RU2427613C2 - Composition of gas-oil - Google Patents

Abstract

FIELD: oil and gas production.

SUBSTANCE: invention refers to composition of gas-oil for utilisation in diesel engine with degree of geometric compression 16 or less equipped with supercharger and EGR containing synthetic base oil FT and content of sulphur 5 mln p. by weight or less, content of oxygen 100 mln p. or less, modulus of volume deformation 1250 MPa or more and 1450 MPa or less, colour by Saybolt +22 or more, lubricating capacity 400 mcm or less, initial boiling point 140°C or more and end boiling point 380°C or less in parametres of distillation and following properties (1)-(3) of fraction of each interval, where (1) cetane number of fraction in interval lower, than 200°C amounts to 40 or more and less, than 60; (2) cetane number of fraction in interval 200°C or more and less, than 280°C amounts to 60 or more and less, than 80; and (3) cetane number of fraction in interval from 280°C or more amounts to 50 or more.

EFFECT: production of fuel of high quality facilitating excellent operation properties, and environment safe which can be utilised at combustion with compression inflammation of homogenous medium.

7 cl, 12 ex, 12 tbl, 1 dwg

Description

FIELD OF THE INVENTION

The present invention relates to gas oil compositions, in particular to gas oil compositions for the summer and winter seasons, suitable for both diesel combustion and compression ignition of a uniform charge.

State of the art

Diesel combustion is called combustion, in which ignition occurs (combustion of a pre-mixed air-fuel mixture), when the fuel injected into the combustion chamber of the engine evaporates, mixes with air and turns into a working air-fuel mixture with the corresponding fuel / engine oil ratio, and the mixture is in the corresponding temperature conditions. It often happens that, regardless of whether the ignition is good or weak, it is estimated by the evaporation parameters determined by the distillation parameters and the cetane number indicating the ability of the fuel to self-ignite. If higher output power is required during combustion in a diesel engine (high load conditions), it is necessary to continue fuel injection even after the onset of spontaneous combustion. In this case, the fuel must ignite while the injected fuel diffuses into the air atmosphere when using liquefied air in the inner part of the internal combustion chamber of the engine (diffusion combustion). Therefore, the requirements for the properties of the fuel are the requirements to facilitate the combustion of pre-mixed air-fuel mixture and diffusion combustion.

There is a combustion mode called compression ignition of a uniform charge relating to these diesel modes, and recently this mode of combustion has attracted attention due to low emissions and excellent fuel efficiency. This mode of combustion differs from the aforementioned diesel combustion in that the entire combustion process of the first is the combustion of the preliminary air-fuel mixture and, thus, is not involved in diffusion combustion. However, as discussed above, ignition is undesirable due to the ability of the fuel to self-ignite, and thus, ignition is considered a difficult to control process, especially under high load conditions. Therefore, there are many engines using the combustion mode, where combustion with compression ignition of a uniform charge proceeds only under conditions of low and medium load, and switches to normal diesel combustion at high loads. Therefore, we can conclude that the properties of the fuel are required so that it can facilitate combustion during compression ignition of a uniform charge under low load conditions and facilitate diesel combustion under high load conditions.

In general, a gas oil composition is prepared by mixing one or more types of base oils obtained by hydrotreating or hydrodesulfurizing direct gas oil or direct kerosene obtained by distillation of crude oil under atmospheric pressure. In particular, it often happens that the constituent fraction of the aforementioned kerosene base oil and gas oil base oil is controlled in such a way as to provide cold flow capability in the winter season. If necessary, the base oils are mixed with additives such as cetane number improvers, detergents and cold flow improvers (see, for example, non-patent document No. 1 below).

As for the fuel for the above combustion when ignited by compression of a uniform charge, the patent document No. 1 proposed a diesel gas oil composition, characterized in that it contains a relatively light catalytic cracking gas oil and has a low cetane number and a high density and aromatic content. In this document, it is noted that this composition can have both excellent low temperature properties and a low NO _x content and low PM properties upon combustion with compression ignition of a uniform charge. However, it is easy to assume that the content of aromatic compounds in the composition will be excessively high, leading to an increase in the emission of unburned fuel. In addition, as discussed above, it often happens now that combustion during compression ignition of a uniform charge is used in parallel with traditional diesel combustion. Thus, it is obvious that the fuel of this document with a low cetane number, high density and high content of aromatic compounds is not at all suitable for combustion when a uniform charge is ignited from compression. In addition, it is also easy to assume that soot or soot will adhere to fuel injection nozzles or EGR control valves (exhaust gas recirculation) due to the high aromatic content. Therefore, the composition of the diesel gas oil of this document obviously cannot be a safe fuel for the environment. Similarly, patent documents No. 2, 3 and 4 disclose that fuel compositions with distillation parameters determined by their purpose are effective for combustion upon compression ignition of a uniform charge. However, as discussed above, the distillation parameters are not chemically included in the rate of self-ignition control of the fuel, and especially provided that the type of combustion is improved upon compression ignition of a uniform charge in which the fuel is injected at an earlier stage, as proposed in the present invention, and distillation parameters are also less efficient. An index, which is determined by the temperature of each particular volume of distillate, such as T90, but not the volume of the fraction, can be a rough standard for estimating the type of fuel, but it does not make sense, since it is not an absolute quantitative indicator. In addition, these fuel compositions do not allow an increase in cetane number, but then they probably allow a decrease in the content of saturated hydrocarbon compounds and, therefore, can be considered as fuels that cannot control ignition at any time. Therefore, it is obvious that the characteristic definitions proposed in these documents cannot be considered as characteristics of fuels that can regulate self-ignition, and, moreover, it is likely that there are still no fuels that are safe for the environment.

In addition, environmentally friendly fuels must be optimized for fuel performance every season, taking into account the environment in which it is used. Fuel with excessively lightweight distillation parameters can often cause jamming of fuel injection pumps, cavitation damage, and problems with ease of starting the engine at high temperatures.

That is, it is very difficult to create high-quality fuel, which can provide at a high level both compliance with the requirements for gas oil compositions, which have excellent performance properties in the summer or winter season, and environmentally friendly properties that can be applied to combustion upon compression-ignition of a uniform charge, and there is no example or fact of detection, on the basis of studies, of such a fuel that sufficiently satisfies personal requirements to properties imposed on a fuel other than the foregoing and a practical process for producing fuel.

(1) Patent Document No. 1: Japanese Patent Laid-Open Publication No. 2006-28493

(2) Patent Document No. 2: Japanese Patent Laid-Open Publication No. 2005-343917

(3) Patent Document No. 3: Japanese Patent Laid-Open Publication No. 2005-343918

(4) Patent Document No. 4: Japanese Patent Laid-Open Publication No. 2005-343919

(5) Non-Patent Document No. 1: Konishi Seiichi, “Nenryo Kogaku Gairon”, Shokabo Publishing Co., Ltd., March, 1991, pages 136-144.

SUMMARY OF THE INVENTION

The present invention was developed taking into account the above considerations and has as its aim the development of a gas oil composition for use in the summer or winter season, suitable for diesel combustion, and combustion under compression ignition of a uniform charge. The present invention was the result of extensive research and study conducted to solve the above problems.

That is, the present invention relates to a gas oil composition for use in a diesel engine with a geometric compression ratio of 16 or less, equipped with a supercharger and an EGR system containing FT synthetic base oil and having a sulfur content of 5 ppm. by mass or less, the oxygen content of 100 million hours or less, volumetric strain modulus 1250 MPa or more and 1450 MPa or less, Saybolt color +22 or more, lubricity 400 μm or less, initial boiling point 140 ° C or higher and final boiling point 380 ° C or lower in parameters distillation, and the following properties (1) - (3) fractions of each interval, where

(1) the cetane number of the fraction in the range lower than 200 ° C. is 40 or more and less than 60;

(2) the cetane number of the fraction in the range of 200 ° C or higher and lower than 280 ° C is 60 or more and less than 80% and

(3) the cetane number of the fraction in the range of 280 ° C. or higher is 50 or more.

The present invention also relates to the aforementioned gas oil composition with quality indicators corresponding to JIS standards for No. 1 gas oil, other than sulfur content, for use in a diesel engine with a geometric compression ratio of 16 or less, equipped with a supercharger and an EGR system containing FT synthetic base oil and having a sulfur content of 5 million hours by mass or less, the oxygen content of 100 million hours by mass or less and a bulk strain modulus of 1250 MPa or more and 1450 MPa or less, Saybolt color +22 or more, lubricity 400 μm or less, initial boiling point 140 ° C or higher and final boiling point 380 ° C or lower among the distillation parameters, and the following properties (1) - (3) fractions in each interval, where

(1) the cetane number of the fraction in the range lower than 200 ° C. is 40 or more and less than 60; and the constituent fraction of the fraction in the total volume of fractions is from 1 percent by volume or more to less than 10 percent by volume;

(2) the cetane number of the fraction in the range of 200 ° C. or higher and lower than 280 ° C. is 60 or more and less than 80, and the constituent fraction of the fraction in the total volume of fractions is 40 percent by volume or more and 98 percent by volume or less ; and

(3) the cetane number of the fraction in the range of 280 ° C. or higher is 50 or more, and the constituent fraction of the fraction in the whole volume of the fractions is 1 percent by volume or more and 59 percent by volume or less.

The present invention also relates to the aforementioned gas oil composition with quality indicators meeting JIS standards for No. 2 gas oil, other than sulfur, for use in a diesel engine with a geometric compression ratio of 16 or less, equipped with a supercharger and an EGR system containing FT synthetic base oil and having a sulfur content of 5 million hours by mass or less, the oxygen content of 100 million hours by mass or less, bulk modulus 1250 MPa or more and 1450 MPa or less, Saybolt color +22 or higher, lubricity 400 μm or less, initial boiling point 140 ° C or higher and final boiling point 360 ° C or lower among the distillation parameters, and the following properties (1) - (3) fractions in each interval, where

(1) the cetane number of the fraction in the range lower than 200 ° C. is 40 or more and less than 60, and the constituent fraction of the fraction in the entire volume of fractions is 10 percent by volume or more and less than 20 percent by volume;

(2) the cetane number of a fraction in the range of 200 ° C. or higher and lower than 280 ° C. is 60 or more and less than 80, and the constituent fraction of the fraction in the entire volume of fractions is 30 percent by volume or more and 89 percent by volume or less ; and

(3) the cetane number of the fraction in the range of 280 ° C. or higher is 50 or more, and the constituent fraction of the fraction in the entire volume of fractions is 1 percent by volume or more and 60 percent by volume or less.

The present invention also relates to the aforementioned gas oil composition with quality indicators that meet JIS standards for grade 3 gas oil, other than sulfur, for use in a diesel engine with a geometric compression ratio of 16 or less, equipped with a supercharger and an EGR system containing FT synthetic base oil and having a sulfur content of 5 million hours by mass or less, the oxygen content of 100 million hours by weight or less, volumetric deformation modulus 1250 MPa or more and 1450 MPa or less, Saybolt color +22 or more, lubricity 400 μm or less, initial boiling point 140 ° C or higher and final boiling point 360 ° C or lower among the distillation parameters, and the following properties (1) - (3) fractions in each interval, where

(1) the cetane number of the fraction in the range lower than 200 ° C is 40 or more and less than 60, and the constituent fraction of the fraction in the total volume of fractions is 20 percent by volume or more and less than 40 percent by volume;

(2) the cetane number of a fraction in the range of 200 ° C. or higher and lower than 280 ° C. is 60 or more and less than 80, and the constituent fraction of the fraction in the entire volume of fractions is 30 percent by volume or more and 78 percent by volume or less ; and

(3) the cetane number of the fraction in the range of 280 ° C. or higher is 50 or more, and the constituent fraction of the fraction in the entire volume of fractions is 1 percent by volume or more and 50 percent by volume or less.

The present invention also relates to the aforementioned gas oil composition with quality indicators meeting JIS standards for grade 3 gas oil, other than sulfur, for use in a diesel engine with a geometric compression ratio of 16 or less, equipped with a supercharger and an EGR system containing FT synthetic base oil and having a sulfur content of 5 million hours by mass or less, the oxygen content of 100 million hours by mass or less, bulk modulus 1250 MPa or more and 1450 MPa or less, Saybolt color +22 or higher, lubricity 400 μm or less, initial boiling point 140 ° C or higher and final boiling point 350 ° C or lower among the distillation parameters, and the following properties (1) - (3) fractions in each interval, where

(1) the cetane number of the fraction in the range lower than 200 ° C. is 40 or more and less than 60, and the constituent fraction of the fraction in the whole volume of fractions is 40 percent by volume or more and 70 percent by volume or less;

(2) the cetane number of a fraction in the range of 200 ° C. or higher and lower than 280 ° C. is 60 or more and less than 80, and the constituent fraction of the fraction in the entire volume of fractions is 20 percent by volume or more and 59 percent by volume or less ; and

(3) the cetane number of the fraction in the range of 280 ° C. or higher is 50 or more, and the constituent fraction of the fraction in the entire volume of fractions is 1 percent by volume or more and 30 percent by volume or less.

The present invention also relates to the aforementioned gas oil composition, where the peroxide number after the accelerated oxidation test is preferably 50 ppm. by weight or less, the aromatic content is preferably 15 percent by volume or less, and the proportion of FT synthetic base oil in the mixture is preferably 20 percent by volume or more.

The present invention is intended to balance a relatively light fraction evaporating at a relatively early stage and a heavy fraction evaporating at a relatively late stage, taking into account not only the ignition phenomenon, but also the evaporation and mixing phenomena with air occurring before the ignition phenomenon. In accordance with which, the present invention can help achieve optimal ignition conditions during combustion with compression ignition of a uniform charge and traditional diesel combustion. Since these ignition phenomena are highly dependent on the compression ratio or the starting conditions of the engine in which the fuel is used, the present invention also imposes some restrictions on the operating conditions of the engine so that the fuel can be most efficient.

The positive results of the invention

According to the present invention, the use of a gas oil composition obtained by the above method with the above requirements regarding fractions makes it possible to obtain high-quality fuel that can provide at a high level both excellent performance in summer or winter seasons, as well as environmentally friendly properties that can be applied to combustion during compression ignition of a uniform charge, where both performance and properties would be difficult to provide read using a traditional fuel composition.

The best way to implement the invention

Below the present invention will be discussed in more detail.

The gas oil composition of the present invention optionally contains FT synthetic base oil. FT synthetic base oil consists of saturated hydrocarbon compounds, and the gas oil composition of the present invention can be easily obtained by adjusting the composition of the mixture of hydrocarbon compounds. There is no particular restriction on the properties of FT synthetic base oils if the properties of the gas oil composition of the present invention are provided. There are no particular restrictions on base oils other than FT synthetic base oils, since the requirements for the properties of the gas oil composition of the present invention are met. However, in order to provide a composition exhibiting sufficiently environmentally friendly properties, it is preferable to mix the following deep hydrogenated petroleum base oils and processed animal or vegetable oils.

The FT synthetic base oil referred to herein refers to various synthetic oils, such as liquid fractions corresponding to naphtha, kerosene and gas oil, obtained by treating a mixed gas containing mainly hydrogen and carbon monoxide (hereinafter often referred to as “synthetic gas”), Fischer-Tropsch reactions (Fischer-Tropsch (FT)); hydrocarbon mixtures obtained by hydrotreating or hydrocracking of these liquid fractions; and hydrocarbon mixtures obtained by hydrotreating or hydrocracking of liquid fractions and FT wax obtained by the Fischer-Tropsch reaction.

The gas oil composition preferably comprises 20 percent by volume or more of FT synthetic base oil. In addition, the composition comprises more preferably 25 percent by volume or more, more preferably 30 percent by volume or more, more preferably 35 percent by volume or more, FT synthetic base oil in order to reduce the possibility of an increase in environmental stress caused by sulfur-containing components or aromatic components, and the implementation is more effective in adjusting the ignition required for combustion with compression ignition of a uniform charge.

There are no specific restrictions on the properties of FT synthetic base oils, since the resulting gas oil composition will have predetermined properties. However, it is preferable to mix FT synthetic base oil with a boiling point in the range of 140 to 380 ° C, given the ease of preparation of the gas oil composition of the present invention.

The mixed gas, which will be the raw material for FT synthetic oil, is obtained by oxidizing a carbon-containing substance using oxygen and / or water and / or carbon dioxide as an oxidizing agent, and then, if necessary, by shifting the reaction using water to adjust composition towards predetermined concentrations of hydrogen and carbon monoxide.

Substances containing carbon that can be used in this document are usually components of a gas consisting of hydrocarbons that are gaseous at normal temperatures, such as natural gas, liquefied petroleum gas and methane gas, petroleum asphalt, biomass, coke, waste such as building materials, and wastepaper, sludge, heavy crude oils that are difficult to dispose of using conventional methods, and mixed gas obtained from high temperatures on unconventional sources oil. However, in the present invention, there are no particular restrictions on raw materials, since a mixed gas containing mainly hydrogen and carbon monoxide can be obtained.

The Fischer-Tropsch reaction requires a metal catalyst. It is preferable to use the metals of group 8 of the periodic table, such as cobalt, ruthenium, rhodium, palladium, nickel and iron, more preferably the metals of group 8, 4 of the period, as an active catalytic component. Alternatively, a mixed metal group containing these metals in suitable amounts may be used. These active metals are usually used in the form of a catalyst obtained by depositing it on a support such as alumina, titanium oxide and silica-alumina. Alternatively, the use of the above active metals in combination with a second metal may improve the performance of the resulting catalyst. Examples of the second metal include alkali and alkaline earth metals, such as sodium, lithium and magnesium, zirconium, hafnium and titanium, which will be used depending on the purpose, such as increasing the conversion rate of carbon monoxide or the likelihood of chain growth (α), which is an indicator of the formation the amount of wax.

The Fischer-Tropsch reaction is a synthesis method for producing liquid fractions and FT wax when mixed gas is used as raw material. It is usually preferable to adjust the ratio of hydrogen to carbon monoxide in the mixed gas in order to efficiently implement the synthesis method. In general, the molar ratio of hydrogen to carbon monoxide in the mixture (hydrogen / carbon monoxide) is preferably 1.2 or more, more preferably 1.5 or more, more preferably 1.8 or more. The ratio is also preferably 3 or less, more preferably 2.6 or less, more preferably 2.2 or less.

The reaction temperature at which the Fischer-Tropsch reaction proceeds in the presence of the above catalyst is preferably 180 ° C. or higher and 320 ° C. or lower, more preferably 200 ° C. or higher and 300 ° C. or lower. At reaction temperatures below 180 ° C, carbon monoxide is difficult to interact, which leads to a tendency to decrease the yield of hydrocarbon. At reaction temperatures above 320 ° C, an increased amount of gas, such as methane, is formed, which leads to a decrease in the efficiency of formation of liquid fractions and FT wax.

There are no specific restrictions on the hourly space velocity of the gas relative to the catalyst. However, preferably it is 500 h ^-1 or more and 4000 h ^-1 or less, more preferably 1000 h ^-1 or more and 3000 h ^-1 or less. An hourly volumetric gas velocity of less than 500 h ^{-1 is} likely to reduce the formation of liquid fuel, while an hourly volumetric gas velocity of more than 400 h ^-1 there is a need to increase the reaction temperature and increase the amount of gas produced, which reduces the yield of the target product.

There are no specific restrictions on the reaction pressure (partial pressure of a synthetic gas consisting of carbon monoxide and hydrogen). However, it is preferably 0.5 MPa or more and 7 MPa or less, more preferably 2 MPa or more and 4 MPa or less. If the reaction pressure is less than 0.5 MPa, the liquid fuel yield will decrease. If the reaction pressure is greater than 7 MPa, then this is not economically feasible, because capital investments in production will increase.

If necessary, the liquid fractions and FT wax formed in the FT reaction described above can be hydrotreated or hydrocracked in any suitable way so as to adjust the distillation parameters or composition to achieve the objectives of the invention.

Hydrotreating or hydrocracking can be selected depending on the purpose, and the present invention is not limited in the choice of either one or both of them to the extent that the gas oil composition of the present invention is obtained.

The catalysts used for hydrotreating are usually those that include an active hydrogenation metal supported on a porous support, but the present invention is not limited thereto, since the same effects are achieved.

The porous carrier is preferably an inorganic oxide. Specific examples include alumina, titanium oxide, zirconium oxide, boron oxide, silica, zeolite, and the like.

Zeolite is a crystalline aluminosilicate, examples of which include zeolites such as faujasite, pentazyl and mordenite. Preferred types of zeolites are faujasite, zeolites of the beta and mordenite type, and particularly preferred are Y-type and beta-type zeolites. Y-type zeolites are preferably ultra stable.

Preferred active metals are the following two types of metals (type A active metal and type B active metal).

An active metal of type A is at least one type of metal selected from the group consisting of metals of group 8 of the periodic table. Preferably, at least one type is selected from the group consisting of Ru, Rh, Ir and Pt, and more preferably Pd and / or Pt. The active metal may be in a combination of these metals, such as Pt-Pd, Pt-Rh, Pt-Ru, Ir-Pd, Ir-Rh, Ir-Ru, Pt-Pd-Rh, Pt-Rh-Ru, Ir- Pd-Rh and Ir-Rh-Ru. A noble metal catalyst formed by these metals can be used after undergoing preliminary reduction treatment in a stream of hydrogen. In general, the catalyst is heated at a temperature of 200 ° C or higher in accordance with a predetermined sequence of operations, circulating a gas containing hydrogen, so that the active metal on the catalyst is reduced and thus exhibits hydrogenation activity.

The type B active metal preferably contains at least one type of metal selected from the group consisting of metals of groups 6A and 8 of the periodic table, preferably two or more types of metals selected from among them. Examples of these metals include Co-Mo, Ni-Mo, Ni-Co-Mo, and Ni-W. When a metal sulfide-based catalyst derived from these metals is used, it must undergo a preliminary desulfurization process.

The metal source may be a conventional inorganic salt or a complex compound such as a salt. The support method can be any support method that is traditionally used for hydrogenation catalysts, such as the method of impregnation and ion exchange. When several metals are applied to a support, they can be applied to the support simultaneously, using their mixed solution or sequentially, using separate solutions containing each metal. The metal-containing solution may be an aqueous solution or an organic solvent based solution.

The reaction temperature at which hydrotreating is carried out using a catalyst consisting of an active metal of type A is preferably 180 ° C or higher and 400 ° C or lower, more preferably 200 ° C or higher and 370 ° C or lower, more preferably 250 ° C or higher and 350 ° C or lower, more preferably 280 ° C or higher and 350 ° C or lower. A reaction temperature higher than 370 ° C. is not preferable since the yield of the middle fraction drops sharply due to an increase in the rate of side reaction, where the liquid fraction or FT wax is broken down to the naphtha fraction. A reaction temperature lower than 270 ° C. is also not preferred because alcohols cannot be removed and thus remain in the reaction system.

The reaction temperature at which hydrotreating is carried out using a catalyst consisting of a type B active metal is preferably 170 ° C or higher or 320 ° C or lower, more preferably 175 ° C or higher and 300 ° C or lower, more preferably 180 ° C or higher and 280 ° C or lower. A reaction temperature higher than 320 ° C. is not preferable because the yield of the middle fraction is reduced due to an increase in the rate of side reaction when the liquid fraction or FT wax is broken down to the naphtha fraction. A reaction temperature lower than 170 ° C. is also not preferred, because alcohols cannot be removed and thus remain in the reaction system.

The hydrogen pressure at which hydrotreating is carried out using a catalyst consisting of type A active metal is preferably 0.5 MPa or higher and 12 MPa or lower, more preferably 1.0 MPa or higher and 5.9 MPa or lower. Although the hydrogenation reaction accelerates at a higher hydrogen pressure, there is usually an optimum point determined by economic considerations.

The hydrogen pressure at which hydrotreating is carried out using a catalyst consisting of an active metal of type B is preferably 2 MPa or higher and 10 MPa or lower, more preferably 2.5 MPa or higher and 8 MPa or lower, more preferably 3 MPa or higher and 7 MPa or lower. Although the hydrogenation reaction accelerates at a higher hydrogen pressure, there is usually an optimum point determined by economic considerations.

The liquid hourly space velocity (LHSV), at which hydrorefining is carried out using a catalyst composed of the active metal A type is preferably 0.1 h ^-1 or greater and 10.0 h ^-1 or less, more preferably 0.3 hours ^{- 1} or more and 3.5 h ^-1 or less. Although lower LHSV is preferable for the reaction, too low LHSV is not economically preferable because it requires an extremely large reactor volume, which entails unnecessary capital investment in the installation.

The liquid hourly space velocity (LHSV) at which hydrotreating is carried out using a catalyst consisting of type B active metal is preferably 0.1 h ^-1 or more and 2 h ^-1 or less, more preferably 0.2 h ^-1 or more and 1.5 h ^-1 or less, more preferably 0.3 h ^-1 or more and 1.2 h ^-1 or less. Although lower LHSV is preferable for the reaction, too low LHSV is not economically preferable because it requires an extremely large reactor volume, which entails unnecessary capital investment in the installation.

The hydrogen / oil ratio in which hydrotreating is carried out using a catalyst consisting of type A active metal is preferably 50 nl / L or more and 1000 nl / L or less, more preferably 70 nl / L or more and 800 nl / L or smaller. Although a higher hydrogen / oil ratio speeds up the reaction, there is usually an optimum point determined by economic considerations.

The hydrogen / oil ratio in which hydrotreating is carried out using a catalyst consisting of an active metal of type B is preferably 100 nl / l or more and 800 nl / l or less, more preferably 120 nl / l or more and 600 nl / l or less, more preferably 150 nl / l or more and 500 nl / l or less. Although a higher hydrogen / oil ratio speeds up the reaction, there is usually an optimum point determined by economic considerations.

The catalysts used for hydrocracking are usually those that include an active hydrogenation metal supported on a solid with acidic properties, but the present invention is not limited thereto, since the same beneficial effects can be achieved.

As for the carrier with solid acidic properties, there are amorphous and crystalline types of zeolites. Specific examples include silica — alumina, silica — magnesia, silica — zirconia, and silica — titania, which are amorphous carrier types, and faujasite, beta, MF1, and mordenite zeolites, preferably Y type and beta -type. Y-type zeolites are preferably those that are ultra stable.

Preferred active metals are the following two types of metals (type A active metal and type B active metal).

The active metal of type A represents at least one type of metal, mainly selected from the group including metals of groups 6A and 8 of the periodic table. Preferably, this is at least one type of metal selected from the group consisting of Ni, Co, Mo, Pt, Pd and W. A noble metal catalyst formed by these metals can be used after undergoing preliminary reduction treatment in a stream of hydrogen. In general, the catalyst is heated at a temperature of 200 ° C or higher in accordance with a predetermined sequence of operations, circulating a gas containing hydrogen, so that the active metal on the catalyst is reduced and thus exhibits hydrogenation activity.

The active metal of type B may be a combination of these metals, such as Pt-Pd, Co-Mo, Ni-Mo, Ni-W and Ni-Co-Mo. When a catalyst based on these metals is used, it must undergo a preliminary desulfurization process before use.

The metal source may be a conventional inorganic salt or a complex compound such as a salt. The support method can be any support method that is traditionally used for hydrogenation catalysts, such as the method of impregnation and ion exchange. When several metals are applied to a support, they can be applied to the support simultaneously using their mixed solution or sequentially using separate solutions containing each metal. The metal-containing solution may be an aqueous solution or an organic solvent based solution.

The reaction temperature at which hydrocracking is carried out using a catalyst consisting of an active metal of type A and an active metal of type B is preferably 200 ° C or higher and 450 ° C or lower, more preferably 250 ° C or higher and 430 ° C or lower , more preferably 300 ° C. or higher and 400 ° C. or lower. A reaction temperature higher than 450 ° C. is not preferable because the yield of the middle fraction drops sharply due to an increase in the rate of side reaction, where the liquid fraction or FT wax is split to a naphtha fraction. A reaction temperature lower than 200 ° C is also not preferred, because the activity of the catalyst decreases sharply.

The hydrogen pressure at which hydrocracking is carried out using a catalyst consisting of an active metal of type A and an active metal of type B is preferably 1 MPa or higher and 20 MPa or lower, more preferably 4 MPa or higher and 16 MPa or lower, more preferably 6 MPa or higher and 13 MPa or lower. Although the hydrogenation reaction is accelerated at a higher hydrogen pressure, the cleavage reaction will rather proceed slowly, and thus, it will be necessary to adjust its conditions by increasing the reaction temperature, which will lead to a short catalyst life. Therefore, usually there is an optimum point determined by economic considerations.

The liquid hourly space velocity (LHSV), at which hydrocracking is carried out using a catalyst composed of the active metal A type is preferably 0.1 h ^-1 or greater and 10.0 h ^-1 or less, more preferably 0.3 hours ^{- 1} or more and 3.5 h ^-1 or less. Although lower LHSV is preferable for the reaction, too low LHSV is not economically preferable because it requires an extremely large reactor volume, which entails unnecessary capital investment in the installation.

The liquid hourly space velocity (LHSV) at which hydrocracking is carried out using a catalyst consisting of type B active metal is preferably 0.1 h ^-1 or more and 2 h ^-1 or less, more preferably 0.2 h ^-1 or more and 1.7 h ^-1 or less, more preferably 0.3 h ^-1 or more and 1.5 h ^-1 or less. Although lower LHSV is preferable for the reaction, too low LHSV is not economically preferable because it requires an extremely large reactor volume, which entails unnecessary capital investment in the installation.

The hydrogen / oil ratio in which hydrocracking is carried out using a catalyst consisting of type A active metal is preferably 50 nl / l or more and 1000 nl / l or less, more preferably 70 nl / l or more and 800 nl / l or less, more preferably 400 nl / l or more and 1500 nl / l or less. Although a higher hydrogen / oil ratio speeds up the reaction, there is usually an optimum point determined by economic considerations.

The hydrogen / oil ratio in which hydrocracking is carried out using a catalyst consisting of an active metal of type B is preferably 150 nl / l or more and 2000 nl / l or less, more preferably 300 nl / l or more and 1700 nl / l or less, more preferably 400 nl / l or more and 1500 nl / l or less. Although a higher hydrogen / oil ratio speeds up the reaction, there is usually an optimum point determined by economic considerations.

The hydrogenation reactor can be a reactor of any design and one or more reaction towers can be used. Hydrogen may be additionally supplied between several reaction towers. The reactor can be equipped with a hydrogen sulfide removal unit and a distillation column for fractional distillation of hydrogenated products to obtain the desired fractions.

The hydrogenation reactor can operate in a reactor mode with a stationary bed. Hydrogen can be supplied to the feedstock in a counterflow or parallel flow mode. Alternatively, the reactor mode may be a combination of counterflow and parallel flow modes, with multiple reaction towers. The feed mode is typically a downdraft mode and is preferably a gas-liquid parallel flow mode. Hydrogen gas can be supplied as a cooler to the middle part of the reactor in order to remove the heat of reaction or increase the partial pressure of hydrogen. The mixed gas, which will be the raw material for FT synthetic oil, is produced by oxidizing a substance containing carbon using oxygen and / or water and / or carbon dioxide and optionally, if necessary, by displacing the reaction using water to adjust it to side of predetermined concentrations of hydrogen and carbon monoxide. Substances containing carbon that can be used in the present invention are typically gas components consisting of hydrocarbons, which at normal temperatures are gases, such as natural gas, liquefied petroleum gas and methane gas, petroleum asphalt, biomass, coke, waste, such as construction materials and waste paper, sludge, heavy crude oils that are difficult to dispose of in the usual way, and mixed gas formed when exposed to elevated temperatures on unconventional sources of oil. However, in the present invention, there are no restrictions on raw materials, since a mixed gas containing mainly hydrogen and carbon monoxide can be obtained.

The above petroleum-based base oil is a hydrocarbon base oil obtained from the processing of crude oil. Examples include direct base oils obtained from atmospheric distillation plants; vacuum base oils obtained by direct processing of heavy oil or residue obtained from a distillation unit operating at atmospheric pressure, from a vacuum distillation unit; base oils of catalytic cracking or hydrocracking obtained by catalytic cracking or vacuum hydrocracking of a heavy base oil or desulfurized fuel; and base hydrotreating or hydrocracking oils obtained by hydrotreating any of these hydrocarbons of petroleum origin. Alternatively, base oils obtained by suitable refining, in addition to crude oil, sources called unconventional oil sources such as oil shale, oil sand and Orinoco resin, and having properties equivalent to those mentioned above, can be used as the base oil in the present invention. base oils.

The above highly hydrogenated petroleum-based base oil is kerosene or a gas oil fraction obtained by hydrotreating and then hydrogenating a predetermined feedstock. Examples of feeds include direct kerosene or gas oils obtained from a distillation unit for atmospheric crude oil; vacuum kerosene or gas oils obtained by processing direct heavy oil or residue from a distillation unit operating at atmospheric pressure on a vacuum distillation unit; and hydrotreated and hydrodesulfurized kerosene or gas oils obtained by hydrogenation of catalytic cracking kerosene, or gas oils obtained by catalytic cracking of desulfurized or undesulfurized vacuum kerosene or gas oil, vacuum heavy gas oil or desulfurized fuel.

When the gas oil fraction is the feed, the hydrotreating conditions can be the same as those determined when a hydrodesulfurization unit is usually used for oil refining. Typically, hydrotreating the gas oil fraction is carried out under conditions where the reaction temperature is from 300 to 380 ° C, the hydrogen pressure is from 3 to 8 MPa, the LHSV is from 0.3 to 2 h ^-1 and the hydrogen / oil ratio is from 100 to 500 nl / l When the kerosene fraction is the feedstock, the conditions for hydrotreating can be the same as those determined when a hydrodesulfurization unit is usually used for oil refining. Typically, hydrotreating the kerosene fraction is carried out under conditions where the reaction temperature is from 220 to 350 ° C, the hydrogen pressure is from 1 to 6 MPa, the LHSV is from 0.1 to 10 h ^-1 and the hydrogen / oil ratio is from 10 to 300 nl / l, preferably conditions under which the reaction temperature is from 250 to 340 ° C, the hydrogen pressure is from 2 to 5 MPa, LHSV is from 1 to 10 h ^-1 and the hydrogen / oil ratio is from 30 to 200 nl / l, more preferably, under conditions where the reaction temperature is from 270 to 330 ° C, the hydrogen pressure is it is from 2 to 4 MPa, LHSV is from 2 to 10 h ^-1 and the hydrogen / oil ratio is from 50 to 200 nl / l.

A lower reaction temperature is advantageous for the hydrogenation reaction, but is not preferred for the desulfurization reaction. A higher hydrogen pressure and a higher hydrogen / oil ratio accelerate the desulfurization and hydrogenation reactions, but there is an optimum point determined by economic considerations. Although lower LHSV is advantageous for the reaction, too low LHSV is not economically preferable because it requires an extremely large reactor volume, which leads to excessive capital investment in the installation.

The catalysts used for hydrotreating can be any of the conventional hydrodesulfurization catalysts. Preferably, the active metals of the catalyst are metals of groups 6A and 8 of the periodic table. Examples of these metals include Co-Mo, Ni-Mo, Co-W, and Ni-W. The carrier may be a porous inorganic oxide containing alumina as the main component. These conditions and the catalyst are not particularly limited, since the properties of the raw materials meet the requirements.

The raw materials used in the present invention are obtained by the hydrotreatment process described above, and it preferably has a sulfur content of 5 ppm. by weight or more and 10 million hours by weight or less and a boiling point of 130 ° C or higher and 380 ° C or lower. Raw materials having a sulfur content and a boiling point at the indicated intervals can easily achieve the properties determined for the next deep hydrogenation process.

Deep hydrogenation base oil is obtained by hydrogenation of the above hydrogenated kerosene or gas oil as a feedstock in the presence of a hydrogenation catalyst.

Conditions for deep hydrogenation are conditions where the reaction temperature is from 170 to 320 ° C, the hydrogen pressure is from 2 to 10 MPa, the LHSV is from 0.1 to 2 h ^-1 and the hydrogen / oil ratio is from 100 to 800 nl / l, preferably conditions where the reaction temperature is from 175 to 300 ° C, the hydrogen pressure is from 2.5 to 8 MPa, the LHSV is from 0.2 to 1.5 h ^-1 and the hydrogen / oil ratio is from 150 to 600 nl / l, more preferably under conditions where the reaction temperature is from 180 to 280 ° C, the hydrogen pressure is about 3 to 7 MPa, LHSV is from 0.3 to 1.2 h ^-1 and the hydrogen / oil ratio is from 150 to 500 Nl / l. A lower reaction temperature is advantageous for the hydrogenation reaction, but is not preferred for the desulfurization reaction. A higher hydrogen pressure and a higher hydrogen / oil ratio accelerate the desulfurization and hydrogenation reactions, but there is an optimum point determined by economic considerations. Although lower LHSV is advantageous for the reaction, too low LHSV is not economically preferable because it requires an extremely large reactor volume, which leads to excessive capital investment in the installation.

Hydrorefining raw material hydrogenation unit can be of any design and one or more reactors can be used in combination with each other. Hydrogen can be additionally fed into the space between several reactors. The hydrorefining unit may be equipped with a gas-liquid separation system or a system for removing hydrogen sulfide.

The hydrogenation reactor can operate in a reactor mode with a stationary bed. Hydrogen can be supplied to the feedstock in a counterflow or forward flow mode. Alternatively, the reactor mode may be a combination of counterflow and forward flow modes with a plurality of reaction towers. The feed mode is typically a downdraft mode and is preferably a gas-liquid by-pass mode. Hydrogen gas can be supplied as a cooler to the middle part of the reactor in order to remove the heat of reaction or increase the partial pressure of hydrogen.

The catalyst used for hydrogenation includes an active hydrogenation metal supported on a porous support. The porous carrier may be an inorganic oxide, such as alumina. Examples of inorganic oxide include alumina, titanium oxide, zirconium oxide, boron oxide, silica and zeolite. In the present invention, the support preferably consists of alumina and at least one oxide selected from the group consisting of titanium dioxide, zirconia, boron oxide, silicon dioxide and zeolite. There are no specific restrictions on the method of obtaining media. Therefore, any method involving the use of raw materials in the form of sols or salts, each of which contains any of the elements, can be applied. Alternatively, the support may be prepared by forming a complex hydroxide or oxide, such as silica — alumina, silica — zirconia, alumina — titania, silica — titania and alumina — boron, followed by addition at any stage of alumina in the form of an alumina gel, hydroxide or a suitable solution. Alumina can be contained in any ratio with other oxides based on a porous carrier. However, the alumina content is preferably 90 percent by mass or less, more preferably 60 percent by mass or less, and more preferably 40 percent by mass or less, by weight of the porous carrier.

Zeolite is a crystalline aluminosilicate. Examples of crystal structure include faujasite, pentasil and mordenite. These zeolites may be those that are ultrastabilized by a specific hydrothermal treatment and / or acid treatment, or such treatment that allows the alumina content to be adjusted. Preferred types of zeolites are faujasite, zeolites beta and mordenite type, and particularly preferred zeolites are zeolites Y and beta types. Type Y zeolites are preferably ultra-stabilized. Ultrastabilized zeolites have a specific microporous structure with so-called micropores 20 Å or smaller in size, as well as newly formed pores with sizes ranging from 20 to 100 Å. Hydrothermal treatment can be carried out under known conditions.

The active metal of the catalyst used for hydrogenation is at least one metal selected from group 6 of the metals of the periodic table, preferably at least one metal selected from among metals such as Ru, Rh, Ir, Pd and Pt , and more preferably Pd and / or Pt. These metals can be used in combination, such as Pt-Pd, Pt-Rh, Pt-Ru, Ir-Pd, Ir-Rh, Ir-Ru, Pt-Pd-Rh, Pt-Rh-Ru, Ir-Pd- Rh and Ir-Rh-Ru. Inorganic salts or complex salts that are conventionally used can be a source of metal from these metals. The method of depositing metal on a support can be one of the methods, such as immersion and ion exchange, which are used for the hydrogenation catalyst. When several metals are applied to a carrier, they can be applied while using their mixed solution. Alternatively, several metals may be supported on a carrier using successive solutions, each of which contains any of these metals. These metal-containing solutions may be aqueous solutions or solutions obtained using an organic solvent.

The metal (s) may be deposited on the porous support after all steps are completed upon receipt of the porous support. Alternatively, the metal (s) may be deposited on the porous support in the form of a suitable oxide, complex oxide or zeolite obtained in the intermediate step of preparing the porous support, and then may be directed to a gel or subjected to thermal concentration and mixing.

There are no specific restrictions on the amount of active metal (s) deposited on a carrier. However, this amount is from 0.1 to 10 percent by weight, preferably from 0.15 to 5 percent by weight, and more preferably from 0.2 to 3 percent by weight, based on the weight of the catalyst.

The catalyst is preferably used after it has undergone a preliminary reduction treatment in a stream of hydrogen. In general, the active metal (s) are exposed to heat at 200 ° C. or higher according to predetermined methods, under conditions of circulation of a gas containing hydrogen, and then reduced, thereby exhibiting their catalytic activity.

The processed oils of animal and vegetable origin mentioned above are base oils consisting of hydrocarbons formed as a result of applying chemical processing processes to oils or fats that produce or form raw materials of vegetable or animal origin to obtain the above oil-based base oils. In particular, process oils of animal and vegetable origin are hydrocarbon-containing mixed base oils obtained by contacting animals or vegetable fats and components derived from them, used as raw materials, with a hydrocracking catalyst containing at least one or more metals selected from group 6A and 8 metals of the periodic table, and inorganic oxide with acidic properties, under hydrogen pressure. Raw materials from technological oil of animal and vegetable origin is necessarily animal or vegetable fat or components derived from them. Examples of animal or vegetable fat or components derived from them used in the present invention include natural or artificially obtained animal or vegetable fats and animal or vegetable fat components derived from them. Examples of starting materials for animal fats and animal oils include beef tallow, milk fat (butter), lard, mutton fat, whale oil, fish oil and liver oil. Examples of starting materials for vegetable fats and vegetable oils include seeds and other parts of coconut, palm tree, olives, safflower, rapeseed (rape blossoms), rice husks, sunflowers, cotton seeds, corn, soybeans, sesame seeds and flax. Fats and oils other than those derived from these materials can also be used in the present invention. The feed may be solid or liquid, but is preferably derived from vegetable fats or vegetable oils for the purpose of easy transport, absorption of carbon dioxide and high performance. Alternatively, waste oils generated by using these animal and vegetable fats in the household, industry, and cooking can be used as raw materials after removing residual materials from these oils.

Examples of a typical composition of the fatty acid portion of the glyceride compounds contained in these types of raw materials include fatty acids, the so-called saturated fatty acids that do not contain unsaturated bonds in the molecule, such as butyric acid (C ₃ H ₇ COOH), 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 so-called unsaturated fatty acids with ERZHAN in the molecule one or more unsaturated bonds, such as oleic acid (C ₁₇ H ₃₃ COOH), linoleic acid (C ₁₇ H ₃₁ COOH), linolenic acid (C ₁₇ H ₂₉ COOH) and ricinoleic acid (C ₁₇ H ₃₂ (OH ) COOH). In general, the hydrocarbon portions of these fatty acids contained in naturally occurring substances are, in most cases, linear chains. However, the fatty acid may be any of those that have a branched structure, i.e. isomers if the requirements for the properties defined by the present invention are satisfied. The unsaturated fatty acid can be any of those whose existence is usually recognized in nature, as well as those that contain an unsaturated bond in a molecule, the position of which is regulated by the conditions of chemical synthesis, if the requirements for the properties defined by the present invention are satisfied.

The above raw materials (animal or vegetable fats and the components formed by them) contain one or more of these fatty acids, which vary depending on the raw materials. For example, coconut oil contains a relatively large amount of saturated fatty acids such as lauric acid and myristic acid, while soybean oil contains a large amount of unsaturated fatty acids such as oleic acid and linoleic acid.

The feed contains a fraction whose boiling point is preferably 250 ° C. or higher, more preferably a fraction whose boiling point is 300 ° C. or higher, and more preferably a fraction whose boiling point is 360 ° C. or higher. If the feed does not contain a fraction whose boiling point is 230 ° C. or higher, the yield of the liquid product will decrease due to an increase in the proportion of gas generated during the production process, possibly leading to an increase in the service life of carbon dioxide.

Alternatively, the feedstock for a process oil of animal or vegetable origin may be a mixture of animal or vegetable fat and components derived therefrom with a petroleum hydrocarbon fraction. In this case, the proportion of the petroleum hydrocarbon fraction is preferably from 10 to 99 percent by volume, more preferably from 30 to 99 percent by volume, and more preferably from 60 to 98 percent by volume, based on the total volume of the feed. If the proportion is less than the lower limit, there may be a need for installations for the disposal of water generated as a by-product. If the proportion exceeds the upper limit, then this is not preferable from the point of view of reducing the service life of carbon dioxide.

The hydrocracking conditions of the feedstock during the hydrogenation process are preferably those when the hydrogen pressure is from 6 to 20 MPa, the hourly space velocity of the liquid (LHSV) is from 0.1 to 1.5 h ^-1 and the hydrogen / oil ratio is from 200 to 2000 nl / l, more preferably, when the hydrogen pressure is from 8 to 17 MPa, the hourly space velocity of the liquid (LHSV) is from 0.2 to 1.1 h ^-1 and the hydrogen / oil ratio is from 300 to 1800 nl / l, more preferably, when the hydrogen pressure is from 10 to 16 MPa, the hourly space velocity of the liquid (LHSV) s leaves from 0.3 to 0.9 h ^-1 and the ratio of hydrogen / oil is from 350 to 1600 nl / L. Each of the parameters is a factor affecting the activity of the reaction. For example, if the hydrogen pressure and the hydrogen / oil ratio are less than the lower limits, then there is a tendency to a decrease in reactivity, and the activity decreases sharply. If the hydrogen pressure and the hydrogen / oil ratio exceed the upper limits, huge investments may be required in the construction of the compressor. A lower hourly space velocity of the liquid is more preferable for carrying out the reactions. However, if the hourly space velocity of the liquid is lower than 0.1 h ^-1 , then huge investments may be required for the construction of an extremely large reactor. If the hourly space velocity of the liquid exceeds 1.5 h ^-1 , then the reaction may not proceed sufficiently.

The gas oil composition of the present invention is a fuel used for diesel engines with a geometric compression ratio of 16 or less, equipped with a supercharger and an EGR system, and necessarily includes FT synthetic base oil, providing the properties discussed below.

The gas oil composition of the present invention is necessarily used for diesel engines with a geometric compression ratio of 16 or less equipped with a supercharger and an ERG system. You can use the gas oil composition for a diesel engine with a geometric compression ratio greater than 16, equipped with a supercharger or EGR system. However, the use of a gas oil composition for a given diesel engine is not preferred from the point of view of the purpose of the present invention, i.e. a reduction in environmental pressure cannot be expected.

The geometric compression ratio is the compression ratio calculated according to the physical specification of the engine. In general, it denotes the value obtained by dividing the internal volume of the cylinder A, determined at the lowest position of the piston, by the internal volume of the cylinder B, determined at the highest position of the piston, and these values for many diesel engines are about 12-22. In modern diesel engines with an electronic control system, a significant compression ratio can be changed by the intake and exhaust valves or by adjusting the pumping pressure. However, in the present invention, the scope of the claims is determined by the degree of geometric compression, taking into account the effect of a significant degree of compression.

Diesel engines for which the gas oil composition of the present invention is intended are necessarily equipped with a supercharger and a device for EGR (exhaust gas recirculation). These devices are used to improve exhaust gas parameters, fuel efficiency and output power. Particularly, during compression ignition of a uniform charge, they are often used to control ignition, and the gas oil composition of the present invention is designed provided that it is used for these purposes.

The present invention does not impose any specific restrictions on other specifications, applications or environmental conditions of use of a diesel engine in which a gas oil composition is used.

The gas oil composition of the present invention is a gas oil composition for use in a diesel engine with a geometric compression ratio of 16 or less, equipped with a supercharger and an EGR system, and contains FT synthetic base oil and has a sulfur content of 5 ppm. by mass or less, the oxygen content of 100 million hours by weight or less, bulk modulus 1250 MPa or more and 1450 MPa or less, Saybolt color +22 or more, lubricity 400 μm or less, initial boiling point 140 ° C or higher and final boiling point 380 ° C or lower in the distillation parameters, and the following properties (1) - (3) for the fraction of each interval:

(1) the cetane number of a fraction of an interval below 200 ° C. is 40 or more and less than 60;

2) the cetane number of the fraction of the interval 200 ° C or higher and lower than 280 ° C is 60 or more and less than 80; and

(3) the cetane number of a fraction of an interval of 280 ° C. or higher is 50 or more.

Alternatively, the gas oil composition of the present invention is a gas oil composition with quality parameters that meet the requirements of JIS standards for grade No. 1 gas oil (hereinafter referred to as "gas oil composition (No. 1)"), except for sulfur content, for use in diesel an engine with a geometric compression ratio of 16 or less, equipped with a supercharger and an EGR system containing FT synthetic base oil and having a sulfur content of 5 ppm. by mass or less, the oxygen content of 100 million hours by weight or less, bulk modulus 1250 MPa or more and 1450 MPa or less, Saybol color +22 or more, lubricity 400 μm or less, initial boiling point 140 ° C or higher and final boiling point 380 ° C or lower in the distillation parameters, and the following properties (1) - (3) fractions for each interval:

(1) the cetane number of a fraction of an interval below 200 ° C. is 40 or more and less than 60, and a constituent fraction of the fraction in the entire volume of fractions is 1 percent by volume or more and less than 10 percent by volume;

2) the cetane number of the fraction of the interval 200 ° C or higher and lower than 280 ° C is 60 or more and less than 80; and the constituent fraction of the fraction in the total volume of fractions is 40 percent by volume or more and 98 percent by volume or less; and

(3) the cetane number of a fraction of an interval of 280 ° C. or higher is 50 or more, and a constituent fraction of the fraction in the entire volume of fractions is 1 percent by volume or more and 59 percent by volume or less.

JIS standard for gas oil No. 1 is a standard that meets the requirements for "type No. 1" defined in LIS K 2204 "Gas oil".

The gas oil composition of the present invention is a gas oil composition with quality parameters that meet the requirements of JIS standards for gas oil grade No. 2 (hereinafter referred to as "gas oil composition (No. 2)"), except for sulfur content, for use in a geometric diesel engine a compression of 16 or less, equipped with a supercharger and an EGR system containing FT synthetic base oil and having a sulfur content of 5 ppm. by mass or less, the oxygen content of 100 million hours by weight or less, bulk modulus 1250 MPa or more and 1450 MPa or less, Saybol color +22 or more, lubricity 400 μm or less, initial boiling point 140 ° C or higher and final boiling point 360 ° C or lower in the distillation parameters, and the following properties (1) - (3) fractions for each interval:

(1) the cetane number of a fraction of an interval below 200 ° C. is 40 or more and less than 60, and a constituent fraction of the fraction in the entire volume of fractions is 10 percent by volume or more and less than 20 percent by volume;

2) the cetane number of the fraction of the interval 200 ° C or higher and lower than 280 ° C is 60 or more and less than 80; and the constituent fraction of the fraction in the total volume of fractions is 30 percent by volume or more and 89 percent by volume or less; and

(3) the cetane number of a fraction of an interval of 280 ° C. or higher is 50 or more, and a constituent fraction of the fraction in the entire volume of the fraction is 1 percent by volume or more and 60 percent by volume or less.

JIS standard for gas oil No. 2 is a standard that meets the requirements for "type No. 2" defined in LIS K 2204 "Gas oil".

The gas oil composition of the present invention is a gas oil composition with quality parameters that meet the requirements of JIS standards for grade 3 gas oil (hereinafter referred to as "gas oil composition (No. 3)"), except for sulfur content, for use in a geometric diesel engine a compression of 16 or less, equipped with a supercharger and an EGR system containing FT synthetic base oil and having a sulfur content of 5 ppm. by mass or less, the oxygen content of 100 million hours by weight or less, bulk modulus 1250 MPa or more and 1450 MPa or less, Saybol color +22 or more, lubricity 400 μm or less, initial boiling point 140 ° C or higher and final boiling point 360 ° C or lower in the distillation parameters, and the following properties (1) - (3) fractions for each interval:

(1) the cetane number of a fraction of an interval below 200 ° C. is 40 or more and less than 60, and a constituent fraction of the fraction in the entire volume of fractions is 20 percent by volume or more and less than 40 percent by volume;

2) the cetane number of the fraction of the interval 200 ° C or higher and lower than 280 ° C is 60 or more and less than 80; and the constituent fraction of the fraction in the entire volume of the fraction is 30 percent by volume or more and 78 percent by volume or less; and

(3) the cetane number of a fraction of an interval of 280 ° C. or higher is 50 or more, and a constituent fraction of the fraction in the entire volume of fractions is 1 percent by volume or more and 50 percent by volume or less.

JIS standard for gas oil No. 3 is a standard that meets the requirements for “type No. 3” defined in LIS K 2204 “Gas oil”.

The gas oil composition of the present invention is a gas oil composition with quality parameters that meet the requirements of JIS standards for grade 3 gas oil (hereinafter referred to as "gas oil composition (No. 3)"), except for sulfur content, for use in a geometric diesel engine a compression of 16 or less, equipped with a supercharger and an EGR system containing FT synthetic base oil and having a sulfur content of 5 ppm. by mass or less, the oxygen content of 100 million hours by weight or less, bulk modulus 1250 MPa or more and 1450 MPa or less, Saybol color +22 or more, lubricity 400 μm or less, initial boiling point 140 ° C or higher and final boiling point 350 ° C or lower in the distillation parameters, and the following properties (1) - (3) fractions for each interval:

(1) the cetane number of a fraction of an interval below 200 ° C. is 40 or more and less than 60, and a constituent fraction of the fraction in the entire volume of fractions is 40 percent by volume or more and 70 percent by volume or less;

2) the cetane number of the fraction of the interval 200 ° C or higher and lower than 280 ° C is 60 or more and less than 80; and the constituent fraction of the fraction in the total volume of fractions is 20 percent by volume or more and 59 percent by volume or less; and

(3) the cetane number of a fraction of an interval of 280 ° C. or higher is 50 or more, and a constituent fraction of the fraction in the entire volume of fractions is 1 percent by volume or more and 30 percent by volume or less.

The JIS standard for special gas oil No. 3 is a standard that meets the requirements for the "special type No. 3" defined in LIS K 2204 "Gas oil".

The sulfur content in the gas oil composition of the present invention is necessarily 5 million hours by weight or less, preferably 3 million hours by weight or less, more preferably 1 million hours by mass or less, in order to reduce toxic substances emitted from the engine and improve the performance of the exhaust after-treatment system. The sulfur content used in this document refers to the mass content of sulfur-containing components based on the total weight of the gas oil composition, measured in accordance with JIS K 2541 "Crude oil and petroleum products - Determination of sulfur content".

The oxygen content in the gas oil composition of the present invention is necessarily 100 million hours by weight or less, preferably 80 ppm by weight or less, more preferably 60 ppm by mass or less, in order to improve oxidation resistance. The oxygen content can be measured on a conventional elemental analysis instrument. For example, the oxygen content is measured by converting the sample to CO or further to CO ₂ on platinum supported on carbon, and measuring its amount with a thermal conductivity detector.

The bulk modulus of the gas oil composition is necessarily 1250 MPa or more and 1450 MPa or less. In general, when a high pressure is applied to a compressible fluid, such as gas oil, the fluid is compressed depending on changes in ambient temperature, pressure, and density (volume per volume flow rate). This compression modulus is defined as the bulk modulus (unit: MPa). When diesel fuel is injected, the bulk modulus of liquid fuel changes at a constant rate, depending on the temperature and pressure of the environment, as well as the physical properties and composition of the fuel. Therefore, for an injection system with injection parameters, when the injection is carried out under high pressure with a high degree of accuracy, as in the case of electronically controlled fuel injection pumps, it is preferable to use a fuel that has a stable digital value of the volumetric deformation module so as to maintain the injection volume or a predetermined speed for the whole system. Therefore, the bulk modulus of the gas oil composition of the present invention is necessarily 1250 MPa or more and 1450 MPa or less, preferably 1270 MPa or more and 1420 MPa or less, more preferably 1300 MPa or more and 1400 MPa or less.

The bulk strain modulus is not a parameter determined by one physical property of the fuel or composition, but should be determined as a result that completely depends on several physical properties and composition. Therefore, from a technical point of view, it is quite appropriate to consider the bulk strain modulus as one of the properties of the fuel, which should be determined among other physical properties and compositions.

Although there is still no officially approved method for measuring the bulk modulus, a brief outline of it will be given in relation to the drawing. The fuel to be measured is filled with a vessel of a certain volume, made of material and having a structure, for which it is possible to show that changes in the volume of the vessel itself, which are the result of changes in ambient temperature and pressure, are significantly less than changes in the volume of fuel, which are the result of the same changes in the surrounding conditions. Therefore, the vessel must be filled only with measured fuel. A piston of a certain volume, made of material and having a design, is inserted into the vessel, for which it is possible to show that the changes in the volume of the piston itself, which are the result of changes in the ambient temperature and pressure, are significantly less than changes in the volume of fuel as a result of the same change in environmental conditions, so that change the volume of the vessel. The measured fuel is compressed in accordance with its indicator of the compression modulus, and, as a result of this, the pressure in the vessel changes. Then measure the pressure to calculate the bulk modulus.

A more detailed description will be given of a method for measuring the bulk modulus of a gas oil composition.

The drawing shows a diagram illustrating an example of the design of a device for measuring the module of volumetric deformation. The inlet valve 2 is located on the upper surface of the vessel of a certain volume 1 and is connected to its inner part, and the exhaust valve 3 is connected to the inlet valve 2 in a certain position. Next, the temperature sensor 4 and the pressure sensor 5 and the piston 6 are located on the side and in the bottom of the vessel 1, respectively, and connected to its inner part. The vessel 1 and the piston 6 are each made of material and have a structure for which the changes in the volume of the vessel and the piston are much smaller than the changes in the volume of fuel when the ambient temperature and pressure change to a predetermined level.

When using the measuring device shown in the drawing, the measured composition of gas oil 100 is first loaded through the inlet valve 2 into the vessel until the vessel is filled with fuel. Then the volume of the vessel is changed using a piston. After that, the fuel is compressed in accordance with its compression module, and as a result, the pressure inside the vessel 1 changes. The temperature and pressure in this compression process is measured using a temperature sensor 4 and a pressure sensor 5, respectively. Based on the measured values, it is possible to calculate the bulk modulus.

The Saybolt color of the gas oil compositions of the present invention is necessarily +22 or more, preferably +25 or more, more preferably +27 or more, in order to remove substances that inhibit oxidation resistance. Saybolt color mentioned in this document refers to a value measured in accordance with JIS K 2580, Petroleum Products - Color Measurement Method - Saybolt Color Measurement Method.

The gas oil compositions of the present invention necessarily have such a lubricity that the HFRR wear spot diameter (WS1.4) is 400 μm or less. If the lubricity is too low, the composition will cause an increase in the torque of the diesel engine equipped with a distribution type injection pump and wear of each pump part when starting the engine, probably leading not only to deterioration of the exhaust gas parameters, but also to destruction of the engine itself. In addition, in an electronically controlled fuel pump providing high pressure injection, wear of the sliding parts will most likely occur. Therefore, with regard to lubricity, the diameter of the HFRR wear spot (WS1.4) of the gas oil composition is necessarily 400 μm or less, preferably 380 μm or less, more preferably 360 μm or less.

Lubricity, i.e. the HFRR wear spot diameter (WS1.4) used herein refers to the lubricity measured in accordance with JIS-5S-50-98 “Gas Oil - Lubricity Test Method” prescribed in the JPI Standard and Manuals Testing Method for Petroleum Products, published by the Japan Petroleum Institute.

The gas oil composition of the present invention is necessarily limited by the constituent fraction of each fraction and its cetane number. That is, the present invention allows to obtain gas oil compositions, each of which meets the requirements of JIS standards for gas oil of grade No. 1, JIS standards for gas oil of grade No. 2, to JIS standards for gas oil of grade No. 3 and LIS standards for gas oil of special grade No. 3, respectively establishing a specific composition of gas oil fractions and specific constituent fractions of fractions. The role of each fraction and the restrictions imposed on them will be discussed below.

It is assumed that the gas oil composition (No. 1) of the present invention will be used in the summer and will have a low ability to restart at high temperatures if the content of the light fraction (fraction with distillation parameters lower than 200 ° C) is too high. However, the composition will have low evaporation parameters if it does not contain a certain amount of light fraction. In addition, if the cetane number of the light fraction to be vaporized is too high, then the composition will cause unintentional self-ignition before it is sufficiently mixed with air, which will lead to the impossibility of combustion with compression ignition of a uniform charge. However, if the cetane number is too low, self-ignition is most likely to be extremely delayed.

The result of various studies in the field of the above trend revealed the need for the cetane number of the fraction with distillation parameters lower than 200 ° C to be 40 or more and less than 60, and that the constituent fraction of the fraction be 1 percent by volume or more and less than 10 percent by volume based on the entire fractional volume of the composition. In addition, the cetane number of the fraction is preferably 42 or more and 58 or less, more preferably 44 or more and 56 or less. The constituent fraction of the fraction is preferably 2 percent by volume or more and 9.5 percent by volume or less, more preferably 3 percent by volume or more and 9 percent by volume or less of the total volume of fractions.

The gas oil composition (No. 1) of the present invention consists mainly of a middle fraction (fraction with distillation parameters in the range from 200 ° C. or higher to less than 280 ° C.). That is, it is necessary to limit the amount of light fraction in order to suppress the violation of the ability to restart at high temperatures, as discussed above, and also to limit the amount of the middle fraction to a certain extent in order to preserve the evaporation parameters. It is preferable to set the cetane number of the middle fraction slightly higher in order to provide positive self-ignition of the composition since the middle fraction is mainly involved in ignition.

The results of various studies in the field of the above trend revealed the need for the cetane number of the middle fraction with distillation parameters in the range of 200 ° C or higher and lower than 280 ° C to be 60 or more and less than 80, and that the constituent fraction of the middle fraction be 40 percent by volume or more and less than 98 percent by volume, calculated on the entire fractional volume of the composition. In addition, the cetane number of the middle fraction is preferably 62 or more and 78 or less, more preferably 64 or more and 76 or less. The constituent fraction of the fraction is preferably 42 percent by volume or more and 97 percent by volume or less, more preferably 45 percent by volume or more and 95 percent by volume or less of the total fractional volume.

The heavy fraction (fraction with distillation parameters from 280 ° C or higher) of the gas oil composition (No. 1) of the present invention is large in calorific value per unit volume and, therefore, is important for improving the output power and fuel efficiency. However, this fraction is likely to form soot if the combustion conditions (temperature, pressure and relationship with air) are not suitably selected. It is necessary to determine the proportion of the heavy fraction in the mixture, taking into account the balance with the above light and medium fractions. The heavy fraction requires considerable time to mix with air, because it has a low evaporation rate, and therefore it cannot be mixed in large quantities. Therefore, the heavy fraction must be excellent in self-ignition properties.

The results of various studies in the field of the above trend revealed the need for the cetane number of the heavy fraction with distillation parameters from 280 ° C or higher to be 50 or more, and that the constituent fraction of the heavy fraction be 1 percent by volume or more and 59 percent by volume or less calculated on the entire fractional volume of the composition. In addition, the cetane number of the heavy fraction is preferably 52 or more, more preferably 54 or more. The constituent fraction of the fraction is preferably 5 percent by volume or more and 55 percent by volume or less, more preferably 10 percent by volume or more and 50 percent by volume or less, more preferably 15 percent by volume or more and 45 percent by volume or less. from the volume of the whole fraction.

It is assumed that the gas oil composition (No. 2) of the present invention will be used in the winter and will have lower calorific value and thus lower fuel efficiency if the content of the light fraction (fraction with distillation parameters lower than 200 ° C) is too high . However, the composition will have low evaporation parameters if it does not contain a certain amount of light fraction. In addition, if the cetane number of the light fraction to be vaporized is too high, then the composition will cause unintentional self-ignition before it is sufficiently mixed with air, which will lead to the impossibility of combustion with compression ignition of a uniform charge. However, if the cetane number is too low, self-ignition is most likely to be extremely delayed.

The result of various studies in the field of the above trend revealed the need for the cetane number of the fraction with distillation parameters lower than 200 ° C to be 40 or more and less than 60, and that the constituent fraction of the fraction be 10 percent by volume or more and less than 20 percent by volume, calculated on the entire fractional volume of the composition. In addition, the cetane number of the fraction is preferably 42 or more and 58 or less, more preferably 44 or more and 56 or less. The constituent fraction of the fraction is preferably 11 percent by volume or more and 19.5 percent by volume or less, more preferably 12 percent by volume or more and 19 percent by volume or less of the volume of all fractions.

The gas oil composition (No. 2) of the present invention consists mainly of a middle fraction (fraction with distillation parameters in the range of 200 ° C. or higher and less than 280 ° C.). That is, it is necessary to limit the amount of light fraction in order to suppress the deterioration of fuel efficiency, as described above, and also to limit the amount of middle fraction in order to preserve the evaporation parameters. It is preferable to set the cetane number of the middle fraction slightly higher in order to provide positive self-ignition of the composition since the middle fraction is mainly involved in ignition.

The results of various studies in the field of the above trend revealed the need for the cetane number of the middle fraction with distillation parameters in the range of 200 ° C or higher and lower than 280 ° C to be 60 or more and less than 80, and that the constituent fraction of the middle fraction be 30 percent by volume or more and less than 89 percent by volume, calculated on the entire fractional volume of the composition. In addition, the cetane number of the middle fraction is preferably 62 or more and 78 or less, more preferably 64 or more and 76 or less. The constituent fraction of the fraction is preferably 32 percent by volume or more and 85 percent by volume or less, more preferably 35 percent by volume or more and 80 percent by volume or less of the total fractional volume.

The heavy fraction (fraction with distillation parameters from 280 ° C or higher) of the gas oil composition (No. 2) of the present invention is large in calorific value per unit volume and, therefore, is important for improving the output power and fuel efficiency. However, this fraction is likely to form soot if the combustion conditions (temperature, pressure and relationship with air) are not suitably selected. In addition, the gas oil composition (No. 2) of the present invention is intended for use in the winter season and is likely to lose low temperature fluidity if it contains too much heavy fraction. It is necessary to determine the proportion of the heavy fraction in the mixture, taking into account the balance with the above light and medium fractions. The heavy fraction requires considerable time to mix with air, because it has a low evaporation rate, and therefore it cannot be mixed in large quantities. Therefore, the heavy fraction should be excellent in self-ignition parameters.

The result of various studies in the field of the above trend revealed the need for the cetane number of the heavy fraction with distillation parameters from 280 ° C or higher to be 50 or more, and that the constituent fraction of the heavy fraction be 1 percent by volume or more and 60 percent by volume or less calculated on the entire fractional volume of the composition. In addition, the cetane number of the heavy fraction is preferably 52 or more, more preferably 54 or more. The constituent fraction of the fraction is preferably 5 percent by volume or more and 55 percent by volume or less, more preferably 10 percent by volume or more and 50 percent by volume or less, more preferably 15 percent by volume or more and 45 percent by volume or less. from all fractional volume.

It is assumed that the gas oil composition (No. 3) of the present invention will be used in the winter and will have lower calorific value and thus lower fuel efficiency if the content of the light fraction (fraction with distillation parameters lower than 200 ° C) is too high. However, the composition will have low evaporation parameters if it does not contain a certain amount of light fraction. In addition, if the cetane number of the light fraction to be vaporized is too high, the composition will cause unintentional self-ignition before it is sufficiently mixed with air, which will result in the inability to burn when a uniform charge is ignited by compression. However, if the cetane number is too low, self-ignition will most likely be extremely delayed.

The result of various studies in the field of the above trend revealed the need for the cetane number of the heavy fraction with distillation parameters lower than 200 ° C to be 40 or more and less than 60 and that the constituent fraction of the fraction should be 20 percent by volume or more and less than 40 percent by volume, calculated on the entire fractional volume of the composition. In addition, the cetane number of the fraction is preferably 42 or more and 58 or less, more preferably 44 or more and 56 or less. The constituent fraction of the fraction preferably corresponds to 21 percent by volume or more and 39.5 percent by volume or less, more preferably 22 percent by volume or more and 39 percent by volume or less of the total fractional volume.

It is assumed that the gas oil composition (No. 3) of the present invention will be used in the winter and will have lower calorific value and thus lower fuel efficiency if the content of the light fraction (fraction with distillation characteristics lower than 200 ° C) is too high. However, the composition will have low evaporation parameters if it does not contain a certain amount of light fraction. In addition, if the cetane number of the light fraction to be vaporized is too high, the composition will cause unintentional self-ignition before it is sufficiently mixed with air, which will lead to the impossibility of combustion by compression ignition with a uniform charge. However, if the cetane number is too low, self-ignition is most likely to be extremely delayed.

The result of various studies in the field of the above trend revealed the need for the cetane number of the heavy fraction with distillation parameters lower than 200 ° C to be 40 or more and less than 60 and that the constituent fraction of the fraction be 20 percent by volume or more and less than 40 percent volume per total fractional volume of the composition. In addition, the cetane number of the fraction is preferably 42 or more and 58 or less, more preferably 44 or more and 56 or less. The constituent fraction of the fraction is preferably 21 percent by volume or more and 39.5 percent by volume or less, more preferably 22 percent by volume or more and 39 percent by volume or less of the total fractional volume.

The gas oil composition (No. 3) of the present invention mainly consists of a middle fraction (fraction with distillation parameters in the range of 200 ° C. or higher and less than 280 ° C.). That is, it is necessary to limit the amount of light fraction in order to suppress the deterioration of fuel efficiency, as described above, and also to limit the amount of middle fraction in order to preserve the evaporation parameters. It is preferable to set the cetane number of the middle fraction slightly higher in order to provide positive self-ignition of the composition, since mainly the middle fraction is involved in ignition.

The result of various studies in the field of the above trend revealed the need for the cetane number of the middle fraction with distillation parameters in the range of 200 ° C or higher and lower than 280 ° C to be 60 or more and less than 80, and that the constituent fraction of the middle fraction be 30 percent by volume or more and less than 78 percent by volume, calculated on the entire fractional volume of the composition. In addition, the cetane number of the middle fraction is preferably 62 or more and 78 or less, more preferably 64 or more and 76 or less. The constituent fraction of the fraction is preferably 32 percent by volume or more and 75 percent by volume or less, more preferably 35 percent by volume or more and 70 percent by volume or less of the total fractional volume.

The heavy fraction (fraction with distillation parameters from 280 ° C or higher) of the gas oil composition (No. 3) of the present invention is large in calorific value per unit volume and, therefore, is important for improving the output power and fuel efficiency. However, this fraction is likely to form soot if the combustion conditions (temperature, pressure and relationship with air) are not suitably selected. In addition, the gas oil composition (No. 3) of the present invention is intended for use in the winter season and is likely to lose low temperature fluidity if it contains too much heavy fraction. It is necessary to determine the proportion of the heavy fraction in the mixture, taking into account the balance with the above light and medium fractions. The heavy fraction requires considerable time to mix with air, because it has a low evaporation rate, and therefore it cannot be mixed in large quantities. Therefore, the heavy fraction must be excellent in self-ignition parameters.

The results of various studies in the field of the above trend revealed the need for the cetane number of the heavy fraction with distillation parameters from 280 ° C or higher to be 50 or more, and that the constituent fraction of the heavy fraction be 1 percent by volume or more and 50 percent by volume or less calculated on the entire fractional volume of the composition. In addition, the cetane number of the heavy fraction is preferably 52 or more, more preferably 54 or more. The constituent fraction of the fraction is preferably 2 percent by volume or more and 47 percent by volume or less, more preferably 3 percent by volume or more and 45 percent by volume or less, more preferably 5 percent by volume or more and 40 percent by volume or less from all fractional volume.

It is assumed that the gas oil composition (special No. 3) of the present invention will be used in the winter and will have a lower calorific value and thus lower fuel efficiency if the content of the light fraction (fraction with distillation parameters lower than 200 ° C) is too high. However, the composition will have low evaporation parameters if it does not contain a certain amount of light fraction. In addition, if the cetane number of the light fraction to be vaporized is too high, the composition will cause unintentional self-ignition before it is sufficiently mixed with air, which will result in the inability to burn when a uniform charge is ignited by compression. However, if the cetane number is too low, self-ignition will most likely be extremely delayed.

The result of various studies in the field of the above trend revealed the need for the cetane number of a fraction with distillation parameters lower than 200 ° C to be 40 or more and less than 60 and that the constituent fraction of the fraction be 40 percent by volume or more and less than 70 percent by volume calculated on the entire fractional volume of the composition. In addition, the cetane number of the fraction is preferably 42 or more and 58 or less, more preferably 44 or more and 56 or less. The constituent fraction of the fraction is preferably 41 percent by volume or more and 69.5 percent by volume or less, more preferably 42 percent by volume or more and 69 percent by volume or less of the total fractional volume.

The gas oil composition (Special No. 3) of the present invention consists mainly of a middle fraction (fractions with distillation parameters in the range of 200 ° C. or higher to less than 280 ° C.). That is, it is necessary to limit the amount of light fraction in order to suppress the deterioration of fuel efficiency, as described above, and also to limit the amount of middle fraction in order to preserve the evaporation parameters. It is preferable to set the cetane number of the middle fraction slightly higher in order to provide positive self-ignition of the composition, since mainly the middle fraction is involved in ignition.

The result of various studies in the field of the above trend revealed the need for the cetane number of the middle fraction with distillation parameters in the range of 200 ° C or higher and lower than 280 ° C to be 60 or more and less than 80, and that the constituent fraction of the middle fraction be equal to 20 percent by volume or more and 59 percent by volume or less, based on the entire fractional volume of the composition. In addition, the cetane number of the middle fraction is preferably 62 or more and 78 or less, more preferably 64 or more and 76 or less. The constituent fraction of the fraction is preferably 22 percent by volume or more and 57 percent by volume or less, more preferably 25 percent by volume or more and 55 percent by volume or less of the total fractional volume.

The heavy fraction (fraction with distillation parameters from 280 ° C or higher) of the gas oil composition (Special No. 3) of the present invention is large in calorific value per unit volume and, therefore, is important for improving the output power and fuel efficiency. However, this fraction is likely to form soot if the combustion conditions (temperature, pressure and relationship with air) are not suitably selected. In addition, the gas oil composition (Special No. 3) of the present invention is intended for use in the winter season and is likely to lose low temperature fluidity if it contains too much heavy fraction. It is necessary to determine the proportion of the heavy fraction in the mixture, taking into account the balance with the above light and medium fractions. The heavy fraction requires considerable time to mix with air, because it has a low evaporation rate, and therefore it cannot be mixed in large quantities. Therefore, the heavy fraction must be excellent in self-ignition parameters.

The result of various studies in the field of the above trend revealed the need for the cetane number of the heavy fraction with distillation parameters from 280 ° C or higher to be 50 or more, and that the constituent fraction of the heavy fraction be 1 percent by volume or more and 30 percent by volume or less per total fractional volume of the composition. In addition, the cetane number of the heavy fraction is preferably 52 or more, more preferably 54 or more. The constituent fraction of the fraction is preferably equal to 1.5 percent by volume or more and 28 percent by volume or less, more preferably 2 percent by volume or more and 26 percent by volume or less of the total fractional volume.

The constituent fraction of each fraction and its cetane number can be measured using the following two types of methods:

(1) the gas oil composition is divided into fractions according to the initial boiling points of 200 ° C, from 200 ° C to 280 ° C and from 280 ° C to the end point, using a distillation unit with such relatively high accuracy that the accuracy of distillation is ± 1 ° C in relation to a given temperature, and after that the fraction of residual oil is about 1 percent by volume, and the constituent fraction of each fraction and its cetane number are measured; and

(2) the base oils to be mixed are first distilled into fractions using the above setup and the constituent fraction of each fraction and its cetane number are measured.

Distillation parameters are measured in accordance with JIS K 2254 “Petroleum Products - Determination of Distillation Parameters” and the cetane number is measured in accordance with “7. Method for determination of cetane number ”, defined by JIS K 2280 standard“ Petroleum products - Fuels - Determination of octane number, cetane number and calculation of cetane index ”.

As for the distillation parameters, the gas oil composition (No. 1) of the present invention necessarily has the above parameters for each fraction, the initial boiling point is 140 ° C or higher, the final point is 380 ° C or lower, and the temperature of 90% distillation is 360 ° C or lower , that is, one of the JIS standards for gas oil No. 1.

If the temperature of 90% of the distillation exceeds 360 ° C, then the release of PM or small particles is likely to increase. Therefore, the temperature of 90% of the distillation is preferably 355 ° C. or lower, more preferably 350 ° C. or lower, more preferably 345 ° C. or lower. There are no specific restrictions on the lower temperature limit of 90% distillation. However, if the temperature of 90% distillation is too low, this will cause a deterioration in fuel efficiency or a decrease in engine output. Therefore, the lower limit of the temperature of 90% distillation is preferably 240 ° C or higher, more preferably 250 ° C or higher, more preferably 260 ° C or higher, more preferably 270 ° C or higher.

The initial boiling point is necessarily 140 ° C or higher. If the initial boiling point is lower than 140 ° C, then the output power of the engine and the ease of starting the engine at high temperature will sharply decrease and worsen. Therefore, the initial boiling point is preferably 145 ° C or higher, more preferably 150 ° C or higher. The endpoint is necessarily 380 ° C or lower. If the endpoint exceeds 380 ° C, then the release of PM or small particles is likely to increase. Therefore, the end point is preferably 375 ° C. or lower, more preferably 370 ° C. or lower.

There are no specific restrictions on the temperature of 10% distillation. However, the lower limit is preferably 160 ° C or higher, more preferably 170 ° C or higher, more preferably 180 ° C or higher in order to suppress a reduction in engine output and impair the ease of starting the engine at high temperature. The upper limit is preferably 250 ° C. or lower, more preferably 245 ° C. or lower, more preferably 230 ° C. or lower in order to suppress deterioration of exhaust gas properties.

As for the distillation parameters, the gas oil composition (No. 2) of the present invention necessarily has the above parameters for each fraction, the initial boiling point is 140 ° C or higher, the final point is 360 ° C or lower, and the temperature of 90% distillation is 350 ° C or lower , that is, one of the JIS standards for gas oil No. 2.

If the temperature of 90% of the distillation exceeds 350 ° C, then the release of PM or small particles is likely to increase. Therefore, the temperature of 90% distillation is preferably 345 ° C or lower, more preferably 340 ° C or lower, more preferably 335 ° C or lower. There are no specific restrictions on the lower temperature limit of 90% distillation. However, if the temperature of 90% distillation is too low, this will cause a deterioration in fuel efficiency or a decrease in engine output. Therefore, the lower limit of the temperature of 90% distillation is preferably 240 ° C or higher, more preferably 250 ° C or higher, more preferably 260 ° C or higher.

The initial boiling point is necessarily 140 ° C or higher. If the initial boiling point is lower than 140 ° C, then the output engine power and ease of starting at high temperature will decrease and deteriorate. Therefore, the initial boiling point is preferably 145 ° C or higher, more preferably 150 ° C or higher. The endpoint is necessarily 360 ° C or lower. If the endpoint exceeds 360 ° C, then the release of PM or small particles is likely to increase. Therefore, the end point is preferably 368 ° C. or lower, more preferably 366 ° C. or lower.

There are no specific restrictions on the temperature of 10% distillation. However, the lower limit is preferably 160 ° C or higher, more preferably 170 ° C or higher, more preferably 180 ° C or higher in order to suppress a decrease in engine output and a decrease in fuel efficiency. The upper limit is preferably 250 ° C. or lower, more preferably 245 ° C. or lower, more preferably 230 ° C. or lower in order to suppress deterioration of exhaust gas properties.

As for the distillation parameters, the gas oil composition (No. 3) of the present invention necessarily has the above parameters for each fraction, the initial boiling point is 140 ° C or higher, the final point is 360 ° C or lower and the temperature of 90% distillation is 350 ° C or lower, that is, it is one of the compositions complying with JIS No. 3 gas oil standards.

If the temperature of 90% of the distillation exceeds 350 ° C, then the release of PM or small particles is likely to increase. Therefore, the temperature of 90% distillation is preferably 345 ° C or lower, more preferably 340 ° C or lower, more preferably 335 ° C or lower. There are no specific restrictions on the lower temperature limit of 90% distillation. However, if the temperature of 90% distillation is too low, this will cause a deterioration in fuel efficiency or a decrease in engine output. Therefore, the lower limit of the temperature of 90% distillation is preferably 240 ° C or higher, more preferably 250 ° C or higher, more preferably 260 ° C or higher.

The initial boiling point is necessarily 140 ° C or higher. If the initial boiling point is lower than 140 ° C, then the output power of the engine and the ease of starting the engine at high temperature will sharply decrease and worsen. Therefore, the initial boiling point is preferably 145 ° C or higher, more preferably 150 ° C or higher. The endpoint is necessarily 360 ° C or lower. If the endpoint exceeds 360 ° C, then the release of PM or small particles is likely to increase. Therefore, the end point is preferably 358 ° C. or lower, more preferably 356 ° C. or lower.

There are no specific restrictions on the temperature of 10% distillation. However, the lower limit is preferably 160 ° C or higher, more preferably 170 ° C or higher, more preferably 180 ° C or higher in order to suppress a decrease in engine output and a decrease in fuel efficiency. The upper limit is preferably 250 ° C. or lower, more preferably 245 ° C. or lower, more preferably 230 ° C. or lower in order to suppress deterioration of exhaust gas properties.

As for the distillation parameters, the gas oil composition (special No. 3) of the present invention necessarily has the above parameters for each fraction, an initial boiling point of 140 ° C or higher, an end point of 350 ° C or lower and a temperature of 90% distillation of 330 ° C or lower, that is, it is one of the compositions complying with JIS special oil standard No. 3.

If the temperature of 90% of the distillation exceeds 330 ° C, then the release of PM or small particles is likely to increase. Therefore, the temperature of 90% distillation is preferably 325 ° C or lower, more preferably 320 ° C or lower, more preferably 315 ° C or lower. There are no specific restrictions on the lower temperature limit of 90% distillation. However, if the temperature of 90% distillation is too low, this will cause a deterioration in fuel efficiency or a decrease in engine output. Therefore, the lower limit of the temperature of 90% distillation is preferably 240 ° C or higher, more preferably 250 ° C or higher, more preferably 260 ° C or higher.

The initial boiling point is necessarily 140 ° C or higher. If the initial boiling point is lower than 140 ° C, then the output power of the engine and the ease of starting the engine at high temperature will sharply decrease and worsen. Therefore, the initial boiling point is preferably 145 ° C or higher, more preferably 150 ° C or higher. The endpoint is necessarily 350 ° C or lower. If the endpoint exceeds 350 ° C, then the release of PM or small particles is likely to increase. Therefore, the end point is preferably 348 ° C. or lower, more preferably 346 ° C. or lower.

There are no specific restrictions on the temperature of 10% distillation. However, the lower limit is preferably 160 ° C or higher, more preferably 170 ° C or higher, more preferably 180 ° C or higher in order to suppress a decrease in engine output and a decrease in fuel efficiency. The upper limit is preferably 250 ° C. or lower, more preferably 245 ° C. or lower, more preferably 230 ° C. or lower in order to suppress deterioration of exhaust gas properties.

The initial boiling point, the temperature of 10% distillation, the temperature of 90% of distillation, and the end point used in this document mean the values measured in accordance with JIS K 2254 "Petroleum products - Determination of distillation parameters."

The cetane index of the gas oil composition (No. 1) of the present invention necessarily meets the requirements of the JIS standard for gas oil No. 1, which is 50 or more. If the cetane index is less than 50, then the concentrations of PM, aldehydes and NO _x are likely to be elevated. For the same reasons, the cetane index is preferably 52 or more, more preferably 55 or more. There are no specific restrictions on the upper limit of the cetane index. However, if the cetane index exceeds 75, it is more likely that soot emissions will increase during vehicle acceleration. Therefore, the cetane index is preferably 75 or less, more preferably 74 or less, more preferably 73 or less.

The cetane indices of the gas oil compositions (No. 2), (No. 3) and (special No. 3) of the present invention necessarily meet the requirements of JIS standards for gas oils No. 2, No. 3 and special No. 3, respectively, and each of them is 45 or more. If the cetane index is less than 45, then it is likely that the concentrations of PM, aldehydes and NO _x will increase. For the same reasons, the cetane index is preferably 47 or more, more preferably 50 or more. There are no specific restrictions on the upper limit of the cetane index. However, if the cetane index is greater than 75, it is more likely that soot emissions will increase during vehicle acceleration. Therefore, the cetane index is preferably 75 or less, more preferably 74 or less, more preferably 73 or less.

As used herein, the term “cetane index” means a value calculated in accordance with “8.4 a method for calculating a cetane index using an equation with variables” prescribed by JIS Standard 2280 “Petroleum Products - Fuels - Determination of Octane Number, Cetane Number and Calculation of Cetane Index” . The cetane index defined by JIS standards is usually applicable to gas oil that does not contain a cetane number improver. However, in the present invention, “8.4 a method for calculating a cetane index using an equation with variables” is applied to a gas oil containing a cetane number improver, and the obtained value is also defined as a cetane index.

There are no particular restrictions on the cetane number of gas oil compositions of the present invention if the requirements for the parameters of each fraction defined above are met. However, the cetane number is preferably 30 or more, more preferably 35 or more, more preferably 40 or more, in order to inhibit detonation during combustion of diesel fuel and to reduce emissions of NO _x , PM and aldehydes in the exhaust gas. In order to reduce black smoke in the exhaust gas, the cetane number is preferably 70 or less, more preferably 68 or less, more preferably 66 or less.

The cetane number used in this document means the cetane number, measured in accordance with "7. The method for determination of cetane number ”, prescribed by the standard JIS K 2280“ Petroleum products - Fuels - Determination of octane number, cetane number and calculation of cetane index ”.

The flash points of the gas oil compositions (No. 1) and (No. 2) of the present invention necessarily meet the requirements of JIS standards for gas oils No. 1 and No. 2, respectively, which are both equal to 50 ° C or higher. A flash point below 50 ° C is not preferred for safety reasons. Therefore, the flash point is preferably 52 ° C or higher, more preferably 54 ° C or higher.

The flash points of the gas oil compositions (No. 3) and (special No. 3) of the present invention necessarily meet the requirements of JIS standards for gas oil No. 3 and special No. 3, respectively, which are both equal to 45 ° C. or higher. A flash point below 45 ° C is not preferred for safety reasons. Therefore, the flash point is preferably 47 ° C or higher, more preferably 50 ° C or higher.

The flash point used in this document means the value measured in accordance with JIS K 2265 "Crude oil and petroleum products - Determination of flash point".

The clogging temperature of the gas oil composition (No. 1) of the present invention necessarily meets the requirement of JIS standard for gas oil No. 1, which is -1 ° C. or lower. The plugging temperature is preferably −5 ° C. or lower in order to prevent clogging of the pre-filter of the diesel car and to maintain the ignition conditions in the electronically controlled fuel pump.

The clogging temperature of the gas oil composition (No. 2) of the present invention necessarily meets the JIS standard for gas oil No. 2, which is −5 ° C. or lower. The plugging temperature is preferably −7 ° C. or lower, more preferably −10 ° C. or lower in order to prevent clogging of the pre-filter of the diesel engine vehicle and to maintain the ignition conditions in the electronically controlled fuel pump.

The clogging temperature of the gas oil composition (No. 3) of the present invention necessarily meets the requirement of JIS standard for gas oil No. 3, which is −12 ° C. or lower. The plugging temperature is preferably −13 ° C. or lower, more preferably −15 ° C. or lower in order to prevent clogging of the pre-filter of the diesel engine vehicle and to maintain the ignition conditions in the electronically controlled fuel pump.

The clogging temperature of the gas oil composition (No. 3) of the present invention necessarily meets the requirement of the JIS standard for special gas oil No. 3, which is −19 ° C. or lower. The plugging temperature is preferably −22 ° C. or lower, more preferably −25 ° C. or lower in order to prevent clogging of the pre-filter of the diesel engine vehicle and to maintain the ignition conditions in the electronically controlled fuel pump.

Clogging temperature used in this document means the clogging temperature, measured in accordance with JIS K 2288 "Gas oil - Determination of the clogging temperature of the cold filter."

The pour point of the gas oil composition (No. 1) of the present invention necessarily meets the JIS standard for gas oil No. 1, which corresponds to -2.5 ° C. or lower. In addition, in order to maintain the starting characteristics at low temperatures or to control the vehicle overall and maintain the ignition conditions in the electronically controlled fuel supply pump, the pour point is preferably −5 ° C. or lower, preferably −7.5 ° C. or lower.

The pour point of the gas oil composition (No. 2) of the present invention necessarily meets the JIS standard for gas oil No. 2, which corresponds to −7.5 ° C. or lower. In addition, in order to maintain the starting characteristics at low temperatures or to control the vehicle overall and maintain the ignition conditions in the electronically controlled fuel supply pump, the pour point is preferably −10 ° C. or lower, preferably −12.5 ° C. or lower.

The pour point of the gas oil composition (No. 3) of the present invention necessarily meets the JIS standard for gas oil No. 1, which corresponds to −20 ° C. or lower. In addition, in order to maintain starting characteristics at low temperatures or to control the vehicle in general and to maintain ignition conditions in an electronically controlled fuel supply pump, the pour point is preferably −22.5 ° C. or lower, preferably −25 ° C. or lower.

The pour point of the gas oil composition (Special No. 3) of the present invention necessarily meets the requirement of JIS Special No. 3 gas oil, which corresponds to −30 ° C. or lower. In addition, in order to maintain the starting characteristics at low temperatures or to maintain the overall controllability of the vehicle and maintain the ignition conditions in the electronically controlled fuel injection pump, the pour point is preferably −32.5 ° C. or lower, preferably −35 ° C. or lower.

The pour point used in this document means the pour point measured in accordance with JIS K 2269 "Test method for the pour point and cloud point of crude oil and petroleum products."

The kinematic viscosity at 30 ° C of the gas oil composition (No. 1) of the present invention necessarily meets the JIS standard for gas oil No. 1, which corresponds to 2.7 mm ² / s or higher, preferably 2.75 mm ² / s or higher, more preferably 2 8 mm ² / s or higher. If the kinematic viscosity is less than 2.7 mm ² / s, it will be difficult to control the duration and timing of the fuel pulse from the pump, and the lubricity in each part of the fuel injection pump installed in the motor will be reduced. There are no specific restrictions on the upper kinematic viscosity at 30 ° C. However, the kinematic viscosity is preferably 5 mm ² / s or less, more preferably 4.8 mm ² / s or less, more preferably 4.5 mm ² / s or less in order to suppress increase in NO _x and PM concentrations in the exhaust gas caused by destabilization of the fuel injection system due to increased resistance in it.

The kinematic viscosity at 30 ° C of the gas oil composition (No. 2) of the present invention necessarily meets the requirement of JIS standard for gas oil No. 2, which corresponds to 2.5 mm ² / s or higher, preferably 2.55 mm ² / s or higher, more preferably 2 6 mm ² / s or higher. If the kinematic viscosity is less than 2.5 mm ² / s, it will be difficult to control the duration and timing of the fuel pulse from the pump, and the lubricity in each part of the fuel injection pump installed in the motor will be reduced. There are no specific restrictions on the upper kinematic viscosity at 30 ° C. However, the kinematic viscosity is preferably 5 mm ² / s or less, more preferably 4.8 mm ² / s or less, more preferably 4.5 mm ² / s or less in order to suppress increase in NO _x and PM concentrations in the exhaust gas caused by destabilization of the fuel injection system due to increased resistance in it.

The kinematic viscosity at 30 ° C of the gas oil composition (No. 3) of the present invention necessarily meets the requirement of JIS standard for gas oil No. 3, which corresponds to 2.0 mm ² / s or higher, preferably 2.05 mm ² / s or higher, more preferably 2 , 1 mm ² / s or higher. If the kinematic viscosity is less than 2.0 mm ² / s, it will be difficult to control the duration and timing of the fuel pulse at the pump, and the lubricity in each part of the fuel injection pump installed in the motor will be reduced. There are no specific restrictions on the upper kinematic viscosity at 30 ° C. However, the kinematic viscosity is preferably 5 mm ² / s or less, more preferably 4.8 mm ² / s or less, more preferably 4.5 mm ² / s or less in order to suppress increase in NO _x and PM concentrations in the exhaust gas caused by destabilization of the fuel injection system due to increased resistance in it.

The kinematic viscosity at 30 ° C of the gas oil composition (Special No. 3) of the present invention necessarily meets the requirement of JIS standard for Special No. 3 gas oil, which corresponds to 1.7 mm ² / s or higher, preferably 1.75 mm ² / s or higher, more preferably 1.8 mm ² / s or higher. If the kinematic viscosity is less than 1.7 mm ² / s, it will be difficult to control the duration and timing of the fuel pulse at the fuel injection pump, and the lubricity in each part of the fuel injection pump installed in the motor will be reduced. There are no specific restrictions on the upper kinematic viscosity at 30 ° C. However, the kinematic viscosity is preferably 5 mm ² / s or less, more preferably 4.8 mm ² / s or less, more preferably 4.5 mm ² / s or less in order to suppress increase in NO _x and PM concentrations in the exhaust gas caused by destabilization of the fuel injection system due to increased resistance in it.

The kinematic viscosity used in this document means the value measured in accordance with JIS K 2283 "Crude oil and petroleum products - Determination of kinematic viscosity and calculation of the viscosity index by kinematic viscosity."

The carbon residue in the residue of 10% distillation of the gas oil compositions of the present invention is necessarily 0.1 percent by weight or less, which meets the requirements of JIS standards for gas oils No. 1, No. 2, No. 3 and special No. 3. In addition, the carbon residue is preferably 0 , 08 percent by mass or less, more preferably 0.05 percent by mass or less in order to reduce the amount of fine particles and PM, to maintain the operational properties of the exhaust after-treatment system installed in the engine, and to warn Nia sediment clogging the filter.

The carbon residue in the residue of 10% distillation used in this document means that the value is measured in accordance with JIS K 2270 "Crude oil and petroleum products - Determination of carbon residue."

The peroxide number of the gas oil compositions of the present invention after the accelerated oxidation test (oxidation resistance test) is preferably 50 ppm. by weight or less, more preferably 40 ppm by weight or less, 30 million hours by weight or less, in terms of storage stability and compatibility with parts. The peroxide value after the accelerated oxidation test used in this document means the residue measured in accordance with JPI-5S-46-96 prescribed in the JPI standard after the accelerated oxidation test at 95 ° C. under oxygen sparging for 16 hours in accordance with ASTM D2274-94. If necessary, the gas oil compositions of the present invention can be mixed with additives such as antioxidants or metal deactivators to reduce the peroxide value.

The aromatic content in the gas oil compositions of the present invention is preferably 15 percent by volume or less, more preferably 14 percent by volume or less, more preferably 13 percent by volume or less, more preferably 12 percent by volume or less. When the content of aromatic compounds in the composition is 15 percent by volume or less, these compounds can suppress the formation of PM, exhibit environmentally friendly properties even when burned in a diesel engine and when ignited by compression of a uniform charge, and it is easy and unconditional to achieve the parameters determined the present invention. The aromatic content used in this document means the content in volume percent (vol.%) Of the aromatic component, measured in accordance with JIS-5S-49-97 "Petroleum products - Determination of hydrocarbon types - High performance liquid chromatography", established by JPI Standard and Manuals Testing Method for Petroleum Products, published by the Japan Petroleum Institute.

There are no particular restrictions on the content of aromatic compounds in the gas oil compositions of the present invention. However, the content of naphthenes is preferably 50 percent by mass or less, more preferably 45 percent by mass or less, more preferably 40 percent by mass or less. When gas oil compositions have a naphthenic content of 50 percent by mass or less, they can inhibit PM formation, be environmentally friendly even when burned in a diesel engine and burn when a uniform charge is ignited by compression, and easily and unconditionally achieve the parameters defined by the present invention. The naphthenic content used in this document means the content in volume percent (vol.%) Of naphthenes measured in accordance with ASTM D2425 Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry.

There are no particular restrictions on the content of normal paraffins (components based on normal paraffins) of the gas oil compositions of the present invention. The content of normal paraffins is preferably 20 percent by mass or more, more preferably 22 percent by mass or more, more preferably 25 percent by mass or more in order to give easier control of ignition during combustion during compression ignition of a uniform charge. The normal paraffin content is a value measured using the GC-FID method, where the column is a methylsilicon-filled capillary column (ULTRA ALLOY-1), the carrier gas is helium, and the detector is a flame ionization detector (FID), under conditions at which the column length is 30 m, the carrier gas flows at a rate of 1.0 ml / min, the separation ratio is 1:79, the injection temperature of the sample is 360 ° C, the column is heated from 145 ° C to 355 ° C (8 ° C / min) and the temperature of the detector is 360 ° C.

There are no particular restrictions on the density at 15 ° C. of the gas oil compositions of the present invention. The density at 15 ° C. is preferably 760 kg / m ³ or higher, more preferably 765 kg / cm ³ or higher and more preferably 770 kg / cm ³ or higher in order to maintain the calorific value of the fuel. The density is preferably 840 kg / cm ³ or lower, more preferably 835 kg / cm ³ or lower in order to reduce the concentrations of NO _x and PM in the exhaust gases. Density used in this document means the density measured in accordance with JIS K 2249 "Crude oil and petroleum products - Determination of density and measurement tables of oil based on standardized temperature (15 ° C)."

There is no particular limitation on the cloud point of the gas oil composition (No. 1) of the present invention. However, the cloud point is preferably −1 ° C. or lower, more preferably −3 ° C. or lower, more preferably −5 ° C. or lower in order to maintain ease of starting the engine at low temperatures and to control the vehicle and to maintain the injection parameters of the injection pump electronically controlled fuel.

There is no particular limitation on the cloud point of the gas oil composition (No. 2) of the present invention. However, the cloud point is preferably −3 ° C. or lower, more preferably −4 ° C. or lower, more preferably −5 ° C. or lower in order to maintain ease of starting the engine at low temperatures and to control the vehicle and to maintain the injection parameters of the injection pump electronically controlled fuel.

There is no particular limitation on the cloud point of the gas oil composition (No. 3) of the present invention. However, the cloud point is preferably −10 ° C. or lower, more preferably −11 ° C. or lower, more preferably −12 ° C. or lower in order to maintain ease of starting the engine at low temperatures and to control the vehicle, and to maintain the injection parameters of the injection pump electronically controlled fuel.

There are no particular restrictions on the cloud point of the gas oil composition (Special No. 3) of the present invention. However, the cloud point is preferably −15 ° C. or lower, more preferably −16 ° C. or lower, more preferably −17 ° C. or lower in order to maintain ease of starting the engine at low temperatures and to control the vehicle and to maintain the injection parameters of the injection pump electronically controlled engine.

The cloud point used in this document means the cloud point measured in accordance with JIS K 2269, Test Method for Flow Point and Cloud Point of Crude Oil and Petroleum Products.

There are no particular restrictions on the water content in the gas oil compositions of the present invention. However, the water content is preferably 100 ppm. by volume, more preferably 50 ppm by volume, more preferably 20 million hours by volume in order to prevent freezing of compositions and corrosion of the internal part of the engine.

The water content used in this document means the value measured in accordance with JIS K 2275 "Crude oil and petroleum products - Determination of water content - Potentiometric Karl Fischer titration method."

The total insoluble content of the gas oil compositions of the present invention after the oxidation resistance test is preferably 2.0 mg / 100 ml or less, more preferably 1.5 mg / 100 ml or less, more preferably 1.0 mg / 100 ml or less and more preferably 0.5 mg / 100 ml or less in terms of storage stability.

The oxidation resistance test used in this document is carried out at a temperature of 95 ° C, under conditions of oxygen sparging for 16 hours, in accordance with ASTM D2274-94. The total insoluble content after the oxidation resistance test used in this document means the value measured in accordance with the above oxidation resistance test.

If necessary, the gas oil compositions of the present invention can be mixed with additives such as cold flow improvers, lubricity improvers, cetane number improvers and detergents, in appropriate amounts.

The gas oil compositions of the present invention can be mixed with a cold flow improver to prevent clogging of the filter of a diesel engine vehicle. The amount of cold flow improver is 200 ml / L or more and 1000 mg / L or less, more preferably 300 mg / L or more and 800 mg / L or less in units of concentration of the active ingredient.

There are no particular restrictions on the cold flow improver, which therefore can be one or more types of cold flow improvers, including ethylenically unsaturated polyester copolymers such as ethylene vinyl acetate copolymers; alkenyl succinic acid amides; linear compounds such as dibehenic acid esters of polyethylene glycols; polar nitrogen-containing compounds consisting of the reaction products of acids such as phthalic acid, ethylenediaminetetraacetic acid and nitriloacetic acid or their anhydrides, and hydrocarbyl substituted amines; and comb-like polymers consisting of copolymers of alkyl fumarates - or alkyl-taconates — an unsaturated ester. Alternatively, the cold flow improvers can be any one or two types selected from copolymers of ethylene and methyl methacrylate, copolymers of ethylene and α-olefin, copolymers of chlorinated methylene vinyl acetate, copolymers based on alkyl esters of unsaturated carboxylic acids, esters synthesized from nitrogen-containing compounds containing hydroxyl group, and saturated fatty acids and salts of esters, esters and amides synthesized from polyhydric alcohols and saturated fatty acids, esters synthesized from polyoxyalkylene glycols and saturated fatty acids, esters synthesized from adducts of alkylene oxides and polyhydric alcohols, or their partial esters and saturated fatty acids, condensates, chlorinated paraffin / naphthalene, alkenyl succinic acid amides and amine salts of sulfobenzoic acid. Of these cold flow improvers, additives based on an ethylene vinyl acetate copolymer are preferred because they can be used for many purposes. Since commercially available products belonging to the class of cold flow improvers are often in a form in which the active components contributing to the low temperature flow (active components) are diluted with a suitable solvent, therefore, the above number of cold flow improvers means the amount of active components (concentration of the active component), when these commercially available products are added to the gas oil compositions of the present invention.

There is no particular restriction on the addition of a lubricity improver to the gas oil composition of the present invention if the lubricity of the resulting composition falls within the above preferred ranges. However, a lubricity improver is preferably added in order to prevent wear of the fuel injection pump. The amount of lubricity enhancer is preferably 20 mg / L or more and 200 mg / L or less, more preferably 50 mg / L or more and 180 mg / L or less, in units of the concentration of the active component. When a lubricity improver is mixed in an amount lying within a given range, a lubricity improver can be effective. For example, in a diesel engine equipped with a distribution type injection pump, a lubricity improver can suppress an increase in torque and can reduce wear on each part of the pump when the engine is running.

There is no particular restriction on the type of lubricity improver, which, therefore, can be any one or more types selected from lubricity enhancers based on carboxylic acids, esters, alcohols and phenols. Of these lubricity enhancers, carboxylic acid and ester based lubricity improvers are preferred. Carboxylic acid-based lubricity enhancers can be linoleic acid, oleic acid, salicylic acid, palmitic acid, myristic acid or hexadecanoic acid, or a mixture of two or more of these carboxylic acids. Examples of an ester-based lubricity improver include carboxylic acid esters and glycerol. The carboxylic acid forming the carboxylic acid ester may be of one or more types. Specific examples of carboxylic acids include linoleic acid, oleic acid, salicylic acid, palmitic acid, myristic acid or hexadecanoic acid.

If necessary, the gas oil compositions of the present invention can be mixed with an appropriate amount of cetane number improver to increase the cetane number of the compositions.

The cetane number improver may be any of various compounds known as cetane number improvers for gas oil. Examples of this cetane number improver include nitrate esters and organic peroxides. These cetane number improvers can be used individually or in combination. Nitrate esters are preferred for use in the present invention. Examples of nitrate esters include various nitrates such as 2-chloroethyl nitrate, 2-ethoxyethyl nitrate, isopropyl nitrate, butyl nitrate, primary amyl nitrate, secondary amyl nitrate, isoamyl nitrate, primary hexyl nitrate, secondary hexyl nitrate, n-heptyl nitrate, n-octyl nitrate, 2-ethylhexyl nitrate, cyclohexyl nitrate and ethylene glycol dinitrates. Particularly preferred are alkyl nitrates containing from 6 to 8 carbon atoms.

The cetane number improver content is preferably 500 mg / L or more, more preferably 600 mg / L or more, more preferably 700 mg / L or more, more preferably 800 mg / L or more, most preferably 900 mg / L or more. If the content of the cetane number improver is less than 500 mg / l, then the effect of increasing the cetane number may not be achieved sufficiently, leading to an increase in the tendency that PM, acetaldehyde and NO _x will not decrease sufficiently in the exhaust gas from diesel engine. There are no specific restrictions on the upper limit of cetane number improver content. However, the upper limit is preferably 1400 mg / L or less, more preferably 1250 mg / L or less, more preferably 1100 mg / L or less, and most preferably 100 mg / L or less, based on the total weight of the gas oil composition.

The cetane number enhancer may be any of those synthesized by conventional methods, or a commercially available product. These products in the list of cetane number improvers are available in a state in which the effective component determining the improvement of the cetane number (i.e., the cetane number improver itself) is diluted with a suitable solvent. In the case where the gas oil composition of the present invention is obtained using any of these commercially available products, the content of the effective component is preferably in the above range.

If necessary, detergents can be added to the gas oil compositions of the present invention. There is no specific restriction on detergents. Examples of detergents include ashless dispersants, for example, imide compounds; alkenyl succinimides, such as polybutenyl succinimide synthesized from polybutenyl succinic anhydride and ethylene polyamines; succinic acid esters such as polybutenyl succinic acid ester synthesized from polyhydric alcohols such as pentaerythritol and polybutenyl succinic anhydride; copolymerized polymers such as copolymers of dialkylaminoethyl methacrylates, polyethylene glycol methacrylates or vinyl pyrrolidone and alkyl methacrylates; and reaction products of carboxylic acids and amines. Of these, alkenyl succinimides and the reaction products of carboxylic acids and amines are preferred. These detergents can be used individually or in combination. When alkenyl succinimide is used, alkenyl succinimide having a molecular weight of from 1000 to 3000 can be used alone or a combination of alkenyl succinimide having a molecular weight of from 700 to 2000 and alkenyl succinimide having a molecular weight of from 10,000 to 20,000 can be used. Carboxylic acids constituting the products interactions of carboxylic acids and amines can be one or more types. Specific examples of carboxylic acids include fatty acids containing from 12 to 24 carbon atoms, and aromatic carboxylic acids containing from 7 to 24 carbon atoms. Examples of fatty acids containing from 12 to 24 carbon atoms include, but are not limited to, linoleic acid, oleic acid, palmitic acid, and myristic acid. Examples of aromatic carboxylic acids containing from 7 to 24 carbon atoms include, but are not limited to, benzoic acid and salicylic acid. Amines that are part of the products of the interaction of carboxylic acids and amines can be one or more types. Typical examples of the amines used in the present invention include, but are not limited to, amines of oleic acid. Various amines may also be used.

There is no specific limit on the amount of detergent mixed. However, this amount is preferably 30 mg / L or more, more preferably 60 mg / L or more, and more preferably 80 mg / L or more, based on the total weight of the composition, because the detergent can act to prevent clogging of the injection nozzle fuel. This action cannot be implemented if the amount is less than 30 mg / L. On the other hand, if the detergent is mixed in too much, its effect, balanced by quantity, is not achieved. Therefore, the amount of detergent is preferably 300 mg / L or less, and more preferably 180 mg / L or less, because the detergent can increase the amounts of NO _x , PM and aldehydes in the exhaust gases from the diesel engine. Conventional products known as detergents are available in a state in which the effective detergent determinant is diluted with a suitable solvent. When these products are mixed with gas oil compositions according to the present invention, the content of the effective component preferably lies in the above range of values.

In order to further enhance the properties of the gas oil compositions of the present invention, other known fuel oil additives (hereinafter referred to as “other additives” for convenience) may be used individually or in combination. Examples of other additives include phenolic or amine type antioxidants; metal deactivators, such as salicylidene derivatives; anti-corrosion agents such as aliphatic amines and alkenyl succinic esters; antistatic agents such as anionic, cationic and amphoteric surfactants; coloring agents such as azo dyes; silicone antifoam agents and anti-icing agents such as 2-methoxyethanol, isopropyl alcohol and polyglycol ethers.

The amounts of other additives may be arbitrarily selected. However, the amount of each of the other additives is preferably 0.5 percent by mass or less, more preferably 0.2 percent by mass or less, based on the total weight of the composition.

As described above, according to the present invention, the use of a gas oil composition obtained by the above method to meet fraction requirements can provide high-quality gas oils that can achieve a high level of excellent performance in the summer or winter season, as well as environmental properties that can be applied to an engine with combustion when ignited by compression of a uniform charge, and operational characteristics and properties were used It is difficult to provide when using traditional gas oil compositions.

Industrial application

The gas oil compositions of the present invention can be suitably used as compositions for the summer and winter season, suitable for combustion in diesel engines and combustion under compression ignition of a uniform charge.

Examples

Further, the present invention will be discussed in more detail using the following examples and comparative examples, which should not be construed as limiting the scope of claims of the invention.

The characteristics of the gas oil compositions were measured by the following methods. The constituent fraction of each fraction and its cetane number were measured after mixing the base oils and distillation.

Density used in this document means the density measured in accordance with JIS K 2249, Crude oil and petroleum products - Determination of density and oil measurement tables based on nominal temperature (15 ° C).

The kinematic viscosity used herein means the viscosity measured in accordance with JIS K 2283, Crude Oil and Petroleum Products - Determination of Kinematic Viscosity and Calculation of Viscosity Index by Kinematic Viscosity.

The flash point used in this document means the value measured in accordance with the standard LIS K 2265 "Crude oil and petroleum products - Determination of flash point".

The sulfur content (sulfur-containing components) used in this document means the mass content of sulfur-containing components based on the total weight of the composition, measured in accordance with LIS K 2541 "Crude oil and petroleum products - Determination of sulfur content".

The oxygen content (oxygen-containing components) used in the present invention means the value measured by the thermal conductivity detector after the samples were burned to CO or, alternatively, further to CO ₂ , on platinum carbon.

All distillation parameters used in this document are values measured in accordance with LIS K 22554, Petroleum Products - Determination of Distillation Parameters. E200-Eibp, E280-E200 and Eep-E280 mean the amount (vol.%) Of the fraction distilled between the initial boiling point and 200 ° C, the amount (vol.%) Of the fraction distilled between 200 ° C and 280 ° C and the amount (vol.%) of the fraction distilled between 280 ° C and the end point.

The normal paraffin-based components used herein mean a value (wt.%) Measured using the above-described GC-FID method.

The aromatic content used in this document means the content in volume percent (vol.%) Of aromatic components, measured in accordance with JPI 58-49-97 "Petroleum products - Determination of types of hydrocarbons - High performance liquid chromatography" prescribed in "JPI Standard and Manuals Testing Method for Petroleum Products ”published by the Japan Petroleum Institute.

The content of naphthenic compounds used in this document means the percentage volume (volume%) of the naphthenic content measured in accordance with ASTM D2524, Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry.

The volumetric strain modulus used in this document is calculated based on the change in pressure in a container of a certain volume, when the test fuel is poured into it, a piston of a certain volume is inserted into the container, as described above.

The cloud point used herein refers to the temperature measured in accordance with JIS K 2269, Test Method for Flow Point and Cloud Point of Crude Oil and Petroleum Products.

The clogging point used in this document means the one measured in accordance with JIS K 2288 “Gas Oil - Determining the Clogging Point of a Cold Filter”.

The pour point used in this document means that measured in accordance with JIS K 2269 "Test method for the temperature of the yield stress and cloud point of crude oil and petroleum products."

The cetane index used in this document means the value calculated in accordance with "8.4 Method for calculating the cetane number using the variable equation" prescribed by JIS K 2280 "Petroleum products - Fuels - Determination of octane number, cetane number and calculation of cetane index". The cetane index used herein, as defined by JIS standards, is generally not applicable to gas oils containing a cetane number improver. However, in the present invention, “8.4 Method for Calculating a Cetane Number Using the Variable Equation” is applied to a gas oil containing a cetane number improver, and the resultant value is also defined as a cetane index.

The cetane number used in this document means a quantity measured in accordance with "7. Method for determination of cetane number "prescribed in JIS K 2280" Petroleum products - Fuels - Determination of octane number, cetane number and calculation of cetane index ".

The color (according to Saybolt) used in this document means the color according to Saybolt, measured in accordance with the standard JIS K 2580 "Petroleum products - color determination method - Saybolt color determination method".

The carbon residue content of the 10% distillation residue used in this document means the value measured in accordance with JIS K 2270 "Crude oil and petroleum products - Determination of carbon residue".

The peroxide value after the oxidation resistance test used in this document means the value measured in accordance with JPI-5S-46-96 prescribed in the “JPI Standard and Manuals Testing Method for Petroleum Products” published by the Japan Petroleum Institute, after accelerated oxidation. compositions at a temperature of 95 ° C under conditions of oxygen sparging for 16 hours in accordance with ASTM D2274-94.

The insoluble content after the oxidation resistance test used in this document means the value measured after accelerated oxidation of the compositions at a temperature of 95 ° C under conditions of oxygen sparging for 16 hours in accordance with ASTM D2274-94.

Lubricity, i.e. HFRR wear spot diameter (WS1.4) used herein means the lubricity measured in accordance with JPI-5S-50-98 Gas Oil - Lubricity Test Method prescribed by JPI Standard and Manuals Testing Method for Petroleum Products ”published by the Japan Petroleum Institute.

The water content used in this document means the value measured in accordance with JIS K 2275 "Crude oil and petroleum products - Determination of water content - Karl Fischer potentiometric titration method".

Examples 1-3 and comparative examples 1-3

Base oils with the parameters shown in table 1 were mixed with the obtained gas oil compositions presented in table 2 (examples 1-3 and comparative examples 1-3). FT 1-3 synthetic base oils are hydrocarbon mixtures obtained by converting natural gas to wax or a middle fraction by FT reaction followed by hydrogenation. Since the reaction conditions (degree of isomerization) vary, the resulting base oils differ in the proportion of saturated hydrocarbons. A highly hydrogenated base oil is a hydrocarbon base oil obtained by additionally hydrogenating a gas oil base oil with a further reduction in sulfur and aromatic compounds. Technological oil obtained from animal or vegetable oil is an oil obtained by hydrogenation of palm oil (the entire component) used as raw material to remove foreign matter. Hydrotreating gas oil corresponds to the commercially available gas oil, which is used in summer. Fuel for high compression is the fuel obtained by mixing FT synthetic oils, base oil after hydrotreating and deeply hydrogenated base oil in suitable quantities for a high compression diesel engine.

The additives used in these examples were as follows:

lubricity improver: a mixture of carboxylic acids containing mainly linoleic acid; and

detergent: a mixture of alkenyl succinimides.

Table 2 presents the constituent fractions of the components of the gas oil compositions thus obtained, and density at 15 ° C, kinematic viscosity at 30 ° C, flash point, sulfur content, oxygen content, distillation parameters, cetane index, cetane number, aromatic content, content of naphthenic compounds, bulk deformation moduli, cloud point, clogging temperature, pour point, color, carbon content in the residue of 10% distillation, non-solution content Mykh and peroxide number after an oxidation resistance test, HFRR wear scar diameter and water content of each composition.

The gas oil compositions used in examples 1-3 were obtained by mixing 20 percent by weight or more of FT synthetic base oils, as indicated in table 2. In addition, as can be seen from table 2, gas oil compositions meeting the property requirements defined in this document were easily prepared, regardless of the circumstances, in Examples 1-3, where FT synthetic base oils were mixed in the range of values defined herein. On the other hand, as can be seen from comparative examples 1-3, where the compositions were obtained without using the above specific base oils, and the compositions were prepared using specific base oils, which, however, in terms of the proportion of each fraction or the like. did not satisfy the definition of the present invention, gas oil compositions according to the present invention were not necessarily obtained.

Further, the following various experiments were carried out using the gas oil compositions of Examples 1-3 and Comparative Examples 1-3. All results are presented in table 3. As can be seen from table 3, the gas oil composition of examples 1-3 showed excellent results regarding NO _x , smoke, fuel efficiency and the period of effective ignition delay during combustion during compression ignition of a uniform charge, and NO _x , smoke, fuel efficiency and ease of starting the engine at high temperatures during normal combustion, compared with gas oil compositions of comparative examples 1-3. Therefore, the gas oil compositions of examples 1-3 are obviously high-quality gas oils that can provide at a high level both excellent practical performance in the summer season and environmentally friendly properties that can be applied to combustion upon ignition from compression of a uniform charge, moreover the effect and properties are difficult to provide when using traditional gas oil compositions.

Combustion test during compression ignition of a uniform charge

The experiment was carried out using an experimental engine, where on the basis of the commercially available engine 1 described below, the piston shape of all cylinders was changed to change the compression ratio to 16, and the regulating part of the electronic injection fuel injection pump with a conventional fuel distribution guide was partially changed, to provide the ability to control the duration of fuel injection. The experiment was carried out under stationary conditions (1200 rpm, 25% of the equivalent load (input power in calories between fuels was constant), fuel injection duration: 30 ° C in front of top dead center, inlet conditions: constant at normal temperature) with NO _x measurement , smoke and fuel efficiency, as well as the period of effective ignition delay. The effective ignition delay period is the value obtained by subtracting the time required before ignition starts from the time required before the ignition of the fuel ends. If this value is positive, it means that almost all the injected fuel had enough time to mix with air, and thus, combustion upon ignition from compression of a uniform charge proceeded more efficiently. However, if this value is negative, this means that combustion begins before the fuel injection is completed, which leads to combustion under conditions of insufficient mixing with air and is accompanied by excessive smoke formation. The fuel efficiency is determined by the relative value of the result for each composition in comparison with comparative example 1, which is taken as 100 (a lower value indicates a better result).

The experience with engine testing was carried out in accordance with document 29, Technical Standard for the 13-Mode Exhaust Emission Test Method for Diesel Vehicles, as revised by the former Japanese Ministry of Transport.

(Engine Specification): Commercially available engine 1

Engine type: in a row of 6 cylinders, a supercharged diesel engine with an EGR system

Engine capacity: 1.4 L

Inner Diameter × Beat: 73 mm × 81.4 mm

Compression ratio: 18.5 (modified so that the compression ratio was 16.0 during the ignition-combustion experiment)

Maximum output power: 72 kW / 4000 rpm

Accepted regulation: 2002 Flue gas emission regulation

Finishing device for exhaust gases: not used.

Diesel combustion experience

A commercially available engine 1 was used without changing the compression ratio or injection system and operated at 3200 rpm - 80% equivalent load (input power in calories between fuels was constant) with NO _x , smoke and fuel efficiency measurements. The results of experiments with the fuel of comparative example 1 were taken as 100, and the results of experiments with other fuels were evaluated in relation to the results of comparative example 1 (lower values indicate better results).

Easy engine start at high temperatures

After carrying out the above-mentioned experiment on combustion in a diesel engine, the temperature in the experimental room was maintained at 35 ° C. After the experiment on combustion in a diesel engine ended, the engines were left idle for about 1 minute. After that, the engine was stopped and left for 5 minutes, and then restarted. After that, if the fuel allowed to start the engine normally, it was rated as “Passed”. If the engine did not start and the start took 10 seconds or more, or was accompanied by shortcomings (uneven operation, twitching, slowing the vehicle speed or engine shutdown), then the fuel was rated as “Failed”.

Table 1 Synthetic base oil FT 1 Synthetic base oil FT 2 Synthetic base oil FT 3 Deep hydrogenated process oil Process oil derived from animal or vegetable oil Gas oil hydrotreatment High Compression Gas Oil Composition Density (15 ° С) kg / m ³ 782 782 768 812 764 831 804 Kinematic viscosity (30 ° C) mm ² / s 3.3 4.0 2,3 3,5 2.2 4.4 4.1 Distillation parameters, ° С 10% distillation temperature 225.5 229.0 183.0 218.0 227.0 230.5 222.0 50% distillation temperature 249.0 299.0 249.0 271.0 249.0 292.0 253.0 90% distillation temperature 302.0 339.5 314.0 323.0 268.0 345.5 315.0 Normal paraffins, wt.% 42.0 29.8 37.6 25,4 86.1 25.6 12,4 Sulfur content, wt.% <1 <1 <1 <1 <1 7 <1

table 2 Example 1 Example 2 Example 3 Comp. example 1 Comp. example 2 Comp. example 3 Synthetic base oil FT 1 60 40 Synthetic base oil FT 2 twenty 40 10 Synthetic base oil FT 3 one hundred Deep hydrogenated process oil twenty Process oil derived from animal or vegetable oil 60 Gas oil hydrotreatment fifty one hundred High Compression Gas Oil Composition one hundred Density (15 ° С), kg / m ³ 788 772 806 768 831 804 Kinematic viscosity (30 ° С), mm ² / s 3,5 2,8 3.8 2,3 4.4 4.1 Flash point, ° C 65 65 58 71 58 65 Sulfur content, million hours by weight <1 <1 four <1 7 <1 The oxygen content of million hours by weight <10 <10 55 120 110 <10 Distillation parameters, ° С Boiling point 175.5 180.0 174.5 159.0 178.0 184.0 10% distillation temperature 224.5 231.0 225.0 183.0 230.5 222.0 50% distillation temperature 255.0 264.0 266.0 249.0 292.0 253.0 90% distillation temperature 322.0 317.5 327.5 314.0 345.5 315.0 End point 359.0 342.0 363.5 334.0 368.5 364.0 E200-eibp The degree of compression, vol.% 8.1 8.1 8.8 44.0 10,2 9.0 Cetane number 50.3 44.1 44,2 62.0 38,0 28.8 E280-E200 The degree of compression, vol.% 51.3 51.3 46.6 36.0 38.7 58.0 Cetane number 67.5 64,4 64.3 81.0 58.0 46.3 Eep-e280 The degree of compression, vol.% 40.6 40.6 44.6 30,0 51.1 33.0 Cetane number 56.8 54.8 54.3 82.0 49.5 54.8 Normal paraffins, wt.% 36,2 63.6 32.6 37.6 25.6 12,4 Cetane index 72.9 87.6 66.8 80.0 60.7 64,2 Cetane number 62.1 58.5 58.9 81.7 55.7 48.1 The content of aromatic compounds, vol.% <1 <1 9.1 <1 17.8 <1 The content of naphthenes, wt.% 12.0 0,0 14.0 <1 40.3 24.0 Volumetric strain modulus, MPa 1380 1340 1400 1190 1460 1370 Cloud point, ° С -8.0 -9.0 -7.0 -10.0 -2.0 -7.0 Clogging temperature, ° С -9.0 -11.0 -8.0 -12.0 -5.0 -11.0 The temperature loss of fluidity, ° C -10.0 -12.5 -10.0 -15.0 -7.5 -12.5 Color (by Saybolt) > +30 > +30 28 > +30 +21 > +30 The carbon residue in the residue of 10% distillation, wt.% 0.00 0.01 0.01 0.00 0.01 0.01 Peroxide number, million hours by weight 2 0 7 one 54 0 The diameter of the wear spot (WS 1.4), microns 360 350 360 420 450 360 The content of insoluble, mg / 100 ml 0.1 0.1 0.1 0.2 0.6 0.1 The water content, million hours by volume 9 12 fourteen 47 44 eighteen Lubricity enhancer, mg / l 150 150 150 150 70 150 Cold flow improver, mg / l - - - - - - Detergent, mg / l - - one hundred - - - Cetane number improver, mg / l - - - - - -

Table 3 Example 1 Example 2 Example 3 Comp. example 1 Comp. example 2 Comp. example 3 Combustion Combustion Combustion Test NO _x , ppm 9 8 9 87 135 139 Smoke BSE 0 0 0 0.4 2.1 1,2 Fuel efficiency 91 92 84 one hundred 94 130 The period of effective ignition delay, ° CA 1,5 1.9 2.0 -3.9 -2.1 3.9 Diesel combustion experience NO _x 90 95 93 one hundred 115 138 Smoke 98 96 98 one hundred 130 153 Fuel efficiency 95 94 91 one hundred 95 101 Experience in ease of starting the engine at high temperatures, 35 ° C Passed Passed Passed It did not pass Passed Passed

Examples 4-6 and comparative examples 4-6

Base oils with the properties shown in table 4 were mixed to obtain the gas oil compositions shown in table 5 (Examples 4-6 and comparative examples 4-6). FT 4-6 synthetic base oils are a mixture of hydrocarbons obtained by converting natural gas to wax or a middle fraction by FT reaction followed by hydrogenation. Since the reaction conditions (degree of isomerization) vary, the resulting base oils differ in the content of saturated hydrocarbons. A deeply hydrogenated base oil is a hydrocarbon base oil obtained by additionally hydrogenating a gas oil base oil with a further reduction in sulfur and aromatic compounds. Technological oil obtained from animal or vegetable oils is an oil obtained by hydrogenation of palm oil (all components), used as raw material, with the removal of foreign substances. Hydrotreating gas oil corresponds to the commercially available gas oil, which is used in winter. High compression fuel is fuel obtained by mixing FT synthetic oils, hydrotreating base oils and deeply hydrogenated base oils in suitable amounts for a high pressure diesel engine. Therefore, this fuel meets the requirements for gas oil compositions of the present invention, with the exception of the fraction of each fraction in the mixture and their cetane number. The compositions of examples 4-6 and comparative examples 4-6 were obtained by mixing these base oils in suitable quantities or using any base oils as a whole.

The additives used in these examples were as follows:

lubricity improver: a mixture of carboxylic acids, mainly containing linoleic acid; and

detergent: alkenyl succinimide mixture

cold flow improver: a mixture of ethylene vinyl acetate copolymers.

Table 5 presents the proportions of the components of the gas oil compositions thus obtained, and density at 15 ° C, kinematic viscosity at 30 ° C, flash point, sulfur content, oxygen content, distillation parameters, cetane index, cetane number, aromatic content, content naphthenic compounds, bulk deformation moduli, cloud point, clogging temperature, pour point, color, carbon residue in the residue of 10% distillation, insoluble and peroxy the number after the oxidation test, the diameter of the HFRR wear spot and the water content of each composition.

The gas oil compositions used in examples 4-6 were obtained by mixing 20 percent by weight or more of FT synthetic base oils, as indicated in table 5. In addition, as can be seen from table 5, gas oil compositions satisfying the property requirements defined in this document, were easily obtained, regardless of the circumstances, in examples 4-6, where FT synthetic base oils were mixed in the range of values defined herein. On the other hand, as can be seen from comparative examples 4-6, where the compositions were obtained without using the above specific base oils, and the composition was prepared using specific base oils, which, however, in terms of the proportion of each fraction or the like. did not satisfy the definition of the present invention, gas oil compositions, as assumed by the present invention, were not necessarily obtained.

Further, the following various experiments were carried out using the gas oil compositions of Examples 4-6 and Comparative Examples 4-6. All results are presented in table 6. As can be seen from table 6, the gas oil composition of examples 4-6 showed excellent results regarding NO _x , smoke, fuel efficiency and the period of effective ignition delay during combustion with compression-ignition uniform charge, and NO _x , smoke, fuel efficiency and ease of starting the engine at low temperatures during normal combustion, compared with gas oil compositions of comparative examples 4-6. Therefore, the gas oil compositions of examples 4-6 are obviously high-quality gas oils that can provide at a high level both excellent practical performance in the winter season and environmentally friendly properties that can be applied to combustion with compression ignition of a uniform charge, moreover the effect and properties are difficult to provide when using traditional gas oil compositions.

Combustion Combustion Combustion Test

The experiment was carried out using an experimental engine, where, on the basis of the previously mentioned commercially available engine 1, described below, the piston shape of all cylinders was changed to change the compression ratio to 16, and the regulating part of the electronic injection fuel injection pump was partially changed with the usual guide- fuel dispenser to provide control of injection time. The experiment was carried out under stationary conditions (1200 rpm, 25% of the equivalent load (input power in calories between fuels was constant), fuel injection duration: 30 ° C in front of top dead center, inlet conditions: constant at normal temperature) with NO _x measurement , smoke and fuel efficiency, as well as the period of effective ignition delay. The effective ignition delay period is the amount obtained by subtracting the time required before ignition starts from the time required before the end of ignition of the fuel. If this value is positive, it means that almost all injected fuel had enough time to mix with air, and thus, combustion with compression ignition by a uniform charge proceeded more efficiently. However, if this value is negative, this means that combustion begins before fuel injection is completed, which leads to combustion under conditions of insufficient mixing with air and is accompanied by excessive smoke formation. Fuel efficiency was determined by the relative value of the result for each composition compared with comparative example 4, which was taken as 100 (a lower value indicates a better result).

The test method for the experience with the engine was carried out in accordance with document 29, Technical Standard for the 13-Mode Exhaust Emission Test Method for Diesel Vehicles, as revised by the former Japanese Ministry of Transport.

Diesel combustion experience

A commercially available engine 1 was used without changing the compression ratio or injection system and operated at 3200 rpm - 80% equivalent load (input power in calories between fuels was constant) with NO _x , smoke and fuel efficiency measurements. The results of experiments with the fuel of comparative example 4 were taken as 100, and the results of experiments with other fuels were evaluated in comparison with the results of comparative example 4 (lower values indicate better results).

Easy engine start at low temperatures

An engine with the same change in compression ratio as in the above-described commercially available engine 1 was mounted on a vehicle 1, discussed below. On a running drum capable of controlling the ambient temperature, each of the gas oil compositions was tested at room temperature by (1) injecting (washing) estimated fuel into the fuel system of the test diesel vehicle; (2) descent of injected fuel; (3) replacing the main filter with a new one; and (4) supplying the estimated fuel to the fuel tank in a certain amount (1/2 of the tank volume of the test vehicle). The experiment was continued by (5) rapidly cooling the ambient temperature from room temperature to 0 ° C; (6) maintaining a temperature of 0 ° C for one hour; (7) gradual cooling at a speed of 1 ° C / h until a predetermined temperature (-10 ° C) is reached; and (8) turning on the motor after a predetermined temperature is stored for one hour. If the engine did not start even after 10 seconds, the engine was restarted twice with an interval of 30 seconds, and the fuel was rated as “Bad” at the moment. If the engine started within 10 seconds, the engine was restarted twice with an interval of 30 seconds, the car remained stationary for 3 minutes, and then accelerated to 60 km / h for 15 seconds and moved at low speed. When a malfunction was observed (uneven operation, “jerking”, a decrease in vehicle speed or engine stop) during acceleration of a vehicle to 60 km / h and driving at a given speed for 20 minutes, the gas oil composition was evaluated as “Failed” in this moment. If the engine worked to the end without any defects, the gas oil composition was evaluated as Passed.

(Vehicle Specifications): Vehicle 1

Engine type: in a row of 4 cylinders, diesel with intercooler of charge air and EGR system

Engine capacity: 1.4 L

Inner Diameter × Beat: 73 mm × 81.4 mm

Compression ratio: 18.5 (changed to 16.0)

Maximum output power: 72 kW / 4000 rpm

Accepted regulation: 2002 Flue gas emission regulation

Vehicle weight: 1060 kg

Transmission: mechanical transmission, 5 speeds.

Exhaust Finisher: Oxidation Catalyst

Table 5 Example 4 Example 5 Example 6 Comp. example 4 Comp. example 5 Comp. example 6 Synthetic base oil FT 4 70 40 Synthetic base oil FT 5 40 10 Synthetic base oil FT 6 one hundred Deep hydrogenated process oil twenty 60 Process oil derived from animal or vegetable oil 10 Gas oil hydrotreatment fifty one hundred High Compression Gas Oil Composition one hundred Density (15 ° С), kg / m ³ 785 798 804 768 831 796 Kinematic viscosity (30 ° С), mm ² / s 3.0 3.2 3.6 2,3 4.4 3.8 Flash point, ° C 62 58 59 71 58 61 Sulfur content, million hours by weight <1 <1 four <1 7 <1 The oxygen content of million hours by weight <10 <10 55 120 110 <10 Distillation parameters, ° С Boiling point 178.0 169.0 165.0 159.0 178.0 164.0 10% distillation temperature 212.0 202.0 210.5 183.0 230.5 205.5 50% distillation temperature 249.0 264.0 262.0 249.0 292.0 250,0 90% distillation temperature 305.5 323.5 325.5 314.0 345.5 316.0 End point 341.0 355.5 358.0 334.0 368.5 354.0 E200-eibp The degree of compression, vol.% 13.8 16,0 13.8 46.0 10,2 16.6 Cetane number 49.0 46.1 44.3 62.0 38,0 26.5 E280-E200 The degree of compression, vol.% 55.3 41.1 44,2 36.0 38.7 52.0 Cetane number 70.8 66,2 65.0 81.0 58.0 41.8 Eep-e280 The degree of compression, vol.% 30.9 42.9 42.1 30,0 51.1 31,4 Cetane number 58.6 56.0 55.6 82.0 49.5 54.3 Normal paraffins, wt.% 43.3 27.3 32,7 37.6 25.6 12,2 Cetane index 72.7 68.8 65.3 80.0 60.7 65.8 Cetane number 64,2 58.8 58.1 81.7 55.7 43,4 The content of aromatic compounds, vol.% <1 <1 9.1 <1 17.8 <1 The content of naphthenes wt.% <1 36.0 14.0 <1 40.3 12.0 Volumetric strain modulus, MPa 1320 1360 1390 1190 1460 1360 Cloud point, ° С -18.0 -12.0 -10.0 -10.0 -2.0 -12.0 Clogging temperature, ° С -20.0 -15.0 -18.0 -12.0 -5.0 -15.0 The temperature loss of fluidity, ° C -22.5 -17.5 -20.0 -15.0 -7.5 -20.0 Color (by Saybolt) > +30 > +30 28 > +30 +21 > +30 The carbon residue in the residue of 10% distillation, wt.% 0.00 0.00 0.01 0.00 0.01 0.00 Peroxide number, million hours by weight 0 0 27 one 54 four The diameter of the wear spot (WS 1.4), microns 350 340 330 420 450 360 The content of insoluble, mg / 100 ml 0.1 0.1 0.1 0.2 0.6 0.1 The water content, million hours by volume 12 2 19 47 44 6 Lubricity enhancer, mg / l 150 150 150 150 70 150 Cold flow improver, mg / l - - 150 - - - Detergent, mg / l - - one hundred - - - Cetane number improver, mg / l - - - - - -

Table 6 Example 4 Example 5 Example 6 Comp. example 4 Comp. example 5 Comp. example 6 Combustion Combustion Combustion Test NO _x , ppm 7 13 12 87 135 144 Smoke BSE 0 0 0 0.4 2.1 1,6 Fuel efficiency 96 94 88 one hundred 94 132 The period of effective ignition delay, ° CA 1,2 1.8 1.9 -3.9 -2.1 3,7 Diesel combustion experience NO _x 88 92 94 one hundred 115 136 Smoke 89 97 98 one hundred 130 149 Fuel efficiency 97 95 91 one hundred 95 one hundred Experience in ease of starting the engine at low temperatures, -10 ° C Passed Passed Passed Passed It did not pass Passed

Examples 7-9 and comparative examples 7-9

The base oils were mixed with the characteristics shown in table 7 to obtain the gas oil compositions shown in table 8 (examples 7-9 and comparative examples 7-9). FT 7-9 synthetic base oils are hydrocarbon mixtures obtained by converting natural gas to wax or a middle fraction by FT reaction followed by hydrogenation. Since the reaction conditions (degree of isomerization) vary, the resulting base oils differ in the content of saturated hydrocarbons. A deeply hydrogenated base oil is a hydrocarbon base oil obtained by additionally hydrogenating a gas oil base oil with a further reduction in sulfur and aromatic compounds. Technological oil obtained from animal or vegetable oils is an oil obtained by hydrogenation of palm oil (all components), used as raw material, with the removal of foreign substances. Hydrotreating gas oil corresponds to the commercially available gas oil, which is used in winter. High compression fuel is fuel obtained by mixing FT synthetic oils, hydrotreating base oils and deeply hydrogenated base oils in suitable amounts for a high pressure diesel engine. Therefore, this fuel meets the requirements for gas oil compositions of the present invention, with the exception of the fraction of each fraction in the mixture and their cetane number. The compositions of examples 7-9 and comparative examples 7-9 were obtained by mixing these base oils in suitable quantities or using any base oils as a whole.

The additives used in these examples were as follows:

lubricity improver: a mixture of carboxylic acids, mainly containing linoleic acid;

detergent: alkenyl succinimide mixture

cold flow improver: a mixture of ethylene vinyl acetate copolymers.

Table 8 presents the proportions of the components of the gas oil compositions thus obtained, and density at 15 ° C, kinematic viscosity at 30 ° C, flash point, sulfur content, oxygen content, distillation parameters, cetane index, cetane number, aromatic content, content naphthenic compounds, bulk strain moduli, cloud point, clogging temperature, pour point, color, carbon residue in the residue of 10% distillation, insoluble and peroxide value after oxidation test, HFRR wear spot diameter and water content in each composition.

The gas oil compositions used in examples 7-9 were obtained by mixing 20 percent by weight or more of FT synthetic base oils, as indicated in table 8. In addition, as can be seen from table 8, gas oil compositions satisfying the properties defined herein were readily obtained, regardless of the circumstances, in Examples 7-9, where FT synthetic base oils were mixed in the range of values defined herein. On the other hand, as can be seen from comparative examples 7-9, where the compositions were obtained without using the above specific base oils, and the composition was prepared using specific base oils, which, however, in terms of the proportion of each fraction or the like. did not satisfy the definition of the present invention, gas oil compositions, as assumed by the present invention, were not necessarily obtained.

Further, the following various experiments were carried out using the gas oil compositions of Examples 7-9 and Comparative Examples 7-9. All results are presented in table 9. As can be seen from table 9, the gas oil composition of examples 7-9 showed excellent results regarding NO _x , smoke, KAD fuel and the period of effective ignition delay during combustion with compression uniform compression ignition, and NO _x , smoke, fuel efficiency and ease of starting at low fuel temperatures during normal combustion, compared with gas oil compositions of comparative examples 7-9. Therefore, the gas oil compositions of examples 7-9 are obviously high-quality gas oils that can achieve a high level of both excellent practical performance in the winter season and environmentally friendly properties that can be applied to combustion with compression ignition of a uniform charge, and the action and properties are difficult to provide when using conventional gas oil compositions.

Combustion Combustion Combustion Test

The experiment was carried out using an experimental engine, where, on the basis of the previously mentioned commercially available engine 1, described below, the piston shape of all cylinders was changed to change the compression ratio to 16, and the regulating part of the electronic injection fuel injection pump was partially changed with the usual guide- a fuel dispenser to provide control over the duration of the injection. The experiment was carried out under stationary conditions (1200 rpm, 25% of the equivalent load (input power in calories between fuels was constant), fuel injection time: 30 ° С before the top dead center, inlet conditions: constant at normal temperature) with NO _x measurement , smoke and fuel efficiency, as well as the period of effective ignition delay. The effective ignition delay period is the amount obtained by subtracting the time required before ignition starts from the time required before the end of ignition of the fuel. If this value is positive, it means that almost all injected fuel had enough time to mix with air, and thus, combustion with compression ignition from a uniform charge proceeded more efficiently. However, if this value is negative, it means that combustion begins before fuel injection is completed, which leads to combustion under conditions of insufficient mixing with air and is accompanied by excessive smoke formation. Fuel efficiency was determined by the relative value of the result for each composition compared with comparative example 7, which was taken as 100 (a lower value indicates a better result).

The engine test was carried out in accordance with document 29, Technical Standard for the 13-Mode Exhaust Emission Test Method for Diesel Vehicles, as revised by the former Ministry of Transport of Japan.

Diesel combustion experience

A commercially available engine 1 was used without changing the compression ratio or injection system and operated at 3200 rpm-80% equivalent load (input power in calories between fuels was constant) with NO _x , smoke and fuel efficiency measurements. The results of experiments with the fuel of comparative example 7 were taken as 100, and the results of experiments with other fuels were evaluated in comparison with the results of comparative example 7 (lower values indicate better results).

Easy engine start at low temperatures

An engine with the same change in compression ratio as in the above-described commercially available engine 1 was mounted on a vehicle 1, discussed below. On a running drum capable of controlling the ambient temperature, each of the gas oil compositions was tested at room temperature by (1) injecting (washing) estimated fuel into the fuel system of the test diesel vehicle; (2) descent of injected fuel; (3) replacing the main filter with a new one; and (4) supplying the estimated fuel to the fuel tank in a certain amount (1/2 of the tank volume of the test vehicle). The experiment was continued by (5) rapidly cooling the ambient temperature from room temperature to -5 ° C; (6) maintaining a temperature of -5 ° C for one hour; (7) gradual cooling at a speed of 1 ° C / h until a predetermined temperature (-15 ° C) is reached; and (8) the motor is turned on after a predetermined temperature is stored for one hour. If the engine did not start even after 10 seconds, the engine was restarted twice with an interval of 30 seconds, and the fuel was rated “Failed” at the moment. If the engine started within 10 seconds, the engine was started twice with an interval of 30 seconds, the car was left stationary for 3 minutes, and then accelerated to 60 km / h for 15 seconds, and it moved at a low speed. When a malfunction was observed (uneven operation, “jerking”, a decrease in vehicle speed or engine stop) during acceleration of a vehicle to 60 km / h and driving at a given speed for 20 minutes, the gas oil composition was evaluated as “Failed” in this moment. If the engine worked to the end without any defects, the gas oil composition was evaluated as Passed.

Table 8 Example 7 Example 8 Example 9 Comp. example 7 Comp. example 8 Comp. example 9 Synthetic base oil FT 7 60 thirty Synthetic base oil FT 8 40 twenty Synthetic base oil FT 9 one hundred Deep hydrogenated process oil twenty 60 Process oil derived from animal or vegetable oil twenty Gas oil hydrotreatment fifty one hundred High Compression Gas Oil Composition one hundred Density (15 ° С), kg / m ³ 777 792 797 768 822 790 Kinematic viscosity (30 ° С), mm ² / s 2.5 2.7 2,8 2,3 3.2 3,1 Flash point, ° C 60 61 59 71 55 58 Sulfur content, million hours by weight <1 <1 four <1 7 <1 The oxygen content of million hours by weight <10 <10 51 120 104 <10 Distillation parameters, ° С Boiling point 170.0 152.0 156.0 159.0 166.0 158.0 10% distillation temperature 197.0 187.0 192.0 183.0 194.0 193.5 50% distillation temperature 233.5 246.5 243.0 249.0 264.0 242.5 90% distillation temperature 305.5 317.0 322.0 314.0 328.5 306.0 End point 346.5 344.5 350,0 334.0 352.0 341.0 E200-eibp The degree of compression, vol.% 25.3 24.7 26.1 46.0 20.6 26,4 Cetane number 48.0 44.0 45,2 62.0 35.5 27.9 E280-E200 The degree of compression, vol.% 48.7 40.8 39.0 36.0 35.7 50,4 Cetane number 67.2 64,2 66.6 81.0 59.6 40,2 Eep-e280 The degree of compression, vol.% 26.0 34.5 34.9 30,0 43.7 23,2 Cetane number 55.7 54.0 54.7 82.0 46.9 55.3 Normal paraffins, wt.% 49.6 27.8 32.6 37.6 25.8 12,2 Cetane index 70.0 65,4 61.9 80.0 56.1 65.9 Cetane number 59.8 55.3 57.0 81.7 57.6 42.0 The content of aromatic compounds, vol.% <1 <1 9.0 <1 18.1 <1 The content of naphthenes wt.% 11.5 34,4 13.8 <1 27.7 11.5 Volumetric strain modulus, MPa 1300 1340 1380 1190 1410 1300 Cloud point, ° С -18.0 -18.0 -15.0 -10.0 -8.0 -18.0 Clogging temperature, ° С -20.0 -20.0 -21.0 -12.0 -14.0 -21.0 The temperature loss of fluidity, ° C -27.5 -27.5 -27.5 -15.0 -21.0 -27.5 Color (by Saybolt) > +30 > +30 28 > +30 +21 > +30 The carbon residue in the residue of 10% distillation, wt.% 0.00 0.00 0.01 0.00 0.01 0.00 Peroxide number, million hours by weight four 3 7 one 51 four Wear spot diameter (WS 1.4) μm 360 340 360 420 460 360 The content of insoluble, mg / 100 ml 0.1 0.1 0.1 0.2 0.4 0.1 The water content, million hours by volume fifteen 9 eighteen 47 41 6 Lubricity enhancer, mg / l 150 150 150 150 70 150 Cold flow improver, mg / l - - 150 - 150 - Detergent, mg / l - - one hundred - - - Cetane number improver, mg / l - - - - - -

Table 9 Example 7 Example 8 Example 9 Comp. example 7 Comp. example 8 Comp. example 9 Combustion Combustion Combustion Test NO _x , ppm eleven 7 9 87 129 142 Smoke BSE 0 0 0 0.4 1,1 1.9 Fuel efficiency 95 91 88 one hundred 97 137 The period of effective ignition delay, ° CA 1.7 2.1 2.2 -3.9 -2.2 3.6 Diesel combustion experience NO _x 91 91 93 one hundred 116 134 Smoke 86 95 95 one hundred 128 141 Fuel efficiency 96 87 88 one hundred 96 99 Experience in ease of starting the engine at low temperatures, -15 ° C Passed Passed Passed It did not pass It did not pass Passed

Examples 10-12 and Comparative Examples 10-12

The base oils were mixed with the characteristics shown in table 10 to obtain the gas oil compositions shown in table 11 (examples 10-12 and comparative examples 10-12). FT 10-12 synthetic base oils are hydrocarbon mixtures obtained by converting natural gas to wax or a middle fraction by FT reaction followed by hydrogenation. Since the reaction conditions (degree of isomerization) vary, the resulting base oils differ in the content of saturated hydrocarbons. A deeply hydrogenated base oil is a hydrocarbon base oil obtained by additionally hydrogenating a gas oil base oil with a further reduction in sulfur and aromatic compounds. Technological oil obtained from animal or vegetable oils is an oil obtained by hydrogenation of palm oil (all components), used as raw material, with the removal of foreign substances. Hydrotreating gas oil corresponds to the commercially available gas oil, which is used in winter. High compression fuel is fuel obtained by mixing FT synthetic oils, hydrotreating base oils and deeply hydrogenated base oils in suitable amounts for a high pressure diesel engine. Therefore, this fuel meets the requirements for gas oil compositions of the present invention, with the exception of the fraction of each fraction in the mixture and their cetane number. The compositions of examples 10-12 and comparative examples 10-12 were obtained by mixing these base oils in suitable amounts or using any base oils as a whole.

The additives used in these examples were as follows:

lubricity improver: a mixture of carboxylic acids, mainly containing linoleic acid;

detergent: alkenyl succinimide mixture

cold flow improver: ethylene-vinyl acetate copolymer blend.

Table 11 shows the proportions of the components of the gas oil compositions thus obtained and the density at 15 ° C, kinematic viscosity at 30 ° C, the ignition temperature, sulfur content, oxygen content, distillation parameters, cetane index, cetane number, aromatic content, content naphthenic compounds, bulk deformation moduli, cloud point, clogging temperature, pour point, color, carbon content in the residue of 10% distillation, insoluble content, p roksidnoe number of the test for the oxidation resistance, wear scar diameter HFRR and the water content in each composition.

The gas oil compositions used in examples 10-12 were obtained by mixing 20 percent by weight or more of FT synthetic base oils, as indicated in table 11. In addition, as can be seen from table 11, gas oil compositions satisfying the properties defined herein were readily obtained, regardless of the circumstances, in Examples 10-12, where FT synthetic base oils were mixed in the range of values defined herein. On the other hand, as can be seen from comparative examples 10-12, where the composition was obtained without using the above specific base oils, and the composition was prepared using specific base oils, which, however, in terms of the proportion of each fraction or the like. did not satisfy the definition of the present invention, gas oil compositions, as assumed by the present invention, were not necessarily obtained.

Further, the following various experiments were carried out using the gas oil compositions of Examples 10-12 and Comparative Examples 10-12. All results are presented in table 12. As can be seen from table 12, the gas oil compositions of examples 10-12 showed excellent results regarding NO _x , smoke, fuel efficiency and the period of effective ignition delay during combustion with compression uniform compression ignition, and NO _x , smoke, fuel efficiency and ease of starting the engine at low temperatures during normal combustion, compared with gas oil compositions of comparative examples 10-12. Therefore, the gas oil compositions of examples 10-12 are obviously high-quality gas oils, which can simultaneously achieve a high level of both excellent practical operational properties in the winter season and environmentally friendly properties, which can be attributed to combustion with ignition from the combustion of a uniform charge, moreover the effect and properties are difficult to provide when using traditional gas oil compositions.

Combustion Combustion Combustion Experience

The experiment was carried out using an experimental engine, where, on the basis of the previously mentioned commercially available engine 1, described below, the piston shape of all cylinders was changed to change the compression ratio to 16, and the regulating part of the electronic injection fuel injection pump was partially changed with the usual guide- a fuel dispenser to provide control over the duration of the injection. The experiment was carried out under stationary conditions (1200 rpm, 25% of the equivalent load (input power in calories between fuels was constant), fuel injection time: 30 ° С before the top dead center, inlet conditions: constant at normal temperature) with NO _x measurement , smoke and fuel efficiency, as well as the period of effective ignition delay. The effective ignition delay period is the amount obtained by subtracting the time required before ignition starts from the time required before the end of ignition of the fuel. If this value is positive, it means that almost all injected fuel had enough time to mix with air, and thus, combustion with compression ignition by a uniform charge proceeded more efficiently. However, if this value is negative, this means that combustion begins before fuel injection is completed, which leads to combustion under conditions of insufficient mixing with air and is accompanied by excessive smoke formation. Fuel efficiency was determined by the relative value of the result for each composition compared with comparative example 7, which was taken as 100 (a lower value indicates a better result).

The engine was tested in accordance with document 29, Technical Standard for the 13-Mode Exhaust Emissions Test Method for Diesel Vehicles, as revised by the former Japanese Ministry of Transport.

Diesel combustion experience

A commercially available engine 1 was used without changing the compression ratio or injection system, it worked at 3200 rpm - 80% equivalent load (input power in calories between the fuels was constant) with the measurement of NO _x , smoke and fuel efficiency. The results of experiments with the fuel of comparative example 10 were taken as 100, and the results of experiments with other fuels were evaluated in comparison with the results of comparative example 10 (lower values indicate better results).

Easy engine start at low temperatures

An engine with the same change in compression ratio as in the above-described commercially available engine 1 was mounted on a vehicle 1, discussed below. On a running drum capable of controlling the ambient temperature, each of the gas oil compositions was tested at room temperature by (1) injecting (washing) estimated fuel into the fuel system of the test diesel vehicle; (2) descent of injected fuel; (3) replacing the main filter with a new one; and (4) supplying the estimated fuel to the fuel tank in a certain amount (1/2 of the tank volume of the test vehicle). The experiment was continued by (5) rapidly cooling the ambient temperature from room temperature to -15 ° C; (6) maintaining a temperature of -15 ° C for one hour; (7) gradual cooling at a speed of 1 ° C / h until a predetermined temperature (-25 ° C) is reached; and (8) turning on the engine after a predetermined temperature is stored for one hour. If the engine did not start even after 10 seconds, the engine was restarted twice with an interval of 30 seconds, and the fuel was rated “Failed” at the moment. If the engine started within 10 seconds, the engine was started twice with an interval of 30 seconds, the car was left stationary for 3 minutes, and then accelerated to 60 km / h for 15 seconds, and it moved at a low speed. When a malfunction was observed (uneven operation, “jerking”, a decrease in vehicle speed or engine stop) during acceleration of a vehicle to 60 km / h and driving at a given speed for 20 minutes, the gas oil composition was evaluated as “Failed” in this moment. If the engine worked to the end without any defects, the gas oil composition was evaluated as Passed.

Table 11 Example 10 Example 11 Example 12 Comp. example 10 Comp. example 11 Comp. example 12 Synthetic base oil FT 10 70 40 Synthetic base oil FT 11 twenty 80 10 Synthetic base oil FT 12 one hundred Deep hydrogenated process oil twenty Process oil derived from animal or vegetable oil 10 Gas oil hydrotreatment fifty one hundred High Compression Gas Oil Composition one hundred Density (15 ° С), kg / m ³ 768 774 789 768 810 779 Kinematic viscosity (30 ° С), mm ² / s 2.1 2.1 2.1 2,3 2.2 2.2 Flash point ° C 54 55 55 71 53 53 Sulfur content, million hours by weight <1 <1 four <1 7 <1 The oxygen content of million hours by weight <10 <10 51 120 102 <10 Distillation parameters, ° С Boiling point 154.5 151.0 152.0 159.0 161.0 150.0 10% distillation temperature 186.5 176.5 183.0 183.0 179.0 180.0 50% distillation temperature 209.0 208.0 211.0 249.0 219.0 207.0 90% distillation temperature 276.5 311.5 301.0 314.0 316.0 305.0 End point 318.0 346.0 338.0 334.0 354.0 350,0 E200-eibp The degree of compression, vol.% 46.2 45.0 43,4 46.0 36,2 45.6 Cetane number 46.5 48.0 44,4 62.0 35.7 29.6 E280-E200 The degree of compression, vol.% 40.9 30,0 37.3 36.0 36,4 31.5 Cetane number 66.9 64.6 64,2 81.0 59.2 44,4 Eep-e280 The degree of compression, vol.% 12.9 25.0 19.3 30,0 27.4 22.8 Cetane number 58.5 55.0 54.7 82.0 49.5 55.2 Normal paraffins, wt.% 39.8 27.3 30.5 37.6 26.2 22.6 Cetane index 65.7 59.5 55.2 80.0 49.1 57.5 Cetane number 56.1 55.0 54.1 81.7 50.1 40.5 The content of aromatic compounds, vol.% <1 <1 8.9 <1 17.9 <1 The content of naphthenes wt.% <1 11.2 13.6 <1 27,2 16.8 Volumetric strain modulus, MPa 1310 1310 1330 1190 1360 1310 Cloud point, ° С <-25 -25.0 -25.0 -10.0 -14.0 -26.0 Clogging temperature, ° С <-35 -33.0 -30.0 -12.0 -21.0 -31.0 The temperature loss of fluidity, ° C <-45 -35.0 -35.0 -15.0 -32.5 -35.0 Color (by Saybolt) > +30 > +30 29th > +30 +27 > +30 The carbon residue in the residue of 10% distillation, wt.% 0.00 0.00 0.01 0.00 0.01 0.00 Peroxide number, million hours by weight one 3 6 one 51 one Wear spot diameter (WS 1.4) μm 360 360 360 420 450 360 The content of insoluble, mg / 100 ml 0.1 0.1 0.1 0.2 0.2 0.1 The water content, million hours by volume 3 8 19 47 21 17 Lubricity enhancer, mg / l 150 150 150 150 150 150 Cold flow improver, mg / l - - 300 - 300 - Detergent, mg / l - - one hundred - - - Cetane number improver, mg / l - - - - - -

Table 12 Example 10 Example 11 Example 12 Comp. example 10 Comp. example 11 Comp. example 12 Combustion Combustion Combustion Test NO _x , ppm 13 fourteen 9 87 141 155 Smoke BSE 0 0 0 0.4 1,5 2.2 Fuel efficiency 93 94 90 one hundred 97 137 The period of effective ignition delay, ° CA 1.9 1.7 1,5 -3.9 -0.3 3.4 Diesel combustion experience NO _x 89 90 91 one hundred 167 138 Smoke 97 94 95 one hundred 113 142 Fuel efficiency 95 93 92 one hundred 96 one hundred Experience in ease of starting the engine at low temperatures, -25 ° С Passed Passed Passed It did not pass It did not pass Passed

Brief Description of the Drawing

The drawing is a schematic view illustrating an example of a device used to measure the bulk modulus of a gas oil composition.

Digital notation

1. Capacity of a certain volume

2. Inlet valve

3. Exhaust valve

4. Temperature sensor

5. Pressure sensor

6. Piston

100. The composition of gas oil.

Claims (7)

1. The gas oil composition for use in a diesel engine with a geometric compression ratio of 16 or less, equipped with a supercharger and EGR, containing FT synthetic base oil and having a sulfur content of 5 million hours by mass or less, the oxygen content of 100 million hours or less, the volumetric strain modulus is 1250 MPa or more and 1450 MPa or less, the Saybolt color is +22 or more and the lubricity is 400 μm or less, the initial boiling point is 140 ° C or higher and the final boiling point is 380 ° C or lower in the parameters distillation, and the following properties (1) - (3) fractions of each interval, where
(1) the cetane number of the fraction in the range lower than 200 ° C. is 40 or more and less than 60;
(2) the cetane number of the fraction in the range of 200 ° C or higher and lower than 280 ° C is 60 or more and less than 80; and
(3) the cetane number of the fraction in the range of 280 ° C. or higher is 50 or more. 2. The gas oil composition according to claim 1 with quality indicators corresponding to JIS standards for grade No. 1 gas oil, other than sulfur content, for use in a diesel engine with a geometric compression ratio of 16 or less equipped with a supercharger and EGR containing FT synthetic base oil having sulfur content 5 million hours by mass or less, the oxygen content of 100 million hours by mass or less and a bulk modulus of 1250 MPa or more and 1450 MPa or less, Saybolt color +22 or more, lubricity 400 μm or less, initial boiling point 140 ° C or higher and final boiling point 380 ° C or lower in the distillation parameters, and the following properties (1) - (3) fractions of each interval, where
(1) the cetane number of the fraction in the range lower than 200 ° C. is 40 or more and less than 60; and a constituent fraction of a fraction in the volume of all fractions is from 1% by volume or more to less than 10% by volume;
(2) the cetane number of the fraction in the range of 200 ° C. or higher and lower than 280 ° C. is 60 or more less than 80, and the constituent fraction of the fraction in the volume of all fractions is 40% by volume or more and 98% by volume or less ; and
(3) the cetane number of the fraction in the range of 280 ° C. or higher is 50 or more, and the constituent fraction of the fraction in the volume of all fractions is from 1% by volume or more and 59% by volume or less. 3. The gas oil composition according to claim 1 with quality indicators that meet JIS standards for gas oil grade No. 2, except for sulfur content, for use in a diesel engine with a geometric compression ratio of 16 or less, equipped with a supercharger and EGR, containing FT synthetic base oil and having sulfur content 5 million hours by mass or less, the oxygen content of 100 million hours by weight or less, bulk modulus 1250 MPa or more and 1450 MPa or less, Saybolt color +22 or higher, lubricity 400 μm or less, initial boiling point 140 ° C or higher and final boiling point 360 ° C or lower in the distillation parameters, and the following properties (1) - (3) fractions of each interval, where
(1) the cetane number of the fraction in the range lower than 200 ° C. is 40 or more and less than 60, and the constituent fraction of the fraction in the volume of all fractions is 10% by volume or more and less than 20% by volume;
(2) the cetane number of the fraction in the range of 200 ° C. or higher and lower than 280 ° C. is 60 or more and less than 80, and the constituent fraction of the fraction in the volume of all fractions is 30% by volume or more and 89% by volume or less ; and
(3) the cetane number of the fraction in the range of 280 ° C. or higher is 50 or more, and the constituent fraction of the fraction in the volume of all fractions is from 1% by volume or more and 60% by volume or less. 4. Gas oil compositions according to claim 1 with quality indicators that meet JIS standards for grade 3 gas oil, except for sulfur content, for use in a diesel engine with a geometric compression ratio of 16 or less, equipped with a supercharger and EGR, containing FT synthetic base oil and having sulfur content 5 million hours by mass or less, the oxygen content of 100 million hours by weight or less, volumetric deformation modulus 1250 MPa or more and 1450 MPa or less, Saybolt color +22 or more, lubricity 400 μm or less, initial boiling point 140 ° C or higher and final boiling point 360 ° C or lower in the distillation parameters, and the following properties (1) - (3) fractions of each interval, where
(1) the cetane number of the fraction in the range lower than 200 ° C. is 40 or more and less than 60, and the constituent fraction of the fraction in the volume of all fractions is 20% by volume or more and less than 40% by volume;
(2) the cetane number of the fraction in the range of 200 ° C or higher to lower than 280 ° C is 60 or more and less than 80, and the constituent fraction of the fraction in the volume of all fractions is 30% by volume or more and 78% by volume or less ; and (3) the cetane number of the fraction in the range of 280 ° C. or higher is 50 or more, and the constituent fraction of the fraction in the volume of all fractions is from 1% by volume or more and 50% by volume or less. 5. Gas oil compositions according to claim 1 with quality indicators that meet JIS standards for grade 3 gas oil, other than sulfur content, for use in a diesel engine with a compression ratio of 16 or less, equipped with a supercharger and EGR containing FT synthetic base oil and having sulfur content 5 million hours by mass or less, the oxygen content of 100 million hours by mass or less, bulk modulus 1250 MPa or more and 1450 MPa or less, Saybolt color +22 or higher, lubricity 400 μm or less, initial boiling point 140 ° C or higher and final boiling point 350 ° C or lower in the distillation parameters, and the following properties (1) - (3) fractions of each interval, where
(1) the cetane number of the fraction in the range lower than 200 ° C. is 40 or more and less than 60, and the constituent fraction of the fraction in the whole volume of fractions is 40% by volume or more and 70% by volume or less;
(2) the cetane number of the fraction in the range of 200 ° C or higher and lower than 280 ° C is 60 or more and less than 80, and the constituent fraction of the fraction in the entire volume of fractions is 20% by volume or more and 59% by volume or less ; and
(3) the cetane number of the fraction in the range of 280 ° C. or higher is 50 or more, and the constituent fraction of the fraction in the whole volume of the fractions is from 1% by volume or more and 30% by volume or less. 6. The gas oil composition according to any one of claims 1 to 5, wherein the peroxide number after the accelerated oxidation test is 50 ppm. by weight or less, and the content of aromatic compounds is 15% by volume or less. 7. The gas oil composition according to any one of claims 1 to 5, wherein the proportion of FT synthetic base oil in the mixture is 20% by volume or more.

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