JP4847171B2 - Diesel fuel composition - Google Patents

Description

  The present invention relates to a diesel fuel composition used in winter, and more particularly to a diesel fuel composition having excellent low-temperature fluidity, fuel efficiency, and environmental performance at the same time.

  Regarding diesel fuel used in low-temperature areas in winter, No. 2 diesel oil (pour point -7.5 ° C or less) and No. 3 diesel oil are used as diesel fuel with the aim of ensuring fluidity according to the usage environment in the current JIS standards. (No more than -20 ° C) and No. 3 diesel oil (No more than -30 ° C). These diesel oils are obtained by applying hydrorefining or hydrodesulfurization treatment to straight-run gas oil obtained from the crude oil atmospheric distillation equipment as a base material, or straight-run kerosene obtained from the crude oil atmospheric distillation equipment to hydrogen. It is produced by blending one or two or more hydrorefined or hydrodesulfurized ones. In particular, in order to ensure low temperature fluidity, the mixing ratio of the kerosene base material and the light oil base material is often controlled. If necessary, a cetane number improver, a detergent, a low temperature fluidity improver, etc. (For example, refer nonpatent literature 1).

  By the way, in recent years, with the aim of improving the atmospheric environment and reducing the environmental burden, there has been a demand for reduction of the sulfur content and aromatic content in the diesel fuel composition that is a fuel for internal combustion engines, and the problem of global warming. Therefore, there is a demand for fuel properties that contribute to further improvement in fuel consumption. As a fuel for low-temperature areas, for example, Patent Document 1 discloses a diesel light oil composition mainly containing a desulfurization dewaxing base material. According to this document, it is described that it is possible to achieve both excellent low-temperature performance, fuel efficiency, and acceleration performance as a diesel engine application. However, the diesel light oil composition shown in this document is a factor that inhibits low-temperature fluidity by dewaxing. Exhaust gas performance due to heavy residue and a large amount of aromatics remaining in the feedstock, mainly due to the base material that has been mainly decomposed from chain saturated hydrocarbon compounds and chemically converted to saturated hydrocarbon compounds having side chains Continue to have concerns about Furthermore, a fuel containing a large amount of aromatic components and a small amount of linear saturated hydrocarbon compound has a problem that the ignition performance becomes unstable because the cetane number becomes low. From the above, it can be said that such a fuel is not suitable as an environmentally friendly fuel.

FT synthetic light oil produced using natural gas or coal as a raw material is attracting attention as an environmentally friendly fuel. However, FT synthetic fuel has a large amount of normal paraffin in the fuel due to its production method, and may precipitate as wax at low temperatures. Is expensive. In addition, since FT synthetic light oil generally has a high cetane index and cetane number and is excellent in self-ignitability, startability at low temperatures can be improved. However, fuel with an excessively high cetane index and cetane number will self-ignite before the air and fuel are sufficiently mixed in the engine, creating a large amount of soot when the vehicle accelerates. Resulting in.
A method of designing a fuel with an increased blending ratio of kerosene fraction to ensure low-temperature fluidity is also conceivable, but if it is lightened, there is a concern about adverse effects on fuel consumption and output, so excessive lightening must be avoided. I must.
In other words, it is very difficult to design a high-quality fuel that can simultaneously achieve the requirements required for a diesel combustion composition having excellent low-temperature fluidity, fuel efficiency, and environmental performance at the same time. There are no examples or knowledge that fully satisfy various performances required for fuel oil and that are based on the study of realistic production methods.
Japanese Patent No. 3729211 Seiichi Konishi, “Introduction to Fuel Engineering”, Saika Hanafusa, March 1991, p. 136-144

  This invention is made | formed in view of this actual condition, The objective is to provide the diesel combustion composition which has the outstanding low-temperature fluidity | liquidity, fuel consumption performance, and environmental performance simultaneously.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the present invention has a distillation property of 10% distillation temperature of 140 ° C. to 200 ° C., 90% by volume distillation temperature of 240 ° C. to 350 ° C., aromatic content of 1% by volume, naphthene compound content. 5% by mass or less, a sulfur content of 10 mass ppm or less, and a hydrocarbon mixture composed of an FT synthetic base material having a linear saturated hydrocarbon content of 16 to 25 carbon atoms of 5% by mass to 70% by mass. Savort color +28 or higher, density at 15 ° C. of 760 kg / obtained by performing de-linear saturated hydrocarbon treatment with zeolite under conditions of reaction temperature of 150 ° C. or higher and 250 ° C. or lower and pressure of 1 MPa or higher and 5 MPa or lower. m ³ or more 830 kg / ^{m 3} or less, 10% distillation temperature of distillation characteristic is 170 ° C. or higher 220 ° C. or less, 50% distillation temperature of 210 ° C. or higher 280 ° C. or less, 90 Distillation temperature is 240 ° C. or more and 325 ° C. or less, cetane index 55 or more and 75 or less, cetane number 55 or more and 70 or less, flash point 50 ° C. or more, peroxide value after accelerated oxidation test is 10 mass ppm or less, cloudy point −10 ° C. Hereinafter, the clogging point is −10 ° C. or less, the pour point is −15 ° C. or less, the aromatic content is 1% by volume or less, the naphthene compound content is 5% by mass or less, the sulfur content is 1 mass ppm or less, and the kinematic viscosity at 30 ° C. 1.7 mm ² / s or more and 4.0 mm ² / s or less, residual carbon content of 10% residual oil is 0.05% by mass or less, and HFRR wear scar diameter (WS1.4) is 400 μm or less. It relates to a diesel fuel composition.

  According to the present invention, by using the diesel fuel composition produced by the above production method, fraction regulation, etc., excellent low temperature fluidity and fuel efficiency performance that has been difficult to realize with conventional fuel compositions, A diesel combustion composition having environmentally compatible performance can be provided.

  Hereinafter, the present invention will be described in detail.

  The feedstock of the diesel fuel composition of the present invention has a distillation property of 10% distillation temperature of 140 ° C to 200 ° C, 90% by volume distillation temperature of 240 ° C to 350 ° C, and aromatic content of 1% by volume. Hereinafter, an FT synthetic substrate having a naphthene compound content of 5 mass% or less, a sulfur content of 10 massppm or less, and a linear saturated hydrocarbon content of 16 to 25 carbon atoms of 5 mass% or more and 70 mass% or less. It is necessary to be a hydrocarbon mixture consisting of

Preferably, the distillation property has a 10% distillation temperature of 150 ° C. or more and 195 ° C. or less, a 90% by volume distillation temperature of 245 ° C. or more and 340 ° C. or less, an aromatic content of 1% by volume or less, and a naphthene compound content of 3%. %, A sulfur content of 5 mass ppm or less, a linear saturated hydrocarbon content of 16 to 25 carbon atoms is a hydrocarbon mixture comprising an FT synthetic substrate having a mass content of 10 mass% to 65 mass%, Preferably, the distillation property has a 10% distillation temperature of 155 ° C. or more and 190 ° C. or less, a 90% by volume distillation temperature of 250 ° C. or more and 330 ° C. or less, an aromatic content of 1% by volume or less, and a naphthene compound content of 1 mass. % Or less, a sulfur content is 1 mass ppm or less, and a linear saturated hydrocarbon content of 16 to 25 carbon atoms is a hydrocarbon mixture comprising an FT synthetic substrate having a content of 15 mass% or more and 60 mass% or less.
If the properties of the feedstock are out of the above range, the reaction efficiency in the subsequent processing is lowered and it becomes difficult to obtain the diesel fuel composition of the present invention.

  Here, the initial boiling point and the 90% by volume distillation temperature are JIS K 2254 "Petroleum products-Distillation test method-Atmospheric pressure distillation test method", and the aromatic content is JIS K 2536 "Petroleum products-Hydrocarbon". The value measured by the fluorescent indicator adsorption method of “type test method”, the naphthene compound content is the value measured according to ASTM D2786 “mass spectrometry”, the sulfur content is JIS K 2541 “crude oil and petroleum products” The value measured by “Sulfur content test method”, the linear saturated hydrocarbon content (C16-C25 nP) having 16 to 25 carbon atoms is a value (mass%) measured using GC-FID. . That is, a capillary column of methyl silicon (ULTRAALLOY-1) is used for the column, helium is used for the carrier gas, a hydrogen ion detector (FID) is used for the detector, a column length of 30 m, a carrier gas flow rate of 1.0 mL / min, and a splitting. It is a value measured under the conditions of ratio 1:79, sample injection temperature 360 ° C., column temperature rising condition 140 ° C. → (8 ° C./min)→355° C., detector temperature 360 ° C.

  The FT synthesis base material is equivalent to naphtha, kerosene, or light oil obtained by applying a Fischer-Tropsch (FT) reaction to a mixed gas (also referred to as synthesis gas) mainly composed of hydrogen and carbon monoxide. It is obtained by purifying liquid fractions, and hydrocarbon mixtures obtained by hydrorefining and hydrocracking them, and FT wax obtained by FT reaction, hydrotreating and hydrocracking them. The base material which consists of a hydrocarbon mixture is shown.

The mixed gas used as the raw material of the FT synthesis base material is obtained by oxidizing a carbon-containing substance using oxygen and / or water and / or carbon dioxide as an oxidizing agent, and further using a shift reaction using water as necessary. It is obtained by adjusting to a predetermined hydrogen and carbon monoxide concentration.
Carbon-containing substances include natural gas, petroleum liquefied gas, methane gas, etc., gas components composed of hydrocarbons that are gaseous at room temperature, petroleum asphalt, biomass, coal, waste such as building materials and garbage, sludge, In addition, mixed gas obtained by exposing heavy crude oil, unconventional petroleum resources, etc. that are difficult to process by ordinary methods to high temperatures is common, but mixed gas mainly composed of hydrogen and carbon monoxide As long as is obtained, the present invention does not limit the raw materials.

  A Fischer-Tropsch reaction requires a metal catalyst. Preferably, the method uses a group 8 metal of the periodic table, for example, cobalt, ruthenium, rhodium, palladium, nickel, iron, etc., more preferably a group 8 group 4 metal as the active catalyst component. Moreover, the metal group which mixed these metals in an appropriate amount can also be used. These active metals are generally used in the form of a catalyst obtained by being supported on a support such as silica, alumina, titania or silica alumina. Further, by using these catalysts in combination with a second metal in addition to the above active metal, the catalyst performance can be improved. Examples of the second metal include zirconium, hafnium, titanium, and the like in addition to alkali metals and alkaline earth metals such as sodium, lithium, and magnesium, and a chain that serves as an index for improving the conversion rate of carbon monoxide and generating wax. It is used appropriately according to the purpose, such as an increase in growth probability (α).

  The Fischer-Tropsch reaction is a synthesis method that generates a liquid fraction and FT wax using a mixed gas as a raw material. In order to efficiently perform this synthesis method, it is generally preferable to control the ratio of hydrogen to carbon monoxide in the mixed gas. The molar mixing ratio of hydrogen to carbon monoxide (hydrogen / carbon monoxide) is preferably 1.2 or more, more preferably 1.5 or more, and even more preferably 1.8 or more. The ratio is preferably 3 or less, more preferably 2.6 or less, and even more preferably 2.2 or less.

  When performing the Fischer-Tropsch reaction using the catalyst, the reaction temperature is preferably 180 ° C. or higher and 320 ° C. or lower, and more preferably 200 ° C. or higher and 300 ° C. or lower. When the reaction temperature is less than 180 ° C., carbon monoxide hardly reacts and the hydrocarbon yield tends to be low. On the other hand, when the reaction temperature exceeds 320 ° C., the amount of gas such as methane increases, and the production efficiency of the liquid fraction and FT wax decreases.

No particular restriction on the gas hourly space velocity relative to the catalyst, but preferably 500h ^-1 or more 4000h ^-1 or less, 1000h ^-1 or more 3000h ^-1 or less is more preferable. If the gas space velocity is less than 500 h ⁻¹ , the productivity of the liquid fuel tends to decrease. If the gas space velocity exceeds 4000 h ⁻¹ , the reaction temperature must be increased, and gas generation increases, resulting in a yield of the target product. It will decline.

  The reaction pressure (partial pressure of synthesis gas composed of carbon monoxide and hydrogen) is not particularly limited, but is preferably 0.5 MPa or more and 7 MPa or less, and more preferably 2 MPa or more and 4 MPa or less. If the reaction pressure is less than 0.5 MPa, the yield of the liquid fuel tends to decrease, and if it exceeds 7 MPa, the amount of capital investment tends to increase, which is uneconomical.

  The FT synthesis substrate can be obtained by hydrorefining or hydrocracking the liquid fraction and FT wax produced by the above FT reaction by any method and adjusting them to the distillation properties, composition, etc. suitable for the purpose. Hydrorefining and hydrocracking may be selected in accordance with the purpose, and selection of only one or a combination of both methods is not limited in any way as long as the fuel composition of the present invention can be produced. .

The catalyst used for hydrorefining is generally a catalyst in which a hydrogenation active metal is supported on a porous carrier, but the present invention does not limit the form of the catalyst as long as the same effect can be obtained.
An inorganic oxide is preferably used as the porous carrier. Specific examples include alumina, titania, zirconia, boria, silica, zeolite, and the like.
Zeolite is a crystalline aluminosilicate, and includes faujasite, pentasil, mordenite, etc., preferably faujasite, beta, mordenite, particularly preferably Y type and beta type. Of these, the Y type is preferably ultra-stabilized.

As the active metal, the following two types (active metal A type and active metal B type) are preferably used.
The active metal A type is at least one metal selected from Group 8 metals of the Periodic Table. Preferably, it is at least one selected from Ru, Rh, Ir, Pd and Pt, more preferably Pd or / and Pt. The active metal may be a 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, Ir-Rh-Ru, and the like. When using a noble metal catalyst composed of these metals, it can be used after pre-reduction treatment in a hydrogen stream. In general, when a gas containing hydrogen is circulated and heat of 200 ° C. or higher is applied according to a predetermined procedure, the active metal on the catalyst is reduced, and hydrogenation activity is exhibited.
Further, as the active metal B type, it contains at least one metal selected from Group 6A and Group 8 metals of the periodic table, and preferably contains two or more metals selected from Groups 6A and 8 What you are doing can also be used. For example, Co-Mo, Ni-Mo, Ni-Co-Mo, and Ni-W can be mentioned. When a metal sulfide catalyst made of these metals is used, it is necessary to include a preliminary sulfidation step.

  As the metal source, a general inorganic salt or a complex salt compound can be used, and as a supporting method, any method of a supporting method used in an ordinary hydrogenation catalyst such as an impregnation method or an ion exchange method can be used. When a plurality of metals are supported, they may be supported simultaneously using a mixed solution, or may be sequentially supported using a single solution. The metal solution may be an aqueous solution or an organic solvent.

The reaction temperature when hydrotreating using a catalyst composed of an active metal A type is preferably 180 ° C. or higher and 400 ° C. or lower, more preferably 200 ° C. or higher and 370 ° C. or lower, and 250 ° C. or higher and 350 ° C. or lower. More preferably, the temperature is 280 ° C. or lower and even more preferably 280 ° C. or higher and 350 ° C. or lower. If the reaction temperature in hydrorefining exceeds 370 ° C., side reactions that decompose into naphtha fractions increase, and the yield of middle fractions is extremely undesirably reduced. On the other hand, when the reaction temperature is lower than 270 ° C., the alcohol component cannot be completely removed and is not preferable.
The reaction temperature when hydrotreating using a catalyst comprising an active metal B type is preferably 170 ° C. or higher and 320 ° C. or lower, more preferably 175 ° C. or higher and 300 ° C. or lower, and 180 ° C. or higher and 280 ° C. More preferably, it is not higher than ° C. If the reaction temperature in the hydrorefining exceeds 320 ° C., side reactions that decompose into naphtha fractions increase, and the yield of middle fractions is extremely undesirably reduced. On the other hand, when the reaction temperature is lower than 170 ° C., the alcohol component cannot be completely removed and is not preferable.

The hydrogen pressure when hydrotreating using a catalyst composed of an active metal A type is preferably 0.5 MPa or more and 12 MPa or less, and more preferably 1.0 MPa or more and 5.0 MPa or less. The higher the hydrogen pressure, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.
The hydrogen pressure when hydrotreating using a catalyst composed of an active metal B type is preferably 2 MPa or more and 10 MPa or less, more preferably 2.5 MPa or more and 8 MPa or less, and 3 MPa or more and 7 MPa or less. More preferably. The higher the hydrogen pressure, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.

The liquid hourly space velocity which hydrorefining is carried out using a catalyst composed of the active metal A type (LHSV) is preferably at 0.1 h ^-1 or more 10.0H ^-1 or less, 0.3h ^-1 or 3 More preferably, it is 5 h ⁻¹ or less. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, an extremely large reaction tower volume is required, resulting in excessive capital investment, which is not economical.
The liquid hourly space velocity which hydrorefining is carried out using a catalyst composed of the active metal B type (LHSV) is preferably at 0.1 h ^-1 or more ^{2h -1} or less, 0.2 h ^-1 or more 1.5h more preferably ^{1 or} less, and more preferably 0.3h ^-1 or 1.2 h ^-1. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, an extremely large reaction tower volume is required, resulting in excessive capital investment, which is not economical.

The hydrogen / oil ratio is preferably 50 NL / L or more and 1000 NL / L or less, more preferably 70 NL / L or more and 800 NL / L or less when hydrotreating using a catalyst composed of an active metal A type. preferable. The higher the hydrogen / oil ratio, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.
The hydrogen / oil ratio when hydrotreating using a catalyst composed of an active metal B type is preferably 100 NL / L or more and 800 NL / L or less, more preferably 120 NL / L or more and 600 NL / L or less. Preferably, it is 150 NL / L or more and 500 NL / L or less. The higher the hydrogen / oil ratio, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.

The catalyst used for hydrocracking is generally one in which a hydrogenation active metal is supported on a carrier having a solid acid property, but the present invention does not limit the form of the catalyst as long as the same effect can be obtained. Absent.
Supports having a solid acid property include amorphous and crystalline zeolites. Specific examples include amorphous silica-alumina, silica-magnesia, silica-zirconia, silica-titania and zeolite faujasite type, beta type, MFI type, and mordenite type. Preferred are faujasite type, beta type, MFI type, and mordenite type zeolite, and more preferred are Y type and beta type. The Y type is preferably ultra-stabilized.

As the active metal, the following two types (active metal A type and active metal B type) are preferably used.
The active metal A type is at least one metal selected from Group 6A and Group 8 metals in the periodic table. Preferably, it is at least one metal selected from Ni, Co, Mo, Pt, Pd and W. When using a noble metal catalyst composed of these metals, it can be used after pre-reduction treatment in a hydrogen stream. In general, when a gas containing hydrogen is circulated and heat of 200 ° C. or higher is applied according to a predetermined procedure, the active metal on the catalyst is reduced, and hydrogenation activity is exhibited.
The active metal B type may be a combination of these metals, and examples thereof include Pt—Pd, Co—Mo, Ni—Mo, Ni—W, and Ni—Co—Mo. Moreover, when using the catalyst which consists of these metals, it is preferable to use after pre-sulfiding.

  As the metal source, a general inorganic salt or a complex salt compound can be used, and as a supporting method, any method of a supporting method used in an ordinary hydrogenation catalyst such as an impregnation method or an ion exchange method can be used. When a plurality of metals are supported, they may be supported simultaneously using a mixed solution, or may be sequentially supported using a single solution. The metal solution may be an aqueous solution or an organic solvent.

  The reaction temperature when performing hydrocracking using a catalyst comprising an active metal A type and an active metal B type is preferably 200 ° C. or higher and 450 ° C. or lower, more preferably 250 ° C. or higher and 430 ° C. or lower. More preferably, the temperature is 300 ° C. or more and 400 ° C. or less. When the reaction temperature in hydrocracking exceeds 370 ° C., side reactions that decompose into a naphtha fraction increase and the yield of the middle fraction is extremely reduced, which is not preferable. On the other hand, when the temperature is lower than 200 ° C., the activity of the catalyst is remarkably lowered, which is not preferable.

  The hydrogen pressure when hydrocracking using a catalyst comprising an active metal A type and an active metal B type is preferably 1 MPa or more and 20 MPa or less, more preferably 4 MPa or more and 16 MPa or less, and 6 MPa or more and 13 MPa. More preferably, it is as follows. The higher the hydrogen pressure is, the more hydrogenation reaction is promoted. However, the decomposition reaction rather slows down and the progress of the reaction needs to be adjusted by increasing the reaction temperature, leading to a decrease in catalyst life. For this reason, there is generally an economical optimum for the reaction temperature.

The liquid hourly space velocity which hydrocracking is carried out using a catalyst composed of the active metal A type (LHSV) is preferably at 0.1 h ^-1 or more ^{10h -1} or less, 0.3h ^-1 over 3.5h ^-More preferably, it is ¹ or less. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, an extremely large reaction tower volume is required, resulting in excessive capital investment, which is not economical.
The liquid hourly space velocity which hydrocracking is carried out using a catalyst composed of the active metal B type (LHSV) is preferably at 0.1 h ^-1 or more ^{2h -1} or less, 0.2 h ^-1 or more 1.7h more preferably ^{1 or} less, and more preferably 0.3h ^-1 or 1.5 h ^-1. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, an extremely large reaction tower volume is required, resulting in excessive capital investment, which is not economical.

The hydrogen / oil ratio is preferably 50 NL / L or more and 1000 NL / L or less, more preferably 70 NL / L or more and 800 NL / L or less when hydrocracking using a catalyst composed of an active metal A type. Preferably, it is 400 NL / L or more and 1500 NL / L or less. The higher the hydrogen / oil ratio, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.
The hydrogen / oil ratio is preferably 150 NL / L or more and 2000 NL / L or less, more preferably 300 NL / L or more and 1700 NL / L or less when hydrocracking using a catalyst composed of an active metal B type. Preferably, it is 400 NL / L or more and 1500 NL / L or less. The higher the hydrogen / oil ratio, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.

The apparatus for hydrotreating may be of any configuration, the reaction towers may be used alone or in combination, hydrogen may be additionally injected between the reaction towers, gas-liquid separation operation, hydrogen sulfide removal equipment, hydrogen It may have a distillation column for fractionating the chemical product and obtaining the desired fraction.
The reaction format of the hydrotreating apparatus can take a fixed bed system. Hydrogen can take either a countercurrent or a cocurrent flow with respect to the feedstock, and may have a plurality of reaction towers and a combination of countercurrent and cocurrent flow. The general format is downflow, and there is a gas-liquid twin parallel flow format. Hydrogen gas may be injected into the middle stage of the reaction tower as a quench for the purpose of removing reaction heat or increasing the hydrogen partial pressure.

In the diesel fuel composition of the present invention, it is necessary to treat the feedstock composed of the above-mentioned FT synthetic base as follows.
That is, it is necessary to subject the raw material oil composed of the FT synthetic base material having the above-described properties to a delinear saturated hydrocarbon treatment with zeolite under conditions of a temperature of 150 ° C. or more and 250 ° C. or less and a pressure of 1 MPa or more and 5 MPa or less.
The reaction temperature for the removal of the linear saturated hydrocarbon is 150 ° C. or higher and 250 ° C. or lower, preferably 180 ° C. or higher and 200 ° C. or lower. When the reaction temperature is less than 150 ° C., a sufficient removal rate of linear saturated hydrocarbon cannot be obtained. On the other hand, when it exceeds 250 degreeC, the removal efficiency of a linear saturated hydrocarbon will fall. Further, the pressure at this time is 1 MPa or more and 5 MPa or less, preferably 1.5 MPa or more and 3 MPa or less. If the pressure is less than 1 MPa, a sufficient removal rate of linear saturated hydrocarbons cannot be obtained. On the other hand, if it exceeds 5 MPa, a sufficient removal rate of linear saturated hydrocarbons cannot be obtained. The zeolite used for the removal of the linear saturated hydrocarbon is not particularly limited, but generally, A-type zeolite is used, and among these, the molecular sieve 5A is preferable.

  The diesel fuel composition of the present invention is a hydrocarbon mixture having the following specific properties obtained through the above treatment.

The diesel fuel composition of the present invention has a Saybolt color of +28 or more, a density at 15 ° C. of 760 kg / m ³ or more and 830 kg / m ³ or less, a distillation property of 10% distillation temperature of 170 ° C. or more and 220 ° C. or less, and 50% distillation. Temperature is 210 ° C to 280 ° C, 90% distillation temperature is 240 ° C to 325 ° C, cetane index 55 to 75, cetane number 55 to 70, flash point 50 ° C to peroxide value after accelerated oxidation test 10 mass ppm or less, clouding point −10 ° C. or less, clogging point −10 ° C. or less, pour point −15 ° C. or less, aromatic content 1 volume% or less, naphthene compound content 5 mass% or less, sulfur content 1 mass ppm or less, kinematic viscosity at 30 ° C. is 1.7 mm ² / s or more 4.0 mm ² / s or less, residual carbon content of 10% residual oil is 0.05% by mass or less, HFRR (WS 1.4) 4 It is necessary that 0μm is less than or equal to.

  As described above, the Saybolt color of the diesel fuel composition of the present invention needs to be +28 or more, preferably +29 or more, and more preferably +30 or more from the viewpoint of removing the oxidation stability inhibitor. preferable. The Saebold color here means a value measured according to JIS K 2580 “Petroleum products—color test method—Saebold color test method”.

The density at 15 ° C. of the diesel fuel composition of the present invention needs to be 760 kg / m ³ or more, preferably 765 kg / m ³ or more, more preferably 770 kg / m ³ or more, from the viewpoint of securing the calorific value. . Further, the density, NOx, from the viewpoint of reducing the emissions of PM, must be at 830 kg / ^{m 3} or less, preferably 825 kg / ^{m 3} or less, 820 kg / ^{m 3} or less is more preferable. In addition, the density here means the density measured by JIS K 2249 “Density test method and density / mass / capacity conversion table of crude oil and petroleum products”.

  The distillation properties in the diesel fuel composition of the present invention include a 10% distillation temperature of 170 ° C to 220 ° C, a 50% distillation temperature of 210 ° C to 280 ° C, and a 90% distillation temperature of 240 ° C to 325 ° C. It is necessary that: If the 10% distillation temperature is less than 170 ° C., the engine output and the startability at low temperatures tend to deteriorate. Therefore, the temperature is preferably 173 ° C. or higher, more preferably 178 ° C. or higher, and further preferably 180 ° C. or higher. On the other hand, if the 10% distillation temperature exceeds 220 ° C, the exhaust gas performance tends to deteriorate, so it is preferably 215 ° C or less, more preferably 210 ° C or less, and even more preferably 205 ° C or less. If the 50% distillation temperature is less than 210 ° C, the engine output and the startability at low temperatures tend to deteriorate. Therefore, the temperature is preferably 215 ° C or higher, more preferably 220 ° C or higher, and further preferably 225 ° C or higher. On the other hand, when the 50% distillation temperature exceeds 280 ° C., the exhaust gas performance tends to deteriorate, so it is preferably 275 ° C. or less, more preferably 270 ° C. or less, and further preferably 265 ° C. or less. Further, if the 90% distillation temperature is less than 240 ° C., the fuel efficiency improvement effect becomes insufficient and the engine output tends to decrease, so that it is preferably 245 ° C. or more, more preferably 250 ° C. or more, more preferably 255 ° C. That's it. On the other hand, when the 90% distillation temperature exceeds 325 ° C., the amount of PM and fine particles discharged tends to increase. Therefore, it is preferably 320 ° C. or less, more preferably 315 ° C. or less, and further preferably 310 ° C. or less. The 10% distillation temperature, 50% distillation temperature, and 90% distillation temperature mentioned here all mean values measured by JIS K 2254 “Petroleum products—Distillation test method—Atmospheric pressure method”.

  The cetane index of the diesel fuel composition of the present invention needs to be 55 or more. When the cetane index is less than 55, the concentration of PM, aldehydes, or NOx in the exhaust gas tends to increase. For the same reason, the cetane index is preferably 57 or more, and more preferably 60 or more. Further, when the cetane index exceeds 75, the soot emission during acceleration tends to deteriorate, so the cetane index needs to be 75 or less, preferably 74 or less, and more preferably 73 or less. The cetane index referred to in the present invention is defined by “Calculation method of cetane index using 8.4 variable equations” in JIS K 2280 “Petroleum products-fuel oil-octane number and cetane number test method and cetane index calculation method”. It means the calculated value. Here, the cetane index in the JIS standard is generally applied to light oil to which no cetane number improver is added, but in the present invention, the above-mentioned " Applying “8.4 Calculation Method of Cetane Index Using Variable Equation”, a value calculated by the calculation method is expressed as a cetane index.

  The cetane number in the diesel fuel composition of the present invention needs to be 55 or more. When the cetane number is less than 55, the concentration of NOx, PM, and aldehydes in the exhaust gas tends to be high, and thus it is preferably 56 or more, more preferably 57 or more. Further, from the viewpoint of reducing black smoke in the exhaust gas, the cetane number needs to be 70 or less, preferably 68 or less, and more preferably 66 or less. Moreover, in the fuel composition of the present invention, an appropriate amount of a cetane number improver can be blended as required to improve the cetane number of the resulting fuel composition. The cetane number referred to here is a cetane number measured in accordance with “7. Cetane number test method” in JIS K 2280 “Petroleum products—Fuel oil—Octane number and cetane number test method and cetane index calculation method”. Means.

  The flash point of the diesel fuel composition of the present invention needs to be 50 ° C. or higher. When the flash point is less than 50 ° C., it is not preferable from the viewpoint of safety. Therefore, the flash point is preferably 52 ° C. or higher, and more preferably 54 ° C. or higher. The flash point in the present invention is a value measured by JIS K 2265 “Crude oil and petroleum product flash point test method”.

The peroxide value after the accelerated oxidation test of the diesel fuel composition of the present invention needs to be 10 mass ppm or less. The peroxide value after the accelerated oxidation test is preferably 8 ppm by mass or less, more preferably 6 ppm by mass or less, and even more preferably 4 ppm by mass or less, from the viewpoint of storage stability and compatibility with members.
The peroxide value after the accelerated oxidation test referred to here is the Petroleum Institute Standard JPI- after conducting the accelerated oxidation test under conditions of 95 ° C. and oxygen bubbling for 16 hours in accordance with ASTM D2274-94. It means the value of peroxide value measured according to 5S-46-96. In order to reduce the peroxide value, an additive such as an antioxidant or a metal deactivator can be appropriately added to the fuel composition for cryogenic regions of the present invention.

  The cloud point of the diesel fuel composition of the present invention needs to be −10 ° C. or lower. Furthermore, from the viewpoint of ensuring low temperature startability or low temperature drivability and maintaining the injection performance of the electronically controlled fuel injection pump, it is preferably −12 ° C. or lower, and more preferably −15 ° C. or lower. The cloud point here means a pour point measured according to JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.

  The clogging point of the diesel fuel composition of the present invention needs to be −10 ° C. or lower. Furthermore, from the viewpoint of preventing the pre-filter blockage of the diesel vehicle and maintaining the injection performance of the electronically controlled fuel injection pump, it is preferably −12 ° C. or lower, and more preferably −15 or lower. Here, the clogging point means a clogging point measured by JIS K 2288 “Light oil—clogging point test method”.

  The pour point of the diesel fuel composition of the present invention needs to be −15 ° C. or lower. Furthermore, from the viewpoint of ensuring low temperature startability or ensuring low temperature drivability and maintaining the injection performance of the electronically controlled fuel injection pump, it is preferably −18 ° C. or lower, and more preferably −20 ° C. or lower. Here, the pour point means a pour point measured according to JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.

  The aromatic content of the diesel fuel composition of the present invention is required to be 1% by volume or less, preferably 0.8% by volume or less, and more preferably 0.5% by volume or less. preferable. When the aromatic content is 1% by volume or less, it is possible to suppress the production of PM and the like and exhibit environmental performance, and more easily and reliably the properties defined in the fuel composition of the present invention. Can be achieved. The aromatic content here was measured in accordance with JPI-5S-49-97 “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method” published by the Japan Petroleum Institute. Means the volume percentage (volume%) of the aromatic content.

  The naphthene content of the diesel fuel composition of the present invention needs to be 5% by mass or less, preferably 3% by mass or less, and more preferably 1% by mass or less. When the naphthene content is 5% by mass or less, it is possible to suppress the production of PM and the like and to exhibit environment-friendly performance, and more easily and reliably achieve the properties defined in the fuel composition of the present invention. can do. Here, the naphthene content means the mass percentage (mass%) of the naphthene measured in accordance with ASTM D2425 “Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry”.

  The sulfur content of the diesel fuel composition of the present invention is required to be 10 mass ppm or less, preferably 8 mass ppm from the viewpoint of reducing harmful exhaust components discharged from the engine and improving the performance of the exhaust gas aftertreatment device. Below, more preferably 5 ppm by mass or less, still more preferably 3 ppm by mass or less, and even more preferably 1 ppm by mass or less. In addition, the sulfur content here means the mass content of the sulfur content based on the total amount of the light oil composition measured by JIS K2541 “Sulfur content test method”.

The kinematic viscosity at 30 ° C. of the diesel fuel composition of the present invention is required to be 1.7 mm ² / s or more, preferably 1.75 mm ² / s or more, and 1.8 mm ² / s or more. It is more preferable that When the kinematic viscosity is less than 1.7 mm ² / s, it tends to be difficult to control the fuel injection timing on the fuel injection pump side, and the lubricity of each part of the fuel injection pump mounted on the engine is impaired. There is a fear. On the other hand, it is necessary that the kinematic viscosity at 30 ° C. or less 4.0 mm ² / s, is preferably 3.9 mm ² / s or less, and more preferably less 3.8 mm ² / s. If the kinematic viscosity exceeds 4.0 mm ² / s, the resistance inside the fuel injection system increases, the injection system becomes unstable, and the concentrations of NOx and PM in the exhaust gas increase, which is not preferable. In addition, kinematic viscosity here means kinematic viscosity measured by JISK2283 "crude oil and petroleum products-kinematic viscosity test method and viscosity index calculation method".

  The water content of the diesel fuel composition of the present invention is preferably 100 ppm by volume or less, more preferably 50 ppm by volume or less, and even more preferably 20 ppm by volume or less, from the viewpoint of preventing freezing at low temperatures. is there. The water content here means a value measured by JIS K 2275 “Crude oil and petroleum products—moisture test method—Karl Fischer coulometric titration method”.

  The residual carbon content of 10% residual oil of the diesel fuel composition of the present invention needs to be 0.05% by mass or less, and 0.04% by mass or less is preferable from the viewpoint of preventing filter clogging by sludge, 0.03 mass% or less is more preferable. The residual carbon content of 10% residual oil here means a value measured by JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.

The HFRR wear scar diameter (WS1.4) of the diesel fuel composition of the present invention needs to be 400 μm or less, and preferably has a lubricating performance of 380 μm or less, more preferably 360 μm or less. When the HFRR wear scar diameter (WS1.4) exceeds 400 μm, especially in a diesel engine equipped with a distributed injection pump, it causes an increase in driving torque of the pump during operation and an increase in wear of each part of the pump, and exhaust gas performance, fine particles The engine itself may be destroyed as well as the performance deterioration. In addition, in an electronically controlled fuel injection pump capable of high-pressure injection, there is a concern about wear on the sliding surface.
The HFRR wear scar diameter (WS1.4) as used in the present invention is a value measured by the Petroleum Institute Standard JPI-5S-50-98 “Light Oil-Lubricity Test Method” issued by the Japan Petroleum Institute. Means.

  In the diesel fuel composition of the present invention, it is preferable to add a proper amount of a lubricity improver, an antifreezing agent, and a low temperature fluidity improver as necessary.

  In order to prevent wear of the fuel injection pump, it is preferable to add a lubricity improver to the diesel fuel composition of the present invention. Moreover, the addition amount is preferably 20 mg / L or more and 200 mg / L or less, more preferably 50 mg / L or more and 180 mg / L or less in terms of active ingredient concentration. When the addition amount of the lubricity improver is within the above range, the effect of the added lubricity improver can be effectively extracted. For example, in a diesel engine equipped with a distributed injection pump, An increase in driving torque can be suppressed and pump wear can be reduced.

The type of the lubricity improver is not particularly limited. For example, one or more of carboxylic acid-based, ester-based, alcohol-based and phenol-based lubricity improvers can be used arbitrarily. . Among these, carboxylic acid-based and ester-based lubricity improvers are preferable.
Examples of the carboxylic acid-based lubricity improver include linoleic acid, oleic acid, salicylic acid, palmitic acid, myristic acid, hexadecenoic acid, and a mixture of two or more of the above carboxylic acids.
Examples of ester-based lubricity improvers include carboxylic acid esters of glycerin. The carboxylic acid constituting the carboxylic acid ester may be one kind or two or more kinds, and specific examples thereof include linoleic acid, oleic acid, salicylic acid, palmitic acid, myristic acid, hexadecenoic acid and the like. There is.
In addition, since this invention presupposes use in a low-temperature environment, what has the unsaturated bond for the fatty-acid structure of these lubricity improvers is more preferable from a viewpoint of ensuring low-temperature fluidity | liquidity.

  It is preferable to add an antifreezing agent to the diesel fuel composition of the present invention from the viewpoint of freezing water in the oil and preventing problems of the fuel filter and the fuel injection system. Moreover, it is preferable that the addition amount is 100 mass ppm or more and 500 mass ppm or less, and it is more preferable that it is 200 mass ppm or more and 400 mass ppm or less. Although the kind of antifreezing agent is not particularly limited, various compounds having an antifreezing function can be arbitrarily used, and examples thereof include 2-methoxyethanol, isopropyl alcohol, polyglycol ether, etc. From the viewpoint of ensuring fluidity, the melting point or pour point of these antifreeze agents is preferably −60 ° C. or lower. However, those having a metal and those having a salt structure, such as sodium acetate, calcium acetate, sodium chloride, and calcium chloride, are not suitable for fuel applications. These antifreeze agents may be used alone or in combination of two or more, but those having a purity of 98% or more of each antifreeze-containing main compound are more preferably used. can do.

  It is preferable to add a low temperature fluidity improver to the diesel fuel composition of the present invention from the viewpoint of preventing the filter blockage of a diesel vehicle. Moreover, the addition amount is preferably 200 mg / L or more and 1000 mg / L or less, more preferably 300 mg / L or more and 800 mg / L or less in terms of active ingredient concentration.

  The type of the low-temperature fluidity improver is not particularly limited. For example, ethylene-unsaturated ester copolymer represented by ethylene-vinyl acetate copolymer, alkenyl succinic acid amide, dibehenate ester of polyethylene glycol Linear compounds such as phthalic acid, ethylenediaminetetraacetic acid, nitriloacetic acid and the like, or polar nitrogen compounds consisting of reaction products of hydrocarbyl-substituted amines, alkyl fumarate or alkyl itaconate-unsaturated esters One kind or two or more kinds of low-temperature fluidity improvers such as a comb polymer made of a copolymer can be used. Further, a copolymer of ethylene and methyl methacrylate, a copolymer of ethylene and α-olefin, a chlorinated methylene-vinyl acetate copolymer, an alkyl ester polymer of unsaturated carboxylic acid, a nitrogen-containing compound having a hydroxyl group And esters synthesized from saturates and saturated fatty acids, esters and amide derivatives synthesized from polyhydric alcohols and saturated fatty acids, esters synthesized from polyoxyalkylene glycols and saturated fatty acids, alkylene oxides of polyhydric alcohols or partial esters thereof Low temperature fluidity improver combining one or more selected from esters synthesized from adducts and saturated fatty acids, chlorinated paraffin / naphthalene condensates, alkenyl succinic acid amides, amine salts of sulfobenzoic acid, etc. can do. Among these, from the viewpoint of versatility, an ethylene-vinyl acetate copolymer additive can be preferably used. In addition, since a commercial product referred to as a low temperature fluidity improver may be diluted with an appropriate solvent for an active ingredient (active ingredient) that contributes to low temperature fluidity, such a commercial product may be used in the present invention. In the case of adding to a light oil composition, the above-mentioned addition amount means the addition amount (active ingredient concentration) as an active ingredient.

Further, for the purpose of further improving the performance of the diesel fuel composition in the present invention, other known fuel oil additives (hereinafter referred to as “other additives” for convenience) can be added alone or in combination of several kinds. . Other additives include, for example, nitrate esters represented by alkyl nitrates having 6 to 8 carbon atoms, cetane number improvers such as organic peroxides; imide compounds, alkenyl succinimides, succinates, Detergents such as polymerized polymers and ashless detergents; antioxidants such as phenols and amines; metal deactivators such as salicylidene derivatives; corrosion inhibitors such as aliphatic amines and alkenyl succinates; anionics Antistatic agents such as cationic and amphoteric surfactants; colorants such as azo dyes; antifoaming agents such as silicon.
The addition amount of other additives can be arbitrarily determined, but the addition amount of each additive is preferably 0.5% by mass or less, more preferably 0. 0% by mass based on the total amount of the fuel composition for cryogenic regions. 2% by mass or less.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to these Examples at all.

(Examples 1-2 and Comparative Examples 1-4)
The FT synthetic base material having the properties shown in Table 1 was used as a raw material oil, and reacted and processed under the conditions for each step shown in Table 2 to prepare diesel fuel compositions shown in Table 3 (Examples 1 and 2). In both Examples 1 and 2, natural gas is subjected to wax and middle distillation by FT reaction, and a hydrocarbon obtained by subjecting this to hydrogenation is used as a raw material oil. However, while Example 1 uses an FT synthesis base material having a relatively high linear saturated hydrocarbon content, Example 2 includes an isomerization reaction during the above hydrotreatment, It is a base material having a high saturated hydrocarbon content having a chain. Comparative Example 1 is a catalyst in which a zeolite is loaded with a metal group selected from Group 6A and Group 8 metals on the conditions of a reaction pressure of 3 MPa, a reaction temperature of 380 ° C., and a liquid space velocity of 0.8 h ⁻¹ . A composition produced by mixing a treated desulfurized and dewaxed base material with a kerosene fraction, and Comparative Examples 2 and 3 were blended without any processing required by the present invention for the FT synthetic base material. Comparative Example 4 is a composition having a low-temperature performance equivalent to JIS No. 3 diesel oil by producing a diesel oil fraction and a kerosene fraction by a general hydrorefining process and blending appropriate amounts thereof.

The additives used in this example are as follows.
Antifreezing agent: 2-methoxyethanol Lubricity improver: Carboxylic acid mixture based on linoleic acid Low temperature fluidity improver: Ethylene-vinyl acetate copolymer Cetane improver: 2-ethylhexyl nitrate

  Formulation ratio of prepared fuel composition, and density at 15 ° C., kinematic viscosity at 30 ° C., flash point, sulfur content, distillation property, aromatic content, naphthene compound for the prepared fuel composition Content, cetane index, cetane number, cloudy point, clogging point, pour point, hue, residual carbon content of 10% residual oil, total insoluble matter and peroxide value after oxidation stability test, moisture, conductivity, The results of measuring the wear scar diameter are shown in Table 3.

The properties of the raw material oil and fuel oil were measured by the following method.
The density refers to a density measured according to JIS K 2249 “Determination method of density of crude oil and petroleum products and density / mass / capacity conversion table”.
The kinematic viscosity refers to a kinematic viscosity measured according to JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.
The flash point indicates a value measured according to JIS K 2265 “Crude oil and petroleum product flash point test method”.
The sulfur content refers to the mass content of the sulfur content based on the total amount of light oil composition measured by JIS K2541 “Sulfur content test method”.
All the distillation properties are values measured by JIS K 2254 "Petroleum products-Distillation test method".
The aromatic content is measured according to the Japan Petroleum Institute method JPI-5S-49-97 “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method” published by the Japan Petroleum Institute. Means the capacity percentage (volume%).
The naphthene compound content (naphthene content) means the mass percentage (mass%) of the naphthene content measured according to ASTM D2425 “Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry”.
NP (C16-C25 linear saturated hydrocarbon content) of C16-C25 means the value (mass%) measured using the above-mentioned GC-FID.

The cloud point means the cloud point measured according to JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.
The clogging point means a clogging point measured by JIS K 2288 “Light oil—clogging point test method”.
The pour point means a pour point measured according to JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.
The cetane index refers to a value calculated according to “Method for calculating cetane index using 8.4 variable equation” in JIS K 2280 “Petroleum products—fuel oil—octane number and cetane number test method and cetane index calculation method”. The cetane index in the JIS standard is not applied to the cetane number improver added, but the cetane index of the cetane index added with the cetane number improver also uses the above “8.4 variable equation”. It shall represent the value calculated by “Calculating method of cetane index”.
The cetane number means a cetane number measured according to “7. Cetane number test method” of JIS K 2280 “Petroleum products—fuel oil—octane number and cetane number test method and cetane index calculation method”.

Hue means the Saybolt color measured according to the Saebold color test method described in JIS K 2580 “Petroleum products—color test method”.
Moisture refers to moisture measured by the Karl Fischer coulometric titration method described in JIS K 2275 “Crude oil and petroleum products—moisture test method”.
The residual carbon content of 10% residual oil means the residual carbon content of 10% residual oil as measured by JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.
The peroxide value (peroxide value) after the oxidation stability test is accelerating oxidation under conditions of 95 ° C. and oxygen bubbling for 16 hours in accordance with ASTM D2274-94, and then the Petroleum Institute Standard JPI-5S- It means a value measured according to 46-96.
The total insoluble content after the oxidation stability test (total insoluble content) means a value measured after accelerated oxidation under conditions of 95 ° C. and oxygen bubbling for 16 hours in accordance with ASTM D2274-94. .
The conductivity means a value measured in accordance with JIS K 2276 “Petroleum product-aviation fuel oil test method”.
Lubrication performance and HFRR wear scar diameter (WS1.4) refer to the lubrication performance measured by the Petroleum Institute Standard JPI-5S-50-98 “Diesel Oil-Lubricity Test Method” issued by the Japan Petroleum Institute. .

As shown in Tables 1 and 2, the fuel compositions used in the Examples are prepared by blending a hydrocarbon base material obtained through a specific process using a FT synthetic base material as a raw material oil.
As is clear from Table 3, in Examples 1 and 2 blended under the conditions specified in the present invention using the base material manufactured through a predetermined process, a fuel composition satisfying the specified properties was easily obtained. And I was able to get it reliably. On the other hand, in Comparative Examples 1 to 4 in which the fuel composition was prepared without using the specific fuel substrate, the fuel composition intended by the present invention is not necessarily obtained.

  Next, using the fuel compositions of Examples 1 and 2 and Comparative Examples 1 to 4, various tests shown below were performed. All test results are shown in Table 4. As can be seen from the results in Table 4, the diesel fuel compositions of Examples 1 and 2 were compared with the diesel oil compositions of Comparative Examples 1 to 4, in a Smoke measurement test under acceleration conditions after cold start, and fuel consumption measurement after cold start. Good results have been obtained in tests, exhaust gas performance tests, and restartability tests after low-temperature start-up, and excellent low-temperature fluidity, fuel economy performance, and environment-friendly performance that were difficult to achieve with conventional fuel compositions are simultaneously achieved It can be ascertained to provide a diesel combustion composition having the same.

(Various performance tests after cold start)
<Startability check>
Using a diesel engine-equipped vehicle (vehicle 1) shown below, on a chassis dynamometer capable of controlling the environmental temperature, at room temperature, (1) flushing (cleaning) the fuel system of the test diesel vehicle with the evaluation fuel (2) Extracting the flushing fuel, (3) Replacing the main filter with a new one, and (4) Placing a prescribed amount of evaluation fuel (1/2 of the fuel tank capacity of the test vehicle) into the fuel tank. Thereafter, (5) the ambient temperature is rapidly cooled from room temperature to −10 ° C., (6) held at −10 ° C. for 1 hour, and (7) to a predetermined temperature (−20 ° C.) at a cooling rate of 1 ° C./h. (8) Hold the engine at a predetermined temperature for 1 hour, and then start the engine. If cranking for 10 seconds is repeated twice at 30-second intervals, it cannot be measured. If it can be started, leave it idle for 30 seconds, then perform the following tests in order.

<1. Accelerated testing>
After the operation of the 10-mode operation pattern described in Appendix 27 “Technical Standards for Diesel Vehicle 10/15 Mode Exhaust Gas Measurement” supervised by the former Ministry of Transport Supervised New Vehicle Examination Criteria 27 The black smoke at that time is measured with a transmission type measuring instrument. The average value of 5 times was computed, the result of the comparative example 1 was set to 100, and each result was compared and quantified relatively.

<2. Restartability test>
After completion of the acceleration test, the engine is stopped and soaked at -20 ° C for 1 hour. After soak, restart the engine. At this time, as in the startability confirmation test described above, measurement is impossible if the engine does not start even after 10 seconds of cranking is repeated twice at 30 second intervals. If the engine can be started, the engine is left for 30 seconds at idling.

<3. Vehicle exhaust gas test and fuel consumption test>
After the restartability test is completed, the transient operation mode simulating the actual travel shown in FIG. 1 is run five times in order to stabilize the engine speed. Thereafter, an operation is performed in the operation mode of FIG. 1 in addition to an interval of idling for 1 minute, and fuel consumption, NOx, and PM are measured during that time. For each exhaust gas performance value, the test result in Comparative Example 1 was set to 100, and each result was relatively compared and quantified. In addition, the test method relating to the vehicle test is in accordance with Annex 27 “Technical Standards for Diesel Vehicle 10/15 Mode Emission Measurement”, supervised by the former Ministry of Transport.

(Vehicle specifications): Vehicle 1
Engine type: Supercharged inline 4 cylinder diesel engine with intercooler Displacement: 3L
Compression ratio: 18.5
Maximum output: 125kW / 3400rpm
Maximum torque: 350Nm / 2400rpm
Regulatory compliance: 1997 exhaust gas regulatory compliance Vehicle weight: 1900 kg
Mission: 4AT
Exhaust gas aftertreatment device: oxidation catalyst

It is a figure which shows the transient operation mode which simulated real driving | running | working.

Claims (4)

10% distillation temperature of distillation property is 140 ° C. or more and 200 ° C. or less, 90% by volume distillation temperature is 240 ° C. or more and 350 ° C. or less, aromatic content is 1% by volume or less, naphthene compound content is 5% by mass or less, A hydrocarbon mixture composed of an FT synthetic base material having a sulfur content of 10 mass ppm or less and a linear saturated hydrocarbon content of from 16 to 25 carbon atoms of 5 mass% or more and 70 mass% or less is used as a feedstock, and the reaction temperature Obtained by performing de-linear saturated hydrocarbon treatment with zeolite under conditions of 150 ° C. or higher and 250 ° C. or lower and pressure of 1 MPa or higher and 5 MPa or lower, Saebold color +28 or higher, density at 15 ° C. is 760 kg / m ³ or higher and 830 kg / m ³ or less, 10% distillation temperature of distillation characteristic is 170 ° C. or higher 220 ° C. or less, 50% distillation temperature of 210 ° C. or higher 280 ° C. or less, 90% distillation temperature of 240 ° C. Upper 325 ° C. or lower, cetane index 55 or higher and 75 or lower, cetane number 55 or higher and 70 or lower, flash point 50 ° C. or higher, peroxide value after accelerated oxidation test is 10 mass ppm or lower, cloudy point −10 ° C. or lower, clogging point − 10 ° C or less, pour point -15 ° C or less, aromatic content 1% by volume or less, naphthene compound content 5% by mass or less, sulfur content 1 mass ppm or less, kinematic viscosity at 30 ° C 1.7 mm ² / s above 4.0 mm ² / s or less, 0.05 wt% carbon residue of the 10% residual oil less, diesel fuel composition, wherein the HFRR wear scar diameter (WS 1.4) is 400μm or less.   The diesel light oil composition according to claim 1, wherein a lubricity improver is added in an active ingredient concentration of 20 mg / L or more and 200 mg / L or less.   The diesel fuel composition according to claim 1, wherein an antifreezing agent is added in an amount of 100 ppm to 500 ppm.   The diesel fuel composition according to claim 1, wherein a low temperature fluidity improver is added in an active ingredient concentration of 200 mg / L or more and 1000 mg / L or less.

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