JP4916219B2 - Method for producing A heavy oil composition - Google Patents

Description

The present invention relates to a method for producing an A heavy oil composition. More specifically, the present invention relates to a method for producing an A heavy oil composition satisfying the JIS class 1 heavy oil standard, which has sufficient performance for recent high performance engines, has excellent low temperature fluidity, and is excellent in filter oil passing performance at low temperatures.

Conventionally, as a base material for heavy oil A, straight-run kerosene obtained from an atmospheric distillation apparatus of crude oil or kerosene subjected to desulfurization treatment, straight-run light diesel oil or light diesel oil subjected to desulfurization treatment, heavy light oil, and light cycle obtained from a cracking device Oil, direct desulfurized oil obtained from direct desulfurization equipment is known. The conventional A heavy oil composition contains one or more of the above-mentioned base materials. In addition, it is manufactured by applying one or more kinds of normal pressure residual oil, direct desorption residual oil, and vacuum residual oil as residual carbon base materials. Moreover, additives such as a cetane number improver and a low temperature fluidity improver are blended with these A heavy oil compositions as necessary (see, for example, Non-Patent Document 1).
Seiichi Konishi, “Introduction to Fuel Engineering”, Saika Hanafusa, March 1991, p. 136-144

A heavy oil is widely used as fuel for external combustion equipment such as boilers, diesel engine equipment fuel for off-road use such as small fishing boats and construction machinery, and gas turbine equipment fuel.
Various combustion equipment using heavy fuel oil A is provided with a filter having an opening of 5 to 250 μm in the fuel system for the purpose of removing foreign substances in the fuel oil. However, when such a combustion device is used in winter, the filter is likely to be clogged with wax precipitated from A heavy oil.

Therefore, in order to solve such problems, studies are being made to improve low-temperature performance such as low-temperature fluidity of A heavy oil, such as blending heavy oil, increasing residual oil, adding low-temperature fluidity improvers, etc. Have been proposed (see, for example, Patent Documents 1 and 2 and Non-Patent Document 1).
However, the A heavy oil obtained by the above-described methods has room for improvement in the following points, and none of them is still sufficient to be put to practical use as A heavy oil. In other words, the increased blending of heavy oil leads to a worsening of the wax precipitation point (cloud point), and the increase in the residual carbon base material may cause an increase in the amount of dust in the combustion gas, but also the solubility in other base materials. The oil permeability of the filter accompanying sludge generation at room temperature is a concern. In addition, the performance of the low temperature fluidity improver depends largely on the compatibility with the base material used, and it is difficult to obtain sufficient low temperature performance as A heavy oil simply by adding.
Japanese Patent Laid-Open No. 9-333583 JP-A-7-97581 Koji Nomura, “Science of Marine Fuel”, Naruyamado, 1994, p. 164-166

  A heavy oil is used as boiler fuel and off-road diesel engine fuel. With the recent increase in output and fuel efficiency of engines used in A heavy oil, A heavy oil has higher performance. Requests are increasing year by year. When heavy fuel oil A is used as the fuel for these high-performance engines, there may be a problem related to combustibility such as deterioration of ignitability and increased occurrence of soot and increased frequency of cleaning in the burner and the furnace. On the other hand, since A heavy oil contains more heavy components than gasoline and kerosene, wax precipitation at low temperatures may be a problem. Wax precipitation at low temperatures may clog a filter for preventing contaminants in the fuel system, and in the worst case, fuel supply may not be possible. As a method for suppressing wax precipitation at low temperatures, a method of adding a fluidity improver is common, but under the actual severe winter conditions, a sufficient effect cannot be exhibited. Conventionally, a test based on a clogging point has been used to judge the filter clogging property at low temperatures. In this test method, the low temperature fluidity is improved by adding a fluidity improver, but in this test method, the cooling rate of the sample oil is rapidly cooled (about 40 ° C./hour). Is very different. It is known that the slower the cooling rate, the larger the precipitated wax and the clogging of the filter, and the evaluation based on the clogging point is insufficient. In general, A heavy oil excellent in low-temperature performance often has poor flammability, and A heavy oil satisfying all these performances is desired. Thus, A heavy oil satisfying both low temperature performance and combustibility has not been obtained. An object of the present invention is to provide an A heavy oil composition that can withstand use in high performance engines in recent years and does not cause clogging of the filter by wax in winter.

As a result of intensive studies to solve the above problems, the present inventors have found that by using a specific base material in combination, the combustibility is high and the filter is not clogged with wax in winter. The present invention has been completed.
That is, the present invention comprises an oil to be treated in which a sulfur-containing hydrocarbon compound is mixed with a component derived from animal and vegetable oils and / or animal oils and fats so that the sulfur content is 1 mass ppm to 2 mass% in the presence of hydrogen; A combination of Co-Mo, Ni-Mo, Ni-Co-Mo and Ni-W with a porous inorganic oxide containing alumina and further containing an inorganic oxide selected from silica, titania, zirconia and boria A sulfide catalyst obtained by converting a catalyst carrying an active metal selected from the above to a sulfide state , a hydrogen pressure of 2 to 13 MPa, a liquid space velocity of 0.1 to 3.0 h ⁻¹ , a hydrogen oil ratio of 150 to 1500 NL / L, 50 vol% distillation temperature of 250 to 350 ° C., which is prepared by contacting under conditions of a reaction temperature one hundred and eighty to four hundred eighty ° C., and environmental containing saturates 90 vol% JIS1 species characterized by mixing an A heavy oil base below 99 volume% 1 volume% or more of 1% by volume to 75% by volume and fluid catalytic cracking gas oil in heavy oil A total amount of the composition in fuel oil A total amount of the composition The present invention relates to a method for producing an A heavy oil composition that satisfies heavy oil standards.

  According to the present invention, it is possible to obtain an A heavy oil composition that is highly combustible, can withstand use in recent high-performance engines, and does not cause clogging of the filter by wax in winter.

Hereinafter, the present invention will be described in detail.
As a constituent of the A heavy oil composition of the present invention, in the presence of hydrogen, a sulfur-containing hydrocarbon compound is mixed with a component derived from animal and vegetable oils and / or animal fats so that the sulfur content is 1 mass ppm to 2 mass%. And a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and a periodic table supported on the porous inorganic oxide A sulfide catalyst containing one or more metals selected from Group 6A and Group 8 elements, hydrogen pressure 2-13 MPa, liquid space velocity 0.1-3.0 h-1, hydrogen oil ratio 150- It is necessary to use an environmentally low load type A heavy oil base material and a fluid catalytic cracking light oil produced by contacting under conditions of 1500 NL / L and a reaction temperature of 180 to 480 ° C.

The environmentally low load type A heavy oil base material according to the present invention is a low sulfur and low oxygen fraction obtained by hydrotreating a predetermined raw material oil.
The raw oil must be a component derived from animal and vegetable oils and / or animal fats. The animal and vegetable oils and fats and components derived from animal and vegetable oils and oils in the present invention refer to animal and vegetable oils and fats that are produced and manufactured naturally or artificially, and components that are produced and produced from these oils and fats. Examples of animal fats and animal oils include beef tallow, milk lipid (butter), pork tallow, sheep fat, whale oil, fish oil, liver oil, and the like. Vegetable oil and vegetable oil ingredients include coconut palm, palm palm, olives, Examples include rapeseed (rapeseed), rice bran, sunflower, cottonseed, corn, soybeans, sesame seeds, and other parts of the linseed, but other fats and oils can be used without problems. These raw oils may be solid or liquid, but it is preferable to use vegetable oils and vegetable oils as raw materials because of ease of handling, high carbon dioxide absorption capacity and high productivity. Moreover, in this invention, the waste oil which used these animal oils and vegetable oils for consumer use, industrial use, food use etc. can also be used as a raw material after adding the removal process of miscellaneous matters.

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

  The sulfur-containing hydrocarbon compound contained in the oil to be treated is not particularly limited, and specific examples include sulfides, disulfides, polysulfides, thiols, thiophenes, benzothiophenes, dibenzothiophenes, and derivatives thereof. The sulfur-containing hydrocarbon compound contained in the oil to be treated may be a single compound or a mixture of two or more. Furthermore, a petroleum hydrocarbon fraction containing a sulfur content may be mixed with the oil to be treated.

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

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

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

  The active metal of the hydrogenation catalyst contains at least one metal selected from Group 6A and Group 8 metals of the periodic table, preferably two or more metals selected from Groups 6A and 8 Contains. For example, Co-Mo, Ni-Mo, Ni-Co-Mo, and Ni-W can be mentioned. In hydrogenation, these metals are converted into sulfides and used.

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

  There are no particular limitations on the raw materials that are precursors of silica, titania, zirconia, and boria, which are carrier constituents other than alumina, and general solutions containing silicon, titanium, zirconium, and boron can be used. For example, silicic acid, water glass and silica sol for silicon, titanium sulfate, titanium tetrachloride and various alkoxide salts for titanium, zirconium sulfate and various alkoxide salts for zirconium, and boric acid for boron, etc. it can. As phosphorus, phosphoric acid or an alkali metal salt of phosphoric acid can be used.

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

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

  The reaction temperature can be arbitrarily set in order to obtain the desired decomposition rate of the feedstock heavy fraction or the desired fraction yield. Furthermore, in order to suppress the oxygen content contained in the distillate treated with the hydrotreating catalyst within the above upper limit, the reaction temperature of the hydrotreating catalyst portion and the reaction temperature of the hydrocracking catalyst portion are arbitrarily set, respectively. Can be set to The average temperature of the entire reactor is generally preferably in the range of 180 to 480 ° C, desirably 220 to 400 ° C, more desirably 260 to 360 ° C. When the reaction temperature is less than the lower limit, the reaction may not proceed sufficiently. When the reaction temperature exceeds the upper limit, decomposition proceeds excessively, and the liquid product fraction tends to decrease. is there.

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

  The environment-friendly type A heavy oil base material in the present invention contains a saturated content of 90% by volume or more, preferably 95% by volume or more. If the saturation is less than this range, the ignitability deteriorates when used as off-road diesel engine fuel, which is not preferable.

The fluid catalytic cracking light oil in this invention refers to the light oil fraction obtained from a fluid catalytic cracking apparatus or a residue fluid catalytic cracking apparatus.
In the present invention, fluid catalytic cracking light oil is used as the A heavy oil base material. Specifically, as its distillation properties, the 50% by volume distillation temperature is 200 to 300 ° C., and the density at 15 ° C. is in the range of 850 to 900 kg / m ³ .
The fluid catalytic cracking light oil in the present invention contains 50% by volume or more, preferably 60% by volume or more of an aromatic component. When the aromatic content is less than this range, the low temperature fluidity and the solubility of the residual carbon base material and the fluidity improver added during the winter season are not preferable.

  The blending ratio of the environment-friendly A heavy oil base material constituting the A heavy oil composition of the present invention is not particularly limited. However, in order to fully exert the effect, the environment-friendly A heavy oil base material is used as the A heavy oil composition. It is preferable to use 1% by volume or more, more preferably 20% by volume or more, more preferably 25% by volume or more, particularly preferably 30% by volume or more, and 35% by volume based on the total amount of the product. Most preferably used. However, since the low-temperature performance tends to deteriorate if the blending ratio of the environment-friendly A heavy oil base is increased, it is preferably used at 99% by volume or less, considering the flammability, and is used at 80% by volume or less. More preferably, it is particularly preferably used at 75% by volume or less.

  Moreover, in order to improve low temperature fluidity, and also to improve the solubility of the residual carbon base material and the fluidity improver added during the winter season, it is conceivable to increase the aromatic content of the A heavy oil product. In order to fully exert its effect, the fluid catalytic cracking diesel oil is preferably used in an amount of 1% by volume or more, more preferably 20% by volume or more, more preferably 25% by volume or more based on the total amount of the A heavy oil composition. It is more preferable to use 30% by volume or more. However, if the aromatic content of heavy oil A is increased, the combustibility tends to deteriorate. Therefore, in consideration of combustibility, it is preferably used at 99% by volume or less, more preferably at 80% by volume or less. Preferably, it is used at 75% by volume or less, more preferably 70% by volume or less. .

  Conventionally, as A heavy oil base material, straight-run gas oil fraction obtained from an atmospheric distillation apparatus or desulfurized gas oil fraction thereof, straight-run kerosene fraction or desulfurized kerosene fraction thereof, hydrocracked light oil, hydrocracked kerosene, Desulfurization of denormalized paraffinic light oil fraction, heavy gas oil fraction, and vacuum gas oil, which is the residue from which normal paraffin content has been removed by extraction of residual oil desulfurized gas oil fraction, hydrodesulfurized gas oil fraction or hydrorefined gas oil fraction Light oil and fluid catalytic cracking kerosene. In the present invention, one or more of these may be used in combination with the environmentally low load type A heavy oil base material and the fluid catalytic cracking light oil.

  The type of the residual carbon base material is not particularly limited, and examples thereof include atmospheric residual oil, residual oil desulfurized heavy oil, vacuum residual oil, slurry oil, and extract oil. These may be used alone or in combination of two or more. Use. Here, the atmospheric residual oil is a residual oil obtained by distilling crude oil at atmospheric pressure using an atmospheric distillation apparatus. The residual oil desulfurized heavy oil is a heavy oil obtained when a normal pressure residual oil or a vacuum residual oil is desulfurized in a residual oil desulfurization apparatus. The vacuum residue is a residue obtained by distilling atmospheric residue under reduced pressure using a vacuum distillation apparatus. A slurry oil is a residual oil obtained from a fluid catalytic cracking apparatus. Extract oil is an aromatic component that is not suitable for lubricating oil among the fractions extracted from the vacuum distillation apparatus for lubricating oil raw material by solvent extraction.

  It is necessary that the A heavy oil composition produced by the present invention is an A heavy oil composition that satisfies the JIS class 1 heavy oil standard obtained by using the aforementioned environmentally low load type A heavy oil base material and fluid catalytic cracking light oil.

The A heavy oil composition of the present invention is required to satisfy the JIS Class 1 heavy oil standard. The JIS Class 1 heavy oil standard is a standard that satisfies “one type” specified in JIS K 2205 “Heavy oil”. Specifically, the flash point is 60 ° C. or higher, the pour point is 5 ° C. or lower, and the residual carbon content is 4% by mass. Hereinafter, it is necessary that the kinematic viscosity at 50 ° C. is 20 mm ² / s or less, the sulfur content is 2.0 mass% or less, the water content is 0.3 volume% or less, and the ash content is 0.05% or less.

  The flash point of the A heavy oil composition of the present invention needs to satisfy 60 ° C. or higher, which is a JIS class 1 heavy oil standard. If the flash point is less than 60 ° C., it cannot be handled as a heavy fuel oil composition for safety reasons. For the same reason, the flash point is preferably 61 ° C. or higher, and more preferably 62 ° C. or higher. In the present invention, the flash point means a value obtained in accordance with JIS K 2265 “Crude oil and petroleum products—flash point test method”.

  Moreover, the pour point of the A heavy oil composition of the present invention needs to satisfy 5 ° C. or less which is the JIS class 1 heavy oil standard. Furthermore, it is preferable that it is 2.5 degrees C or less from a viewpoint of low temperature fluidity | liquidity. Here, the pour point means a pour point measured by JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.

  The residual carbon content in the heavy oil composition A of the present invention needs to satisfy 4 mass% or less, which is a JIS class 1 heavy oil standard. Furthermore, it is preferably 3% by mass or less, more preferably 2% by mass or less, from the viewpoint of reducing fine particles and PM and maintaining the performance of the exhaust gas aftertreatment device mounted on the engine. The residual carbon content here means a residual carbon content measured by JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.

  Although there is no restriction | limiting in particular about the 10% residual carbon content of the A heavy oil composition of this invention, From the point of "the residual carbon content of 10% residual oil 0.2 mass% or more" which is a tax exemption condition of A heavy oil on tax law It is desired to be 0.2% by mass or more. However, from the standpoint of preventing filter clogging by sludge, it is preferably 0.8% by mass or less, and more preferably 0.6% by mass or less. The 10% residual carbon content here means the residual carbon content measured by JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.

The kinematic viscosity at 50 ° C. of the heavy oil composition A of the present invention needs to be 20 mm ² / s or less, which is JIS Class 1 heavy oil standard, preferably 18 mm ² / s or less, and 15 mm ² / s or less. It is more preferable that If the kinematic viscosity exceeds 20 mm ² / s, the resistance inside the fuel injection system increases, the injection system becomes unstable, and the concentrations of NOx and PM in the exhaust gas increase. The kinematic viscosity here means the kinematic viscosity measured by JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.

  The sulfur content in the heavy oil composition A of the present invention needs to satisfy 2% by mass or less, which is a JIS class 1 heavy oil standard. Furthermore, from the viewpoint of reducing fine particles and PM, and from the viewpoint of maintaining the performance of the exhaust gas aftertreatment device mounted on the engine, it is preferably 1.5% by mass or less, and more preferably 1% by mass or less. A sulfur content here means the residual carbon content measured by JISK2541 "crude oil and petroleum products-sulfur content test method".

  In the heavy oil A composition of the present invention, the water content needs to satisfy 0.3 vol% or less, which is a JIS class 1 heavy oil standard. Furthermore, from the viewpoint of adverse effects on the member, it is preferably 0.2% by volume or less, and more preferably 0.1% by volume or less. In addition, the water | moisture content said by this invention means the value measured by JISK2275 "moisture test method (crude oil and petroleum products)".

  In the heavy oil A composition of the present invention, the ash content needs to satisfy 0.05 mass% or less, which is a JIS class 1 heavy oil standard. Furthermore, from the viewpoint of reducing fine particles and PM, the content is preferably 0.04% by mass or less, and more preferably 0.03% by mass or less. The ash content in the present invention means a value measured by JIS K 2272 “Crude oil and petroleum product ash content and sulfate ash test method”.

The cetane index of the A heavy oil composition of the present invention is not particularly limited, but the cetane index is preferably 45 or more and more preferably 50 or more from the viewpoint of combustibility. In the present invention, the cetane index means a value obtained in accordance with JIS K 2204-1992 “light oil”. That is, it is calculated by the following formula.
[Cetane index (C) = 0.49083 + 1.06577 (X)-0.0010522 (X) ² ]
[X = 97.833 (log A) ² +2.2088 B log A + 0.01247 B ² −423.51 log A−4.7808 B + 419.59]
A: (9/5) [50% distillation temperature at 101.3 kPa (760 mmHg) (° C.)] + 32
B: API volume (50 volume% distillation temperature (° C.) at 101.3 kPa (760 mmHg) is measured according to JIS K 2254 “Petroleum products-distillation test method”, and the API degree is JIS K 2249 “crude oil and petroleum products— Calculated from the density at 15 ° C. by “density test method and density / mass / capacity conversion table”

  Although there is no restriction | limiting in particular about the cloud point of A heavy oil composition of this invention, It is preferable that it is 7 degrees C or less from the point which reduces wax precipitation at the time of the low temperature which obstruct | occludes the filter for a contaminant prevention in a fuel system | strain. 6 ° C. or lower is more preferable, 5 ° C. or lower is even more preferable, and 4 ° C. or lower is most preferable. In the present invention, the cloud point means a value obtained in accordance with JIS K 2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”.

  The CFPP (clogging point) of the A heavy oil composition of the present invention is not particularly limited, but it is preferably −3 ° C. or lower because it is superior in terms of preventing filter clogging due to wax in winter. It is more preferably −5 ° C. or lower, and most preferably −7 ° C. or lower. In the present invention, CFPP means a value obtained in accordance with JIS K 2288 “Diesel Oil—Clogging Point Test Method”.

  Although there is no restriction | limiting in particular about the correction | amendment clogging point of A heavy oil composition of this invention, Since it is more excellent at the point of prevention of the filter clogging by wax in winter, it is preferable that it is -3 degrees C or less, and -5 degrees C or less It is more preferable that If the corrected clogging point is higher than −3 ° C., the filter clogging of the pump or burner tends to occur in winter, which is not preferable. In addition, the correction clogging point as used in the field of this invention means the value measured by the correction method 4 described in the description of Petroleum Institute standard JPI-5S-47-96 "Low temperature fluidity test method of A heavy oil".

  Further, the nitrogen content of the A heavy oil composition of the present invention is not particularly limited, but in order to reduce harmful substances in the exhaust gas, it is preferably 0.02% by mass or less, and 0.015% by mass or less. More preferably, it is most preferably 0.01% by mass or less. In the present invention, the nitrogen content means a value representing a value obtained according to JIS K 2609 “Crude oil and petroleum products—nitrogen content test method”.

Moreover, although there is no restriction | limiting about the distillation property of A heavy oil composition of this invention, Usually, what satisfy | fills the following property is preferable.
10 vol% distillation temperature (T10): 180-260 ° C
50 volume% distillation temperature (T50): 250-330 degreeC
90 volume% distillation temperature (T90): 300-380 degreeC
In the present invention, the distillation property means a value obtained according to JIS K 2254 “Petroleum products—Distillation test method”.

Although there is no restriction | limiting in particular about the density of A heavy oil composition of this invention, Usually, it is preferable that it is 750-920 kg / m < ³ >. In the present invention, the density means a value obtained based on JIS K 2249 “Crude oil and petroleum products—density test method and density / mass / capacity conversion table”.

  Moreover, an additive can be mix | blended with the A heavy oil composition of this invention as needed. Various additives such as cetane number improvers, antioxidants, stabilizers, dispersants, metal deactivators, microbial disinfectants, auxiliary agents, antistatic agents, discriminating agents, colorants, etc. These additives can be added as appropriate. Among these, it is preferable to add a fluidity improver because it is excellent in the effect of preventing filter clogging by wax in winter. As the fluidity improver, for example, polymer-type additives such as ethylene-vinyl acetate copolymer and ethylene-α-olefin copolymer, oil-soluble dispersant-type additives, and alkersuccinic acid can be used. Moreover, although there is no restriction | limiting about the addition amount of a fluid improvement agent, it is preferable that it is 0.001-0.1 volume% on the basis of A heavy oil composition whole quantity, and is 0.01-0.05 mass%. It is more preferable.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

[Examples 1 and 2 and Comparative Examples 1 to 3]
Each base material (environmentally friendly type A heavy oil base material, fluid catalytic cracking light oil, straight-run gas oil, normal pressure residual oil) having the properties shown in Table 1 is mixed at a volume ratio as shown in each example of Table 2 A heavy oil compositions of Examples 1 and 2 and Comparative Examples 1 to 3 were prepared, and the properties of each of these prepared compositions are shown in Table 2. About each sample oil (each composition), low temperature fluidity performance evaluation and flammability performance evaluation were performed by the following method. The results are shown in Table 3.

(Low temperature fluidity performance evaluation)
A 20 L pail can was prepared as a sample container, and a hole into which the sample suction tube was inserted was provided on the top surface of the pail can. The hole was formed at the midpoint of a straight line connecting the center of the upper surface and the point on the outer periphery. On the other hand, a copper tube having an outer diameter of 10 mm was prepared as a sample suction tube, and one end of the copper tube was connected to the inlet of a filter (Nepon Corporation, code No. 120267) via a silicon rubber tube. Moreover, the outlet of the filter was connected to a suction pump through a copper tube. As the suction pump, a pump capable of adjusting the oil flow rate within a range of 1 to 10 L / hr was used.
Next, about 15 L of a sample (A heavy oil composition) having a temperature of 20 to 25 ° C. is put in the above-mentioned pail can, a lid with a sample suction tube is put in the hole on the top surface of the pail can, and then the pail can and the filter are cooled to a low temperature. The pump was accommodated in a thermostat, the pump was driven, and the pump pressure was adjusted so that the oil flow rate was 9.5 ± 0.2 L / hr. As the low-temperature thermostatic bath, a thermostatic bath having a program temperature adjusting function and capable of cooling to −30 ° C. or less within a temperature system of ± 0.5 ° C. was used. After the pail can and the filter were accommodated in the low-temperature thermostatic chamber, the inside of the low-temperature thermostatic chamber was cooled with a predetermined temperature profile, and the suction pump was driven. More specifically, the sample was cooled from a temperature 8 ° C. higher than the cloud point of the sample to a predetermined temperature at a cooling rate of 1 ° C./hr. The temperature was held for 3 hours, and the oil passage limit was determined by measuring the pressure with a pressure gauge. Judgment of the oil passage limit is accepted when the differential pressure is 33 kPa (250 mmHg) or less during oil passage for 60 minutes at the holding temperature, and is rejected when it exceeds 33 kPa, and held at 1 ° C intervals until it fails. The test was repeated at a lower temperature. The highest temperature (clogging temperature) at which the judgment was rejected was used as an index for evaluating the low temperature performance. In addition, the sample was replaced with new oil for each test. A clogging temperature of -3 ° C. or lower was judged good (◯), and a temperature of −2 ° C. or higher was judged bad (x). The obtained results are shown in Table 3.

(Flammability performance evaluation)
The combustion performance was evaluated by measuring the ignition delay by the following method. Ignition delay adversely affects engine performance and exhaust gas, and is a major cause of trouble in recent high-performance engines. Using a fuel ignitability tester having a combustion chamber volume of 1 liter, fuel was injected into air having a pressure of 45 barrels and a temperature of 450 ° C., and the time from injection to ignition was measured as the ignition delay time. An ignition delay time of 5 ms or less was judged as good (◯), and 5 ms or more was judged as bad (x). The obtained results are shown in Table 3.

  As is apparent from the results in Table 3, the A heavy oil compositions of Examples 1 and 2 according to the present invention are both excellent in ignitability and excellent in combustibility, have sufficient performance for recent high-performance engines, and are excellent. It can be seen that the filter has excellent oil passing performance at low temperatures.

Claims (5)

In the presence of hydrogen, to-be-treated oil obtained by mixing a sulfur-containing hydrocarbon compound with a component derived from animal and vegetable oils and / or animal fats so that the sulfur content is 1 mass ppm to 2 mass%, alumina, and silica An active metal selected from a combination of Co—Mo, Ni—Mo, Ni—Co—Mo and Ni—W is included in the porous inorganic oxide including an inorganic oxide selected from titania, zirconia and boria. A sulfide catalyst obtained by converting the supported catalyst into a sulfide state is a hydrogen pressure of 2 to 13 MPa, a liquid space velocity of 0.1 to 3.0 h ⁻¹ , a hydrogen oil ratio of 150 to 1500 NL / L, a reaction temperature of 180 to 50 vol% distillation temperature of 250 to 350 ° C., which is prepared by contacting under conditions of 480 ° C., and a heavy oil environment-a heavy oil base containing saturates 90 vol% A fuel oil composition satisfying the JIS1 or heavy oil standard, which comprises mixing 1 volume% to 75 volume% or less and fluid catalytic cracking gas oil below 99 volume% 1 volume% or more in heavy oil A total amount of the composition in Narubutsu total amount Manufacturing method . The total content of inorganic oxides other than alumina in the porous inorganic oxide is 1 to 20% by weight, A method for producing an A heavy oil composition that satisfies the JIS Class 1 heavy oil standard according to claim 1 . 2. The sulfur-containing hydrocarbon compound is sulfide, disulfide, polysulfide, thiol, thiophene, benzothiophene, dibenzothiophene, derivatives thereof, or petroleum-based hydrocarbon fraction containing a sulfur content. The manufacturing method of A heavy oil composition which satisfy | fills JIS class 1 heavy oil specification of description. Method for producing heavy oil A composition satisfying JIS1 or heavy oil standard of claim 1, 50 vol% distillation temperature of the fluidized catalytic cracking gas oil is characterized by a 200 to 300 [° C.. Method for producing heavy oil A composition satisfying JIS1 or heavy oil standard of claim 1, fluid catalytic cracking gas oil is characterized by the early days containing the aromatic content of 50 vol% or more.