WO2009020056A1 - Gas oil composition - Google Patents

Abstract

A gas oil composition obtained by mixing 5-70 vol.% hydrotreated petroleum oil with 95-30 vol.% gas oil base obtained by mixing a hydrocracked gas oil fraction and/or a dewaxed gas oil base with an environmentally friendly gas oil base produced by contacting a raw oil with a catalyst comprising a given porous inorganic oxide and an active metal under given reaction conditions, the raw oil being one obtained by mixing an animal/vegetable fat and/or an ingredient derived from an animal/vegetable fat with a sulfur-containing hydrocarbon compound. The gas oil composition has a 90% running temperature of 360°C or lower, sulfur content of 10 mass ppm or lower, oxygen content of 1 mass% or lower, fatty acid/alkyl ester content of 3.5 mass% or lower, total acid value of 0.13 mg-KOH/g or less, methanol content of 0.01 mass% or lower, glyceride content of 0.01 mass% or lower, and cold filter plugging point of -5°C or lower. The gas oil composition is excellent in life-cycle CO2 emission characteristics and oxidative stability and in member stability.

Description

 Gas oil composition

[Technical field]

The present invention relates to an environmentally low load light oil base produced using animal and vegetable fats and / or triglyceride-containing hydrocarbons derived from animal and vegetable fats and oils, and atmospheric pressure obtained by treating crude oil and the like with an atmospheric distillation device. A hydrocracked gas oil fraction obtained by further hydrocracking a vacuum gas oil obtained by processing a light residual oil in a vacuum distillation unit (hereinafter referred to as a hydrocracked gas oil fraction purified from raw oil) ) And / or a dewaxed light oil base obtained by further hydrodewaxing a light oil fraction obtained by treating crude oil etc. with an atmospheric distillation unit (hereinafter referred to as refined degassed from crude oil etc.) It is also referred to as a wax-based diesel oil base.) Excellent life cycle co ₂ emission characteristics and oxidation stability obtained by mixing diesel oil refined from raw oil, etc., and petroleum-based hydrotreated oil with kerosene fraction , And low temperature It relates excellent gas oil composition kinematic properties.

[Background]

 Conventional gas oil base materials include straight-run diesel oil obtained from crude oil atmospheric distillation equipment, hydrotreated or hydrodesulfurized, and straight-run kerosene obtained from crude oil distillation equipment using hydrogen. Those subjected to hydrotreating or hydrodesulfurization are known. Conventional diesel oil compositions are manufactured by blending one or more of the above diesel oil base and kerosene base. In addition, these light oil compositions are blended with additives such as cetane improvers and cleaners as needed (for example, Non-Patent Document 1 (Sonichi Konishi, “Introduction to Fuel Engineering”, Bund, 1 9 9 March 1, p. 1 3 6-1 4 4).

Patent Document 1 (Japanese Patent Laid-Open No. 2 0 03-1-7 1 6 70) discloses a method for producing hydrocarbons using natural fats and oils or derivatives thereof and edible waste oil as raw materials. Characterized by reacting natural fats and oils, waste natural fats and oils or derivatives thereof with activated hydrogen in the presence of a catalyst selected from the group consisting of metal catalysts, alloy catalysts, metal-supported catalysts and alloy-supported catalysts. A method for producing hydrocarbons is disclosed. Patent Document 2 (Japanese Patent Publication No. 2 0 0 5—5 3 8 2 0 4) discloses plants and / or plants. For diesel engines containing from 0.1 to 99% by volume of components or mixture of components prepared from biological raw materials of animal or fish origin and from 0 to 20% by volume of components containing oxygen A fuel composition is disclosed. Both components are said to be mixed with diesel components based on crude oil and / or fractions from the Fitzish Tropsch process.

 Patent Document 3 (Japanese Patent Laid-Open No. 2000-184-88) discloses a methyl ester or an ethyl ester of a saturated or unsaturated fatty acid having 6 to 20 carbon atoms constituting the fatty acid. Or an environmentally friendly diesel fuel composition comprising a mixture thereof.

However, it is very difficult to design a high-quality fuel that can simultaneously achieve the required performance at the same time as life cycle C 0 ₂ emission characteristics, oxidation stability, and low-temperature performance. However, it does not disclose a practical manufacturing method that satisfies the various performances.

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 respond to the global warming problem, there is a need for fuel properties that contribute to further fuel economy and are effective in reducing carbon dioxide (C o ₂ ). And biodiesel fuel, which is a renewable energy (hereinafter also referred to as BDF), is being studied as an alternative fuel.

BDF is mainly a mixture of fatty acid alkyl esters made from natural animal and vegetable oils and fats. Influence of aromatic compounds and exhaust gas aftertreatment catalysts that are considered to have a large contribution to soot formation in exhaust gas Because it contains almost no sulfur, which is said to be large, and itself is an oxygen-containing compound with oxygen in the molecule, it is attracting attention as a promising candidate for alternative fuels. In addition, because it is plant-derived, it is positioned as one of the renewable energies, so the international carbon dioxide reduction protocol concluded in 1997, the so-called Kyoto Protocol, emits carbon dioxide caused by BDF. BDF also has a policy merit in that it is a rule that is not recorded as a quantity. However, fatty acid alkyl esters made from natural animal and vegetable oils and fats are inherently heavy components, and the burn-off property of engine combustion and the like deteriorates, and there is a concern of increasing unburned hydrocarbon emissions during combustion. In addition, fatty acid alkyl esters are acid-containing Because it is an elemental compound, there is a concern of increasing emissions 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 temperatures. In the case of BDF containing many unsaturated fatty acid groups, its chemical composition is inferior in oxidative stability, and there is concern about the deterioration of hue and the generation of sludge and adverse effects on engine parts. Furthermore, fatty acid glyceride, which is a raw material when purifying fatty acid alkyl esters, alkyl alcohol and a glycerin mixture which is a by-product are extremely concerned about adverse effects on engine members and fuel injection systems.

 These tendencies were not seen in existing diesel oils, and as such, not only when using BDF alone, but also when mixing with existing diesel 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, etc. than before when mixing with existing light oil.

Therefore, fatty acid alkylesters made from natural animal and plant fats and oils are used to provide gas oil compositions that have excellent low-temperature performance, life cycle CO ₂ emission characteristics and oxidation stability as well as reduction of harmful exhaust components. These performance improvements cannot be achieved simultaneously with the use of a BDF mixture. Furthermore, because these engine performances are closely related to other fuel properties, it is very difficult to design a high-quality fuel that can simultaneously achieve these required performances at a high level, and as a commercial fuel oil There are no examples or knowledge that fully satisfy the required performance and consider practical manufacturing methods.

[Disclosure of the Invention]

The present invention has been made in view of such a situation, and an object of the present invention is to provide an environment-friendly light oil base material produced using raw materials of animal and vegetable fats and oils and / or triglyceride-containing hydrocarbons derived from animal and vegetable fats and oils. Hydrocracked gas oil fraction refined from crude oil, etc. and / or dewaxed gas oil base refined from crude oil, etc., and petroleum hydrotreated oil having kerosene fraction, light oil refined from crude oil, etc. Excellent life cycle co ₂ emission characteristics and oxidation stability obtained by mixing, and low temperature fluidity The object is to provide an excellent gas oil composition.

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

 That is, the first aspect of the present invention is [A] a mixture of animal and vegetable oils and / or animal and plant oils and fats-derived components containing a sulfur-containing hydrocarbon compound so that the sulfur content is 1 mass ppm to 2 mass% in the presence of hydrogen. A processing oil, a porous inorganic oxide comprising two or more elements selected from aluminum, potassium, zirconium, boron, titanium and magnesium, and a periodic rule supported by the porous inorganic oxide Table 6 A catalyst containing one or more metals selected from Group A and Group 8 elements, hydrogen pressure 2 to 13 MPa, liquid space velocity 0.:! To 3.0 h— hydrogen / Fraction produced by contacting under conditions of oil ratio 1 50-1 500 NL / L, reaction temperature 1 50-480 ° C

(Environmental low load gas oil base) 10-90% by volume, (i) Vacuum gas oil obtained by processing crude oil, etc. with atmospheric distillation equipment, followed by treatment with vacuum distillation equipment Oil base material A-1 obtained by further mixing hydrocracked gas oil fraction obtained by further hydrocracking (boiling range: 200-350 ° C) 90-10% by volume or (ii) Diesel oil base obtained by mixing 90 to 10% by volume of a dewaxed light oil base obtained by further hydrotreating and dewaxing a light oil fraction obtained by treating crude oil etc. with an atmospheric distillation unit A— Gas oil base material A consisting of 2 to 95-30% by volume [B] Petroleum hydrotreated oil (light oil base material B) obtained by hydrotreating a light oil fraction refined from crude oil, etc. 90% distillation temperature obtained by mixing 70% by volume, 360 ° C or less, sulfur content is 10 mass ppm or less, oxygen content is 1 mass. /. The fatty acid alkyl ester content is 3.5 mass% or less, the total acid value is 0.13 mg KOHZg or less, the methanol content is 0.01 mass% or less, the glyceride content is 0.01 mass% or less, and the clogging point is 5 ° C or less. The present invention relates to a gas oil composition comprising gas oil base materials A and B characterized by the above. The second aspect of the present invention is: [Α '] Petroleum-based base material having animal and vegetable oils and fats and 10 to 90% by volume of components derived from straw or animal and vegetable oils and a light oil fraction refined from crude oil in the presence of hydrogen. An oil to be treated mixed with 90 to 10% by volume is combined with a porous inorganic oxide composed of two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium. A periodic catalyst supported by the porous inorganic oxide, a catalyst containing one or more metals selected from Group 6 Group 8 and Group 8 elements; By contacting under conditions of hydrogen pressure 2 to 13 MPa, liquid space velocity 0.1 to 3.0 h ¹ , hydrogen / oil ratio 150 to 1500 NL / L, reaction temperature 150 to 480 ° C Distillate to be produced (environmental low-load gas oil base) 10-90% by volume, (i ') Atmospheric residual oil obtained by treating crude oil, etc. with atmospheric distillation equipment, then treated with vacuum distillation equipment Hydrocracked gas oil fraction obtained by further hydrocracking the vacuum gas oil obtained in this way

(Oil boiling range: 200-350 ° C) obtained by mixing 90 to 10% by volume of light oil base material A'-1 and NO or (ii ') obtained by treating crude oil etc. with atmospheric distillation equipment Gas oil base A obtained by mixing 90 to 10% by volume of a dewaxed light oil base obtained by further hydrodewaxing a diesel oil fraction, light oil base A consisting of 12, 95-30 Obtained by mixing 5 to 70% by volume of petroleum oil hydrotreated oil (light oil base B ') obtained by hydrotreating kerosene fraction refined from crude oil etc. 90% distillation temperature is 360 ° C or less, sulfur content is 10 mass ppm or less, oxygen content is 1 mass. / ₀ or less, Fatty acid alkyl ester content 3.5 mass% or less, Total acid _value 0.13 mgKOH / g or less, Methanol content 0.01 mass% or less, Glyceride content 0.01 mass% or less, Clogging point 1 ° The present invention relates to a light oil composition comprising light oil bases A ′ and B ′, which is characterized by C or less.

[The invention's effect]

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, and a hydrocracked gas oil fraction purified from crude oil and the like. It is difficult to achieve with conventional diesel oil compositions by mixing dewaxed diesel oil base material refined from Z or crude oil, etc., diesel oil refined from crude oil, etc., and petroleum hydrotreated oil having kerosene fraction A light oil composition having excellent life cycle CO ₂ emission characteristics and oxidation stability and good low-temperature performance is provided.

[Best Mode for Carrying Out the Invention]

 Hereinafter, the present invention will be described in detail.

The environment-friendly light oil base material according to the present invention is a low-sulfur, low-oxygen fraction obtained by hydrotreating a predetermined raw material oil. Predetermined feedstock oils and animals Mixed oil (treated oil) obtained by mixing sulfur-containing hydrocarbon compounds with components derived from animal and vegetable oils and fats so that the sulfur content is 1 mass ppm to 2 mass%, or animal and vegetable oils and fats or animal or vegetable oils and fats This is a mixed oil (treated oil) obtained by mixing 10 to 90% by volume of a derived component and 90 to 10% by volume of a petroleum base material having a light oil fraction refined from crude oil or the like.

 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 or manufactured naturally or artificially and / or a component that is produced and produced from these oil and fat. Examples of animal fats and animal oil ingredients include beef tallow, milk fat (butter), pork tallow, sheep fat, whale oil, fish oil, liver oil, etc. Examples of vegetable oil and vegetable oil ingredients include coconut palm, olive palm, olive Examples include seeds and other parts such as bananas, rapeseed (rapeseed flowers), rice bran, sunflower, cottonseed, corn, soybeans, sesame seeds, flax, etc. No problem. These raw oils may be solid or liquid, but it is preferable to use vegetable oils and plant oils as raw materials because of their ease of handling, high carbon dioxide absorption capacity and high productivity. In the present invention, waste oils obtained by using these animal oils and plant oils for consumer use, industrial use, food use, etc. can also be used as raw materials after adding a step of removing impurities.

A typical composition of the fatty acid portion of glyceride compounds contained in animal and vegetable oils and fats and components derived from animal and vegetable fats and oils is butyric acid (C ₃ H ₇₎ , a fatty acid having no unsaturated bond in the molecular structure called saturated fatty acid. COOH), caproic acid (CsH COO H), force prillic acid (C ₇ H ₁₅ COOH), force puric acid (C ₉ H ₁₉ COOH), lauric acid (CuH ^ 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 CO OH), an unsaturated fatty acid having one or more unsaturated bonds Linoleic acid (C ₁₇ H ₃₁ COOH), linolenic acid (C ₁₇ H ₂₉ COOH), ricinolenic acid (C ₁₇ H ₃₂ (OH) COOH) and the like. The hydrocarbon part of these fatty acids in natural substances is generally linear, but it is a structure having a side chain, that is, an isomer, as long as the properties defined in the present invention are satisfied in the present invention. Can also be used. Further, the position of the unsaturated bond in the molecule of the unsaturated fatty acid is the same in nature as long as it satisfies the properties defined in the present invention. Not only those that have been confirmed to exist in general, but also those that have been set at any position by chemical synthesis can 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 vary depending on the raw material. 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.

 Sulfur-containing hydrocarbon compounds that are mixed with animal and vegetable oils and / or animal and vegetable oil-derived components to form treated oils are not particularly limited. Phen, dibenzothiophene and their derivatives. 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 instead 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 P pm to 2 mass%, preferably 10 mass p 111 to 1 mass%.

The hydrogenation conditions of the raw oil (treated oil) are as follows: hydrogen pressure 2 to 13 MPa, liquid space velocity 0.:! To 3.0 h ¹ , hydrogen / oil ratio 1 50 to: I 500 NLZL . it is desirable to carried out at a hydrogen pressure 3～12MP a, liquid hourly space velocity 0. 2 to 2 O h one ^1, and more preferably conditions such hydrogen / oil ratio 200～1200NL / L, the hydrogen pressure 4 ~: L 0 More desirable conditions are 5 MPa, liquid space velocity 0.25 to 1.0 h ¹ , hydrogen oil ratio 300 to: L 00 NLZL. These conditions are factors that influence the reaction activity.For example, if the hydrogen pressure and the hydrogen oil ratio do not satisfy the lower limit values, there is a risk of causing a decrease in reactivity or a rapid decrease in activity. If the pressure hydrogen / oil ratio exceeds the above upper limit, excessive capital investment such as compressors may be required. The lower the liquid space velocity, the more advantageous the reaction. However, when 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, in order to obtain the desired decomposition rate of the heavy feedstock oil fraction or the desired fraction yield. Set in the range of ~ 360 ° C. The reaction temperature is less than the lower limit. If not, the reaction may not proceed sufficiently. If the upper limit is exceeded, decomposition proceeds excessively and the liquid product fraction tends to decrease.

 The type of hydrotreating reactor may be a fixed bed system. In other words, 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. A general format is downflow, and a gas-liquid twin-cocurrent format can be used. 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 hydrotreated in the reactor is fractionated into predetermined fractions through a gas-liquid separation process, a rectification process, and the like. At this time, if sulfur is contained in the water or feedstock produced during the reaction, hydrogen sulfide may be generated. However, there is a possibility that hydrogen sulfide is generated between the reactors and in the product recovery process. Liquid separation equipment and other by-product gas removal equipment 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 reaction is possible as much as possible. In order to maintain the hydrogen pressure throughout the reactor, it may be introduced between several reactors between the catalyst beds. The hydrogen thus introduced is referred to as quench hydrogen. In this case, the ratio of the quench hydrogen to hydrogen introduced accompany the feedstock is desirably 1 0-6 0 volume _^0/0, more preferably from 1 5 to 5 0 volume. / ₀ . If the ratio of quench hydrogen is lower than the lower limit, the reaction at the subsequent reaction site may not proceed sufficiently, and if it exceeds the upper limit, the reaction near the reactor inlet may not proceed sufficiently. .

As the support for the hydrogenation catalyst, a porous inorganic oxide comprising 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 other carrier constituents include silica, titania, zircoure, polya, and magnesia. Desirably, it is a composite oxide containing at least one kind 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, sufficient catalyst surface area can be obtained. However, if the amount exceeds 20% by weight, the acidity of the carrier may increase, leading to a decrease in activity due to coke formation. When phosphorus is included as a carrier constituent, its content is preferably 1 to 5% by weight in terms of oxide, and more preferably 2 to 3.5% by weight.

 There are no particular limitations on the raw materials that are precursors of silica, titania, zircoua, polya, and magnesia, which are carrier constituents other than alumina, and use a solution containing general silicon, titanium, zirconium, boron, and magnesium. Can do. For example, for key substances, such as key acid, water glass, and silica sol, for titanium, titanium sulfate, titanium tetrachloride and various alkoxide salts, for zirconium, zirconium sulfate, various alkoxide salts, for boron, for boric acid, etc. For Nesium, magnesium nitrate or the like can be used. As phosphorus, phosphoric acid or phosphoric acid metal salt of phosphoric acid can be used.

 It is desirable that the raw materials for the carrier component other than alumina be added in any step prior to the firing of the carrier. For example, it may be added to an aqueous aluminum solution in advance and then an aluminum hydroxide gel containing these components, or may be added to a prepared aluminum hydroxide gel, or water may be added to a commercially available alumina intermediate or bermite powder. Alternatively, an acidic aqueous solution 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 sort of active metal. It is considered that the activity is affected by the interaction.

 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 types selected from Groups 6A and 8 Contains the above metals. For example, Co-Mo, Ni-Mo, Nii-Co-Mo, Ni-W, etc. are used for hydrogenation by converting these metals to the sulfide state. It is preferable to do.

The active metal content is, 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 conversion. is there. If the total loading of W and Mo is less than 12% by weight, The activity may decrease, and if it exceeds 35% by weight, the metal may not be effectively dispersed, and the activity may decrease as well. Further, the total supported amount of O ₀ and] ^ 1 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 may not be effectively dispersed and may be similarly active. 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 in which a catalyst carrier is impregnated with a solution containing an active metal salt is preferably employed. In addition, an equilibrium adsorption method, a pore-fi 1 1 ing method, an incipient-wetness method, and the like are preferably employed. For example, the pore-fi 1 1 ing method is a method in which the pore volume of the support is measured in advance and impregnated with the same volume of metal salt solution, but the impregnation method is not particularly limited. However, it can be impregnated by an appropriate method depending on the amount of metal supported and the physical properties of the catalyst carrier.

As described above, an environmentally low-load diesel fuel base material is produced by hydrotreating the oil to be treated, which is a mixture of animal and vegetable oils and fats and Z or animal and vegetable oils and components, and containing sulfur-containing hydrocarbon compounds under specified conditions. Is done. The first light oil composition of the present invention comprises: [A] 10 to 90% by volume of the environmentally low load light oil base produced as described above, and (i) treatment of crude oil and the like with an atmospheric distillation apparatus. The hydrocracked gas oil fraction (boiling range: 2 ° 0 to 3 5 0) obtained by further hydrocracking the vacuum gas oil obtained by subsequently treating the atmospheric residue oil obtained by the subsequent distillation with a vacuum distillation apparatus ° C) 9 0 ~ 10 capacity. Gas oil base A-1 obtained by mixing / ₀ and / or (ii) a dehydration obtained by further hydrodewaxing a light oil fraction obtained by treating crude oil or the like with an atmospheric distillation apparatus. A light oil base material A 9 consisting of light oil base material A-2 obtained by mixing 90 to 10% by volume of wax light oil base material into 9 to 30% by volume of [B] light refined from crude oil, etc. It consists of light oil bases A and B, which are mixed with 5 to 70% by volume of petroleum hydrotreated oil (light oil base B) obtained by hydrotreating an oil fraction. The hydrocracked gas oil fraction is obtained by further hydrocracking the reduced pressure gas oil obtained by processing the atmospheric residue oil obtained by processing crude oil, etc. with an atmospheric distillation device, followed by the reduced pressure distillation device. This is a fraction having a boiling range of 200 to 350 ° C.

 The hydrocracking treatment method is not particularly limited, but a heavy feedstock 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, there are used amorphous carriers such as silica-alumina, silica-magnesia, silica-zircoua, silica-titania, and crystalline carriers such as zeolite modified with various modifications. Hydrogenation ability is demonstrated by supporting two or three kinds of metals such as Ni, Co, Mo, W, Pd, Pt, etc., but in particular, Co-Mo, Ni-Mo N i—W are preferred.

 The hydrogen pressure in hydrocracking is usually 5 MPa to 20 MPa, preferably 8 MPa to 15 MPa. The reaction temperature is usually 350 ° C or higher and 430 ° C or lower. The liquid space velocity is usually 0.1 / h or more and 1. OZh or less, preferably 0.2 / h or more and 0.4 Zh or less.

 In the present invention, the dewaxed light oil base material is obtained by removing the wax from the light oil base material. Specifically, a normal paraffin component having 20 or more carbon atoms is preferably 15% by volume or less, more preferably. Is 12% by volume or less, more preferably 10% by volume or less. When the normal paraffin component having 20 or more carbon atoms exceeds the above range, the low temperature fluidity of the product gas oil becomes insufficient, and the cloud point and pour point may not be sufficiently lowered. The cloud point of the dewaxed light oil base is preferably in the range of 120 ° C to 15 ° C.

The method of hydrodewaxing treatment is not particularly limited. For example, a dewaxing catalyst such as zeolite is used, and the pressure is 3 to 7 MPa in the range of 310 ° C to 380 ° C. It can be performed at a liquid hourly space velocity (LHSV) of ¹ hr.

 The mixing ratio of the low-energy diesel oil base and hydrocracked diesel oil fraction in light oil base A-1 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 preferred.

Light oil base material A—The mixing ratio of the environmentally low load light oil base material and the dewaxed light oil base material in A-2 is 20-80 volume%: preferably 80 to 20 volume _^0/0, 40-60 volume%: 60-4 0% by volume is more preferable.

 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 unit, or a straight distillation obtained from an atmospheric distillation device. Petroleum systems such as vacuum gas oil obtained by treating heavy oil and residual oil with a vacuum distillation unit, catalytic cracking gas oil obtained by catalytic cracking or hydrocracking of vacuum heavy gas oil or desulfurized heavy oil, or hydrocracked gas oil Examples include hydrotreated gas oil or hydrodesulfurized gas oil obtained by hydrotreating hydrocarbons (petroleum hydrocarbons having a gas oil fraction). These petroleum-based hydrotreated oils can be constituted 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 (petroleum hydrocarbons having a gas oil fraction) are usually as follows: reaction temperature 170 to 320 ° C, hydrogen pressure 2 to 10 MPa, LHSV0.:! To 2 h-hydrogen / Oil ratio is 100-800NL / L. The reaction temperature is preferably 1 75 ° C to 300 ° C, hydrogen pressure 2.5 to 8 MPa, LH SV 0.2 to 1.5 h ¹ , hydrogen / oil ratio 150 to 600 NL / L, more preferably The reaction temperature is 1-80 ° C to 280 ° C, the hydrogen pressure is 3 to 7 MPa, the LHS VO. 3 to 1.2 h ¹ , and the hydrogen Z oil ratio 1 50 to 50 ONL / 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 hydrogen Z oil ratio, the more accelerated the desulfurization and hydrogenation reaction. The lower the LHSV, the better the reaction. However, if it is too low, a very large reaction column volume is required, which is disadvantageous because of excessive capital investment.

 The apparatus for hydrotreating the feedstock may be of any configuration, and the reaction towers may be used alone or in combination, and hydrogen may be additionally injected between the reaction towers. You may have hydrogen removal equipment.

As the reaction mode of the hydrotreating apparatus, a fixed bed system is preferably adopted. Hydrogen can take either a countercurrent or cocurrent flow format with respect to the feedstock oil, or may have a plurality of reaction towers and a combination of countercurrent and cocurrent flow. The general format is downflow, and the gas-liquid twin-cocurrent format is preferred. Hydrogen gas may be injected into the middle stage of the reaction tower as a tent to remove reaction heat or increase the hydrogen partial pressure. The 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, zircoa, polya, silica, or zeolite, and in the present invention, at least one of titania, zircoa, polya, silica, and zeolite is composed of alumina. What you have is 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, after preparing a composite hydroxide or composite oxide such as silica alumina, silica zirconia, alumina titania, silica titia, and alumina polya, it is prepared in the form of alumina gel or other hydroxides or in an appropriate solution. You may add and prepare in arbitrary processes of a process. The ratio of alumina to other oxides is a force capable of taking an arbitrary ratio with respect to the porous carrier, preferably 90 mass ° / ₀ or less of alumina, more preferably 60 mass% or less, more preferably 40 mass%. It is below mass%.

 Zeolite is a crystalline aluminosilicate, such as faujasite, pentasil, mordenite, etc., which has been ultra-stabilized by prescribed hydrothermal treatment and / or acid treatment, or contains alumina in zeolite The amount can be adjusted. Preferably used are faujasite and mordenite, particularly preferably Y type and beta type. Y-type is preferably ultra-stabilized. Zeolite super-stabilized by hydrothermal treatment has a new pore structure in the range of 20 to 10 OA in addition to the original microporous structure of 2 OA or less. A pore is formed. 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, it is a combination of Mo or W and C0 or Ni. For example, Co—Mo, Co — W, N i—M o, N i—W, C o _N i—M o, C o One N i—W, etc. can be used. As the metal source, a general inorganic salt or a complex salt compound can be used. As the loading method, any of the loading methods used in usual hydrogenation catalysts such as impregnation method and ion exchange method can be used. If multiple metals are supported, they can be supported simultaneously using a mixed solution. Alternatively, it may be supported sequentially using a single solution. The metal solution may be an aqueous solution or an organic solvent.

 Metal loading may be carried out after the completion of the entire process of preparing the porous support, and there is a further gel blending process after pre-loading on the appropriate oxide, composite oxide, zeolite in the intermediate process of porous support preparation. Let's heat concentrate and knead.

The amount of active metal supported is not particularly limited, but the total amount of metal is 0.1 to 10 mass relative to the catalyst mass. / ₀ , preferably 0.1 to 5 to 5% by mass, more preferably 0.2 to 3% by 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 given in accordance with a predetermined procedure, the active metal on the catalyst is reduced and hydrogenation activity is expressed. As described above, a petroleum oil hydrotreated oil (light oil base material B) is produced by hydrotreating a light oil fraction refined from crude oil or the like.

The first light oil composition of the present invention comprises the light oil base A and the light oil base B, and the mixing ratio of the light oil base A: the light oil base B is 95 to 30% by volume: 5 to 70. a volume%, preferably 90 to 35 volume _^0/0: a 10-65 volume%, more preferably 85 to 40 volume%: 1 5-60 volume% Dearu. In addition, the second light oil composition of the present invention comprises: [A,] a petroleum-based oil having 10 to 90% by volume of the aforementioned vegetable oil and / or animal and vegetable oil-derived component and a light oil fraction refined from the aforementioned crude oil or the like. Porous oil composed of two or more elements selected from aluminum, silicon, zirconium, boron, titanium, and magnesium. An inorganic oxide and a catalyst containing one or more metals selected from Group A and Group 8 elements of the periodic table supported on the porous inorganic oxide, hydrogen pressure 2 to 13 MPa, liquid Fraction produced by contacting under the conditions of space velocity 0.1 to 3.0 h- ¹ , hydrogen / oil ratio 1 50 to 1 500 NL / L, reaction temperature 1 50 to 480 ° C (environmental low load Type light oil base) 10 ~ 90% by volume, () Normal obtained by processing crude oil etc. with atmospheric distillation equipment 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 treating the pressure residue oil with a vacuum distillation device Mixed Gas oil base material obtained by combining A'-1 and / or (ii ') Dewaxed gas oil obtained by further hydrodewaxing a gas oil fraction obtained by treating crude oil etc. with an atmospheric distillation unit Diesel oil base material A'_2 obtained by mixing 90 ~ 10% by volume of the base material. Diesel oil base material A '_ 2 to 95 ~ 30% by volume. [Β'] Kerosene fraction purified from crude oil etc. Petroleum hydrotreated oil (light oil base material B ′) obtained by raw material treatment is mixed with 5 to 70 vol% of light oil base materials A ′ and B ′ satisfying predetermined performance.

10 to 90 volumes of the aforementioned vegetable oil and / or animal and vegetable oil-derived component. / ₀ , petroleum-based hydrocarbons (petroleum-based base materials) with light oil fractions refined from the aforementioned crude oil, etc. 90〜

10 capacity. The hydrogenation conditions for producing an environmentally light diesel base material by hydrotreating the oil to be treated mixed with / ₀ are derived from the animal and plant oils and / or animal and plant oils and fats in the first aspect of the present invention. The same conditions as those used when hydrotreating the oil to be treated, in which sulfur-containing hydrocarbon compounds are mixed as components, are adopted.

The mixing ratio of the components derived from vegetable oils and / or animal and vegetable oils and oil-based hydrocarbons (petroleum base materials) having a light oil fraction refined from crude oil, etc. is preferably 20 to 80% by volume: 80 to 20% by volume ⁰ / ₀ , more preferably 40 to 60% by volume: 60 to 40% by volume.

 Light oil base material A '— The mixing ratio of the low environmental load type light oil base material and the hydrocracked light oil fraction is preferably 20 to 80% by volume: 80 to 20% by volume, and 40 to 60% by volume: 60 to 40 Volume% is more preferable.

Gas oil base material A '- 2 in the environment friendly base gas oil mixing ratio of dewaxing the gas oil fraction, 20 to 80 volume%: preferably 80 to 20 volume _^0/0, 40-60 volume%: 60 ~ 40% by volume is more preferred.

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

Hydrotreating conditions described above feedstocks (petroleum hydrocarbon having a kerosene fraction) is generally a reaction temperature two hundred and twenty to three hundred fifty ° C, the hydrogen pressure l~6MP a, LHSV0 1~:. LO h one ^1, hydrogen / Oil ratio is 10 to 300 NL / L. Preferably reaction temperature 250 ° C ~ 340 ° C, hydrogen pressure 2 ~ 5MPa, LHSV1 ~: LO h hydrogen / oil ratio 30 ~ 200 NL / L, more preferably reaction temperature 27O 0 C to 3 30 0 C, hydrogen pressure 2 to 4 MPa, LHSV 2 to: LO h- ¹ hydrogen / oil ratio 5 0 to 2 0 0 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 desulfurization and hydrogenation reactions are promoted, but there is an economically optimal point. The lower the LHSV is, the better the reaction is. However, if it is too low, a very large reaction column volume is required, which is disadvantageous because it requires excessive capital investment.

 The apparatus for hydrotreating the feedstock may be of any configuration, and the reaction towers may be used alone or in combination, and hydrogen may be additionally injected between the reaction towers. You may have hydrogen removal equipment.

 As the reaction mode of the hydrotreating apparatus, a fixed bed system is preferably adopted. Hydrogen can take either a countercurrent or cocurrent flow format with respect to the feedstock oil, or may have a plurality of reaction towers and a combination of countercurrent and cocurrent flow. The general format is downflow, and the gas-liquid twin-cocurrent format is preferred. Hydrogen gas may be injected into the middle column 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, zircoia, polya, silica, or zeolite. In the present invention, at least one of titaair, zircoa, polya, silica, and zeolite is composed of alumina. What you have is 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. In addition, once a composite hydroxide or composite oxide such as silica alumina, silica zirconia, alumina titania, silica titania, or alumina polya is prepared, it is prepared in the form of alumina gel or other hydroxides or in an appropriate solution. You may add and prepare in arbitrary processes of a process. The ratio of alumina to other oxides is a force S that can take an arbitrary ratio with respect to the porous carrier, preferably 90% by mass or less, more preferably 60% by mass or less, more preferably 40% by mass of alumina. It is below mass%. These conditions and the catalyst are not particularly limited as long as the properties of the feedstock are satisfied.

Zeolite is a crystalline aluminosilicate, faujasite, pentaci And those that have been super-stabilized by a predetermined hydrothermal treatment and / or acid treatment, or those in which the alumina content in the zeolite is adjusted can be used. Preferably used are faujasite and mordenite, particularly preferably Y type and beta type. Y-type is preferably ultra-stabilized. Zeolite super-stabilized by hydrothermal treatment has a new structure in the range of 20 to 10 OA in addition to the original microporous structure called micropores below 2 OA. A pore is formed. 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, N i—M o, N i—W, C o—N i—M o, C o One N i—W, etc. can be used. As the metal source, a general inorganic salt or a complex salt compound can be used. As the loading method, any of the loading methods used in usual hydrogenation catalysts such as impregnation method and ion exchange method can be used. Further, 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 process for preparing the porous support, or after further supporting on the appropriate oxide, composite oxide or zeolite in the intermediate process for preparing the porous support. Alternatively, heat concentration and kneading may be performed.

The amount of active metal supported is not particularly limited, but is 0.1 to 10% by mass, preferably 0.15 to 5% by mass in terms of the total amount of metal with respect to the catalyst mass. / ₀ , more preferably 0.2 to 3% by 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 given in accordance with a predetermined procedure, the active metal on the catalyst is reduced and hydrogenation activity is expressed. As described above, a kerosene fraction refined from crude oil or the like is hydrotreated to produce petroleum hydrotreated oil (light oil base material B ′). The second light oil composition of the present invention comprises the light oil base material A ′ and the light oil base material B ′, and the mixing ratio of the light oil base material A ′: the light oil base material B ′ is 95 to 30% by volume: 5-70 a capacity _^0/0, preferably from 90 to 35 volume percent is: 1 5-60 volume%: a 10 to 65 volume _^0/0, and more preferable properly is 85-40% by volume. The light oil composition of the present invention comprises the above-mentioned base material, has a 90% distillation temperature of 360 ° C. or less, a sulfur content of 10 mass p pni or less, and an oxygen content of 1 mass. /. Hereinafter, a fatty acid alkyl es ether fraction 3.5 wt _^0/0 or less, a total acid number 0.1 3MgK_〇_HZg hereinafter methanol content 0.01 wt% or less, glyceride fraction 0.01 mass. /. The following is a light oil composition having a clogging point of 1 ° C. or less.

 The clogging point (CFPP) of the light oil composition of the present invention must satisfy the JIS No. 2 light oil standard — 5 ° C or less, and from the standpoint of preventing pre-filter clogging of diesel vehicles. The temperature is preferably 6 ° C or lower, more preferably 17 ° C or lower. Here, the clogging point refers to the clogging point measured by JI S K 2288 “Test method for light oil clogging point”.

 In addition, the pour point of the gas oil composition of the present invention needs to satisfy 17.5 ° C or less which is the J I S 2 gas oil standard. Further, from the viewpoint of low temperature startability or low temperature drivability, and also from the viewpoint of maintaining the injection performance of the electronically controlled fuel injection pump, it is preferably 110 ° C or lower. Here, the pour point means the pour point measured according to JISK 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.

 The sulfur content of the gas oil composition of the present invention is required to be 10 mass ppm or less, preferably 5 mass p from the viewpoint of reducing harmful exhaust components discharged from the engine and improving the performance of the exhaust gas aftertreatment device. pm or less, more preferably 3 mass p pm or less, and even more preferably 1 mass p pm or less. In addition, the sulfur content here means the mass content of the sulfur content based on the total amount of the gas oil composition measured by JIS K 2541 “Sulfur content test method”.

The oxygen content of the light oil composition of the present invention needs to be 1% by mass or less from the viewpoint of improving oxidation stability, preferably 0.8% by mass or less, more preferably 0.6% by mass or less, More preferably 0.4 mass% or less, most preferably 0.2 mass% or less It is. 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. If 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 J I S K 2 2 6 5 “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 N O X 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 refers to the cetane index using the 8.4 variable equation of JISK 2280 “Petroleum product-fuel oil-octane number and cetane number test method and cetane index calculation method”. It means the value calculated by “Calculation method”. Here, the cetane index in the above JIS standard is generally applied to light oil to which no cetane number improver is added. However, in the present invention, the cetane index is also applied to a light oil composition to which a cetane number improver is added. Applying the above “8.4 Calculation method of cetane index using variable equation”, the value calculated by this calculation method is expressed as cetane index.

 The cetane number in the light oil composition of the present invention is preferably 52 or more, more preferably 54 or more, and further preferably 55 or more. If the cetane number is less than 52, 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 90 or less, more preferably 88 or less, and even more preferably 85 or less. In the light oil composition of the present invention, an appropriate amount of a cetane number improver can be blended as necessary to improve the cetane number of the obtained light oil composition. The cetane number here is measured in accordance with “7. Cetane number test method” in JISK 2280 “Petroleum products / Fuel oil / octane number / cetane number test method and cetane index calculation method”. Means cetane number.

The density of the light oil composition of the present invention at 15 ° C is 7500 k from the viewpoint of securing the calorific value. is preferably GZm ³ or more, more preferably 760 k gZm ³ or more, 7 7 0 kg / m ³ or more is more preferable. Further, the density, NOx, from the viewpoint of reducing the emissions of PM, 8 50 preferably kg Roh m ³ or less, more preferably 845 k gZ m ³ or less, 840 kg / m ³ or less Is more preferable. The density here means the density measured according to JISK 2249 “Density test method and density / mass / capacity conversion table for crude oil and petroleum products”.

 The light oil composition of the present invention has a lubricating performance such that the HFRR wear scar diameter (WS 1.4) is preferably 460 βm or less, more preferably 430 μm or less, and further preferably 410 μm or less. desirable. When the HFRR wear scar diameter (WS 1.4) exceeds 46 0; / m, especially in a diesel engine equipped with a distributed injection pump, the driving torque of the pump during operation will increase and the wear of each part of the pump will increase. Cause deterioration of exhaust gas performance and fine particle performance as well as the engine itself may be destroyed. There is also concern about wear on the sliding surface of electronically controlled fuel injection pumps capable of high-pressure injection.

 The HFRR wear scar diameter (WS 1.4) referred to in the present invention is measured by the Petroleum Institute Standard JPI-5 S-50-98 “Light Oil-Lubricity Test Method” published by the Japan Petroleum Institute. Value.

The aromatic content in the light oil composition of the present invention is not particularly limited, but it is preferably 20% by volume or less, more preferably from the viewpoint of enhancing the environmental impact reduction effect and reducing NOx and PM. 19% by volume or less, more preferably 18% by volume or less. The aromatic content in the present invention is measured in accordance with the Petroleum Institute Method JPI-5 S-49-97 “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method” published by the Japan Petroleum Institute. It means the volume percentage of the aromatic content (capacity. / ₀ ). The water content of the light oil composition of the present invention is preferably not more than 300 volumes p pm from the viewpoint of adverse effects on the components to the fuel tank and the like, and suppression of hydrolysis of ester compounds, and is preferably 250 volumes p pm More preferably, it is more preferably 200 capacity or less. The moisture here is the moisture specified in JISK 2275 5 “Moisture test method (crude oil and petroleum products) j”.

The distillation property in the light oil composition of the present invention requires that the 90% by volume distillation temperature be 360 ° C or less, preferably 340 ° C or less, more preferably 3 30 ° C or lower, more preferably 320 ° C or lower. When the 90 vol% distillation temperature exceeds 360 ° C, the emission of PM and fine particles tends to increase. The 90 volume% distillation temperature is preferably 280 ° C or higher, more preferably 285 ° C or higher, more preferably 290 ° C or higher, and even more preferably 295 ° C or higher. If the 90% volume distillation temperature is less than 280 ° C, the fuel efficiency improvement effect will be insufficient and the engine output will tend to decrease. The 90% by volume distillation temperature here means a value measured in accordance with JISK 2254 "Petroleum product one distillation test method one atmospheric pressure method".

There is no particular restriction on the kinematic viscosity at 30 ° C of the gas oil composition of the present invention, 2. is preferably 5 mm ² / s or more, 2. more preferably 7 mm ² / s or more, 2 More preferably, it is 9 mm 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 poor. Further, the kinematic viscosity at 30 ° C of the light oil composition of the present invention is preferably 5 mm ² // s or less, more preferably 4.7 mm ² ks or less, 4. More preferably 5 mm ² / s or less If the kinematic viscosity exceeds 5 mm ² / s, the internal resistance of the fuel injection system increases, the injection system becomes unstable, and NO in the exhaust gas The concentration of x and PM will become high The kinematic viscosity here means the kinematic viscosity measured by JISK 2283 “Crude oil and petroleum products kinematic viscosity test method and viscosity index calculation method”.

The carbon content of 10% residual oil in the light oil composition of the present invention is not particularly limited. From the viewpoint of reducing fine particles and soot, and maintaining the performance of the exhaust gas aftertreatment device mounted on the engine, 0.1% by mass or less is preferable, 0.08% by mass or less is more preferable, and 0.06% by mass. It is more preferable that the value is ₀ or less. The residual carbon content of 10% residual oil here refers to the residual carbon content of 10% residual oil as measured by JISK 2270 “Testing method for residual carbon content of crude oil and petroleum products”.

In the light oil composition of the present invention, it is necessary that the total acid value is 0.13 mgK0H / g or less from the viewpoint of adverse effects on engine members. The total acid value indicates the amount of free fatty acids in the mixture. There is concern about the sound. Therefore, the total acid value is preferably 0.1 Omg KOHZg or less, more preferably 0.08 mgKOH / g or less, and further preferably 0.05 mg KOHZg or less. The total acid value here means the total acid value measured by JISK 2501 “Testing method for neutralization of petroleum products and lubricants”.

 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 burn-out property in the engine combustion and 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. Here, the fatty acid alkyl ester content means the fatty acid alkyl ester content measured according to 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 the methanol content measured according to JIS K 2536 and EN 14110.

 In the light oil composition of the present invention, from the viewpoint of adverse effects on the fuel injection system, the amount of dalyceride needs to be 0.01% by mass or less. 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. Here, glyceride content means glyceride content measured according to EN 14105.

 In the light oil composition of the present invention, an appropriate amount of a cetane number improver can be blended as necessary 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 nitrates and organic peroxides. One of these cetane number improvers may be used alone, or two or more thereof may be used in combination.

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-ethoxytyl nitrate, isopropyl nitrate, butyl nitrate, primary amyl nitrate, secondary amyl nitrate, isoamyl nitrate, Various nitriles such as primary hexyl nitrate, secondary hexyl nitrate, n-heptyl nitrite, n-octatinoleate, 2-ethenolehexenolate nitrate, cyclohexenolate nitrate, ethylene glycol <geninate In particular, an alkyl nitrate having 6 to 8 carbon atoms is preferable. The content of the cetane number improver is preferably not less than 500 ppm by mass, more preferably not less than 600 ppm by mass, and more preferably not less than 700 ppm by mass. It is particularly preferably 800 ppm by mass or more, and most preferably 900 ppm by mass or more. If the content of cetane improver is less than 500 ppm by mass, sufficient cetane number improvement effect will not be obtained, and PM, aldehydes, and even NOx in diesel engine exhaust gas will not be reduced sufficiently. There is a tendency. In addition, the upper limit of the content of the cetane number improver is not particularly limited, but it is preferably 1400 mass ppm or less, preferably 1250 massppm or less, based on the total amount of the light oil composition. More preferably, it is more preferably 110 mass 111 or less, and most preferably 100 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 by diluting an active ingredient that contributes to improving the cetane number (ie, the cetane number improver itself) with an appropriate solvent. . When the light oil composition of the present invention is prepared using such a commercially available product, the content of the active ingredient in the light oil composition is preferably within the above 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. Ester-based lubricity improvers include glycerin carboxylic acid esters. The carboxylic acid constituting the carboxylic acid ester may be one kind or two or more kinds. Specific examples thereof include linoleic acid, oleic acid, salicylic acid, palmitic acid, myristic acid, hexadecenoic acid, etc. There is.

 The blending amount of the lubricity improver is not particularly limited as long as the HFRR wear scar diameter (WS 1.4) is within the above-mentioned preferable range, but is preferably 35 mass ppm or more based on the total amount of the composition. More preferably, it is 50 mass p pm or more. When the blending amount of the lubricity improver is within the above range, the effectiveness of the blended lubricity improver can be effectively extracted. For example, in a diesel engine equipped with a distributed injection pump, The increase in driving torque of the pump inside can be suppressed, and pump wear can be reduced. In addition, the upper limit of the amount added is preferably not more than 150 mass p pm on the basis of the total amount of the composition because an effect commensurate with the amount of addition cannot be obtained even if it is added more than that, and it is preferable that the upper limit of the amount is 10 mass p pm The following is more preferable.

 Examples of the detergent include imide compounds; alkenyl succinic acid imides such as polybutyric succinic acid imide synthesized from polybutyric succinic anhydride and ethylene polyamines; pentaerythritol, etc. Estenoles of succinic acid such as polybutyrsuccinic acid ester synthesized from polyhydric alcohols of polybutene succinic anhydride; copolymers of dianoloxy ^ / aminoamino ^ methacrylate, polyethyleneglycol ^ / methacrylate, burpyrrolidone, etc. and alkyl methacrylate And ashless detergents such as a reaction product of carboxylic acid and amine. Among them, alkenyl succinic acid imide and a reaction product of carboxylic acid and amine are preferable. These detergents can be used alone or in combination of two or more.

 Examples of using alkenyl succinic acid imide are alkenyl succinic acid having a molecular weight of about 1 000 to 3000, and alkenyl succinic acid having a molecular weight of about 700 to 2000 and a molecular weight of 1 Sometimes used in admixture with alkenyl succinic acid imide of about 0000-20000.

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 a fatty acid having 1 to 24 carbon atoms and a carbon number of 7 -24 aromatic carboxylic acids and the like. C 1-2 fatty acids Examples thereof include, but are not limited to, linoleic acid, oleic acid, palmitic acid, myristic acid, and the like. Examples of the aromatic carboxylic acid having 7 to 24 carbon atoms include benzoic acid and salicylic acid, but are not limited thereto. Further, the amine constituting the reaction product of the carboxylic acid and the amine may be one type or two or more types. The amine used here is typically oleiramine, but is not limited thereto, and various amines can be used.

 The amount of the detergent is not particularly limited, but in order to bring out the effect of incorporating the detergent, specifically, the effect of suppressing the clogging of the fuel injection nozzle, the amount of the detergent is based on the total amount of the composition. It is preferably at least ppm by mass, more preferably at least 60 ppm by mass, and even more preferably at least 80 ppm by mass. There is a possibility that the effect does not appear even if an amount less than 30 mass p pm is added. On the other hand, if the amount is too large, a corresponding effect cannot be expected.On the other hand, there is a risk of increasing NO x, PM, aldehydes, etc. in the diesel engine exhaust gas. Is preferably 300 ppm by mass or less, more preferably 180 ppm by mass or less.

 As in the case of the cetane improver described above, the active ingredients that contribute to improving lubricity or cleaning were diluted with an appropriate solvent in those sold as lubricity improvers or detergents. It is customary to obtain it in the state. 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 enhancing 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 amides; antioxidants such as phenols and amines; and metal inertness such as salicylidene derivatives. Anti-icing agents such as polydalicol ethers; Corrosion inhibitors such as aliphatic amines and alkenyl succinic acid esters; Antistatic agents such as ayuonic, cationic and amphoteric surfactants; Coloring of azo dyes Agents: Silicon-based antifoaming agents and the like. The addition amount of other additives can be arbitrarily determined. 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.

[Industrial applicability]

According to the present invention, using an environmentally low load type light oil base material made from animal and vegetable oils and / or ingredients derived from animal and vegetable oils, it has excellent life cycle CO ₂ emission characteristics and oxidation stability, and excellent low-temperature fluidity. A light oil composition is provided.

[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.

(Examples 1 to 6 and comparative examples:! To 4)

 The oil to be treated with 5 mass ppm of dimethyl disulphide (D MDS) as a sulfur-containing hydrocarbon compound added to vegetable oils and fats having the properties shown in Table 1 is reacted under the reaction conditions shown in Table 2. A loaded light oil base was prepared.

 In addition, the oil to be treated in which 80% by volume of the vegetable oil having the properties shown in Table 1 is mixed with 20% by volume of the petroleum-based light oil base material having the properties shown in Table 1 is reacted under the reaction conditions shown in Table 2. The environmentally low load type light oil base material shown in 3 was prepared.

 Table 3 shows the properties of fatty acid alkyl esters obtained by esterifying the vegetable oils shown in Table 1. These fatty acid alkyl esters are methyl ester compounds obtained by reaction with methanol. Here, the fatty acid alkyl esters are stirred in the presence of an alkali catalyst (sodium methylate) at 70 ° C for about 1 hour. A transesterification reaction in which an ester compound was obtained by contact reaction was used.

 Light oil composition by blending the low environmental load diesel oil base shown in Table 3, methyl esterified vegetable oil and petroleum oil hydrorefined oil, hydrocracked diesel oil, and dewaxed diesel oil base A product was produced (Examples 1 to 6 and Comparative Examples 1 to 4).

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, good Results of measurement of aromatic content, cetane number and cetane index, residual carbon content of 10% residual oil, moisture, clogging point, oxidation stability test (acid value before and after accelerated test), and life cycle c

0 ₂ Emissions calculation results are shown in Table 4 and Table 5.

 The properties of fuel oil were measured by the following method.

 Density refers to the density measured by J I S K 2 2 4 9 “Density test method for crude oil and petroleum products and density 'mass-capacity conversion table”.

 Kinematic viscosity refers to the kinematic viscosity measured by J I S K 2 2 8 3 “Crude oil and petroleum products – kinematic viscosity test method and viscosity index calculation method”.

 Sulfur content refers to the mass content of the sulfur content based on the total amount of light oil composition measured by J I S K 2 5 4 1 “Sulfur content test method”.

 The oxygen content was measured by elemental analysis.

 Distillation properties are all values measured by J I S Κ 2 2 5 4 “Petroleum product one distillation test method”.

 The aromatic content is measured according to the Petroleum Institute method JPI-5S-4 9-9 7 "Hydrocarbon type test method-High performance liquid chromatograph method" published by the Japan Petroleum Institute. Means volume percentage (volume%) of quantity.

 Moisture means the moisture specified in JIS K 2 27 5 “Moisture test method (crude oil and petroleum products)”.

 The flash point is the value measured by J I S K 2 2 6 5 “Crude oil and petroleum product flash point test method”.

 The total acid value means the total acid value measured by JI S K 2 5 0 1 “Testing method for neutralization of petroleum products and lubricants”.

 The clogging point is the clogging point measured by JI S K 2 2 8 8 “Test method for light oil clogging point”.

 The cetane index was calculated according to `` Calculation method of cetane index using 8.4 variable equations '' in JISK 2280 “Petroleum products—Fuel oil one octane number and cetane number test method and cetane index calculation method”. Refers to the value. The cetane number is J I S K

2 2 8 0 Refers to the cetane number measured in accordance with “7. Cetane Number Test Method” in “Petroleum Products / Fuel Oil-Octane Number and Cetane Number Test Method and Cetane Index Calculation Method”. Taste.

(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 C0 ₂ ”) is based on CO ₂ emissions, fuel consumption and fuel density when the above vehicle test is performed. Calculated as emissions per calorific value.

In addition, C_〇 ₂ (hereinafter referred to as "Well to Tank C0 _2".) That occurred to the fuel oil supply to the vehicle tank from mining, mining of raw materials and crude oil source, transport, processing, delivery, oil supply to the car both It was calculated as the sum of CO ₂ emissions in the series of flows up to. In calculating “rWell to Tank C0 ₂ ”, the calculation was performed taking into account the carbon dioxide emissions shown in (1 B) to (5 B) below. As data necessary for such calculation, refinery operation performance data possessed by the present inventors was used.

 (1 B) Carbon dioxide emissions associated with the use of fuel in various processing equipment and boilers.

(2 B) In the treatment using hydrogen, the amount of carbon dioxide emitted during the reforming reaction in the hydrogen production equipment.

 (3 B) Carbon dioxide emissions associated with catalyst regeneration when passing through equipment that involves continuous catalyst regeneration such as catalytic cracking equipment.

 (4 B) Carbon dioxide emissions when diesel oil compositions are manufactured or unloaded in Yokohama, delivered from Yokohama to Sendai, and refueled in Sendai.

 (5 B) The amount of carbon dioxide emissions when animal and vegetable oils 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 fats and ingredients derived from animal and vegetable fats and oils, the so-called Kyoto Protocol rules that carbon dioxide derived from these fuels is not counted as emissions. In this calculation, this was applied to “Tank to Wheel C0 ₂ ” generated during combustion.

The emissions calculated in this way (“Tank to Wheel C0 ₂ ” and “Well to Tank C0 ₂ ”, and their total life cycle C0 ₂ (LC) are shown in Table 4. It is shown in Table 5. In addition, the comparative example 1 is set to 100, and the results of comparing and quantifying each result are also shown.

(Oxidation stability test)

1 The fuel was accelerated and degraded under conditions of 15 hours at 15 ° C and oxygen publishing, and oxidation before and after the test was measured. The total acid value here means the total acid value measured according to JISK ²⁵ 01 “Testing method for neutralization of petroleum products and lubricants”. The light oil compositions used in the examples and comparative examples are as shown in Table 4 and Table 5. Petroleum hydrotreating, which is a water environment low load type light oil base, a methyl esterified vegetable oil, and a petroleum base It is produced by blending oil at a specific ratio.

As is clear from Table 4 and Table 5, the environmentally low-loading diesel oil base material, and the environmentally low-loading diesel oil base material and petroleum-based hydrotreated oil are mixed and used in the range defined by the present invention. In Examples 1 to 6 blended in the range, 95% distillation temperature is 360 ° C or less, sulfur content is 10 mass ppm or less, oxygen content is 1 mass% or less, fatty acid methyl ester content is 3.5 mass% or less, Total acid value increase 0.13 mgKOH / g or less, methanol content 0.01 mass. Easily and reliably obtain a light oil composition that satisfies the properties of ₀ or less, glyceride content of 0.01 mass% or less, and a clogging point of 5 ° C or less and low carbon dioxide emissions in the life cycle. I was able to. On the other hand, in Comparative Examples 1 to 4 in which a light oil composition was prepared without using the specific environment-friendly light oil base, the light oil composition that is the object of the present invention is not necessarily obtained.

2008/063823 Table 1

 Table 2

Table 3

Table 4

Table 5

Claims

The scope of the claims

1. [A] In the presence of hydrogen, to-be-treated oil in which animal and vegetable oils and / or manakos are mixed with animal and vegetable oil and fat-containing sulfur-containing hydrocarbon compounds so that the sulfur content is 1 mass ppm to 2 mass%, A porous inorganic oxide containing two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and a periodic table 6A group supported on the porous inorganic oxide And a catalyst containing one or more metals selected from Group 8 elements, hydrogen pressure 2 to 13 MPa, liquid space velocity 0.1 to 3.0 h "\ hydrogen / oil ratio 1 50 to 1) 500 NL / L, reaction temperature: 1 to 90% by volume of a fraction produced by contact under conditions of 50 to 480 ° C (environmental low load gas oil base), and (i) crude oil, etc. Atmospheric pressure residue oil obtained by treatment with a pressure distillation apparatus, and further reduced pressure gas oil obtained by treatment with a vacuum distillation apparatus is further hydrogenated. Hydrocracked gas oil fraction obtained by cracking (boiling range: 200 to 350 ° C) Light oil base materials A-1 and Z obtained by mixing 90 to 10% by volume or (ii) crude oil, etc. It consists of a light oil base A-2 obtained by mixing 90 to 10% by volume of a dewaxed light oil base obtained by further hydrodewaxing a light oil fraction obtained by treatment with an atmospheric distillation apparatus. Gas oil base material A 95 to 30% by volume [B] 5 to 70% by volume of petroleum hydrotreated oil (light oil base material B) obtained by hydrotreating light oil fraction refined from crude oil, etc. 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, and total acid value is 0.13 mgK. ○ HZg or less, Methanol content 0.01 mass / ₀ or less, Glyceride content 0.01 mass% or less, Clogging point 1 5 ° C or less A gas oil composition comprising gas oil base materials A and B.

2. [Α '] Animal and vegetable oils and / or animal and vegetable oil and fat-derived components in the presence of hydrogen 10 to 90 volumes. / ₀ and petroleum base material with light oil fraction refined from crude oil etc. 90 ~ 10% by volume is selected from Aluminum, Ca, Zirconium, Boron, Titanium and Magnesium 2 Contains one or more metals selected from Group 6 and Group 8 elements of the Periodic Table supported by porous inorganic oxides composed of more than one element and the porous inorganic oxides The catalyst to be used, hydrogen pressure 2 ~ 1 3 MP a, liquid hourly space velocity ^{0.:! ~ 3. 0 h _1} , hydrogen / oil ratio of 1 50~1 500NLZL, fraction is prepared by contacting under the conditions of reaction temperature 1 50 to 480 ° C

(Environmental low load gas oil base) 10-90% by volume, (i ') Reduced pressure obtained by treating crude oil etc. with atmospheric distillation equipment and then with atmospheric distillation equipment Diesel oil base A'-1 obtained by mixing 90 to 10% by volume of hydrocracked gas oil fraction (boiling range: 200 to 350 ° C) obtained by further hydrocracking gas oil Or (ii ') Obtained by mixing 90 to 10% by volume of a dewaxed gas oil base obtained by further hydrodewaxing a gas oil fraction obtained by treating crude oil or the like with an atmospheric distillation apparatus. Petroleum hydrotreated oil obtained by hydrotreating kerosene fraction refined from crude oil, etc. to 95-30% by volume of diesel fuel base A '— 2

90% distillation temperature is 360 ° C or less, sulfur content is 10 mass ppm or less, oxygen content is 1 mass% or less, and fatty acid alkyl is obtained by mixing 5 to 70 vol% (light oil base material Β,). Ester content 3.5% by mass or less, total acid value 0.13mgKOH / g or less, methanol content 0.01% by mass or less, glyceride content 0.01% by mass or less, clogging point 1 ° C or less A gas oil composition comprising gas oil bases A ′ and B ′ characterized by