WO2007111152A1 - Composition de combustible - Google Patents

Composition de combustible Download PDF

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Publication number
WO2007111152A1
WO2007111152A1 PCT/JP2007/055307 JP2007055307W WO2007111152A1 WO 2007111152 A1 WO2007111152 A1 WO 2007111152A1 JP 2007055307 W JP2007055307 W JP 2007055307W WO 2007111152 A1 WO2007111152 A1 WO 2007111152A1
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Prior art keywords
less
mass
content
hydrocarbon
volume
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PCT/JP2007/055307
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English (en)
Japanese (ja)
Inventor
Hideaki Sugano
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Nippon Oil Corporation
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Priority claimed from JP2006086374A external-priority patent/JP4847170B2/ja
Priority claimed from JP2006086375A external-priority patent/JP4847171B2/ja
Application filed by Nippon Oil Corporation filed Critical Nippon Oil Corporation
Publication of WO2007111152A1 publication Critical patent/WO2007111152A1/fr

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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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • C—CHEMISTRY; METALLURGY
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • 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
    • C10G2300/1022—Fischer-Tropsch products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

Definitions

  • diesel fuel used in low-temperature areas in winter the current JI s standard focuses on ensuring fluidity according to the usage environment, and is No. 2 diesel oil (pour point 1 7.5 ° C or less) as diesel fuel.
  • Three grades are set: No. 3 light oil (same 20 ° C or less) and Special 3 light oil (same 30 ° C or less).
  • These diesel oils are obtained by applying hydrorefining or hydrodesulfurization treatment to straight-run gas oil obtained from crude oil atmospheric distillation equipment, and hydrogen to straight-run kerosene obtained from crude oil atmospheric distillation equipment. It is manufactured by blending one or more hydrorefining or hydrodesulfurized ones.
  • the blending ratio of the above kerosene base and light oil base is often controlled, and cetane number improvers, detergents, low temperature fluidity improvers, etc. as necessary Are added (for example, see Non-Patent Document 1).
  • Patent Document 1 discloses a diesel light oil composition mainly containing a desulfurized and desulfurized base material. According to this document, it is possible to achieve both excellent low-temperature performance, fuel efficiency, and acceleration performance for diesel engine applications.
  • the diesel gas oil composition shown in this document mainly decomposes linear saturated hydrocarbon compounds, which are low-temperature fluidity inhibiting factors, by dewaxing into saturated hydrocarbon compounds having side chains. Since it is mainly made of chemically converted base materials, it continues to have concerns about exhaust gas performance due to the heavy and aromatic residues in the feedstock. Furthermore, a fuel containing a large amount of aromatic components and a small amount of linear saturated hydrocarbon compounds has a problem that the ignition performance becomes unstable because the cetane number becomes low. From the above, it can be said that such a fuel is not suitable as an environmentally friendly fuel.
  • FT synthetic light oil produced using natural gas or coal as a raw material is attracting attention as an environmentally friendly fuel, but FT synthetic fuel has a lot of normal paraffin in the fuel due to its production method, and may precipitate as wax at low temperatures High nature.
  • FT synthetic gas oils generally have a high cetane index and cetane number, and are excellent in self-ignitability, so that startability at low temperatures can be improved.
  • fuel with an excessively high cetane index and cetane number will self-ignite before the air and fuel are sufficiently mixed in the engine, so a large amount of soot will be generated when the vehicle accelerates. It will generate.
  • a method of designing a fuel with an increased blending ratio of kerosene fraction to ensure low-temperature fluidity can be considered, but if it is lightened, there is a concern about adverse effects on fuel consumption and output, so avoid excessive lightening. There must be.
  • the current JIS standard prescribes product performance in Japan, so the standard that can cope with the lowest temperature is a special grade 3 diesel oil (pour point 1 30) for diesel engines. ° C or below), and kerosene for heating.
  • these fuels are likely to lose their fluidity in extremely cold regions such as the inland region of Heilongjiang, China, the Russian Siberian region, the Alaska region of the United States, the Arctic region and Antarctica.
  • environmental measures have been demanded even in areas that are not restricted by exhaust gas regulations, and the application of environmentally friendly fuels is becoming more common as a social requirement.
  • Patent Document 1 discloses a diesel light oil composition mainly containing a desulfurization and desulfurization base material, but the diesel light oil composition can be applied to a plurality of uses with one kind of fuel. It lacks flexibility as a fuel and is not suitable as a fuel for heating. Furthermore, in general, fuel in such a cryogenic region is not in a situation where it can be arbitrarily refilled whenever it is used, so it is often forced to store for a relatively long period of time at a cryogenic temperature. Various performances should never deteriorate.
  • the low temperature fluidity in the cryogenic region the flexibility that can be used for multiple applications, and the performance as an environmentally friendly fuel, as well as the ability to maintain fuel performance at extremely low temperatures, meet these requirements at a high level. It is very difficult to design a high-quality fuel that can be achieved simultaneously with the above, and it will satisfy the performance required for other fuel oils. Does not exist.
  • Patent Document 1 Japanese Patent No. 3 7 2 9 2 1 1
  • Non-patent document 1 Seiichi Konishi, “Introduction to Fuel Engineering”, Suikabo, March 1991, p.136-144
  • the present invention has been made in view of such a situation, and an object of the present invention is to provide a diesel combustion composition for use in winter having excellent low-temperature fluidity, fuel efficiency, and environmental performance. Another object of the present invention is to provide a fuel composition for a cryogenic region satisfying all of the low-temperature fluidity in a cryogenic region, the flexibility to cope with a plurality of uses, and the performance as an environment-friendly fuel.
  • the present invention provides: [I] 10% distillation temperature of distillation properties is not less than 140 ° C and not more than 200 ° C. Below, 90% by volume distillation temperature is 240 ° C or more and 350 ° C or less, aromatic content is 1% by volume or less, naphthene compound content is 5% by mass or less, sulfur content is 10% by mass or less, carbon number Hydrocarbon mixture X consisting of FT synthetic base material with a linear saturated hydrocarbon content of 16 to 25 from 5% to 70% by weight, or [ii] Initial boiling point of 140 ° C or higher 2% 0 Below 90 ° C, 90 volumes with distillation properties.
  • Hydrodesulfurization treatment with a catalyst containing any one of 1—W, Ni—Mo, Co—Mo, Co—W, or Ni—Co—Mo gives hydrocarbon mixture B, ( 2)
  • the hydrocarbon mixture C obtained by removing the light portion of the hydrocarbon mixture B in the range of 1% by volume to 40% by volume is used as the feedstock, and the reaction temperature is from 150 ° C to 250 ° C, pressure
  • Omn ⁇ Zs or less relates to a fuel composition characterized in that the residual carbon content of 10% residual oil is 0.1% by mass or less.
  • the distillation property is 10 ° /.
  • Distillation temperature is 140 ° C or more and 200 ° C or less
  • 90 vol% Distillation temperature is 240 ° C or more and 350 ° C or less
  • Aromatic content is 1 vol% or less
  • Naphthene compound content is 5 mass% or less
  • Sulfur content is 10 mass ppm or less
  • linear saturated hydrocarbon content of carbon number 16 to 25 is 5 mass% or more and 70 mass% or less.
  • the fuel composition according to the above which is a diesel fuel composition, characterized by having a HFRR wear scar diameter (WS 1.4) of 400 / zm or less.
  • Step 3 The hydrocarbon mixture C is subjected to a reaction temperature of 150 ° C to 25 ° C, pressure IMP a to 5 MPa 10 volumes of linear saturated hydrocarbons by zeolite.
  • the present invention also has an initial boiling point of 140 ° C to 200 ° C, a distillation property of 90% by volume, a distillation temperature of 200 ° C to 300 ° C, an aromatic content of 20% by volume, and linear saturation.
  • Hydrocarbon mixture A with a hydrocarbon content of 25% by mass or more, a linear saturated hydrocarbon content of 10 to 15 carbon atoms, a content of 20% by mass or more, and a sulfur content of 300% by mass or less is A feedstock (Step 1)
  • the hydrocarbon mixture A is reacted at a reaction temperature of 250 ° C. or higher and 3 10 ° C.
  • a hydrocarbon mixture B is obtained by hydrodesulfurization treatment using a catalyst containing orally, and a hydrocarbon mixture B is obtained.
  • Step 2 A light portion of the hydrocarbon mixture B is removed within a range of 1% by volume to 40% by volume.
  • C (Step 3) The hydrocarbon mixture C is removed at a reaction temperature of 150 ° C.
  • diesel fuel manufactured by the above manufacturing method, fraction regulation, etc. By using the fuel composition, it is possible to provide a diesel combustion composition that has excellent low-temperature fluidity, fuel efficiency, and environment-friendly performance that are difficult to realize with conventional fuel compositions. Further, according to the present invention, by using the fuel composition for cryogenic regions produced by the above production method, fraction regulation, etc., it has been difficult to realize by using the conventional fuel composition. It is possible to provide a fuel composition for an extremely low temperature region that satisfies all of the low temperature fluidity in the region, the flexibility that can be used for multiple applications, and the performance as an environmentally friendly fuel.
  • the feedstock of the fuel composition of the present invention comprises: [I] 10% distillation temperature of distillation property is 140 ° C to 200 ° C, 90% by volume distillation temperature is 240 ° C to 350 ° C, aroma Group content is 1% by volume or less, naphthene compound content is 5% by mass or less, sulfur content is 10 mass ppm or less, and linear saturated hydrocarbon content of 16 to 25 carbon atoms is 5% by mass or more 70 Hydrocarbon mixture X consisting of FT synthetic substrate with mass% or less, or [ ⁇ ] Initial boiling point is 140 ° C or higher and 200 ° C or lower, 90% distillation temperature of distillation property is 200 ° C or higher and 300 ° C or higher In the following, the aromatic content is 20% by volume or less, and the linear saturated hydrocarbon content is 25 mass.
  • the hydrocarbon mixture X composed of the above FT synthetic substrate has a distillation property of 10% distillation temperature of 140 ° C to 200 ° C, 90% by volume distillation temperature of 240 ° C to 350 ° C, aromatic The content is 1 vol% or less, the naphthene compound content is 5 mass% or less, the sulfur content is 10 mass ppm or less, and the linear saturated hydrocarbon content of 16 to 25 carbon atoms is 5 mass. It is a hydrocarbon mixture comprising an FT synthesis base material of / o or more and 70% by mass or less, and preferably 10% distillation temperature of distillation property is 150 ° C or more and 1 95 ° C or less and 90 volumes.
  • Distillation temperature is 245 ° C or more and 340 b C or less, and aromatic content is 1 volume. /.
  • FT synthetic base material is equivalent to naphtha, kerosene, and light oil obtained by applying Fischer-Tropsch (FT) reaction to a mixed gas containing hydrogen and carbon monoxide as main components (sometimes referred to as synthesis gas). Liquid fractions, and hydrocarbon mixtures obtained by hydrotreating, hydrocracking them, and obtained by FT reaction It indicates a base material made of a hydrocarbon mixture obtained by refining FT wax, hydrotreating and hydrocracking it.
  • FT Fischer-Tropsch
  • Carbon-containing substances include natural gas, petroleum liquefied gas, methane gas, etc., gas components composed of hydrocarbons that are gaseous at normal temperature, waste such as petroleum asphalt, biomass, coal, building materials and garbage, Generally, mixed gas obtained by exposing sludge and heavy crude oil, unconventional petroleum resources, etc., which are difficult to process by ordinary methods, to high temperatures, is mainly composed of hydrogen and carbon monoxide. As long as the mixed gas to be obtained is obtained, the present invention does not limit the raw material.
  • the Fischer-Tropsch reaction requires a metal catalyst.
  • the method uses a group 8 metal of the periodic table, for example, cobalt, ruthenium, rhodium, palladium, nickel, iron, etc., more preferably a group 8 group 4 metal as an active catalyst component. .
  • the metal group which mixed these metals in an appropriate amount can also be used.
  • These active metals are generally used in the form of a catalyst obtained by being supported on a support such as silica, alumina, titania or silica alumina.
  • the catalyst performance can be improved by using a second metal in combination with the active metal in addition to the above-mentioned active metal.
  • the Fischer-Tropsch reaction is a synthesis method that uses a mixed gas as a raw material to produce a liquid fraction and FT wax.
  • it is generally preferable to control the ratio of hydrogen to carbon monoxide in the mixed gas.
  • the molar mixing ratio of hydrogen to carbon monoxide is preferably 1.2 or more, more preferably 1.5 or more, and even more preferably 1.8 or more. I like it. Further, this ratio is preferably 3 or less, more preferably 2.6 or less, and even more preferably 2.2 or less.
  • the reaction temperature is preferably 180 ° C. or higher and 320 ° C. or lower, and preferably 20 ° C.
  • reaction temperature is less than 180 ° C, carbon monoxide hardly reacts and the hydrocarbon yield tends to be low.
  • reaction temperature exceeds 3220 ° C, the amount of methane and other gases produced increases, and the production efficiency of liquid fractions and FT batteries decreases.
  • the gas space velocity with respect to the catalyst is not particularly limited, but is preferably 5 0 0 h— 1 or more and 4 0 0 0 h— 1 or less, and more preferably 1 0 0 0 h— 1 or more and 3 0 0 0 h— 1 or less. If the gas space velocity is less than 1 000 h, the productivity of liquid fuel tends to decrease, and if it exceeds 4 000 h- 1 , the reaction temperature must be increased and gas generation is large. The yield of the target product decreases. '
  • reaction pressure partial pressure of synthesis gas consisting of carbon monoxide and hydrogen
  • reaction pressure is not particularly limited
  • reaction pressure is less than 0.5 M Pa, the yield of the solid fuel tends to decrease, and if it exceeds 7 M Pa, the capital investment tends to be large, which is uneconomical.
  • the FT synthesis substrate can be obtained by hydrorefining or hydrocracking the liquid fraction or FT wax produced by the above FT reaction by any method and adjusting it to the distillation properties, composition, etc. that meet the purpose.
  • Hydrorefining and hydrocracking may be selected in accordance with the purpose, and selection of either one or a combination of both methods is not limited in any way as long as the fuel composition of the present invention can be produced. .
  • the catalyst used for hydrorefining is generally a catalyst in which a hydrogenation active metal is supported on a porous carrier, but the present invention does not limit the form of the catalyst as long as the same effect can be obtained.
  • An inorganic oxide is preferably used as the porous carrier.
  • Specific examples include alumina, titaure, zirconia, polya, silica, and zeolite.
  • active metal A type active metal A type
  • active metal B Type active metal B
  • the active metal type A is at least one metal selected from Group 8 metals of the Periodic Table. Preferably, at least one selected from Ru, Rh; Ir, Pd and Pt, more preferably Pd or Z and Pt.
  • the active metal may be a combination of these metals. For example, P t—P d, P t—Rh, P t ⁇ R u, I r ⁇ P d, I r ⁇ R h, I r and Ru , Pt-Pd-Rh, Pt_Rh-Ru, Ir-Pd-Rh, Ir-Rh-Ru.
  • a noble metal catalyst composed of these metals, it can be used after pre-reduction treatment in a hydrogen stream. In general, when a gas containing hydrogen is circulated and heat of 200 ° C. or higher is applied according to a predetermined procedure, the active metal on the catalyst is reduced, and hydrogenation activity is exhibited.
  • the active metal B type it contains at least one kind of metal selected from Group 6A and Group 8 metal of the periodic table, and preferably two or more kinds selected from Group 6A and Group 8 Those containing these metals can also be used.
  • metals selected from Group 6A and Group 8 metal of the periodic table, and preferably two or more kinds selected from Group 6A and Group 8 Those containing these metals can also be used.
  • Co-Mo, Ni-Mo, Ni-Co-Mo, and Ni-W can be mentioned.
  • a metal sulfide catalyst composed of these metals it is necessary to include a preliminary sulfidation step.
  • a general inorganic salt or a complex salt compound can be used, and as the supporting method, any of the supporting methods used in ordinary hydrogenation catalysts such as impregnation method and ion exchange method can be used. be able to.
  • the metal solution may be an aqueous solution or an organic solvent.
  • the reaction temperature when hydrorefining using an active metal A type catalyst is preferably 180 ° C or higher and 400 ° C or lower, more preferably 200 ° C or higher and 370 ° C or lower, More preferably 250 ° C or more and 350 ° C or less,
  • reaction temperature in hydrorefining is 280 ° C or higher and 350 ° C or lower.
  • a temperature exceeding 370 ° C is not preferable because side reactions that decompose into a naphtha fraction increase and the yield of the middle fraction extremely decreases.
  • the reaction temperature is lower than 270 ° C., the alcohol content cannot be completely removed, which is not preferable.
  • the reaction temperature when hydrorefining using a catalyst comprising an active metal type B is preferably 1 70 ° C or higher and 320 ° C or lower, and 1 75 ° C or higher and 300 ° C or lower. More preferably, it is 180 ° C or higher and 280 ° C or lower. If the reaction temperature in hydrorefining exceeds 320 ° C, the side reaction that decomposes into the naphtha fraction increases and the yield of the middle fraction is extremely reduced. Also, if the reaction temperature is below 170 ° C, the alcohol content cannot be completely removed, which is preferable.
  • the hydrogen pressure when hydrotreating using an active metal type A catalyst is preferably 0.5 MPa or more and 1 2 MPa or less, and 1.0 MPa or more and 5. OMP a or less. It is more preferable that The higher the hydrogen pressure, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.
  • the hydrogen pressure when hydrotreating using a catalyst comprising an active metal type B is preferably 2 MPa to 10 MPa, more preferably 2.5 MPa to 8 MPa. Preferably, it is 3 MPa or more and 7 MPa or less. The higher the hydrogen pressure, the more hydrogenation reaction is promoted, but generally there is an optimal point economically. .
  • the liquid hourly space velocity which hydrorefining is carried out using a catalyst composed of the active metal A type (LHS V) is preferably 0. lh 1 or 10. It 0 h 1 less, 0. 3 h- 1 or more 3. More preferably 5 h 1 or less.
  • LHS V active metal A type
  • the ratio of hydrogen oil when hydrorefining using an active metal A type catalyst is 5. ! : More than 000 NLZL, more preferably more than 70 NLZL and less than 800 NL / L. The higher the hydrogen / oil ratio, the faster the hydrogenation reaction, but generally there is an optimal point economically.
  • the catalyst used for hydrocracking is generally a catalyst in which a hydrogenation active metal is supported on a carrier having a solid acid property, but the present invention is not limited in any way as long as the catalyst can achieve the same effect. is not.
  • Supports having solid acid properties include amorphous and crystalline zeolites. Specifically, there are amorphous silica-alumina, silica-magnesia, silica gel, silica-titania and zeolite, faujasite type, beta type, MFI type, and mordenite type. Preferred are faujasite type, beta type, MFI type and mordenite type zeolite, more preferred are Y type and beta type. The Y type is preferably ultra-stabilized.
  • the active metal A type is mainly at least one metal selected from Group 6A and Group 8 metals of the Periodic Table. Preferably, it is at least one metal selected from Ni, Co, Mo, Pt, Pd and W.
  • a precious metal catalyst composed of these metals it can be used after pre-reduction treatment in a hydrogen stream. In general, when a gas containing hydrogen is circulated and heat of 200 ° C. or higher is applied according to a predetermined procedure, the active metal on the catalyst is reduced, and hydrogenation activity is exhibited.
  • the active metal B type may be a combination of these metals. Examples include Pt—Pd, Co—Mo, Ni—Mo, Ni—W, and Ni—Co—Mo. Can be mentioned. In addition, when using a catalyst made of these metals, it is preferable to use it after preliminary sulfidation.
  • a general inorganic salt or a complex salt compound can be used, and as a loading method, any of the loading methods used in ordinary hydrogenation catalysts such as impregnation method and ion exchange method should be used. Can do.
  • a plurality of metals When a plurality of metals are supported, they may be supported simultaneously using a mixed solution, or may be sequentially supported using a single solution.
  • the metal solution may be an aqueous solution or an organic solvent.
  • the hydrogen pressure when hydrocracking using a catalyst composed of active metal A type and active metal B type is preferably IMP a or more and 2 OMP a or less, and 4 MPa or more and 16 MPa or less. Is more preferably 6 MPa or more and 13 MPa or less.
  • the higher the hydrogen pressure the more the hydrogenation reaction is promoted.
  • the decomposition reaction rather slows down and the progress of the reaction needs to be adjusted by increasing the reaction temperature, leading to a decrease in catalyst life. Therefore, there is generally an economic optimal point for the reaction temperature.
  • the liquid hourly space velocity which hydrocracking is carried out using a catalyst composed of the active metal A type (LHS V) is preferably 0. 1 h- 1 or more 10 h- 1 or less, 0. 3 h one 1 More preferably, it is not more than 3.5 h to 1 .
  • LHS V active metal A type
  • the liquid hourly space velocity which hydrocracking is carried out using a catalyst composed of the active metal B type (LHS V) is preferably 0. 1 h- 1 or more 2 h- 1 or less, 0. 2 h one 1 or 1. more preferably 7 h one 1 or less, and further preferably 0.1 311- 1 or 1. a lower S h- 1 or more.
  • LHS V active metal B type
  • the hydrogen Z oil ratio when hydrocracking using an active metal type A catalyst is preferably 50 NL L or more and 1000 NL / L or less, more preferably 70 NL / L or more and 800 NLZL or less. Preferably 40. More preferably, it is 500 NL / L or less. Higher hydrogen / oil ratio promotes hydrogenation reaction In general, there is an optimum point economically.
  • the hydrogen oil ratio is preferably 150 NL / L or more and 2000 NLL or less, and 300 NL / L or more and 1 700 NL / L or less. Is more preferably 400 NL / L or more and 1 500 NLZL or less. A higher hydrogen / oil ratio promotes the hydrogenation reaction, but generally there is an optimal point in the economy.
  • the apparatus for hydrotreating may have any configuration, the reaction towers may be used alone or in combination, and hydrogen may be additionally injected between the reaction towers, gas-liquid separation operation, hydrogen sulfide removal equipment, It may have a distillation column to fractionate the hydrogenation product and obtain the desired fraction.
  • the reaction format of the hydrotreating apparatus can take a fixed bed system.
  • Hydrogen can take either a countercurrent or cocurrent flow format with respect to the feedstock, or it can have a plurality of reaction towers and a combination of countercurrent and cocurrent flow.
  • the general format is downflow, and there is a gas-liquid co-current format.
  • Hydrogen gas may be injected into the middle stage of the reaction tower as a tent to remove reaction heat or increase the hydrogen partial pressure.
  • the hydrocarbon mixture A used as the feedstock for the fuel composition for the cryogenic region of the present invention has an initial boiling point of 140 ° C or higher and 200 ° C or lower and a distillation capacity of 90 volumes. /.
  • Distillation temperature is 220 ° C or more and 290 ° C or less, aromatics content is 17% by volume or less, linear saturated hydrocarbon content is 28% by mass or more, carbon number is 10 to 15 and linear saturated carbonization
  • Distillation temperature is 230 ° C or more and 285 ° C or less, aromatic content is 15% by volume or less, and linear saturated hydrocarbon content is 30 mass. /.
  • the linear saturated hydrocarbon content of 10 to 15 carbon atoms is 25 mass% or more, and the sulfur content is 50 mass ppm or less. If the properties of the hydrocarbon mixture A deviate from the above range, the reaction efficiency in the subsequent processing is lowered, making it difficult to obtain the fuel composition for the cryogenic region of the present invention. It is not preferable.
  • the first boiling point, 90% by volume distillation temperature is JISK 2254 “Petroleum product one distillation test method one atmospheric pressure distillation test method”
  • the aromatic content is JISK 2536 “Petroleum product one hydrocarbon” Value measured by the fluorescent indicator adsorption method of “Type test method”
  • linear saturated hydrocarbon content normal paraffin content
  • linear saturated hydrocarbon content of 10 to 15 carbon atoms is a value measured using a GC-FID (mass 0/0).
  • Sulfur content is the value measured by J I S K 2541 “Crude oil and petroleum products – Sulfur content test method”.
  • the hydrocarbon mixture A is not particularly limited other than having the above-mentioned specified properties, but for reasons of improving exhaust gas performance as an environmentally friendly fuel in addition to petroleum-based substrates, FT synthesis substrates, animals and plants It is preferable that it is processing oil derived from oil.
  • Petroleum base material is a hydrocarbon base material obtained by processing crude oil.
  • straight base material obtained from atmospheric distillation equipment, straight-run heavy oil obtained from atmospheric distillation equipment.
  • non-conventional petroleum resources such as oil shells, oil sands, orinocotal, etc., are treated appropriately and the base materials finished to the same performance as the above base materials are also petroleum-based. Can be used according to the substrate.
  • the FT synthetic substrate is as described above.
  • Processed oil derived from animals and plants is obtained by applying the chemical reaction process applied when obtaining the above-mentioned petroleum base material to the oils and fats produced and produced from animal and plant raw materials. It is the base material comprised with the hydrocarbon. More specifically, it has at least one metal selected from Group 6A and Group 8 of the Periodic Table and acid properties using a hydrocarbon fraction containing components derived from animal and vegetable oils and animal fats as raw material oil.
  • a hydrocarbon-containing mixed base material which is brought into contact with a hydrocracking catalyst containing an inorganic oxide under hydrogen pressure.
  • the raw material oil for the processed oil derived from animals and plants must be derived from animals and plants oils and animal oils.
  • animal / vegetable fat / oil / opin / vegetable fat / oil-derived component refers to a natural or artificially produced or manufactured animal / vegetable.
  • Animal fats and oils include beef tallow, milk lipids (butter), pork tallow, sheep fat, whale oil, fish oil, liver oil, etc.
  • Vegetable oils and vegetable oil ingredients include coconut palm, olive palm, olives, Rapeseed (rapeseed), rice bran, sunflower, cottonseed, corn, soybean, sesame seeds, and other parts, but other fats and oils can be used without problems. .
  • These raw oils may be solid or liquid, but it is preferable to use vegetable oils and vegetable oils as raw materials because of ease of handling, carbon dioxide absorption capacity and low productivity.
  • 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 of 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.
  • CsHnCOOH Forced prillic acid C?”
  • a structure having a side chain that is, The position of the unsaturated bond in the molecule of the unsaturated fatty acid is generally confirmed in nature as long as it satisfies the properties defined in the present invention. Not only what you have, Those set at an arbitrary position by chemical synthesis can also be used.
  • the above-mentioned raw material oils have one or more of these fatty acids, and the fatty acids they have vary 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.
  • the feedstock preferably contains a fraction at 250 ° C or higher, more preferably contains a fraction at 300 ° C or higher, and contains a fraction at 360 ° C or higher. More preferably. If it does not contain a fraction with a boiling point of 230 ° C or higher, the production of gas will increase during production, which may reduce the yield of liquid products and increase life cycle carbon dioxide.
  • the ratio of the petroleum hydrocarbon fraction is preferably 10 to 99% by volume, more preferably 30 to 99% by volume, and more preferably 60 to 98% by volume based on the total volume of the feedstock. If the proportion of petroleum-based hydrocarbon fraction is less than 10% by volume, it may be necessary to install equipment required to treat by-product water, and the proportion of petroleum-based hydrocarbon fraction is 99 volume. When it exceeds%, it is not preferable from the viewpoint of reducing the life cycle carbon dioxide.
  • the hydrocracking conditions in the hydrotreating are as follows: hydrogen pressure 6-2 OMPa, liquid space velocity (LHSV) 0.1-1.5 h— 1 , hydrogen / oil ratio 200-2000 NL / L. . it is desirable to take place, the hydrogen pressure 8 to 1 7MP a, liquid hourly space velocity 0. 2 to 1 1 h- 1, and more preferably conditions such hydrogen / oil ratio 300 ⁇ 1 800 NLZL, hydrogen pressure. 10 to: I 6MP a, liquid hourly space velocity 0. 3 ⁇ 0. 9 h _1, hydrogen / oil ratio 350 conditions such 160 ON L / L is even more desirable.
  • the hydrocarbon mixture A which is a raw material oil, is treated in the following steps (1) and (2) to obtain a hydrocarbon mixture C. '
  • the hydrocarbon composition A is mixed with a reaction temperature of 250 ° C. or higher and 30 ° C. or lower, a hydrogen pressure of 5 MPa or higher and 1 OMP a or lower, LHSVO 5 h— 1 or higher, 3. O h— 1 below, under conditions where the hydrogen hydrocarbon capacity ratio (hydrogen / oil ratio) is 0.15 or more and 0.6 or less, N i— W, N i— Mo, C o— Mo, C o— W, or N i — Hydrodesulfurization treatment is performed with a catalyst containing any of C o— M o to obtain hydrocarbon mixture B.
  • the reaction temperature of the hydrodesulfurization treatment is 250 ° C or higher and 310 ° C or lower, preferably 280 ° C or higher and 305 ° C or lower.
  • the reaction temperature is less than 250 ° C, a sufficient hydrodesulfurization reaction rate cannot be obtained.
  • the reaction temperature exceeds 310 ° C, the hydrodesulfurization reaction becomes insufficient in terms of reaction equilibrium.
  • the hydrogen pressure in the hydrodesulfurization treatment is 5 MPa or more and 10 MPa or less, and preferably 7 MPa or more and 9 MPa or less.
  • LHSV in the hydrodesulfurization treatment is 0. 5 h- 1 or more 3. 0 h- 1 or less, preferably 1 h- 1 or more 2 h one 1 below.
  • the hydrogen / hydrocarbon volume ratio is 0.15 or more and 0.6 or less, preferably 0.2 or more and 0.4 or less.
  • the hydrogen pressure is less than 5 MPa, and when the hydrogen hydrocarbon volume ratio is less than 0.15, the effect of promoting desulfurization reaction or hydrogenation reaction is insufficient.
  • the hydrogen pressure exceeds 1 OMPa and the hydrogen / hydrocarbon capacity ratio exceeds 0.6, the equipment cost increases and becomes inefficient.
  • the catalyst used for hydrodesulfurization treatment must contain any of Ni 1 W, Ni i-Mo, Co—Mo, Co—W, and Ni—Co—Mo as the active metal of the catalyst. It is.
  • An inorganic oxide is preferably used as the porous carrier. Specific examples of the inorganic oxide include alumina, titania, zirconia, boria, silica, and zeolite. Among these, at least one of titaure, zircoair, polya, silica, and zeolite is composed of alumina. Are preferably used in the present invention.
  • the amount of the active metal supported is not particularly limited, but the total amount of metal oxides relative to the catalyst mass is preferably 20% by mass or more and 35% by mass or less.
  • the catalyst is preferably used after presulfiding with hydrogen and sulfur compounds.
  • a gas containing hydrogen and a sulfur compound is circulated, and the active metal on the catalyst is presulfided by applying heat of 200 ° C or higher according to a predetermined procedure, and hydrogenation and desulfurization activity is expressed. become.
  • step (2) light mixture (generally boiling point 200 ° C or less) is stripped (removed) from hydrocarbon mixture B obtained in step (1) to obtain hydrocarbon mixture C.
  • the amount of strip is from 1% by volume to 40% by volume, preferably from 10% by volume to 37% by volume, more preferably from 20% by volume to 35% by volume, based on hydrodesulfurized oil. It is as follows. When stripping is not performed or when the strip amount is not sufficient, the load of the removal device for linear saturated hydrocarbon (normal paraffin) in the subsequent stage increases and the removal efficiency decreases. In addition, if the strip amount is excessive (over 40% by volume), the time required for the strip process increases and the energy consumption during production increases.
  • the fuel composition of the present invention comprises a feedstock comprising the above-mentioned hydrocarbon mixture X or hydrocarbon mixture C under the conditions of a temperature of 150 ° C. to 250 ° C. and a pressure of 1 MPa to 5 MPa. It can be obtained by delinearization saturated hydrocarbon treatment with zeolite.
  • the reaction temperature for the removal of the straight chain saturated hydrocarbon is 150 ° C or higher and 250 ° C or lower, preferably 180 ° C or higher and 200 ° C or lower. When the reaction temperature is less than 150 ° C, a sufficient removal rate of linear saturated hydrocarbons cannot be obtained. On the other hand, if the temperature exceeds 250 ° C, the removal efficiency of straight chain saturated hydrocarbons decreases.
  • the pressure at this time is IMP a or more and 5 MPa or less, preferably 1.5 MPa or more and 3 MPa or less. If the pressure is less than 1 MPa, a sufficient removal rate of linear saturated hydrocarbons cannot be obtained. On the other hand, if it exceeds 5M Pa, a sufficient removal rate of linear saturated hydrocarbons cannot be obtained.
  • the zeolite used for the removal of the linear saturated hydrocarbon is not particularly limited, but generally, A-type zeolite is used, and among these, molecular sieve 5A is preferable.
  • hydrocarbon mixture X consisting of FT synthetic base material is used as raw material oil, and reaction temperature 1 50 ° C or more and 250 ° C or less, pressure IMP a or more and 5MPa or less by zeolite Distilled saturated hydrocarbons obtained by performing de-linear saturated hydrocarbon treatment, density of +28 or higher, density at 15 ° C of 760 kg / m 3 or higher, 8 30 k gZm 3 or lower, distillation property of 10% Temperature is 1 ⁇ 0 ° C to 220 ° C, 50% distillation temperature is 210 ° C to 280 ° C, 90% distillation temperature is 240 ° C to 3'25 ° C, Cetane index 5 5 or more and 75 or less, Cetane number 5 5 or more and 70 or less, Flash point 50 ° C or more, Peroxide value after accelerated oxidation test is 10 mass p pm or less, Cloudy point — 10 0 ° C or less, Clogging point 1 10 ° C or less
  • the initial boiling point is 140 ° C. or higher and 200 ° C. or lower
  • the 90% by volume distillation temperature of the distillation property is 200 ° C. or higher and 300 ° C. or lower
  • the aromatic content Is 20 vol% or less
  • linear saturated hydrocarbon content is 25 mass% or more
  • linear saturated hydrocarbon content of 10 to 15 carbon atoms is 20 mass% or more
  • sulfur content is 300 mass p.
  • the hydrocarbon mixture A is reacted at a reaction temperature of 250 ° C or higher and 30 ° C or lower, and a hydrogen pressure of 5 MPa or higher and 1 OMPa or lower. Lower, LHSVO.
  • Step 2 Light weight of hydrocarbon mixture B 1 capacity for the part. /. Removal of hydrocarbon mixture C in the range of 40% by volume or less to obtain hydrocarbon mixture C, (Step 3) The hydrocarbon mixture C is subjected to a reaction temperature of 150 ° C to 250 ° C and a pressure of IMP a to 5 MPa.
  • the hydrocarbon mixture D obtained by removing 10% or more of linear saturated hydrocarbons by zeolite in 80% by volume or more of the total fuel composition, and the color at the color of +28 or more, 15 ° C 740 kg / m 3 or more and 840 k gZm 3 or less, 10% distillation temperature of distillation property is 1 70 ° C or more and 220 ° C or less, 90% distillation temperature is 220 ° C or more and 300 ° C or less, cetane index 45 'Or more, cetane number 48 or more, flash point 45 ° C or more, reaction test result is neutral, copper plate corrosion is 1 or less, peroxide value after accelerated oxidation test is 10 mass p pm or less, pour point is 60 ° C or less, sulfur content 10 mass p pm or less, kinematic viscosity at 30 ° C 1.
  • a preferred embodiment of the present invention is an initial boiling point of 140 ° C. or higher and 200 ° C. or lower and a distillation property of 90 volumes. /.
  • Distillation temperature of 200 to 300 ° C, aromatic content of 20% by volume or less, linear saturated hydrocarbon content of 25% by mass or more, carbon number of 10 to 15 and linear saturated hydrocarbon content of 15 or less Is a hydrocarbon mixture A having a sulfur content of not less than 20 mass% and a sulfur content of not more than 300 mass ppm, (Step 1) using the hydrocarbon mixture A as a reaction temperature of 250 ° C to 3 10 ° C, hydrogen pressure 5 MP a more 10MP a less, LHSVO. 5 h- 1 or more 3.
  • Hydrocarbon mixture D is 80 to 100% by volume with respect to the total fuel composition, and the total content of linear saturated hydrocarbon compounds having 16 to 20 carbon atoms is 10 masses. /. 0 to 2.0 volumes of an FT synthetic base material, the total of which is 2% by mass or less, and the total content of straight chain saturated hydrocarbon compounds having 21 to 25 carbon atoms.
  • the fuel composition for the cryogenic region of the present invention is obtained through the steps (1) to (3) from the viewpoint of ensuring the low temperature fluidity and good exhaust gas performance required for the environment-friendly fuel. Containing 80 to 100% by volume of the hydrocarbon mixture D with respect to the total fuel composition, and more than 0% by volume and less than 20% by volume of the FT synthetic base material having specific properties with respect to the total fuel composition Can be blended.
  • the FT synthetic base material that can be blended has a total content of linear saturated hydrocarbon compounds of 16 to 20 carbon atoms in a total of 10% by mass or less, and linear saturated carbonization of 21 to 25 carbon atoms.
  • FT synthesis base material characterized in that the total content of hydrogen compounds is 2% by mass or less, more preferably the total content of linear saturated hydrocarbon compounds having 16 to 20 carbon atoms is 8% by mass %, And the total content of linear saturated hydrocarbon compounds having 2 to 1 and 25 or less carbon atoms is 1.8% by mass or less, and more preferably 16 to 20 carbon atoms.
  • FT synthetic base material with a total content of hydrocarbon compounds of 6 mass% or less and a total content of linear saturated hydrocarbon compounds with 21 to 25 carbon atoms of 1.5 mass% or less More preferably, the total content of straight chain saturated hydrocarbon compounds having 16 to 20 carbon atoms is 5 quality. The total content of straight-chain saturated hydrocarbon compounds with a carbon content of 21 or less and 25 or less is 1 mass. »The following are FT synthetic substrates. When blending FT synthetic substrates and other substrates outside this range, it is difficult to achieve both low-temperature fluidity and environmental performance. Become.
  • the FT synthetic substrate here refers to a hydrocarbon substrate obtained by the above-mentioned production method.
  • the linear saturated hydrocarbon compound content (mass.
  • the fuel composition of the present invention has the following specific properties obtained through the above treatment.
  • the fuel color of the fuel composition of the present invention is +28 or more, preferably from +29 or more, and more preferably from +30 or more, from the viewpoint of removing oxidation stability inhibitors.
  • “Saebold color” means a value measured according to JIS 2580 “One-color test method for petroleum products—Saebold color test method”.
  • Density at 15 ° C of the diesel fuel composition of the present invention, in terms of calorific value ensuring is a 760 k gZm 3 or more, preferably 765 kg / m 3 or more, more preferably 770 kg Zm 3 or more.
  • the density, NOx, from the viewpoint of reducing the emission of PM it is 830 k gZm 3 or less, preferably 825 kg / m 3 or less, 820 k gZm 3 or less is more preferable.
  • the density of the fuel composition for cryogenic regions of the present invention at 15 ° C is 740 kg / m 3 or more, preferably 750 kg / m 3 or more, and 755 kg / m 3 from the viewpoint of securing a calorific value.
  • the above is more preferable.
  • the density is 840 kg / m 3 or less, preferably 830 kg / m 3 or less, and more preferably 820 kg / m 3 or less from the viewpoint of reducing NOx and PM emissions.
  • the density here means the density measured according to JISK 22.49 “Density test method and density / mass / capacity conversion table for crude oil and petroleum products”.
  • the distillation properties of the diesel fuel composition of the present invention are as follows: 10% distillation temperature is 170 ° C to 220 ° C, 50% distillation temperature is 210 ° C to 280 ° C, 90% distillation temperature is 240 ° C or more and 325 ° C or less. If the 10% distillation temperature is less than 1 70 ° C, engine output and startability at low temperatures tend to deteriorate, so preferably 173 ° C or more, more preferably 1 78 ° C or more, more preferably 180 ° C or higher.
  • the 10% distillation temperature exceeds 220 ° C
  • the exhaust gas performance tends to deteriorate. Therefore, it is preferably 215 ° C or lower, more preferably 210 ° C or lower, and even more preferably 205. C or less.
  • the 50% distillation temperature does not reach 210 ° C, engine output and startability at low temperatures tend to deteriorate. It is preferably 220 ° C or higher, more preferably 225 ° C or higher.
  • the 50% distillation temperature exceeds 280 ° C
  • the exhaust gas performance tends to deteriorate. Therefore, it is preferably 275 ° C or less, more preferably 270 ° C or less, and further preferably 265 ° C or less.
  • the 90% distillation temperature does not reach 240 ° C, the fuel efficiency improvement effect will be insufficient and the engine output will tend to decrease. Therefore, it is preferably 24'5 ° C or higher, more preferably 250 ° C or higher, more preferably 255 ° C or higher.
  • the 90% distillation temperature exceeds 325 ° C, the emission of PM and fine particles tends to increase. Therefore, it is preferably 320 ° C or less, more preferably 315 ° C or less, more preferably 31 0 ° C or less.
  • the 90% distillation temperature is less than 220 ° C, the fuel efficiency improvement effect will be insufficient, and the engine output tends to decrease. Therefore, it is preferably 225 ° C or higher, more preferably 230 ° C or higher, more preferably Is above 235 ° C.
  • the 90% distillation temperature exceeds 300 ° C, the emission of PM and fine particles tends to increase, so it is preferably 295 ° C or less, more preferably 290 ° C or less, and even more preferably 285 It is below ° C.
  • the 10% distillation temperature, 50% distillation temperature, and 90% distillation temperature mentioned here all mean values measured according to JIS K 2254 “Petroleum product one distillation test method one atmospheric pressure method”.
  • the diesel fuel composition of the present invention has a cetane index of 55 or more.
  • the cetane index is preferably 57 or more, more preferably 60 or more.
  • the cetane index must be 75 or less, preferably 74 or less, and 73 or less Is more preferable.
  • the cetane index of the fuel composition for cryogenic regions of the present invention is 45 or more.
  • the cetane index is preferably 46 or more, more preferably 47 or more.
  • the cetane index referred to in the present invention is the calculation of the cetane index using the 8.4 variable equation of JISK 2280 “Petroleum products / fuels / octane number / cetane number test method and cetane index calculation method”. Value calculated by “method”.
  • the cetane index in the above JIS standard is generally applied to light oil to which no cetane number improver is added.
  • the cetane index is also applied to a fuel composition to which a cetane number improver is added. Applying the above “8.4 Calculation method of cetane index using variable equation”, the value calculated by this calculation method is expressed as cetane index.
  • the cetane number in the diesel fuel composition of the present invention is 55 or more.
  • the concentration of N0x, PM and aldehydes in the exhaust gas tends to be high, so it is preferably 56 or more, more preferably 57 or more.
  • the cetane number needs to be 70 or less, preferably 68 or less, and more preferably 66 or less.
  • an appropriate amount of a cetane number improver can be blended to improve the cetane number of the resulting fuel composition.
  • the cetane number in the fuel composition for the cryogenic region of the present invention is 48 or more.
  • the concentration of NOx, PM and aldehydes in the exhaust gas tends to be high, so it is preferably 48.5 or more, more preferably 49 or more. is there.
  • the cetane number is preferably 90 or less, more preferably 85 or less, and further preferably 80 or less.
  • an appropriate amount of a cetane number improver can be blended to improve the cetane number of the resulting fuel composition.
  • the cetane number here is measured in accordance with “7. Cetane number test method” of “JISK 2 28 0“ Petroleum products / Fuel oil / Octane number and cetane number test method and cetane index calculation method ”. Means cetane number.
  • the flash point of the diesel fuel composition of the present invention is 50 ° C or higher. Flash point is 50 ° C If the temperature is less than 5, it is not preferable from the viewpoint of safety, so the flash point is preferably 52 ° C or higher, more preferably 54 ° C or higher.
  • the flash point of the fuel assembly for a cryogenic region of the present invention is 45 ° C. or higher.
  • the flash point is preferably 47 ° C or higher, more preferably 49 ° C or higher.
  • the flash point in the present invention is a value measured by J I S K 2 2 6 5 “Crude oil and petroleum product flash point test method”.
  • the result of the reaction test of the fuel composition for the cryogenic region of the present invention shows neutrality. If the result of the reaction test is not neutral, it is not preferable because the possibility that the corrosion effect on the metal member by the fuel becomes obvious will increase. In addition, the result of the reaction test as used in the field of this invention shows the value measured by JI S K 2 2 5 2 “Petroleum product one reaction test method”.
  • the copper plate corrosion of the fuel composition for the cryogenic region of the present invention is 1 or less, and is preferably la. If the corrosion of the copper plate is not less than 1, the possibility of the corrosion effect on the metal parts due to the fuel increases, resulting in problems in stability and long-term storage.
  • the copper plate corrosion referred to in the present invention is a value measured by JI S K 2 5 1 3 “Petroleum product-copper plate corrosion test method”.
  • the peroxide value of the fuel composition of the present invention after the accelerated oxidation test is 10 ⁇ mass p.pm or less.
  • the peroxide value after the accelerated oxidation test is preferably 8 mass ppm or less, more preferably 6 mass pp ⁇ or less, and even more preferably 4 mass ppm or less from the viewpoints of storage stability and compatibility with parts. .
  • the peroxide value after the accelerated oxidation test here refers to the accelerated oxidation test under the conditions of 95 ° C, oxygen publishing and 16 hours in accordance with AS TM D 2 2 7 4-94. This means the value of the peroxide value measured in accordance with the Petroleum Institute Standard JPI-5S-4 6-6 96 after implementation.
  • an additive such as an antioxidant or a metal deactivator can be appropriately added to the fuel composition for cryogenic regions of the present invention.
  • the cloud point of the diesel fuel composition of the present invention is 110 ° C. or less.
  • the clogging point of the diesel fuel composition of the present invention is 1 1 ° C or less. Further, from the viewpoint of preventing the pre-filter closing of the diesel vehicle and maintaining the injection performance in the electronically controlled fuel injection pump, it is preferably 1 12 ° C. or less, and 1 15 or less. Is more preferable.
  • the clogging point means the clogging point measured by JISK 2 2 8 8 “Test method for one clogging point of light oil”.
  • the pour point of the diesel fuel composition of the present invention is 115 ° C. or less. Furthermore, from the viewpoint of ensuring low temperature startability or low temperature drivability, and maintaining the injection performance of the electronically controlled fuel injection pump, it is preferably 118 ° C or less, and preferably 120 ° C or less. It is more preferable.
  • the pour point of the fuel composition for the cryogenic region of the present invention is 160 ° C. or lower. Furthermore, from the viewpoint of low-temperature startability or low-temperature operability at extremely low temperatures, and from the viewpoint of maintaining the injection performance of the electronically controlled fuel injection pump, it is preferable that the temperature is 162 ° C or lower. .
  • the pour point means the pour point measured according to J I S K 2 2 6 9 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.
  • the aromatic content of the diesel fuel composition of the present invention is 1% by volume or less, preferably 0.8% by volume or less, and 0.5% by volume. /. It is more preferable that When the aromatic content is 1% by volume or less, production of soot and the like can be suppressed and environmental performance can be exhibited, and the properties specified in the fuel composition of the present invention can be more easily achieved. And it can be achieved reliably.
  • the aromatic content here is based on the JPI-5 S-4 9 1 9 7 “Hydrocarbon type test method—High performance liquid chromatographic method” published by the Japan Petroleum Institute. It means the volume percentage (volume%) of the aromatic content measured.
  • the naphthene content of the diesel fuel composition of the present invention is 5 mass. /.
  • the content is preferably 3% by mass or less, and 1% by mass. /. The following is more preferable.
  • the naphthene content is AS TM D 2 4 2 5 "Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass. Means naphthene content of mass percentage is measured according to Spectrometry "(mass 0/0).
  • the sulfur content of the diesel fuel composition of the present invention is 1.0 mass p pm or less, preferably 8 mass p pm or less, from the viewpoint of reducing harmful exhaust components discharged from the engine and improving the performance of the exhaust gas aftertreatment device. Preferably it is 5 mass p pm or less, more preferably 3 mass p pm or less, even more preferably 1 mass p pm or less.
  • the sulfur content here means the mass content of the sulfur content based on the total amount of the light oil composition measured by JISK2541 “Sulfur content test method”.
  • Kinematic viscosity at 30 ° C of the diesel fuel composition of the present invention 1. is a 7 mm 2 / s or more, 1. is preferably 75 mm 2 / s or more, the 1. 8 mm 2 / s or less It is more preferable. If the kinematic viscosity is less than 1.7 mm 2 Z s, it tends to be difficult to control the fuel injection timing on the fuel injection bump side, and the lubricity of each part of the fuel injection pump mounted on the engine is impaired. There is a fear. Hand, the kinematic viscosity at 30 ° C is required to be 4. It Omm 2 / s or less, preferably 3 is 9 mm 2 Roh s or less, that 3.
  • kinematic viscosity exceeds 4.0 mm 2 / s, the resistance inside the fuel injection system increases, the injection system becomes unstable, and the concentrations of NO x and PM in the exhaust gas increase, which is not preferable.
  • Kinematic viscosity at 30 ° C for cryogenic locations for fuel compositions of the present invention 1. is a 6 mm 2 / s or more, preferably 1. at 6 5 mm 2 / s or more, 1. 7 mm 2 / More preferably, it is s or more.
  • the kinematic viscosity is less than 1.6 mm 2 / s, it tends to be difficult to control the fuel injection timing on the fuel injection pump side, and the lubricity of each part of the fuel injection pump mounted on the engine is low. There is a risk of damage.
  • the upper limit of kinematic viscosity at 30 ° C must be 5.0 mm 2 / s, preferably 4 mm 2 // s or less, more preferably Srnni 2 / s or less. That's right. If the kinematic viscosity exceeds 5.0 mm 2 // s, the resistance inside the fuel injection system increases, the injection system becomes unstable, and the concentrations of NO x and PM in the exhaust gas increase, which is not preferable.
  • the kinematic viscosity here means the kinematic viscosity measured according to JISK2283 “Crude oil and petroleum products kinematic viscosity test method and viscosity index calculation method”.
  • the kinematic viscosity in an 30 ° C cryogenic locations for fuel compositions of the present invention is less 30 mm 2 / s, preferably not more than 28 mm 2 / s, not more than 26 mm 2 / s More preferred.
  • kinematic viscosity exceeds 3 Omm 2 / s, workability is impaired at extremely low temperatures, which is not preferable.
  • kinematic viscosity here means kinematic viscosity measured according to JISK 2283 “Crude oil and petroleum product single kinematic viscosity test method and viscosity index calculation method”.
  • the water content of the fuel composition of the present invention is preferably 100 capacity p pm or less, more preferably 50 capacity p pm or less, and still more preferably 20 capacity from the viewpoint of preventing freezing at low temperatures. ppm or less.
  • the moisture content here means a value measured according to JIS K 22 75 “Crude oil and petroleum products – One moisture test method – Karl Fischer-type coulometric titration method”.
  • the residual carbon content of 10% residual oil of the diesel fuel composition of the present invention is 0.05% by mass or less, and preferably 0.04% by mass or less from the viewpoint of preventing filter clogging by sludge. 03 mass% or less is more preferable.
  • the residual carbon content of the residual oil is 0.1% by mass or less, and from the viewpoint of preventing filter clogging by sludge, it is preferably 0.08% by mass or less, and more preferably 0.05% by mass or less.
  • the residual carbon content of 10% residual oil here means the value measured by J ISK 2270 “Testing method for residual carbon content of crude oil and petroleum products”.
  • the HFRR wear scar diameter (WS 1.4) referred to in the present invention is the Petroleum Institute Standard JPI-5 S-50-98 “Diesel Oil-Lubricity Test” issued by the Japan Petroleum Institute. Means the value measured by
  • a lubricity improver to the fuel composition of the present invention.
  • the addition amount is preferably 20 mg / L or more and 20 OmgZL or less, more preferably 50 mgZL or more and 180 mg / L or less in terms of active ingredient concentration.
  • the added amount of the lubricity improver is within the above range, the effect of the added lubricity improver can be effectively extracted.
  • a diesel engine equipped with a distributed injection pump It is possible to suppress the increase in driving torque and reduce pump wear.
  • the type of the lubricity improver is not particularly limited.
  • one or more of the carboxylic acid-based, ester-based, and alcohol-based opiphenol-based lubricity improvers can be used arbitrarily. It is. Among these, carboxylic acid-based and ester-based lubricity improvers are preferable. .
  • carboxylic acid-based lubricity improver examples include linoleic acid, oleic acid, salicylic acid, palmitic acid, myristic acid, hexadecenoic acid and a mixture of two or more of the above carboxylic acids.
  • Ester-based lubricity improvers include glycerin carboxylic acid esters.
  • the carboxylic acid constituting the carboxylic acid ester may be one kind or two or more kinds. Specific examples thereof include linoleic acid, oleic acid, salicylic acid, palmitic acid, myristic acid, hexadecenoic acid, etc. There is.
  • the fatty acid structure of these lubricity improvers is preferably one having an unsaturated bond from the viewpoint of securing low-temperature fluidity.
  • an antifreezing agent to the fuel composition of the present invention from the viewpoint of preventing the inconvenience of the fuel filter and the fuel injection system due to freezing of water in the oil.
  • the addition amount is preferably 100 mass ppm or less and 500 mass ppm or less, more preferably 200 mass ppm or more and 400 mass ppm or less.
  • the type of antifreezing agent is not particularly limited, but various compounds having an antifreezing function can be arbitrarily used, such as 2-methoxyethanol, isopropyl alcohol. Examples thereof include coal and polydaryl alcohol, but from the viewpoint of securing low temperature fluidity, the melting point or pour point of these antifreeze agents is preferably 160 ° C. or lower.
  • cryoprotectants may be used singly or in combination of two or more, but more than those in which the purity of each antifreeze-containing main compound is 98% or more. It can be preferably used. .
  • a low temperature fluidity improver to the fuel composition of the present invention from the viewpoint of preventing filter blockage of a diesel vehicle.
  • the amount added is preferably 2 OO mg / L or more and 100 O mg / L or less in terms of the active ingredient concentration, and is preferably 300 mg or more and 80 O mg / L or less. More preferred.
  • the type of the low temperature fluidity improver is not particularly limited.
  • linear compounds such as oxalic acid amide, dibehenate of polyethylene glycol, acid such as phthalic acid, ethylenediammine tetraacetic acid, utlyloacetic acid and its hydrohydric acid
  • acid such as phthalic acid, ethylenediammine tetraacetic acid, utlyloacetic acid and its hydrohydric acid
  • low-temperature fluidity improvers such as comb polymers made of polar nitrogen compounds, alkyl fumarate or alkyltaconate monounsaturated ester copolymers may be used.
  • a copolymer of ethylene and methyl methacrylate a copolymer of ethylene and ⁇ -olefin, a chlorinated methylene monoacetic acid butyl copolymer, an alkyl ester polymer of unsaturated carboxylic acid, and a hydroxyl group
  • Esters or salts thereof synthesized from nitrogen-containing compounds and saturated fatty acids, esters and amide derivatives synthesized from polyhydric alcohols and saturated fatty acids, esters synthesized from polyoxyalkylene glycols and saturated fatty acids, polyhydric alcohols or One or two kinds selected from an alkylene oxide adduct of the partial ester and an ester synthesized from a saturated fatty acid, a chlorinated paraffin / naphthalene condensate, an alkenyl succinic acid amide, an amine salt of sulfobenzoic acid, etc.
  • a low temperature fluidity improver combining the above can also be used.
  • an ethylene monoacetate butyl copolymer additive can be preferably used.
  • the active ingredient (active ingredient) contributing to the low temperature fluidity is diluted with an appropriate solvent. Therefore, when such a commercial product is added to the light oil composition of the present invention, the above addition amount means the addition amount (active ingredient concentration) as an active ingredient.
  • other known fuel oil additives hereinafter referred to as “other additives” for convenience
  • other additives may be added alone or in combination of several kinds. it can.
  • cetane number improvers such as nitrate esters represented by alkyl nitrates having 6 to 8 carbon atoms and organic peroxides; imido compounds, alkenyl succinic acid imides, and succinic acids.
  • Detergents such as esters, copolymer polymers, and ashless detergents; Antioxidants such as phenols and amines; Metal deactivators such as salicylidene derivatives; Corrosion inhibitors such as aliphatic amines and alkellesuccinates
  • An antistatic agent such as an ionic, cationic or amphoteric surfactant; a coloring agent such as an azo dye; an antifoaming agent such as a silicon.
  • the addition amount of other additives can be arbitrarily determined.
  • the addition amount of each additive is preferably not more than 0.5% by mass, more preferably not more than 0.5% by mass, based on the total amount of the fuel composition for cryogenic regions. 2 mass. / 0 or less.
  • the present invention by using the diesel fuel composition manufactured by the above-described manufacturing method, fraction regulation, etc., it is possible to achieve an excellent low temperature that is difficult to realize with a conventional fuel composition. It is possible to provide a diesel combustion composition having fluidity, fuel efficiency, and environmental performance at the same time. In addition, by using a fuel composition for cryogenic regions produced by the above production method, fraction regulation, etc., low temperature fluidity in a cryogenic region, which was difficult to achieve with conventional fuel compositions, is achieved. It is possible to provide a fuel composition for extremely low temperatures that satisfies all the flexibility required for multiple applications and the performance as an environmentally friendly fuel.
  • the fuel composition of the present invention has excellent low-temperature fluidity, fuel efficiency, and environment-friendly performance at the same time, so that it can be used as a diesel fuel in winter, and has low-temperature fluidity in a cryogenic region and flexibility that can be used for multiple applications.
  • it is suitably used as a fuel composition for cryogenic regions satisfying all the performance as an environmentally friendly fuel.
  • the properties of the feedstock oil and fuel oil were measured by the following method.
  • Density refers to the density measured by J I S K 2 2 4 9 “Density test method for crude oil and petroleum products and density 'mass, volume conversion table”.
  • Flash point indicates the value measured by J I S K 2 2 6 5 “Crude oil and petroleum product flash point test method”.
  • the sulfur content refers to the mass content of the sulfur content based on the total amount of the diesel fuel composition measured by JI S K 2 5 4 1 “Sulfur content test method”.
  • Aromatic content is measured according to the Petroleum Institute Method JPI-5S-4 9-9 7 "Hydrocarbon Type Test Method-High Performance Liquid Chromatograph Method" published by the Japan Petroleum Institute. Means the volume percentage of the content (capacity. / 0 ).
  • Linear saturated hydrocarbon content 0 1 0—. 1 5 1 1? (Linear saturated hydrocarbon content with carbon number of 10 or more and 15 or less), C ll—C 15 n P, C 1 6—C 2 0 n P, C 1 6—C 2 5 n P Means the value (% by mass) measured using the above-mentioned GC-FID.
  • Cloudy point means the cloud point measured according to JISK 2 26 9 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.
  • the clogging point means the clogging point measured by JI S K 2 2 8 8 “Test method for light oil clogging point”. ⁇
  • Pour point means the pour point measured according to J I S K 2 26 9 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.
  • the cetane index is the value calculated by ⁇ Calculation method of cetane index using 8.4 variable equations '' in JISK 2 28 ⁇ Petroleum products / fuel oil / octane number and cetane number test method and cetane index calculation method ''. Point to. Note that the cetane index in the above JIS standard does not apply to the cetane number improver added, but in the present invention, the cetane index of the cetane number improver added also has the above 8.4 variable equation. It shall represent the value calculated by “Calculation method of cetane index used”.
  • Cetane number means the cetane number measured in accordance with “7. Cetane number test method” of JISK 2 28 0 “Petroleum products / Fuel oil / Octane number and cetane number test method and cetane index calculation method”. .
  • Reaction test refers to the reaction measured by JI S K 2 2 5 2 “Petroleum products—Reaction test method”.
  • Residual carbon content of 10% residual oil means the residual carbon content of 10% residual oil as measured by JIS K 2 27 0 “Testing method for residual carbon content of crude oil and petroleum products”.
  • Conductivity means a value measured according to JI S K 2276 “Petroleum products – Aviation fuel oil test method”. '
  • Lubrication performance and HFRR wear scar diameter are the lubrication performance measured by the Petroleum Institute Standard JPI-5 S-50-98 “Diesel Oil-Lubricity Test Method” published by the Japan Petroleum Institute Point to.
  • Comparative Example 1 the reaction pressure is 3 MPa, the reaction temperature is 380 ° C, and the liquid space velocity is 0.8 h under a catalyst in which a metal group selected from metals of Group 6A and Group 8 is supported on zeolite.
  • Comparative Examples 2 and 3 show no treatment required by the present invention for an FT synthetic base material.
  • Comparative Example 4 light oil and kerosene fractions were produced by a general hydrorefining process, and they were mixed in appropriate amounts to have low temperature performance equivalent to JIS No. 3 diesel oil. It is a composition.
  • the additives used in this example are as follows.
  • Lubricant improver Carboxylic acid mixture based on linoleic acid
  • Low temperature fluidity improver ethylene monoacetate butyl copolymer
  • Cetane improver 2-Ethylhexyl nitrate
  • the fuel compositions used in the examples are prepared by preparing a hydrocarbon base material obtained through a specific process using a FT synthetic base material as a raw material oil.
  • a fuel composition satisfying the specified properties was easily obtained. I was able to get it reliably and reliably.
  • Comparative Examples 1 to 4 in which the fuel composition was prepared without using the specific fuel substrate, the target fuel composition of the present invention was not necessarily obtained.
  • a diesel engine-equipped vehicle shown below, on a chassis dynamometer capable of controlling the ring temperature, at room temperature, (1) flushing (cleaning) the fuel system of the test diesel vehicle with the evaluation fuel ), (2;) Pull out the flushing fuel, (3) Replace the main filter with a new one, (4) Fill the fuel tank with the prescribed amount of fuel to be evaluated (1/2 of the fuel tank capacity of the test vehicle) . Then, (5) rapidly cool the ambient temperature from room temperature to 110 ° C, hold it at (6) —10 ° C for 1 hour, and then (7) set the specified temperature (at a cooling rate of 1 ° C / h) (8) Hold the engine at the specified temperature for 1 hour, and then start the engine. If it does not start after repeating 10 seconds of cranking twice at intervals of 30 seconds, measurement is impossible. If it can be started, leave it idle for 30 seconds, and then perform the following tests in order.
  • Vehicle specifications Vehicle 1
  • Example 5 The raw material oil having the properties shown in Table 5 was reacted and processed under the conditions for each process shown in Table 6 to prepare fuel compositions for extreme fridges shown in Table 7.
  • Examples 3, 4, and 5 were obtained by subjecting different raw material oils to respective process treatments under different conditions.
  • Example 3 a fourth embodiment performs a high degree of hydrorefining process including a ring-opening reaction of aromatic content with respect to petroleum coal hydrocarbons are those the resulting et hydrocarbons as a raw material oil Hydrocarbons obtained by subjecting natural gas to wax and middle distillation by FT reaction and hydrotreating it are used as feedstock.
  • Example 5 the oil obtained from palm palm (not separated for each fraction, used in the hall state) was hydrorefined and carbonized after removing unnecessary alcohol.
  • Example 6 is obtained by blending the synthetic fuel base material shown in Table 5 after the fuel oil composition of Example 3 was produced.
  • the blended synthetic fuel base material consists of a hydrocarbon mixture obtained by subjecting natural gas to wax and middle distillate by FT reaction and hydrotreating it, and the isomerization reaction has progressed relatively. It contains a saturated hydrocarbon compound having a side chain.
  • Comparative Example 5 shows a reaction pressure of 3 MPa, a reaction temperature of 3800 ° C, and a liquid space velocity under a catalyst in which a metal group selected from metals of Group 6A and Group 8 of the periodic table is supported on zeolite.
  • the additives used in this example are as follows.
  • Antifreeze 2-methoxetanol Lubricant improver: Carboxylic acid mixture based on linoleic acid
  • Low temperature fluidity improver ethylene monoacetate butyl copolymer
  • Cetane improver 2-Ethinorehexinolenate
  • Formulation ratio of prepared fuel composition, and density at 15 ° C, kinematic viscosity at 30 ° C, kinematic viscosity at 30 ° C, flash point, sulfur content for this prepared fuel composition Amount, distillation properties, aromatic content, cetane index, cetane number, pour point, hue, residual carbon content of 10% residual oil, results of reaction test, copper plate corrosion, moisture, total failure after oxidation stability test
  • Table 7 shows the results of measurement of dissolved content, peroxide value, conductivity, and wear scar diameter.
  • the fuel compositions used in the examples and comparative examples were prepared by blending hydrocarbon base materials obtained through specific processes and FT synthetic base materials having specific properties at specific ratios. '
  • Fuel consumption was measured using the aforementioned diesel engine-equipped vehicle (vehicle 1).
  • the test mode was a transient operation mode simulating actual driving shown in Fig. 1.
  • the smoke measurement uses a transmission type measuring instrument.
  • the test result in Comparative Example 5 was set to 100, and each result was relatively compared and quantified.
  • the test methods related to vehicle tests are in accordance with Appendix 27 “Technical Standards for Diesel Vehicles 10-15 Mode Emission Measurements”, attached to the new standards for new automobile examinations supervised by the former Ministry of Transport.
  • the target fuel composition is stored in a freezer that can be controlled at a constant temperature of 30 ° C for 1 month. After the storage, the appearance is checked. If sediment or turbidity occurs, it is judged as (X). Sampling the fuel composition supernatant (within 1 cm from the liquid level) after storage and measuring the pour point, and if the same performance as before storage is obtained (Yes) .
  • Table 5
  • Fig. 1 is a diagram showing a transient operation mode that simulates actual driving.

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

Abstract

L'invention concerne une composition de combustible pour la saison hivernale ayant toutes les propriétés excellentes de coulabilité à basse température, de performances kilométriques, et de performances de protection de l'environnement. La composition de combustible est obtenue en soumettant un mélange hydrocarboné ayant des propriétés spécifiques comme huile d'alimentation à un traitement d'élimination des hydrocarbures saturés linéaires par une zéolite dans les conditions d'une température réactionnelle de 150-250 °C et d'une pression de 1-5 MPa. La composition a une couleur Saybolt de +28 ou plus, une densité à 15 °C de 740-840 kg/m3, une température de régime à 10 %, comme propriété de distillation, de 170-220 °C, un indice de cétane calculé de 45 ou plus, un indice de cétane de 48 ou plus, un point d'éclair de 45 °C ou plus, un indice de peroxyde après un test d'oxydation accélérée de 10 ppm en masse ou moins, un point d'écoulement de -15 °C ou moins, une teneur en soufre de 10 ppm en masse ou moins, une viscosité dynamique à 30 °C de 1,6-5,0 mm2/s, et une teneur en carbone résiduel dans l'huile résiduelle à 10 % de 0,1 % en masse ou moins.
PCT/JP2007/055307 2006-03-27 2007-03-09 Composition de combustible WO2007111152A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006086374A JP4847170B2 (ja) 2006-03-27 2006-03-27 極低温地向け燃料組成物
JP2006-086374 2006-03-27
JP2006-086375 2006-03-27
JP2006086375A JP4847171B2 (ja) 2006-03-27 2006-03-27 ディーゼル燃料組成物

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003524679A (ja) * 1999-04-06 2003-08-19 サゾル テクノロジー（プロプライアタリー）リミティド 合成ナフサ燃料を製造する方法およびその方法により製造された合成ナフサ燃料
JP2004285155A (ja) * 2003-03-20 2004-10-14 Japan Energy Corp 環境対応軽油およびその製造方法
JP2004323625A (ja) * 2003-04-23 2004-11-18 Japan Energy Corp 環境対応軽油およびその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003524679A (ja) * 1999-04-06 2003-08-19 サゾル テクノロジー（プロプライアタリー）リミティド 合成ナフサ燃料を製造する方法およびその方法により製造された合成ナフサ燃料
JP2004285155A (ja) * 2003-03-20 2004-10-14 Japan Energy Corp 環境対応軽油およびその製造方法
JP2004323625A (ja) * 2003-04-23 2004-11-18 Japan Energy Corp 環境対応軽油およびその製造方法

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Title
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