JP2009040855A - Gas oil composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas oil composition comprising a low-environmental load type gas oil base material produced from a triglyceride-containing hydrocarbon which is a component derived from an animal and vegetable oil and fat as a raw material and exhibiting excellent life-cycle CO<SB>2</SB>emission characteristics and oxidation stability and further excellent member stability. <P>SOLUTION: The gas oil composition is produced by mixing 95-30 vol.% of a gas oil base material with 5-70 vol.% of a petroleum-based hydrotreated oil. The gas oil base material is obtained by mixing 10-90 vol.% of the low-environmental load type gas oil base material with 90-10 vol.% of a hydrocracked gas oil fraction. The low-environmental load type gas oil base material is produced by bringing an oil to be treated into contact with a catalyst comprising a prescribed porous inorganic oxide and an active metal in the presence of hydrogen under prescribed reaction conditions. The oil to be treated is prepared by mixing the animal and vegetable oil and fat and/or the component derived from the animal and vegetable oil and fat with a sulfur-containing hydrocarbon compound. The gas oil composition has ≤360°C 90% recovered temperature, ≤10 mass ppm sulfur content, ≤1 mass% oxygen content, ≤3.5 mass% content of a fatty acid alkyl ester, ≤0.13 mgKOH/g total acid value, ≤0.01 mass% methanol content, ≤0.01 mass% glyceride content and ≤-5°C cold filter plugging point. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to an atmospheric low-residue oil obtained by treating an environmentally low load light oil base material and crude oil or the like produced using animal and vegetable oils and / or triglyceride-containing hydrocarbons derived from animal and vegetable oils and fats with an atmospheric distillation apparatus. A hydrocracked gas oil fraction obtained by further hydrocracking a vacuum gas oil obtained by subsequent treatment with a vacuum distillation apparatus (hereinafter also referred to as a hydrocracked gas oil fraction purified from crude oil or the like), Oil composition obtained by mixing gas oil refined from crude oil, etc., and petroleum-based hydrotreated oil having a kerosene fraction, having excellent life cycle CO ₂ emission characteristics and oxidation stability, and excellent low-temperature fluidity It is about things.

Conventionally, as the base material for light oil, hydrogenated straight-run kerosene obtained from crude oil atmospheric distillation equipment, hydrogenated or hydrodesulfurized straight-oil light oil obtained from crude oil atmospheric distillation equipment The thing etc. which performed the process and the hydrodesulfurization process 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).
Patent Document 1 (Japanese Patent Application Laid-Open No. 2003-171670) discloses natural fats and oils, waste natural fats and oils for the purpose of providing a method for producing hydrocarbons using natural fats and oils or derivatives thereof and edible waste oils as raw materials. Disclosed is a method for producing hydrocarbons, characterized by reacting the derivative with activated hydrogen in the presence of a catalyst selected from the group consisting of a metal catalyst, an alloy catalyst, a metal-supported catalyst, and an alloy-supported catalyst. Yes.
Patent Document 2 (Japanese Patent Publication No. 2005-538204) discloses 0.1 to 99% by volume of a component or a mixture of components prepared from biological raw materials originating from plants and / or animals and / or fish. And the fuel composition for diesel engines which contains 0-20 volume% of components containing oxygen is disclosed. Here both components are said to be mixed with diesel components based on crude oil and / or fractions from the Fischer-Tropsch process.
Patent Document 3 (Japanese Patent Application Laid-Open No. 2004-189885) discloses an environment-friendly type comprising a methyl ester or ethyl ester of a saturated or unsaturated fatty acid having 6 to 20 carbon atoms, or a mixture thereof. A diesel fuel composition is disclosed.
However, it is very difficult to design a high-quality fuel that can simultaneously achieve the required performance such as life cycle CO ₂ emission characteristics, oxidation stability, and low-temperature performance at a high level, and there are various demands for commercial fuel oil. It does not disclose a manufacturing method that satisfies the performance sufficiently and is realistic.
JP 2003-171670 A JP 2005-538204 A JP 2004-189885 A Seiichi Konishi, “Introduction to Fuel Engineering”, Saika Hanafusa, March 1991, p. 136-144

By the way, in recent years, reduction of sulfur content and aromatic content in light oil, which is a fuel for internal combustion engines, has been demanded with the aim of promptly improving the air environment and reducing the environmental load. At the same time, in order to cope with the global warming problem, there is a demand for fuel properties that contribute to further improvement in fuel efficiency and reduce carbon dioxide (CO ₂ ). Synthetic fuels and renewable energy are one of the solutions. The use of biodiesel fuel, which is energy (hereinafter also referred to as BDF), as an alternative fuel is being studied.

  BDF is mainly a mixture of fatty acid alkyl esters made from natural animal and plant oils and fats. Influence of poisoning on aromatic compounds and exhaust gas aftertreatment catalysts that are considered to have a large contribution to soot formation in exhaust gas Since it is an oxygen-containing compound that has almost no sulfur content and has oxygen in the molecule, it has attracted attention as a promising candidate for alternative fuels. In addition, because it is plant-derived, it is positioned as renewable energy, so the international carbon dioxide reduction protocol signed in 1997, the so-called Kyoto Protocol, does not count carbon dioxide derived from BDF as an emission amount. The BDF also has a policy merit.

  However, fatty acid alkyl esters using natural animal and vegetable oils and fats as raw materials are inherently heavy, and there is a concern that unburned hydrocarbon emissions during combustion may increase due to poor burn-off in engine combustion and the like. In addition, since fatty acid alkyl esters are oxygen-containing compounds, there is a concern of increasing the emission of aldehydes during combustion. In the case of BDF containing a large amount of fatty acid alkyl ester having many saturated fatty acid groups, it is solid even at room temperature, so it is inferior in handling as a fuel, and it is difficult to ensure fluidity at low temperature. In the case of BDF containing a lot of unsaturated fatty acid groups, its chemical composition is inferior in oxidative stability, and there is concern about deterioration of hue, generation of sludge, and adverse effects on engine members. Furthermore, the fatty acid glyceride, the alkyl alcohol, and the glycerin mixture, which is a by-product, which are raw materials for purifying the fatty acid alkyl ester are extremely concerned about adverse effects on engine members and fuel injection systems.

These tendencies are not seen in the existing light oil, etc., so not only when using BDF alone, but also when mixing with existing light oil, etc. In addition to paying attention to the properties of the BDF itself, it is necessary to pay more attention to oxidation stability, low-temperature performance, combustibility, and the like even when mixed with existing light oil.
Therefore, regarding the provision of a light oil composition that has excellent life cycle CO ₂ emission characteristics and oxidation stability as well as reduction of harmful exhaust components, and good low-temperature performance, BDF, which is a mixture of fatty acid alkyl esters made from natural animal and vegetable oils and fats, is used. In use, these performance improvements cannot be achieved simultaneously. Furthermore, because these engine performances are closely related to other fuel properties, it is very difficult to design high-quality fuels that can simultaneously achieve these required performances at a high level, and are required as commercial fuel oils. There are no examples or knowledge based on the examination of practical manufacturing methods that satisfy the various performances.

The present invention has been made in view of such a situation, and the object thereof is an environmentally low load type light oil base material, crude oil, etc. produced from animal and vegetable oils and / or triglyceride-containing hydrocarbons derived from animal and vegetable oils and fats. To life cycle CO ₂ emission characteristics and oxidation stability obtained by mixing hydrocracked gas oil fraction refined from oil, gas oil refined from crude oil, etc. and petroleum hydrotreated oil having kerosene fraction An object of the present invention is to provide a light oil composition that is excellent and has excellent low-temperature fluidity.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.

That is, the first of the present invention is an oil to be treated in which sulfur-containing hydrocarbon compounds are mixed with animal and vegetable oils and / or components derived from animal and vegetable oils and fats so that the sulfur content is 1 mass ppm to 2 mass% in the presence of hydrogen. Porous inorganic oxides containing two or more elements selected from aluminum, silicon, zirconium, boron, titanium, and magnesium, and periodic groups 6A and 6C supported on the porous inorganic oxides A catalyst containing one or more metals selected from Group 8 elements, a hydrogen pressure of 2 to 13 MPa, a liquid space velocity of 0.1 to 3.0 h ⁻¹ , a hydrogen / oil ratio of 150 to 1500 NL / L, a reaction temperature A normal pressure residue oil obtained by treating 10 to 90% by volume of a fraction (environmental low load gas oil base material) produced by contacting under conditions of 150 to 480 ° C. and crude oil etc. with an atmospheric distillation apparatus. Continued It is obtained by mixing 90 to 10% by volume of a hydrocracked gas oil fraction (boiling point range: 200 to 350 ° C.) obtained by further hydrocracking a vacuum gas oil obtained by treating with a vacuum distillation apparatus. Obtained by mixing 5-70 vol% of petroleum-based hydrotreated oil (light oil substrate B) obtained by hydrotreating gas oil fraction refined from crude oil etc. into light oil substrate A95-30 vol% 90% distillation temperature is 360 ° C. or less, sulfur content is 10 mass ppm or less, oxygen content is 1 mass% or less, fatty acid alkyl ester content is 3.5 mass% or less, total acid value is 0.13 mg KOH / g or less, methanol content The present invention relates to a light oil composition comprising light oil base materials A and B, characterized by being 0.01% by mass or less, a glyceride content of 0.01% by mass or less, and a clogging point of −5 ° C. or less.

The second aspect of the present invention is a petroleum-based base material having 10 to 90% by volume of animal and vegetable oils and / or animal and vegetable oils and fat-derived components and a light oil fraction refined from crude oil and the like in the presence of hydrogen. A porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and a period carried on the porous inorganic oxide A catalyst containing one or more metals selected from the elements of Group 6A and Group 8 of the table, hydrogen pressure 2-13 MPa, liquid space velocity 0.1-3.0 h ⁻¹ , hydrogen / oil ratio 150 Crude oil or the like is treated with an atmospheric distillation apparatus to 10 to 90% by volume of a fraction (environmental low load type light oil base material) produced by contact under conditions of ˜1500 NL / L and reaction temperature of 150 to 480 ° C. Obtained 90 to 10% by volume of hydrocracked gas oil fraction (boiling range: 200 to 350 ° C.) obtained by further hydrocracking the vacuum gas oil obtained by subsequently treating the atmospheric residue with a vacuum distillation apparatus Gas oil base material A ′ obtained in the process of 95 to 30% by volume of petroleum-based hydrotreated oil (light oil base material B ′) obtained by hydrotreating kerosene fraction refined from crude oil or the like 90% distillation temperature obtained by mixing 70% by volume, 360 ° C. or less, sulfur content 10 mass ppm or less, oxygen content 1% by mass or less, fatty acid alkyl ester content 3.5% by mass or less, total acid value 0 A gas oil composition comprising gas oil bases A ′ and B ′, having a methanol content of 0.01 mass% or less, a glyceride content of 0.01 mass% or less, and a clogging point of −5 ° C. or less. It is about things.

According to the present invention, an environmentally low load gas oil base produced using animal and vegetable fats and / or triglyceride-containing hydrocarbons derived from animal and vegetable fats and oils, a hydrocracked gas oil fraction purified from crude oil, and the like, and crude oil By mixing gas-oil refined from oil, petroleum-based hydrotreated oil having kerosene fraction, it has excellent life cycle CO ₂ emission characteristics and oxidation stability, which were difficult to realize with conventional gas oil compositions. A light oil composition having a low temperature performance is provided.

Hereinafter, the present invention will be described in detail.
The environmentally low load light oil base material according to the present invention is a low sulfur and low oxygen fraction obtained by hydrotreating a predetermined raw material oil. The predetermined raw material oil is a mixed oil (treated oil) obtained by mixing a sulfur-containing hydrocarbon compound with a component derived from animal and vegetable oils and / or animal and vegetable oils and fats so that the sulfur content is 1 mass ppm to 2 mass%, Alternatively, a mixed oil (treated oil) obtained by mixing 10 to 90% by volume of a component derived from animal and vegetable oils and / or animal and vegetable fats and oils and 90 to 10% by volume of a petroleum base material having a light oil fraction refined from crude oil or the like. It is.

  The animal and vegetable oil and / or animal and vegetable oil / fat-derived component in the present invention refers to an animal and vegetable oil and / or fat that is produced and / or produced naturally or artificially and / or a component that is produced and / or produced from these oil and fat. Examples of animal fats and animal oil materials include beef tallow, milk lipid (butter), pork tallow, sheep fat, whale oil, fish oil, liver oil, and the like. Examples include rapeseed (rapeseed), rice bran, sunflower, cottonseed, corn, soybeans, sesame seeds, and other parts of the linseed, but other fats and oils can be used without problems. These raw oils may be solid or liquid, but it is preferable to use vegetable oils and vegetable oils as raw materials because of ease of handling, high carbon dioxide absorption capacity and high productivity. Moreover, in this invention, the waste oil which used these animal oils and vegetable oils for consumer use, industrial use, food use etc. can also be used as a raw material after adding the removal process of miscellaneous matters.

As a typical composition of the fatty acid part of the glyceride compound contained in the animal and vegetable oils and fats and components derived from animal and vegetable oils and fats, butyric acid (C ₃ H ₇ COOH) which is a fatty acid having no unsaturated bond in a molecular structure called saturated fatty acid , Caproic acid (C ₅ H ₁₁ COOH), caprylic acid (C ₇ H ₁₅ COOH), capric acid (C ₉ H ₁₉ COOH), lauric acid (C ₁₁ H ₂₃ COOH), myristic acid (C ₁₃ H ₂₇ COOH) , Palmitic acid (C ₁₅ H ₃₁ COOH), stearic acid (C ₁₇ H ₃₅ COOH), and oleic acid (C ₁₇ H ₃₃ COOH), an unsaturated fatty acid having one or more unsaturated bonds, linoleic acid (C ₁₇ H ₃₁ COOH), linolenic acid _{(C 17} H 29 COOH), ricinoleic acid _(C 17 _{H 32 (} H) COOH) and the like. The hydrocarbon part of these fatty acids in natural substances is generally linear, but it is used in the present invention even if it has a structure having a side chain, that is, an isomer, as long as the properties defined in the present invention are satisfied. be able to. Further, the position of the unsaturated bond in the molecule of the unsaturated fatty acid is not limited to those generally found in nature as long as the properties defined in the present invention are satisfied in the present invention. The set one can also be used.
Animal and vegetable oils and fats and components derived from animal and vegetable oils have one or more of these fatty acids, and the fatty acids they have differ depending on the raw materials. For example, coconut oil has a relatively large amount of saturated fatty acids such as lauric acid and myristic acid, while soybean oil has a large amount of unsaturated fatty acids such as oleic acid and linoleic acid.

Although it does not restrict | limit especially as a sulfur-containing hydrocarbon compound which mixes with animal and vegetable fat and / or animal and vegetable fat origin components, and forms a to-be-processed oil, Specifically, sulfide, disulfide, polysulfide, thiol, thiophene, benzothiophene, dibenzo Examples include thiophene and derivatives thereof. The sulfur-containing hydrocarbon compound contained in the oil to be treated may be a single compound or a mixture of two or more. Alternatively, a petroleum hydrocarbon fraction containing a sulfur content may be used in place of the sulfur-containing hydrocarbon compound.
The mixing ratio of the sulfur-containing hydrocarbon compound is such that the sulfur content of the oil to be treated is 1 mass ppm to 2 mass%, preferably 10 mass ppm to 1 mass%.

The hydrogenation conditions of the raw material oil (the oil to be treated) are performed under the conditions of a hydrogen pressure of 2 to 13 MPa, a liquid space velocity of 0.1 to 3.0 h ⁻¹ , and a hydrogen / oil ratio of 150 to 1500 NL / L. Desirably, conditions such as hydrogen pressure 3-12 MPa, liquid space velocity 0.2-2.0 h ⁻¹ , hydrogen / oil ratio 200-1200 NL / L are more desirable, hydrogen pressure 4-10.5 MPa, liquid space velocity 0.25. The conditions of -1.0 h < ^-1 > and hydrogen oil ratio 300-1000 NL / L are further desirable. All of these conditions are factors that influence the reaction activity. For example, when the hydrogen pressure and the hydrogen / oil ratio are less than the lower limit values, there is a risk of causing a decrease in reactivity or a rapid decrease in activity. When the pressure and the hydrogen / oil ratio exceed the upper limit values, there is a possibility that excessive equipment investment such as a compressor may be required. The lower the liquid space velocity, the more advantageous the reaction. However, if the liquid space velocity is less than the lower limit, a very large reaction tower volume is required, which tends to result in excessive capital investment. Tend not to progress sufficiently.

  The reaction temperature is preferably in the range of 150 to 480 ° C., preferably 220 to 400 ° C., more preferably 260 to 360 ° C., in order to obtain the decomposition rate of the target raw material heavy oil fraction or the target fraction yield. Set to range. When the reaction temperature is less than the lower limit, the reaction may not proceed sufficiently. When the reaction temperature exceeds the upper limit, decomposition proceeds excessively, and the liquid product fraction tends to decrease. is there.

  The type of the hydrotreating reactor may be a fixed bed system. That is, hydrogen can take either a countercurrent or a cocurrent flow with respect to the raw material oil, or a combination of countercurrent and cocurrent flow having a plurality of reaction towers. As a general format, it is a down flow, and a gas-liquid twin parallel flow format can be adopted. In addition, the reactors may be used singly or in combination, and a structure in which one reactor is divided into a plurality of catalyst beds may be adopted. In the present invention, the distillate oil hydrotreated in the reactor is fractionated into predetermined fractions through a gas-liquid separation step, a rectification step and the like. At this time, there is a possibility that hydrogen sulfide may be generated if the moisture or raw material oil produced by the reaction contains sulfur, but gas-liquid separation equipment is used between the reactors or in the product recovery process. And other by-product gas removal devices may be installed.

  In general, hydrogen gas is introduced from the inlet of the first reactor before or after passing through the heating furnace, but separately from this, the temperature in the reactor is controlled and the reactor is as much as possible. It may be introduced between the catalyst beds or between a plurality of reactors in order to maintain the hydrogen pressure throughout. The hydrogen thus introduced is referred to as quench hydrogen. At this time, the ratio of quench hydrogen to hydrogen introduced accompanying the feedstock is desirably 10 to 60% by volume, more desirably 15 to 50% by volume. When the ratio of quench hydrogen is lower than the lower limit, the reaction at the subsequent reaction site may not proceed sufficiently, and when it exceeds the upper limit, the reaction near the reactor inlet may not proceed sufficiently.

  As a support for the hydrogenation catalyst, a porous inorganic oxide containing two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium is used. Generally, it is a porous inorganic oxide containing alumina, and examples of other carrier constituents include silica, titania, zirconia, boria, magnesia and the like. Desirably, it is a complex oxide containing at least one selected from alumina and other constituent components. Moreover, phosphorus may be included as another component. The total content of components other than alumina is preferably 1 to 20% by weight, and more preferably 2 to 15% by weight. If the total content of components other than alumina is less than 1% by weight, a sufficient catalyst surface area cannot be obtained and the activity may be lowered. If it exceeds 20% by weight, the acidity of the support May increase, leading to a decrease in activity due to coke formation. When phosphorus is included as a carrier constituent, the content is preferably 1 to 5% by weight, more preferably 2 to 3.5% by weight in terms of oxide.

  The raw material to be a precursor of silica, titania, zirconia, boria, magnesia, which is a carrier constituent other than alumina, is not particularly limited, and a solution containing general silicon, titanium, zirconium, boron, magnesium can be used. . For example, silicic acid, water glass and silica sol for silicon, titanium sulfate, titanium tetrachloride and various alkoxide salts for titanium, zirconium sulfate and various alkoxide salts for zirconium, boric acid for boron, magnesium for magnesium, etc. Magnesium nitrate or the like can be used. As phosphorus, phosphoric acid or an alkali metal salt of phosphoric acid can be used.

  It is desirable that the raw materials for the carrier constituents other than alumina be added in any step prior to the firing of the carrier. For example, an aluminum hydroxide gel containing these components may be added to an aluminum aqueous solution in advance, or may be added to a prepared aluminum hydroxide gel, or water or an acidic aqueous solution may be added to a commercially available alumina intermediate or boehmite powder. May be added to the kneading step, but a method of coexisting at the stage of preparing aluminum hydroxide gel is more desirable. Although the mechanism of the effect of these carrier constituents other than alumina has not been elucidated, it is thought that they form a complex oxide state with aluminum, which increases the surface area of the carrier and some interaction with the active metal. It is considered that the activity is affected by producing the action.

  The active metal of the hydrogenation catalyst contains at least one metal selected from Group 6A and Group 8 metals of the periodic table, preferably two or more metals selected from Groups 6A and 8 Contains. For example, Co—Mo, Ni—Mo, Ni—Co—Mo, Ni—W, and the like can be mentioned. In hydrogenation, it is preferable to convert these metals into a sulfide state.

  As for the content of the active metal, for example, the total supported amount of W and Mo is preferably 12 to 35% by weight, more preferably 15 to 30% by weight based on the catalyst weight in terms of oxide. If the total supported amount of W and Mo is less than 12% by weight, the activity may decrease due to a decrease in the number of active sites. If it exceeds 35% by weight, the metal is not effectively dispersed, and similarly It may cause a decrease in activity. The total supported amount of Co and Ni is preferably 1.5 to 10% by weight, more preferably 2 to 8% by weight based on the catalyst weight in terms of oxide. If the total supported amount of Co and Ni is less than 1.5% by weight, a sufficient cocatalyst effect may not be obtained and the activity may be reduced. If it is more than 10% by weight, the metal is effective. In the same manner, there is a possibility of causing activity.

  In any catalyst of the hydrogenation catalyst, the method of incorporating the active metal into the catalyst is not particularly limited, and a known method applied when producing a normal desulfurization catalyst can be used. Usually, a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed. Further, an equilibrium adsorption method, a pore-filling method, an incident-wetness method, and the like are also preferably employed. For example, the pore-filling method is a method in which the pore volume of the support is measured in advance and impregnated with the same volume of the metal salt solution, but the impregnation method is not particularly limited, and the amount of metal supported Further, it can be impregnated by an appropriate method depending on the physical properties of the catalyst support.

  As described above, an environment-friendly light oil base material is produced by hydrotreating an oil to be treated, in which a sulfur-containing hydrocarbon compound is mixed with a component derived from animal and vegetable fats and / or animal and plant fats and oils under predetermined conditions. .

  The first light oil composition of the present invention is prepared by subjecting the atmospheric low-residue light oil base material produced above to 10 to 90% by volume and the atmospheric residual oil obtained by treating crude oil or the like with an atmospheric distillation apparatus, followed by decompression. A gas oil base obtained by mixing 90 to 10% by volume of a hydrocracked gas oil fraction (boiling point range: 200 to 350 ° C.) obtained by further hydrocracking a vacuum gas oil obtained by treating with a distillation apparatus. A predetermined performance is obtained by mixing 95 to 30% by volume of the material A with 5 to 70% by volume of a petroleum hydrotreated oil (light oil base material B) obtained by hydrotreating a light oil fraction refined from crude oil or the like. It consists of filled light oil bases A and B.

The above hydrocracked gas oil fraction is obtained by further hydrocracking a vacuum gas oil obtained by treating a crude oil etc. with an atmospheric distillation apparatus and subsequently treating an atmospheric residue oil with a vacuum distillation apparatus. The boiling point range is 200 to 350 ° C.
The hydrocracking treatment method is not particularly limited, but a heavy feed oil such as vacuum gas oil is passed over a catalyst having a dual function of cracking and hydrogenation under high-temperature and high-pressure hydrogen conditions, Examples of the hydrocracking method include desulfurization and denitrogenation as well as hydrocracking. The resolution of the catalyst tends to be attributed to the porous solid acid support. As the solid acid carrier, amorphous carriers such as silica-alumina, silica-magnesia, silica-zirconia, and silica-titania, and crystalline carriers such as zeolite subjected to various modifications and modifications are used. The hydrogenating ability is exhibited by being supported by combining two or three kinds of metals such as Ni, Co, Mo, W, Pd, and Pt. Among them, a combination of Co-Mo, Ni-Mo, and Ni-W Is preferred.
The hydrogen pressure in hydrocracking is usually 5 MPa or more and 20 MPa or less, preferably 8 MPa or more and 15 MPa or less. Moreover, reaction temperature is 350 degreeC or more and 430 degrees C or less normally. The liquid space velocity is usually from 0.1 / h to 1.0 / h, preferably from 0.2 / h to 0.4 / h.

  The mixing ratio of the environmentally low load type light oil base and the hydrocracked light oil fraction in the light oil base A is preferably 20 to 80% by volume: 80 to 20% by volume, and 40 to 60% by volume: 60 to 40% by volume. More preferred.

Petroleum hydrotreated oil (light oil base material B) having a gas oil fraction refined from crude oil, etc., is a straight-run gas oil obtained from a crude oil atmospheric distillation device, and a straight-run heavy oil obtained from an atmospheric distillation device Petroleum hydrocarbons such as catalytic cracked light oil or hydrocracked diesel oil obtained by catalytic cracking or hydrocracking of vacuum gas oil, vacuum heavy gas oil or desulfurized heavy oil obtained by treating oil and residual oil with a vacuum distillation unit Examples include hydrotreated gas oil or hydrodesulfurized gas oil obtained by hydrotreating (petroleum hydrocarbon having a light oil fraction).
These petroleum-based hydrotreated oils can be configured by blending a plurality of light oil fraction base materials and kerosene fraction base materials within a range that satisfies a predetermined condition.

The hydrotreating conditions of the above-mentioned feedstock oil (petroleum hydrocarbon having a light oil fraction) are usually a reaction temperature of 170 to 320 ° C., a hydrogen pressure of 2 to 10 MPa, LHSV of 0.1 to 2 h ⁻¹ , and a hydrogen / oil ratio of 100. -800 NL / L. The reaction temperature is preferably 175 ° C to 300 ° C, the hydrogen pressure is 2.5 to 8 MPa, the LHSV is 0.2 to 1.5 h ^-1 , and the hydrogen / oil ratio is 150 to 600 NL / L, more preferably the reaction temperature is 180 ° C to 280 ° C. The hydrogen pressure is 3 to 7 MPa, the LHSV is 0.3 to 1.2 h ⁻¹ , and the 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 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.

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.

  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 adopted using raw materials in a state of various sols, salt compounds, etc. corresponding to each element. Furthermore, after preparing a composite hydroxide or composite oxide such as silica alumina, silica zirconia, alumina titania, silica titania, alumina boria, etc., the preparation process in the state of alumina gel and other hydroxides or in a suitable 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% by mass or less, more preferably 60% by mass or less, more preferably 40% by mass or less. .

  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.

  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 or W and Co or Ni. For example, Co—Mo, Co—W, Ni—Mo, Combinations such as Ni-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.

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.

As described above, a petroleum oil hydrotreated oil (light oil base material B) is produced by hydrotreating a gas oil fraction refined from crude oil or the like.
The 1st light oil composition of this invention consists of the said light oil base material A and the said light oil base material B, and the mixing ratio is 95-30 volume%: light oil base material A: light oil base material B: 5-70 volume. %, Preferably 90-35% by volume: 10-65% by volume, more preferably 85-40% by volume: 15-60% by volume.

Further, the second light oil composition of the present invention comprises a petroleum hydrocarbon (petroleum-based hydrocarbon) having a light oil fraction refined from the aforementioned crude oil or the like in 10 to 90% by volume of the aforementioned vegetable oil and / or animal and vegetable oil-derived component. Substrate) A porous inorganic oxide composed of two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and an oil to be treated mixed with 90 to 10% by volume, and the porous material A catalyst containing one or more metals selected from Group 6A and Group 8 elements of the periodic table supported on a porous inorganic oxide, a hydrogen pressure of 2 to 13 MPa, a liquid space velocity of 0.1 to 3. 0h ⁻¹ , hydrogen / oil ratio 150-1500 NL / L, fraction produced by contacting under conditions of reaction temperature 150-480 ° C. (environmental low load type light oil base material) Etc. A hydrocracked gas oil fraction (boiling point range: 200 to 350 ° C.) obtained by further hydrocracking a vacuum gas oil obtained by subsequently treating a normal pressure residue oil obtained by treating with a distillation device with a vacuum distillation device. ) Is obtained by hydrotreating a kerosene fraction refined from crude oil or the like into a light oil base A'95-30 volume% obtained by mixing 90-10 volume%) The material B ′) is composed of light oil bases A ′ and B ′ mixed in an amount of 5 to 70% by volume and satisfying a predetermined performance.

The above-mentioned vegetable oil and / or animal and vegetable oil-derived component 10 to 90% by volume was mixed with 90 to 10% by volume of a petroleum hydrocarbon (petroleum base material) having a light oil fraction refined from the above crude oil or the like. The hydrogenation conditions for producing an environmentally low load type light oil base material by hydrotreating the oil to be treated include mixing the sulfur-containing hydrocarbon compound with the animal and vegetable oil and / or animal and vegetable oil-derived component in the first aspect of the present invention. The same conditions as those used when hydrotreating the treated oil are employed.
The mixing ratio of the petroleum-based hydrocarbon (petroleum-based substrate) having a light oil fraction refined from vegetable oil and / or animal and vegetable oil-derived components and crude oil or the like is preferably 20 to 80% by volume: 80 to 20% by volume. Yes, more preferably 40 to 60% by volume: 60 to 40% by volume.

  The mixing ratio of the environmentally low load light oil base and the hydrocracked light oil fraction in the light oil base A ′ is preferably 20 to 80% by volume: 80 to 20% by volume, and 40 to 60% by volume: 60 to 40% by volume. Is more preferable.

  Petroleum hydrotreated oil (gas oil base material B ') having kerosene fraction refined from crude oil, etc., hydrocracked together with straight-run kerosene and hydrocracked gas oil obtained by atmospheric distillation of crude oil Examples thereof include hydrotreated kerosene obtained by hydrotreating petroleum hydrocarbons such as kerosene (petroleum hydrocarbons having a kerosene fraction).

The hydrotreating conditions of the above-mentioned raw material oil (petroleum hydrocarbon having a kerosene fraction) are usually as follows: reaction temperature 220 to 350 ° C., hydrogen pressure ^{1 to} 6 MPa, LHSV 0.1 to 10 h ⁻¹ , hydrogen / oil ratio 10 ~ 300NL / L. Preferably, the reaction temperature is 250 ° C. to 340 ° C., the hydrogen pressure is 2 to 5 MPa, LHSV ^{1 to} 10 h ⁻¹ , and the hydrogen / oil ratio is 30 to 200 NL / L, more preferably the reaction temperature is 270 ° C. to 330 ° C., and the hydrogen pressure is 2 to 4 MPa. , LHSV 2 to 10 h ⁻¹ , hydrogen / oil ratio 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.

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.

  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 used as the porous 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 adopted using raw materials in a state of various sols, salt compounds, etc. corresponding to each element. Furthermore, after preparing a composite hydroxide or composite oxide such as silica alumina, silica zirconia, alumina titania, silica titania, alumina boria, etc., the preparation process in the state of alumina gel and other hydroxides or in a suitable 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% by mass or less, more preferably 60% by mass or less, more preferably 40% by mass or less. . These conditions and the catalyst are not particularly limited as long as the properties of the raw material oil are satisfied.

  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.

  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 or W and Co or Ni. For example, Co—Mo, Co—W, Ni—Mo, Combinations such as Ni-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.

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.

As described above, a kerosene fraction refined from crude oil or the like is hydrotreated to produce a petroleum hydrotreated oil (light oil base material B ′).
The 2nd light oil composition of this invention consists of the said light oil base material A 'and the said light oil base material B', The mixing ratio is light oil base material A ': Light oil base material B' is 95-30 volume%: It is 5-70 volume%, Preferably it is 90-35 volume%: 10-65 volume%, More preferably, it is 85-40 volume%: 15-60 volume%.

  The gas oil composition of the present invention is composed of the above-mentioned base material, 90% distillation temperature is 360 ° C. or less, sulfur content is 10 mass ppm or less, oxygen content is 1 mass% or less, fatty acid alkyl ester content is 3.5 mass%. The light oil composition has a total acid value of 0.13 mg KOH / g or less, a methanol content of 0.01% by mass or less, a glyceride content of 0.01% by mass or less, and a clogging point of −5 ° C. or less.

  The clogging point (CFPP) of the light oil composition of the present invention must satisfy −5 ° C. or less which is JIS No. 2 diesel oil standard, and further −6 ° C. or less from the viewpoint of preventing the prefilter blockage of a diesel vehicle. It is preferable that it is -7 degreeC or less. Here, the clogging point refers to a clogging point measured by JIS K 2288 “Light oil—clogging point test method”.

  Moreover, the pour point of the light oil composition of this invention needs to satisfy | fill -7.5 degrees C or less which is a JIS2 light oil specification. Furthermore, from the viewpoint of low temperature startability or low temperature drivability, and from the viewpoint of maintaining injection performance in the electronically controlled fuel injection pump, it is preferably −10 ° 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”.

  The sulfur content of the light oil composition of the present invention needs to be 10 mass ppm 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 5 mass ppm or less, More preferably, it is 3 mass ppm or less, 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 K 2541 “Sulfur Content Test Method”.

The oxygen content of the light oil composition of the present invention is required to be 1% by mass or less, preferably 0.8% by mass or less, more preferably 0.6% by mass or less, from the viewpoint of improving oxidation stability. Preferably it is 0.4 mass% or less, Most preferably, it is 0.2 mass% or less. The oxygen content can be measured with a general elemental analyzer. For example, the sample is converted to CO on platinum carbon, or further converted to CO ₂ and then measured using a thermal conductivity detector. You can also.

The flash point of the light oil composition of the present invention is preferably 45 ° C. or higher. When the flash point is less than 45 ° C., it cannot be handled as a light oil composition for safety reasons. For the same reason, the flash point is preferably 54 ° C. or higher, more preferably 58 ° 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 cetane index of the light oil composition of the present invention is preferably 45 or more. When the cetane index is less than 45, the concentration of PM, aldehydes, or NOx in the exhaust gas tends to increase. For the same reason, the cetane index is preferably 48 or more, and most preferably 51 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.

  The cetane number in the light oil composition of the present invention is preferably 52 or more, more preferably 54 or more, and further preferably 55 or more. When the cetane number is less than 52, the concentrations of NOx, PM and aldehydes in the exhaust gas tend to be high. Further, from the viewpoint of reducing black smoke in the exhaust gas, the cetane number is preferably 90 or less, more preferably 88 or less, and even more preferably 85 or less. Moreover, in the light oil composition of this invention, a cetane number improver can be mix | blended with an appropriate quantity as needed, and the cetane number of the light oil composition obtained can be improved. 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.

Density at 15 ℃ of the gas oil composition of the present invention, in terms of calorific value ensuring, is preferably 750 kg / ^{m 3} or more, more preferably 760 kg / ^{m 3} or more, more preferably 770 kg / ^{m 3} or more. Further, the density, NOx, from the viewpoint of reducing the emission of PM, it is preferably 850 kg / ^{m 3} or less, more preferably 845 kg / ^{m 3} or less, more preferably 840 kg / ^{m 3} or less. 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 light oil composition of the present invention desirably has a lubricating performance such that the HFRR wear scar diameter (WS1.4) is preferably 460 μm or less, more preferably 430 μm or less, and even more preferably 410 μm or less. When the HFRR wear scar diameter (WS1.4) exceeds 460 μm, especially in a diesel engine equipped with a distribution type 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. 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.

  Although there is no restriction | limiting in particular in the aromatic content in the light oil composition of this invention, it is preferable that it is 20 volume% or less from a viewpoint of improving an environmental impact reduction effect and NOx and PM reduction, More preferably, it is 19 volume% or less. More preferably, it is 18 volume% or less. The aromatic content in the present invention was measured in accordance with 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 aromatic content.

  The water content of the light oil composition of the present invention is preferably 300 ppm by volume or less, more preferably 250 ppm by volume or less, from the viewpoint of adverse effects on members to fuel tanks and the like and suppression of hydrolysis of ester compounds. Preferably, it is 200 volume ppm or less. In addition, the water | moisture content here is the water prescribed | regulated by JISK2275 "moisture test method (crude oil and petroleum products)."

  As the distillation property in the light oil composition of the present invention, the 90% by volume distillation temperature needs to be 360 ° C. or less, preferably 340 ° C. or less, more preferably 330 ° C. or less, and further preferably 320 ° C. or less. is there. When the 90 vol% distillation temperature exceeds 360 ° C, the amount of PM and fine particles discharged tends to increase. The 90% by volume distillation temperature is preferably 280 ° C. or higher, more preferably 285 ° C. or higher, further preferably 290 ° C. or higher, and even more preferably 295 ° C. or higher. If the 90% by volume distillation temperature is less than 280 ° C., the fuel efficiency improvement effect becomes insufficient and the engine output tends to decrease. In addition, 90 volume% distillation temperature here means the value measured based on JISK2254 "petroleum product-distillation test method-normal pressure method".

The kinematic viscosity at 30 ° C. of the light oil composition of the present invention is not particularly limited, but is preferably 2.5 mm ² / s or more, more preferably 2.7 mm ² / s or more, and 2.9 mm. More preferably, it is ² / s or more. If the kinematic viscosity is less than 2.5 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. Moreover, kinematic viscosity at 30 ° C. of the gas oil compositions of the present invention is preferably at most ^{5 mm} 2 / s, more preferably not more than 4.7 mm ² / s, or less 4.5 mm ² / s Is more preferable. If the kinematic viscosity exceeds 5 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. 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".

  Although there is no restriction | limiting in particular about the residual carbon content of 10% residual oil in the light oil composition of this invention, From a viewpoint of fine particle and PM reduction viewpoint, and a viewpoint of the performance maintenance of the exhaust gas aftertreatment apparatus mounted in an engine, it is 0. It is preferably 1% by mass or less, more preferably 0.08% by mass or less, and further preferably 0.06% by mass or less. The residual carbon content of 10% residual oil here means the residual carbon content of 10% residual oil measured by JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.

  In the light oil composition of the present invention, the total acid value needs to be 0.13 mgKOH / g or less from the viewpoint of adverse effects on engine members. Since the total acid value indicates the amount of free fatty acid in the mixture, if this value is large, there is a concern that the acidic compound may adversely affect the member. Therefore, the total acid value is preferably 0.10 mgKOH / g or less, more preferably 0.08 mgKOH / g or less, and even more preferably 0.05 mgKOH / g or less. The total acid value referred to here means the total acid value measured by JIS K 2501 “Petroleum products and lubricating oils—neutralization number test method”.

  In the light oil composition of the present invention, the fatty acid alkyl ester content is required to be 3.5% by mass or less from the viewpoint of deterioration of burnout in engine combustion or the like. Preferably it is 2.0 mass% or less, More preferably, it is 1.0 mass% or less, More preferably, it is 0.5 mass% or less. The fatty acid alkyl ester content here means the fatty acid alkyl ester content measured in accordance with EN 14103.

  In the light oil composition of the present invention, the methanol content must be 0.01% by mass or less from the viewpoint of adverse effects on the fuel injection system. Preferably it is 0.008 mass% or less, More preferably, it is 0.006 mass% or less, More preferably, it is 0.005 mass% or less. The methanol content here means a methanol content measured according to JIS K 2536 and EN 14110.

  In the light oil composition of the present invention, the glyceride content must be 0.01% by mass or less from the viewpoint of adverse effects on the fuel injection system. Preferably it is 0.008 mass% or less, More preferably, it is 0.006 mass% or less, More preferably, it is 0.005 mass% or less. The glyceride content here means a glyceride content measured in accordance with EN 14105.

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.

  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 ˜8 is preferred.

  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. It is particularly preferable that it is 900 mass ppm 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.

  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.

  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.

  The blending amount of the lubricity improver is not particularly limited as long as the HFRR wear scar diameter (WS1.4) is within the above-mentioned preferable range, 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.

  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.

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.

  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.

  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.

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) to be described later are added alone or in combination of several kinds. You can also. 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.

  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.

(Examples 1-3 and Comparative Examples 1-3)
A treated oil obtained by adding 5 mass ppm of dimethyl disulfide (DMDS) as a sulfur-containing hydrocarbon compound to a vegetable oil having the properties shown in Table 1 is reacted under the reaction conditions shown in Table 2, and the environmental conditions shown in Table 3 are reduced. A loaded light oil base was prepared.
Moreover, the to-be-processed oil which mixed 20 volume% of petroleum-based light oil base materials which have the property shown in Table 1 with 80 volume% of vegetable fats and oils which have the property shown in Table 1 is made to react on the reaction conditions shown in Table 2, and The environmentally low load light oil base material shown was prepared.
Table 3 shows the properties of the fatty acid alkyl ester obtained by esterifying the vegetable oil shown in Table 1. These fatty acid alkyl esters are methyl ester compounds obtained by reaction with methanol. Here, they are stirred at 70 ° C. for about 1 hour in the presence of an alkali catalyst (sodium methylate) to directly react with alkyl alcohol. Thus, an ester exchange reaction for obtaining an ester compound was used.
A light oil composition was produced by blending the low-environment light oil base material, the methyl esterified product of vegetable oil and fat, the petroleum hydrorefined oil and hydrocracked light oil shown in Table 3 (Examples) 1-3 and Comparative Examples 1-3).

The blending ratio of the blended diesel oil composition, and the blended diesel oil composition, density at 15 ° C., kinematic viscosity at 30 ° C., flash point, sulfur content, oxygen content, distillation properties, aromatic content, cetane number and Table 4 shows the results of measurement of residual carbon content of 10% residual oil, moisture, clogging point, oxidation stability test (acid value before and after acceleration test), and calculation results of life cycle CO ₂ emissions. .

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 the gas oil composition measured by JIS K2541 “Sulfur content test method”.
The oxygen content was measured by elemental analysis.
All the distillation properties are values measured by JIS K 2254 "Petroleum products-Distillation test method".
The aromatic content is the volume percentage of the aromatic content measured according to the Petroleum Institute Method JPI-5S-49-97 “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method” published by the Japan Petroleum Institute. (Capacity%).

Moisture means the moisture specified by JIS K 2275 “Moisture test method (crude oil and petroleum products)”.
The flash point indicates a value measured according to JIS K 2265 “Crude oil and petroleum product flash point test method”.
The total acid value means the total acid value measured according to JIS K 2501 “Petroleum products and lubricating oils—neutralization number test method”.
The clogging point refers to a clogging point measured by JIS K 2288 “Light oil—clogging point test method”.
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 number means a cetane number measured according to “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”.

(Life cycle CO ₂ calculation)
Life Cycle CO ₂ includes a CO ₂ generated due to combustion of the gas oil compositions in a vehicle equipped with a diesel engine, is calculated by dividing the CO ₂ generated from mining to the fuel oil supply to the vehicle tank.
CO ₂ generated by combustion (hereinafter referred to as “Tank to Wheel CO ₂ ”) is the unit heat generation of each light oil composition based on the CO ₂ emission amount, the travel fuel consumption, and the fuel density when the vehicle test is performed. Calculated as emissions per unit.
In addition, CO ₂ generated from mining to fueling the vehicle tank (hereinafter referred to as “Well to Tank CO ₂ ”) is used for mining, transporting, processing, distributing, and refueling the vehicle. It was calculated as the sum of CO ₂ emissions in a series of flows. In calculating “Well to Tank CO ₂ ”, calculation was performed in consideration of the carbon dioxide emission shown in the following (1B) to (5B). As data necessary for such calculation, refinery operation performance data possessed by the present inventors was used.

(1B) Carbon dioxide emissions associated with the use of fuel in various processing equipment, boilers and other facilities.
(2B) In the treatment using hydrogen, the amount of carbon dioxide emission accompanying the reforming reaction in the hydrogen production apparatus.
(3B) Carbon dioxide emission associated with catalyst regeneration when passing through an apparatus with continuous catalyst regeneration, such as a catalytic cracker.
(4B) Carbon dioxide emissions when a light oil composition is manufactured or unloaded in Yokohama, delivered from Yokohama to Sendai, and refueled in Sendai.
(5B) The amount of carbon dioxide emitted when animal and vegetable oils and fats and components derived from animal and vegetable oils and fats are produced in Malaysia and the surrounding area and manufactured in Yokohama.

In addition, when using animal and vegetable oils and fats and components derived from animal and vegetable oils and fats, the so-called Kyoto Protocol applies the rule that carbon dioxide resulting from these fuels is not counted as emissions. In this calculation, this was applied to “Tank to Wheel CO ₂ ” generated during combustion.
Thus calculated “Tank to Wheel CO ₂ ” and “Well to
Each emission amount of “Tank CO ₂ ” and life cycle CO ₂ (LC) which is the sum of these is shown in Table 4, respectively. In addition, the comparative example 1 is set to 100, and the numerical value which comparatively compared and quantified each result is also shown collectively.

(Oxidation stability test)
The fuel was accelerated and deteriorated at 115 ° C. under oxygen bubbling for 16 hours, and the oxidation before and after the test was measured. The total acid value referred to here means the total acid value measured by JIS K 2501 “Petroleum products and lubricating oils—neutralization number test method”.

  As shown in Table 4, the light oil compositions used in the examples and comparative examples specified a water environment low load type light oil base, a methyl esterified vegetable oil and a petroleum hydrotreated oil which is a petroleum base. It is manufactured by mixing at a ratio.

  As is clear from Table 4, the environmentally low load type light oil base material, and the environmentally low load type light oil base material and petroleum hydrotreated oil were mixed and used within the range defined in the present invention. In Examples 1 to 3, the 95% distillation temperature is 360 ° C. or less, the sulfur content is 10 mass ppm or less, the oxygen content is 1 mass% or less, the fatty acid methyl ester content is 3.5 mass% or less, and the total acid value increase is 0. Gas oil that satisfies the properties of .13 mg KOH / g or less, methanol content of 0.01% by mass or less, glyceride content of 0.01% by mass or less, and clogging point of -5 ° C. or less, and has low carbon dioxide emission in the life cycle. The composition could be obtained easily and reliably. On the other hand, in Comparative Examples 1 to 3 in which a light oil composition was prepared without using the above specific environment-friendly light oil base material, the light oil composition targeted by the present invention was not necessarily obtained.

Claims (2)

In the presence of hydrogen, to-be-treated oil in which a sulfur-containing hydrocarbon compound is mixed with animal and vegetable oils and / or components derived from animal and vegetable oils so that the sulfur content is 1 mass ppm to 2 mass%, and aluminum, silicon, zirconium, boron, A porous inorganic oxide comprising two or more elements selected from titanium and magnesium, and one kind selected from elements of Group 6A and Group 8 of the periodic table supported by the porous inorganic oxide The catalyst containing the above metal is contacted under conditions of a hydrogen pressure of 2 to 13 MPa, a liquid space velocity of 0.1 to 3.0 h ⁻¹ , a hydrogen / oil ratio of 150 to 1500 NL / L, and a reaction temperature of 150 to 480 ° C. 10% to 90% by volume of a fraction (environmental low load gas oil base material) produced by treating the crude oil and the like with an atmospheric distillation apparatus, and then treating with an atmospheric distillation apparatus. Gas oil base A 95 to 30% by volume obtained by mixing 90 to 10% by volume of a hydrocracked gas oil fraction (boiling range: 200 to 350 ° C.) obtained by further hydrocracking the vacuum gas oil obtained The 90% distillation temperature is 360% obtained by mixing 5-70 vol% of petroleum hydrotreated oil (light oil base B) obtained by hydrotreating a gas oil fraction refined from crude oil or the like. ° C or less, sulfur content is 10 mass ppm or less, oxygen content is 1 mass% or less, fatty acid alkyl ester content is 3.5 mass% or less, total acid value is 0.13 mgKOH / g or less, methanol content is 0.01 mass% or less, glyceride content A gas oil composition comprising gas oil base materials A and B, having a mass point of 0.01 mass% or less and a clogging point of -5 ° C or less. In the presence of hydrogen, an oil to be treated is prepared by mixing 10 to 90% by volume of a component derived from animal and vegetable oils and / or animal and vegetable oils and 90 to 10% by volume of a petroleum-based base material having a light oil fraction refined from crude oil or the like. , Porous inorganic oxides containing two or more elements selected from silicon, zirconium, boron, titanium and magnesium, and groups 6A and 8 of the periodic table carried on the porous inorganic oxides A catalyst containing one or more metals selected from the above elements, a hydrogen pressure of 2 to 13 MPa, a liquid space velocity of 0.1 to 3.0 h ⁻¹ , a hydrogen / oil ratio of 150 to 1500 NL / L, a reaction temperature of 150 to 10% to 90% by volume of a fraction (environmental low load gas oil base material) produced by contacting under conditions of 480 ° C., followed by atmospheric pressure residue oil obtained by treating crude oil etc. with an atmospheric distillation device Decrease A gas oil base material obtained by mixing 90 to 10% by volume of a hydrocracked gas oil fraction (boiling range: 200 to 350 ° C.) obtained by further hydrocracking a vacuum gas oil obtained by treating with a distillation apparatus. Obtained by mixing 5-70 vol% petroleum hydrotreated oil (light oil base material B ') obtained by hydrotreating kerosene fraction refined from crude oil etc. with A'95-30 vol% 90% distillation temperature is 360 ° C. or less, sulfur content is 10 mass ppm or less, oxygen content is 1 mass% or less, fatty acid alkyl ester content is 3.5 mass% or less, total acid value is 0.13 mg KOH / g or less, methanol content A light oil composition comprising light oil bases A ′ and B ′ having a content of 0.01% by mass or less, a glyceride content of 0.01% by mass or less and a clogging point of −5 ° C. or less.