CN101415799B

CN101415799B - Gas oil composition

Info

Publication number: CN101415799B
Application number: CN200780012382.8A
Authority: CN
Inventors: 菅野秀昭
Original assignee: Nippon Oil Corp
Current assignee: Eneos Corp
Priority date: 2006-03-31
Filing date: 2007-03-09
Publication date: 2013-01-02
Anticipated expiration: 2027-03-09
Also published as: CN101415799A; JP2007270109A; JP5000174B2

Abstract

Provided is a winter gas oil composition satisfactory in environmental load reduction, low-temperature performance and fuel consumption, obtained by adding a lubricity improver and a low-temperature fluidity improver according to prescribed steps to a composition which contains at least 60% by volume of an F-T synthesis base oil and has a sulfur content of 5ppm by mass or below, an aromatic content of 10% by volume or below, an oxygen content of 100ppm or below, a density of 760 to 840kg/m<3>, an end point of 360 DEG C or below, a total insoluble content of 0.5mg/100mL or below as determined after accelerated oxidation test, an HFRR wear scar diameter (WS1.4) of 400 mu m or below, and a specific relationship among n-parafin contents and a sum thereof.

Description

Gas oil composition

[invention field]

The present invention relates to mainly contain the gas oil composition of Fischer-Tropsch synthetic base oil, relate more specifically to realize together carrying capacity of environment reduction, cryogenic properties and low fuel consumption and the gas oil composition that is suitable for using in the winter time.

[background of invention]

Usually, produce gas oil composition by being in harmonious proportion the base oil of one or more types, described base oil is by making the straight chain gas oil or the straight chain kerosene that are produced by crude oil atmospheric distillation produce through hydrofining or hydrogenating desulfurization.Especially, normal conditions are to adjust the harmonic proportion of aforementioned kerosene base oil and gas oil base oil with the cold flowability during guaranteeing in the winter time.If necessary, for example cetane number improver, purification agent and cold flow improving agent are in harmonious proportion (referring to, following non-patent literature No.1 for example) with these base oils and additive.

Lower sulphur content and aromaticity content are believed to be suppressed at and generate unwanted component for example NOx and PM in the engine exhaust.From this viewpoint, caused concern with for example following fuel as the fuel that helps Reducing the burden on the environment: corresponding to the liquid distillate of petroleum naphtha, kerosene and gas oil, reaction produces these liquid distillates through Fischer-Tropsch (FT) by making the gas mixture that mainly contains hydrogen and carbon monoxide (hereinafter can often be called " synthetic gas ") that is produced by Sweet natural gas, coal, biomass or greasy filth; Produce hydrocarbon mixture by hydrofining or these liquid distillates of hydrocracking; The hydrocarbon mixture that produces with the liquid distillate that is produced by fischer-tropsch reaction by hydrofining or hydrocracking and Fischer-Tropsch wax.

Yet because fischer-tropsch reaction itself contains the process that generates wax, the straight chain saturation alkane of the product of the hydrotreatment of fischer-tropsch reaction product (n-paraffin) compounds content is relatively large.Point out, particularly when containing heavy n-paraffin compound, they might be with the form deposition of wax.And the Fischer-Tropsch synthetic base oil is the hydrocarbon mixture that mainly contains aforementioned n-paraffin and have the stable hydrocarbon (isoparaffin) of side chain, and so common poor solubility in oil.Therefore, highly depend on its oil-soluble group (straight chained alkyl etc.) be dissolved in oil fuel for example the gas oil additives might be difficult to the dissolving.In these additives, owing to the restriction of the solubleness of fuel, might use the conventional cold flow improver (CFI) by the vinyl-vinyl acetate copolymer compositions of mixtures.

Patent documentation No.1 only discloses the synthol that contains gas oil fraction by Fischer-Tropsch synthetic base oil production in embodiment.Yet this gas oil is the extremely light fuel that contains a large amount of kerosene(oil)fractions, because the document plans to solve the problem relevant with the cold-starting ability, and therefore can not select to improve with cold flow improver the technology of cryogenic properties.The result is, density significantly reduces, and kinematic viscosity and volume calorific value can not be avoided, and undeniablely in addition is, the defective that this reduction will cause that fuel consumption significantly worsens, the injection pump card is stung, cavitation infringement and high temperature are restarted the ability aspect.Namely, be very difficult to design so high-quality fuel, the high grade requirements that its gas oil composition that can realize having following character is looked for, the carrying capacity of environment that has this gas oil composition simultaneously reduces character, fabulous winter Practical Performance and to the inhibition of deterioration in fuel consumption, and based on research, except the abundant elaboration of front, do not satisfy example or the discovery of such fuel of the required various character of fuel and the practical approach of producing described fuel.

(1) patent documentation No.1:

Japanese Patent Laid-Open No.2005-529213

(2) non-patent literature No.1::Konishi Seiichi, " Nenryo KogakuGairon ", Shokabo Publishing Co., Ltd., in March, 1991,136-144 page or leaf

[summary of the invention]

Consider said circumstances, made the present invention, its objective is provides the gas oil composition that mainly contains the Fischer-Tropsch synthetic base oil, provides more specifically such gas oil composition, it can realize carrying capacity of environment reduction, cryogenic properties and low fuel consumption simultaneously, and is suitable for using in the winter time.

As for addressing the above problem the result who studies widely and explore who is implemented by the inventor, the present invention is accomplished.That is, the present invention relates to gas oil composition, it comprises the gas oil composition that is selected from following gas oil composition (A) to (C) and the additive that adds according to following steps 1 and 2:

[I] gas oil composition (A), it comprises 60 volume % or the more Fischer-Tropsch synthetic base oil of the total amount that accounts for this gas oil composition, and its sulphur content is 5 quality ppm or lower, and its aromaticity content is 10 volume % or lower, its oxygen level is 100 quality ppm or lower, and its density is 760kg/m ³Or larger and be 840kg/m ³Or less, in distillation characteristics, its 90% distillation temperature is 280 ℃ or higher and be that 330 ℃ or lower and final boiling point are 360 ℃ or lower, its insolubles content behind oxidation-stabilized property testing is 0.5mg/100mL or less, its HFRR wear print diameter (WS1.4) is 400 μ m or less, its cloud point is-15 ℃ or lower, its cold filter clogging temperature is-25 ℃ or lower, its pour point is-32.5 ℃ or lower, its total content of n-paraffin with 20-30 carbon atom is less than 2 quality %, its total content with n-paraffin of 20-30 carbon atom is 0.2 or larger and be 0.6 or less divided by the determined value of total content of the hydrocarbon with 20-30 carbon atom beyond the described n-paraffin, and the relation that has between the content (CnP) of every kind of n-paraffin of 15-20 carbon atom is restricted to C20P＜C19P＜C18P＜C17P＜C16P＜C15P;

[II] gas oil composition (B), it comprises 60 volume % or the more Fischer-Tropsch synthetic base oil of the total amount that accounts for this gas oil composition, its sulphur content is 5 quality ppm or lower, its aromaticity content is 10 volume % or lower, its oxygen level is 100 quality ppm or lower, and its density is 760kg/m ³Or larger and be 840kg/m ³Or less, in distillation characteristics, its 90% distillation temperature is 280 ℃ or higher and be that 350 ℃ or lower and final boiling point are 360 ℃ or lower, its insolubles content behind oxidation-stabilized property testing is 0.5mg/100mL or less, its HFRR wear print diameter (WS1.4) is 400 μ m or less, its cloud point is-5 ℃ or lower, its cold filter clogging temperature is-20 ℃ or lower, its pour point is-25 ℃ or lower, its total content with n-paraffin of 20-30 carbon atom is 2 quality % or larger and less than 4 quality %, its total content with n-paraffin of 20-30 carbon atom is 0.2 or larger and be 0.6 or less divided by the determined value of total content of the hydrocarbon with 20-30 carbon atom beyond the described n-paraffin, and the relation that has between the content (CnP) of every kind of n-paraffin of 20-25 carbon atom is restricted to C20P〉C21P〉C22P〉C23P〉C24P〉C25P; With

[III] gas oil composition (C), it comprises 60 volume % or the more Fischer-Tropsch synthetic base oil of the total amount that accounts for this gas oil composition, its sulphur content is 5 quality ppm or lower, its aromaticity content is 10 volume % or lower, its oxygen level is 100 quality ppm or lower, and its density is 760kg/m ³Or larger and be 840kg/m ³Or less, in distillation characteristics, its 90% distillation temperature is 280 ℃ or higher and be that 350 ℃ or lower and final boiling point are 360 ℃ or lower, its insolubles content behind oxidation-stabilized property testing is 0.5mg/100mL or less, its HFRR wear print diameter (WS1.4) is 400 μ m or less, its cloud point is-3 ℃ or lower, its cold filter clogging temperature is-10 ℃ or lower, its pour point is-12.5 ℃ or lower, its total content with n-paraffin of 20-30 carbon atom is 4 quality % or larger and less than 6 quality %, its total content with n-paraffin of 20-30 carbon atom is 0.2 or larger and be 0.6 or less divided by the determined value of total content of the hydrocarbon with 20-30 carbon atom beyond the described n-paraffin, and the relation that has between the content (CnP) of every kind of n-paraffin of 20-25 carbon atom is restricted to C20P〉C21P〉C22P〉C23P〉C24P〉C25P and (C24P-C25P)/C24P〉(C22P-C23P)/C22P〉(C20P-C21P)/C20P;

(step 1) by pipeline mediation, action of forced stirring or leave standstill enough time with the lubricity improver that comprises lipid acid and/or fatty acid ester by take active ingredient 20mg/L or more and mix with described gas oil composition as 300mg/L or amount still less; With

(step 2) by pipeline mediation, action of forced stirring or leave standstill enough time with the cold flow improver of compound that comprises vinyl-vinyl acetate copolymer and/or have a surface-active action by take active ingredient 20mg/L or more and mix with described gas oil composition as 1000mg/L or amount still less.

Perhaps, gas oil composition of the present invention preferably in the step that is added between step 1 and 2 by pipeline mediation, action of forced stirring or leave standstill enough time and 200mg/L or more and for 500mg/L or purification agent still less mix, described purification agent comprises polyether amine compound, polybutylene-based amine compound, alkenyl succinic diamide compound or alkenyl succinimide compound.Preferably, described lubricity improver, purification agent and cold flow improver contain solvent separately, and it is 10 ℃ or higher chemical substance that this solvent does not contain fusing point.Preferably, the peroxide value of described gas oil composition after the accelerated oxidation test is 50 quality ppm or less, and the kinematic viscosity under 30 ℃ is 2.5mm ²/ s or larger and be 5.0mm ²/ s or less, cetane index are 45 or larger, and water-content is 100 volume ppm or less.

Purpose of the present invention is as follows.If fuel by wax content wherein by excessive lightization and the method for extreme reduction is produced, it will affect adversely, to be difficult to solubilising additive with the fuel with low oily solubleness of being produced by the Fischer-Tropsch synthetic base oil separately, and cause them might represent their original advantageous effects.Therefore, the present invention plan to create and propose by add additive for example CFI give the effect of the fuel that oily solubleness reduces to improve the needed Quality Design method of cold flow ability.

[effect of the present invention]

According to the present invention, the gas oil composition that use is produced by aforesaid method, to satisfy the above-mentioned requirements that cut etc. is proposed, so that may easily produce the gas oil composition that is suitable for use in winter, it can realize carrying capacity of environment reduction, cryogenic properties and low fuel consumption simultaneously, and these character are difficult to realize by conventional gas oil composition always.

[preferred forms of the present invention]

Below the present invention will be described in more detail.

Gas oil composition of the present invention must contain the Fischer-Tropsch synthetic base oil.Described Fischer-Tropsch synthetic base oil is comprised of saturated hydrocarbon compound, and gas oil composition of the present invention can easily be produced by the temper of adjusting this hydrocarbon compound.As long as satisfied the characteristic of gas oil composition of the present invention, there is not particular restriction for the characteristic of this Fischer-Tropsch synthetic base oil.As long as realized the characteristic of gas oil composition of the present invention, the base oil beyond the described Fischer-Tropsch synthetic base oil there is not particular restriction.Yet, show enough environmental friendliness character in order to make described composition, below preferred the mediation by the oil base oil of height hydrotreatment and animal-or plant-derivative finished oil.

The alleged Fischer-Tropsch synthetic base oil of this paper represents various synthetic oils, for example corresponding to the liquid distillate of petroleum naphtha, kerosene and gas oil, it can be by the mixed gas (hereinafter can often be called " synthetic gas ") that mainly contains hydrogen and carbon monoxide is produced through Fischer-Tropsch (FT) reaction; Such liquid distillate is carried out the hydrocarbon mixture that hydrofining or hydrocracking produce; With the liquid distillate that produces by fischer-tropsch reaction and Fischer-Tropsch wax are carried out the hydrocarbon mixture that hydrofining or hydrocracking produce.

Described gas oil composition preferably comprises 60 volume % or more described Fischer-Tropsch synthetic base oil.In addition, described composition more preferably comprises 70 volume % or more, more preferably 80 volume % or more described Fischer-Tropsch synthetic base oil, and target is to reduce by sulphur component or the caused chance that increases the weight of environmental pressure of aromatic component.

The described gas mixture that will become the raw material of described Fischer-Tropsch synthesis oil can be by coming the oxidation carbonaceous material to produce with oxygen and/or water and/or carbonic acid gas as oxygenant, and in addition, if necessary, produce by the conversion reaction that makes water, in predetermined hydrogen and carbon monoxide concentration, to adjust.

The spendable carbonaceous material of this paper is normally by the gaseous fraction that forms for the hydrocarbon of gas under normal temps, for example for example material of construction and rubbish, greasy filth, reluctant heavy crude and make unconventional petroleum resources be exposed to the mixed gas that produces under the temperature of rising in due form of Sweet natural gas, liquefied petroleum gas (LPG) and methane gas, petroleum pitch, biomass, coke, refuse.Yet, in the present invention, as long as can produce the gas mixture that mainly contains hydrogen and carbon monoxide, these raw materials are not had particular restriction.

Described fischer-tropsch reaction needs metal catalyst.The 8th family's metal of preferred life cycle table, for example cobalt, ruthenium, rhodium, palladium, nickel and iron, more preferably the metal in the 8th family in the 4th cycle is as active catalyst component.Perhaps, can use the hybrid metal group of these metals that contain sufficient quantity.These reactive metals use with the form that they is loaded on the catalyzer that carrier for example produced on aluminum oxide, titanium dioxide and the silica-alumina usually.Perhaps, above-mentioned reactive metal and the second metallic combination of the performance that can promote resulting catalyzer are used.Described bimetallic example comprises basic metal or alkaline-earth metal for example sodium, lithium and magnesium, zirconium, hafnium and titanium, it can use according to purpose, described purpose for example increases transformation efficiency or the chain growth probability (α) of carbon monoxide, and α is the index of the turnout of wax.

Described fischer-tropsch reaction is to use gas mixture as the synthetic method of raw material production liquid distillate and Fischer-Tropsch wax.Usually preferably the ratio of the hydrogen in the described gas mixture and carbon monoxide is regulated effectively to implement this synthetic method.Usually, the mole mixture ratio of hydrogen and carbon monoxide (hydrogen/carbon monoxide) is preferably 1.2 or larger, and more preferably 1.5 or larger, more preferably 1.8 or larger.This ratio also is preferably 3 or less, and more preferably 2.6 or less, more preferably 2.2 or less.

The temperature of reaction of implementing fischer-tropsch reaction with aforementioned catalyzer is preferably 180 ℃ or higher and be 320 ℃ or lower, more preferably 200 ℃ or higher and be 300 ℃ or lower.Be lower than under 180 ℃ the temperature of reaction, carbon monoxide is difficult to reaction, the trend that causes the hydrocarbon productive rate to reduce.Be higher than under 320 ℃ the temperature of reaction, gas for example methane increases ground and generates, and causes the production efficiency of liquid distillate and Fischer-Tropsch wax to reduce.

With regard to described catalyzer, there is not particular restriction for gaseous hourly space velocity.Yet it is preferably 500h ^-1Or more and be 4000h ^-1Or lower, more preferably 1000h ^-1Or more and be 3000h ^-1Or lower.Less than 500h ^-1Gaseous hourly space velocity might reduce the production of liquid fuel, and greater than 4000h ^-1Gaseous hourly space velocity cause needs to improve temperature of reaction and increase the amount of gas to be generated, cause the yield of target product to reduce.

There is not particular restriction for reaction pressure (dividing potential drop of the synthetic gas that is formed by carbon monoxide and hydrogen).Yet it is preferably 0.5MPa or larger and for 7MPa or less, more preferably 2MPa or larger and be 4MPa or less.If reaction pressure is less than 0.5MPa, the productive rate of liquid fuel is tending towards reducing.If reaction pressure is unfavorable economically greater than 7MPa, because the amount of investment on equipment will increase.

If necessary, can carry out hydrofining or hydrocracking to liquid distillate and the Fischer-Tropsch wax that produces by above-mentioned fischer-tropsch reaction in any suitable mode, to adjust distillation characteristics or composition, to realize purpose of the present invention.Depend on described purpose, can select hydrofining or hydrocracking, and the invention is not restricted to any selection or to the two selection, its degree is to produce gas oil composition of the present invention.

Be used for hydrorefined catalyzer and normally comprise those of the hydrogenation active metals that loads on the porous support, as long as but can obtain same effect, the invention is not restricted to this.

Described porous support is preferably inorganic oxide.Specific examples comprises aluminum oxide, titanium dioxide, zirconium white, boron oxide, silicon-dioxide, zeolite etc.

Zeolite is crystal aluminosilicate, and the example comprises faujusite, pentasil and mordenite type zeolite.Preferably faujusite, β and mordenite type zeolite, and particularly preferably be Y-type and β-type zeolite.Y-type zeolite is preferably overstable.

For reactive metal, those of preferably following two types (reactive metal A type and reactive metal Type Bs).

Described reactive metal A type is at least a those the metal types that is selected from periodictable the 8th family.It preferably is selected from least a type of Ru, Rh, Ir, Pd and Pt, and is more preferably Pd and/or Pt.Described reactive metal can be the combination of these metals, for example Pt-Pd, Pt-Rh, Pt-Ru, Ir-Pd, Ir-Rh, Ir-Ru, Pt-Pd-Rh, Pt-Rh-Ru, Ir-Pd-Rh and Ir-Rh-Ru.The noble metal catalyst that is formed by these metals can be under the hydrogen stream through using after pre--reduction processing.Usually, according to preset program, described catalyzer is contained in 200 ℃ or higher temperature and circulation under the condition of gas of hydrogen and heat, so that the reactive metal on the catalyzer is reduced and therefore represent hydrogenation activity.

Described reactive metal Type B preferably contains those at least a metal that is selected from periodictable 6A family and 8 families, and hope is two or more metals that are selected from wherein.The example of these metals comprises Co-Mo, Ni-Mo, Ni-Co-Mo and Ni-W.When using the metal sulfide catalyst that is formed by these metals, it must pass through pre-vulcanization process.

Described source metal can be conventional inorganic salt or complexing salt compound.Carrying method can be any carrying method that has been generally used for hydrogenation catalyst, for example dipping and ion-exchange techniques.When the load various metals, the mixing solutions that can use them carries out simultaneously the independent solution that load or use contain every kind of metal with them and successively carries out load.Metallic solution can be the aqueous solution or solution with an organic solvent.

Temperature of reaction when the catalyzer that use is comprised of reactive metal A type carries out hydrofining is preferably 180 ℃ or higher and be 400 ℃ or lower, more preferably 200 ℃ or higher and be 370 ℃ or lower, more preferably 250 ℃ or higher and be 350 ℃ or lower, more preferably 280 ℃ or higher and be 350 ℃ or lower.The temperature of reaction that is higher than 370 ℃ is not preferred, because the productive rate of middle runnings extremely reduces, this is to be increased by the side reaction that wherein liquid distillate or Fischer-Tropsch wax are cracked into naphtha fraction to cause.Therefore the temperature of reaction that is lower than 270 ℃ neither be preferred, because alcohol can not be removed and stay in the reaction system.

Temperature of reaction when the catalyzer that use is comprised of the reactive metal Type B carries out hydrofining is preferably 170 ℃ or higher and be 320 ℃ or lower, and more preferably 175 ℃ or higher and be 300 ℃ or lower, more preferably 180 ℃ or higher and be 280 ℃ or lower.The temperature of reaction that is higher than 320 ℃ is not preferred, because the productive rate of middle runnings extremely reduces, this is to be increased by the side reaction that wherein liquid distillate or Fischer-Tropsch wax are cracked into naphtha fraction to cause.Therefore the temperature of reaction that is lower than 170 ℃ neither be preferred, because alcohol can not be removed and stay in the reaction system.

Hydrogen pressure when using the catalyzer that is comprised of reactive metal A type to carry out hydrofining is preferably 0.5MPa or larger and be 12MPa or less, more preferably 1.0MPa or larger and be 5.0MPa or less.Although higher hydrogen pressure is conducive to hydrogenation reaction, an optimum point is arranged usually on economic implications.

Hydrogen pressure when using the catalyzer that is comprised of the reactive metal Type B to carry out hydrofining is preferably 2MPa or larger and be 10MPa or less, 2.5MPa or larger and be 8MPa or less more preferably, more preferably 3MPa or larger and be 7MPa or less.Although higher hydrogen pressure is conducive to hydrogenation reaction, an optimum point is arranged usually on economic implications.

The little hourly space velocity of liquid (LHSV) when the catalyzer that use is comprised of reactive metal A type carries out hydrofining is preferably 0.1h ^-1Or larger and be 10.0h ^-1Or less, 0.3h more preferably ^-1Or larger and be 3.5h ^-1Or less.Although lower LHSV is conducive to this reaction, too low LHSV is not preferred economically, because this needs great reactor volume, causes excessive facility investment.

The little hourly space velocity of liquid (LHSV) when the catalyzer that use is comprised of the reactive metal Type B carries out hydrofining is preferably 0.1h ^-1Or larger and be 2h ^-1Or less, 0.2h more preferably ^-1Or larger and be 1.5h ^-1Or less, 0.3h more preferably ^-1Or larger and be 1.2h ^-1Or less.Although lower LHSV is conducive to this reaction, too low LHSV is not preferred economically, because this needs great reactor volume, causes excessive facility investment

Hydrogen when using the catalyzer that is comprised of reactive metal A type to carry out hydrofining/oil ratio example is preferably 50NL/L or larger and be 1000NL/L or less, more preferably 70NL/L or larger and be 800NL/L or less.Although higher hydrogen/oil ratio example is conducive to this reaction, an optimum point is arranged usually on economic implications.

Hydrogen when using the catalyzer that is comprised of the reactive metal Type B to carry out hydrofining/oil ratio example is preferably 100NL/L or larger and be 800NL/L or less, 120NL/L or larger and be 600NL/L or less more preferably, more preferably 150NL/L or larger and be 500NL/L or less.Although higher hydrogen/oil ratio example is conducive to this reaction, an optimum point is arranged usually on economic implications.

The catalyzer that is used for hydrocracking normally comprises those of the hydrogenation active metals that loads on the carrier with solid acid character, as long as but obtain same effect, the invention is not restricted to this.

As for described carrier with solid acid character, have amorphous and the crystalline zeolite type.Concrete example comprises unbodied silica-alumina, silica-magnesia, silicon-dioxide-zirconium white and silica-titania, and the zeolite of faujusite, β, MFI and mordenite type, preferred Y type and β type.Y-type zeolite is overstable those preferably.

For described reactive metal, those of preferably following two types (reactive metal A type and reactive metal Type Bs).

Described reactive metal A type is those the metal of at least a type that mainly is selected from periodictable 6A family and the 8th family.It preferably is selected from the metal of at least a type of Ni, Co, Mo, Pt, Pd and W.The noble metal catalyst that is formed by these metals can be under the hydrogen stream through using after pre--reduction processing.Usually, according to preset program, described catalyzer is contained in 200 ℃ or higher temperature and circulation under the condition of gas of hydrogen and heat, so that the reactive metal on the catalyzer is reduced and therefore represent hydrogenation activity.

Described reactive metal Type B can be the combination of these metals, for example Pt-Pd, Co-Mo, Ni-Mo, Ni-W and Ni-Co-Mo.When using the catalyzer that is formed by these metals, it must pass through pre-vulcanization process before use.

Temperature of reaction when the catalyzer that use is comprised of reactive metal A type and reactive metal Type B carries out hydrocracking is preferably 200 ℃ or higher and be 450 ℃ or lower, more preferably 250 ℃ or higher and be 430 ℃ or lower, more preferably 300 ℃ or higher and be 400 ℃ or lower.The temperature of reaction that is higher than 450 ℃ is not preferred, because the productive rate of middle runnings extremely reduces, this is to be increased by the side reaction that wherein liquid distillate or Fischer-Tropsch wax are cracked into naphtha fraction to cause.The temperature of reaction that is lower than 200 ℃ neither be preferred, because the active of catalyzer extremely reduces.

Hydrogen pressure when using the catalyzer that is comprised of reactive metal A type and reactive metal Type B to carry out hydrocracking is preferably 1MPa or larger and be 20MPa or less, 4MPa or larger and be 16MPa or less more preferably, more preferably 6MPa or larger and be 13MPa or less.Although higher hydrogen pressure is conducive to hydrogenation reaction, it is quite slow that cracking reaction will be carried out ground, and therefore need to regulate by improving temperature of reaction their carrying out, and cause the working life of catalyzer short.Therefore, an optimum point is arranged usually on economic implications.

The little hourly space velocity of liquid (LHSV) when the catalyzer that use is comprised of reactive metal A type carries out hydrocracking is preferably 0.1h ^-1Or larger and be 10.0h ^-1Or less, 0.3h more preferably ^-1Or larger and be 3.5h ^-1Or less.Although lower LHSV is conducive to this reaction, too low LHSV is not preferred economically, because this needs great reactor volume, causes excessive facility investment.

The little hourly space velocity of liquid (LHSV) when the catalyzer that use is comprised of the reactive metal Type B carries out hydrocracking is preferably 0.1h ^-1Or larger and be 2h ^-1Or less, 0.2h more preferably ^-1Or larger and be 1.7h ^-1Or less, 0.3h more preferably ^-1Or larger and be 1.5h ^-1Or less.Although lower LHSV is conducive to this reaction, too low LHSV is not preferred economically, because this needs great reactor volume, causes excessive facility investment.

Hydrogen when using the catalyzer that is comprised of reactive metal A type to carry out hydrocracking/oil ratio example is preferably 50NL/L or larger and be 1000NL/L or less, 70NL/L or larger and be 800NL/L or less more preferably, more preferably 400NL/L or larger and be 1500NL/L or less.Although higher hydrogen/oil ratio example is conducive to this reaction, an optimum point is arranged usually on economic implications.

Hydrogen when using the catalyzer that is comprised of the reactive metal Type B to carry out hydrocracking/oil ratio example is preferably 150NL/L or larger and be 2000NL/L or less, 300NL/L or larger and be 1700NL/L or less more preferably, more preferably 400NL/L or larger and be 1500NL/L or less.Although higher hydrogen/oil ratio example is conducive to this reaction, an optimum point is arranged usually on economic implications.

The reactor that is used for hydrogenation can have any structure, and can use single or multiple reaction towers.Supply of hydrogen between a plurality of reaction towers extraly.Described reactor can have be used to the equipment that removes hydrogen sulfide and be used for the distillation tower of the cut that the fractionation hydrogenation products wants with generation.

The reaction pattern of hydrogenator can be the fixed bed pattern.Can with adverse current or and stream pattern with hydrogen supply in raw material.Perhaps, for a plurality of reaction towers, reaction pattern can be counter-flow pattern and the also combination of stream mode.The supply of raw material pattern is generally katabatic drainage, and is preferably solution-air and stream mode.For shifting out reaction heat or increasing hydrogen partial pressure, hydrogen can be used as the middle portion that the chilling agent is fed to reactor.

Petroleum-based base oil above-mentioned is the hydrocarbon base oil that is produced by the crude oil machining.Example comprises: the straight chain base oil that common air distillation unit produces; In the underpressure distillation unit, straight chain heavy oil or the residual oil that produces by the air distillation unit is carried out the decompression base oil that machining produces; The oil fuel of decompression heavy basestock or desulfurization is carried out catalytic cracking base oil or the hydrocracking base oil that catalytic cracking or hydrocracking produce; With these petroleum hydrocarbons any carried out hydrofining base oil or the hydrogenating desulfurization base oil that hydrofining produces.Perhaps, except crude oil, the machining that the resource (for example resinous shale, oil-sand and Orinoco tar) that is known as the non-conventional oil resource is suited produces has base oil with the character of aforementioned basic oil properties equivalence and can be used as base oil among the present invention.

The petroleum base base oil of above-mentioned height hydrogenation is by predetermined raw material is carried out hydrofining and then carries out kerosene or the gas oil fraction that hydrotreatment produces.The example of described raw material comprises: straight chain kerosene or gas oil that the air distillation unit by crude oil produces; In the underpressure distillation unit, straight chain heavy oil or the residual oil that produces by the air distillation unit is carried out decompression kerosene or the gas oil that machining produces; With hydrorefined and kerosene or gas oil hydrogenating desulfurization, it carries out the kerosene of the catalytic cracking that catalytic cracking produces or gas oil by the oil fuel to decompression kerosene desulfurization or undesulfured or gas oil, decompression heavy gas oil or desulfurization and carries out hydrotreatment and produce.

When described raw material is gas oil fraction, hydrorefined condition can be when the hydrogenating desulfurization unit is generally used for refining of petroleum determined those.Usually, the hydrofining of gas oil fraction is carried out under the following conditions: temperature of reaction is 300-380 ℃, and hydrogen pressure is 3-8MPa, and LHSV is 0.3-2h ^-1, and hydrogen/oil ratio example is 100-500NL/L.When described raw material is kerosene(oil)fraction, hydrorefined condition can be when the hydrogenating desulfurization unit is generally used for refining of petroleum determined those.Usually, the hydrofining of kerosene(oil)fraction is carried out under the following conditions: temperature of reaction is 220-350 ℃, and hydrogen pressure is 1-6MPa, and LHSV is 0.1-10h ^-1, and hydrogen/oil ratio example is 10-300NL/L, preferred condition is: temperature of reaction is 250-340 ℃, and hydrogen pressure is 2-5MPa, and LHSV is 1-10h ^-1, and hydrogen/oil ratio example is 30-200NL/L, and more preferably carry out under the following conditions: temperature of reaction is 270-330 ℃, and hydrogen pressure is 2-4MPa, and LHSV is 2-10h ^-1, and hydrogen/oil ratio example is 50-200NL/L.

Lower temperature of reaction is favourable for hydrogenation reaction, but is not preferred for desulphurization reaction.Higher hydrogen pressure and higher hydrogen/oil ratio example is conducive to desulfurization and hydrogenation reaction, but at economic implications an optimum point is arranged.Although lower LHSV is favourable for reaction, too low LHSV is not preferred economically, because this needs great reactor volume, causes excessive facility investment.

Being used for hydrorefined catalyzer can be any conventional Hydrobon catalyst.Preferably, the reactive metal of this catalyzer is 6A family and the 8th family's metal of periodictable.The example of these metals comprises Co-Mo, Ni-Mo, Co-W and Ni-W.Carrier can be to contain aluminum oxide as the porous inorganic oxide of main ingredient.As long as the characteristic of described raw material is satisfied, these conditions and catalyzer are had no particular limits.

The raw material that uses in the present invention produces by above-mentioned hydrofinishing process, and its sulphur content is preferably 5 quality ppm or more and be 10 quality ppm or less, and its boiling point is preferably 130 ℃ or higher and be 380 ℃ or lower.Sulphur content and the boiling point raw material in these scopes can guarantee easily to be embodied as the feature of following height method of hydrotreating defined.

In the presence of hydrogenation catalyst, to as the above-mentioned hydrogenation of raw material kerosene or gas oil carry out hydrotreatment, produce thus the height hydrotreatment base oil.

The condition of height hydrogenation is these: temperature of reaction is 170-320 ℃, and hydrogen pressure is 2-10MPa, and LHSV is 0.1-2h ^-1, and hydrogen/oil ratio example is 100-800NL/L, preferred condition is: temperature of reaction is 175-300 ℃, and hydrogen pressure is 2.5-8MPa, and LHSV is 0.2-1.5h ^-1, and hydrogen/oil ratio example is 150-600NL/L, and more preferably carry out under the following conditions: temperature of reaction is 180-280 ℃, and hydrogen pressure is 3-7MPa, and LHSV is 0.3-1.2h ^-1, and hydrogen/oil ratio example is 150-500NL/L.Lower temperature of reaction is conducive to hydrogenation reaction but is not preferred for desulphurization reaction.Higher hydrogen pressure and higher hydrogen/oil ratio example is conducive to desulfurization and hydrogenation reaction, but at economic implications an optimum point is arranged.Although lower LHSV is favourable for reaction, too low LHSV is not preferred economically, because this needs great reactor volume, causes excessive facility investment.

Be used for to have any structure to the unit that is carried out hydrotreatment by the raw material of hydrofining, and can use the combination of single reactor or a plurality of reactors.Can extraly hydrogen be imported in the interval between a plurality of reactors.This hydrofining unit can be furnished with gas-liquid separation system or hydrogen sulfide removal system.

The reaction pattern of described hydrogenator can be the fixed bed pattern.Can with adverse current or and stream pattern with hydrogen supply in raw material.Perhaps, for a plurality of reaction towers, reaction pattern can be counter-flow pattern and the also combination of stream mode.The supply of raw material pattern is generally katabatic drainage, and is preferably solution-air and stream mode.For shifting out reaction heat or increasing hydrogen partial pressure, hydrogen can be used as the middle portion that the chilling agent is fed to reactor.

The catalyzer that is used for hydrotreatment comprises the hydrogenation active metals that loads on the porous support.Described porous support can be for example aluminum oxide of inorganic oxide.The example of described inorganic oxide comprises aluminum oxide, titanium dioxide, zirconium white, boron oxide, silicon-dioxide and zeolite.In the present invention, described carrier is preferably by aluminum oxide be selected from least a of titanium dioxide, zirconium white, boron oxide, silicon-dioxide and zeolite and form.Be not particularly limited for the method for producing carrier.Therefore, can adopt raw-material any method of using solation or salt compound form, described raw-material each contain any of described element.Perhaps, described carrier can be prepared as follows: generate compound oxyhydroxide or oxide compound, then for example silica alumina, silicon-dioxide zirconium white, aluminum oxide titanium dioxide, silicon dioxide and titanium dioxide and aluminum oxide boron oxide add the aluminum oxide of alumina gel, oxyhydroxide or suitable solution form in any step.Based on described porous support, can contain aluminum oxide with any ratio with other oxide compound.Yet the content of aluminum oxide is preferably 90 quality % of described porous support quality or still less, more preferably 60 quality % or still less, and more preferably 40 quality % or still less.

Zeolite is crystal aluminosilicate.The example of crystalline structure comprises faujusite, pentasil and mordenite.Those that these zeolites can be adjusted by those or its alumina content of special hydrothermal treatment consists and/or acid treatment institute super stabilizing.Preferred zeolite is those of faujusite, β and mordenite type, and particularly preferred zeolite is Y and beta type those.Y-type zeolite particularly preferably is super stabilizing.The zeolite of described super stabilizing has special microporous structure, and so-called 20

Or less micropore, also have newly-generated 20-100

Figure 2007800123828100002G2007800123828D0014130132QIETU

Hole in the scope.Can under known conditions, carry out hydrothermal treatment consists.

The reactive metal that is used for the catalyzer of hydrotreatment is at least a metal that is selected from periodictable the 8th family's metal, is preferably selected from least a metal of Ru, Rh, Ir, Pd and Pt, and more preferably Pd and/or Pt.These metals can be used in combination, for example Pt-Pd, Pt-Rh, Pt-Ru, Ir-Pd, Ir-Rh, Ir-Ru, Pt-Pd-Rh, Pt-Rh-Ru, Ir-Pd-Rh and Ir-Rh-Ru.The source metal of these metals can be inorganic salt or the complexing salt compound that is used by routine.The method of the described metal of load can be any method for hydrogenation catalyst, for example dipping and ion-exchange.When the load various metals, can be simultaneously with their mixing solutions come load they.Perhaps, can come successively load various metals with any solution that contains separately described metal.These metallic solutions can be the aqueous solution or the solution that with an organic solvent produces.

Described metal loads on the porous support after can finishing in steps in the institute for the preparation of described porous support.Perhaps, described metal can load on the porous support with suitable oxide compound, the form of composite oxides, or loads on the zeolite that produces in the intermediate stage for preparing this porous support, then can carry out the gel preparation or the concentrated and kneading through heating.

For being not particularly limited by the amount of the reactive metal of load, yet based on the quality of described catalyzer, its amount is 0.1-10 quality %, preferred 0.15-5 quality %, and more preferably 0.2-3 quality %.

Described catalyzer preferably uses after process prereduction is processed under the hydrogen stream at it.Usually, according to preset program, described reactive metal is contained in 200 ℃ or higher temperature and circulation under the condition of gas of hydrogen and heat, then reduction represents catalytic activity thus.

The base oil that the derivative finished oil of above-mentioned described animal or plant is comprised of hydrocarbon, the derivative finished oil of this animal or plant are that the chemical reaction method that will be used for producing above-mentioned petroleum-based base oil is applied to by the animal or plant starting material and obtains or the oil that produces or fat upper and production.More specifically, the derivative finished oil of described animal or plant is the mixed base oil that contains hydrocarbon, it is by making animal or plant fat contact to produce with hydrocracking catalyst under hydrogen pressure with the therefrom derivative component as raw material, and described hydrocracking catalyst contains at least a or various metals that is selected from periodictable 6A family and the 8th family's metal and has acid inorganic oxide.The raw material of the finished oil that described animal or plant is derivative must be animal or plant fat or derived from the component of animal or plant fat.The employed described animal or plant fat of this paper or comprise natural or the artificial or artificial animal or plant fat that produces and the animal or plant lipid fraction that is therefrom derived derived from the example of the component of animal or plant fat.The raw-material example of animal tallow and animal oil comprises tallow, butterfat (cream), lard, suet, whale oil, fish oil and liver oil.The raw-material example of vegetation fat and vegetables oil comprises seed and other parts, palm tree, olive, safflower, grape (grape flower), rice bran, Sunflower Receptacle, cottonseed, corn, soybean, sesame and the Semen Lini of coconut.Those fat or oil in addition that produced by these materials also can be used among the present invention.Described raw material can be solid or liquid, but preferably results from vegetation fat or vegetables oil, and purpose is for easy operation, carbon dioxide absorption and high productive capacity.Perhaps, these animal and plant oil are prepared the resulting waste oil of purpose for family expenses, industry and food and after removing residuals from these oil, can be used as described raw material.

The example of the general composition of the fatty acid part of contained glyceride compounds comprises lipid acid in these raw materials, the so-called saturated fatty acid that does not have unsaturated link(age) in molecule, for example butyric acid (C ₃H ₇COOH), caproic acid (C ₅H ₁₁COOH), sad (C ₇H ₁₅COOH), capric acid (C ₉H ₁₉COOH), lauric acid (C ₁₁H ₂₃COOH), tetradecanoic acid (C ₁₃H ₂₇COOH), palmitinic acid (C ₁₅H ₃₁COOH), stearic acid (C ₁₇H ₃₅COOH); And the so-called unsaturated fatty acids that in molecule, has one or more unsaturated link(age)s oleic acid (C for example ₁₇H ₃₃COOH), linolic acid (C ₁₇H ₃₁COOH), linolenic acid (C ₁₇H ₂₉COOH) and ricinolic acid (C ₁₇H ₃₂(OH) COOH).Usually, the hydrocarbon of these contained lipid acid part mainly is straight chain in the material that occurring in nature exists.Yet as long as the character of the present invention regulation is satisfied, described lipid acid can be any those of side-chain structure of having, i.e. isomer.Described unsaturated fatty acids can be any occurring in nature usually understanding those existences and per molecule has a unsaturated link(age) those, as long as character given to this invention is satisfied, the position of unsaturated link(age) can be adjusted by chemosynthesis.

Above-mentioned raw materials (animal or plant fat and the component that therefrom derives) contains the one or more of of these lipid acid, and this depends on starting material and changes.For example, Oleum Cocois contains relatively a large amount of saturated fatty acids for example lauric acid and tetradecanoic acid, and soybean oil contains a large amount of unsaturated fatty acidss for example oleic acid and linolic acid.

Described raw material contains boiling point and is preferably 250 ℃ or higher cut, and more preferably boiling point is 300 ℃ or higher cut, and more preferably boiling point is 360 ℃ or higher cut.If it is 230 ℃ or higher cut that described raw material does not contain boiling point, the yield of product liquid will reduce, because the gas that generates has in process of production increased, this might cause increase the cycling time (life cycle) of carbonic acid gas.

Perhaps, the raw material of the derivative finished oil of described animal or plant can be animal or plant fat and therefrom derivative component and the mixture of petroleum hydrocarbon cut.In this case, the ratio of described petroleum hydrocarbon cut is preferably the 10-99 volume % of described raw material cumulative volume, more preferably 30-99 volume %, and more preferably 60-98 volume %.If this ratio may be for the treatment of the equipment of water byproduct less than described lower limit.If this ratio is greater than the described upper limit, from reducing the carbonic acid gas angle of cycling time, this is not preferred.

The condition of in the hydrotreatment process described raw material being carried out hydrocracking wishes it is such: hydrogen pressure is 6-20MPa, and the little hourly space velocity of liquid (LHSV) is 0.1-1.5h ^-1, and hydrogen/oil ratio example is 200-2000NL/L; Wish that wherein hydrogen pressure is 8-17MPa, the little hourly space velocity of liquid (LHSV) is 0.2-1.1h ^-1, and hydrogen/oil ratio example is 300-1800NL/L; Wish that wherein hydrogen pressure is 10-16MPa, the little hourly space velocity of liquid (LHSV) is 0.3-0.9h ^-1, and hydrogen/oil ratio example is 350-1600NL/L.Each condition is the factor that reactive behavior is exerted one's influence.For example, if hydrogen pressure and hydrogen/oil ratio example less than described lower limit, reactivity is tending towards reducing, and activity is tending towards rapid reduction.If hydrogen pressure and hydrogen/oil ratio example surpasses the described upper limit, may need the huge plant investment for compressor.The little hourly space velocity of lower liquid more is conducive to this reaction often.Yet, if the little hourly space velocity of liquid is lower than 0.1h ^-1, may need huge plant investment to have the reactor of Extremely volume with structure.If the little hourly space velocity of liquid surpasses 1.5h ^-1, described reaction is often carried out insufficient.

Gas oil composition of the present invention must mainly contain the Fischer-Tropsch synthetic base oil and have characteristic as described below.

Gas oil composition of the present invention comprises the gas oil composition that is selected from following gas oil composition (A) to (C) and the additive that adds according to following steps 1 and 2:

The sulphur content of gas oil composition of the present invention is necessary for 5 quality ppm or less, preferred 3 quality ppm or less, more preferably 1 quality ppm or less, the effect that purpose is to reduce the toxic substance of engine emission and improves exhausted gas post-processing system.The employed sulphur content of this paper represents the sulphur component based on the mass content of gas oil composition total mass, and it is measured according to JIS K2541 " mensuration of crude oil and petroleum products-sulphur content ".

The aromaticity content of gas oil composition of the present invention is necessary for 10 volume % or less, preferred 8 volume % or less, more preferably 5 volume % or less, more preferably 3 volume % or less, most preferably 1 volume % or less.When the aromaticity content of described composition is 10 volume % or more hour, it can suppress the generation of PM, represents environmental friendliness character and easily and definitely realize the characteristic of defined among the present invention.Aromaticity content used herein represents volume percent (volume %) content of the aromatic component that the JPI-5S-49-97 " mensuration-high performance liquid chromatography of petroleum products-hydrocarbon types " according to defined in the petroleum products testing method JPI standard of publishing in Japan petroleum institute and the guide surveys.

The oxygen level of gas oil composition of the present invention is necessary for 100 quality ppm or less, preferred 80 quality ppm or less, and more preferably 60 quality ppm or less, purpose is to improve oxidative stability.Can measure oxygen level with the ultimate analysis equipment of routine.For example, by on platinum carbon, sample being converted into CO or being further converted to CO ₂And measure oxygen level with the amount that thermal conductivity detector is measured them.

The density of gas oil composition of the present invention under 15 ℃ is preferably 760kg/m ³Or higher, 765kg/m more preferably ³Or higher, and 770kg/m more preferably ³Or higher, purpose is to keep calorific value.This density is preferably 840kg/m ³Or lower, 835kg/m more preferably ³Or lower, and be preferably 830kg/m ³Or lower, purpose is to reduce the discharging of NOx and PM.Density used herein represents the density surveyed according to JIS K 2249 " mensuration of crude oil and petroleum products-density and based on the petroleum measurement tables of reference temperature (15 ℃) ".

With regard to distillation characteristics, 90% distillation temperature of described gas oil composition (A) is necessary for 330 ℃ or lower.If this 90% distillation temperature surpasses 330 ℃, PM or fine grain discharging might increase.Therefore, this 90% distillation temperature is preferably 327 ℃ or lower, more preferably 325 ℃ or lower.If this 90% distillation temperature is too low, it will cause the deterioration of fuel consumption or the reduction of engine output.Therefore, this lower limit 90% distillation temperature is necessary for 280 ℃ or higher, and preferred 285 ℃ or higher, more preferably 290 ℃ or higher.For gas oil composition (B) and (C), this 90% distillation temperature is necessary for 350 ℃ or lower.If this 90% distillation temperature surpasses 350 ℃, PM or fine grain discharging might increase.Therefore, this 90% distillation temperature is preferably 345 ℃ or lower, and more preferably 340 ℃ or lower, more preferably 335 ℃ or lower.If this 90% distillation temperature is too low, it will cause the deterioration of fuel consumption or the reduction of engine output.Therefore, this lower limit 90% distillation temperature is necessary for 280 ℃ or higher, and preferred 285 ℃ or higher, more preferably 290 ℃ or higher.

The initial boiling point of gas oil composition of the present invention is necessary for 140 ℃ or higher.If this initial boiling point is lower than 140 ℃, engine output and high startup temperature ability often will extremely reduce and worsen.Therefore, this initial boiling point is preferably 145 ℃ or higher, more preferably 150 ℃ or higher.Described final boiling point is preferably 360 ℃ or lower.If this final boiling point is greater than 360 ℃, PM or fine grain discharging may increase.Therefore, this final boiling point is preferably 368 ℃ or lower, more preferably 366 ℃ or lower.

There is not particular restriction for 10% distillation temperature.Yet lower limit is preferably 160 ℃ or higher, and more preferably 170 ℃ or higher, more preferably 180 ℃ or higher, purpose is to suppress the reduction of engine output and the deterioration of fuel consumption.The upper limit is preferably 250 ℃ or lower, and more preferably 245 ℃ or lower, more preferably 230 ℃ or lower, purpose is to suppress the deterioration of exhaust gas properties.Described initial boiling point used herein, 10% distillation temperature, 90% distillation temperature and final boiling point represent the measured value according to JIS K2254 " mensuration of petroleum products-distillation characteristics ".

Consider storage stability, the total insoluble substance content of gas oil composition of the present invention behind oxidation-stabilized property testing is necessary for 1.0mg/100mL or lower, more preferably 0.8mg/100mL or lower, more preferably 0.5mg/100mL or lower.Oxidation-stabilized property testing used herein is carrying out under 16 hours in bubble oxygen under 95 ℃ according to ASTM D2274-94.Total insoluble substance content behind the alleged oxidation-stabilized property testing of this paper represents according to the measured value of aforementioned oxidation-stabilized property testing.

Gas oil composition of the present invention must have such oilness: HFRR wear print diameter (WS1.4) is 400 μ m or less.If oilness is too low, when engine driven, the driving torque that said composition will cause particularly being furnished with the diesel motor of profile injection pump increases, and the wearing and tearing on each parts of pump increase, and might not only cause the deterioration of exhaust gas properties but also cause the fault of engine self.Also have making the high pressure injection become possible automatically controlled fuel charge, also may wear and tear at slide unit.Therefore, with regard to oilness, the HFRR wear print diameter (WS1.4) of described gas oil composition is necessary for 400 μ m or less, preferred 380 μ m or less, more preferably 360 μ m or less.The employed oilness of this paper, namely, HFRR fraze (WS1.4) expression is according to the measured oilness of JPI-5S-50-98 " testing method of gas oil-oilness ", and the method has regulation in petroleum products testing method JPI standard that Japan petroleum institute publishes and guide.

Cloud point about gas oil composition of the present invention, the cloud point of described gas oil composition (A) is necessary for-15 ℃ or lower, more preferably-16 ℃ or lower, more preferably-17 ℃ or lower, purpose is to guarantee cold-starting ability and driving force, and purpose is to keep the injection efficiency of automatically controlled fuel charge.The cloud point of described gas oil composition (B) is necessary for-5 ℃ or lower, and preferred-6 ℃ or lower, more preferably-8 ℃ or lower, purpose is to guarantee cold-starting ability and driving force, and purpose is to keep the injection efficiency of automatically controlled fuel charge.The cloud point of described gas oil composition (C) is necessary for-3 ℃ or lower, and more preferably-4 ℃ or lower, more preferably-5 ℃ or lower, purpose is to guarantee cold-starting ability and driving force, and purpose is to keep the injection efficiency of automatically controlled fuel charge.

Cloud point used herein represents the pour point surveyed according to JIS K 2269 " pour point of crude oil and petroleum products and the testing method of cloud point ".

About the cold filter clogging temperature of gas oil composition of the present invention, the cold filter clogging temperature of described gas oil composition (A) is necessary for-25 ℃ or lower.And this cold filter clogging temperature is preferably-26 ℃ or lower, and more preferably-27 ℃ or lower, purpose is to prevent the silting up of prefilter of the automobile take diesel oil as fuel, and keeps the injection efficiency of automatically controlled fuel charge.The cold filter clogging temperature of described gas oil composition (B) is necessary for-20 ℃ or lower.And this cold filter clogging temperature is preferably-21 ℃ or lower, and more preferably-22 ℃ or lower, purpose is to prevent the silting up of prefilter of the automobile take diesel oil as fuel, and keeps the injection efficiency of automatically controlled fuel charge.The cold filter clogging temperature of described gas oil composition (C) is necessary for-10 ℃ or lower.And this cold filter clogging temperature is preferably-11 ℃ or lower, and more preferably-12 ℃ or lower, purpose is to prevent the silting up of prefilter of the automobile take diesel oil as fuel, and keeps the injection efficiency of automatically controlled fuel charge.

Cold filter clogging temperature used herein represents the cold filter clogging temperature surveyed according to JIS K 2288 " mensuration of gas oil-cold filter clogging temperature ".

About the pour point of gas oil composition of the present invention, the pour point of described gas oil composition (A) is necessary for-32.5 ℃ or lower.And, preferred-35 ℃ or lower of this pour point, the injection efficiency that purpose is to guarantee cold-starting ability or driving force and keeps automatically controlled fuel charge.The pour point of described gas oil composition (B) is necessary for-25 ℃ or lower.And, preferred-22.5 ℃ or lower of this pour point, the injection efficiency that purpose is to guarantee cold-starting ability or driving force and keeps automatically controlled fuel charge.The pour point of described gas oil composition (C) is necessary for-12.5 ℃ or lower.And, preferred-15 ℃ or lower of this pour point, the injection efficiency that purpose is to guarantee cold-starting ability or driving force and keeps automatically controlled fuel charge.

Pour point used herein represents the pour point surveyed according to JIS K 2269 " pour point of crude oil and petroleum products and the testing method of cloud point ".

In the present invention, having the total content of the n-paraffin of 20-30 carbon atom in the described gas oil composition (A) must be less than 2 quality % of this gas oil composition total mass.If the total content of these heavy n-paraffin is 2 quality % or more, will cause at low temperatures the deposition of wax.Therefore, preferred 1.8 quality % of this total content or still less, more preferably 1.6 quality % or still less.And, in order to improve this gas oil basis oil additives solubleness, total content with n-paraffin of 20-30 carbon atom is necessary for 0.2 or larger and be 0.6 or less divided by the determined value of total content of the hydrocarbon with 20-30 carbon atom beyond the described n-paraffin, be preferably 0.22 or larger and be 0.57 or less, more preferably 0.25 or larger and be 0.55 or less.If should be worth less than 0.2, additive solubleness will extremely reduce.If should be worth greater than 0.6, will weaken the cold flow ability.And carbon number (n) must satisfy the relation that is limited by C20P＜C19P＜C18P＜C17P＜C16P＜C15P for the content (CnP) of every kind of n-paraffin in the 15-20 scope.As long as this relation is satisfied, effect owing to this n-paraffin that exists with aforementioned content, resulting composition will have corresponding to temperature variation the stable Wax Sediment Velocity of external temperature when for example said composition is cooled, and can guarantee that cold flow improver stably represents its character.

The total content of the straight chain saturation alkane of the described 20-30 of a having carbon atom is the value of using GC-FID to measure with the content with straight chain saturation alkane of 15-20 carbon atom, its center pillar is the capillary column (ULTRA ALLOY-1) that is formed by methylsiloxane, carrier gas is that helium and detector are flame ionization detector (FID), condition is that wherein column length is 30m, carrier gas flux is 1.0mL/min, splitting ratio (ratio of division) is 1:79, the sample implantation temperature is 360 ℃, with this post from 140 ℃ be heated to 355 ℃ (8 ℃/min), and detector temperature is 360 ℃.

For described gas oil composition (B), the total content of its n-paraffin with 20-30 carbon atom is necessary for 2 quality % of this gas oil composition total mass or more and less than 4 quality %.If the total content of these heavy n-paraffin is 4 quality % or more, will cause at low temperatures the deposition of wax.If this total content is less than 2 quality %, the amount of heavy n-paraffin will reduce, and causes utilizing this heavy n-paraffin to reduce as the performance effect of the cold flow improver of growth core.And, in order to improve this gas oil basis oil additives solubleness, total content with n-paraffin of 20-30 carbon atom is necessary for 0.2 or larger and be 0.6 or less divided by the determined value of total content of the hydrocarbon with 20-30 carbon atom beyond the described n-paraffin, be preferably 0.22 or larger and be 0.57 or less, more preferably 0.25 or larger and be 0.55 or less.If should be worth less than 0.2, additive solubleness will extremely reduce.If should be worth greater than 0.6, will weaken the cold flow ability.And carbon number (n) must satisfy by C20P for the content (CnP) of every kind of n-paraffin in the 20-25 scope〉C21P〉C22P〉C23P〉C24P〉relation that limits of C25P.As long as this relation is satisfied, effect owing to this n-paraffin that exists with aforementioned content, resulting composition will have corresponding to temperature variation the stable Wax Sediment Velocity of external temperature when for example composition is cooled, and can guarantee that cold flow improver stably represents its character.

The total content of the straight chain hydrocarbon of the described 20-30 of a having carbon atom is the value of using GC-FID to measure with the content with straight chain saturation alkane of 20-25 carbon atom, its center pillar is the capillary column (ULTRA ALLOY-1) that is formed by methylsiloxane, carrier gas is that helium and detector are flame ionization detector (FID), condition is that wherein column length is 30m, carrier gas flux is 1.0mL/min, splitting ratio is 1:79, the sample implantation temperature is 360 ℃, with this post from 140 ℃ be heated to 355 ℃ (8 ℃/min), and detector temperature is 360 ℃.

For described gas oil composition (C), the total content of its n-paraffin with 20-30 carbon atom is necessary for 4 quality % of this gas oil composition total mass or more and less than 6 quality %.If the total content of these heavy n-paraffin is 6 quality % or more, will cause at low temperatures the deposition of wax.If this total content is less than 4 quality %, the amount of heavy n-paraffin will reduce, and causes utilizing this heavy n-paraffin to reduce as the performance effect of the cold flow improver of growth core.And, in order to improve this gas oil basis oil additives solubleness, total content with n-paraffin of 20-30 carbon atom is necessary for 0.2 or larger and be 0.6 or less divided by the determined value of total content of the hydrocarbon with 20-30 carbon atom beyond the described n-paraffin, be preferably 0.22 or larger and be 0.57 or less, more preferably 0.25 or larger and be 0.55 or less.If should be worth less than 0.2, additive solubleness will extremely reduce.If should be worth greater than 0.6, will weaken the cold flow ability.And carbon number (n) must satisfy by C20P for the content (CnP) of every kind of n-paraffin in the 20-25 scope〉C21P〉C22P〉C23P〉C24P〉relation that limits of C25P is also also satisfied with (C24P-C25P)/C24P〉(C22P-C23P)/C22P〉(C20P-C21P)/ relation that C20P limits.

At this, " (C24P-C25P)/C24P〉(C22P-C23P) " is that amount by the n-paraffin with 24 and 25 carbon atoms is divided by the determined value of the amount of the n-paraffin with 24 carbon atoms.Also have, " (C22P-C23P)/C22P〉(C20P-C21P)/C20P " calculated by same mode.These relations are that the present inventor furthers investigate and make great efforts to obtain.Described relation is intended to represent heavy n-paraffin sedimentation rate with respect to temperature in simple mode.As long as these relations are satisfied, effect owing to this n-paraffin that exists with aforementioned content, resulting composition will have corresponding to temperature variation the stable Wax Sediment Velocity of external temperature when for example composition is cooled, and can guarantee that cold flow improver stably represents its character.

The total content of the straight chain saturation alkane of the described 20-30 of a having carbon atom is the value of using GC-FID to measure with the content with straight chain saturation alkane of 20-25 carbon atom, its center pillar is the capillary column (ULTRA ALLOY-1) that is formed by methylsiloxane, carrier gas is that helium and detector are flame ionization detector (FID), condition is that wherein column length is 30m, carrier gas flux is 1.0mL/min, splitting ratio is 1:79, the sample implantation temperature is 360 ℃, with this post from 140 ℃ be heated to 355 ℃ (8 ℃/min), and detector temperature is 360 ℃.

Consider storage stability and with the consistency of parts, the peroxide value of gas oil composition of the present invention after accelerated oxidation test (oxidation-stabilized property testing) is preferably 50 quality ppm or less, more preferably 40 quality ppm or less, 30 quality ppm or less.Peroxide value after the accelerated oxidation used herein test represents according to ASTM D2274-94 in the value of surveying according to the JPI-5S-46-96 that stipulates in the JPI standard after bubble oxygen is carried out the accelerated oxidation test under 16 hours under 95 ℃.If necessary, gas oil composition of the present invention can with additive for example oxidation inhibitor or metal passivator blend to reduce peroxide value.

The kinematic viscosity of gas oil composition of the present invention under 30 ℃ is preferably 2.5mm ²/ s or higher, more preferably 2.55mm ²/ s or higher, more preferably 2.6mm ²/ s or higher.If kinematic viscosity is lower than 2.5mm ²/ s, the fuel injection length that will be difficult to be controlled at the fuel charge side is selected, and will reduce the oilness on each parts of the fuel charge that is installed on the engine.There is not particular restriction for the upper limit kinematic viscosity under 30 ℃.Yet this kinematic viscosity is preferably 5.0mm ²/ s or lower, more preferably 4.8mm ²/ s or lower, more preferably 4.5mm ²/ s or lower, purpose is to suppress the increase by the NOx in the caused waste gas of fuel injection system unstability and PM concentration, and this unstability is owing to wherein resistance increment.Kinematic viscosity used herein represents the value surveyed according to JIS K2283 " mensuration of crude oil and petroleum products-kinematic viscosity and calculate viscosity index by kinematic viscosity ".

The cetane index of gas oil composition of the present invention is preferably 45 or larger.If this cetane index is lower than 45, might increase the concentration of PM, aldehydes and NOx in the waste gas.By the same token, this cetane index more preferably 47 or larger, more preferably 50 or larger.The upper limit for cetane index does not have particular restriction.Yet, if cetane index greater than 80, might increase the discharging of cigarette ash in the vehicle accelerating period.Therefore, cetane index is preferably 78 or less, and more preferably 75 or less, more preferably 73 or less.The employed cetane index of this paper represents the value calculated according to " 8.4 use the methods of variable formula calculated cetane indexs " of defined among the JIS K2280 " mensuration of petroleum products-fuel-octane value, cetane value and the calculating of cetane index ".Usually be applied to not contain the gas oil of cetane number improver by the defined cetane index of this JIS standard.Yet, in the present invention, " 8.4 use the method for variable formula calculated cetane index " is applied to contain the gas oil of cetane number improver, and the value that obtains thus also is defined as cetane index.

As long as obtain satisfactorily above-mentioned characteristic, there is not particular restriction for the cetane value of gas oil composition of the present invention.Yet described cetane value is preferably 45 or larger, more preferably 47 or larger, more preferably 50 or larger, and the discharging that purpose is to suppress the pinking in the diesel combustion process and reduces NOx in the waste gas, PM and aldehydes.In order to reduce the black smoke in the waste gas, cetane value is preferably 80 or lower, and more preferably 78 or lower, more preferably 75 or lower.Cetane value used herein represents the cetane value surveyed according to " the 7. cetane value testing method " of regulation among the JIS K 2280 " mensuration of petroleum products-fuel-octane value, cetane value and the calculating of cetane index ".

The water-content of gas oil composition of the present invention is preferably 100 volume ppm, more preferably 50 volume ppm, and more preferably 20 volume ppm, purpose is to prevent that described composition from freezing and prevent the engine interior corrosion.Water-content used herein represents the value surveyed according to JIS K 2275 " mensuration of crude oil and petroleum products-water-content-potentiometric titration Karl Fischer titration ".

The flash-point of gas oil composition of the present invention is preferably 45 ℃ or higher.Consider from security standpoint, the flash-point that is lower than 45 ℃ is not preferred.Therefore, flash-point is preferably 47 ℃ or higher, more preferably 50 ℃ or higher.The employed flash-point of this paper represents the value surveyed according to JIS K2265 " crude oil and petroleum products-flashing test ".

Carbon residue for 10% distillation leftover of gas oil composition of the present invention does not have particular restriction.Yet, the carbon residue of this 10% distillation leftover is preferably 0.1 quality % or less, 0.08 quality % or less more preferably, more preferably 0.05 quality % or less, purpose is to reduce fine particle and PM, keep the performance that is installed in the exhausted gas post-processing system on the engine, and prevent that greasy filth silts strainer up.The carbon residue of 10% distillation leftover used herein represents the carbon residue surveyed according to JIS K2270 " mensuration of crude oil and petroleum products-carbon residue ".

In the present invention, be necessary to make described gas oil composition at first by pipeline mediation, action of forced stirring or leave standstill enough time and mix (step 1) with lubricity improver, then by pipeline mediation, action of forced stirring or leave standstill enough time and mix (step 2) with cold flow improver.Perhaps, depend on the desired character of fuel, can between step 1 and step 2, provide one wherein by pipeline mediation, action of forced stirring or leave standstill enough time mixes purification agent with described gas oil composition step.And, according to this situation, also can be with suitable other additive of amount blend cetane number improver for example.

The such method of pipeline Harmonic representation of the conduct of mentioning mixes described gas oil composition with additive method, in the method additive is joined in the approach that transmits between for example storage tank and storage tank, productive unit and productive unit or productive unit and storage tank under the pressure in the described gas oil composition with diffusion and mixing, until described composition is delivered to the downstream from the upstream with it.Described action of forced stirring represents such method, in the method when described gas oil composition is present in storage tank or the productive unit, to wherein adding additive and by carrying out pump circulation with pump and stirring to force diffusion and mix with agitator.Leave standstill the such method of expression, in the method any gas oil composition that additive is joined by several different methods or in storage tank or in productive unit, leave standstill enough time with by naturally spreading and natural convection is spread and mixed.In these blending meanss any, can heat described gas oil to improve mixing efficiency.

About step 1 and 2, as long as can by preparing gas oil composition of the present invention in accordance with the order that adds additive with the method that described gas oil composition mixes with additive, then step 1 and 2 not had particular restriction.Therefore, can use for any adding method of producing gas oil composition at refinery.About adding the method for cold flow improver, often use such method, in the method, join in the gas oil to be produced after cold flow improver diluted with solvent, kerosene or gas oil, or in the method, cold flow improver is heated rear the adding under the temperature higher 10 ℃ than envrionment temperature.

Preferably, in the present invention the additive that uses does not contain the solvent that fusing point is 10 ℃ or higher chemical substance.If using fusing point is 10 ℃ or higher solvent, this solvent will earlier deposit than the wax in the described gas oil, causes the deterioration of its cryogenic properties.Fusing point is that the example of 10 ℃ or higher solvent comprises that hydroxyl bond wherein is incorporated into the saturated alcohol (for example dodecanol) on the straight chained alkyl with 11 or more carbon atom and end position group and has the compound of phenolic group.For Reducing the burden on the environment, preferably in these additives or solvent, do not use so-called Endocrine Disrupting Chemicals or endocrine disruptor, these materials ban use of from the environment protection angle.

Be necessary in gas oil composition of the present invention, to add lubricity improver.In order to prevent the wearing and tearing of fuel charge, with the densitometer of active ingredient, the amount of described lubricity improver is necessary for 20mg/L or more and be 300mg/L or still less, preferred 50mg/L or more and be 200mg/L or still less.When described lubricity improver when falling into the amount blend in these scopes, described lubricity improver can represent its effect effectively.For example, in the diesel motor of being furnished with the profile injection pump, described lubricity improver can suppress that driving torque does not increase and the wearing and tearing on each parts of pump when reducing engine driven.

Described lubricity improver must be those types that contain the compound with polar group, comprises lipid acid and/or fatty acid ester.Concrete title for described compound does not have particular restriction, and therefore, described lubricity improver can be selected from carboxylic acid group, ester group, alcohol radical and phenolic group lubricity improver any or multiple.In these lubricity improvers, preferably carboxylic acid group and ester group lubricity improver.The mixture of two or more that described carboxylic acid group's lubricity improver can be linolic acid, oleic acid, Whitfield's ointment, palmitinic acid, tetradecanoic acid or hexadecylenic acid or these carboxylic acids.The example of described ester group lubricity improver comprises the carboxylicesters of glycerine.The carboxylic acid that forms this carboxylicesters can be one or more types.The specific examples of this carboxylic acid comprises linolic acid, oleic acid, Whitfield's ointment, palmitinic acid, tetradecanoic acid or hexadecylenic acid.The molecular-weight average of the active ingredient of described lubricity improver is preferably 200 or larger and be 1000 or less, to strengthen the solubleness to described gas oil composition.

Must add cold flow improver in gas oil composition of the present invention by the pre-arranged procedure, purpose is that the strainer that prevents the automobile take diesel oil as fuel silts up.With the densitometer of active ingredient, the amount of this cold flow improver is necessary for 20mg/L or more and be 1000mg/L or still less, more preferably 300mg/L or more and be 800mg/L or still less.

Described cold flow improver must be vinyl-vinyl acetate copolymer and/or the compound with surface-active action.Example with cold flow improver of surface-active action comprises one or more types that are selected from following material: the multipolymer of ethene and methyl methacrylate, the multipolymer of ethene and alpha-olefin, methylene dichloride-vinyl acetate copolymer, the alkyl ester copolymer of unsaturated carboxylic acid, by the synthetic ester of the nitrogenous compound with hydroxyl and saturated fatty acid and the salt of this ester, by polyvalent alcohol and synthetic ester and the amide derivatives of saturated fatty acid, by polyoxyalkylene glycol and the synthetic ester of saturated fatty acid, oxyalkylene affixture and the synthetic ester of saturated fatty acid by polyvalent alcohol or its part ester, chloroalkane hydrocarbon/naphthalene condenses, the amine salt of alkenyl succinic acid amides and sulfosalicylic acid.

Except above illustrative cold flow improver, gas oil composition of the present invention can contain any or broad variety that is selected from following material: the alkenyl succinic diamide; Straight chain compound is two docosane acid esters of polyoxyethylene glycol for example; By the acid polar nitrogen compounds that forms of the reaction product of the amine that replaces of phthalic acid, ethylenediamine tetraacetic acid (EDTA) and nitrilo acetic acid or their acid anhydrides and alkyl for example; With by fumaric acid alkyl ester-or comb-shaped polymer that the methylene-succinic acid alkyl ester-the unsaturated ester multipolymer forms.

Because the product that is known as cold flow improver that is available commercially is in the form that solvent diluted that wherein the contributive active ingredient of low-temperature fluidity (active ingredient) is suited usually.Therefore, the scale of above cold flow improver shows the amount (active ingredient concentration) of described active ingredient when such product that is available commercially is added in the gas oil composition of the present invention.

If necessary, can in gas oil composition of the present invention, add purification agent.Yet, be necessary after adding lubricity improver and before the adding cold flow improver, to add purification agent, or purification agent and lubricity improver add simultaneously.Component for purification agent does not have particular restriction.The example of purification agent comprises: ashless dispersant, and polyether amine compound for example, it is the reaction product of butylene oxide ring and amine; Polybutylene-based amine compound, it is the reaction product of isobutylene copolymers and amine; Imide compound; Alkenyl succinimide is for example by polybutylene-based succinyl oxide and the synthetic polybutylene-based succinimide of ethylene polyamine; Succinate is for example by the polyvalent alcohol synthetic polybutylene-based succinate of tetramethylolmethane and polybutylene-based succinyl oxide for example; The polymkeric substance of copolymerization is the multipolymer of methacrylic acid dialkyl amido ethyl ester, methacrylic acid macrogol ester or vinyl pyrrolidone and alkyl methacrylate for example; Reaction product with carboxylic acid and amine.In these, the reaction product of alkenyl succinimide and carboxylic acid and amine preferably.These purification agents can be used singly or in combination.When using alkenyl succinimide, can use separately molecular weight to be the alkenyl succinimide of 1000-3000, or to be used in combination alkenyl succinimide and the molecular weight that molecular weight is 700-2000 be the alkenyl succinimide of 10000-20000.The carboxylic acid that consists of the reaction product of carboxylic acid and amine can be one or more types.The specific examples of described carboxylic acid comprises the lipid acid with 12-24 carbon atom and has the aromatic carboxylic acid of 7-24 carbon atom.Example with lipid acid of 12-24 carbon atom includes but not limited to linolic acid, oleic acid, palmitinic acid and tetradecanoic acid.Example with aromatic carboxylic acid of 7-24 carbon atom includes but not limited to phenylformic acid and Whitfield's ointment.The amine that consists of the reaction product of carboxylic acid and amine can be one or more types.The representative instance of amine used herein includes but not limited to oleyl amine (oleic amines).Also can use various kinds of amine.

Blending amount for purification agent does not have particular restriction.Yet based on the total mass of described composition, this amount is preferably 20mg/L or more, and more preferably 50mg/L or more, and more preferably 100mg/L or more silt up to prevent the fuel injection nozzle because purification agent can be brought into play its effect.If should measure less than 20mg/L, can not obtain this effect.On the other hand, if the blending amount of purification agent is excessive, can not obtain the effect with its amount phase equilibrium.Therefore, the amount of purification agent is preferably 500mg/L or less, more preferably 300mg/L or less, and more preferably 200mg/L or less is because purification agent can increase NOx, PM in the diesel engine exhaust and the amount of aldehydes.The purification agent that is available commercially is usually with the state that solvent diluted that wherein suited for the contributive active principle of peace and quiet effect and obtain.In the situation with such product and gas oil composition blend of the present invention, the content of described active principle preferably drops in the above-mentioned scope.

If necessary, gas oil composition of the present invention can with the cetane number improver blend of sufficient quantity to strengthen the cetane value of said composition.

Described cetane number improver can be multiple compounds any that is known as the gas oil cetane number improver.The example of such cetane number improver comprises nitric ether and organo-peroxide.These cetane number improvers can be used singly or in combination.Preferred use is nitric ether among the present invention.The example of described nitric ether comprises multiple nitric ether for example nitric acid 2-chloroethene ester, nitric acid 2-ethoxy ethyl ester, isopropyl nitrate, nitric acid butyl ester, nitric acid uncle pentyl ester, the secondary pentyl ester of nitric acid, isoamyl nitrate, primary hexyl nitrates ester, the secondary own ester of nitric acid, the positive heptyl ester of nitric acid, nitric acid n-octyl, nitric acid 2-ethylhexyl, cyclohexyl nitrate and glycol dinitrate.Particularly preferably be the alkyl nitrate ester selected with 6-8 carbon atom.

The content of described cetane number improver is preferably 500mg/L or more, more preferably 600mg/L or more, more preferably 700mg/L or more, more preferably 800mg/L or more, most preferably 900mg/L or more.If the content of described cetane number improver is less than 500mg/L, described cetane value improvement effect may not fully obtain, and the trend that causes is that PM, aldehydes and the NOx in the waste gas of diesel motor can not fully reduce.Upper limit content for described cetane number improver does not have particular restriction.Yet based on the total mass of described gas oil composition, this upper limit is preferably 1400mg/L or less, more preferably 1250mg/L or less, more preferably 1100mg/L or less, and 1000mg/L or less most preferably.

Described cetane number improver can be according to any of synthetic those of ordinary method or the product that is available commercially.Such product of cetane number improver by name can obtain with the state that solvent diluted that wherein the contributive active principle of the improvement of cetane value (that is, cetane number improver itself) is suited.In the situation of any preparation gas oil composition of the present invention that uses such product that is available commercially, the content of this active principle preferably falls into above-mentioned scope.

In order further to strengthen the character of gas oil composition of the present invention, also can be used alone or in combination other known fuel oil additive (hereinafter being called for simplicity, " other additive ").The example of described other additive comprises phenolic antioxidant and amine (aminic) oxidation inhibitor; Metal passivator is the salicylidene derivative for example; Corrosion inhibitor is aliphatic amine and succsinic acid alkenyl ester for example; Anti static additive is anionic, cationic and amphoterics for example; Tinting material is azoic dyestuff for example; Siloxanes defoamer and freezing agent be 2-methyl cellosolve, Virahol and polyglycol ether for example.

Can select arbitrarily the amount of described other additive.Yet based on the total mass of described composition, the amount of every kind of other additive is preferably 0.5 quality % or still less, more preferably 0.2 quality % or still less.

For other specification, their application of the diesel motor that uses gas oil composition of the present invention with use the environment of described gas oil composition not have particular restriction.

As mentioned above, according to the present invention, use gas oil composition by aforesaid method production to satisfy requirement to cut etc., might easily produce such gas oil composition, this gas oil composition is suitable for use in winter, and realized that simultaneously carrying capacity of environment reduction, cryogenic properties and low fuel consumption, these character are difficult to realize with conventional gas oil composition always, even if the gas oil composition that mainly contains the Fischer-Tropsch synthetic base oil of the present invention.

[industrial applicability]

The present invention can provide the gas oil composition that is suitable for use in winter, and this gas oil composition can be realized carrying capacity of environment reduction, low-temperature performance and low fuel consumption simultaneously.

[embodiment]

Hereinafter, will describe in more detail the present invention by following examples and Comparative Examples, these embodiment and Comparative Examples should not be construed as limiting the scope of the invention.

Measure by the following method the characteristic of gas oil composition.After base oil is by blend and distillation, measure the proportion of composing of every kind of cut and their cetane value.

The alleged density of this paper represents the density surveyed according to JIS K2249 " mensuration of crude oil and petroleum products-density and based on the petroleum measurement tables of reference temperature (15 ℃) ".

The alleged kinematic viscosity of this paper represents the viscosity surveyed according to JIS K2283 " mensuration of crude oil and petroleum products-kinematic viscosity and calculate viscosity index by kinematic viscosity ".

The alleged flash-point of this paper represents the value surveyed according to JIS K2265 " crude oil and petroleum products-flashing test ".

The alleged sulphur content of this paper represents the sulphur component based on the mass content of described composition total mass, and it is measured according to JIS K2541 " mensuration of crude oil and petroleum products-sulphur content ".

The alleged oxygen level of this paper is illustrated in sample is converted into CO or is further converted to CO at platinum carbon ₂The measured value of rear use thermal conductivity detector.

All alleged distillation characteristicss of this paper represent the value surveyed according to JIS K 2254 " mensuration of petroleum products-distillation characteristics ".

The content of the n-paraffin of each carbon number (hereinafter being called " CnP "), the total content that has the content (hereinafter being called " C20-C30P ") of the n-paraffin of 20-30 carbon atom and the content of the hydrocarbon with 20-30 carbon atom except the n-paraffin of the described 20-30 of a having carbon atom (hereinafter being called " the C20-C30 hydrocarbon content except C20-C30P ") and have a n-paraffin of 20-30 carbon atom is the value (quality %) surveyed with GC-FID or by the value of its calculating divided by the determined value of total content (the C20-C30 hydrocarbon content of C20-C30P/ except C20-C30P) of the hydrocarbon with 20-30 carbon atom beyond the n-paraffin of the described 20-30 of a having carbon atom, namely, those that measure under the following conditions: its center pillar is the capillary column (ULTRA ALLOY-1) that is formed by methylsiloxane, carrier gas is that helium and detector are flame ionization detector (FID), condition is that wherein column length is 30m, carrier gas flux is 1.0mL/min, splitting ratio is 1:79, the sample implantation temperature is 360 ℃, with this post from 140 ℃ be heated to 355 ℃ (8 ℃/min), and detector temperature is 360 ℃.

The cetane index that this paper is alleged and cetane value represent the value calculated according to " 8.4 use the methods of variable formula CalcdCIs " of defined among the JIS K2280 " mensuration of petroleum products-fuel-octane value, cetane value and the calculating of cetane index ".

The alleged cloud point of this paper represents the cloud point surveyed according to JIS K2269 " pour point of crude oil and petroleum products and the testing method of cloud point ".

Cold filter clogging temperature used herein represents the cold filter clogging temperature surveyed according to JIS K2288 " mensuration of gas oil-cold filter clogging temperature ".

The alleged pour point of this paper represents the pour point surveyed according to JIS K2269 " pour point of crude oil and petroleum products and the testing method of cloud point ".

The carbon residue content of 10% distillation leftover that this paper is alleged represents the carbon residue content surveyed according to JIS K2270 " mensuration of crude oil and petroleum products-carbon residue ".

The alleged aromaticity content of this paper represents volume percent (volume %) content of the aromatic component that the JPI-5S-49-97 " mensuration-high performance liquid chromatography of petroleum products-hydrocarbon types " according to defined in the petroleum products testing method JPI standard of publishing in Japan petroleum institute and the guide surveys.

The value that the JPI-5S-46-96 that peroxide value behind the alleged oxidation-stabilized property testing of this paper represents to make described composition to stipulate in the petroleum products testing method JPI standard of publishing according to Japan petroleum institute after bubble oxygen is carried out accelerated oxidation under 16 hours under 95 ℃ and guide according to ASTM D2274-94 surveys.

Insolubles content behind the alleged oxidation-stabilized property testing of this paper be illustrated in make described composition according to ASTM D2274-94 in the value of carrying out surveying after the accelerated oxidation under 16 hours in bubble oxygen under 95 ℃.

The oilness that this paper is alleged, namely, HFRR fraze (WS1.4) expression is according to the measured oilness of JPI-5S-50-98 " testing method of gas oil-oilness ", and the method has regulation in the petroleum products testing method JPI standard of being published by Japan petroleum institute and guide.

The alleged water-content of this paper represents the water-content surveyed according to JIS K2275 " mensuration of crude oil and petroleum products-water-content-potentiometric titration Karl Fischer titration ".

(embodiment 1 and 2 and Comparative Examples 1)

The base oil that blend has a listed characteristic in the table 1 is with the listed gas oil composition of production table 2 (embodiment 1 and 2 and Comparative Examples 1).Fischer-Tropsch synthetic base oil 1 and 2 is to be that then wax or middle runnings carry out the hydrocarbon mixture that hydrotreatment produces by fischer-tropsch reaction with conversion of natural gas.The reaction conditions that is used for every kind of Fischer-Tropsch synthetic base oil changes.Fischer-Tropsch synthetic base oil 1 is the base oil that produces by positive enforcement isomerization.Fischer-Tropsch synthetic base oil 2 is not lie in isomerized processing and the base oil that produces by wherein too many emphasis.The base oil of described height hydrotreatment is by further the gas oil base oil being carried out the hydrocarbon base oil that hydrotreatment is produced with further reduction sulphur content and aromaticity content.Described finished oil derived from animal oil or vegetables oil is the oil that is produced to remove foreign matter as the plam oil (total composition) of raw material by hydrotreatment.Described hydrorefined gas oil is corresponding to the JIS No.2 gas oil that uses in the winter time that is available commercially.Come as a whole production example 1 and 2 and the gas oil composition of Comparative Examples 1 with these base oils of sufficient quantity blend or with described base oil any.

Employed additive is as follows in these embodiments:

Lubricity improver: by the Infineum R655 (active ingredient: contain the straight chained alkyl ester mixture as the lipid acid of raw material, molecular-weight average: 250MW) of Infineum Japan Ltd. manufacturing

Purification agent: alkenyl succinimide mixture

Cold flow improver: by the Infineum R240 (active ingredient: vinyl-vinyl acetate copolymer mixture, solvent: alkylbenzene) (fusing point :-50 ℃ or lower) of Infineum Japan Ltd. manufacturing

In embodiment 1, add additive by predetermined process, that is, wherein add lubricity improver and then fully mix and action of forced stirring, and then the adding cold flow improver fully mixes and the step of action of forced stirring.In embodiment 2, also add additive by predetermined process, that is, wherein add lubricity improver and purification agent and then fully mix and action of forced stirring, and then the adding cold flow improver fully mixes and the step of action of forced stirring.In Comparative Examples 1, only add cold flow improver.Confirm that in these embodiments it is 10 ℃ or higher solvent that employed these additives do not contain boiling point.

Table 2 has been listed the blend ratio of gas oil composition of such preparation and the density under 15 ℃ of every kind of composition, kinematic viscosity under 30 ℃, flash-point, sulphur content, oxygen level, distillation characteristics, the content of the n-paraffin of every kind of carbon number (CnP), content (C20-C30P) with n-paraffin of 20-30 carbon atom, has the total content of n-paraffin of 20-30 carbon atom divided by the determined value of total content of the hydrocarbon with 20-30 carbon atom beyond the described n-paraffin, cetane index, cetane value, aromaticity content, cloud point, cold filter clogging temperature, pour point, the carbon residue content of 10% distillation leftover, insolubles content behind the oxidation-stabilized property testing and peroxide value, wear print diameter and water-content.

Come gas oil composition used in production example 1 and 2 by blend 60 quality % or the more Fischer-Tropsch synthetic base oil of listing such as table 2.And by table 2 obviously as seen, among the embodiment 1 and 2 of therein described Fischer-Tropsch synthetic base oil blend in the scope of this paper regulation, the gas oil composition that satisfies the characteristic of this paper defined is easy to produce, not failure.On the other hand, by Comparative Examples 1 obviously as seen, when described composition does not have characteristic given to this invention or mixes with the additive of being scheduled to not according to the restriction of step 1 of the present invention and 2, can not produce the gas oil composition that the present invention wants.

Then, use embodiment 1 and 2 and the gas oil composition of Comparative Examples 1 carry out following various test.It is all that the results are shown in Table 3.From table 3 obviously as seen, compare with the gas oil composition of Comparative Examples 1, embodiment 1 and 2 gas oil composition are to have carrying capacity of environment to reduce those of character, it is being fabulous aspect fuel consumption character and the cold-starting ability, with therefore be to realize that fabulous fuel consumption character and winter low temperature start the high-quality fuel of ability at high level, these character are difficult to realize with conventional gas oil composition.

(diesel combustion test)

Use every kind of gas oil composition under test pattern shown in Figure 1, to drive vehicle 1, to measure NOx, cigarette and fuel consumption.To use the resulting result of fuel of Comparative Examples 1 to be defined as 100, and the result of other fuel is compared and relative evaluation (the better result of less value representation) with the result of Comparative Examples 1.

(cold-starting aptitude tests)

Use described vehicle 1 and on the chassis resistance dynamometer of temperature that can control environment, every kind of gas oil composition is tested, and test is at room temperature undertaken by following steps: (1) tests the fuel system of diesel vehicle with fuel flushing (washing) to be evaluated; (2) discharge this flushing fuel; (3) be new strainer with main filter replacement; (4) fuel to be evaluated is fed to fuel container with concrete amount (fuel tank capacity of testing vehicle 1/2).Then be that (5) are quickly cooled to-15 ℃ with envrionment temperature from room temperature; (6) temperature is remained on-15 ℃ lower 1 hour; (7) cool off gradually with the speed of 1 ℃/h until reach preset temperature (25 ℃); (8) remain under this preset temperature starting engine after 1 hour in temperature.If this engine even rotate at each 10 seconds crank can not start after repeating twice with 30 seconds interval, this fuel is be evaluated as " defective " at the moment.If this engine rotates with 30 seconds interval at each 10 seconds crank and repeats to start in twice o'clock, with its idle running 3 minutes, then through 15 seconds vehicle is accelerated to 60km/h, and drive under the low speed.When vehicle accelerated to 60km/h and running defective (vibration, rolling, the speed of a motor vehicle reduce or engine stop) was observed in driving in 20 minutes in the process under this speed, this gas oil composition was be evaluated as " defective " at the moment.If this running of an engine is until finish without any defective, this gas oil composition is be evaluated as " qualified ".

(vehicle specification): vehicle 1

Engine type: the interior cooling of charge diesel motor of coaxial 4 cylinders of being furnished with EGR

Discharge capacity: 1.4L

Interior diameter * stroke: 73mm * 81.4mm

Compression ratio: 18.5 (changing to 16.0)

Maximum output: 72kW/4000rpm

The rules that adopt: 2002 exhaust emission regulations

Car weight: 1060kg

Transmission: 5-speed manual transmission

Exhaust gas aftertreatment: oxide catalyst

Table 1

Table 2

Table 3

(embodiment 3 and 4 and Comparative Examples 2)

The base oil that blend has a listed characteristic in the table 4 is with the listed gas oil composition of production table 5 (embodiment 3 and 4 and Comparative Examples 2).Fischer-Tropsch synthetic base oil 3 and 4 is to be that then wax or middle runnings carry out the hydrocarbon mixture that hydrotreatment produces by fischer-tropsch reaction with conversion of natural gas.The reaction conditions that is used for every kind of Fischer-Tropsch synthetic base oil changes.Fischer-Tropsch synthetic base oil 3 is the base oils that produce by positive enforcement isomerization.Fischer-Tropsch synthetic base oil 4 is not lie in isomerized processing and the base oil that produces by wherein too many emphasis.The base oil of described height hydrotreatment is by further the gas oil base oil being carried out the hydrocarbon base oil that hydrotreatment is produced with further reduction sulphur content and aromaticity content.Described finished oil derived from animal oil or vegetables oil is to remove the oil that foreign matter produces by hydrotreatment as the plam oil (total composition) of raw material.Described hydrorefined gas oil is corresponding to the JIS No.2 gas oil that uses in the winter time that is available commercially.Come as a whole production example 3 and 4 and the gas oil composition of Comparative Examples 2 with these base oils of sufficient quantity blend or with described base oil any.

Employed additive is as follows in these embodiments:

Purification agent: alkenyl succinimide mixture

In embodiment 3, add additive by predetermined process, that is, wherein add lubricity improver and then fully mix and action of forced stirring, and then the adding cold flow improver fully mixes and the step of action of forced stirring.In embodiment 4, also add additive by predetermined process, that is, wherein add lubricity improver and purification agent and then fully mix and action of forced stirring, and then the adding cold flow improver fully mixes and the step of action of forced stirring.In Comparative Examples 2, only add cold flow improver.Confirm that in these embodiments it is 10 ℃ or higher solvent that employed these additives do not contain boiling point.

Table 5 has been listed the blend ratio of gas oil composition of such preparation and the density under 15 ℃ of every kind of composition, kinematic viscosity under 30 ℃, flash-point, sulphur content, oxygen level, distillation characteristics, the content of the n-paraffin of every kind of carbon number (CnP), content (C20-C30P) with n-paraffin of 20-30 carbon atom, has the total content of n-paraffin of 20-30 carbon atom divided by the determined value of total content of the hydrocarbon with 20-30 carbon atom beyond the described n-paraffin, cetane index, cetane value, aromaticity content, cloud point, cold filter clogging temperature, pour point, the carbon residue content of 10% distillation leftover, insolubles content behind the oxidation-stabilized property testing and peroxide value, wear print diameter and water-content.

Come gas oil composition used in production example 3 and 4 by blend 60 quality % or the more Fischer-Tropsch synthetic base oil of listing such as table 5.And by table 5 obviously as seen, among the embodiment 3 and 4 of therein described Fischer-Tropsch synthetic base oil blend in the scope of this paper regulation, the gas oil composition that satisfies the characteristic of this paper defined is easy to produce, not failure.On the other hand, by Comparative Examples 2 obviously as seen, when described composition does not have characteristic given to this invention or mixes with the additive of being scheduled to not according to the regulation of step 1 of the present invention and 2, can not produce the gas oil composition that the present invention wants.

Then, use embodiment 3 and 4 and the gas oil composition of Comparative Examples 2 carry out following various test.It is all that the results are shown in Table 6.From table 6 obviously as seen, compare with the gas oil composition of Comparative Examples 2, embodiment 3 and 4 gas oil composition are to have carrying capacity of environment to reduce those of character, it is being fabulous aspect fuel consumption character and the cold-starting ability, with therefore be to realize that fabulous fuel consumption character and winter low temperature start the high-quality fuel of ability at high level, these character are difficult to realize with conventional gas oil composition.

(diesel combustion test)

Use every kind of gas oil composition under test pattern shown in Figure 1, to drive vehicle 1, to measure NOx, cigarette and fuel consumption.To use the resulting result of fuel of Comparative Examples 2 to be defined as 100, and the result of other fuel is compared and relative evaluation (the better result of less value representation) with the result of Comparative Examples 2.

(cold-starting aptitude tests)

Table 4

Table 5

Table 6

(embodiment 5 and 6 and Comparative Examples 3)

The base oil that blend has a listed characteristic in the table 7 is with the listed gas oil composition of production table 8 (embodiment 5 and 6 and Comparative Examples 3).Fischer-Tropsch synthetic base oil 5 and 6 is to be that then wax or middle runnings carry out the hydrocarbon mixture that hydrotreatment produces by fischer-tropsch reaction with conversion of natural gas.The reaction conditions that is used for every kind of Fischer-Tropsch synthetic base oil changes.Fischer-Tropsch synthetic base oil 5 is the base oils that produce by positive enforcement isomerization.Fischer-Tropsch synthetic base oil 6 is not lie in isomerized processing and the base oil that produces by wherein too many emphasis.The base oil of described height hydrotreatment is by further the gas oil base oil being carried out the hydrocarbon base oil that hydrotreatment is produced with further reduction sulphur content and aromaticity content.Described finished oil derived from animal oil or vegetables oil is to remove the oil that foreign matter produces by hydrotreatment as the plam oil (total composition) of raw material.Described hydrorefined gas oil is corresponding to the JIS No.2 gas oil that uses in the winter time that is available commercially.Come as a whole production example 5 and 6 and the gas oil composition of Comparative Examples 3 with these base oils of sufficient quantity blend or with described base oil any.

Employed additive is as follows in these embodiments:

Purification agent: alkenyl succinimide mixture

In embodiment 5, add additive by predetermined process, that is, wherein add lubricity improver and then fully mix and action of forced stirring, and then the adding cold flow improver fully mixes and the step of action of forced stirring.In embodiment 6, also add additive by predetermined process, that is, wherein add lubricity improver and purification agent and then fully mix and action of forced stirring, and then the adding cold flow improver fully mixes and the step of action of forced stirring.In Comparative Examples 3, only add cold flow improver.Confirm that in these embodiments it is 10 ℃ or higher solvent that employed these additives do not contain boiling point.

Table 8 has been listed the blend ratio of gas oil composition of such preparation and the density under 15 ℃ of every kind of composition, kinematic viscosity under 30 ℃, flash-point, sulphur content, oxygen level, distillation characteristics, the content of the n-paraffin of every kind of carbon number (CnP), content (C20-C30P) with n-paraffin of 20-30 carbon atom, has the total content of n-paraffin of 20-30 carbon atom divided by the determined value of total content of the hydrocarbon with 20-30 carbon atom beyond the described n-paraffin, cetane index, cetane value, aromaticity content, cloud point, cold filter clogging temperature, pour point, the carbon residue content of 10% distillation leftover, insolubles content behind the oxidation-stabilized property testing and peroxide value, wear print diameter and water-content.

Come gas oil composition used in production example 5 and 6 by blend 60 quality % or the more Fischer-Tropsch synthetic base oil of listing such as table 8.And by table 8 obviously as seen, among the embodiment 5 and 6 of therein described Fischer-Tropsch synthetic base oil blend in the scope of this paper regulation, the gas oil composition that satisfies the characteristic of this paper defined is easy to produce, not failure.On the other hand, by Comparative Examples 3 obviously as seen, when described composition does not have characteristic given to this invention or mixes with the additive of being scheduled to not according to the regulation of step 1 of the present invention and 2, can not produce the gas oil composition that the present invention wants.

Then, use embodiment 5 and 6 and the gas oil composition of Comparative Examples 3 carry out following various test.It is all that the results are shown in Table 9.From table 9 obviously as seen, compare with the gas oil composition of Comparative Examples 3, embodiment 5 and 6 gas oil composition are to have carrying capacity of environment to reduce those of character, it is being fabulous aspect fuel consumption character and the cold-starting ability, with therefore be to realize that fabulous fuel consumption character and winter low temperature start the high-quality fuel of ability at high level, these character are difficult to realize with conventional gas oil composition.

(diesel combustion test)

Use every kind of gas oil composition under test pattern shown in Figure 1, to drive vehicle 1, to measure NOx, cigarette and fuel consumption.To use the resulting result of fuel of Comparative Examples 3 to be defined as 100, and the result of other fuel is compared and relative evaluation (the better result of less value representation) with the result of Comparative Examples 3.

(cold-starting aptitude tests)

Table 7

Table 8

Table 9

[accompanying drawing summary]

Fig. 1 is the schematic diagram of the excessive drive pattern of Reality simulation running.

Claims

1. gas oil composition, it comprises the gas oil composition that is selected from following gas oil composition A to C and the additive that adds according to following steps 1 and 2:

Gas oil composition A, it comprises the Fischer-Tropsch synthetic base oil more than or equal to 60 volume % of the total amount that accounts for this gas oil composition, its sulphur content is for being less than or equal to 5 quality ppm, its aromaticity content is for being less than or equal to 10 volume %, its oxygen level is for being less than or equal to 100 quality ppm, and its density under 15 ℃ is more than or equal to 760kg/m ³And for being less than or equal to 840kg/m ³In distillation characteristics, its 90% distillation temperature for more than or equal to 280 ℃ and for be less than or equal to 330 ℃ with final boiling point for being less than or equal to 360 ℃, its insolubles content behind oxidation-stabilized property testing is for being less than or equal to 0.5mg/100mL, its HFRR wear print diameter under WS1.4 is for being less than or equal to 400 μ m, its cloud point is for being less than or equal to-15 ℃, its cold filter clogging temperature is for being less than or equal to-25 ℃, its pour point is for being less than or equal to-32.5 ℃, its total content of n-paraffin with 20-30 carbon atom is less than 2 quality %, its total content with n-paraffin of 20-30 carbon atom is more than or equal to 0.2 and for being less than or equal to 0.6 divided by the determined value of total content of the hydrocarbon with 20-30 carbon atom beyond the described n-paraffin, and the relation that has between the content CnP of every kind of n-paraffin of 15-20 carbon atom is restricted to C20P＜C19P＜C18P＜C17P＜C16P＜C15P;

Gas oil composition B, it comprises the Fischer-Tropsch synthetic base oil more than or equal to 60 volume % of the total amount that accounts for this gas oil composition, its sulphur content is for being less than or equal to 5 quality ppm, its aromaticity content is for being less than or equal to 10 volume %, its oxygen level is for being less than or equal to 100 quality ppm, and its density under 15 ℃ is more than or equal to 760kg/m ³And for being less than or equal to 840kg/m ³In distillation characteristics, its 90% distillation temperature for more than or equal to 280 ℃ and for be less than or equal to 350 ℃ with final boiling point for being less than or equal to 360 ℃, its insolubles content behind oxidation-stabilized property testing is for being less than or equal to 0.5mg/100mL, its HFRR wear print diameter under WS1.4 is for being less than or equal to 400 μ m, its cloud point is for being less than or equal to-5 ℃, its cold filter clogging temperature is for being less than or equal to-20 ℃, its pour point is for being less than or equal to-25 ℃, its total content with n-paraffin of 20-30 carbon atom is more than or equal to 2 quality % and less than 4 quality %, its total content with n-paraffin of 20-30 carbon atom is more than or equal to 0.2 and for being less than or equal to 0.6 divided by the determined value of total content of the hydrocarbon with 20-30 carbon atom beyond the described n-paraffin, and the relation that has between the content CnP of every kind of n-paraffin of 20-25 carbon atom is restricted to C20P＞C21P＞C22P＞C23P＞C24P＞C25P; With

Gas oil composition C, it comprises the Fischer-Tropsch synthetic base oil more than or equal to 60 volume % of the total amount that accounts for this gas oil composition, its sulphur content is for being less than or equal to 5 quality ppm, its aromaticity content is for being less than or equal to 10 volume %, its oxygen level is for being less than or equal to 100 quality ppm, and its density under 15 ℃ is more than or equal to 760kg/m ³And for being less than or equal to 840kg/m ³In distillation characteristics, its 90% distillation temperature for more than or equal to 280 ℃ and for be less than or equal to 350 ℃ with final boiling point for being less than or equal to 360 ℃, its insolubles content behind oxidation-stabilized property testing is for being less than or equal to 0.5mg/100mL, its HFRR wear print diameter under WS 1.4 is for being less than or equal to 400 μ m, its cloud point is for being less than or equal to-3 ℃, its cold filter clogging temperature is for being less than or equal to-10 ℃, its pour point is for being less than or equal to-12.5 ℃, its total content with n-paraffin of 20-30 carbon atom is more than or equal to 4 quality % and less than 6 quality %, its total content with n-paraffin of 20-30 carbon atom is more than or equal to 0.2 and for being less than or equal to 0.6 divided by the determined value of total content of the hydrocarbon with 20-30 carbon atom beyond the described n-paraffin, and has relation between the content CnP of every kind of n-paraffin of 20-25 carbon atom and be restricted to C20P＞C21P＞C22P＞C23P＞C24P＞C25P and (C24P-C25P)/C24P＞(C22P-C23P)/C22P＞(C20P-C21P)/C20P;

Step 1: by pipeline mediation, action of forced stirring or leave standstill enough time with the lubricity improver that comprises lipid acid and/or fatty acid ester by mixing with described gas oil composition more than or equal to 20mg/L and the amount that is less than or equal to 300mg/L in active ingredient; With

Step 2: by pipeline mediation, action of forced stirring or leave standstill enough time with the cold flow improver of compound that comprises vinyl-vinyl acetate copolymer and/or have a surface-active action by mixing with described gas oil composition more than or equal to 20mg/L and the amount that is less than or equal to 1000mg/L in active ingredient.

2. the gas oil composition of claim 1, wherein in the step that is added between step 1 and 2 by pipeline mediation, action of forced stirring or leave standstill enough time with described gas oil composition with mix more than or equal to 20mg/L and the purification agent that is less than or equal to 500mg/L, described purification agent comprises polyether amine compound, polybutylene-based amine compound, alkenyl succinic diamide compound or alkenyl succinimide compound.

3. the gas oil composition of claim 1, wherein said lubricity improver and cold flow improver contain solvent separately, and this solvent does not contain fusing point and is the chemical substance more than or equal to 10 ℃.

4. the gas oil composition of claim 2, wherein said lubricity improver, purification agent and cold flow improver contain solvent separately, and this solvent does not contain fusing point and is the chemical substance more than or equal to 10 ℃

5. each the gas oil composition of claim 1-4, the peroxide value of wherein said gas oil composition after the accelerated oxidation test is for being less than or equal to 50 quality ppm, and the kinematic viscosity under 30 ℃ is more than or equal to 2.5mm ²/ s and for being less than or equal to 5.0mm ²/ s, cetane index are more than or equal to 45, and water-content is for being less than or equal to 100 volume ppm.