JP2007308576A - Gas oil composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas oil composition excellent in life cycle CO<SB>2</SB>exhaust characteristics and in oxidation stability, low temperature startability and low temperature flowability. <P>SOLUTION: This gas oil composition having a 90% distillation temperature of ≤360°C, a total aromatic content of ≤15 vol.%, a cetane index of ≥45, a sulfur content of ≤1 mass ppm, an oxygen content of ≤1 mass%, a triglyceride content of ≤0.01 mass%, an acid value of ≤0.13 mgKOH, an acid value-increasing amount of 0.12 mgKOH/g after an oxidation stability test, a cloud filter plugging point (CFPP) of ≤-5°C, a pour point (PP) of ≤-10°C, and an isoparaffin/n-paraffin ratio of ≥0.80 is produced by mixing a gas oil base material having an isoparaffin/n-paraffin ratio of ≥0.2 and obtained by contacting animal or vegetable oils or fats and/or animal or vegetable fats or fats-originated components with a periodic table groups 6A and 8 element catalysts carried on a carrier containing crystalline molecular sieve in conditions comprising a hydrogen pressure of 2 to 13 MPa, a liquid space velocity of 0.1 to 3.0 h<SP>-1</SP>, a hydrogen oil ratio of 250 to 1,500 NL/L, and a temperature of 150 to 380°C, with a hydrogenated refined oil refined from crude oil or the like in a ratio of 30 to 50 vol.%:70 to 50 vol.%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention comprises an environmentally low load type light oil base produced using animal and vegetable oils and / or triglyceride-containing hydrocarbons derived from animal and vegetable oils and fats, and has life cycle CO ₂ emission characteristics, ignitability, oxidation stability and The present invention relates to a light oil composition excellent in low temperature performance.

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 Since it is an oxygen-containing compound that has almost no sulfur content and has oxygen in the molecule, it has attracted attention as a promising candidate for alternative fuels. In addition, because it is plant-derived, it is positioned as renewable energy, so the international carbon dioxide reduction protocol signed in 1997, the so-called Kyoto Protocol, does not count carbon dioxide derived from BDF as an emission amount. The BDF also has a policy merit.

However, fatty acid alkyl esters using natural animal and vegetable oils and fats as raw materials are inherently heavy, and there is a concern that unburned hydrocarbon emissions during combustion may increase due to poor burn-off in engine combustion and the like. In the case of BDF containing many fatty acid alkyl esters 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 a lot of unsaturated fatty acid groups, its chemical composition is inferior in oxidative stability, and there is concern about deterioration of hue, generation of sludge, and adverse effects on engine members. Furthermore, the fatty acid glyceride, the alkyl alcohol, and the glycerin mixture, which is a by-product, 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 BDF itself, it is necessary to pay more attention to oxidation stability, low-temperature performance, combustibility, and the like when mixing with existing light oil.

Therefore, fatty acid alkyls made from natural animal and vegetable fats and oils are provided for the provision of light oil compositions that reduce CO ₂ in the life cycle as well as reducing harmful exhaust components, have little effect on components, and have excellent oxidation stability and low-temperature performance. These performance improvements cannot be achieved simultaneously with the use of BDF which is an ester mixture. 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 the actual situation, and its purpose is to contain an environment-friendly light oil base material produced from raw materials of animal and vegetable oils and fats derived from animal and vegetable oils and triglycerides. Cycle CO ₂ emission characteristics and oxidation stability, low temperature startability,
Another object of the present invention is to provide a gas oil composition having excellent low temperature fluidity.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the present invention contains a component derived from animal and vegetable oils and / or animal oils and one or more metals selected from elements of Groups 6A and 8 of the periodic table carried on a carrier containing crystalline molecular sieve. Is obtained by bringing the catalyst to contact with the catalyst under the 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 250 to 1500 NL / L, and a reaction temperature of 150 to 380 ° C. / 90% distillate produced by mixing 30-50 vol%: 70-50 vol% hydrorefined oil refined from crude oil etc. with a light oil base material having a normal paraffin ratio of 0.2 or more Outlet temperature is 360 ° C. or less, total aromatic content is 15% by volume or less, cetane index is 45 or more, sulfur content is 1 mass ppm or less, oxygen content is 1 mass% or less, triglyceride content is 0 01 mass% or less, acid value 0.13 mgKOH / g or less, acid value increase after oxidation stability test is 0.12 mgKOH / g or less, clogging point (CFPP) is −5 ° C. or less, pour point (PP ) Is −10 ° C. or lower, and the ratio of isoparaffin / normal paraffin is 0.80 or higher in the paraffin content contained in the refined oil.

Further, the present invention is a mixed oil obtained by mixing 10 to 90 volumes of animal and vegetable fats and / or animal fats and oils, and petroleum base material having a sulfur content of 15 ppm or less obtained by refining crude oil or the like: 90 to 10 vol%. And a catalyst containing one or more metals selected from Group 6A and Group 8 elements on a periodic table supported on a carrier containing crystalline molecular sieve, hydrogen pressure 2-13 MPa, liquid space velocity 0 .1 to 3.0 h ⁻¹ , hydrogen oil ratio 250 to 1500 NL / L, light oil base material having a ratio of isoparaffin / normal paraffin obtained by contact under a reaction temperature of 150 to 380 ° C. of 0.2 or more And 30-50% by volume: 70-50% by volume of hydrorefined oil refined from crude oil, etc., 90% distillation temperature is 360 ° C. or less, total aromatic content 15% by volume The cetane index is 45 or more, the sulfur content is 1 mass ppm or less, the oxygen content is 1 mass% or less, the triglyceride content is 0.01 mass% or less, the acid value is 0.13 mgKOH / g or less, and the oxidation stability The amount of increase in acid value after the test is 0.12 mgKOH / g or less, the clogging point (CFPP) is −5 ° C. or less, and the pour point (PP) is −10 ° C. or less. The ratio of isoparaffin / normal paraffin is 0.80 or more.

According to the present invention, the conventional light oil composition and fatty acid alkyl ester mixture can be obtained by containing an environmentally low load type light oil base material produced from the above-mentioned animal and vegetable oils and fats and triglyceride-containing hydrocarbons. It is possible to provide a light oil composition excellent in all of life cycle CO ₂ emission characteristics, oxidation stability, member influence and ignitability, and low-temperature fluidity, which has been difficult to realize with BDF.

Hereinafter, the present invention will be described in detail.
As constituents of the gas oil composition of the present invention, groups 6A and 8 of the periodic table carried on a carrier containing a hydrocarbon fraction containing components derived from animal and vegetable oils and / or animal oils and a crystalline molecular sieve An environmentally low load type light oil base material of a hydrocarbon-containing mixed fraction obtained by contacting with a catalyst containing one or more metals selected from these elements is used.

The environmentally low load gas oil base according to the present invention is a low sulfur gas oil fraction, a kerosene fraction, or a mixture thereof obtained by hydrotreating a predetermined raw material oil.
The raw oil must be a hydrocarbon fraction containing components derived from animal and vegetable oils and animal fats. The animal and vegetable oils and fats and components derived from animal and vegetable oils and oils in the present invention refer to animal and vegetable oils and fats that are naturally produced or artificially produced and produced, and components that are produced and produced from these fats and oils. Examples of animal fats and animal oil materials include beef tallow, milk fat (butter), pork tallow, sheep fat, whale oil, fish oil, liver oil, and the like. Vegetable oils and vegetable oil materials 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 portion of the glyceride compound contained in these raw materials, butyric acid (C ₃ H ₇ COOH), which is a fatty acid having no unsaturated bond in the 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), which is 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 (OH)} COOH) Hitoshigakyo It is. 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.
The above-mentioned raw material oils (animal and vegetable oils and fats and components derived from animal and vegetable oils and fats) 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.

  The feedstock oil preferably contains a fraction of 250 ° C or higher, more preferably contains a fraction of 300 ° C or higher, and contains a fraction of 360 ° C or higher. Further preferred. When a fraction having a boiling point of 250 ° C. or higher is not contained, the production of a gas component is increased during production, so that the yield of the liquid product is decreased and life cycle carbon dioxide may be increased.

  Moreover, as raw material oil, you may use what mixed the petroleum-type hydrocarbon fraction with the animal and vegetable oil and fat and the component derived from animal and vegetable oil and fat. When mixing the feedstock oil, the sulfur content of the petroleum hydrocarbon fraction needs to be 10 ppm or less. The sulfur content is more preferably 1 to 5 ppm. The mixing ratio is desirably 10 to 99% by volume, more desirably 30 to 99% by volume, and even more desirably 60 to 98% by volume based on the total volume of the feedstock. When the ratio of petroleum hydrocarbon fraction is less than the lower limit, equipment required for treatment of by-product water may be required, and the ratio of petroleum hydrocarbon fraction exceeds the upper limit. When exceeding, it is not preferable from a viewpoint of life-cycle carbon dioxide reduction.

  The petroleum-based hydrocarbon fraction may include a fraction obtained by distillation of crude oil or a fraction obtained by a reaction such as hydrodesulfurization, hydrocracking, fluid catalytic cracking, or catalytic reforming. The mixing amount of these fractions can be arbitrarily set as long as the oxygen content and sulfur content contained in the oil to be treated satisfy the predetermined concentration range. Furthermore, you may mix together with the synthetic oil obtained via a chemical-derived compound and a Fischer-Tropsch reaction.

  The oxygen content contained in the raw material oil is preferably 0.1 to 15% by mass, more preferably 1 to 15% by mass, still more preferably 3 to 14% by mass, and particularly preferably 5 based on the total amount of the raw material oil. ~ 13% by weight. If the oxygen content is less than 0.1% by mass, it tends to be difficult to stably maintain the deoxygenation activity and desulfurization activity. On the other hand, if the oxygen content exceeds 15% by mass, equipment required for the treatment of by-product water is required, the interaction between water and the catalyst carrier becomes excessive, and the activity decreases or the catalyst strength decreases. To do.

  The sulfur content contained in the oil to be treated is preferably 15 mass ppm or less, more preferably 10 mass ppm or less, still more preferably 5 mass ppm or less, based on the total amount of the oil to be treated. When the sulfur content exceeds 15 mass ppm, it tends to be difficult to stably maintain the deoxygenation activity, and the sulfur content contained in the hydrorefined oil tends to increase. When used as a fuel for a diesel engine or the like, there is a concern about an adverse effect on the engine exhaust gas purification device. In addition, the sulfur content in this invention means the mass content of the sulfur content measured based on the method of JISK2541 "Sulfur content test method" or ASTM-5453.

The hydrotreating conditions of the raw material oil are hydrogen pressure 2 to 13 MPa, liquid space velocity (LHSV) 0.1 to 3.0 h ⁻¹ , hydrogen oil ratio (hydrogen / oil ratio) 150 to 1500 NL / L, preferably Is more preferably hydrogen pressure 2.5 to 10 MPa, liquid space velocity 0.5 to 2.0 h ⁻¹ , hydrogen oil ratio 380 to 1200 NL / L, hydrogen pressure 3 to 8 MPa, space velocity 0.8 to It is more preferable that they are 1.8h < ^-1 > and hydrogen oil ratio 350-1000NL / L. These conditions are factors that influence the reaction activity. For example, when the hydrogen pressure and the hydrogen oil ratio are less than the above lower limit values, the reactivity tends to decrease or the activity rapidly decreases. is there. On the other hand, when the hydrogen pressure and the hydrogen oil ratio exceed the above upper limit values, there is a tendency that excessive equipment investment such as a compressor is required. Further, the lower the liquid space velocity tends to be advantageous for the reaction, but if the liquid space velocity is less than the above lower limit value, there is a tendency that an extremely large internal volume reactor is required and excessive equipment investment is required, When the liquid space velocity exceeds the above upper limit, the reaction tends not to proceed sufficiently.

  As the type of the reactor, a fixed bed system can be adopted. That is, hydrogen can adopt either a countercurrent or a parallel flow type with respect to the oil to be treated. Moreover, it is good also as a form which combined the countercurrent and the parallel flow using several reactors. As a general format, it is a down flow, and a gas-liquid twin parallel flow format can be adopted. Moreover, the reactor may be used alone or in combination, and a structure in which one reactor is divided into a plurality of catalyst beds may be adopted.

  In general, hydrogen gas is introduced from the inlet of the first reactor along with the oil to be treated before or after passing through the heating furnace, but separately from this, the temperature in the reactor is controlled. In order to maintain the hydrogen pressure throughout the reactor, hydrogen gas may be introduced between the catalyst beds or between a plurality of reactors. The hydrogen thus introduced is generally called quench hydrogen. The ratio of quench hydrogen to hydrogen gas introduced along with the oil to be treated is preferably 10 to 60% by volume, and more preferably 15 to 50% by volume. If the rate of quench hydrogen is less than 10 volumes, the reaction at the subsequent reaction site tends not to proceed sufficiently. If the rate of quench hydrogen exceeds 60% by volume, the reaction near the reactor inlet does not proceed sufficiently. Tend.

The crystalline molecular sieve contained in the catalyst used in the present invention preferably contains at least silicon in order to impart sufficient hydrodeoxygenation activity and hydroisomerization activity. More preferably, it contains aluminum, zirconium, boron, titanium, gallium, zinc, and phosphorus as constituent elements other than silicon, and further contains aluminum, zirconium, boron, titanium, and phosphorus in addition to silicon. More preferred. By containing these elements, the hydrodeoxygenation reaction and the skeletal isomerization reaction of hydrocarbon can be promoted at the same time, and the low temperature performance improvement of the refined oil can be achieved.
The ratio of {number of silicon atoms} / {number of atoms of elements other than silicon} is preferably 3 or more for elements excluding oxygen among the elements constituting the crystalline molecular sieve. More preferably, it is 10 or more, and still more preferably is 30 or more. When the said ratio is less than 3, the decomposition reaction of paraffin is promoted, and there is a possibility that the activity decreases due to coking.
The pore diameter of the crystalline molecular sieve is preferably 0.8 nm or less, and more preferably 0.65 nm or less. When the zeolite pore diameter is larger than 0.8 nm, there is a concern that a paraffin decomposition reaction occurs. The crystal structure of the crystalline molecular sieve is not particularly limited, and examples thereof include FAU, AEL, MFI, MMW, TON, MTW, * BEA, MOR and the like as defined by the International Zeolite Society.
The method for synthesizing the crystalline molecular sieve contained in the catalyst used in the present invention is not particularly limited, and as is generally known, hydrothermal synthesis using a component raw material and an amine compound as a structure indicator. The method etc. can be used. Examples of the constituent raw material include sodium silicate, colloidal silica, alkoxide silicate and the like in the case of a silicon-containing compound, and aluminum hydroxide and sodium aluminate in the case of aluminum. Examples of the structure directing agent include tetrapropylammonium salt.
In addition, the crystalline molecular sieve may be subjected to hydrothermal treatment with steam or the like, immersion treatment with an alkaline or acidic aqueous solution, ion exchange, surface treatment with a basic or acidic gas such as chlorine gas or ammonia, etc. The physical properties can be adjusted by combining the steps.

  In the catalyst used in the present invention, examples of the constituent other than the crystalline molecular sieve include inorganic oxides selected from aluminum, silicon, zirconium, boron, titanium and magnesium. These inorganic oxides can be used as a bonding agent for forming crystalline molecular sieves, and can also function as active components for promoting hydrodeoxygenation and hydroisomerization. Two or more selected from boron, titanium and magnesium are preferred. The content of the crystalline molecular sieve in the entire catalyst is preferably 2 to 90% by mass, more preferably 5 to 85% by mass, and even more preferably 10 to 80% by mass. When the content is less than 2% by mass, hydrodeoxygenation activity and hydroisomerization activity as a catalyst are not sufficient, and when the initial content exceeds 90% by mass, catalyst moldability is not easy, There is a risk of hindrance to industrial production.

  Regarding the constituents other than the crystalline molecular sieve in the catalyst used in the present invention, the method of introducing silicon, zirconium, boron, titanium and magnesium, which are constituent elements other than aluminum, into the support is not particularly limited, and contains these elements. A solution to be used may be used as a raw material. For example, for silicon, silicic acid, water glass, silica sol, etc., for boron, boric acid, etc., for phosphorous, phosphoric acid and alkali metal salts of phosphoric acid, for titanium, titanium sulfide, titanium tetrachloride and various alkoxide salts For zirconium, zirconium sulfate and various alkoxide salts can be used.

  It is preferable to add the raw materials for the carrier constituents other than the above-described aluminum oxide in the step prior to the firing of the carrier. For example, after adding the said raw material previously to aluminum aqueous solution, the aluminum hydroxide gel containing these structural components may be prepared, and the said raw material may be added with respect to the prepared aluminum hydroxide gel. Alternatively, the above raw materials may be added in a step of adding water or an acidic aqueous solution to a commercially available aluminum oxide intermediate or boehmite powder and kneading them, but it is more preferable to coexist at the stage of preparing aluminum hydroxide gel. Although the mechanism of the effect of the carrier constituents other than aluminum oxide has not necessarily been elucidated, it is presumed that it forms a complex oxide state with aluminum, which increases the surface area of the carrier and the interaction with the active metal. It is considered that the activity is affected by producing the action.

The carrier containing the crystalline molecular sieve carries one or more metals selected from Group 8 elements of the periodic table. 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 catalyst used in the present invention is preferably subjected to a 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 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.

  The method for incorporating these active metals into the catalyst is not particularly limited, and a known method applied when producing an ordinary desulfurization catalyst can be used. Usually, a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed. In addition, 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 carrier is measured in advance and impregnated with a metal salt solution having the same volume. The impregnation method is not particularly limited, and it can be impregnated by an appropriate method according to the amount of metal supported and the physical properties of the catalyst carrier.

Furthermore, in the present invention, a light oil composition satisfying a predetermined performance can be produced by mixing the environmentally low load light oil base produced above and a hydrorefined oil refined from crude oil or the like.
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 Examples include light oil or hydrodesulfurized light oil.
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 hydrorefining of the hydrorefined oil can be performed using a hydrodesulfurization apparatus common in petroleum refining. In general, in the case of a light oil fraction, the reaction is performed under the conditions of a reaction temperature of 300 to 380 ° C., a hydrogen pressure of 3 to 8 MPa, LHSV 0.3 to 2 h ⁻¹ , and a hydrogen / oil ratio of 100 to 500 NL / L.
As a catalyst used for hydrorefining, a general hydrodesulfurization catalyst can be applied. As the active metal, normally, Group 6A and Group 8 metals of the periodic table are preferably used, and examples thereof include Co—Mo, Ni—Mo, Co—W, and Ni—W. As the carrier, a porous inorganic oxide mainly composed of alumina is used. These conditions and the catalyst are not particularly limited as long as the properties of the raw material oil are satisfied.

Moreover, the hydrorefined oil can use what hydrotreated the above-mentioned raw material oil in presence of a hydrogenation catalyst. 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.

The apparatus for hydrotreating the feedstock may be of any configuration, the reaction towers may be used alone or in combination, and hydrogen may be additionally injected between the reaction towers, gas-liquid separation operation or hydrogen sulfide. You may have the removal equipment.
A fixed bed system is preferably employed as the reaction mode of the hydrotreating apparatus. Hydrogen can take either a countercurrent or cocurrent flow with respect to the feedstock, and may have a plurality of reaction towers and a combination of countercurrent and cocurrent. As a general format, it is a down flow, and a gas-liquid twin parallel flow format is preferable. Hydrogen gas may be injected into the middle stage of the reaction tower as a quench for the purpose of removing reaction heat or increasing the hydrogen partial pressure.

  The catalyst used for the hydrotreatment is a catalyst in which a hydrogenation active metal is supported on a porous carrier. An inorganic oxide is mentioned as a porous support | carrier. Specific inorganic oxides include alumina, titania, zirconia, boria, silica, or zeolite. In the present invention, at least one of titania, zirconia, boria, silica, and zeolite is composed of alumina. Things are good. The production method is not particularly limited, but any preparation method can be employed using raw materials in various sols, salt compounds, and the like corresponding to each element. Furthermore, once the composite hydroxide or composite oxide such as silica alumina, silica zirconia, alumina titania, silica titania, and alumina boria is prepared, the preparation process in the state of alumina gel and other hydroxides or in an appropriate solution state It may be prepared by adding at any step. The ratio of alumina to other oxides can be any ratio with respect to the porous carrier, but preferably alumina is 90% by mass or less, more preferably 60% by mass or less, and more preferably 40% by mass or less. .

  Zeolite is a crystalline aluminosilicate, such as faujasite, pentasil, mordenite, etc., which is ultra-stabilized by a predetermined hydrothermal treatment and / or acid treatment, or one whose alumina content in the zeolite is adjusted is used. be able to. Preferably, faujasite and mordenite, particularly preferably Y type and beta type are used. The Y-type is preferably ultra-stabilized, and the ultra-stabilized zeolite by hydrothermal treatment forms new pores in the range of 20 to 100% in addition to the original pore structure called micropores of 20 cm or less. . Known conditions can be used for the hydrothermal treatment conditions.

  The active metal of the catalyst used for the hydrotreatment is at least one metal selected from Group 8 metals of the periodic table. Preferably, it is at least one selected from Ru, Rd, Ir, Pd and Pt, more preferably Pd or / and Pt. The active metal may be a combination of these metals. For example, Pt-Pd, Pt-Rh, Pt-Ru, Ir-Pd, Ir-Rh, Ir-Ru, Pt-Pd-Rh, Pt-Rh-Ru , Ir-Pd-Rh, Ir-Rh-Ru, etc. can be employed. As the metal source, a general inorganic salt or a complex salt compound can be used, and as a supporting method, any method of a supporting method used in an ordinary hydrogenation catalyst such as an impregnation method or an ion exchange method can be used. When a plurality of metals are supported, they may be supported simultaneously using a mixed solution, or may be sequentially supported using a single solution. The metal solution may be an aqueous solution or an organic solvent.

Metal loading may be performed after the completion of the entire preparation process of the porous support, or after further preloading on an appropriate oxide, composite oxide, zeolite in the intermediate process of porous support preparation, Heat concentration and kneading may be performed.
The amount of the active metal supported is not particularly limited, but is 0.1 to 10% by mass, preferably 0.15 to 5% by mass, and more preferably 0.2 to 3% by mass with respect to the catalyst mass.
The catalyst is preferably used after a preliminary reduction treatment in a hydrogen stream. In general, when a gas containing hydrogen is circulated and heat of 200 ° C. or higher is applied according to a predetermined procedure, the active metal on the catalyst is reduced, and hydrogenation activity is exhibited.

  In the present invention, hydrorefined oil of the kerosene fraction can be used in addition to the hydrorefined oil of the light oil fraction. Such a kerosene fraction can be a kerosene fraction obtained by hydrotreating a predetermined feedstock. The raw oil is mainly straight-run kerosene obtained by atmospheric distillation of crude oil, but hydrocracked kerosene produced together with hydrocracked light oil and hydrogen obtained by hydrotreating the above kerosene fraction. Refined kerosene can be used. It is also possible to use synthetic kerosene made from natural gas, asphalt, coal, biomass and the like.

The hydrorefined oil kerosene fraction of the present invention can be obtained by hydrotreating (desulfurizing and refining) the above-described raw material oil in the presence of a hydrogenation catalyst.
The hydrotreating conditions are usually a reaction temperature of 220 to 350 ° C., a hydrogen pressure of ^{1 to} 6 MPa, an LHSV of 0.1 to 10 h ⁻¹ , and a hydrogen / oil ratio of 10 to 300 NL / L. Preferably, the reaction temperature is 250 ° C. to 340 ° C., the hydrogen pressure is 2 to 5 MPa, the LHSV is ^{1 to} 10 h ⁻¹ , and the hydrogen / oil ratio is 30 to 200 NL / L, more preferably the reactivity is 270 ° C. to 330 ° C., the hydrogen pressure is 2 to 4 MPa. , LHSV 2 to 10 h ⁻¹ , hydrogen / oil ratio 50 to 200 NL / L. The lower the reaction temperature, the more advantageous for the hydrogenation reaction, but not for the desulfurization reaction. The higher the hydrogen pressure and the hydrogen / oil ratio, the more the desulfurization and hydrogenation reactions are promoted, but there is an optimal point economically. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, a very large reaction tower volume is required, resulting in an excessive capital investment.

The apparatus for hydrotreating the feedstock may be of any configuration, the reaction towers may be used alone or in combination, and hydrogen may be additionally injected between the reaction towers, gas-liquid separation operation or hydrogen sulfide. You may have the removal equipment.
A fixed bed system is preferably employed as the reaction mode of the hydrotreating apparatus. Hydrogen can take either a countercurrent or cocurrent flow with respect to the feedstock, and may have a plurality of reaction towers and a combination of countercurrent and cocurrent. As a general format, it is a down flow, and a gas-liquid twin parallel flow format is preferable. Hydrogen gas may be injected into the middle stage of the reaction tower as a quench for the purpose of removing reaction heat or increasing the hydrogen partial pressure.

  The catalyst used for the hydrotreatment is a catalyst in which a hydrogenation active metal is supported on a porous carrier. As the porous carrier, a porous inorganic oxide mainly composed of alumina is used. Specific inorganic oxides include alumina, titania, zirconia, boria, silica, or zeolite. In the present invention, at least one of titania, zirconia, boria, silica, and zeolite is composed of alumina. Things are good. The production method is not particularly limited, but any preparation method can be employed using raw materials in various sols, salt compounds, and the like corresponding to each element. Furthermore, once the composite hydroxide or composite oxide such as silica alumina, silica zirconia, alumina titania, silica titania, and alumina boria is prepared, the preparation process in the state of alumina gel and other hydroxides or in an appropriate solution state It may be prepared by adding at any step. The ratio of alumina to other oxides can be any ratio with respect to the porous carrier, but preferably alumina is 90% by mass or less, more preferably 60% by mass or less, and more preferably 40% by mass or less. . These conditions and the catalyst are not particularly limited as long as the properties of the raw material oil are satisfied.

  Zeolite is a crystalline aluminosilicate, such as faujasite, pentasil, mordenite, etc., which is ultra-stabilized by a predetermined hydrothermal treatment and / or acid treatment, or one whose alumina content in the zeolite is adjusted is used. be able to. Preferably, faujasite and mordenite, particularly preferably Y type and beta type are used. The Y-type is preferably ultra-stabilized, and the ultra-stabilized zeolite by hydrothermal treatment forms new pores in the range of 20 to 100% in addition to the original pore structure called micropores of 20 cm or less. . Known conditions can be used for the hydrothermal treatment conditions.

  The active metal of the catalyst used for the hydrotreatment is at least one metal selected from Group 6A metals of the periodic table. Preferably, it is at least one selected from Mo and W. The active metal may be a combination of a Group 6A metal and a Group 8 metal, specifically, a combination of Mo or W and Co or Ni. For example, Co—Mo, Co—W, Ni—Mo, Combinations such as Ni-W, Co-Ni-Mo, and Co-Ni-W can be employed. As the metal source, a general inorganic salt or a complex salt compound can be used, and as a supporting method, any method of a supporting method used in an ordinary hydrogenation catalyst such as an impregnation method or an ion exchange method can be used. When a plurality of metals are supported, they may be supported simultaneously using a mixed solution, or may be sequentially supported using a single solution. The metal solution may be an aqueous solution or an organic solvent.

Metal loading may be performed after the completion of the entire preparation process of the porous support, or after further preloading on an appropriate oxide, composite oxide, zeolite in the intermediate process of porous support preparation, Heat concentration and kneading may be performed.
The amount of the active metal supported is not particularly limited, but is 0.1 to 10% by mass, preferably 0.15 to 5% by mass, and more preferably 0.2 to 3% by mass with respect to the catalyst mass.
The catalyst is preferably used after a preliminary reduction treatment in a hydrogen stream. In general, when a gas containing hydrogen is circulated and heat of 200 ° C. or higher is applied according to a predetermined procedure, the active metal on the catalyst is reduced, and hydrogenation activity is exhibited.

In the present invention, the step of hydrotreating the oil to be treated includes a first hydrogenation step of removing 70% by mass or more of oxygen contained in the oil to be treated, and a remaining oxygen content of 95% by mass with respect to the oil to be treated. % Of the paraffin contained in the refined oil, and the ratio of isoparaffin / normal paraffin is preferably 0.2 or more. If the oxygen content removal rate in the first step is less than 70% by mass, the hydrodeoxygenation and hydroisomerization reaction in the second hydrogenation step may not proceed sufficiently.
In the first hydrogenation step, groups 6A and 8 in the periodic table supported by a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium. It is preferable to use a catalyst containing one or more metals selected from group elements, and the active metal may be one or more elements selected from Pd, Pt, Rh, Ir, Au, Ni, and Mo. Further preferred.
In the second hydrogenation step, a catalyst containing one or more metals selected from elements of Group 8 of the periodic table supported on a carrier containing crystalline molecular sieve can be used.
In addition, the catalyst used in the second hydrogenation step may be used alone or in a plurality of types. For the purpose of improving the stability of the refined oil, a catalyst having hydrogenation activity may be charged after the second hydrogenation step. Good.

  The light oil composition produced by the present invention uses the above-mentioned environmentally low load type light oil base material of the hydrocarbon-containing mixed fraction, and has a sulfur content of 5 mass ppm or less and an oxygen content of 1 mass% or less. It is a thing.

  The sulfur content of the gas oil composition of the present invention is required to be 5 ppm by mass or less, preferably 4 ppm by mass from the viewpoint of reducing harmful exhaust components discharged from the engine and improving the performance of the exhaust gas aftertreatment device. Below, more preferably 3 ppm by mass or less, still more preferably 2 ppm by mass or less, and even more preferably 1 ppm by mass or less. In addition, the sulfur content here means the mass content of the sulfur content based on the total amount of the light oil composition measured by JIS K2541 “Sulfur content test method”.

The oxygen content of the gas oil composition of the present invention needs 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. More preferably, it is 0.4% by mass or less, and still more preferably 0.2% by 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 satisfy 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 needs to be 0.01% by mass or less, preferably 0.008% by mass, and more preferably 0.005% by mass, taking into account the influence on members and the like. % Or less. In addition, the triglyceride as used in the field of this invention shows the value measured based on EN14105.

  The cetane index of the light oil composition of the present invention needs to satisfy JIS No. 2 light oil standard of 45 or more. When the cetane index is less than 45, the concentration of PM, aldehydes, or NOx in the exhaust gas tends to increase. For the same reason, the cetane index is preferably 48 or more, and most preferably 51 or more. The cetane index referred to in the present invention is defined by “Calculation method of cetane index using 8.4 variable equations” in JIS K 2280 “Petroleum products-fuel oil-octane number and cetane number test method and cetane index calculation method”. It means the calculated value.

  The cetane number in the light oil composition of the present invention is preferably 52 or more, more preferably 54 or more, and further preferably 55 or more. When the cetane number is less than 52, the concentrations of NOx, PM and aldehydes in the exhaust gas tend to be high. Further, from the viewpoint of reducing black smoke in the exhaust gas, the cetane number is preferably 90 or less, more preferably 88 or less, and even more preferably 85 or less. Moreover, in the light oil composition of this invention, a cetane number improver can be mix | blended with an appropriate quantity as needed, and the cetane number of the light oil composition obtained can be improved. The cetane number referred to here is a cetane number measured in accordance with “7. Cetane number test method” in JIS K 2280 “Petroleum products—Fuel oil—Octane number and cetane number test method and cetane index calculation method”. Means.

Density at 15 ℃ of the gas oil composition of the present invention, in terms of calorific value ensuring, is preferably 750 kg / ^{m 3} or more, more preferably 760 kg / ^{m 3} or more, more preferably 770 kg / ^{m 3} or more. Further, the density, NOx, from the viewpoint of reducing the emission of PM, it is preferably 850 kg / ^{m 3} or less, more preferably 845 kg / ^{m 3} or less, more preferably 840 kg / ^{m 3} or less. In addition, the density here means the density measured by JIS K 2249 “Density test method and density / mass / capacity conversion table of crude oil and petroleum products”.

The light oil composition of the present invention desirably has a lubricating performance such that the HFRR wear scar diameter (WS1.4) is preferably 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 required to be 15% by volume or less from the viewpoint of enhancing the environmental load reduction effect and reducing NOx and PM. It is preferably 13% by volume or less, more preferably 10% by volume or less. The aromatic content in the present invention is measured in accordance with the Petroleum Institute Method JPI-5S-49-97 “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method” issued 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, 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. Is more preferable, and it is further more preferable that 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)."

Among the paraffin components contained in the light oil composition of the present invention, the ratio of isoparaffin / normal paraffin needs to be 0.80 or more in order to ensure low temperature performance. Preferably it is 0.90 or more, More preferably, it is 1.00 or more. In addition, the isoparaffin part and normal paraffin part as used in the field of this invention can be obtained using GC-TOFMS. In GC-TOFMS, first, constituent components of a sample are separated by gas chromatography, and each separated component is ionized. Next, based on the fact that the flight speed when a constant acceleration voltage is applied to the ions varies depending on the mass of the ions, the ions are mass separated, and a mass spectrum is obtained based on the difference in arrival time to the ion detector. . As the ionization method in GC-TOFMS, the FI ionization method is preferable because generation of fragment ions can be suppressed and measurement accuracy of isoparaffins can be further improved. The measurement apparatus and measurement conditions in the present invention are shown below.
(GC department)
Apparatus: HEWLETT PACKARD, HP6890 Series GC System & Injector
Column: A client HP-5 (30 m × 0.32 mmφ, 0.25 μm-film)
Carrier gas: He, 1.4 mL / min (constant flow)
Inlet temperature: 320 ° C
Injection mode: split (split ratio = 1: 100)
Oven temperature: held at 50 ° C. for 5 minutes, heated at 5 ° C./minute, and held at 320 ° C. for 6 minutes.
Injection volume: 1 μL
(TOFMS Department)
Device: JEOL Ltd., JMS-T100GC
Counter electrode voltage: 10.0 kV
Ionization method: FI + (field ionization)
GC interface temperature: 250 ° C
Measurement mass range: 35-500

  The clogging point (CFPP) of the light oil composition of the present invention needs to satisfy −5 ° C. or less which is JIS No. 2 light oil standard. Furthermore, it is preferably −6 ° C. or lower, more preferably −7 ° C. or lower, from the viewpoint of preventing the prefilter blockage of the diesel vehicle. Here, the clogging point refers to a clogging point measured according to JIS K 2288 “Light oil—clogging point test method”.

  Moreover, the pour point of the light oil composition of this invention needs to satisfy | fill -7.5 degrees C or less which is a JIS2 light oil specification. Furthermore, from the viewpoint of low temperature startability or low temperature drivability, and from the viewpoint of maintaining injection performance in the electronically controlled fuel injection pump, it is preferably −10 ° C. or lower. Here, the pour point means a pour point measured by JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.

  The distillation property in the light oil composition of the present invention needs to satisfy a 90% distillation temperature of 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 needs to satisfy 0.1 mass% or less, which is a JIS No. 2 light 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”.

  Moreover, it is preferable that the acid value of the light oil composition of this invention is 0.13 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. Therefore, the acid value is preferably 0.13 mgKOH / g or less, more preferably 0.10 mgKOH / g or less, and further preferably 0.08 mgKOH / g or less. In addition, an acid value here means the acid value measured by JISK2501 "Petroleum products and lubricating oil-neutralization number 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 members. 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 in the present invention is performed 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, for example, low-temperature fluidity improvers such as ethylene-vinyl acetate copolymer and alkenyl succinic acid amide; antioxidants such as phenols and amines; metal deactivators such as salicylidene derivatives; Anti-icing agents such as polyglycol ethers; corrosion inhibitors such as aliphatic amines and alkenyl succinic acid esters; antistatic agents such as anionic, cationic and amphoteric surfactants; colorants such as azo dyes; Antifoaming agents and the like.
The addition amount of other additives can be arbitrarily determined, but the addition amount of each additive is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, based on the total amount of the light oil composition. is there.

A gas oil composition containing an environmentally low load gas oil base produced using the animal and vegetable oil and fat of the present invention as a raw material and a triglyceride-containing hydrocarbon which is a component derived from the animal and vegetable oil and fat has life cycle CO ₂ emission characteristics, oxidation stability, member It is excellent in all effects and cold startability.

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

(Examples 1-3 and Comparative Examples 1-3)
The reaction shown in Table 2 is a vegetable oil or fat having the properties shown in Table 1, or a mixed oil obtained by mixing petroleum-based hydrorefined oil 1 and vegetable oil in a ratio of 20:80. The reaction was carried out under conditions to prepare an environmentally low load light oil base material shown in Table 3.
Moreover, the property of the fatty-acid alkylester obtained by esterifying the vegetable oil shown in Table 1 is shown. These fatty acid alkyl esters are methyl ester compounds obtained by reaction with methanol. Here, they are stirred at 70 ° C. for about 1 hour in the presence of an alkali catalyst (sodium methylate) to directly react with alkyl alcohol. A transesterification reaction was used to obtain an ester compound.
A light oil composition was prepared by blending the environmentally low load type light oil base material shown in Table 3, the methyl esterified vegetable oil and the hydrorefined oil which is a petroleum base material (Examples 1 and 2 and Comparative Example 1). ~ 3).
In addition, the additive used was as follows.
・ Lubricity improver: Carboxylic acid mixture based on linoleic acid ・ Detergent: Carboxylic acid mixture based on oleic acid and oleylamine
Reaction product Low temperature fluidity improver: ethylene-vinyl acetate copolymer

  The blending ratio of the blended diesel oil composition and the blended diesel oil composition, density at 15 ° C., kinematic viscosity at 30 ° C., flash point, sulfur content, oxygen content, distillation properties, aromatic content Content, cetane number and cetane index, pour point, clogging point, residual carbon content of 10% residual oil, ash content, moisture, total insoluble matter after oxidation stability test, peroxide value, conductivity, wear scar diameter The results of measuring are shown in Table 4.

The properties of the fuel oil were measured by the following method.
The density refers to a density measured according to JIS K 2249 “Determination method of density of crude oil and petroleum products and density / mass / capacity conversion table”.
The kinematic viscosity refers to a kinematic viscosity measured according to JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.
The sulfur content refers to the mass content of the sulfur content based on the total amount of light oil composition measured by JIS K2541 “Sulfur content test method”.
The oxygen content was measured by elemental analysis.

All the distillation properties are values measured by JIS K 2254 "Petroleum products-Distillation test method".
The aromatic content is measured according to the Japan Petroleum Institute method JPI-5S-49-97 “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method” published by the Japan Petroleum Institute. Means the capacity percentage (volume%).
Moisture means the moisture specified by JIS K 2275 “Moisture test method (crude oil and petroleum products)”.
The flash point indicates a value measured according to JIS K 2265 “Crude oil and petroleum product flash point test method”.
The total acid value means the total acid value measured according to JIS K 2501 “Petroleum products and lubricating oils—neutralization number test method”.

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

Lubrication performance and HFRR wear scar diameter (WS1.4) refer to the lubrication performance measured by the Petroleum Institute Standard JPI-5S-50-98 “Diesel Oil-Lubricity Test Method” issued by the Japan Petroleum Institute. .
The clogging point refers to a clogging point measured by JIS K 2288 “Light oil—clogging point test method”.
The pour point refers to a pour point measured according to JIS K 2269 “Crude point of petroleum and petroleum products and a cloud point test method of petroleum products”.
The residual carbon content of 10% residual oil means the residual carbon content of 10% residual oil as measured by JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.
Ash content means a value measured by JIS K 2272 “Crude oil and petroleum product ash and sulfate ash test method”.
The total insoluble matter after the oxidation stability test means a value measured under conditions of 95 ° C. and oxygen bubbling for 16 hours in accordance with ASTM D2274-94.
The peroxide value means a value measured according to the Petroleum Institute Standard JPI-5S-46-96.
The conductivity means a value measured in accordance with JIS K 2276 “Petroleum product-aviation fuel oil test method”.

  As shown in Table 4, the diesel oil compositions used in the examples and comparative examples were formulated with a specific proportion of environmentally low-load diesel oil base, methyl esterified vegetable oil and hydrorefined oil as a petroleum base. It is manufactured.

  As is apparent from Table 4, the environmentally low load type light oil base material, and the environmental low load type light oil base material and the hydrorefined oil were mixed and used, and were blended within the range defined by the present invention. 1 and 2, the sulfur content is 5 mass ppm or less, the oxygen content is 1 mass% or less, the 90% distillation temperature is 360 ° C. or less, the total aromatic content is 15 vol% or less, and the cetane index is 45 The sulfur content is 1 mass ppm or less, the oxygen content is 1 mass% or less, the triglyceride content is 0.01 mass% or less, the acid value is 0.13 mgKOH / g or less, and the acid value is increased after the oxidation stability test. The amount is 0.12 mgKOH / g or less, the clogging point (CFPP) is −5 ° C. or less, the pour point (PP) is −10 ° C. or less, and the ratio of isoparaffin / normal paraffin in the paraffin content contained in the product is 0.80 or more The oil composition could be obtained easily and reliably. On the other hand, in Comparative Examples 1 to 3 in which a light oil composition was prepared without using the above specific environment-friendly light oil base material, the light oil composition targeted by the present invention was not necessarily obtained.

  Next, various tests shown below were performed using the light oil compositions of Examples 1 to 3 and Comparative Examples 1 to 3. All test results are shown in Table 5. As can be seen from the results in Table 5, the light oil compositions of Examples 1 to 3 have less carbon dioxide emissions in the life cycle and excellent low temperature startability than the light oil compositions of Comparative Examples 1 to 3. It is clear that it has excellent oxidation stability.

(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.
Table 5 shows the emission amounts of the life cycle CO ₂ (LC), which is the sum of “Tank to Wheel CO ₂ ” and “Well to Tank CO ₂ ” thus calculated. In addition, the comparative example 1 is set to 100, and the numerical value which comparatively compared and quantified each result is also shown collectively.

(Low temperature startability)
(1) Flushing (cleaning) the fuel system of the test diesel vehicle with the evaluation fuel on the chassis dynamometer capable of controlling the environmental temperature using the vehicle 1 and (2) extracting the flushing fuel (3 ) Replacing the main filter with a new one, (4) Placing the prescribed amount of evaluation fuel (1/2 of the fuel tank capacity of the test vehicle) into the fuel tank. Then, (5) rapidly cool the ambient temperature from room temperature to 5 ° C, (6) hold at 5 ° C for 1 hour, and (7) until it reaches a predetermined temperature (-7 ° C) at a cooling rate of 1 ° C / h. Slowly cool, and (8) hold the engine at a predetermined temperature for 1 hour, and then start the engine. If the engine does not start even after 10 seconds of cranking is repeated twice at 30 second intervals, it is not possible (x), and if the engine is started between two times of cranking is repeated (O).

(Oxidation stability test)
In accordance with ASTM D2274-94, the fuel is accelerated and deteriorated under the conditions of 115 ° C. and oxygen bubbling for 16 hours, and the change in hue before and after the test is observed. If not, it was judged as “Yes”.

This is a transient operation mode that simulates actual driving in a vehicle exhaust gas test and a fuel consumption test.

Claims (2)

A component containing one or more metals selected from Group 6A and Group 8 elements of a periodic table supported on a carrier containing animal and plant fats and / or animal fats and a crystalline molecular sieve; The ratio of isoparaffin / normal paraffin obtained by contacting under conditions of pressure 2 to 13 MPa, liquid space velocity 0.1 to 3.0 h ⁻¹ , hydrogen oil ratio 250 to 1500 NL / L, reaction temperature 150 to 380 ° C. Produced by mixing 30-50 vol%: 70-50 vol% hydrorefined oil refined from crude oil etc. with a light oil base of 0.2 or higher, 90% distillation temperature is 360 ° C or lower The total aromatic content is 15% by volume or less, the cetane index is 45 or more, the sulfur content is 1 mass ppm or less, the oxygen content is 1 mass% or less, and the triglyceride content is 0.01 mass% or less. The acid value increased 0.13 mgKOH / g or less after the oxidation stability test, the clogging point (CFPP) was −5 ° C. or less, and the pour point (PP) was −10 ° C. or less. And a ratio of isoparaffin / normal paraffin in the paraffin content contained in the product is 0.80 or more. Animal and vegetable fats and / or animal fats and oils: 10 to 90 volumes and a mixed oil obtained by refining crude oil or the like and a petroleum-based base material having a sulfur content of 15 ppm or less: 90 to 10 vol% is obtained as a crystalline molecular sieve. A catalyst containing one or more metals selected from Group 6A and Group 8 elements on a periodic table supported on a carrier containing hydrogen, a hydrogen pressure of 2 to 13 MPa, a liquid space velocity of 0.1 to 3. From a light oil base material having a ratio of isoparaffin / normal paraffin of 0.2 or more obtained by contacting under conditions of 0h ⁻¹ , hydrogen oil ratio 250-1500 NL / L, reaction temperature 150-380 ° C., crude oil, etc. Manufactured by mixing 30-50% by volume of refined hydrorefined oil: 70-50% by volume, 90% distillation temperature is 360 ° C. or less, total aromatic content is 15% by volume or less, cetane finger Is 45 mass%, sulfur content is 1 mass ppm or less, oxygen content is 1 mass% or less, triglyceride content is 0.01 mass% or less, acid value is 0.13 mgKOH / g or less, and the acid after the oxidation stability test The paraffin content is 0.12 mgKOH / g or less, the clogging point (CFPP) is −5 ° C. or less, the pour point (PP) is −10 ° C. or less, and the paraffin content contained in the product is isoparaffin / normal. A gas oil composition having a paraffin ratio of 0.80 or more.

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