass. It is preferable that the oxygen content is not more than ppm and the oxygen content is 0.3 mass% or less.
  • the sulfur content is preferably 7 mass ppm or less and the oxygen content is 0.3 mass% or less. More preferably, the sulfur content is 3 mass ppm or less and the oxygen content is 0.2 mass% or less. If the sulfur and oxygen contents exceed the above upper limits, filters and catalysts used in diesel engine exhaust gas treatment equipment, and further In addition, the engine and other components may be affected.
  • the ratio of isoparaffin to normal paraffin in the paraffin content in the fraction is preferably 0.2 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. If this ratio is less than 0.2, the distillate cannot maintain sufficient fluidity in a low-temperature environment, or the crystals that precipitate in the low-temperature environment clog the diesel engine fuel filter. May occur and cause trouble.
  • the hydrorefined oil produced by the present invention can be suitably used particularly as a diesel light oil or heavy oil base material.
  • the hydrorefined oil may be used alone as a diesel light oil or heavy oil base material! However, it can be used as a diesel light oil or heavy base material mixed with components such as other base materials.
  • a light oil fraction and Z or kerosene fraction obtained in a general petroleum refining process, and a residual fraction obtained by the hydrorefining method of the present invention can be mixed.
  • synthetic gas oil or synthetic kerosene obtained via a Fischer-Tropsch reaction can be mixed using so-called synthesis gas, which is also composed of hydrogen and carbon monoxide, as a raw material.
  • These synthetic light oils and kerosene are characterized by containing almost no aromatics, mainly consisting of saturated hydrocarbons, and high cetane numbers.
  • a known method can be used as a method for producing the synthetic gas, and is not particularly limited.
  • the hydrorefining step of hydrotreating the oil to be treated removes 70 mass% or more of the initial oxygen content contained in the oil to be treated to obtain the first refined oil.
  • a second hydrogenation step of removing the oxygen content remaining in the first refined oil to obtain a second refined oil so that 95% by mass or more of the initial oxygen content is removed In the second hydrogenation step, the ratio of isoparaffin to normal paraffin (mass of isoparaffin Z mass of normal paraffin) is 0.2 or more in the paraffin content of the second refined oil at 150 to 350 ° C.
  • the hydrodeoxygenation and hydroisomerization reaction in the second hydrogenation process may not proceed sufficiently.
  • at least one of the first hydrogenation step and the second hydrogenation step is carried out in the presence of hydrogen in the presence of the oxygen-containing hydrocarbon compound.
  • a porous inorganic oxide containing two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium force and it is preferable to use a catalyst containing one or more metals (active metals) selected from Group 6A and Group 8 element forces of the periodic table supported on the porous inorganic oxide.
  • the active metal is more preferably at least one element selected from Pd, Pt, Rh, Ir, Au, Ni and Mo.
  • the carrier containing the crystalline molecular sieve, and the elements of Group 6A and Group 8 of the periodic table (preferably Group 8) supported on the carrier It is preferable to use a catalyst containing one or more kinds of metals selected from these elements.
  • the catalyst used in the second hydrogenation step is charged with a catalyst having hydrogenation activity after the second hydrogenation step for the purpose of improving the stability of refined oil that may be used alone or in combination. Good.
  • 3,000 g of water glass No. 3 was added to 3000 g of an aqueous sodium aluminate solution having a concentration of 5% by mass and placed in a container kept at 65 ° C.
  • 3000 g of a 2.5 mass% aqueous solution of aluminum sulfate was prepared in another container kept at 65 ° C., and the aqueous solution containing sodium aluminate was added dropwise thereto.
  • the end point is when the pH of the mixed solution reaches 7.0, and The rally-like product was filtered through a filter to obtain a cake-like slurry.
  • the cake-like slurry was transferred to a container equipped with a reflux condenser, 150 ml of distilled water and 10 g of 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 75 ° C for 20 hours.
  • the slurry was put in a kneading apparatus, heated to 80 ° C. or higher and kneaded while removing moisture to obtain a clay-like kneaded product.
  • the obtained kneaded product was extruded into a shape of a cylinder having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 550 ° C. to obtain a molded carrier.
  • a 3000 g aqueous solution of sodium aluminate having a concentration of 5% by mass was placed in a container kept at 65 ° C.
  • 3000 g of an aluminum sulfate aqueous solution having a concentration of 2.5% by mass was prepared, and the aforementioned sodium aluminate aqueous solution was added dropwise thereto.
  • the resulting slurry product was filtered off through a filter to obtain a cake slurry.
  • the cake-like slurry was transferred to a container equipped with a reflux condenser, and 150 ml of distilled water and 10 g of a 27% ammonia aqueous solution were added, followed by heating and stirring at 75 ° C for 20 hours.
  • the slurry was put into a kneading apparatus, heated to 80 ° C. or higher and kneaded while removing moisture to obtain a clay-like kneaded product.
  • the obtained kneaded product was extruded into a shape of a cylinder having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 550 ° C. to obtain a molded carrier.
  • a first reaction tube (inner diameter 20 mm) filled with catalyst A-1 (50 ml) and a second reaction tube (inner diameter 20 mm) also filled with catalyst A-1 (50 m1) are connected in series to a fixed bed flow reactor. Installed. Thereafter, the catalyst was reduced for 6 hours under the conditions of an average catalyst layer temperature (reaction temperature) of 320 ° C., a hydrogen partial pressure of 5 MPa, and a hydrogen gas amount of 83 mlZ.
  • a mixed oil obtained by mixing 70 parts by volume of the same palm oil as used in Example 1 and 30 parts by volume of petroleum-based desulfurized light oil was used as the oil to be treated, and the reaction temperature of the first and second reaction tubes was 260 ° C.
  • the hydrorefining was performed in the same manner as in Example 1 except that.
  • Petroleum desulfurized gas oil has a density of 0.838 gZml, a sulfur content of 15 ppm by mass, and an initial boiling point and end point of 211 ° C and 365 ° C, respectively.
  • the density of the oil to be treated is 0.893 gZml, containing oxygen. The abundance is 8.2 mass% and the sulfur content is 4.2 mass ppm.
  • boehmite powder Catalyst Kasei Kogyo Co., Ltd.
  • silica alumina powder Catalyst Kasei Kogyo Co., Ltd.
  • the synthesized proton type ZSM-5 (the ratio of the number of atoms of the key Z-aluminum: 40) as zeolite is added so as to be 65% by mass of the total amount of the catalyst in terms of oxide, and further kneaded. did.
  • the obtained kneaded product was extruded into a cylinder shape having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 500 ° C. to obtain a molded carrier.
  • boehmite powder Catalyst Kasei Kogyo Co., Ltd.
  • silica alumina powder Catalyst Kasei Kogyo Co., Ltd.
  • the synthesized proton-type ZSM-2 2 2 (the ratio of the number of atoms of the key Z-aluminum: 45) as zeolite is added so as to be 65% by mass of the total amount of the catalyst in terms of oxide, and further kneaded. did.
  • the obtained kneaded product was extruded into a cylinder shape having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 500 ° C. to obtain a molded carrier.
  • platinum and palladium were supported on 10 g of the obtained molded carrier to obtain catalyst B-2.
  • the supported amount of platinum and noradium in catalyst B-2 was 0.5% by mass of platinum and 0.7% by mass of noradium based on the total amount of the catalyst.
  • the cake-like slurry was transferred to a container equipped with a reflux condenser, 150 ml of distilled water and 10 g of 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 75 ° C for 20 hours.
  • the slurry was put in a kneading apparatus, heated to 80 ° C. or higher and kneaded while removing moisture to obtain a clay-like kneaded product.
  • the obtained kneaded product was extruded into a cylinder shape having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 550 ° C. to obtain a molded carrier.
  • the aluminum content of the molded carrier was 90.1% by mass in terms of acid aluminum, and the key content was 9.9% by mass in terms of key acid.
  • the first reaction tube (inner diameter 20mm) filled with catalyst A-2 (50ml) and the second reaction tube (inner diameter 20mm) also filled with catalyst A-2 (50m1) are connected in series to a fixed bed flow reactor. Installed. Thereafter, the catalyst was reduced for 6 hours under the conditions of an average catalyst layer temperature of 320 ° C, a hydrogen partial pressure of 5 MPa, and a hydrogen gas amount of 83 mlZmin. The adsorbed amount of carbon monoxide per lg of catalyst A-2 in the reduced state was 0.037 mmol.
  • the first reaction tube was filled with catalyst C-2 (50 ml)
  • the second reaction tube was filled with catalyst A-2 (50 ml)
  • hydrorefining was carried out in the same manner as in Example 3.
  • the results obtained are shown in Table 3. Note that the amount of carbon monoxide adsorbed per lg of catalyst C 2 in the reduced state was 0.038 mmol o
  • the refined oils obtained by hydrorefining in Examples 3 to 5 and Comparative Example 5 were subjected to distillation to remove the fraction lighter than the boiling point of 150 ° C, and then the cloud point of the residue (kerosene oil fraction). Measured in accordance with JIS K2 269 “Pour point of crude oil and petroleum products and cloud point test method for petroleum products”. Further, with respect to the paraffin content in the residue, the mass ratio of isoparaffin to normal paraffin (mass of isoparaffin Z mass of normal paraffin) was measured. The results are shown in Table 3.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé d'hydroraffinage impliquant une étape d'hydroraffinage dans laquelle une huile à traiter est mise en contact avec un catalyseur en présence d'hydrogène dans des conditions d'une pression d'hydrogène de 2 à 13 MPa, d'une vitesse spatio-temporelle de liquide allant de 0,1 à 3,0 h-1, d'un rapport hydrogène/huile allant de 150 à 1500 NL/L et d'une température de réaction allant de 150 à 380 °C de façon à produire de ce fait une huile purifiée. L'huile contient un composé hydrocarboné oxygéné. Le catalyseur comprend : un support qui comprend un oxyde inorganique poreux ayant au moins deux éléments choisis parmi l'aluminium, le silicium, le zirconium, le bore, le titane et le magnésium ; et au moins un métal choisi parmi les éléments appartenant aux groupes 6A et 8 dans le tableau périodique, qui est supporté sur le support.
PCT/JP2007/059972 2006-05-17 2007-05-15 Procédé d'hydroraffinage WO2007132857A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009072468A1 (fr) * 2007-12-07 2009-06-11 Nippon Oil Corporation Procédé de fabrication d'hydrocarbure liquide
US20160257889A1 (en) * 2015-03-05 2016-09-08 Battelle Memorial Institute Pre-processing Bio-oil Before Hydrotreatment

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102464997B (zh) * 2010-11-04 2015-07-22 中国石油化工股份有限公司 生物油脂生产马达燃料的加氢方法
CN102464994B (zh) * 2010-11-04 2015-07-22 中国石油化工股份有限公司 一种生物油脂生产马达燃料的加氢方法
CN102464992A (zh) * 2010-11-04 2012-05-23 中国石油化工股份有限公司 生物油脂生产优质马达燃料的加氢方法
CN102911698B (zh) * 2011-08-01 2015-04-01 中国石油化工股份有限公司 生物油脂生产优质马达燃料的加氢方法
CN102911696B (zh) * 2011-08-01 2015-04-01 中国石油化工股份有限公司 生物油脂生产马达燃料的加氢处理方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59108088A (ja) * 1982-11-10 1984-06-22 Honda Motor Co Ltd パラフイン系炭化水素の製造法
JP2003171670A (ja) * 2001-12-07 2003-06-20 Kawaken Fine Chem Co Ltd 炭化水素類の製造方法および炭化水素類製造用触媒
US20040230085A1 (en) * 2002-09-06 2004-11-18 Juha Jakkula Process for producing a hydrocarbon component of biological origin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59108088A (ja) * 1982-11-10 1984-06-22 Honda Motor Co Ltd パラフイン系炭化水素の製造法
JP2003171670A (ja) * 2001-12-07 2003-06-20 Kawaken Fine Chem Co Ltd 炭化水素類の製造方法および炭化水素類製造用触媒
US20040230085A1 (en) * 2002-09-06 2004-11-18 Juha Jakkula Process for producing a hydrocarbon component of biological origin

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009072468A1 (fr) * 2007-12-07 2009-06-11 Nippon Oil Corporation Procédé de fabrication d'hydrocarbure liquide
US20160257889A1 (en) * 2015-03-05 2016-09-08 Battelle Memorial Institute Pre-processing Bio-oil Before Hydrotreatment

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