JP4567948B2 - Light oil composition and method for producing the same - Google Patents

Description

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【図面の簡単な説明】
【図１】排ガス試験における試験モードを示す図である。
【図２】粒子数の測定に使用する走査型モビリティ粒径分析装置の概略図である。
【符号の説明】
ａ 荷電分布制御部
ｂ 分級部
ｃ 粒子数計測部[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a gas oil composition having a low sulfur content and a method for producing the same. More specifically, the present invention relates to a gas oil composition that reduces particulate matter (PM) and fine particles discharged from an engine, improves fuel consumption, has little influence on members, and has excellent low-temperature startability, and a method for producing the same. .
[0002]
[Prior art]
Conventionally, as the base material for light oil, straight-run gas oil obtained from crude oil atmospheric distillation equipment is hydrorefined or hydrodesulfurized, and straight-run kerosene obtained from crude oil atmospheric distillation equipment is hydrogenated. Those subjected to hydrorefining treatment or hydrodesulfurization treatment are known. Conventional gas oil compositions are produced by blending one or more of the above gas oil base and kerosene base. Moreover, additives, such as a cetane number improver and a detergent, are mix | blended with these light oil compositions as needed (for example, refer nonpatent literature 1).
[0003]
[Non-Patent Document 1]
Seiichi Konishi, “Introduction to Fuel Engineering”, Suikabo, March 1991, p. 136-144
[0004]
[Problems to be solved by the invention]
By the way, in recent years, reduction of the sulfur content and the aromatic content in light oil, which is a fuel for internal combustion engines, has been demanded with the aim of improving the air environment and reducing the environmental load. At the same time, in order to cope with the global warming problem, fuel properties that contribute to further improvement in fuel efficiency are required, and density is a major factor.
[0005]
However, the conventional gas oil base contains an aromatic content of about 40% by volume at maximum, and on average about 20% by volume. In addition, the gas oil fraction contains several percent of polycyclic aromatic components having two or more rings, which are considered to have a large ability to generate particulate matter (hereinafter also referred to as PM). In general, the aromatic content cannot be sufficiently reduced by hydrorefining or hydrodesulfurization treatment, so it is necessary to introduce a dearomatic process. However, existing equipment may not provide the desired light oil base material. Refining costs will increase significantly.
[0006]
In general, kerosene base has a lower aromatic content than light oil base (up to about 30% by volume, average about 15% by volume). It is possible to reduce the aromatic content. However, the light oil composition simply obtained in this manner is low in density and very light, which causes a deterioration in fuel consumption and a decrease in output. Furthermore, the mixing of the light oil base material and the kerosene base material also reduces the kinematic viscosity of the composition, which easily causes problems on the lubrication surface of the fuel injection pump and the like.
[0007]
Therefore, synthetic light oil and synthetic kerosene using natural gas, asphalt, coal, etc. as raw materials have attracted attention. These fuel base materials are characterized by containing almost no aromatic content or sulfur content. However, in view of the influence on the members used in the fuel injection system, when such a fuel is used, particularly in an aged car, the rubber member used is rather contracted, resulting in fuel leakage ( (Leakage) may occur. Moreover, since it is a base material mainly composed of paraffin, there is a concern about precipitation of wax during low temperature start-up.
[0008]
Therefore, regarding the reduction of sulfur content and the required reduction of aromatic content, take into consideration appropriate values that can simultaneously reduce harmful exhaust components, especially particulate matter (PM), maintain fuel efficiency, and affect the components. These performance improvements cannot be achieved simultaneously by simple reduction. Furthermore, because these engine performances are related to properties other than aromatics, it is very difficult to design high-quality fuels that can simultaneously achieve these required performances at a high level, and are also required as commercial fuel oils. There are no examples or knowledge based on the examination of practical manufacturing methods that satisfy the various performances.
[0009]
The present invention has been made in view of such a situation, and its purpose is to reduce particulate matter (PM) and fine particles discharged from the engine when used as diesel fuel, to improve fuel consumption, An object of the present invention is to provide a light oil composition that has little influence on members and has excellent performance at low temperature startability, and a method for producing the same.
[0010]
[Means for Solving the Problems]
  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention uses a petroleum hydrocarbon hydrorefined oil having a sulfur content of 5 ppm to 10 ppm and a boiling point range of 150 ° C. to 380 ° C. as a feedstock, and reacts in the presence of a hydrogenation catalyst. Temperature 170-320 ° C, hydrogen pressure 2-10MPa, LHSV 0.1-2h^-1The 90% distillation temperature obtained by deep hydrogenation at a hydrogen / oil ratio of 100 to 800 NL / L is 200 ° C. or higher and 380 ° C. or lower, and the density at 15 ° C. is 780 kg / m.³More than 870kg / m³Hereinafter, deep hydrorefined gas oil having a sulfur content of 5 ppm by mass or less, a naphthene content of 30% by volume or more and an aromatic content of 1% by volume or less is 20% by volume or more, and an unrefined oil And / or hydrorefined oil as a raw material oil, reaction temperature 220 to 350 ° C., hydrogen pressure 1 to 6 MPa, LHSV 0.1 to 10 h in the presence of a hydrogenation catalyst^-1, Sulfur content obtained by hydrogenation at a hydrogen / oil ratio of 10 to 300 NL / L, 5 mass ppm or less, Total aromatic content 25 vol% or less, Bicyclic or aromatic content 1 volume %, Naphthene content 20 volume% or more, low sulfur kerosene having a boiling range of 140-300 ° C. 20 volume% or more, sulfur content 5 mass ppm or less, total aromatic content 3 volume % To 12% by volume, the content of alkylbenzene having 14 or less carbon atoms in the aromatic component is 80% or more, the content of naphthene is 30% by volume or more, and the density at 15 ° C. is 810 kg / m.³840 kg / m or more³Below, clogging point -10 ° C or lessThe kinematic viscosity at 30 ° C is 2 mm ² / S or more 5mm ² / S or less, distillation property 90% distillation temperature 280 ° C. or higher and 350 ° C. or lower, cetane number 50 or higher and 70 or lower, HFRR wear scar diameter (WS 1.4) 400 μm or lowerIt is related with the light oil composition characterized by these.
[0012]
In addition, the present invention uses a hydrorefined oil of petroleum hydrocarbon having a sulfur content of 5 mass ppm or more and 10 mass ppm or less and a boiling point range of 150 ° C. or more and 380 ° C. or less as a raw material oil and a reaction temperature in the presence of a hydrogenation catalyst. 170-320 ° C., hydrogen pressure 2-10 MPa, LHSV 0.1-2 h^-1The 90% distillation temperature obtained by deep hydrogenation at a hydrogen / oil ratio of 100 to 800 NL / L is 200 ° C. or higher and 380 ° C. or lower, and the density at 15 ° C. is 780 kg / m.^ThreeMore than 870kg / m^ThreeHereinafter, deep hydrorefined gas oil having a sulfur content of 5 ppm by mass or less, a naphthene content of 30% by volume or more and an aromatic content of 1% by volume or less is 20% by volume or more, and an unrefined oil And / or hydrorefined oil as a raw material oil, reaction temperature 220 to 350 ° C., hydrogen pressure 1 to 6 MPa, LHSV 0.1 to 10 h in the presence of a hydrogenation catalyst^-1, Sulfur content obtained by hydrogenation at a hydrogen / oil ratio of 10 to 300 NL / L, 5 mass ppm or less, Total aromatic content 25 vol% or less, Bicyclic or more aromatic content 1 vol% or less By blending 20% by volume or more of low sulfur kerosene having a naphthene content of 20% by volume or more and a boiling point range of 140 to 300 ° C., the sulfur content is 5 mass ppm or less, and the total aromatic content is 3% by volume or more. 12% by volume or less, and the content of alkylbenzene having 14 or less carbon atoms in the aromatic component is 80% or more, the content of naphthene is 30% by volume or more, and the density at 15 ° C. is 810 kg / m.^Three840 kg / m or more^ThreeHereinafter, the present invention relates to a method for producing a light oil composition, which comprises producing a light oil composition having a clogging point of −10 ° C. or lower.
[0013]
According to the present invention, it is difficult to realize with a conventional light oil composition by using a deep oil hydrorefined gas oil having the above-mentioned specific properties and a low oil kerosene having the above-mentioned specific properties in combination. Thus, a diesel fuel composition that has reduced particulate matter (PM) and fine particles discharged from the engine, improved fuel efficiency, has little effect on members, and has excellent performance at low temperature startability is provided.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
In the present invention, a petroleum hydrocarbon hydrorefined oil having a sulfur content of 5 ppm to 10 ppm and a boiling point range of 150 ° C. to 380 ° C. is used as a feedstock, and the reaction temperature is present in the presence of a hydrogenation catalyst. 170-320 ° C., hydrogen pressure 2-10 MPa, LHSV 0.1-2 h^-1The 90% distillation temperature obtained by deep hydrogenation at a hydrogen / oil ratio of 100 to 800 NL / L is 200 ° C. or higher and 380 ° C. or lower, and the density at 15 ° C. is 780 kg / m.^ThreeMore than 870kg / m^ThreeHereinafter, a deep hydrorefined gas oil having a sulfur content of 5 mass ppm or less, a naphthene content of 30% by volume or more and an aromatic content of 1% by volume or less is used.
[0015]
The deep hydrorefined gas oil according to the present invention is a gas oil fraction obtained by hydrotreating a predetermined feedstock. Examples of the raw oil include straight-run gas oil obtained from a crude oil atmospheric distillation apparatus, straight-run heavy oil obtained from an atmospheric distillation apparatus and residual oil obtained by treating the crude oil with a vacuum distillation apparatus, Catalytic cracked diesel oil and hydrocracked diesel oil obtained by catalytic cracking or hydrocracking of light diesel oil or desulfurized heavy oil, hydrorefined diesel oil and hydrodesulfurized diesel oil obtained by hydrorefining these petroleum hydrocarbons, etc. Can be mentioned.
[0016]
The hydrorefining of the petroleum-based hydrocarbons is performed using a hydrodesulfurization apparatus generally used in petroleum refining. Generally, the reaction temperature is 300 to 380 ° C., the hydrogen pressure is 3 to 8 MPa, and the LHSV is 0.3 to 2 h.^-1The hydrogen / oil ratio is 100 to 500 NL / L.
As a catalyst used for hydrorefining, a general hydrodesulfurization catalyst can be applied. As the active metal, normally, Group 6A and Group 8 metals of the periodic table are preferably used, and examples thereof include Co—Mo, Ni—Mo, Co—W, and Ni—W. As the carrier, a porous inorganic oxide mainly composed of alumina is used. These conditions and the catalyst are not particularly limited as long as the properties of the raw material oil are satisfied.
[0017]
The raw material oil of the deep hydrorefining gas oil in the present invention is obtained by the hydrorefining process described above, and it is necessary that the sulfur content is 5 mass ppm to 10 mass ppm and the boiling point range is 150 ° C. to 380 ° C. is there. When the sulfur content and boiling point range of the feedstock oil are within the above ranges, the properties defined in the deep hydrorefined gas oil of the present invention can be achieved easily and reliably.
[0018]
The deep hydrorefined gas oil of the present invention is obtained by hydrotreating the above-mentioned feedstock in the presence of a hydrogenation catalyst.
The hydrotreating conditions are as follows: reaction temperature 170-320 ° C., hydrogen pressure 2-10 MPa, LHSV 0.1-2 h.^-1The hydrogen / oil ratio is 100 to 800 NL / L. Preferably, the reaction temperature is 175 to 300 ° C., the hydrogen pressure is 2.5 to 8 MPa, and the LHSV is 0.2 to 1.5 h.^-1, Hydrogen / oil ratio 150-600 NL / L, more preferably reaction temperature 180 ° C.-280 ° C., hydrogen pressure 3-7 MPa, LHSV 0.3-1.2 h^-1The hydrogen / oil ratio is 150 to 500 NL / L. The lower the reaction temperature, the more advantageous for the hydrogenation reaction, but not for the desulfurization reaction. The higher the hydrogen pressure and the hydrogen / oil ratio, the more the desulfurization and hydrogenation reactions are promoted, but there is an optimal point economically. The lower the LHSV, the better the reaction, but if it is too low, it is disadvantageous because it requires an extremely large reaction column volume and excessive capital investment.
[0019]
The apparatus for hydrotreating the feedstock may be of any configuration, the reaction towers may be used alone or in combination, and hydrogen may be additionally injected between the reaction towers, gas-liquid separation operation or hydrogen sulfide. You may have the removal equipment.
A fixed bed system is preferably employed as the reaction mode of the hydrotreating apparatus. Hydrogen can take either a countercurrent or cocurrent flow with respect to the feedstock, and may have a plurality of reaction towers and a combination of countercurrent and cocurrent. As a general format, it is a down flow, and a gas-liquid twin parallel flow format is preferable. 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.
[0020]
The catalyst used for the hydrotreatment is a catalyst in which a hydrogenation active metal is supported on a porous carrier. An inorganic oxide is mentioned as a porous support | carrier. Specific inorganic oxides include alumina, titania, zirconia, boria, silica, or zeolite. In the present invention, at least one of titania, zirconia, boria, silica, and zeolite is composed of alumina. Things are good. The production method is not particularly limited, but any preparation method can be employed using raw materials in various sols, salt compounds, and the like corresponding to each element. Furthermore, once the composite hydroxide or composite oxide such as silica alumina, silica zirconia, alumina titania, silica titania, and alumina boria is prepared, the preparation process in the state of alumina gel and other hydroxides or in an appropriate solution state It may be prepared by adding at any step. The ratio of alumina to other oxides can be any ratio with respect to the porous carrier, but preferably alumina is 90% or less, more preferably 60% or less, more preferably 40% or less.
[0021]
Zeolite is a crystalline aluminosilicate, such as faujasite, pentasil, mordenite, etc., which is ultra-stabilized by a predetermined hydrothermal treatment and / or acid treatment, or one whose alumina content in the zeolite is adjusted is used. be able to. Preferably, faujasite and mordenite, particularly preferably Y type and beta type are used. The Y-type is preferably ultra-stabilized, and the ultra-stabilized zeolite by hydrothermal treatment forms new pores in the range of 20 to 100% in addition to the original pore structure called micropores of 20 cm or less. . Known conditions can be used for the hydrothermal treatment conditions.
[0022]
The active metal of the catalyst used for the hydrotreatment is at least one metal selected from Group 8 metals of the periodic table. Preferably, it is at least one selected from Ru, Rd, 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, etc. can be employed. 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.
[0023]
Metal loading may be performed after the completion of the entire preparation process of the porous support, or after further preloading on an appropriate oxide, composite oxide, zeolite in the intermediate process of porous support preparation, Heat concentration and kneading may be performed.
The amount of the active metal supported is not particularly limited, but is 0.1 to 10% by mass, preferably 0.15 to 5% by mass, and more preferably 0.2 to 3% by mass with respect to the catalyst mass.
The catalyst is preferably used after a preliminary 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.
[0024]
The 90% distillation temperature (hereinafter also referred to as T90) of the deep hydrorefined gas oil according to the present invention is 200 ° C. or higher in order to suppress adverse effects on the operation performance associated with the lightening of excessive distillation properties. And preferably 210 ° C. or higher, more preferably 220 ° C. or higher, further preferably 230 ° C. or higher, and even more preferably 240 ° C. or higher. The T90 needs to be 380 ° C. or less, preferably 370 ° C. or less, more preferably 360 ° C. or less, and further preferably, from the viewpoint of suppressing an increase in particulate matter (PM) discharged from the engine. Is 350 ° C. or lower, more preferably 340 ° C. or lower. The 90% distillation temperature here means a value measured by JIS K 2254 “Petroleum product-distillation test method”.
[0025]
Further, the density of the deep hydrorefined gas oil according to the present invention at 15 ° C. is 780 kg / m from the viewpoint of securing the calorific value.^ThreeOr more, preferably 790 kg / m^ThreeOr more, more preferably 800 kg / m^ThreeThat's it. The density is 870 kg / m from the point of reducing NOx and PM emissions.^ThreeOr less, preferably 860 kg / m^ThreeOr less, more preferably 850 kg / m^ThreeOr less, more preferably 840 kg / m^ThreeIt is as follows. 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”.
[0026]
Further, the sulfur content of the deep hydrorefined gas oil according to the present invention needs to be 5 ppm by mass or less from the viewpoint of reducing harmful exhaust components discharged from the engine and improving the performance of the exhaust gas aftertreatment device, preferably It is 3 mass ppm or less, more preferably 2 mass ppm or less, and still more preferably 1 mass ppm 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”.
[0027]
The naphthene content of the deep hydrorefined gas oil according to the present invention needs to be 30% by volume or more, preferably 32% by volume or more, and more preferably 35% by volume or more. When the naphthene content of the deep hydrorefined gas oil is within the above range, the properties defined in the gas oil composition of the present invention can be achieved more easily and reliably. The naphthene content mentioned here is the volume percentage (volume%) of naphthene measured according to ASTM D2786 “Standard Test Method for Hydrocarbon Types Analysis of Gas-Oil Saturates Fractions by High Ionizing Voltage Mass Spectrometry”. Means.
[0028]
The aromatic content of the deep hydrorefined gas oil according to the present invention needs to be 1% by volume or less, preferably 0.8% by volume or less, and preferably 0.5% by volume or less. More preferred. When the aromatic content of the deep hydrorefined gas oil is within the above range, the properties defined in the gas oil composition of the present invention can be achieved more easily and reliably. In addition, aromatic content here is measured based on the Petroleum Institute Journal 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.
[0029]
The light oil composition in the present invention contains 20% by volume or more of the specific deep hydrorefined light oil. The blending amount of the deep hydrorefining gas oil according to the present invention can be appropriately set according to the blending amount of other base materials and the practical performance (for example, low-temperature flow performance and lubrication performance) as a commercial fuel oil. In order to simultaneously reduce the particulate matter (PM) and fine particles discharged from the fuel, improve fuel efficiency, have little influence on the member, and achieve excellent performance at low temperature startability, preferably 30% by volume or more, More preferably, it is 40 volume% or more, More preferably, it is 50 volume% or more.
When the content of the deep hydrorefined gas oil is less than 20% by volume, the above-described effects of the present invention cannot be achieved at the same time.
[0030]
In the present invention, unrefined oil and / or hydrorefined oil is used as raw material oil together with deep hydrorefined light oil, reaction temperature is 220 to 350 ° C., hydrogen pressure is 1 to 6 MPa, LHSV0 in the presence of a hydrogenation catalyst. .1-10h^-1, Sulfur content obtained by hydrogenation at a hydrogen / oil ratio of 10 to 300 NL / L, 5 mass ppm or less, Total aromatic content 25 vol% or less, Bicyclic or aromatic content 1 volume %, A low-sulfur kerosene having a naphthene content of 20% by volume or more and a boiling point range of 140 to 300 ° C. is used.
[0031]
Such low sulfur kerosene is a kerosene fraction obtained by hydrotreating a predetermined feedstock. The raw oil is mainly straight-run kerosene obtained by atmospheric distillation of crude oil, but hydrocracked kerosene produced together with hydrocracked light oil and hydrogen obtained by hydrotreating the above kerosene fraction. Examples include chemical kerosene, natural gas, asphalt, and synthetic kerosene made from coal.
[0032]
A raw material oil as a hydrorefined oil is obtained by hydrorefining a petroleum hydrocarbon using a general hydrodesulfurization apparatus in petroleum refining. Usually, reaction temperature 220-350 ° C, hydrogen pressure 1-6MPa, LHSV 0.1-10h^-1The hydrogen / oil ratio is 10 to 300 NL / L.
A general hydrodesulfurization catalyst can be applied as the catalyst. As the active metal, Group 6A and Group 8 metals of the periodic table are usually used, and examples thereof include Co—Mo, Ni—Mo, Co—W, and Ni—W. As the carrier, a porous inorganic oxide mainly composed of alumina is used. These conditions and the catalyst are not particularly limited as long as the properties of the raw material oil are satisfied.
[0033]
The low sulfur kerosene of the present invention can be obtained by hydrotreating (desulfurizing and refining) the above-mentioned feedstock in the presence of a hydrogenation catalyst.
The hydrotreating conditions are: reaction temperature 220-350 ° C., hydrogen pressure 1-6 MPa, LHSV 0.1-10 h.^-1The hydrogen / oil ratio is 10 to 300 NL / L. Preferably, the reaction temperature is 250 ° C. to 340 ° C., the hydrogen pressure is 2 to 5 MPa, and the LHSV is 1 to 10 h.^-1The hydrogen / oil ratio is 30 to 200 NL / L, more preferably the reactivity is 270 ° C. to 330 ° C., the hydrogen pressure is 2 to 4 MPa, and LHSV 2 to 10 h.^-1The hydrogen / oil ratio is 50 to 200 NL / L. The lower the reaction temperature, the more advantageous for the hydrogenation reaction, but not for the desulfurization reaction. The higher the hydrogen pressure and the hydrogen / oil ratio, the more the desulfurization and hydrogenation reactions are promoted, but there is an optimal point economically. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, a very large reaction tower volume is required, resulting in an excessive capital investment.
[0034]
The apparatus for hydrotreating the feedstock may be of any configuration, the reaction towers may be used alone or in combination, and hydrogen may be additionally injected between the reaction towers, gas-liquid separation operation or hydrogen sulfide. You may have the removal equipment.
A fixed bed system is preferably employed as the reaction mode of the hydrotreating apparatus. Hydrogen can take either a countercurrent or cocurrent flow with respect to the feedstock, and may have a plurality of reaction towers and a combination of countercurrent and cocurrent. As a general format, it is a down flow, and a gas-liquid twin parallel flow format is preferable. 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.
[0035]
The catalyst used for the hydrotreatment is a catalyst in which a hydrogenation active metal is supported on a porous carrier. An inorganic oxide is mentioned as a porous support | carrier. Specific inorganic oxides include alumina, titania, zirconia, boria, silica, or zeolite. In the present invention, at least one of titania, zirconia, boria, silica, and zeolite is composed of alumina. Things are good. The production method is not particularly limited, but any preparation method can be employed using raw materials in various sols, salt compounds, and the like corresponding to each element. Furthermore, once the composite hydroxide or composite oxide such as silica alumina, silica zirconia, alumina titania, silica titania, and alumina boria is prepared, the preparation process in the state of alumina gel and other hydroxides or in an appropriate solution state It may be prepared by adding at any step. The ratio of alumina to other oxides can be any ratio with respect to the porous carrier, but preferably alumina is 90% or less, more preferably 60% or less, more preferably 40% or less.
[0036]
Zeolites are crystalline aluminosilicates such as faujasite, pentasil, mordenite, etc., which are ultra-stabilized by a predetermined hydrothermal treatment and / or acid treatment, or those whose alumina content in the zeolite is adjusted. be able to. Preferably, faujasite and mordenite, particularly preferably Y type and beta type are used. The Y type is preferably ultra-stabilized, and the zeolite that has been super-stabilized by hydrothermal treatment forms new pores in the range of 20 to 100 加 え in addition to the original pore structure called micropores of 20 Å or less. . Known conditions can be used for the hydrothermal treatment conditions.
[0037]
The active metal of the catalyst used for the hydrotreatment is at least one metal selected from Group 6A metals of the periodic table. Preferably, it is at least one selected from Mo and W. The active metal may be a combination of a Group 6A metal and a Group 8 metal, specifically, a combination of Mo, W and Co, Ni. For example, Co—Mo, Co—W, Ni—Mo, Ni Combinations such as -W, Co-Ni-Mo, and Co-Ni-W can be employed. 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.
[0038]
Metal loading may be performed after the completion of the entire preparation process of the porous support, or after further preloading on an appropriate oxide, composite oxide, zeolite in the intermediate process of porous support preparation, Heat concentration and kneading may be performed.
The amount of the active metal supported is not particularly limited, but is 0.1 to 10% by mass, preferably 0.15 to 5% by mass, and more preferably 0.2 to 3% by mass with respect to the catalyst mass.
The catalyst is preferably used after a preliminary 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.
[0039]
The low-sulfur kerosene according to the present invention is obtained by the above-described hydrorefining treatment, and has a sulfur content of 5 mass ppm or less, a total aromatic content of 25 vol% or less, and a bicyclic or higher aromatic content of 1 vol. %, Naphthene content 20% by volume or more, and boiling point range 140 ° C. or more and 300 ° C. or less are required.
[0040]
In order to easily and reliably achieve the desired properties in the light oil composition of the present invention, the properties of this low sulfur kerosene are as follows: sulfur content 5 mass ppm or less, total aromatic content 25 volume% or less, 2 A low-sulfur kerosene having a ring or higher aromatic content of 1% by volume or less, a naphthene content of 20% by volume or more, and a boiling point range of 140 to 300 ° C. is used.
[0041]
Further, the sulfur content of the low sulfur kerosene is required to be 5 mass ppm or less, preferably 3 mass ppm or less, more preferably 2 mass ppm or less, from the viewpoint of reducing the load on the exhaust gas aftertreatment device. More preferably, it is 1 mass ppm 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”.
[0042]
In addition, the aromatic content of the low sulfur kerosene needs to be 25% by volume or less in order to suppress deterioration of exhaust gas performance. It is preferably 20% by volume or less, more preferably 15% by volume or less. Similarly, the aromatic content of two or more rings must be 1% by volume or less, preferably 0.8% by volume or less, and more preferably 0.5% by volume or less. In addition, aromatic content here and aromatic content of 2 or more rings are the Petroleum Institute Journal JPI-5S-49-97 “Hydrocarbon Type Test Method—High Speed Liquid” published by the Japan Petroleum Institute. It means the volume percentage (volume%) of the aromatic content measured according to “chromatographic method”.
[0043]
The naphthene content of the low sulfur kerosene according to the present invention is required to be 20% by volume or more, preferably 25% by volume or more, and preferably 30% by volume or more from the viewpoint of fuel efficiency and output maintenance. Is more preferable, and 35% by volume or more is even more preferable. When the naphthene content of the low sulfur kerosene is within the above range, the properties defined in the light oil composition of the present invention can be achieved more easily and reliably. The naphthene content, the volume percentage (volume%) of naphthene measured in accordance with ASTM D2786 “Standard Test Method for Hydrocarbon Types Analysis of Gas-Oil Saturates Fractions by High Ionizing Voltage Mass Spectrometry”. means.
[0044]
The boiling point range of low sulfur kerosene should be 140 to 300 ° C. in order to suppress adverse effects on operating performance and the like due to excessive lightening of distillation properties and to suppress deterioration of exhaust gas performance due to increased heavy components. Necessary, preferably 145 to 290 ° C, more preferably 150 to 280 ° C, still more preferably 150 to 270 ° C. Here, T90 means a value measured according to JIS K 2254 “Petroleum product-distillation test method”.
[0045]
Further, the density of the kerosene base material at 15 ° C. is not particularly limited, but is preferably 750 kg / m in order to easily and reliably achieve the desired properties in the light oil composition of the present invention.^ThreeOr more, more preferably 760 kg / m^ThreeOr more, more preferably 770 kg / m^ThreeThat's it. The density is preferably 820 kg / m.^ThreeOr less, more preferably 810 kg / m^ThreeOr less, more preferably 800 kg / m^ThreeIt is as follows. 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".
[0046]
The blending amount of the low sulfur kerosene according to the present invention can be set as appropriate according to the content of the deep hydrorefined gas oil and the practical performance as a commercial fuel oil (for example, low-temperature flow performance and lubrication performance). In view of the reduction effect, the improvement effect of fuel consumption, the influence on the members, etc., in order to enhance the effect, it is preferably 70% by volume or less, more preferably 60% by volume or less, further preferably 50% by volume or less, and still more preferably Is 40% by volume or less, most preferably 30% by volume or less.
[0047]
In the category satisfying the fuel properties required by the present invention, the light oil composition in the present invention, in addition to deep hydrorefined light oil and low sulfur kerosene, other light oil bases, other kerosene bases, synthetic light oils and One or more kinds of synthetic kerosene can be blended.
[0048]
Other light oil bases and other kerosene bases specifically include straight run diesel oil / kerosene obtained from crude oil atmospheric distillation equipment, straight run heavy oil and residual oil obtained from atmospheric distillation equipment Gasoline oil / kerosene obtained by treating the gas oil in a vacuum distillation unit, and hydrorefined gas oil / kerosene obtained by hydrotreating the above light oil in a hydrorefining device according to the sulfur content. Hydrodesulfurized diesel oil / kerosene obtained by hydrodesulfurization in one or more stages, hydrocracked diesel oil / kerosene obtained by hydrocracking the above various diesel oil bases, etc. can be used.
[0049]
The properties of these light oil bases are not particularly limited, but in order to easily and reliably achieve the desired properties in the light oil composition of the present invention, it is preferable to have the specific properties described later.
The sulfur content of the light oil / kerosene base material is preferably 10 mass ppm or less, more preferably 5 mass ppm or less, still more preferably 3 mass ppm or less, and most preferably 1 mass ppm 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”.
[0050]
The aromatic content of the light oil / kerosene base is not particularly limited, but is preferably 5% by volume or less, more preferably 3% by volume or less, and further preferably 1% by volume or less. preferable. In addition, aromatic content here is measured based on the Petroleum Institute Journal JPI-5S-49-97 “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method” published by the Japan Petroleum Institute. It means the volume percentage (volume%) of the aromatic content.
[0051]
The above-mentioned synthetic light oil and synthetic kerosene refer to synthetic light oil and synthetic kerosene obtained by chemically synthesizing natural gas, asphalt, coal and the like as raw materials. Chemical synthesis methods include indirect liquefaction method and direct liquefaction method, and typical synthesis methods include Fischer-Trops synthesis method, but the synthetic light oil used in the present invention is limited by these production methods. is not. Synthetic light oil and synthetic kerosene are generally composed of saturated hydrocarbons, and are composed of normal paraffins, isoparaffins, and naphthenes. That is, synthetic light oil and synthetic kerosene generally contain almost no aromatic content.
[0052]
In order to easily and reliably achieve the desired properties in the light oil composition of the present invention, the synthetic light oil and the synthetic kerosene preferably have specific properties described later.
The density of the synthetic light oil at 15 ° C. is preferably 720 kg / m^ThreeOr more, more preferably 730 kg / m^ThreeOr more, more preferably 740 kg / m^ThreeOr more, more preferably 750 kg / m^ThreeThat's it. The density is preferably 840 kg / m.^ThreeOr less, more preferably 830 kg / m^ThreeOr less, more preferably 820 kg / m^ThreeBelow, even more preferably 810 kg / m^ThreeIt is as follows.
The density of synthetic kerosene at 15 ° C. is preferably 700 kg / m.^ThreeOr more, more preferably 710 kg / m^ThreeOr more, more preferably 720 kg / m^ThreeOr more, more preferably 730 kg / m^ThreeThat's it. The density is preferably 800 kg / m.^ThreeOr less, more preferably 790 kg / m^ThreeOr less, more preferably 780 kg / m^ThreeBelow, even more preferably 770 kg / m^ThreeIt is as follows.
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".
[0053]
The sulfur content of the synthetic light oil and the synthetic kerosene is preferably 5 ppm by mass or less, more preferably 3 ppm by mass or less, still more preferably 2 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”.
[0054]
In the light oil composition of the present invention, if necessary, an appropriate amount of a cetane number improver can be blended to improve the cetane number of the resulting light oil composition.
As the cetane number improver, various compounds known as light oil cetane number improvers can be arbitrarily used, and examples thereof include nitrate esters and organic peroxides. These cetane number improvers may be used alone or in combination of two or more.
[0055]
In the present invention, it is preferable to use a nitrate ester among the cetane number improvers described above. Such nitrate esters include 2-chloroethyl nitrate, 2-ethoxyethyl nitrate, isopropyl nitrate, butyl nitrate, primary amyl nitrate, secondary amyl nitrate, isoamyl nitrate, primary hexyl nitrate, Various nitrates such as secondary hexyl nitrate, n-heptyl nitrate, n-octyl nitrate, 2-ethylhexyl nitrate, cyclohexyl nitrate, and ethylene glycol dinitrate are included. An alkyl nitrate of 6-8 is preferred.
[0056]
The content of the cetane improver is preferably 500 ppm by mass or more based on the total amount of the composition, more preferably 600 ppm by mass or more, further preferably 700 ppm by mass or more, and 800 ppm by mass or more. Even more preferably, it is most preferably 900 ppm by mass or more. When the content of the cetane number improver is less than 500 ppm by mass, a sufficient cetane number improving effect cannot be obtained, and PM, aldehydes, and further NOx in diesel engine exhaust gas tend not to be sufficiently reduced. Further, the upper limit of the content of the cetane number improver is not particularly limited, but is preferably 1400 mass ppm or less, more preferably 1250 mass ppm or less, based on the total amount of the light oil composition, and 1100 mass ppm or less. It is more preferable that it is 1000 mass ppm or less.
[0057]
As the cetane number improver, one synthesized according to a conventional method may be used, or a commercially available product may be used. In addition, what is marketed as a cetane number improver is usually obtained in a state where an active ingredient contributing to cetane number improvement (that is, cetane number improver itself) is diluted with an appropriate solvent. When preparing the light oil composition of this invention using such a commercial item, it is preferable that content of the said active ingredient in a light oil composition becomes in the above-mentioned range.
[0058]
In the light oil composition of the present invention, additives other than the cetane number improver can be blended as necessary, and in particular, a lubricity improver and / or a detergent is preferably blended.
As the lubricity improver, for example, one or more of carboxylic acid-based, ester-based, alcohol-based, and phenol-based lubricity improvers can be arbitrarily used. 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.
[0059]
The blending amount of the lubricity improver is not particularly limited as long as the HFRR wear scar diameter (WS1.4) is within a preferable range described later, but is preferably 35 ppm by mass or more based on the total amount of the composition, and 50 ppm by mass. More preferably. When the blending amount of the lubricity improver is within the above range, the effectiveness of the blended lubricity improving agent 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. Further, the upper limit of the blending amount is preferably 150 mass ppm or less on the basis of the total amount of the composition, and more preferably 105 mass ppm or less because an effect commensurate with the addition amount cannot be obtained even if it is added more. preferable.
[0060]
Examples of the detergent include imide compounds; alkenyl succinimides such as polybutenyl succinimides synthesized from polybutenyl succinic anhydrides and ethylene polyamines; polyhydric alcohols such as pentaerythritol and polybutyls. Succinic acid esters such as polybutenyl succinic acid ester synthesized from tenyl succinic anhydride; copolymer polymers such as dialkylaminoethyl methacrylate, polyethylene glycol methacrylate, vinyl pyrrolidone and alkyl methacrylate copolymers, carboxylic acids and amines Ashless detergents such as reaction products of alkenyl succinic acid imide and reaction products of carboxylic acid and amine are preferred. These detergents can be used alone or in combination of two or more.
[0061]
Examples of using an alkenyl succinimide include a case where an alkenyl succinimide having a molecular weight of about 1000 to 3000 is used alone, an alkenyl succinimide having a molecular weight of about 700 to 2000, and an alkenyl succinimide having a molecular weight of about 10,000 to 20000. May be used in combination.
The carboxylic acid constituting the reaction product of the carboxylic acid and the amine may be one type or two or more types. Specific examples thereof include fatty acids having 12 to 24 carbon atoms and carbon atoms having 7 to 24 carbon atoms. An aromatic carboxylic acid etc. are mentioned. Examples of the fatty acid having 12 to 24 carbon atoms include linoleic acid, oleic acid, palmitic acid, myristic acid, and the like, but are not limited thereto. In addition, examples of the aromatic carboxylic acid having 7 to 24 carbon atoms include benzoic acid and salicylic acid, but are not limited thereto. Moreover, the amine which comprises the reaction product of carboxylic acid and an amine may be 1 type, or may be 2 or more types. The amine used here is typically oleylamine, but is not limited thereto, and various amines can be used.
[0062]
The blending amount of the cleaning agent is not particularly limited, but in order to bring out the effect of blending the cleaning agent, specifically, the effect of suppressing clogging of the fuel injection nozzle, the blending amount of the cleaning agent is 30 mass ppm based on the total amount of the composition. It is preferable to set it as the above, It is more preferable to set it as 60 mass ppm or more, It is further more preferable to set it as 80 mass ppm or more. Even if an amount less than 30 ppm by mass is added, the effect may not appear. On the other hand, if the amount is too large, an effect commensurate with that cannot be expected, and conversely, NOx, PM, aldehydes, etc. in the diesel engine exhaust gas may increase, so the amount of detergent contained is 300 mass. It is preferably not more than ppm, and more preferably not more than 180 mass ppm.
[0063]
As in the case of the above cetane improver, those commercially available as lubricity improvers or detergents are in a state where the active ingredients contributing to lubricity improvement or cleaning are diluted with an appropriate solvent, respectively. It is usually obtained at When such a commercial product is blended in the light oil composition of the present invention, the content of the active ingredient in the light oil composition is preferably within the above range.
[0064]
Further, for the purpose of further improving the performance of the light oil composition in the present invention, other known fuel oil additives (hereinafter referred to as “other additives” for convenience) described later may be added alone or in combination of several kinds. it can. Other additives include, for example, low-temperature fluidity improvers such as ethylene-vinyl acetate copolymer and alkenyl succinic acid amide; antioxidants such as phenols and amines; metal deactivators such as salicylidene derivatives; Anti-icing agents such as polyglycol ethers; corrosion inhibitors such as aliphatic amines and alkenyl succinic acid esters; antistatic agents such as anionic, cationic and amphoteric surfactants; colorants such as azo dyes; Antifoaming agents and the like.
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 0.2% by mass or less, based on the total amount of the light oil composition. is there.
[0065]
  As described above, the light oil composition of the present invention comprises 20% by volume or more of the specific deep hydrorefined light oil, 20% by volume or more of the specific low sulfur kerosene, and a synthetic light oil blended as necessary. And a synthetic kerosene, a cetane number improver, a lubricity improver, a detergent and other additives. More specifically, as a whole light oil composition, the sulfur content is 5 mass ppm or less, Aromatic content 3 vol% to 12 vol%, aromatic benzene content of 14 or less carbon atoms in aromatic content is 80% or higher, naphthene content is 30 vol% or higher, density at 810 kg / m³840 kg / m or more³Hereinafter, the clogging point (CFPP) of −10 ° C. or less is achieved at the same time. MoreIn addition,In addition to this, the kinematic viscosity at 30 ° C. is 2 mm.²/ S or more 5mm²/ S or less, distillation property 90% distillation temperature 280 ° C. or higher and 350 ° C. or lower, cetane number 50 or higher and 70 or lower, HFRR wear scar diameter (WS 1.4) 400 μmLess thanIs achieved at the same time.
[0066]
The sulfur content in the light oil composition of the present invention is required to be 5 mass ppm or less as described above, preferably 3 mass ppm or less, more preferably 2 mass ppm or less, and even more preferably 1 mass% or less. It is. When the sulfur content exceeds 5 mass ppm, the effect of reducing the environmental load becomes insufficient. The sulfur content here means the sulfur content based on the total amount of the light oil composition, measured by JIS K 2541 “Sulfur Content Test Method”.
[0067]
The aromatic content in the light oil composition of the present invention needs to be 12% by volume or less from the viewpoint of NOx and PM reduction. More preferably, it is 10 volume% or less. The aromatic content needs to be 3% by volume or more, preferably 5% by volume or more. If the aromatic content is less than 3% by volume, there is a concern about the influence on the material used for the injection pump.
[0068]
Among the aromatic components in the light oil composition of the present invention, the alkylbenzene content ratio composed of 14 or less carbon atoms (C14) or less needs to be 80% or more of the total aromatic content. When the content of the alkylbenzene having 14 or less carbon atoms is lower than 80%, there is a large amount of heavy aromatics, so that NOx and PM may increase. Therefore, 80% or more is necessary, preferably 85% or more, more preferably 90% or more, and further preferably 95% or more.
The aromatic content of two or more rings in the aromatic content is preferably 1% by volume or less, more preferably 0.5% by volume or less, and still more preferably 0.2% by volume or less. . When the aromatic content of the two or more rings exceeds the upper limit, NOx and PM emissions in the exhaust gas increase, and the effect of reducing the environmental load becomes insufficient. In addition, aromatic content here is measured based on the Petroleum Institute Journal 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. For the calculation of the alkylbenzene (partial aromatic content) ratio of 14 or less carbon atoms, mass spectrometry by the FI ionization method was applied. Derived from alkylbenzene having 14 or less carbon atoms from mass analysis under measurement conditions in accordance with “type analysis of lubricating base oil by mass spectrometer” (Hamakawa Satoshi, Nisseki Review, Vol. 33, No. 4, P135-142) The peak intensity and the peak intensity derived from the total aromatic component were measured and summed, and the ratio was calculated by dividing the both by calculating the ratio (%) of alkylbenzene having 14 or less carbon atoms.
[0069]
In the light oil composition of the present invention, the naphthene compound content is preferably 95% by volume or less, more preferably 90% by volume or less, from the viewpoint of influence on exhaust gas performance, 85 More preferably, it is not more than volume%, and most preferably not more than 80 volume%. Further, the content of the naphthene compound is required to be 30% by volume or more from the viewpoint of fuel economy and output improvement, preferably 32% by volume or more, and more preferably 35% by volume or more. The naphthene compound content in the present invention is a volume percentage (volume%) of naphthene measured according to ASTM D2786 “Standard Test Method for Hydrocarbon Types Analysis of Gas-Oil Saturates Fractions by High Ionizing Voltage Mass Spectrometry”. ).
[0070]
The density at 15 ° C. in the light oil composition of the present invention is 810 kg / m 2 in terms of fuel efficiency and acceleration.^ThreeOr more, preferably 815 kg / m^ThreeMore preferably, 820 kg / m^ThreeThat's it. In addition, the density is 840 kg / m from the viewpoint of a decrease in PM concentration in the exhaust gas.^ThreeOr less, preferably 835 kg / m^ThreeOr less, more preferably 830 kg / m^ThreeIt is as follows. 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”.
[0071]
The clogging point (CFPP) of the light oil composition of the present invention is required to be −10 ° C. or lower and preferably −12.5 ° C. or lower from the viewpoint of preventing the prefilter clogging of a diesel vehicle. Even more preferably, it is −15 ° C. or lower. Here, the clogging point refers to a clogging point measured according to JIS K 2288 “Light oil—clogging point test method”.
[0072]
The distillation property in the light oil composition of the present invention is not particularly limited to the 10% distillation temperature, but is preferably 250 ° C. or less, more preferably 240 ° C. or less, further preferably 230 ° C. or less, and even more preferably 225. ° C or lower, most preferably 220 ° C or lower. If the 10% distillation temperature exceeds the upper limit, the exhaust gas performance tends to deteriorate. The 10% distillation temperature is preferably 160 ° C or higher, more preferably 170 ° C or higher, and further preferably 180 ° C or higher. If the 10% distillation temperature is less than the lower limit, engine output and startability at high temperatures tend to deteriorate.
[0073]
As a distillation property in the light oil composition of the present invention, a 90% distillation temperature is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, and further preferably 330 ° C. or lower. When the 90% distillation temperature exceeds the upper limit, the amount of PM and fine particles discharged tends to increase. The 90% distillation temperature is preferably 280 ° C. or higher, more preferably 285 ° C. or higher, further preferably 290 ° C. or higher, even more preferably 295 ° C. or higher, and most preferably 300 ° C. or higher. If the 90% distillation temperature is less than the lower limit, the fuel efficiency improvement effect becomes insufficient and the engine output tends to decrease. The 10% distillation temperature and 90% distillation temperature here mean values measured by JIS K 2254 “Petroleum product-distillation test method”.
[0074]
The kinematic viscosity at 30 ° C. of the light oil composition of the present invention is 2 mm.²/ S or more, preferably 2.2 mm²/ S or more is preferable, and 2.4 mm²/ S or more is more preferable. The kinematic viscosity is 2mm²If it is less than / s, the fuel injection timing control on the fuel injection pump side tends to be difficult, and the lubricity in each part of the fuel injection pump mounted on the engine may be impaired.
Further, the kinematic viscosity at 30 ° C. of the light oil composition of the present invention is 5 mm.²/ S or less, preferably 4.7 mm²/ S or less is more preferable, 4.5 mm²/ S or less is more preferable. The kinematic viscosity is 5mm²If it exceeds / 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.
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".
[0075]
The cetane number in the light oil composition of the present invention is preferably 50 or more, more preferably 52 or more, and further preferably 54 or more. When the cetane number is less than 50, the concentration of NOx, PM and aldehydes in the exhaust gas tends to be high. Further, from the viewpoint of reducing black smoke in the exhaust gas, the cetane number is preferably 70 or less, more preferably 68 or less, and further preferably 66 or less. 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.
[0076]
Although there is no restriction | limiting in particular regarding the cetane index of the light oil composition of this invention, It is preferable that it is 48 or more. When the cetane index is less than 48, the concentration of PM, aldehydes, or NOx in the exhaust gas tends to increase. For the same reason, the cetane index is more preferably 50 or more, and further preferably 52 or more. 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 a cetane number improver is not 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.
[0077]
  The light oil composition of the present invention preferably has a HFRR wear scar diameter (WS1.4) of 400 μm or less.Under andIt is desirable to have the following lubricating performance. When the HFRR wear scar diameter (WS1.4) exceeds 400 μm, especially in a diesel engine equipped with a distributed injection pump, it increases the driving torque of the pump during operation and increases the wear of each part of the pump. 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 “Diesel Oil-Lubricity Test Method” issued by the Japan Petroleum Institute. Means.
[0078]
In the light oil composition of the present invention, the ash content is preferably less than 0.01% by mass. If the ash content exceeds the upper limit, the ash becomes the core of PM during the combustion process in the engine, and the total amount of PM and the amount of nanoparticles increase. Further, even when the ash is discharged as it is, the ash is deposited on the exhaust gas post-processing device, and the performance of the post-processing device may be deteriorated. Furthermore, an adverse effect on the fuel injection system can be considered.
The ash content in the present invention means a value measured by JIS K 2272 “Crude oil and petroleum product ash content and sulfate ash test method”.
[0079]
In addition, the pour point in the light oil composition of the present invention is preferably −10 ° C. or less from the viewpoint of low temperature startability or low temperature operability and maintenance of injection performance in the electronically controlled fuel injection pump. More preferably, the temperature is -15 ° C or lower, further preferably -15 ° C or lower, and most preferably -20 ° C or lower. Here, the pour point means a pour point measured by JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.
[0080]
In the light oil composition of the present invention, from the viewpoint of storage stability, the total insoluble content after the oxidation stability test is preferably 2.0 mg / 100 mL or less, more preferably 1.0 mg / 100 mL or less. Preferably, it is more preferably 0.5 mg / 100 mL or less, still more preferably 0.3 mg / 100 mL or less, and most preferably 0.1 mg / 100 mL or less. The oxidation stability test here is conducted under conditions of 95 ° C. and oxygen bubbling for 16 hours in accordance with ASTM D2274-94. The total insoluble matter after the oxidation stability test here means a value measured in accordance with the oxidation stability test.
[0081]
In the light oil composition of the present invention, the peroxide value after the oxidation stability test is preferably 10 ppm by mass or less, more preferably 5 ppm by mass or less, and further preferably from the viewpoint of storage stability and compatibility with members. Is 2 ppm by mass or less, and more preferably 1 ppm by mass or less. Here, the peroxide value means a value measured in accordance with the Petroleum Institute Standard JPI-5S-46-96.
To the light oil composition of the present invention, additives such as an antioxidant and a metal deactivator can be appropriately added in order to reduce the total insoluble matter and the peroxide value.
[0082]
Moreover, although the electrical conductivity in the light oil composition in this invention is not specifically limited, From the point of safety, it is preferable that it is 50 pS / m or more.
In order to improve the electrical conductivity, an antistatic agent or the like can be appropriately added to the light oil composition of the present invention. Here, the conductivity means a value measured in accordance with JIS K 2276 “Petroleum products—aviation fuel oil test method”.
【The invention's effect】
As described above, the light oil composition of the present invention is a conventional light oil composition comprising a deep hydrorefined light oil having the above-mentioned specific properties and a low-sulfur kerosene having the above-mentioned specific properties. It can reduce the particulate matter (PM) and fine particles discharged from the engine, which has been difficult to realize with a product, improve fuel efficiency, have little influence on the components, and have excellent performance at low temperature startability .
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, this invention is not limited to these Examples at all.
[0083]
(Examples 1-3 and Comparative Examples 1-2)
The hydrorefined light oil and untreated kerosene were hydrotreated under the conditions shown in Table 1 to obtain deep hydrorefined light oil and low sulfur kerosene. Table 2 shows the properties of hydrorefined gas oil and untreated kerosene. Table 2 also shows the properties of the deep hydrorefined gas oil and low sulfur kerosene. Table 2 also shows the properties of hydrocracked light oil and synthetic light oil used as base materials for light oil compositions in Examples and Comparative Examples.
[0084]
Various base materials and additives were blended to prepare light oil compositions shown in Table 3 (Examples 1 to 3 and Comparative Examples 1 and 2).
In addition, the additive used was as follows.
Cetane number improver: 2-ethylhexyl nitrate
Lubricant improver: Carboxylic acid mixture based on linoleic acid
Detergent: Reaction product of oleic amine and carboxylic acid mixture based on oleic acid
Low temperature fluidity improver: ethylene-vinyl acetate copolymer
[0085]
The blending ratio of the blended diesel oil composition, and the blended diesel oil composition, the density at 15 ° C., the kinematic viscosity at 30 ° C., the sulfur content, the distillation property, the aromatic content, and the fragrance of two or more rings Group content, C14 or lower alkylbenzene ratio, naphthene content, cetane index and cetane number, wear scar diameter, clogging point, pour point, ash content, oxidative stability test Table 3 shows the results of measurement of dissolved content, peroxide value, and conductivity.
[0086]
The properties of the 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 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”.
[0087]
All the distillation properties are values measured by JIS K 2254 "Petroleum products-Distillation test method".
The aromatic content and the aromatic content of two or more rings are determined by the Petroleum Institute Method JPI-5S-49-97 “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method” published by the Japan Petroleum Institute. It means the volume percentage (volume%) of the aromatic content that has been observed and complied with.
The ratio of alkylbenzenes having 14 or less carbon atoms (partial aromatic content) was determined by applying mass analysis by the FI ionization method, and “type analysis of lubricant base oil by mass spectrometer” (Satoshi Hamakawa, Nisseki Review, Vol. 33, No. 4, by mass spectrometry under measurement conditions based on P135-142), the peak intensity derived from alkylbenzene having 14 or less carbon atoms and the peak intensity derived from total aromatics are respectively measured and summed, and both are removed. The ratio (%) of alkylbenzene having 14 or less carbon atoms was calculated.
The naphthene compound content means a volume percentage (volume%) of naphthene measured in accordance with ASTM D2786 “Standard Test Method for Hydrocarbon Types Analysis of Gas-Oil Saturates Fractions by High Ionizing Voltage Mass Spectrometry”.
[0088]
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”.
[0089]
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. .
The clogging point refers to a clogging point measured by JIS K 2288 “Light oil—clogging point test method”.
The pour point refers to a pour point measured according to JIS K 2269 “Crude point of petroleum and petroleum products and a cloud point test method of petroleum products”.
Ash content means a value measured by JIS K 2272 “Crude oil and petroleum product ash and sulfate ash test method”.
The total insoluble matter after the oxidation stability test means a value measured under conditions of 95 ° C. and oxygen bubbling for 16 hours in accordance with ASTM D2274-94.
The peroxide value means a value measured according to the Petroleum Institute Standard JPI-5S-46-96.
The conductivity means a value measured in accordance with JIS K 2276 “Petroleum product-aviation fuel oil test method”.
[0090]
As shown in Table 3, the light oil compositions used in the examples and comparative examples are prepared by preparing several kinds of light oil bases at a specific blending ratio.
As is apparent from Table 3, the 90% distillation temperature (T90), the density at 15 ° C., the sulfur content, the naphthene content, and the aromatic content are all within the ranges defined in the present invention. Deep hydrorefined gas oil is 20% by volume or more, and the sulfur content, aromatic content, bicyclic or higher aromatic content, naphthene content, and boiling range are all within the ranges specified in the present invention. In Examples 1 to 3 containing 20% by volume or more of the low sulfur kerosene, the sulfur content is 5 mass ppm or less, the total aromatic content is 3% by volume to 12% by volume, carbon of the aromatic content. The alkylbenzene content ratio of several 14 or less is 80% or more, the naphthene content is 30% by volume or more, and the density at 15 ° C. is 810 kg / m.^Three840 kg / m or more^ThreeHereinafter, a light oil composition having a clogging point of −10 ° C. or lower could be obtained easily and reliably. On the other hand, in Comparative Examples 1 and 2 in which a light oil composition was prepared without using the above-described specific deep hydrorefined light oil and low-sulfur kerosene, the light oil composition targeted by the present invention is not necessarily obtained.
[0091]
Next, various tests shown below were performed using the light oil compositions of Examples 1 to 3 and Comparative Examples 1 and 2. All test results are shown in Table 4. As can be seen from the results in Table 4, the light oil compositions of Examples 1 to 3 have less PM and the number of particles, better fuel efficiency, and better acceleration performance than the light oil compositions of Comparative Examples 1 and 2. It is clear that the low temperature startability is good and the rubber swelling performance is excellent.
[0092]
The test method related to the engine unit test conforms to Annex 29 “Technical Standards for Diesel Vehicle 13-Mode Emission Measurement” supervised by the former Ministry of Transport. It conforms to Appendix 27 “Technical Standards for Diesel Vehicle 10/15 Mode Exhaust Gas Measurement”.
[0093]
(Vehicle exhaust gas test, fuel consumption test)
PM and fuel consumption were measured using the following diesel engine vehicle (vehicle 1). PM collected the exhaust gas diluted in the whole dilution tunnel with a fluorocarbon-coated glass fiber filter and analyzed it. The test mode is performed in a transient operation mode that simulates the actual driving shown in FIG. 1, the exhaust gas component is calculated as an emission amount per 1 km of the test mode, and the result when the fuel of Comparative Example 1 is tested is set to 100. The results were relatively compared and quantified. For fuel consumption, the fuel volume flow rate consumed during the test mode is corrected for fuel temperature, and the weight value is replaced with the result when the fuel of Comparative Example 1 is used as 100. Turned into.
[0094]
(Vehicle specifications): Vehicle 1
Engine type: Supercharged inline 4-cylinder diesel with intercooler
Displacement: 3L
Compression ratio: 18.5
Maximum output: 125kW / 3400rpm
Maximum torque: 350Nm / 2400rpm
Compliance with regulations: 1997 emissions regulations compliance
Vehicle weight: 1900kg
Mission: 4AT
Exhaust gas aftertreatment device: oxidation catalyst
[0095]
(Measurement of fine particles)
When measuring the number of particles, the scanning mobility particle size analyzer shown in FIG. 2 was used to separate and detect the number of particles for each particle size. That is, in the apparatus shown in FIG. 2, a charge distribution control unit a, a classification unit b, and a particle number measurement unit c are provided in order from the upstream side of the flow path through which the diluted exhaust gas sample passes. The fine particles in the diluted exhaust gas are in an equilibrium charge distribution state in the charge distribution control unit a, and are classified (separated) in accordance with the electric mobility of each particle in the classification unit b. And the particle | grain count part c measures the particle | grains isolate | separated for every particle size.
In the test, the vehicle 1 is operated in the test mode shown in FIG. 1 in the same manner as the exhaust gas test, and particles collected during the test period by the above apparatus are classified into a total number of particles and particles (nanoparticles) having a diameter of 100 nm or less. The results when the fuel of Comparative Example 1 was used as a test were set as 100, and the results were relatively compared and quantified.
[0096]
(Vehicle driving performance / acceleration performance evaluation)
Evaluation was performed using the above-described diesel engine-equipped vehicle (vehicle 1) on a chassis dynamometer (gradient condition: 5%) maintained at an environmental temperature of 25 ° C. and an environmental humidity of 60%. In the test, after the vehicle is sufficiently warmed up, the vehicle is maintained at a constant speed of 40 km / h, the throttle (accelerator) is fully opened after a predetermined time, and the time until the vehicle reaches 60 km / h is measured. And the improvement effect of acceleration performance was judged.
[0097]
(Low temperature startability)
On the chassis dynamometer that can control the environmental temperature using the vehicle 2, at room temperature, (1) flush the fuel system of the test diesel vehicle with the evaluation fuel, (2) extract the flushing fuel, (3) ▼ Replace the main filter with a new one, and ④Put the specified amount of evaluation fuel (1/2 of the fuel tank capacity of the vehicle under test) into the fuel tank. Then, (5) rapidly cool the ambient temperature from room temperature to 5 ° C, (6) hold at 5 ° C for 1 hour, and (7) set a predetermined temperature (-12, -14 ° 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 the engine does not start even after 10 seconds of cranking is repeated twice at 30 second intervals, it is not possible (x), and if the engine is started between two times of cranking is repeated (◯).
[0098]
(Vehicle specifications): Vehicle 2
Engine type: Supercharged inline 4-cylinder diesel with intercooler
Displacement: 3.2L
Compression ratio: 17
Maximum output: 130kW / 3800rpm
Maximum torque: 380 Nm / 2000 rpm
Regulatory compliance: 1998 exhaust gas regulatory compliance
Vehicle weight: 2150 kg
Mission: 4AT
Exhaust gas aftertreatment device: oxidation catalyst
[0099]
(Rubber swelling test)
In order to confirm the influence on the rubber member used in the O-ring or the like of the engine part, a soaking test was performed according to the following procedure. Conforms to MIL R6855, with acrylonitrile, which is one of the compounds constituting the rubber, having a combined acrylonitrile mass center value of nitrile rubber (medium nitrile rubber) that is 25% or more and 35% or less of the total as a rubber member to be evaluated. Then, the test fuel is heated and held at 100 ° C., and the test rubber member is immersed in it for 70 hours. Evaluation is made by comparing and quantifying the volume change of the test rubber member after 70 hours. Judgment is that the volume change rate absolute value before and after the test is ± 20% or more is rejected (x), the case of ± 10% or more and within ± 20% is borderline (△), and the case is within ± 10% (○).
[0100]
[Table 1]

[0101]
[Table 2]

[0102]
[Table 3]

[0103]
[Table 4]

[Brief description of the drawings]
FIG. 1 is a diagram showing a test mode in an exhaust gas test.
FIG. 2 is a schematic view of a scanning mobility particle size analyzer used for measuring the number of particles.
[Explanation of symbols]
a Charge distribution controller
b Classifier
c Particle Count Unit

Claims (2)

A petroleum hydrocarbon hydrorefined oil having a sulfur content of 5 mass ppm to 10 mass ppm and a boiling point range of 150 ° C. or higher and 380 ° C. or lower as a raw material oil, a reaction temperature of 170 to 320 ° C. in the presence of a hydrogenation catalyst, 90% distillation temperature obtained by deep hydrotreating at a hydrogen pressure of 2 to 10 MPa, LHSV 0.1 to 2 h ⁻¹ and a hydrogen / oil ratio of 100 to 800 NL / L is a density at 200 ° C. to 380 ° C. and 15 ° C. There 780 kg / ^{m 3} or more 870 kg / ^{m 3} or less, sulfur content is 5 ppm by mass or less, a naphthene content and aromatic content above 30% by volume the amount of content is not more than 1 volume% deep hydrotreated gas oil 20% by volume or more, and raw oil is unrefined oil and / or hydrorefined oil, reaction temperature is 220 to 350 ° C., hydrogen pressure is 1 to 6 MPa in the presence of a hydrogenation catalyst, L HSV 0.1-10 h ⁻¹ , sulfur content obtained by hydrotreating with hydrogen / oil ratio 10-300 NL / L 5 mass ppm or less, total aromatic content 25 volume% or less, 2 or more rings 1% by volume or less of aromatic content, 20% by volume or more of naphthenic content, 20% by volume or more of low sulfur kerosene having a boiling range of 140 to 300 ° C. Aromatic content 3% to 12%, aromatic benzene content of 14 or less carbon atoms in aromatics 80% or more, naphthene content 30% or more, 15 ° C. density 810kg / m ³ or more 840kg / ^{m 3} or less, clogging point -10 ° C. or less, a kinematic viscosity at 30 ° C. is ^{2 mm} 2 / s or more ^{5 mm} 2 / s or less, distillation properties 90% distillation temperature of 280 ° C. or higher 350 ° C. or less, a cetane number 5 70 inclusive, HFRR wear scar diameter (WS 1.4) gas oil composition characterized in that it is 400μm or less. A petroleum hydrocarbon hydrorefined oil having a sulfur content of 5 mass ppm to 10 mass ppm and a boiling point range of 150 ° C. or higher and 380 ° C. or lower as a raw material oil, a reaction temperature of 170 to 320 ° C. in the presence of a hydrogenation catalyst, 90% distillation temperature obtained by deep hydrotreating at a hydrogen pressure of 2 to 10 MPa, LHSV 0.1 to 2 h ⁻¹ and a hydrogen / oil ratio of 100 to 800 NL / L is a density at 200 ° C. to 380 ° C. and 15 ° C. There 780 kg / ^{m 3} or more 870 kg / ^{m 3} or less, sulfur content is 5 ppm by mass or less, a naphthene content and aromatic content above 30% by volume the amount of content is not more than 1 volume% deep hydrotreated gas oil 20% by volume or more, and raw oil is unrefined oil and / or hydrorefined oil, reaction temperature is 220 to 350 ° C., hydrogen pressure is 1 to 6 MPa in the presence of a hydrogenation catalyst, L HSV 0.1-10 h ⁻¹ , sulfur content obtained by hydrotreating with hydrogen / oil ratio 10-300 NL / L 5 mass ppm or less, total aromatic content 25 volume% or less, 2 or more rings By blending 20 vol% or more of low sulfur kerosene having an aromatic content of 1 vol% or less, a naphthene content of 20 vol% or more, and a boiling point range of 140 to 300 ° C, a sulfur content of 5 mass ppm or less, Aromatic content 3% to 12%, aromatic benzene content of 14 or less carbon atoms in aromatics 80% or more, naphthene content 30% or more, 15 ° C. density 810kg / m ³ or more 840kg A method for producing a light oil composition, comprising producing a light oil composition having a / m ³ or less and a clogging point of -10 ° C or less.

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