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WO2007064019A1 - Composition de gaz combustible liquefie - Google Patents

Composition de gaz combustible liquefie Download PDF

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Publication number
WO2007064019A1
WO2007064019A1 PCT/JP2006/324306 JP2006324306W WO2007064019A1 WO 2007064019 A1 WO2007064019 A1 WO 2007064019A1 JP 2006324306 W JP2006324306 W JP 2006324306W WO 2007064019 A1 WO2007064019 A1 WO 2007064019A1
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WO
WIPO (PCT)
Prior art keywords
hydrocarbon
fuel gas
mol
gas composition
less
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
PCT/JP2006/324306
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English (en)
Japanese (ja)
Inventor
Manabu Watanabe
Masanori Hirose
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eneos Corp
Original Assignee
Nippon Oil Corp
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Filing date
Publication date
Application filed by Nippon Oil Corp filed Critical Nippon Oil Corp
Publication of WO2007064019A1 publication Critical patent/WO2007064019A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • 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
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/12—Liquefied petroleum gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/18—Crystalline alumino-silicate carriers the catalyst 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1018—Biomass of animal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/28—Propane and butane
    • 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 liquefied fuel gas composition, and in particular, using at least one metal selected from Groups 6A and 8 of the Periodic Table using a hydrocarbon fraction containing components derived from animal and vegetable oils and animal fats as a feedstock. And hydrogen containing an inorganic oxide with acid properties
  • the present invention relates to a liquefied fuel gas composition containing hydrocarbons obtained by contacting a hydrocracking catalyst with hydrogen under pressure.
  • Non-Patent Document 1 Regard the quality of liquefied petroleum gas (autogas) for automobiles, there are examples that have been studied with the aim of further reducing exhaust gas (see, for example, Patent Document 1), but examples of studies on reducing carbon dioxide. There is no.
  • Patent Document 1 Japanese Patent Laid-Open No. 10-1 2 10 70
  • Non-Patent Document 1 ⁇ LP Gas 'Data Required (LP Gas' Data Required Editorial Committee) ", industry bulletin, supervised by the Science and Technology Agency, Resource Bureau, 1 96 4 years, p. 1 6 6 Used in Japan About one-quarter of LPG is provided by domestic production and about 34 by import.
  • LP Gas'Data Required LP Gas' Data Required Editorial Committee
  • p. 1 6 6 Used in Japan About one-quarter of LPG is provided by domestic production and about 34 by import.
  • biomass-derived fuel which is the most renewable energy.
  • Use as a fuel is being studied.
  • fuels that can be mixed directly with gasoline and light oil, which are conventional fossil fuels, such as bioethanol, ETB, and biodiesel are being investigated.
  • biomass-derived liquefied fuel gas compositions that can be directly mixed with conventional liquefied petroleum gas.
  • hydrocarbon fractions containing animal and vegetable fats and animal fats and oils as feedstocks, starting from groups 6A and 8 of the periodic table.
  • a liquefied fuel gas composition using a hydrocarbon obtained by contacting a hydrocracking catalyst containing at least one selected metal and an inorganic oxide having acid properties with hydrogen under pressure is found, and the present invention Has been completed. That is, the present invention provides a feedstock consisting of a hydrocarbon fraction containing a component derived from animal and vegetable fats and / or animal fats and at least one metal selected from Groups 6A and 8 of the periodic table.
  • the present invention relates to a liquefied fuel gas composition characterized by containing a hydrocarbon having 9 9.0 mol% or less and a C 4 hydrocarbon of 1.0 mol% or more and 99.0 mol% or less.
  • the present invention also provides a mixed oil obtained by mixing a hydrocarbon hydrocarbon fraction containing a component derived from animal and vegetable fats and oils and Z or animal fats and a petroleum hydrocarbon fraction having a kerosene fraction purified from crude oil or the like at an arbitrary ratio.
  • a feedstock comprising: a hydrocracking catalyst containing at least one metal selected from Groups 6A and 8 of the Periodic Table and an inorganic oxide having acid properties under hydrogen pressure.
  • a sulfur content of 10 mass ppm or less and a carbon number of 3 hydrocarbons obtained by the above is 1.0 mol% or more and 99.0 mol. /.
  • the hydrocarbon having 4 carbon atoms is 1.0 mol% or more and 99.0 mol. Contains hydrocarbons that are less than or equal to 0
  • the present invention relates to a liquefied fuel gas composition.
  • a hydrocarbon fraction containing animal and vegetable fats and oils and components derived from Z or animal fats is used as a raw material oil.
  • a mixed oil obtained by mixing animal and vegetable oils and / or hydrocarbon fractions containing animal fats and oils at an arbitrary ratio is used as a raw material oil.
  • animal and vegetable fats and oils and animal fats and oils-derived components in the present invention refer to animal and vegetable fats and oils and animal and vegetable fats and oils components that are produced or manufactured naturally or artificially.
  • animal fats and animal oils include beef tallow, milk lipid (batter), pork tallow, sheep fat, whale oil, fish oil, liver oil, etc.
  • Vegetable oils and vegetable oil ingredients include coconut palm, olive palm, olive, There are seeds and other parts such as banana, rapeseed (rapeseed), rice bran, sunflower, cottonseed, corn, soybeans, sesame seeds, Amami, etc. There is no problem in use.
  • raw oils may be solid or liquid, but it is preferable to use vegetable oils or vegetable oils as raw materials because of easy handling and high carbon dioxide absorption.
  • waste oils obtained by using these animal oils and vegetable oils for consumer use, industrial use, food use, etc. can be used as raw materials after adding a step for removing impurities.
  • Typical compositions of the fatty acid part of the glyceride compounds contained in these raw materials include butyric acid (C 3 H 7 COOH) and caproic acid, which are fatty acids having no unsaturated bonds in the molecular structure called saturated fatty acids.
  • Myristic acid (C! 3 H 27 COOH), palmitic acid (C! 5 H 3 i COOH), stearic acid (C 17 H 35 COOH), and unsaturated fatty acids with one or more unsaturated bonds
  • Examples include oleic acid (C 7 H 33 COOH), linoleic acid (C 17 H 31 COO H), linolenic acid (C i 7 H 29 COOH), and ricinolenic acid (C 17 H 32 (OH) CO OH).
  • the hydrocarbon part of these fatty acids in natural substances is generally straight chain, but as long as the properties defined in the present invention are satisfied in the present invention, even a structure having a side chain, that is, an isomer is used. can do.
  • the position of the unsaturated bond in the molecule of the unsaturated fatty acid is not limited to those generally found in nature as long as the properties specified in the present invention are satisfied in the present invention, but are also set at arbitrary positions by chemical synthesis. It can also be used.
  • the above-mentioned raw oils have one or more of these fatty acids, and the fatty acids they have differ depending on the raw materials.
  • coconut oil has a relatively large amount of saturated fatty acids such as lauric acid and myristic acid
  • soybean oil has a large amount of unsaturated fatty acids such as oleic acid and linoleic acid. .
  • Petroleum hydrocarbon fractions with kerosene fractions refined from crude oil, etc. used by mixing them in any proportion with hydrocarbon fractions containing animal and vegetable fats and / or animal fats and oils.
  • the fraction obtained in the refining process can be used.
  • the fraction hydrodesulfurization apparatus, hydrocracking apparatus, hydrocracking apparatus, and residual oil direct desulfurization corresponding to a predetermined boiling range obtained from an atmospheric distillation apparatus or a vacuum distillation apparatus.
  • a fraction having a corresponding boiling range obtained from an apparatus, a fluid catalytic cracker, or the like may be mixed alone, or corresponding fractions from a plurality of apparatuses may be mixed.
  • the petroleum hydrocarbon fraction has at least a boiling point
  • the boiling point range in this specification is a value measured according to the method described in JI S K 2 2 5 4 “Distillation test method” or A STM — D 8 6.
  • Petroleum containing raw material oil consisting of hydrocarbon fractions containing components derived from animal and vegetable oils and fats or animal oils, or hydrocarbons containing components derived from animal and vegetable oils and / or animal oils and oils having kerosene fractions refined from crude oil, etc.
  • the mixed oil in which the hydrocarbon fractions are mixed in an arbitrary ratio is the raw material oil.
  • an inorganic oxide having at least one metal selected from Group 6A and Group 8 of the periodic table and an acid property is used.
  • the hydrocracking catalyst contained is brought into contact with hydrogen under pressure.
  • the hydrocracking catalyst contains at least one type of metal selected from Group 6A and Group 8 metals of the periodic table, and preferably two or more types from Group 6A and Group 8. Contains the above metals.
  • C o—M o, N i -M o, N i—C o—M o, N i—W are preferable, N i—M o, N i—C o—M o, N i— W is selected.
  • these metals are converted into sulfides and used in the same manner as the pretreatment catalyst for hydrogenation.
  • these composite oxides contain zeolite.
  • the ratio of alumina to other components can be any ratio to the support, but the alumina content is 96% of the support weight. / 0 or less, preferably 90 weight. It is more desirable that it be less than 0 .
  • the alumina content exceeds 96% by weight, sufficient acidity cannot be obtained, and it tends to be difficult to exhibit a predetermined hydrocracking activity.
  • zeolite crystal skeleton used in hydrocracking catalysts.
  • alumina, titania, polya, gallium, and other components that form the zeolite crystal skeleton used in hydrocracking catalysts.
  • Many types of crystal structures of zeolite have been reported, such as faujasite, beta, mordenite, and pentasil.
  • the faujasite type, beta type, and pentasil type are more preferable, and particularly the faujasite type and beta type are even more desirable in that sufficient hydrocracking activity is exhibited.
  • zeolites those having an alumina content adjusted according to the stoichiometric ratio of raw materials at the start of synthesis, or those subjected to a predetermined hydrothermal treatment and / or acid treatment can be used.
  • ultra-stabilized Y type that is super-stabilized by hydrothermal treatment and / or acid treatment is most desirable.
  • This ultra-stabilized Y-type 2 In addition to the fine pore structure called Miku mouth pores below OA, new pores are formed in the range of 20 to 10 OA, which provides a good reaction field for converting the oxygen content of fats and oils.
  • the volume of the pores having the pore diameter is preferably 0.03 ml / g or more, more preferably 0,04 4 m 1 / g.
  • the pore volume mentioned here can be generally determined by a mercury intrusion method.
  • Known conditions can be used as the hydrothermal treatment conditions.
  • the molar ratio of silica and alumina is preferably 10 to 120, more preferably 15 to 70, and even more preferably 20 to 50. If the molar ratio of silica Z-alumina is higher than 120, the acidity is low, and sufficient hydrocracking activity may not be exhibited. On the other hand, when the molar ratio of silica Z alumina is lower than 10, the acidity is too strong, and there is a risk that the activity is rapidly lowered by promoting the coke formation reaction.
  • the content of zeoli cake is preferably 2 to 80% by weight, more preferably 4 to 75% by weight, based on the weight of the carrier. If the zeolite content is less than the lower limit, the hydrocracking activity may not be exhibited. If the zeolite content exceeds the upper limit, the acidity is too strong and the coke formation reaction There is a risk of promoting.
  • a hydrogenation pretreatment catalyst containing at least one metal selected from Group 6A and Group 8 of the periodic table and hydrogen pressure is used. It is preferable to contact with the hydrocracking catalyst under hydrogen pressure after contacting with.
  • the active metal of the hydrogenation pretreatment catalyst contains at least one metal selected from Group 6A and Group 8 metals of the periodic table, and preferably selected from Group 6A and Group 8 Contains two or more metals.
  • Co-Mo, Ni-M--o, Ni-Co-Mo, Ni--W, and these metals are converted to sulfide during the pretreatment of hydrogenation. To use.
  • a porous inorganic oxide is used as the support for the hydrogenation pretreatment catalyst.
  • it is a porous inorganic oxide containing alumina, and other carrier constituents include siri force, titania, zircoua, and polya.
  • it is a complex oxide containing at least one selected from alumina and other constituent components.
  • phosphorus may be included as another component.
  • the total free Yuryou ingredient other than alumina is 1 to 2 0 weight 0/0, 2-1 5 to contain by weight% Is more desirable. If the content is less than 1% by weight, a sufficient catalyst surface area cannot be obtained, and the activity may be lowered. If the content exceeds 20% by weight, the acidity of the support increases. There is a risk of reducing the activity due to the generation of the core.
  • phosphorus is included as a carrier constituent, its content is preferably 1 to 5% by weight, more preferably 2 to 3.5% by weight in terms of oxide.
  • the raw material that is a precursor of silica, titania, zircoure, and polya, which are carrier constituents other than alumina, and a solution containing general silicon, titanium, zirconium, and boron
  • a solution containing general silicon, titanium, zirconium, and boron can be used.
  • calcium for acid, water glass, silica sol, titanium sulfate for titanium, titanium tetrachloride and various alkoxide salts, zirconium for zirconium sulfate and various alkoxide salts, boron for boric acid, etc. Can be used.
  • phosphorus phosphoric acid or an alkali metal salt of phosphoric acid can be used.
  • the raw materials for the carrier constituents other than these aluminas are added in any step prior to the firing of the carrier.
  • it may be added to an aluminum aqueous solution in advance and then an aluminum hydroxide gel containing these components, may be added to a prepared aluminum hydroxide gel, or water or an acidic aqueous solution may be added to a commercially available alumina intermediate or boehmite powder.
  • a method of coexisting at the stage of preparing aluminum hydroxide gel is more desirable.
  • the active metal content is, for example, the total supported amount of W and Mo is preferably 12 to 35% by weight, more preferably 15 to 30% by weight based on the catalyst weight in terms of oxide conversion. is there. If the total supported amount of W and Mo is less than the lower limit, the activity may decrease due to a decrease in the number of active points.If the upper limit is exceeded, the metal is not effectively dispersed, Similarly, the activity may be reduced.
  • the total supported amount of 0 and ⁇ 1 is preferably 1.5 to 10% by weight, more preferably 2 to 8% by weight based on the catalyst weight in terms of oxide. If the total supported amount of cobalt and nickel is less than 1.5% by weight, a sufficient promoter effect may not be obtained and the activity may decrease. If it is higher than% by weight, the metal will not disperse effectively and may lead to activity as well o
  • the catalytic reaction conditions under hydrogen pressure are as follows: hydrogen pressure 5 to 20 MPa, liquid space velocity (LHSV) 0.:! To 2.2 h 1 , hydrogen Z oil ratio 300 to: I 500 N LZL Desirable conditions are: hydrogen pressure 6.5 to 18 MPa, liquid space velocity 0.2 to 2.0 h 1 , hydrogen / oil ratio 300 to 1 500 NL / L. Pressure 8 ⁇ 15MPa, Liquid space velocity 0.3 ⁇ : I.5h Hydrogen Oil ratio 350 ⁇ 1000N LZL and when the conditions are even more desirable.
  • the liquefied fuel gas composition of the present invention contains such a hydrocarbon, and its content is at least 1.0% by volume, preferably at least 20.0% by volume, more preferably at 98.0%. It is more than volume%.
  • the liquefied fuel gas composition of the present invention comprises a propane mixture which is a hydrocarbon having 3 carbon atoms as a main component and a butane mixture which is a hydrocarbon having 4 carbon atoms.
  • the ratio of the two can be arbitrarily defined according to the location of use and season.
  • the propane mixture is mainly composed of propane and propylene
  • the butane mixture is mainly composed of butane and butylene.
  • the composition of the liquefied fuel gas composition of the present invention can contain a small amount of ethane mixture, butadiene, pentane and the like.
  • the ethane mixture is composed of ethane and ethylene, and the content of the ethane mixture in the liquefied fuel gas composition is preferably 5 mol% or less.
  • the content of butadiene in the liquefied fuel gas composition is preferably 5 mol 0/0 below 0.1, the content of pentane 2 mol 0 /. The following is preferable.
  • the liquefied fuel gas composition of the present invention preferably has a residue at 105 ° C of 10 mass ppm or less. 105.
  • the C residue content is more preferably 5 mass ppm or less, and particularly preferably 2 mass ppm or less from the viewpoint of reducing the deposit generation rate and the frequency of drain extraction.
  • the residue at 105 ° C here is a value measured according to the method specified in ASTM D 2 1 58, but the initial sample amount is 10 OmL as described in the AS TM method.
  • the value to be measured By changing the set temperature from 38 ° C to 75 ° C and 1,05 ° C in order, and finally weighing the remaining residue at 105 ° C. The value to be measured.
  • the holding time at each temperature is not 5 minutes described in the AS TM method, but a sufficient time is taken until almost no evaporation is observed at that temperature.
  • the liquefied fuel gas composition of the present invention preferably has a pH of the residue at 105 ° C of 6 or more.
  • the pH of the residue at 105 ° C is less than 6, there is a risk of increased deposit formation inside the vaporizer.
  • the pH is preferably 8 or less in terms of preventing corrosion between the fuel line and the vaporizer. More preferably, the pH is 6-7, and even more preferably the pH is 7.
  • 105 at 11 residue means that the residue at 105 ° C obtained by the above method for measuring the residue at 105 ° C is 1000 times the amount of distilled water (residue is 1 mg). In the following cases, 1 mL of distilled water) is added and stirred, and then the value obtained by measuring the pH of the aqueous phase with a pH test paper.
  • the sulfur content of the liquefied fuel gas composition of the present invention is preferably 0.02 mass% or less on the basis of the total amount of liquefied fuel gas from the viewpoint of preventing corrosion of the fuel line and preventing sulfur oxide emission into the exhaust gas, More preferably, the content is 0.01% by mass or less, more preferably 0.005% by mass or less, and 0.001% by mass. Most preferably, it is less than or equal to 0 .
  • the sulfur content here means a value measured by J I S K 2240 “Liquefied petroleum gas (LP gas) single sulfur content test method”.
  • the vapor pressure at 40 ° C of the liquefied fuel gas composition of the present invention is preferably 0.28 MPa or more, more preferably 0.38 MPa or more from the viewpoint of securing startability at low temperatures. .
  • it is preferably 1.55 MPa or less, 1. 25 MPa or less is more preferable, and 0.52 MPa or less is most preferable.
  • the vapor pressure at 40 ° C here refers to the value measured by J I S K 2240 “Liquid fossil oil gas (LP gas) one vapor pressure test method”.
  • the density at 15 ° C of the liquefied fuel gas composition of the present invention is preferably 0.500 gZcm 3 or more from the viewpoint of improving fuel efficiency, while it is 0.620 from the viewpoint of preventing heavy components from being mixed. preferably GZC m 3 or less, 0. e OO gZcm 3 below Is more preferable. ,
  • the density at 15 ° C. means a value measured by J I S K 2 2 40 “Liquefied petroleum gas (L P G) —Density test method”.
  • the copper plate corrosion of the liquefied fuel gas composition of the present invention is preferably 1 or less, more preferably la, from the viewpoint of preventing corrosion of fuel piping.
  • copper plate corrosion here means the value measured by JISK 2240. “Liquefied petroleum gas (LP gas) monocopper plate corrosion test method”.
  • the liquefied fuel gas composition of the present invention can be suitably used as a fuel for automobiles.
  • the liquefied fuel gas composition of the present invention comprises at least one selected from Group 6A and Group 8 of the periodic table using a hydrocarbon fraction containing components derived from animal and vegetable oils and animal fats as a feedstock.
  • the liquefied fuel gas compositions of Examples 1 and 2 were prepared using hydrocarbons obtained by contacting a hydrocracking catalyst containing hydrogen under pressure of hydrogen.
  • a liquefied fuel gas composition of Comparative Example 1 was prepared using butane, propane, imported propane, and imported propane produced from a refinery. Table 1 shows the properties of each liquefied fuel gas composition used in Examples and Comparative Examples.
  • an exhaust gas test was conducted and an exhaust gas evaluation was carried out by the following method. The results are shown in Table 2. Again. Then the discharge of these Examples and Comparative Example 0 2 La I conducted Fusaikuru assess the (LCA), were shown in Table 2 by calculating the discharged is C0 2.
  • composition analysis of propane, butane, etc. is the value measured by JIS K 2240 “Liquefied petroleum gas (LL gas) one composition analysis method (gas chromatograph method)”.
  • the initial sample amount was changed from 10 OmL described in the AS TM method to 4 L according to the method specified in ASTM D 2 1 58, and the set temperature was 38 described in the AS TM method. It is a value measured by weighing the residue remaining at 105 ° C in the order of 75 ° C and 105 ° C in order from ° C.
  • the pH of the residue at 05 ° C is 10 000 times the amount of distilled water (residue content is 1 mg). In the following cases, 1 mL of distilled water) is added and stirred, and then the pH of the aqueous phase is obtained by measuring with a pH test paper (pH test paper manufactured by Toyo Roshi Kaisha).
  • Sulfur content is a value measured by J I S K 2240 “Liquefied petroleum gas (LP gas) — Sulfur content test method IV”.
  • Vapor pressure at 40 ° C is a value measured by J I S K 2240 “Liquefied petroleum gas (L ⁇ gas)-Vapor pressure test method”.
  • Density at 5 ° C is a value measured according to JIS K 2240, “Liquefied Petroleum Gas (LPG) — Density Test Method”.
  • Copper plate corrosion is a value measured according to JIS K 2240 “Liquid petroleum gas (LP gas) monocopper plate corrosion test method”. .
  • Fuel supply system Electronically controlled carburetor
  • Table 2 As shown in Table 2, it can be seen that the liquefied fuel gas composition of the present invention can reduce exhaust gas components (THC, CO, NO x) compared to conventional LPG fuel.
  • the present invention provides a liquefied fuel gas composition excellent in the effect of reducing exhaust gas and CO 2 emission from components derived from animal and vegetable fats and oils.

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

Abstract

L’invention concerne une composition de gaz combustible liquéfié en tant que combustible issu d’une biomasse, obtenue en mettant une matière brute à base d’huile en contact avec un catalyseur d’hydrogénolyse sous pression d’hydrogène. La matière brute à base d’huile est composée de matières grasses et d’huiles animales et végétales et/ou d’un distillat hydrocarboné contenant un composant dérivé de matières grasses et d’huiles animales et végétales ; et le catalyseur d’hydrogénolyse contient au moins un métal choisi parmi les éléments du groupe 6A et du groupe 8 du tableau périodique et un oxyde inorganique ayant des propriétés acides. La composition de gaz combustible liquéfié contient un hydrocarbure ayant une teneur en soufre inférieure ou égale à 10 ppm en masse, une teneur en hydrocarbures ayant 3 atomes de carbone supérieure ou égale à 1,0 % en moles, mais inférieure ou égale à 99,0 % en moles, et une teneur en hydrocarbures ayant 4 atomes de carbone supérieure ou égale à 1,0 % en moles, mais inférieure ou égale à 99,0 % en moles.
PCT/JP2006/324306 2005-11-30 2006-11-29 Composition de gaz combustible liquefie Ceased WO2007064019A1 (fr)

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JP2005-347278 2005-11-30
JP2005347278A JP4925653B2 (ja) 2005-11-30 2005-11-30 液化燃料ガス組成物の製造方法

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WO2007064019A1 true WO2007064019A1 (fr) 2007-06-07

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JP (1) JP4925653B2 (fr)
KR (1) KR20080071580A (fr)
CN (1) CN101341232A (fr)
WO (1) WO2007064019A1 (fr)

Cited By (27)

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US7915460B2 (en) 2007-09-20 2011-03-29 Uop Llc Production of diesel fuel from biorenewable feedstocks with heat integration
US7982079B2 (en) 2008-09-11 2011-07-19 Uop Llc Integrated process for production of diesel fuel from renewable feedstocks and ethanol denaturizing
US7982078B2 (en) 2007-09-20 2011-07-19 Uop Llc Production of diesel fuel from biorenewable feedstocks with selective separation of converted oxygen
US7982075B2 (en) 2007-09-20 2011-07-19 Uop Llc Production of diesel fuel from biorenewable feedstocks with lower hydrogen consumption
US7982076B2 (en) 2007-09-20 2011-07-19 Uop Llc Production of diesel fuel from biorenewable feedstocks
US7982077B2 (en) 2007-09-20 2011-07-19 Uop Llc Production of diesel fuel from biorenewable feedstocks with selective separation of converted oxygen
US7999142B2 (en) 2007-09-20 2011-08-16 Uop Llc Production of diesel fuel from biorenewable feedstocks
US7999143B2 (en) 2007-09-20 2011-08-16 Uop Llc Production of diesel fuel from renewable feedstocks with reduced hydrogen consumption
US8003834B2 (en) 2007-09-20 2011-08-23 Uop Llc Integrated process for oil extraction and production of diesel fuel from biorenewable feedstocks
US8039682B2 (en) 2008-03-17 2011-10-18 Uop Llc Production of aviation fuel from renewable feedstocks
US8058492B2 (en) 2008-03-17 2011-11-15 Uop Llc Controlling production of transportation fuels from renewable feedstocks
US8193399B2 (en) 2008-03-17 2012-06-05 Uop Llc Production of diesel fuel and aviation fuel from renewable feedstocks
US8193400B2 (en) 2008-03-17 2012-06-05 Uop Llc Production of diesel fuel from renewable feedstocks
US8198492B2 (en) 2008-03-17 2012-06-12 Uop Llc Production of transportation fuel from renewable feedstocks
US8283506B2 (en) 2008-12-17 2012-10-09 Uop Llc Production of fuel from renewable feedstocks using a finishing reactor
US8304592B2 (en) 2008-06-24 2012-11-06 Uop Llc Production of paraffinic fuel from renewable feedstocks
US8314274B2 (en) 2008-12-17 2012-11-20 Uop Llc Controlling cold flow properties of transportation fuels from renewable feedstocks
US8324438B2 (en) 2008-04-06 2012-12-04 Uop Llc Production of blended gasoline and blended aviation fuel from renewable feedstocks
US8329967B2 (en) 2008-04-06 2012-12-11 Uop Llc Production of blended fuel from renewable feedstocks
US8329968B2 (en) 2008-04-06 2012-12-11 Uop Llc Production of blended gasoline aviation and diesel fuels from renewable feedstocks
US8329969B2 (en) 2008-04-06 2012-12-11 Uop Llc Fuel and fuel blending components from biomass derived pyrolysis oil
US8471081B2 (en) 2009-12-28 2013-06-25 Uop Llc Production of diesel fuel from crude tall oil
US8471079B2 (en) 2008-12-16 2013-06-25 Uop Llc Production of fuel from co-processing multiple renewable feedstocks
US8742183B2 (en) 2007-12-21 2014-06-03 Uop Llc Production of aviation fuel from biorenewable feedstocks
US8766025B2 (en) 2008-06-24 2014-07-01 Uop Llc Production of paraffinic fuel from renewable feedstocks
US8900443B2 (en) 2011-04-07 2014-12-02 Uop Llc Method for multi-staged hydroprocessing using quench liquid
US8921627B2 (en) 2008-12-12 2014-12-30 Uop Llc Production of diesel fuel from biorenewable feedstocks using non-flashing quench liquid

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* Cited by examiner, † Cited by third party
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EP2480638A4 (fr) * 2009-09-25 2013-07-03 Exxonmobil Res & Eng Co Production de carburant à partir d'une charge contenant un triglycéride et/ou un alkyl ester d'acide gras
US8816144B2 (en) * 2012-10-04 2014-08-26 Gas Technology Institute Direct production of fractionated and upgraded hydrocarbon fuels from biomass

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JPH0397784A (ja) * 1989-07-25 1991-04-23 Hans Schur 液体燃料混合物、その製造方法及び２ストロークエンジンのためのその使用
JPH08283748A (ja) * 1994-12-13 1996-10-29 Shell Internatl Res Maatschappij Bv 炭化水素転化方法

Patent Citations (2)

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JPH0397784A (ja) * 1989-07-25 1991-04-23 Hans Schur 液体燃料混合物、その製造方法及び２ストロークエンジンのためのその使用
JPH08283748A (ja) * 1994-12-13 1996-10-29 Shell Internatl Res Maatschappij Bv 炭化水素転化方法

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7915460B2 (en) 2007-09-20 2011-03-29 Uop Llc Production of diesel fuel from biorenewable feedstocks with heat integration
US7982078B2 (en) 2007-09-20 2011-07-19 Uop Llc Production of diesel fuel from biorenewable feedstocks with selective separation of converted oxygen
US7982075B2 (en) 2007-09-20 2011-07-19 Uop Llc Production of diesel fuel from biorenewable feedstocks with lower hydrogen consumption
US7982076B2 (en) 2007-09-20 2011-07-19 Uop Llc Production of diesel fuel from biorenewable feedstocks
US7982077B2 (en) 2007-09-20 2011-07-19 Uop Llc Production of diesel fuel from biorenewable feedstocks with selective separation of converted oxygen
US7999142B2 (en) 2007-09-20 2011-08-16 Uop Llc Production of diesel fuel from biorenewable feedstocks
US7999143B2 (en) 2007-09-20 2011-08-16 Uop Llc Production of diesel fuel from renewable feedstocks with reduced hydrogen consumption
US8003834B2 (en) 2007-09-20 2011-08-23 Uop Llc Integrated process for oil extraction and production of diesel fuel from biorenewable feedstocks
US8742183B2 (en) 2007-12-21 2014-06-03 Uop Llc Production of aviation fuel from biorenewable feedstocks
US8193400B2 (en) 2008-03-17 2012-06-05 Uop Llc Production of diesel fuel from renewable feedstocks
US8058492B2 (en) 2008-03-17 2011-11-15 Uop Llc Controlling production of transportation fuels from renewable feedstocks
US8193399B2 (en) 2008-03-17 2012-06-05 Uop Llc Production of diesel fuel and aviation fuel from renewable feedstocks
US8039682B2 (en) 2008-03-17 2011-10-18 Uop Llc Production of aviation fuel from renewable feedstocks
US8198492B2 (en) 2008-03-17 2012-06-12 Uop Llc Production of transportation fuel from renewable feedstocks
US8324438B2 (en) 2008-04-06 2012-12-04 Uop Llc Production of blended gasoline and blended aviation fuel from renewable feedstocks
US8329967B2 (en) 2008-04-06 2012-12-11 Uop Llc Production of blended fuel from renewable feedstocks
US8329968B2 (en) 2008-04-06 2012-12-11 Uop Llc Production of blended gasoline aviation and diesel fuels from renewable feedstocks
US8329969B2 (en) 2008-04-06 2012-12-11 Uop Llc Fuel and fuel blending components from biomass derived pyrolysis oil
US8304592B2 (en) 2008-06-24 2012-11-06 Uop Llc Production of paraffinic fuel from renewable feedstocks
US8766025B2 (en) 2008-06-24 2014-07-01 Uop Llc Production of paraffinic fuel from renewable feedstocks
US7982079B2 (en) 2008-09-11 2011-07-19 Uop Llc Integrated process for production of diesel fuel from renewable feedstocks and ethanol denaturizing
US8921627B2 (en) 2008-12-12 2014-12-30 Uop Llc Production of diesel fuel from biorenewable feedstocks using non-flashing quench liquid
US8471079B2 (en) 2008-12-16 2013-06-25 Uop Llc Production of fuel from co-processing multiple renewable feedstocks
US8314274B2 (en) 2008-12-17 2012-11-20 Uop Llc Controlling cold flow properties of transportation fuels from renewable feedstocks
US8283506B2 (en) 2008-12-17 2012-10-09 Uop Llc Production of fuel from renewable feedstocks using a finishing reactor
US8471081B2 (en) 2009-12-28 2013-06-25 Uop Llc Production of diesel fuel from crude tall oil
US8900443B2 (en) 2011-04-07 2014-12-02 Uop Llc Method for multi-staged hydroprocessing using quench liquid

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JP4925653B2 (ja) 2012-05-09
JP2007153940A (ja) 2007-06-21
CN101341232A (zh) 2009-01-07
KR20080071580A (ko) 2008-08-04

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