JP5072609B2 - Method for producing light oil composition - Google Patents

Description

The present invention is a mixture of an environmentally low load type light oil base produced from animal and vegetable oils and / or triglyceride-containing hydrocarbons derived from animal and plant oils and fats and a hydrorefined oil having a light oil fraction refined from crude oil, etc. the fraction obtained by obtained by mixing a cold flow improver, excellent life cycle CO ₂ emission properties and oxidation stability, it relates and gas oil composition with excellent low temperature fluidity.

Conventionally, as the base material for light oil, straight-run gas oil obtained from crude oil atmospheric distillation equipment is hydrorefined or hydrodesulfurized, and straight-run kerosene obtained from crude oil atmospheric distillation equipment is hydrogenated. Those subjected to hydrorefining treatment or hydrodesulfurization treatment are known. Conventional gas oil compositions are produced by blending one or more of the above gas oil base and kerosene base. Moreover, additives, such as a cetane number improver and a detergent, are mix | blended with these light oil compositions as needed (for example, refer nonpatent literature 1).
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 urgently 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 Because it contains almost no sulfur content, it is attracting 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.
JP 2004-189885 A

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 fatty acid alkyl ester having many saturated fatty acid groups, it is solid even at room temperature, so that it is inferior in handling as a fuel and it is difficult to ensure fluidity at low temperature. On the other hand, in the case of BDF containing many 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, are raw materials used for refining the fatty acid alkyl ester, which 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. By adding and mixing an appropriate amount of a low-temperature fluidity improver to the fraction obtained by mixing hydrorefined oil having a gas oil fraction refined from 1, it has excellent life cycle CO ₂ emission characteristics and oxidation stability And it is providing the light oil composition excellent in low-temperature fluidity | liquidity.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the present invention comprises an oil to be treated in which a sulfur-containing hydrocarbon compound is mixed with animal and vegetable oils and / or animal and plant oils and fat-derived components 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 groups 6A and 8 of the periodic table supported by the porous inorganic oxide A sulfide catalyst containing one or more metals selected from the elements of: hydrogen pressure 2-13 MPa, liquid space velocity 0.1-3.0 h ⁻¹ , hydrogen / oil ratio 150-1500 NL / L, reaction temperature 180 A fraction obtained by hydrotreating under the condition of ˜480 ° C. (first stage) is further obtained from aluminum, silicon, zirconium, boron, titanium, magnesium and zeolite. A hydrogen pressure of 2 to 13 MPa using a catalyst containing at least one metal selected from the group consisting of a porous inorganic oxide composed of a substance and a group 8 element of the periodic table supported on the porous inorganic oxide, Low environmental load obtained by further hydrotreating (second stage) under conditions of a liquid space velocity of 0.1 to 3.0 h ⁻¹ , a hydrogen / oil ratio of 250 to 1500 NL / L, and a reaction temperature of 150 to 380 ° C. by the hydrotreated oils 90-80% by volume obtained by purifying the mold base gas oil 10-20 volume percent and crude oil were mixed, and the cold flow improver is added 10 to 1000 mass ppm, 90 % Distillation temperature is 360 ° C or lower, flash point is 45 ° C or higher, cetane number is 50 or higher, clogging point is -5 ° C or lower, (cloud point-clogging point) is + 6 ° C or higher, and sulfur content is 10 Mass ppm or less, oxygen content is 1 mass% or less, The glyceride content is 0.01% by mass or less, the fatty acid alkyl ester content is 3.5% by mass or less, the total acid value is 0.13 mg KOH / g or less, and the acid value increase after the oxidation stability test is 0.12 mg KOH / g. It is related with the manufacturing method of the light oil composition characterized by obtaining the light oil composition which is the following.

The present invention also relates to the method for producing a gas oil composition as described above, wherein the ratio of the amount of isoparaffin to the total amount of paraffin of the environmentally low load gas oil base is 0.20 or more and 0.80 or less. is there.

According to the present invention, it has been difficult to realize with a conventional light oil composition by including an environmentally low load light oil base material produced using a raw material of animal and vegetable oils and fats and triglyceride-containing hydrocarbons derived from animal and vegetable oils and fats. Provided is a light oil composition that has excellent life cycle CO ₂ emission characteristics and excellent oxidation stability and low-temperature fluidity that have been difficult to achieve with conventional fuels derived from animal and vegetable oils.

Hereinafter, the present invention will be described in detail.
As a constituent of the light oil composition of the present invention, in the presence of hydrogen, a sulfur-containing hydrocarbon compound was mixed with animal and vegetable oils and / or components derived from animal and vegetable oils so that the sulfur content was 1 mass ppm to 2 mass%. A porous inorganic oxide comprising an oil to be treated and two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and a periodic table 6A supported on the porous inorganic oxide A sulfide catalyst containing at least one metal selected from Group 8 and Group 8 elements, hydrogen pressure 2-13 MPa, liquid space velocity 0.1-3.0 h ⁻¹ , hydrogen / oil ratio 150-1500 NL / L, a fraction obtained by hydrotreating under the reaction temperature of 180 to 480 ° C. (first stage) is further mixed with aluminum, silicon, zirconium, boron, titanium, magnesium and Hydrogen pressure 2 using a catalyst containing at least one metal selected from the group consisting of a porous inorganic oxide composed of a substance selected from zeolite and a group 8 element of the periodic table supported on the porous inorganic oxide ~ 13 MPa, liquid space velocity 0.1-3.0 h ⁻¹ , hydrogen / oil ratio 250-1500 NL / L, reaction temperature 150-380 ° C. An environment-friendly light oil base material is used.

The environmentally low load light oil base according to the present invention is a low sulfur light oil fraction, kerosene fraction, or a mixture thereof obtained by hydrotreating a predetermined raw material oil under specific conditions.
As the predetermined raw material oil, the sulfur content of the sulfur-containing hydrocarbon compound in the component derived from animal and vegetable fats and / or animal and plant fats and oils is 1 mass ppm to 2 mass%, preferably 1 mass ppm to 1 mass%. Mixed oil to be treated is used.
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 oils include beef tallow, milk lipid (butter), pork tallow, sheep fat, whale oil, fish oil, liver oil, and the like. Vegetable oil and vegetable oil ingredients include coconut palm, palm palm, olives, 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.

  In addition, the sulfur-containing hydrocarbon compound contained in the raw oil (treated oil) is not particularly limited, and specific examples include sulfides, disulfides, polysulfides, thiols, thiophenes, benzothiophenes, dibenzothiophenes, and derivatives thereof. It is done. The sulfur-containing hydrocarbon compound contained in the oil to be treated may be a single compound or a mixture of two or more. Furthermore, you may mix the petroleum hydrocarbon fraction containing a sulfur content with animal and vegetable fats and oils and animal fats and oil-derived components.

In the present invention, the raw oil (treated oil) is subjected to a two-stage hydrotreatment,
A predetermined environmental low load type light oil base material is manufactured.

The conditions for the hydrogenation treatment (first stage) of the raw material oil are the conditions in which the hydrogen pressure is 2 to 13 MPa, the liquid space velocity is 0.1 to 3.0 h ⁻¹ , and the hydrogen / oil ratio is 150 to 1500 NL / L. More preferably, the hydrogen pressure is 3 to 12 MPa, the liquid space velocity is 0.2 to 2.0 h ⁻¹ , the hydrogen / oil ratio is 200 to 1200 NL / L, and the hydrogen pressure is 4 Even more desirable are conditions of ˜10.5 MPa, liquid space velocity of 0.25 to 1.0 h ⁻¹ , and hydrogen / oil ratio of 300 to 1000 NL / L.
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 can be arbitrarily set in order to obtain the desired decomposition rate of the feedstock heavy fraction or the desired fraction yield. Furthermore, in order to suppress the oxygen content contained in the distillate treated by the pretreatment catalyst in the hydrotreatment (first stage) within the above upper limit value, the pretreatment catalyst in the hydrotreatment (first stage). The reaction temperature of the part and the reaction temperature of the hydrocracking catalyst part can be arbitrarily set. The average temperature of the entire reactor is generally preferably in the range of 180 to 480 ° C, desirably 220 to 400 ° C, more desirably 260 to 360 ° C. 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.

  As a catalyst for the hydrotreatment (first stage), a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and the porous inorganic oxide A sulfide catalyst containing at least one metal selected from elements of Group 6A and Group 8 of the periodic table supported on is used.

  As the support for the hydrotreating (first stage) 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, zirconia, boria, titania, 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, 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. On the other hand, if the content exceeds 20% by weight, the acid content of the carrier Properties 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, zirconia, boria, titania, and magnesia, which are carrier components other than alumina, is not particularly limited, and a solution containing general silicon, zirconium, boron, titanium, or 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, and boric acid for boron, etc. it can. For magnesium, 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, it may be added to an aluminum aqueous solution in advance and then an aluminum hydroxide gel containing these components, 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. Although it may be added to the step of adding and kneading, 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 hydrotreating (first stage) catalyst contains at least one metal selected from Group 6A and Group 8 metals of the periodic table, preferably selected from Group 6A and Group 8 Contains two or more metals. For example, Co—Mo, Ni—Mo, Ni—Co—Mo, Ni—W, and the like can be mentioned. In the hydrogenation treatment (first stage), these metals are used after being converted to 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 the lower limit, the activity may decrease due to the decrease in the number of active points. If the upper limit is exceeded, 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 that the activity is reduced.

  In any of the above-mentioned hydrotreating (first stage) catalysts, the method of incorporating an active metal into the catalyst is not particularly limited, and a known method applied when producing a normal desulfurization catalyst may be used. it can. 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.

  The reactor type of the hydrotreatment (first stage) 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 hydrorefined 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 or more, more desirably 15 to 50% by volume or more. 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.

The fraction obtained by the above hydrogenation process (first stage) is further subjected to a second stage hydrogenation process.
The conditions for the hydrogenation treatment (second stage) are as follows: the hydrogen pressure is 2 to 13 MPa, the liquid space velocity is 0.1 to 3.0 h ⁻¹ , and the hydrogen / oil ratio is 250 to 1500 NL / L. More preferably, the hydrogen pressure is 2.5 to 10 MPa, the liquid space velocity is 0.5 to 2.0 h ⁻¹ , and the hydrogen / oil ratio is 380 to 1200 NL / L. The hydrogen pressure is 3 to Even more desirable is a condition of 8 MPa, a liquid space velocity of 0.8 to 1.8 h ⁻¹ , and a hydrogen / oil ratio of 350 to 1000 NL / L.
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. If the hydrogen / oil ratio exceeds the upper limit, 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 can be arbitrarily set in order to obtain the desired decomposition rate of the feedstock heavy fraction or the desired fraction yield. Furthermore, in order to suppress the oxygen content contained in the distillate treated by the pretreatment catalyst in the hydrotreatment (second stage) within the above upper limit value, the pretreatment catalyst in the hydrotreatment (second stage). The reaction temperature of the part and the reaction temperature of the hydrocracking catalyst part can be arbitrarily set. The average temperature of the entire reactor is generally preferably in the range of 150 to 380 ° C, desirably 180 to 350 ° C, more desirably 210 to 330 ° C. 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 catalyst for the hydrogenation treatment (second stage) is a porous inorganic oxide composed of a material selected from aluminum, silicon, zirconium, boron, titanium, magnesium and zeolite, and is supported on the porous inorganic oxide. A catalyst containing at least one metal selected from Group 8 elements of the periodic table is used.
Examples of the porous inorganic oxide used as a carrier for the hydrotreating (second stage) catalyst include alumina, titania, zirconia, boria, silica, and zeolite. Of these, in the present invention, among these, titania, zirconia, boria, Of those, at least one of silica and zeolite and those composed of alumina are preferable. Although the manufacturing method is not particularly limited, an arbitrary preparation method can be adopted using raw materials in a state of various sols and salt compounds corresponding to each element. Furthermore, once the composite hydroxide or composite oxide such as silica alumina, silica zirconia, alumina titania, silica titania, and alumina boria is prepared, the preparation process in the state of alumina gel and other hydroxides or in an appropriate solution state It may be prepared by adding at any step. The ratio of alumina to other oxides can be any ratio with respect to the porous carrier, but preferably alumina is 90% by mass or less, more preferably 60% by mass or less, more preferably 40% by mass or less. , Preferably 10% by mass or more, more preferably 20% by mass or more.

  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.

  As an active metal of the hydrotreating (second stage) catalyst, one or more metals selected from Group 8 elements of the periodic table are used. Among these metals, it is preferable to use one or more metals selected from Pd, Pt, Rh, Ir, Au, and Ni, and it is more preferable to use them in combination. Suitable combinations include, for example, Pd—Pt, Pd—Ir, Pd—Rh, Pd—Au, Pd—Ni, Pt—Rh, Pt—Ir, Pt—Au, Pt—Ni, Rh—Ir, Rh— Au, Rh—Ni, Ir—Au, Ir—Ni, Au—Ni, Pd—Pt—Rh, Pd—Pt—Ir, Pt—Pd—Ni, and the like can be given. Of these, combinations of Pd—Pt, Pd—Ni, Pt—Ni, Pd—Ir, Pt—Rh, Pt—Ir, Rh—Ir, Pd—Pt—Rh, Pd—Pt—Ni, Pd—Pt—Ir Is more preferable, and a combination of Pd—Pt, Pd—Ni, Pt—Ni, Pd—Ir, Pt—Ir, Pd—Pt—Ni, and Pd—Pt—Ir is even more preferable.

  The total content of active metals based on the catalyst mass is preferably 0.1 to 2% by mass, more preferably 0.2 to 1.5% by mass, and 0.5 to 1.3% by mass as the metal. Even more preferred. If the total supported amount of the metal is less than 0.1% by mass, the active sites tend to decrease and sufficient activity cannot be obtained. On the other hand, if it exceeds 2% by mass, the metal is not effectively dispersed and sufficient activity tends not to be obtained.

  In any of the above hydrotreating (second stage) catalysts, 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 may be used. it can. 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.

  The hydrotreating (second stage) catalyst used in the present invention is preferably subjected to reduction treatment of the active metal contained in the catalyst before being subjected to the reaction. Although the reduction conditions are not particularly limited, the reduction is performed by treatment at a temperature of 200 to 400 ° C. in a hydrogen stream. Preferably, the treatment is performed in the range of 240 to 380 ° C. When the reduction temperature is less than 200 ° C., the reduction of the active metal does not proceed sufficiently and the hydrodeoxygenation and hydroisomerization activity may not be exhibited. Further, when the reduction temperature exceeds 400 ° C., the aggregation of the active metal proceeds, and there is a possibility that the activity cannot be exhibited similarly.

  The reactor type of the hydrotreatment (second stage) 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 hydrorefined 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 or more, more desirably 15 to 50% by volume or more. 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.

By the above two-stage hydrotreating, an environmentally low load gas oil base material which is a constituent of the present invention is obtained.
In the environmentally low load type light oil base material, the ratio of the amount of isoparaffin to the total amount of paraffin in the base material is preferably 0.20 or more and 0.80 or less. The ratio is more preferably 0.30 or more and 0.75 or less, and further preferably 0.40 or more and 0.70 or less. If the ratio of the amount of isoparaffin is less than 0.20, since the amount of normal paraffin is large, the nucleating agent of the fluidity improver cannot be co-crystallized, and it becomes difficult to refine the precipitated wax by the fluidity improver. When the ratio of the amount of isoparaffin exceeds 0.80, the cetane number as the base material is lowered, and the combustibility as the product light oil is lowered.

  The gas oil composition of the present invention is a mixture of the above-mentioned environmentally low load gas oil base and a hydrorefined oil refined from crude oil described below at a predetermined ratio, and a predetermined amount of a low-temperature fluidity improver is added. It is manufactured by.

The hydrorefined oil refined from the crude oil, etc., is obtained by treating straight-run gas oil obtained from a crude oil atmospheric distillation device, straight-run heavy oil or residual oil obtained from an atmospheric distillation device with a vacuum distillation device. Hydrocracked gas oil, hydrocracked gas oil obtained by catalytic cracking or hydrocracking of vacuum gas oil, vacuum heavy gas oil or desulfurized heavy oil obtained by hydrocracking, and hydrorefining of these petroleum hydrocarbons Light oil or hydrodesulfurized light oil, straight-run kerosene obtained by atmospheric distillation of crude oil, hydrocracked kerosene produced with hydrocracked light oil, hydrorefined kerosene obtained by hydrotreating the above kerosene fraction, etc. Is mentioned.
These hydrorefined oils can be constituted by blending a plurality of light oil fraction base materials and kerosene fraction base materials in a category that satisfies a predetermined condition. In addition, synthetic light oil synthesized from natural gas, asphalt, coal, biomass or the like can be used.

The hydrotreating process for producing the hydrorefined oil can be performed using a general hydrodesulfurization apparatus in petroleum refining. The hydrotreating conditions are usually a reaction temperature of 170 to 320 ° C., a hydrogen pressure of 2 to 10 MPa, an LHSV of 0.1 to 2 h ⁻¹ , and a hydrogen / oil ratio of 100 to 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.
As a catalyst used for hydrorefining, a general hydrodesulfurization catalyst can be applied. As the active metal, normally, Group 6A and Group 8 metals of the periodic table are preferably used, and examples thereof include Co—Mo, Ni—Mo, Co—W, and Ni—W. As the carrier, a porous inorganic oxide mainly composed of alumina is used. These conditions and the catalyst are not particularly limited as long as the properties of the raw material oil are satisfied.

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.

In the present invention, the mixing ratio of the hydrorefined oil refined from the above-mentioned environmentally low load type light oil base and crude oil is 10 to 20 % by volume of the environmentally low load type light oil base, and the hydrogen refined from crude oil etc. Refined oil is 90-80 % by volume.
The above mixed oil is blended with a low temperature fluidity improver in order to improve low temperature performance. A mixture ratio is 10-1000 mass ppm with respect to mixed oil, Preferably it is 50-750 mass ppm, More preferably, it is 100-500 mass ppm, More preferably, it is 150-300 mass ppm. Although the kind of low-temperature fluidity improver is not particularly limited, general materials such as ethylene-vinyl acetate copolymer and alkenyl succinic acid amide can be used.

  The light oil composition of the present invention has a 90% distillation temperature of 360 ° C. or lower, a flash point of 45 ° C. or higher, a cetane number of 50 or higher, a clogging point of −5 ° C. or lower, a sulfur content of 10 mass ppm or lower, and an oxygen content. 1% by mass or less, triglyceride content 0.01% by mass or less, fatty acid alkyl ester content 3.5% by mass or less, total acid value 0.13 mgKOH / g or less, and increase in acid value after oxidation stability test Is preferably 0.12 mgKOH / g or less and (clouding point-clogging point) value of + 5 ° C. or more.

  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 according to JIS K 2288 “Light oil—clogging point test method”.

(Cloud point - plugging point) of the gas oil composition of the present invention the value of the good Mashiku + 6 ° C. or higher, still more preferably + 7 ° C. or higher. When the value of (clouding point−clogging point) is small, it is necessary to mix a large amount of kerosene fraction in order to lower the clogging point. If the amount of kerosene fraction increases, the density and kinematic viscosity of the product will decrease, which may conflict with the JIS standards for light oil, and may have an adverse effect on actual vehicle performance. In addition, since kerosene fractions are tightly demanded in winter, reducing the amount of kerosene fraction mixed in light oil will lead to cost reduction in commercialization. The cloud point here means a cloud point measured by JIS K 2269 “Crude 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 7 mass ppm or less, More preferably, it is 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, More 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 needs to be 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 triglyceride content of the light oil composition of the present invention is required to be 0.01% by mass or less, preferably 0.008% by mass or less, more preferably 0.005% by mass considering the influence on the member. % Or less. In addition, the triglyceride content as used in the field of this invention shows the value measured based on EN14105.

  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 according to EN14103.

  The cetane number in the light oil composition of the present invention needs to be 50 or more, preferably 52 or more, more preferably 54 or more, and further preferably 55 or more. When the cetane number is less than 50, the concentration of NOx, PM and aldehydes in the exhaust gas tends to be high. Further, from the viewpoint of reducing black smoke in the exhaust gas, the cetane number is preferably 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 410 μm or less, more preferably 400 μm or less. When the HFRR wear scar diameter (WS1.4) exceeds 410 μm, especially in a diesel engine equipped with a distribution type injection pump, it causes an increase in the 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 “Light Oil-Lubricity Test Method” issued by the Japan Petroleum Institute. Means.

  The aromatic content in the light oil composition of the present invention is preferably 15% by volume or less, more preferably 13% by volume or less, and further preferably 10% by volume from the viewpoint of enhancing the environmental load reduction effect and reducing NOx and PM. % 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 the 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 a distillation property in the light oil composition of the present invention, it is necessary that the 90% distillation temperature is 360 ° C. or lower. Preferably it is 340 degrees C or less, More preferably, it is 330 degrees C or less, More preferably, it is 320 degrees C or less. When the 90% distillation temperature exceeds the upper limit, the amount of PM and fine particles discharged tends to increase. The 90% distillation temperature is preferably 280 ° C. or higher, more preferably 285 ° C. or higher, further preferably 290 ° C. or higher, and even more preferably 295 ° C. or higher. If the 90% distillation temperature is less than the lower limit, the fuel efficiency improvement effect becomes insufficient and the engine output tends to decrease.

The kinematic viscosity at 30 ° C. of the light oil composition of the present invention is not particularly limited, but is required to be 2.5 mm ² / s or 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 composition 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".

  The residual carbon content of 10% residual oil in the light oil composition of the present invention is required to be not more than 0.1% by mass, which is JIS No. 2 diesel oil standard. Furthermore, it is preferably 0.08% by mass or less and more preferably 0.06% by mass or less from the viewpoint of reducing fine particles and PM and maintaining the performance of the exhaust gas aftertreatment device mounted on the engine. preferable. 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”.

  Further, the total acid value of the light oil composition of the present invention is required to be 0.13 mgKOH / g or less, preferably 0.10 mgKOH / g or less, more preferably 0.08 mgKOH / g or less. 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. In addition, the total acid value here means the acid value measured by JIS K 2501 "Petroleum products and lubricating oil-neutralization value test method".

  The light oil composition of the present invention needs to have an acid value increase of 0.12 mgKOH / g or less after the oxidation stability test from the viewpoint of storage stability and compatibility with parts. The amount of increase in the acid value is more preferably 0.10 mgKOH / g or less, and further preferably 0.08 mgKOH / g or less. The oxidation stability test referred to in the present invention is conducted under the conditions of 115 ° C. and oxygen bubbling for 16 hours in accordance with ASTM D2274-94.

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 6-8 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. Even more preferably, it is most preferably 900 ppm by mass or more. When the content of the cetane number improver is less than 500 ppm by mass, a sufficient cetane number improving effect cannot be obtained, and PM, aldehydes, and further NOx in diesel engine exhaust gas tend not to be sufficiently reduced. Further, the upper limit of the content of the cetane number improver is not particularly limited, but is preferably 1400 mass ppm or less, more preferably 1250 mass ppm or less, based on the total amount of the light oil composition, and 1100 mass ppm or less. It is more preferable that it is 1000 mass ppm or less.

  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 phenol-based and amine-based antioxidants; 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 such as silicon.
The addition amount of other additives can be arbitrarily determined, but the addition amount of each additive is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, based on the total amount of the light oil composition. is there.

The gas oil composition containing the low-energy environmental light load base oil produced using the animal and vegetable oil and fat of the present invention and the triglyceride-containing hydrocarbon which is a component derived from the animal and vegetable oil and fat, has life cycle CO ₂ emission characteristics, low temperature fluidity, and oxidation stability. It is excellent in all of the properties.

  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 1-2 and Comparative Examples 1-4)
A vegetable oil having the properties shown in Table 1 was used, and 5 mass ppm of a sulfur compound (DMDS; dimethyl disulfide) was added to the vegetable oil to prepare a raw oil (treated oil). This oil to be treated was hydrotreated under the reaction conditions shown in Tables 2 and 3 to prepare environment-friendly light oil base materials 1 to 4.
Moreover, the vegetable oil and fat shown in Table 1 was esterified to obtain an alkyl esterified product of the vegetable oil and fat. The alkyl esterified product of vegetable oil is a methyl ester compound obtained by the reaction of vegetable oil and methanol. Here, stirring is performed at 70 ° C. for about 1 hour in the presence of an alkali catalyst (sodium methylate). A transesterification reaction was used in which an ester compound was obtained by directly reacting with an alkyl alcohol.
A light oil composition was produced by blending the environmentally low load light oil base, the methyl esterified vegetable oil and the hydrogenated refined oil shown in Table 4 (Examples 1-2 and Comparative Examples 1-4).

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, cloud point, clogging point, (cloud point) -Clogging point), distillation properties, aromatic content, cetane number, residual carbon content of 10% residual oil, fatty acid methyl ester content, methanol content, glyceride content, total acid value, oxidation stability test (before and after accelerated test) Table 5 shows the calculation results of acid value) and 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 flash point indicates a value measured by JIS K 2265 “Crude oil and petroleum product flash point test method”.
The sulfur content refers to the mass content of the sulfur content based on the total amount of the gas oil composition measured by JIS K2541 “Sulfur content test method”.
The oxygen content was measured by elemental analysis.
The cloud point means a cloud point measured by JIS K 2269 “Crude point of petroleum and petroleum products and petroleum product cloud point test method”.
The clogging point refers to a clogging point measured by JIS K 2288 “Light oil—clogging point test method”.

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%).
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 cetane number means a cetane number measured according to “7. Cetane number test method” of JIS K 2280 “Petroleum products—fuel oil—octane number and cetane number test method and cetane index calculation method”.
The residual carbon content of 10% residual oil means the residual carbon content of 10% residual oil measured by JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.
The fatty acid methyl ester content means the fatty acid methyl ester content measured according to EN14103.
A triglyceride content shows the value measured based on EN14105.

(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 ”).
) Was calculated as the emission amount per unit calorific value of each light oil composition based on the CO ₂ emission amount, the running fuel consumption and the fuel density when the vehicle test was conducted.
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.

(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. In addition, an acid value here means the total acid value measured by JISK2501 "Petroleum products and lubricating oil-neutralization number test method."

  As shown in Table 5, the light oil compositions used in the examples and comparative examples were prepared by blending a water environment low load type light oil base material, methyl esterified vegetable oil and hydrogenated refined oil at a specific ratio. It is.

  As is apparent from Table 5, the low-temperature fluidity improver is mixed with the environmentally low load gas oil base and the hydrorefined oil obtained by hydrotreating in two stages under predetermined conditions. In Examples 1 and 2 blended within the range defined by the present invention, the 90% distillation temperature is 360 ° C. or lower, the flash point is 45 ° C. or higher, the cetane number is 50 or higher, the clogging point is −5 ° C. or lower, ( Cloud point-clogging point) value is + 5 ° C. or higher, sulfur content is 10 mass ppm or less, oxygen content is 1 mass% or less, triglyceride content is 0.01 mass% or less, fatty acid alkyl ester content is 3.5 mass% or less, acid A gas oil composition having a value of 0.13 mg KOH / g or less and an increase in acid value after the oxidation stability test of 0.12 mg KOH / g or less could be obtained easily and reliably. On the other hand, in Comparative Examples 1 to 4 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 obtained by mixing a sulfur-containing hydrocarbon compound with animal and vegetable oil and / or animal and vegetable oil-derived components so that the sulfur content is 1 mass ppm to 2 mass%, and aluminum, silicon, zirconium, Porous inorganic oxides comprising two or more elements selected from boron, titanium and magnesium, and metals selected from Group 6A and Group 8 elements carried on the porous inorganic oxide And a sulfide catalyst containing at least one kind of hydrogen 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 180 to 480 ° C. The fraction obtained by hydrotreating at the first stage is further composed of a substance selected from aluminum, silicon, zirconium, boron, titanium, magnesium and zeolite A hydrogen pressure of 2 to 13 MPa and a liquid space velocity of 0. 1 using a catalyst containing at least one metal selected from the group consisting of porous inorganic oxides and elements selected from Group 8 elements supported on the porous inorganic oxides. ^{1 to} 3.0 h ⁻¹ , hydrogen / oil ratio 250 to 1500 NL / L, environmentally low load type light oil base material 10 obtained by further hydrotreating (second stage) under the conditions of reaction temperature 150 to 380 ° C. by the 20 volume% and hydrotreated oils 90-80% by volume obtained by refining crude oil were mixed, and the cold flow improver is added 10 to 1000 weight ppm, distillation temperature 90% 360 ° C or lower, flash point 45 ° C or higher, cetane number 50 or higher, clogging point -5 ° C or lower, (cloud point-clogging point) value + 6 ° C or higher, sulfur content 10 mass ppm or lower, oxygen The content is 1% by mass or less, and the triglyceride content is 0.00. Gas oil composition having 01% by mass or less, fatty acid alkyl ester content of 3.5% by mass or less, total acid value of 0.13 mgKOH / g or less, and acid value increase after oxidation stability test of 0.12 mgKOH / g or less A process for producing a light oil composition, characterized in that a product is obtained . 2. The method for producing a light oil composition according to claim 1, wherein the ratio of the amount of isoparaffin to the total amount of paraffin in the environmentally low load light oil base is 0.20 or more and 0.80 or less.