Fuel oil composition for internal combustion engines and method for producing the same

Abstract

To provide a fuel oil composition for an internal combustion engine and a method for producing the same, wherein the fuel oil composition for the internal combustion engine makes effective use of an ethylene bottom oil and satisfies extremely strict requirements for oil passage performance and storage stability performance, while also satisfying other performances, that is, combustion performance, environmental performance and lubrication performance.SOLUTION: A fuel oil composition for an internal combustion engine comprises a specific content of animal and vegetable oils and ethylene bottom oil that satisfy specific properties, the composition satisfies (1) a sulfur content of 0.400 mass% or less, (2) a kinematic viscosity at 50°C of 50.0 mm2 / s or more to 100.0 mm2 / s or less, (3) a CCAI of 835 or less, and (4) a latent sediment of 0.10 mass% or less, and furthermore, a production method uses the fuel oil composition for the internal combustion engine.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a fuel oil composition for internal combustion engines and a method for producing the same. [Background technology]

[0002] Class 3 heavy oil of JIS K2205:2006 (hereinafter also referred to as "C heavy oil") has a higher calorific value per unit volume than kerosene, light oil, and Class A heavy oil (Class 1 heavy oil of JIS K2205:2006), and can reduce the amount (volume) of fuel oil used. It is also inexpensive, so it is widely used as fuel oil for internal combustion engines such as marine diesel engines, and as fuel oil for external combustion engines such as power generation boilers. On the other hand, C heavy oil generally has a higher sulfur content and carbon residue than kerosene, diesel, A heavy oil, etc., and is known to have a greater environmental impact and to be more prone to sludge generation, which is likely to cause clogging of fuel oil filters. In response to this, C heavy oil compositions have been proposed that contain desulfurized fractions such as desulfurized kerosene and light cycle oil, and undesulfurized diesel fractions, with 15°C density, 50°C kinematic viscosity, carbon residue, asphaltene content, sulfur content, and aromatic content falling within specified ranges (see, for example, Patent Document 1). Other proposed compositions include C heavy oil compositions containing vegetable oil, slurry oil, vacuum residue, etc. (see, for example, Patent Document 2), and C heavy oil compositions blended with hydrotreated ethylene bottom oil (see, for example, Patent Document 3).

[0003] Known marine fuel oils include fuel oils that satisfy ISO 8217 "Petroleum products - Fuels (class F) - Specification of marine fuels." Because such marine fuel oils can clog fuel oil filters, heavy oil compositions have been proposed that contain a specified amount of directly desulfurized heavy oil that has specified properties such as sulfur content, carbon residue content, asphaltene content, density at 15°C, and total sediment by hot filtration (ISO 10307-1) (see, for example, Patent Document 4). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-203802 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-227933 [Patent Document 3] Japanese Patent Application Laid-Open No. 2012-012460 [Patent Document 4] Japanese Patent Application Laid-Open No. 2014-028977 Summary of the Invention [Problem to be solved by the invention]

[0005] However, even when the internal combustion engine fuel oil composition having the improved oil passing performance is used, particularly when the internal combustion engine fuel oil composition is used in a large diesel engine such as a diesel engine for a large ship, the frequency of clogging of the fuel oil filter tends to increase during normal use, and the frequency of clogging tends to be even higher when used after long-term storage in a fuel oil tank on the ship. Therefore, internal combustion engine fuel oil compositions are required to have storage stability performance that maintains room temperature oil passing performance, especially even after long-term storage, and the required performance is becoming more strict. In addition, marine diesel engines for such large ships and the like sometimes employ a type equipped with a centrifugal separator as a pretreatment device for the fuel oil composition, and this type of diesel engine requires particularly strict storage stability performance.

[0006] In particular, when used in large diesel engines such as those on large ships, the environment in which internal combustion engine fuel oil compositions are used changes significantly, and therefore internal combustion engine fuel oil compositions are required to adapt to these changes in the environment. Among these, it is important to have ignition performance without ignition delay and stable combustion performance (sometimes collectively referred to as "combustion performance"). The C heavy oil composition described in Patent Document 2 has been proposed as having excellent ignition and combustion properties. However, its CCAI (Calculated Carbon Aromaticity Index) is high at 860 and 872, respectively, and does not satisfy the combustion performance required in recent years.

[0007] In recent years, preventing environmental pollution has been cited as one of the most important global issues, and as part of its air pollution prevention measures, the International Maritime Organization (IMO) has strengthened regulations requiring all ships to have a sulfur content in fuel oil of 0.5 mass% or less, down from the current 3.5 mass% or less, starting in 2020. Therefore, there is an urgent need to reduce the sulfur content of marine fuel oil compositions to 0.5 mass% or less, thereby improving environmental performance and reducing the burden on the environment. However, the sulfur contents of the C heavy oil compositions described in Patent Document 1 all exceed 2 mass%, and the sulfur content of the C heavy oil composition described in Patent Document 2 is 1.3 to 1.5 mass%, which are unsatisfactory in terms of environmental performance.

[0008] In addition to the above performance, viscosity suitability, i.e., a suitable kinematic viscosity, is also required. As described in Patent Document 1, a method of using a desulfurized light oil fraction such as desulfurized light oil is available as a method for obtaining a product equivalent to heavy oil C. The use of a desulfurized light oil fraction can reduce the sulfur content. On the other hand, the use of a desulfurized light oil fraction results in a too low kinematic viscosity, which makes the composition incompatible with the range of use of various devices, such as pumps and flow meters, for delivering the fuel oil composition to engines, and is also one of the factors that deteriorate the lubrication performance.

[0009] The C heavy oil composition described in Patent Document 3 is an effective means for effectively utilizing ethylene bottom oil. Ethylene bottom oil is a fraction (bottom oil) produced in an ethylene production plant in which feedstock oil such as naphtha fraction is thermally cracked together with steam to produce ethylene, propylene, etc. This ethylene bottom oil has a strong odor and poor ignition properties and stability, so it has no uses other than as a fuel oil for boilers, etc., and is becoming surplus in plant facilities such as refineries that do not have boiler equipment.

[0010] However, the method described in Patent Document 3 requires hydrotreating ethylene bottom oil, which can disrupt the supply and demand balance of hydrogen within plant facilities and can make the process more expensive. Furthermore, the sulfur content of the C heavy oil composition described in Patent Document 3 is 2.62 to 2.88 mass%, so like the C heavy oil compositions described in Patent Documents 1 and 2, it cannot be said to be satisfactory in terms of environmental performance.

[0011] Thus, conventional heavy oil C and the above-mentioned fuel oil compositions for internal combustion engines with improved oil permeability cannot be said to fully satisfy all of these performance requirements. Furthermore, in applications where particularly strict storage stability performance is required, such as marine diesel engines equipped with a centrifugal separator as a pretreatment device for the fuel oil composition, it is extremely difficult to simultaneously satisfy all of these performance requirements. Under these circumstances, an object of the present invention is to provide a fuel oil composition for internal combustion engines that effectively utilizes ethylene bottom oil, meets extremely strict requirements for oil passing performance and storage stability, and also satisfies other performance requirements, namely, combustion performance, environmental performance, and lubrication performance, and a method for producing the same. [Means for solving the problem]

[0012] The present inventors have conducted extensive research in light of the above problems and have found that the following invention can solve the problems. That is, the present invention provides a fuel oil composition for internal combustion engines having the following configurations and a method for producing the same.

[0013] 1. A fuel oil composition for internal combustion engines, comprising an animal or vegetable oil that satisfies both of the following (a1) and (a2), and an ethylene bottom oil that satisfies all of the following (b1) to (b3), wherein the content of the animal or vegetable oil, based on the total volume of the composition, is 15.0% by volume or more and 35.0% by volume or less, and the content of the ethylene bottom oil, based on the total volume of the composition, is 0.20 times or more the content of the animal or vegetable oil, based on the total volume of the composition, and the composition satisfies all of the following (1) to (4): (a1) Sulfur content is 0.02% by mass or less (a2) Kinematic viscosity at 50°C is 20.0 mm 2 / s or more 50.0mm 2 / s or less (b1) Sulfur content is 0.30% by mass or less (b2) Kinematic viscosity at 50°C is 10.0 mm 2 / s or more 50.0mm 2 / s or less (b3) Aromatic content is 80.0% by volume or more (1) Sulfur content is 0.400% by mass or less (2) Kinematic viscosity at 50°C is 50.0 mm 2 / s or more 100.0mm 2 / s or less (3) CCAI is 835 or less (4) Potential sediment is 0.10% by mass or less 2. A fuel oil composition for internal combustion engines according to item 1 above, further comprising a directly desiccant heavy oil fraction that satisfies both of the following (c1) and (c2), wherein the content of the directly desiccant heavy oil fraction based on the total amount of the components is 50.0% by volume or more and 70.0% by volume or less. (c1) Sulfur content is 0.50% by mass or more and 0.60% by mass or less (c2) Kinematic viscosity at 50°C is 100.0 mm 2 / s or more 200.0mm 2 / s or less 3. The fuel oil composition for internal combustion engines according to 1 or 2 above, which is used in a marine diesel engine equipped with a centrifugal separator as a pretreatment device. 4. Animal and vegetable oils that satisfy both the following (a1) and (a2); and an ethylene bottom oil satisfying all of the following (b1) to (b3), The content of the animal and vegetable oil based on the total amount of the composition is 15.0% by volume or more and 35.0% by volume or less, The ethylene bottom oil is mixed so that the content of the ethylene bottom oil based on the total amount of the composition is 0.20 times or more the content of the animal and vegetable oil based on the total amount of the composition. A method for producing a fuel oil composition for internal combustion engines, which satisfies all of the following (1) to (4): (a1) Sulfur content is 0.02% by mass or less (a2) Kinematic viscosity at 50°C is 20.0 mm 2 / s or more 50.0mm 2 / s or less (b1) Sulfur content is 0.30% by mass or less (b2) Kinematic viscosity at 50°C is 10.0 mm 2 / s or more 50.0mm 2 / s or less (b3) Aromatic content is 80.0% by volume or more (1) Sulfur content is 0.400% by mass or less (2) Kinematic viscosity at 50°C is 50.0 mm 2 / s or more 100.0mm 2 / s or less (3) CCAI is 835 or less (4) Potential sediment is 0.10% by mass or less 5. A method for producing a fuel oil composition for internal combustion engines according to 4 above, further comprising mixing a directly decomposed heavy oil fraction that satisfies both of the following (c1) and (c2) so that the content of the fraction based on the total amount of the composition is 50.0% by volume or more and 70.0% by volume or less: (c1) Sulfur content is 0.50% by mass or more and 0.60% by mass or less (c2) Kinematic viscosity at 50°C is 100.0 mm 2 / s or more 200.0mm 2 / s or less [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a fuel oil composition for internal combustion engines that effectively utilizes ethylene bottom oil, meets extremely strict requirements for oil passing performance and storage stability, and also satisfies other performance requirements, namely, combustion performance, environmental performance, and lubrication performance, and a method for producing the same. DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, a fuel oil composition for internal combustion engines according to an embodiment of the present invention (hereinafter, sometimes simply referred to as "the present embodiment") will be specifically described. Note that the present invention is not limited to the following embodiment, and can be practiced with any modifications within the scope that does not impair the effects of the invention. In addition, in this specification, the numerical values associated with "greater than or equal to," "less than or equal to," and "to" in describing a numerical range are numerical values that can be arbitrarily combined. For example, when a certain numerical range is described as "A to B" and "C to D," the numerical ranges "A to D" and "C to B" are also included.

[0016] [Fuel oil composition for internal combustion engines] The fuel oil composition for internal combustion engines of this embodiment comprises an animal or vegetable oil that satisfies both of the following (a1) and (a2), and an ethylene bottom oil that satisfies all of the following (b1) to (b3), wherein the content of the animal or vegetable oil, based on the total volume of the composition, is 15.0 vol% or more and 35.0 vol% or less, and the content of the ethylene bottom oil, based on the total volume of the composition, is 0.20 times or more the content of the animal or vegetable oil, based on the total volume of the composition, and satisfies all of the following (1) to (4): (a1) Sulfur content is 0.02% by mass or less (a2) Kinematic viscosity at 50°C is 20.0 mm 2 / s or more 50.0mm 2 / s or less (b1) Sulfur content is 0.30% by mass or less (b2) Kinematic viscosity at 50°C is 10.0 mm 2 / s or more 50.0mm 2 / s or less (b3) Aromatic content is 80.0% by volume or more (1) Sulfur content is 0.400% by mass or less (2) Kinematic viscosity at 50°C is 50.0 mm 2 / s or more 100.0mm 2 / s or less (3) CCAI is 835 or less (4) Potential sediment is 0.10% by mass or less

[0017] (Composition and properties of fuel oil composition for internal combustion engines) The fuel oil composition for internal combustion engines of this embodiment satisfies the composition and properties specified in the following (1) to (4).

[0018] (1) Sulfur content The sulfur content of the fuel oil composition for internal combustion engines of this embodiment is 0.400% by mass or less. If the sulfur content exceeds 0.400% by mass, the increase in sulfur oxides in exhaust gas increases the burden on the environment, thereby reducing environmental performance, and the increase in acid dew point makes acid dew point corrosion more likely to occur. From the viewpoint of improving environmental performance and suppressing the occurrence of corrosion, the sulfur content is preferably 0.395% by mass or less, more preferably 0.385% by mass or less, even more preferably 0.380% by mass or less, and even more preferably 0.375% by mass or less. Furthermore, from the viewpoint of environmental performance, the lower the sulfur content, the better. As described above, the sulfur content is usually 0.010% by mass or more. In consideration of the ease of production of the fuel oil composition of this embodiment, the sulfur content is preferably 0.050% by mass or more, more preferably 0.100% by mass or more. In this specification, the sulfur content is measured by selecting a measurement method depending on the content, and when the content is 0.01 to 5 mass%, it is a value measured in accordance with JIS K 2541-4:2003 (Crude oil and petroleum products - Determination of sulfur content - Part 4: Radioactive excitation method).

[0019] (2) Kinematic viscosity at 50°C The kinematic viscosity of the fuel oil composition for internal combustion engines of this embodiment at 50°C is 50.0 mm 2 / s or more 100.0mm 2 / s or less. If the kinematic viscosity at 50°C is not within the above range, it may be difficult to adapt the composition to the range of use of various devices such as pumps and flow meters, the lubricating performance may not be ensured, and the composition may not be usable as a fuel oil composition for internal combustion engines. Furthermore, there may be cases where the combustion performance is reduced, the handling properties are reduced, and the heating temperature at the engine inlet is reduced. To make it easier to fit into the range of use of the above various equipment, and to improve lubrication and combustion performance, as well as ease of handling, the kinematic viscosity at 50°C is 95.0mm. 2 / s or less, preferably 90.0 mm 2 / s or less, more preferably 85.0 mm 2 / s or less, and even more preferably 80.0 mm 2 / s or less, and the lower limit is preferably 55.0 mm 2 / s or more, preferably 60.0 mm 2 / s or more. In this specification, the kinematic viscosity at 50°C is a value measured in accordance with JIS K 2283:2000 (Testing method for kinematic viscosity of crude oil and petroleum products).

[0020] (3) CCAI: Calculated Carbon Aromaticity Index The CCAI of the fuel oil composition for internal combustion engines of this embodiment is 835 or less. If the CCAI is greater than 835, combustion performance will decrease. From the viewpoint of improving combustion performance, the CCAI is preferably 833 or less, more preferably 830 or less, and even more preferably 825 or less. The lower limit is not particularly limited, and is usually 750 or more, 775 or more, or 800 or more, from the viewpoint of combustion performance. In this specification, CCAI is a value calculated using the calculation formula described in Annex F of ISO 8217-2012.

[0021] (4) Potential sediment The latent sediment content of the fuel oil composition for internal combustion engines of this embodiment is 0.10% by mass or less. If the latent sediment content is greater than 0.10% by mass, storage stability will decrease. From the viewpoint of improving storage stability, the latent sediment content is preferably 0.09% by mass or less, more preferably 0.08% by mass or less. Furthermore, the lower limit is preferably as low as possible from the viewpoint of storage stability, and although there are no particular restrictions, it is usually 0.01% by mass or more. In this specification, the total sediment potential is defined as the amount of sludge remaining on a filter paper obtained by leaving a sample (the fuel oil composition for internal combustion engines of the present embodiment) at 100°C for 24 hours and passing it through the filter paper, in accordance with ISO10307-2A (Thermal Aging).

[0022] Furthermore, in addition to the properties and composition of (1) to (4) above, the fuel oil composition for internal combustion engines of this embodiment preferably further satisfies at least one selected from the following properties (5) to (12), and it is particularly preferable that it satisfies all of the following properties (5) to (12):

[0023] (5) Carbon residue The carbon residue content of the fuel oil composition for internal combustion engines of this embodiment is preferably 5.0% by mass or less, more preferably 4.9% by mass or less, even more preferably 4.7% by mass or less, and even more preferably 4.5% by mass or less, and although there is no particular lower limit, it is usually 0.1% by mass or more. If the carbon residue content is within the above range, the combustion performance of the fuel oil composition for internal combustion engines is improved, and the effect of reducing soot generation due to poor combustion is improved, allowing for more stable operation of the internal combustion engine. In this specification, the carbon residue is a value measured in accordance with JIS K 2270-1:2009 (Crude oil and petroleum products - Determination of carbon residue - Part 1: Conradson method).

[0024] (6) Filtration time gradient The slope of the filtration time of the fuel oil composition for internal combustion engines of this embodiment is preferably 0.12 or less, more preferably 0.10 or less, even more preferably 0.07 or less, and still more preferably 0.60 or less. There is no particular lower limit, and the smaller the value, the better, and it is usually 0.01 or more. The slope of the filtration time (Tn) is a value calculated based on the calculation method for the slope of the filtration time (Tn) described in the Examples.

[0025] (7) Density at 15°C The density of the fuel oil composition for internal combustion engines of this embodiment at 15°C is preferably 0.9300 g / cm3 or more, more preferably 0.9320 g / cm 3 More preferably, 0.9350 g / cm 3 The upper limit is preferably 0.9600 g / cm 3 or less, more preferably 0.9580 g / cm 3 or less, more preferably 0.9550 g / cm 3 If the density at 15°C is within the above range, the sludge separation performance in a centrifugal separator installed as a pre-treatment device before a diesel engine for a large ship or the like is improved, and the oil passing performance and storage stability are improved. In addition, the gross calorific value is also improved. In this specification, the density at 15°C is a value measured in accordance with JIS K 2249-1:2011 (Crude oil and petroleum products - Determination of density - Part 1: vibration method).

[0026] (8) Flash point The flash point of the fuel oil composition for internal combustion engines of this embodiment is preferably 70.0°C or higher, more preferably 90.0°C or higher, even more preferably 110.0°C or higher, still more preferably 120.0°C or higher, and particularly preferably 130.0°C or higher. If the flash point is within the above range, handling safety is improved. There is no particular upper limit, but it is usually 200.0°C or lower. In this specification, the flash point is a value measured in accordance with JIS K 2265-3:2007 (Crude oil and petroleum products - Flash point test method - Part 3: Pensky-Martens closed-cell method).

[0027] (9) Pour point The pour point of the fuel oil composition for internal combustion engines of this embodiment is preferably 20.0° C. or lower, more preferably 15.0° C. or lower, and even more preferably 12.5° C. or lower. A pour point of 20.0° C. or lower improves the flowability of the fuel oil composition in tanks, piping, etc. at low temperatures. The lower the pour point, the better, and there is no particular restriction on the lower limit, but it is usually about −10.0° C. or higher. In this specification, the pour point is a value measured in accordance with JIS K 2269:1987 (Testing method for pour point and cloud point of crude oil and petroleum products).

[0028] (10) Moisture content The water content of the fuel oil composition for internal combustion engines of this embodiment is preferably 0.20% by volume or less, more preferably 0.15% by volume or less, and even more preferably 0.10% by volume or less. If the water content is within the above range, a decrease in storage stability (sludge formation due to an emulsion of asphaltene and water) can be suppressed, and clogging due to sludge can be prevented. The lower limit is preferably as low as possible, and is not particularly limited, and may be 0.0% by volume. In this specification, the water content is a value measured in accordance with JIS K 2275-3:2015 (Crude oil and petroleum products - Determination of water content - Part 3: Karl Fischer coulometric titration method).

[0029] (11)Ash content The ash content of the fuel oil composition for internal combustion engines of this embodiment is preferably 0.020% by mass or less, more preferably 0.015% by mass or less, and even more preferably 0.010% by mass or less. When the ash content is within the above range, storage stability and combustion performance are improved, and wear of cylinders, nozzles, etc. can be further suppressed, thereby reducing the environmental load caused by exhaust gases. In this specification, the ash content is a value measured in accordance with JIS K 2272:1998 (Crude oil and petroleum products - Testing method for ash content and sulfated ash content).

[0030] (12) Total heat generation The total calorific value of the fuel oil composition for internal combustion engines of this embodiment is preferably 40,000 (kJ / L) or more, more preferably 40,500 (kJ / L) or more, even more preferably 41,000 (kJ / L) or more, and still more preferably 41,400 (kJ / L) or more. If the total calorific value is within the above range, the amount of fuel oil composition used can be reduced, thereby improving fuel economy. In this specification, the gross calorific values of animal and vegetable oils, desulfurized gas oil fractions, and cracked gas oil fractions were measured in accordance with JIS K2279:2003 (Crude oil and petroleum products - Calorific value test methods and calculation-based estimation methods) and estimated (estimated using the calculation formula for crude oil, kerosene, gas oil, A-type heavy oil, and B-type heavy oil specified in "6. Gross calorific value estimation method, 6.3 e)1)"). In addition, the gross calorific values of fuel oil compositions, ethylene bottom oils, directly desulfurized heavy oil fractions, and cracked heavy oil fractions were measured in accordance with JIS K2279:2003 (Crude oil and petroleum products - Calorific value test methods and calculation-based estimation methods) and estimated (estimated using the calculation formula for C-type heavy oil specified in "6. Gross calorific value estimation method, 6.3 e)1)".

[0031] (animal and vegetable oil) The fuel oil composition for internal combustion engines of this embodiment contains an animal or vegetable oil that satisfies both of the following (a1) and (a2) in an amount of 15.0% by volume or more and 35.0% by volume or less based on the total volume of the composition. If the animal or vegetable oil is not contained in the above-mentioned amount, excellent storage stability and combustion performance cannot be obtained in relation to the ethylene bottom oil that is used in combination with the animal or vegetable oil. (a1) Sulfur content is 0.02% by mass or less (a2) Kinematic viscosity at 50°C is 20.0 mm 2 / s or more 50.0mm 2 / s or less

[0032] The "animal and vegetable oil" used in this embodiment includes "animal oil" derived from animals and "vegetable oil" derived from plants. In the fuel oil composition of this embodiment, either "animal oil" or "vegetable oil" can be used as the "animal and vegetable oil". For example, a single "animal oil" or multiple types of "animal oil" can be used, a single "vegetable oil" or multiple types of "vegetable oil" can be used, or a combination of "animal and vegetable oil" and "vegetable oil" can be used. First, we will explain the "vegetable oil" that can be included in "animal and vegetable oil."

[0033] (vegetable oil) The term "vegetable oil" used in this embodiment refers to plant-derived oils and fats obtained by squeezing, extracting, refining, etc., lipids contained in plants, and hydrocarbon fractions derived from plant-derived oils and fats. More specifically, examples include crude oil obtained by squeezing and extracting natural vegetable oil raw materials; refined oils that have undergone various refining processes, such as filtration to remove suspended impurities contained in crude oil, degumming to remove phospholipids, deacidification to remove free fatty acids, bleaching to remove pigments, and dewaxing to remove wax; and processed oils and fats that have undergone processes such as hardening, fractionation, interesterification, and hydrogenation. Furthermore, triglycerides artificially synthesized by esterification of fatty acids with glycerin, the main component of vegetable oil (which typically accounts for 95 to 98% by mass of vegetable oil), may also be used. In this embodiment, the vegetable oil may be any of the above-mentioned crude oil, refined oil, processed oils and fats, etc., but considering the quality and cost as a fuel oil composition, crude oil and refined oil are preferred, and among refined oils, refined oil obtained by removing suspended impurities contained in crude oil by filtration is preferred. In addition, (a1) and (a2) and other properties (a3) to (a4) described later are also suitable. 15 ) properties.

[0034] Examples of vegetable oils obtained from natural plants include those obtained from vegetable oil raw materials such as seeds such as soybeans, rapeseeds, flaxseeds, safflower seeds, sunflower seeds, palm kernels, cottonseeds, grape seeds, pumpkin seeds, camellia seeds, tea seeds, borage seeds, perilla seeds, sesame seeds, perilla seeds, and cacao; nuts such as coconuts, macadamia nuts, hazelnuts, walnuts, and peanuts; fruit pulp such as olives, palm kernels, and avocados; and by-products such as soybean germ, wheat germ, and corn germ, as well as rice bran.

[0035] In this embodiment, the vegetable oil can be any oil selected from the above vegetable oil raw materials without any particular limitations. In consideration of the ease of obtaining vegetable oils that satisfy both (a1) and (a2) below, and the quality and cost as a fuel oil composition, palm oil obtained from at least one of palm kernel and palm oil, rapeseed oil, soybean oil, coconut oil, etc. are preferred. In addition, the vegetable oils that satisfy (a1) and (a2) below and other properties (a3) to (a4) are also preferred. 15) properties.

[0036] Although vegetable oils may have different names depending on the part of a plant that is the vegetable oil raw material, in this specification, they are treated as belonging to the oils bearing the name of the plant that is the vegetable oil raw material, regardless of which part is used. Furthermore, as mentioned above, oils obtained by separating the main components (glyceride compounds) through a refining process may have different names depending on the main components, but in this specification they are treated as belonging to the oils bearing the name of the plant that is the vegetable oil raw material.

[0037] For example, palm oil in the narrow sense refers to vegetable oil obtained from the fruit (flesh) of the palm tree, but vegetable oil obtained from the fruit (flesh) is also sometimes called palm oil, and vegetable oil obtained from the palm kernel (the seed part of the palm tree) is sometimes called palm kernel oil. Thus, even when palm is used as the vegetable oil raw material, the name may differ depending on which part of the palm tree is used. In this specification, both palm kernel oil and palm oil are treated as belonging to the palm oil category. Furthermore, fractionated glyceride compounds composed of oleic acid contained in palm oil and fractionated glycerides composed of stearic acid are sometimes called palm olein and palm stearin, respectively. In this specification, these fractionated oils such as palm olein and palm stearin are also considered to belong to palm oil.

[0038] The oil components contained in these vegetable oils are glyceride compounds, and although it is difficult to generalize as their content can vary depending on the type of vegetable oil raw material and manufacturing method, it is usually 95 to 98 mass% based on the total amount of vegetable oil. Glyceride compounds are ester compounds of saturated or unsaturated fatty acids and glycerin, and the glyceride compounds contained in vegetable oils vary depending on the vegetable oil raw material. The saturated or unsaturated fatty acids that make up the glyceride compounds are usually saturated or unsaturated fatty acids with 6 to 22 carbon atoms.

[0039] Among the above vegetable oils, the most preferred ones, namely palm oil, rapeseed oil, soybean oil and coconut oil, will be described below with regard to the composition of fatty acids constituting the glyceride compounds contained in these vegetable oils.

[0040] The glyceride compounds contained in palm oil (a vegetable oil obtained from the flesh of palm palms) cannot be generalized because they can vary depending on the origin and variety of palm, as well as the manufacturing method, but the fatty acid composition that makes up the glyceride compounds is usually 0.5 to 1.5 mass% myristic acid (14 carbon atoms, saturated acid), 40.0 to 50.0 mass% palmitic acid (16 carbon atoms, saturated acid), and palmitoleic acid. (C16, unsaturated acid) is 0.1 to 1.5% by mass, stearic acid (C18, saturated acid) is 1.5 to 4.0% by mass, oleic acid (C18, unsaturated acid) is 35.0 to 45.0% by mass, linoleic acid (C18, unsaturated acid) is 5.0 to 12.5% by mass, linolenic acid (C18, unsaturated acid) is 0.5 to 1.5% by mass, and arachidic acid (C20, saturated acid) is 0.01 to 1.0% by mass. The fatty acid composition of the glyceride compounds contained in palm kernel oil (a vegetable oil obtained from the seeds of palm palms) is typically 1.5 to 2.5 mass% caprylic acid (8 carbon atoms, saturated acid), 2.0 to 3.5 mass% capric acid (10 carbon atoms, saturated acid), 45.0 to 55.0 mass% lauric acid (12 carbon atoms, saturated acid), 10.0 to 20.0 mass% myristic acid (14 carbon atoms, saturated acid), 5.0 to 10.0 mass% palmitic acid (16 carbon atoms, saturated acid), 1.5 to 3.5 mass% stearic acid (18 carbon atoms, saturated acid), 15.0 to 22.5 mass% linoleic acid (18 carbon atoms, unsaturated acid), and 1.0 to 3.0 mass% linolenic acid (18 carbon atoms, unsaturated acid).

[0041] The glyceride compounds contained in rapeseed oil cannot be generalized because they vary depending on the origin and variety of rapeseed (for example, native species, low erucic acid species, etc.), the manufacturing method, etc., but the fatty acid composition that makes up the glyceride compounds in native species is usually palmitic acid (16 carbon atoms, saturated acid) 2.0 to 5.0 mass%, palmitoleic acid (16 carbon atoms, unsaturated acid) 0.1 to 0.5 mass%, stearic acid (18 carbon atoms, saturated acid) 0.5 to 2.0 mass%, oleic acid (18 carbon atoms, unsaturated acid) 0.5 to 2.0 mass%, acid) is 10.0 to 20.0% by mass, linoleic acid (18 carbon atoms, unsaturated acid) is 10.0 to 20.0% by mass, the sum of linolenic acid (18 carbon atoms, unsaturated acid), octadecatetraenoic acid (18 carbon atoms, unsaturated acid) and arachidic acid (20 carbon atoms, saturated acid) is 7.5 to 12.5% by mass, gondoic acid (20 carbon atoms, unsaturated acid) is 5.0 to 12.0% by mass, behenic acid (22 carbon atoms, saturated acid) is 0.5 to 1.0% by mass, and erucic acid (22 carbon atoms, unsaturated acid) is 35.0 to 45.0% by mass. In addition, in the case of low erucic acid species, palmitic acid (carbon number 16, saturated acid) is usually 2.5 to 7.0 mass%, palmitoleic acid (carbon number 16, unsaturated acid) is 0.1 to 0.6 mass%, stearic acid (carbon number 18, saturated acid) is 0.0 to 2.5 mass%, (carbon number 18, unsaturated acid) is 50.0 to 60.0 mass%, linoleic acid (carbon number 18, unsaturated acid) is 15.0 to 25.0 mass%, linolenic acid (carbon number 18, unsaturated acid) is 15.0 to 25.0 mass%, The total of octadecatetraenoic acid (18 carbon atoms, unsaturated acid), octadecatetraenoic acid (18 carbon atoms, unsaturated acid), arachidic acid (20 carbon atoms, saturated acid) is 7.5 to 12.5 mass%, gondoic acid (20 carbon atoms, unsaturated acid) is 1.0 to 7.0 mass%, behenic acid (22 carbon atoms, saturated acid) is 0.1 to 1.0 mass%, and erucic acid (22 carbon atoms, unsaturated acid) is 3.0 to 7.5 mass%.

[0042] The glyceride compounds contained in soybean oil cannot be generalized because they can vary depending on the origin and variety of soybeans, the manufacturing method, etc., but the fatty acid composition that makes up the glyceride compounds is usually 8.0 to 15.0 mass% palmitic acid (16 carbon atoms, saturated acid), 2.0 to 6.0 mass% stearic acid (18 carbon atoms, saturated acid), 15.0 to 25.0 mass% oleic acid (18 carbon atoms, unsaturated acid), 50.0 to 60.0 mass% linoleic acid (18 carbon atoms, unsaturated acid), and 5.0 to 12.5 mass% linolenic acid (18 carbon atoms, unsaturated acid).

[0043] The glyceride compounds contained in coconut oil (palm oil) cannot be generalized because they can vary depending on the origin and variety of coconut, the manufacturing method, etc., but the fatty acid composition that makes up the glyceride compounds is as follows: caprylic acid (8 carbon atoms, saturated acid) 4.0 to 7.5 mass%, capric acid (10 carbon atoms, saturated acid) 5.0 to 8.0 mass%, lauric acid (12 carbon atoms, saturated acid) 47.5 to 55.0 mass%, myristic acid (14 carbon atoms, saturated acid) 15.0 to 20.0 mass%, palmitic acid (16 carbon atoms, saturated acid) 5.0 to 10.0 mass%, stearic acid (18 carbon atoms, saturated acid) 1.0 to 5.0 mass%, and oleic acid (18 carbon atoms, unsaturated acid) 0.5 to 2.0 mass%.

[0044] The vegetable oil may contain one or more of the above glyceride compounds artificially synthesized by esterification of fatty acids with glycerin.

[0045] (animal oil) Examples of the "animal oil" used in this embodiment include oils derived from mammals such as beef tallow, lard, mutton tallow, horse oil, and mink oil, oils derived from birds such as chicken oil, and fats from aquatic animals such as fish (e.g., cod, herring, tuna, sardines, saury, mackerel, etc.), dolphins, whales, sharks, and squid, as well as body oils and liver oils obtained from specific parts of the animals.

[0046] As with the "vegetable oil," any of crude oil, refined oil, processed fats and oils may be used as the "animal oil." However, considering the quality and cost as a fuel oil composition, crude oil and refined oil are preferred, and among refined oils, refined oil obtained by removing suspended impurities contained in crude oil by filtration is preferred. In addition, (a1) and (a2) and other properties (a3) to (a4) described later are also suitable. 15 ) properties.

[0047] The animal and vegetable oils used in the fuel oil composition for internal combustion engines of this embodiment are preferably vegetable oils, and among the vegetable oils, palm oil, rapeseed oil, soybean oil, and coconut oil are preferred as described above, with palm oil and rapeseed oil being more preferred. Vegetable oils have the following properties (a1) and (a2) and other properties (a3) to (a 15 ) and, in relation to the ethylene bottom oil used in combination with the animal and vegetable oil, excellent oil passing performance and storage stability, as well as combustion performance, environmental performance and lubrication performance, are likely to be obtained.

[0048] Next, the properties of animal and vegetable oils will be described. The animal and vegetable oil used in this embodiment satisfies both of the following (a1) and (a2). By adopting the animal and vegetable oil obtained from the animal and vegetable oils described above, the animal and vegetable oil used in this embodiment satisfies the following (a1) and (a2), as well as (a3) to (a4). 15 ) and other properties. (a1) Sulfur content is 0.02% by mass or less (a2) Kinematic viscosity at 50°C is 20.0 mm 2 / s or more 50.0mm 2 / s or less

[0049] (a1) Sulfur content The sulfur content of the animal and vegetable oil is 0.02% by mass or less. If the sulfur content of the animal and vegetable oil exceeds 0.02% by mass, the environmental performance of the fuel oil composition for internal combustion engines of this embodiment will be reduced in relation to the content of the animal and vegetable oil and the ethylene bottom oil used in combination with the animal and vegetable oil. From the viewpoint of improving environmental performance, the sulfur content of the animal and vegetable oil is preferably 0.015% by mass or less, and more preferably 0.01% by mass or less.

[0050] (a2) Kinematic viscosity at 50°C The kinematic viscosity of animal and vegetable oils at 50°C is 20.0 mm 2 / s or more 50.0mm 2 If the kinematic viscosity of the animal or vegetable oil is not within the above range, the lubricating performance and combustion performance of the fuel oil composition for internal combustion engines of this embodiment will be reduced in relation to the content of the animal or vegetable oil and the ethylene bottom oil used in combination with the animal or vegetable oil, and the composition will be less suitable for use in various types of equipment, and handleability will be reduced. Considering the improvement of lubrication performance and combustion performance, ease of adaptation to the range of use of various equipment, and improvement of handling, the kinematic viscosity of the animal and vegetable oil at 50°C is preferably 22.0 mm 2 / s or more, preferably 25.0 mm 2 / s or more, more preferably 27.0 mm 2 / s or more, and the upper limit is preferably 45.0 mm 2 / s or less, preferably 40.0 mm 2 / s or less, more preferably 35.0 mm 2 / s or less.

[0051] In addition to the above properties (a1) and (a2), the animal and vegetable oils used in this embodiment further have the following properties (a3) to (a 15 ) and particularly, it is preferable that the following properties (a3) to (a 15 It is preferable that all of the above properties are satisfied.

[0052] (a3) Carbon residue The residual carbon content of the animal and vegetable oil is preferably 0.50% by mass or less, more preferably 0.40% by mass or less, and even more preferably 0.35% by mass or less, and although there is no particular lower limit, it is usually 0.10% by mass or more. When the carbon residue content is within the above range, the carbon residue content of the fuel oil composition for internal combustion engines of this embodiment tends to fall within the above preferred range in relation to the content of the animal and vegetable oil and the ethylene bottom oil used in combination with the animal and vegetable oil, As a result, the combustion performance of the fuel oil composition for internal combustion engines is improved and the effect of reducing soot generation due to poor combustion is improved, enabling more stable operation of the internal combustion engine.

[0053] (a4) Density at 15°C The density of the animal and vegetable oil at 15°C is preferably 0.9000 g / cm 3 More preferably, 0.9050 g / cm 3 More preferably, 9100 g / cm 3 The upper limit is preferably 0.9300 g / cm 3 or less, more preferably 0.9200 g / cm 3 The following is the result. When the density at 15°C is within the above range, the density at 15°C of the internal combustion fuel oil composition of this embodiment is likely to fall within the above preferred range in relation to the animal and vegetable oil content and the ethylene bottom oil used in combination with the animal and vegetable oil. As a result, the sludge separation performance in a centrifugal separator installed as a pre-treatment device before a diesel engine for a large ship or the like is improved, and the oil passing performance and storage stability are improved. The gross calorific value is also improved.

[0054] (a5) Flash point The flash point of the animal or vegetable oil is preferably 100.0°C or higher, more preferably 150.0°C or higher, even more preferably 200.0°C or higher, and even more preferably 240.0°C or higher. When the flash point is within the above range, the flash point of the fuel oil composition for internal combustion engines of the present embodiment is likely to fall within the above preferred range in relation to the content of the animal and vegetable oil and the ethylene bottom oil used in combination with the animal and vegetable oil, thereby improving safety in handling.

[0055] (a6) Pour point The pour point of the animal or vegetable oil is preferably 30.0° C. or lower, more preferably 27.5° C. or lower, and even more preferably 25.0° C. or lower. The lower limit is not particularly limited, and is usually about −25.0° C. or higher. When the pour point is 30.0°C or less, the pour point of the fuel oil composition for internal combustion engines of this embodiment tends to fall within the above-mentioned preferred range in relation to the content of the animal and vegetable oil and the ethylene bottom oil used in combination with the animal and vegetable oil, resulting in improved flowability of the fuel oil composition in tanks, piping, etc. at low temperatures.

[0056] (a7) Moisture content The water content of the animal and vegetable oil is preferably 0.20% by volume or less, more preferably 0.15% by volume or less, and even more preferably 0.10% by volume or less. When the water content of the animal and vegetable oil is within the above range, the water content of the fuel oil composition for internal combustion engines of this embodiment is more likely to fall within the above preferred range in relation to the content of the animal and vegetable oil and the ethylene bottom oil used in combination with the animal and vegetable oil. As a result, a decrease in storage stability (sludge formation due to an emulsion of asphaltene and water) can be suppressed, and clogging due to sludge can be prevented. Furthermore, the lower the lower limit, the better, and there is no particular restriction, and it may be 0.0% by volume.

[0057] (a8) Ash content The ash content of the animal and vegetable oil is preferably 0.020% by mass or less, more preferably 0.015% by mass or less, and even more preferably 0.010% by mass or less. When the ash content is within the above range, the ash content of the fuel oil composition for internal combustion engines of this embodiment is likely to fall within the above preferred range in relation to the content of the animal and vegetable oil and the ethylene bottom oil used in combination with the animal and vegetable oil. As a result, storage stability and combustion performance are improved, and wear of cylinders, nozzles, etc. can be further suppressed, thereby reducing the environmental load caused by exhaust gases. There is no particular restriction on the lower limit, and it may be 0.0% by mass.

[0058] (a9) Nitrogen content The nitrogen content of the animal and vegetable oil is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and even more preferably 0.1% by mass or less. If the nitrogen content is 0.3% by mass or less, the content of nitrogen-containing compounds such as nitrogen oxides in the exhaust gas is reduced, thereby improving environmental performance. As for the lower limit of the nitrogen content, the lower the better, and although there is no particular limit, it is 0.0% by mass or more. In this specification, the nitrogen content is a value measured by the CHN Coder method. Measurement by the CHN Coder method can be performed using an elemental analyzer such as a carbon / hydrogen / nitrogen simultaneous determination apparatus.

[0059] (a 10 ) carbon content The carbon content of the animal and vegetable oil is not particularly limited, and is usually 74.0% by mass or more and 80.0% by mass or less. In this specification, the carbon content is a value measured by the CHN Coder method. Measurement by the CHN Coder method can be performed using an elemental analyzer such as a carbon, hydrogen, and nitrogen simultaneous determination apparatus.

[0060] (a 11 ) Hydrogen content The hydrogen content of the animal and vegetable oil is not particularly limited, and is usually 9.0 mass % or more and 14.0 mass % or less. In this specification, the carbon content is a value measured by the CHN Coder method. Measurement by the CHN Coder method can be performed using an elemental analyzer such as a carbon, hydrogen, and nitrogen simultaneous determination apparatus.

[0061] (a 12 )Oxygen content The oxygen content of the animal and vegetable oil is preferably 9.0% by mass or more, more preferably 10.0% by mass or more, and even more preferably 10.5% by mass or more. When the oxygen content is within the above range, combustion performance is improved. There is no particular upper limit, and it is usually 15.0% by mass or less. In this specification, the oxygen content is a value calculated based on JIS M8813:2006 (Coals and cokes - Methods for elemental analysis) Appendix 5 (Calculation method for oxygen content), and is a value obtained by subtracting the above carbon content, hydrogen content, nitrogen content, sulfur content, and ash content from the total (100 mass%).

[0062] (a 13 ) Total heat generation The gross calorific value of the animal and vegetable oils is preferably 39,500 (kJ / L) or more, more preferably 40,000 (kJ / L) or more, and even more preferably 40,500 (kJ / L) or more. When the gross calorific value is within the above range, the gross calorific value of the fuel oil composition for internal combustion engines of this embodiment is more likely to fall within the above preferred range in relation to the content of the animal and vegetable oils and the ethylene bottom oil used in combination with the animal and vegetable oils. As a result, when the gross calorific value is within the above range, the amount of fuel oil composition used can be reduced, thereby improving fuel economy.

[0063] (a 14 ) Total Sediment (TSE) The total sediment content (TSE) of animal and vegetable oils is preferably 0.05% by mass or less, more preferably 0.03% by mass or less, and even more preferably 0.01% by mass or less. When the total sediment content (TSE) is 0.05% by mass or less, the oil passing performance and storage stability are improved. The lower the total sediment content (TSE), the better, and although there is no particular limitation, it is 0.0% by mass or more. Total sediment (TSE) can be measured in accordance with ISO 10307-1.

[0064] (a 15 )90% by volume distillation temperature The 90% by volume distillation temperature of the animal and vegetable oil is not particularly limited, but is usually 310° C. or higher and 380° C. or lower. From the viewpoint of improving combustion performance, the temperature is preferably 315° C. or higher, more preferably 320° C. or higher, and even more preferably 330° C. or higher, with the upper limit being preferably 370° C. or lower, more preferably 360° C. or lower, and even more preferably 355° C. or lower. In this specification, the distillation properties are values measured in accordance with JIS K2254:1998 (Petroleum products - Distillation test methods).

[0065] (Animal and vegetable oil content) In the fuel oil composition for internal combustion engines of this embodiment, the content of the animal and vegetable oil is 15.0% by volume or more and 35.0% by volume or less based on the total amount of the composition. If the content of the animal and vegetable oil is outside this range, the environmental performance, combustion performance, lubricity, oil passability, and storage stability will be reduced in relation to the ethylene bottom oil used in combination with the animal and vegetable oil. From the viewpoint of improving the environmental performance, combustion performance, lubricity, oil passability, and storage stability, the content of the animal and vegetable oil is preferably 17.5% by volume or more, more preferably 20.0% by volume or more, and even more preferably 25.0% by volume or more, with the upper limit being preferably 32.5% by volume or less, more preferably 30.0% by volume or less. In the present embodiment, the animal and vegetable oils may be used singly or in combination of two or more. When two or more types are used in combination, the total amount thereof may be within the above content range.

[0066] (Ethylene bottom oil) The fuel oil composition for internal combustion engines of this embodiment contains an ethylene bottom oil that satisfies all of the following (b1) to (b3), and the content thereof, based on the total amount of the composition, is 0.20 times or more the content of the animal and vegetable oils, based on the total amount of the composition: If the ethylene bottom oil is not contained in the above content, it cannot be said that the ethylene bottom oil is being effectively utilized, and excellent storage stability cannot be obtained in relation to the animal and vegetable oils used in combination with the ethylene bottom oil and their contents, and excellent combustion performance, environmental friendliness, and lubrication performance may not be obtained. (b1) Sulfur content is 0.30% by mass or less (b2) Kinematic viscosity at 50°C is 10.0 mm 2 / s or more 50.0mm 2 / s or less (b3) Aromatic content is 80.0% by volume or more

[0067] The ethylene bottom oil used in this embodiment is a fraction (bottom oil) produced in an ethylene production plant that produces ethylene, propylene, etc. by thermally cracking a feedstock oil such as a naphtha fraction together with steam, and satisfies all of the above (b1) to (b3). The ethylene bottom oil has the following properties (b1) to (b3), and further (b4) to (b 16 ) will be explained below.

[0068] (b1) Sulfur content The sulfur content of the ethylene bottom oil is 0.30% by mass or less. If the sulfur content of the ethylene bottom oil exceeds 0.30% by mass, the environmental performance of the fuel oil composition for internal combustion engines of this embodiment will be reduced in relation to the animal and vegetable oils used in combination with the ethylene bottom oil and their contents. From the viewpoint of improving environmental performance, the sulfur content of the ethylene bottom oil is preferably 0.28 mass % or less, more preferably 0.25 mass % or less, and even more preferably 0.22 mass % or less.

[0069] (b2) Kinematic viscosity at 50°C The kinematic viscosity of ethylene bottom oil at 50°C is 10.0 mm 2 / s or more 50.0mm 2 If the kinematic viscosity of the ethylene bottom oil is not within the above range, the lubricating performance and combustion performance of the internal combustion fuel oil composition of this embodiment will be reduced depending on the animal and vegetable oil used in combination with the ethylene bottom oil and the content thereof, and the composition will be less suitable for use in various types of equipment, and handleability will be reduced. In consideration of the improvement of lubrication performance and combustion performance, ease of adaptation to the range of use of various equipment, and improvement of handling, the kinematic viscosity of the ethylene bottom oil at 50°C is preferably 15.0 mm 2 / s or more, preferably 20.0 mm 2 / s or more, more preferably 25.0 mm 2 / s or more, and the upper limit is preferably 45.0 mm 2 / s or less, preferably 40.0 mm 2 / s or less, more preferably 35.0 mm 2 / s or less.

[0070] (b3) Aromatic content The aromatic content of the ethylene bottom oil is 80.0% by volume or more. If the aromatic content is outside this range, the oil passing performance and storage stability will be reduced in relation to the animal and vegetable oils used in combination with the ethylene bottom oil and their contents. From the viewpoint of improving oil passability and storage stability, the aromatic content of the ethylene bottom oil is preferably 83.0% by volume or more, more preferably 85.0% by volume or more, and even more preferably 90.0% by volume or more.

[0071] In this specification, the aromatic content, saturated content and olefin content of the desulfurized gas oil fraction, cracked gas oil fraction, straight-run gas oil fraction, vacuum gas oil fraction, desulfurized cracked gas oil fraction, straight-run gas oil fraction and hydrocracked gas oil fraction are values measured by the High Performance Liquid Chromatography method for petroleum products - Hydrocarbon type testing methods specified in JPI-5S-49-2007. The aromatic content, saturated content, resin content and asphaltene content of the ethylene bottoms, direct decomposition heavy oil fraction, cracked heavy oil fraction, atmospheric distillation residue fraction and vacuum distillation residue fraction are values measured by the TLC / FID method specified in IP-469 (International Standard Test Methods (IP Test Methods)).

[0072] In addition to the above properties (b1) to (b3), the ethylene bottom oil used in this embodiment further has the following properties (b4) to (b 16 ) and particularly, it is preferable that the following (b4) to (b 16 It is preferable that all of the above properties are satisfied.

[0073] (b4) Residual carbon content The carbon residue content of the ethylene bottom oil is preferably 10.0 mass % or less, more preferably 9.0 mass % or less, and even more preferably 8.8 mass % or less, with no particular lower limit, and is usually 0.00 mass % or more. When the carbon residue content is within the above range, the carbon residue content of the fuel oil composition for internal combustion engines of this embodiment is likely to be within the above preferred range in relation to the animal and vegetable oils used in combination with the ethylene bottom oil and their contents, which results in improved combustion performance of the fuel oil composition for internal combustion engines and an improved effect of reducing soot generation due to poor combustion, enabling more stable operation of the internal combustion engine.

[0074] (b5) Density at 15°C The density of the ethylene bottom oil at 15°C is preferably 0.9750 g / cm 3 More preferably, 1.0000 g / cm 3 More preferably, 1.0250 g / cm 3 The upper limit is preferably 1.1500 g / cm 3 or less, more preferably 1.1000 g / cm 3 or less, more preferably 1.0750 g / cm 3 The following is the result. When the density at 15°C is within the above range, the density at 15°C of the internal combustion fuel oil composition of this embodiment is likely to fall within the above preferred range in relation to the animal and vegetable oils used in combination with the ethylene bottom oil and their contents. As a result, the sludge separation performance in a centrifugal separator installed as a pre-treatment device before a diesel engine for a large ship or the like is improved, and the oil passing performance and storage stability are improved. The gross calorific value is also improved.

[0075] (b6) Flash point The flash point of the ethylene bottom oil is preferably 70.0°C or higher, more preferably 80.0°C or higher, and even more preferably 90.0°C or higher. When the flash point is within the above range, the flash point of the fuel oil composition for internal combustion engines of the present embodiment is likely to fall within the above preferred range in relation to the animal and vegetable oils used in combination with the ethylene bottom oil and their contents, thereby improving safety in handling.

[0076] (b7) Pour point The pour point of the ethylene bottom oil is preferably 0.0° C. or lower, more preferably −5.0° C. or lower, and even more preferably −10.0° C. or lower. The lower limit of the pour point is not particularly limited, and is usually about −35.0° C. or higher. When the pour point is −0.0° C. or lower, the pour point of the fuel oil composition for internal combustion engines of this embodiment tends to fall within the above-mentioned preferred range in relation to the animal and vegetable oils used in combination with the ethylene bottom oil and their contents, resulting in improved flowability of the fuel oil composition in tanks, piping, etc. at low temperatures.

[0077] (b8) Moisture content The water content of the ethylene bottom oil is preferably 0.20% by volume or less, more preferably 0.15% by volume or less, and even more preferably 0.10% by volume or less. When the water content of the ethylene bottom oil is within the above range, the water content of the fuel oil composition for internal combustion engines of this embodiment is likely to fall within the above preferred range in relation to the animal and vegetable oils used in combination with the ethylene bottom oil and their contents. As a result, deterioration in storage stability (sludge formation due to an emulsion of asphaltene and water) can be suppressed, and clogging due to sludge can be prevented. Furthermore, the lower the water content, the better, and there is no particular limit, and it may be 0.0% by volume.

[0078] (b9)Ash content The ash content of the ethylene bottom oil is preferably 0.020% by mass or less, more preferably 0.015% by mass or less, and even more preferably 0.010% by mass or less. There is no particular lower limit, and the ash content may be 0.0% by mass. When the ash content is within the above range, the ash content of the fuel oil composition for internal combustion engines of this embodiment tends to fall within the above preferred range in relation to the animal and vegetable oils used in combination with the ethylene bottom oil and their contents, which results in improved storage stability and combustion performance, and further suppression of wear on cylinders, nozzles, etc., thereby reducing the environmental load caused by exhaust gases.

[0079] (b 10 )Nitrogen content The nitrogen content of the ethylene bottom oil is preferably 0.20% by mass or less, more preferably 0.10% by mass or less. When the nitrogen content is 0.20% by mass or less, the content of nitrogen-containing compounds such as nitrogen oxides in the exhaust gas is reduced, thereby improving environmental performance. As for the lower limit, the lower the nitrogen content, the better, and there is no particular restriction, but it is 0.0 mass % or more.

[0080] (b 11 ) carbon content The carbon content of the ethylene bottom oil is not particularly limited, and is usually 90.0 mass % or more and 93.0 mass % or less.

[0081] (b 12 ) Hydrogen content The hydrogen content of the ethylene bottom oil is not particularly limited, and is usually 7.0 mass % or more and 10.0 mass % or less.

[0082] (b 13 )Oxygen content The oxygen content of the ethylene bottom oil is usually 0.1% by mass or less, and may be 0.0% by mass.

[0083] (b 14 ) Total heat generation The gross calorific value of the ethylene bottom oil is preferably 42,000 (kJ / L) or more, more preferably 43,000 (kJ / L) or more, and even more preferably 44,000 (kJ / L) or more. When the gross calorific value is within the above range, the gross calorific value of the fuel oil composition for internal combustion engines of this embodiment is likely to fall within the above preferred range in relation to the animal and vegetable oils used in combination with the ethylene bottom oil and their contents. As a result, when the gross calorific value is within the above range, the amount of fuel oil composition used can be reduced, thereby improving fuel economy.

[0084] (b 15 ) Total Sediment (TSE) The total sediment content (TSE) of the ethylene bottom oil is preferably 0.05% by mass or less, more preferably 0.03% by mass or less, and even more preferably 0.02% by mass or less. When the total sediment content (TSE) is 0.05% by mass or less, the oil passing performance and storage stability are improved. The lower the total sediment content (TSE), the better, and although there is no particular limit, it is 0.0% by mass or more.

[0085] (b 16 ) Saturates content, resin content, and asphaltene content The saturates content of the ethylene bottom oil is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, and even more preferably 3.0% by mass or less, and the asphaltene content is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, and even more preferably 1.0% by mass or less. There are no particular restrictions on the lower limits of these values, and they are usually 0.1% by mass or more. The resin content is preferably 3.0% by mass or more and 10.0% by mass or less, and more preferably 5.0% by mass or more and 8.0% by mass or less. When the saturated content of the ethylene bottom oil is within the above range, combustion performance is improved, and when the resin content and asphaltene content are within the above range, clogging of fuel oil filters due to sludge generation is further suppressed, thereby improving oil passing performance, storage stability, and combustion performance.

[0086] (Ethylene bottom oil content) The content of ethylene bottom oil in the fuel oil composition for internal combustion engines of this embodiment is at least 0.20 times the content of the above-mentioned animal and vegetable oils based on the total amount of the composition. If it is less than 0.20 times, as mentioned above, it cannot be said that the ethylene bottom oil is being effectively utilized, and excellent storage stability cannot be obtained in relation to the animal and vegetable oils used in combination with the ethylene bottom oil and their contents. Furthermore, excellent combustion performance, environmental friendliness, and lubrication performance may not be obtained. From the viewpoint of more effectively utilizing the ethylene bottom oil and improving oil passivation performance, storage stability, combustion performance, environmental performance, and lubrication performance, the content of the ethylene bottom oil is preferably 0.22 times or more, more preferably 0.25 times or more, and even more preferably 0.30 times or more, the content of the animal and vegetable oils based on the total amount of the composition, and the upper limit is preferably 2.5 times or less, more preferably 2.0 times or less, even more preferably 1.5 times or less, and even more preferably 1.1 times or less.

[0087] The content of the ethylene bottom oil is not particularly limited as long as it satisfies the relationship with the content of the animal and vegetable oils described above, but the absolute value is preferably 6.0% by volume or more, more preferably 8.0% by volume or more, and the upper limit is preferably 28.0% by volume or less, more preferably 25.0% by volume or less, and even more preferably 22.5% by volume or less.

[0088] (directly decomposed heavy oil fraction) The fuel oil composition for internal combustion engines of this embodiment preferably contains a directly desulfurized heavy oil fraction that satisfies both of the following (c1) and (c2) in an amount of 50.0% by volume or more and 70.0% by volume or less based on the total volume of the composition. The directly desulfurized heavy oil fraction is a heavy oil fraction obtained by directly desulfurizing atmospheric distillation residue and / or vacuum distillation residue in a desulfurization unit. (c1) Sulfur content is 0.50% by mass or more and 0.60% by mass or less (c2) Kinematic viscosity at 50°C is 100.0 mm 2 / s or more 200.0mm 2 / s or less When the fuel oil composition for internal combustion engines of this embodiment contains the directly decomposed heavy oil fraction in the above-mentioned content, in relation to the above-mentioned animal and vegetable oils and their contents, and the ethylene bottom oil and their contents, it is possible to improve in a balanced manner not only the oil passing performance and storage stability performance, but also the combustion performance, environmental performance, and lubrication performance.

[0089] (c1) Sulfur content The sulfur content of the directly desulfurized heavy oil fraction is preferably 0.60% by mass or less, more preferably 0.58% by mass or less, and even more preferably 0.56% by mass or less. When the sulfur content of the directly desulfurized heavy oil fraction is 0.60% by mass or less, the environmental performance of the fuel oil composition for internal combustion engines of this embodiment is likely to be improved in relation to the animal and vegetable oils and the content thereof, and the ethylene bottom oil and the content thereof, which are used in combination with the directly desulfurized heavy oil fraction. From the viewpoint of improving environmental performance, the lower the content, the better. However, taking into consideration the capacity of the direct desulfurization unit, the production volume and quality of the directly desulfurized heavy oil fraction, ease of availability, and the like, the lower limit is preferably 0.50% by mass or more, and more preferably 0.53% by mass or more.

[0090] (c2) Kinematic viscosity at 50°C The kinematic viscosity of the directly decomposed heavy oil fraction at 50°C is preferably 100.0 mm 2 / s or more, preferably 110.0 mm 2 / s or more, more preferably 130.0 mm 2 / s or more, and the upper limit is preferably 200.0 mm 2 / s or less, preferably 190.0 mm 2 / s or less, more preferably 180.0 mm 2 When the kinematic viscosity of the directly desiccant heavy oil fraction is within the above range, the lubrication performance and combustion performance of the internal combustion fuel oil composition of this embodiment are improved in relation to the animal and vegetable oils and the content thereof, and the ethylene bottom oil and the content thereof, which are used in combination with the directly desiccant heavy oil fraction, and the composition is more likely to be adapted to the range of use of various equipment, and handleability is likely to be improved.

[0091] In addition, the directly decomposed heavy oil fraction preferably used in this embodiment has the following properties (c3) to (c4) in addition to the properties (c1) and (c2) described above: 16 ) and particularly, the following (c3) to (c 16 It is preferable that all of the above properties are satisfied.

[0092] (c3) Aromatic content The aromatic content of the directly decomposed heavy oil fraction is preferably 50.0% by volume or more, more preferably 52.0% by volume or more, and the upper limit is preferably 65.0% by volume or less, more preferably 63.0% by volume or less. When the aromatic content of the directly decomposed heavy oil fraction is within the above range, the oil passing performance and storage stability are improved in relation to the animal and vegetable oils and the content thereof, and the ethylene bottom oil and the content thereof, which are used in combination with the directly decomposed heavy oil fraction. Also, the directly decomposed heavy oil fraction is easily available.

[0093] (c4) Residual carbon content The residual carbon content of the directly decomposed heavy oil fraction is preferably 7.0 mass% or less, more preferably 6.0 mass% or less, and even more preferably 5.0 mass% or less, with no particular lower limit, and is usually 2.0 mass% or more. When the carbon residue content is within the above range, the carbon residue content of the fuel oil composition for internal combustion engines of this embodiment tends to fall within the above preferred range in relation to the animal and vegetable oils and their contents, and the ethylene bottom oil and their contents, which are used in combination with the directly decomposed heavy oil fraction. As a result, the combustion performance of the fuel oil composition for internal combustion engines is improved, and the effect of reducing soot generation due to poor combustion is improved, enabling more stable operation of the internal combustion engine.

[0094] (c5) Density at 15°C The density of the directly decomposed heavy oil fraction at 15°C is preferably 0.9000 g / cm 3 More preferably, 0.9050 g / cm 3 More preferably, 0.9100 g / cm 3 The upper limit is preferably 0.9500 g / cm 3 or less, more preferably 0.9400 g / cm3 More preferably, 0.9350 g / cm or less 3 The following is the result. When the density at 15°C is within the above range, the density at 15°C of the internal combustion fuel oil composition of this embodiment tends to fall within the above preferred range in relation to the animal and vegetable oils and their contents, and the ethylene bottom oil and their contents, which are used in combination with the directly decomposed heavy oil fraction. As a result, the sludge separation performance in a centrifugal separator installed as a pretreatment device before a diesel engine for a ship such as a large vessel is improved, and the oil passing performance and storage stability are also improved. The gross calorific value is also improved.

[0095] (c6) Flash point The flash point of the directly decomposed heavy oil fraction is preferably 100.0°C or higher, more preferably 150.0°C or higher, and even more preferably 180.0°C or higher. When the flash point is within the above range, the flash point of the fuel oil composition for internal combustion engines of this embodiment is likely to fall within the above preferred range in relation to the animal and vegetable oils and the ethylene bottom oil and the ethylene bottom oil used in combination with the directly decomposed heavy oil fraction, thereby improving safety in handling.

[0096] (c7) Pour point The pour point of the directly decomposed heavy oil fraction is preferably 20.0° C. or lower, more preferably 15.0° C. or lower, and even more preferably 10.0° C. or lower. The lower limit of the pour point is preferably as low as possible, and is not particularly limited, but is usually about −10.0° C. or higher. When the pour point is 20.0°C or less, the pour point of the fuel oil composition for internal combustion engines of this embodiment tends to fall within the above-mentioned preferred range in relation to the animal and vegetable oils and the content thereof, and the ethylene bottom oil and the content thereof, which are used in combination with the directly decomposed heavy oil fraction, thereby improving the flowability of the fuel oil composition in tanks, piping, etc. at low temperatures.

[0097] (c8) Moisture content The water content of the directly decomposed heavy oil fraction is preferably 0.20% by volume or less, more preferably 0.15% by volume or less, and even more preferably 0.10% by volume or less. When the water content of the directly decomposed heavy oil fraction is within the above range, the water content of the fuel oil composition for internal combustion engines of this embodiment is more likely to be within the above preferred range in relation to the animal and vegetable oils and the content thereof, and the ethylene bottom oil and the content thereof, which are used in combination with the directly decomposed heavy oil fraction. As a result, a decrease in storage stability (sludge formation due to an emulsion of asphaltene and water) can be suppressed, and clogging due to sludge can be prevented. The lower limit is preferably as low as possible, and there is no particular restriction, and it may be 0.0% by volume.

[0098] (c9)Ash content The ash content of the directly desiccant heavy oil fraction is preferably 0.020% by mass or less, more preferably 0.015% by mass or less, and even more preferably 0.010% by mass or less. There is no particular lower limit, and it may be 0.0% by mass. When the ash content is within the above range, the ash content of the fuel oil composition for internal combustion engines of this embodiment tends to fall within the above preferred range in relation to the animal and vegetable oils and the content thereof, and the ethylene bottom oil and the content thereof, which are used in combination with the directly desiccant heavy oil fraction. As a result, storage stability and combustion performance are improved, and wear of cylinders, nozzles, etc. can be further suppressed, thereby reducing the environmental impact of exhaust gases.

[0099] (c 10 )Nitrogen content The nitrogen content of the directly decomposed heavy oil fraction is preferably 0.3 mass% or less, more preferably 0.2 mass% or less, and even more preferably 0.1 mass% or less. When the nitrogen content is 0.3 mass% or less, the content of nitrogen-containing compounds such as nitrogen oxides in the exhaust gas is reduced, thereby improving environmental performance. As for the lower limit, the lower the nitrogen content, the better, and there is no particular restriction, but it is 0.0 mass % or more.

[0100] (c 11 ) carbon content The carbon content of the directly decomposed heavy oil fraction is not particularly limited, and is usually 86.0 mass % or more and 91.0 mass % or less.

[0101] (c 12 ) Hydrogen content The hydrogen content of the directly decomposed heavy oil fraction is not particularly limited, and is usually 11.0 mass % or more and 14.0 mass % or less.

[0102] (c 13 )Oxygen content The oxygen content of the directly decomposed heavy oil fraction is usually 0.1 mass % or less, and may be 0.0 mass %.

[0103] (c 14 ) Total heat generation The gross calorific value of the directly desiccant heavy oil fraction is preferably 40,000 (kJ / L) or more, more preferably 40,500 (kJ / L) or more, and even more preferably 41,000 (kJ / L) or more. When the gross calorific value is within the above range, the gross calorific value of the fuel oil composition for internal combustion engines of this embodiment is more likely to fall within the above preferred range in relation to the animal and vegetable oils and the content thereof, and the ethylene bottom oil and the content thereof, which are used in combination with the directly desiccant heavy oil fraction. As a result, when the gross calorific value is within the above range, the amount of fuel oil composition used can be reduced, thereby improving fuel economy.

[0104] (c 15 ) Total Sediment (TSE) The total sediment content (TSE) of the directly decomposed heavy oil fraction is preferably 0.10% by mass or less, more preferably 0.07% by mass or less, and even more preferably 0.05% by mass or less. When the total sediment content (TSE) is 0.10% by mass or less, the oil passing performance and storage stability are improved. Regarding the lower limit, the less the total sediment (TSE) the better, and there is no particular limitation, but it is 0.0 mass % or more.

[0105] (c 16 ) Saturates content, resin content, and asphaltene content The saturated content of the directly decomposed heavy oil fraction is preferably 20.0 mass% or more and 50.0 mass% or less, more preferably 30.0 mass% or more and 40.0 mass% or less, the resin content is preferably 2.0 mass% or more and 10.0 mass% or less, more preferably 3.0 mass% or more and 7.0 mass% or less, and the asphaltene content is preferably 5.0 mass% or less and more preferably 4.0 mass% or less. There is no particular lower limit, and it is usually 1.0 mass% or more. When the saturated content is within the above range, combustion performance is improved, and when the resin content and asphaltene content are within the above range, clogging of the fuel oil filter due to sludge generation is further suppressed, thereby improving oil passing performance, storage stability, and combustion performance.

[0106] (content of direct decomposition heavy oil fraction) The content of the directly decomposed heavy oil fraction contained in the fuel oil composition for internal combustion engines of this embodiment based on the total amount of the composition is preferably 50.0% by volume or more, more preferably 52.0% by volume or more, and even more preferably 55.0% by volume or more, with the upper limit being preferably 70.0% by volume or less, more preferably 68.0% by volume or less, and even more preferably 65.0% by volume or less. When the content of the directly desiccant heavy oil fraction is within the above range, in relation to the animal and vegetable oils and the content thereof, and the ethylene bottom oil and the content thereof, which are used in combination with the directly desiccant heavy oil fraction, it is possible to achieve a balanced improvement in combustion performance, environmental performance, and lubrication performance in addition to oil passing performance and storage stability.

[0107] (Other fractions) The fuel oil composition for internal combustion engines of this embodiment may contain other fractions in addition to the above-mentioned animal and vegetable oils and ethylene bottom oil, and the preferably used directly decomposed heavy oil fraction. There are no particular restrictions on the other fractions, and any fractions can be used as long as the fuel oil composition for internal combustion engines satisfies the composition and properties (1) to (4) above. From the viewpoint of achieving a balanced improvement in combustion performance, environmental performance, and lubrication performance in addition to oil passing performance and storage stability, the following light oil fractions, heavy oil fractions, etc. are preferred.

[0108] (heavy oil fraction) The fuel oil composition for internal combustion engines of this embodiment may contain, as the heavy oil fraction of other fractions, for example, an atmospheric distillation residual oil fraction, a vacuum distillation residual oil fraction, or a cracked heavy oil fraction. Atmospheric distillation residue (residual oil obtained by atmospheric distillation of crude oil in an atmospheric distillation unit) Vacuum distillation residue oil fraction (residual oil obtained by vacuum distilling atmospheric distillation residue oil in a vacuum distillation unit) Cracked heavy oil fraction (heavy oil fraction obtained by fluid catalytic cracking of directly decomposed heavy oil fraction)

[0109] (Properties of other heavy oil fractions) The heavy oil fraction that can be used in this embodiment preferably has the following properties, for example: When the heavy oil fraction has the following properties, it is possible to improve combustion performance, environmental performance, and lubrication performance in a balanced manner, in addition to oil passing performance and storage stability. The sulfur content is preferably 1.20% by mass or less, more preferably 1.00% by mass or less, and even more preferably 0.85% by mass or less, and the lower limit is usually 0.30% by mass or more. The kinematic viscosity at 50°C is preferably 30.00 mm 2 / s or more, preferably 50.00 mm 2 / s or more, more preferably 100.0 mm 2 / s or more, and the upper limit is preferably 200.0 mm 2 / s or less, preferably 195.0 mm 2 / s or less, more preferably 190.0 mm 2 / s or less. The residual carbon content is preferably 10.0% by mass or less, more preferably 9.0% by mass or less, and even more preferably 7.5% by mass or less, with the lower limit usually being 2.0% by mass or more. The density at 15°C is preferably 1.3000 g / cm 3 or less, more preferably 1.2000 g / cm 3 or less, more preferably 1.1000 g / cm 3 or less, even more preferably 1.0000 g / cm 3The lower limit is usually 0.9000 g / cm 3 That's all. The flash point is preferably 140.0°C or higher, more preferably 150.0°C or higher, and even more preferably 160.0°C or higher. The pour point is preferably 25.0°C or less, more preferably 20.0°C or less, even more preferably 17.5°C or less, and even more preferably 15.0°C or less. The water content is preferably 0.20% by volume or less, more preferably 0.15% by volume or less, and even more preferably 0.10% by volume or less. The ash content is preferably 0.020% by mass or less, more preferably 0.015% by mass or less, and even more preferably 0.010% by mass or less. The nitrogen content is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and even more preferably 0.1% by mass or less, the carbon content is usually 85.0% by mass or more and 91.0% by mass or less, and preferably 90.0% by mass or less, the hydrogen content is usually 9.0% by mass or more and 14.0% by mass or less, and the oxygen content is usually 0.1% by mass or less, and may be 0.0% by mass. The total calorific value is preferably 39,000 (kJ / L) or more, more preferably 39,500 (kJ / L) or more, and even more preferably 40,000 (kJ / L) or more. The total sediment (TSE) content is preferably 0.10% by mass or less, more preferably 0.07% by mass or less, and even more preferably 0.05% by mass or less. The aromatic content is preferably 50.0% by mass or more, more preferably 55.0% by mass or more, and although there is no particular upper limit, it is, for example, 75.0% by mass or less, preferably 65.0% by mass or less. The saturated content is preferably 15.0% by mass or more and 45.0% by mass or less, more preferably 25.0% by mass or more and 40.0% by mass or less, the resin content is preferably 2.0% by mass or more and 10.0% by mass or less, more preferably 3.5% by mass or more and 6.5% by mass or less, and the asphaltene content is preferably 5.0% by mass or less and more preferably 4.0% by mass or less. There is no particular lower limit, and it is usually 1.0% by mass or more.

[0110] When a heavy oil fraction from the above-mentioned other fractions is used, its content based on the total amount of the composition is preferably 1.0% by volume or more, more preferably 3.0% by volume or more, from the viewpoint of improving combustion performance, environmental performance, and lubrication performance in a balanced manner, in addition to oil passing performance and storage stability, and the upper limit is preferably 15.0% by volume or less, more preferably 10.0% by volume or less, and even more preferably 9.0% by volume or less. When two or more heavy oil fractions are contained, the total content of the heavy oil fractions should be within the above range.

[0111] (light oil fraction) The fuel oil composition for internal combustion engines of this embodiment may contain, as the light oil fraction of other fractions, light oil fractions such as straight-run light oil fraction, vacuum light oil fraction, desulfurized light oil fraction, cracked light oil fraction, desulfurized cracked light oil fraction, straight-run light oil fraction, and hydrocracked light oil fraction. Straight-run diesel fraction (diesel fraction obtained by atmospheric distillation of crude oil in an atmospheric distillation unit) Vacuum diesel fraction (a diesel fraction obtained by vacuum distilling atmospheric distillation residue in a vacuum distillation unit) Desulfurized diesel fraction (straight-run diesel fraction, diesel fraction obtained by desulfurizing straight-run diesel fraction and / or vacuum diesel fraction) Cracked diesel fraction (diesel fraction obtained by fluid catalytic cracking of direct desulfurized heavy oil fraction and / or vacuum desulfurized diesel fraction) Desulfurized cracked diesel fraction (diesel fraction obtained by desulfurizing cracked diesel fraction) Directly desulfurized diesel fraction (diesel fraction obtained by directly desulfurizing atmospheric distillation residue in a desulfurization unit) Hydrocracked diesel fraction (a diesel fraction obtained by hydrocracking vacuum diesel fraction in a hydrocracker)

[0112] (Properties of other diesel fractions) The diesel fraction that can be used in this embodiment preferably has the following properties, for example: When the diesel fraction has the following properties, it is possible to improve combustion performance, environmental performance, and lubrication performance in a balanced manner, in addition to oil passing performance and storage stability. The sulfur content is usually 0.50% by mass or less, more preferably 0.30% by mass or less, and even more preferably 0.10% by mass or less, with the lower limit usually being 0.01% by mass or more. The kinematic viscosity at 50°C is preferably 5.00 mm 2 / s or less, preferably 3.00 mm 2 / s or less, more preferably 2.50 mm 2 / s or less, and the lower limit is usually 1.00 mm 2 / s or more, preferably 1.50 mm 2 / s or more. The residual carbon content is preferably 0.10% by mass or less, more preferably 0.05% by mass or less, and even more preferably 0.02% by mass or less, with no particular lower limit, and is usually 0.00% by mass or more. The density at 15°C is preferably 0.8000 g / cm 3 More preferably, 0.8200 g / cm 3 More preferably, 0.8300 g / cm 3 The upper limit is preferably 0.9400 g / cm 3 or less, more preferably 0.9300 g / cm 3 More preferably, 0.9200 g / cm or less 3 The following is the result. The flash point is preferably 60.0°C or higher, more preferably 65.0°C or higher. The pour point is preferably 0.0° C. or lower, more preferably −2.5° C. or lower, and even more preferably −5.0° C. or lower. The lower limit of the pour point is preferably as low as possible, and is not particularly limited, but is usually about −30.0° C. or higher. The water content is preferably 0.20% by volume or less, more preferably 0.15% by volume or less, and even more preferably 0.10% by volume or less. The ash content is preferably 0.020% by mass or less, more preferably 0.015% by mass or less, and even more preferably 0.010% by mass or less. The nitrogen content is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and even more preferably 0.1% by mass or less, the carbon content is usually 85.0% by mass or more and 91.0% by mass or less, the hydrogen content is usually 9.0% by mass or more and 14.0% by mass or less, and the oxygen content is usually 0.1% by mass or less, and may be 0.0% by mass. The total calorific value is preferably 38,000 (kJ / L) or more, more preferably 39,000 (kJ / L) or more, and even more preferably 39,500 (kJ / L) or more. The total sediment (TSE) content is preferably 0.05% by mass or less, more preferably 0.03% by mass or less, and even more preferably 0.01% by mass or less. The aromatic content is preferably 15.0% by mass or more, more preferably 20.0% by mass or more, and although there is no particular upper limit, it is, for example, 75.0% by mass or less. The olefin content is preferably 10.0% by volume or less, more preferably 5.0% by volume or less, and there is no particular lower limit, and the lower the better, it may even be 0% by mass. The saturated content is preferably 15.0% by volume or more, more preferably 20.0% by volume or more, and the upper limit is preferably 80.0% by volume or less, more preferably 77.0% by volume or less. The 90% by volume distillation temperature is not particularly limited, but is usually 300°C or higher and 360°C or lower, preferably 315°C or higher, more preferably 320°C or higher, with the upper limit being preferably 350°C or lower, more preferably 345°C or lower.

[0113] When a diesel fraction from one of the above-mentioned other fractions is used, its content based on the total amount of the composition is preferably 1.0% by volume or more, more preferably 3.0% by volume or more, with the upper limit being preferably 15.0% by volume or less, more preferably 10.0% by volume or less, and even more preferably 9.0% by volume or less, from the viewpoint of improving combustion performance, environmental performance, and lubrication performance in a balanced manner, in addition to oil passing performance and storage stability. When two or more diesel fractions are contained, the total content of the diesel fractions should be within the above range.

[0114] (Various additives) To the internal combustion engine fuel oil composition of this embodiment, various additives such as antioxidants, low-temperature fluidity improvers, lubricity improvers, cetane number improvers, combustion promoters, detergents, sludge dispersants, antifungal agents, etc. may be appropriately selected and blended as needed within the range that allows the above-mentioned various properties to be maintained. Furthermore, coumarin may be blended from the viewpoint of diesel oil delivery tax.

[0115] (Application) The fuel oil composition for internal combustion engines of this embodiment is a fuel oil composition that satisfies extremely strict requirements for oil passing performance and storage stability, while also satisfying other performance requirements, namely, combustion performance, environmental performance, and lubrication performance. Therefore, it is used as a fuel oil composition for internal combustion engines, and is particularly suitable for use in internal combustion engines such as large marine diesel engines equipped with a centrifugal separator as a pretreatment device.

[0116] [Method for producing fuel oil composition for internal combustion engines] The method for producing a fuel oil composition for internal combustion engines of the present embodiment includes the steps of: An animal or vegetable oil that satisfies both of the following (a1) and (a2); and an ethylene bottom oil satisfying all of the following (b1) to (b3), The content of the animal and vegetable oil based on the total amount of the composition is 15.0% by volume or more and 35.0% by volume or less, The ethylene bottom oil is mixed so that the content of the ethylene bottom oil based on the total amount of the composition is 0.20 times or more the content of the animal and vegetable oil based on the total amount of the composition. The method for producing a fuel oil composition for internal combustion engines satisfies all of the following (1) to (4): (a1) Sulfur content is 0.02% by mass or less (a2) Kinematic viscosity at 50°C is 20.0 mm 2 / s or more 50.0mm 2 / s or less (b1) Sulfur content is 0.30% by mass or less (b2) Kinematic viscosity at 50°C is 10.0 mm 2 / s or more 50.0mm 2 / s or less (b3) Aromatic content is 80.0% by volume or more (1) Sulfur content is 0.400% by mass or less (2) Kinematic viscosity at 50°C is 50.0 mm 2 / s or more 100.0mm 2 / s or less (3) CCAI is 835 or less (4) Potential sediment is 0.10% by mass or less

[0117] The animal and vegetable oils and ethylene bottom oils used in the production method of this embodiment are the same as those described as being contained in the fuel oil composition for internal combustion engines of this embodiment, and the contents of these animal and vegetable oils and ethylene bottom oils are also the same. It is also the same that a directly decomposed heavy oil fraction is preferably used, and that other fractions such as various heavy oil fractions and various light oil fractions can also be used.

[0118] There are no particular restrictions on the order in which the animal and vegetable oils, ethylene bottom oil, and preferably used directly desiccant heavy oil fraction, other various light oil fractions, heavy oil fractions, and various additives are blended. For example, the ethylene bottom oil, directly desiccant heavy oil fraction, other various light oil fractions, heavy oil fractions, and further various additives may be added sequentially to the animal and vegetable oil and mixed; the various additives may be mixed in advance, and then the animal and vegetable oil, ethylene bottom oil, directly desiccant heavy oil fraction, and other various light oil fractions and heavy oil fractions are mixed; or the other various light oil fractions and heavy oil fractions may be mixed in advance, and then the animal and vegetable oil, ethylene bottom oil, directly desiccant heavy oil fraction, and various additives are mixed. [Example]

[0119] Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The properties of each substrate were determined according to the following methods as described above.

[0120] [Property measurement] The properties of the various base materials used in the Examples and Comparative Examples, including animal and vegetable oils (palm oil, rapeseed oil), ethylene bottom oil, directly desulfurized heavy oil fraction, desulfurized light oil fraction, cracked light oil fraction, and cracked heavy oil fraction, as well as the properties of the fuel oil compositions of the Examples and Comparative Examples, were measured by the following methods. The properties of the various base materials are shown in Table 1. The properties of the fuel oil compositions are shown in Tables 2 and 3. Sulfur content: Measured in accordance with JIS K 2541-4:2003 (Crude oil and petroleum products - Determination of sulfur content - Part 4: Radioactive excitation method). Kinematic viscosity at 50°C: Measured in accordance with JIS K 2283:2000 (Testing method for kinematic viscosity of crude oil and petroleum products). CCAI: Calculated using the formula given in Annex F of ISO 8217-2012. Latent sediment: A sample (the fuel oil composition for internal combustion engines of the present embodiment) was left at 100°C for 24 hours in accordance with ISO10307-2A (Thermal Aging), and the amount of sludge remaining on the filter paper obtained by passing it through the filter paper was measured. Carbon residue: Measured in accordance with JIS K 2270-1:2009 (Crude oil and petroleum products - Determination of carbon residue - Part 1: Conradson method). Density at 15°C: Measured in accordance with JIS K 2249-1:2011 (Crude oil and petroleum products - Determination of density - Part 1: Vibration method). Flash point: Measured in accordance with JIS K 2265-3:2007 (Crude oil and petroleum products - Flash point test method - Part 3: Pensky-Martens closed-cell method). Pour point: The cracked light oil fraction was measured in accordance with JIS K2269:1987 (Test method for pour point and cloud point of crude oil and petroleum products). Moisture content: Measured in accordance with JIS K 2275-3:2015 (Crude oil and petroleum products - Determination of moisture - Part 3: Karl Fischer coulometric titration method). Ash content: Measured in accordance with JIS K 2272:1998 (Crude oil and petroleum products - Testing method for ash content and sulfated ash content). Gross calorific value: For animal and vegetable oils (palm oil, rapeseed oil), desulfurized diesel fraction, and cracked diesel fraction, the values were measured in accordance with JIS K2279:2003 (Crude oil and petroleum products - Calorific value testing methods and methods for estimating by calculation) and estimated (using the formula for crude oil, kerosene, diesel, A-class fuel oil, and B-class fuel oil specified in "6. Gross calorific value estimation method, 6.3 e)1)"). For fuel oil composition, ethylene bottoms oil, directly desulfurized fuel oil fraction, and cracked fuel oil fraction, the values were measured in accordance with JIS K2279:2003 (Crude oil and petroleum products - Calorific value testing methods and methods for estimating by calculation) and estimated (using the formula for C-class fuel oil specified in "6. Gross calorific value estimation method, 6.3 e)1)". Nitrogen, carbon and hydrogen contents: Nitrogen, carbon and hydrogen contents were measured by the CHN Coder method using an elemental analyzer such as a carbon, hydrogen and nitrogen simultaneous determination device. Oxygen content: A value calculated based on JIS M8813:2006 (Coals and cokes - Elemental analysis methods) Appendix 5 (Calculation method for oxygen content), and is calculated by subtracting the above carbon content, hydrogen content, nitrogen content, sulfur content, and ash content from 100% by mass. Total Sediment Existence (TSE): Measured according to ISO 10307-1. 90% distillation temperature: The 90% distillation temperature in the distillation properties is a value measured in accordance with JIS K2254:1998 (Petroleum products - Distillation test method). Aromatic content, saturates content, and olefin content: For desulfurized gas oil fraction, cracked gas oil fraction, straight-run gas oil fraction, vacuum gas oil fraction, desulfurized cracked gas oil fraction, straight-run gas oil fraction, and hydrocracked gas oil fraction, the aromatics, saturates, and olefins content were measured using the High Performance Liquid Chromatography method specified in JPI-5S-49-2007, Petroleum Products - Hydrocarbon Type Testing Method. Aromatic content, saturates content, resin content, and asphaltene content: For ethylene bottoms, direct decomposition heavy oil fraction, cracked heavy oil fraction, atmospheric distillation residue fraction, and vacuum distillation residue fraction, these were measured by the TLC / FID method specified in IP-469 (International Standard Test Methods (IP Test Methods)).

[0121] [Performance evaluation criteria] Each performance was evaluated on the following scales 1 to 5, with the worst evaluation being the overall evaluation. A rating of C indicates failure. The evaluation of each performance is shown in Table 2.

[0122] 1. Oil passing performance The oil permeability of the fuel oil compositions of each Example and Comparative Example was evaluated by calculating the slope of filtration time (Tn) using the following method and by the following criteria. A: The slope of the filtration time (Tn) was 0.07 or less. B: The slope of the filtration time (Tn) was more than 0.07 and 0.12 or less. C: The slope of the filtration time (Tn) was greater than 0.12.

[0123] (Calculation method of filtration time slope) For the fuel oil composition, the slope of the filtration time was calculated based on the following method. (i) Measurement samples were taken into three graduated test tubes used in "JIS K2601:1998 - Crude Oil Testing Methods - 14. Water Debris Test Method 14.2 Water Debris Tester" (hereinafter also referred to as "Water Debris Tester") up to the 100 mL mark. Then, using the centrifuge used in the Water Debris Tester, the samples were centrifuged for 55 minutes at 60°C and a relative centrifugal force of 600. (ii) Prepare three 50 mL beakers and dispense the top 50 mL of the sample from the three centrifuged graduated test tubes into each 50 mL beaker. After dispensing, weigh the beaker to the nearest 0.1 mg and define the mass as M1 (g). Then, heat the dispensed sample for 15 minutes in a thermostatic bath maintained at 85±1°C. (iii) A filter paper (Whatman No. 4 (55 mm diameter)) with pores of 20 to 25 μm, which has been dried in a dryer at 110°C for 20 minutes, is placed in the filtration apparatus (hereinafter referred to as the filtration apparatus) specified in the actual sediment test method of JPI-5S-60-2000. An upper funnel is then placed on top of it and secured to prevent sample leakage. At this time, a packing with a 28 mm diameter hole is placed on top to adjust the diameter of the filtration surface to 28 mm. A vacuum pump capable of suction at an exhaust speed of 12 L / min is then attached to the other end of the vacuum bottle. The upper funnel is also heated to 85±1°C, the same temperature as the sample. (iv) Pour the first heated sample into the center of the filter paper, taking care not to let the sample touch the inner wall of the funnel. One minute after starting to pour the filter paper, start the vacuum pump and begin filtration. Measure the time required from the start of filtration until the sample is filtered and the entire filter paper is exposed (only the filtering surface with an inner diameter of 28 mm is required), and define the measured time required for filtration as t (seconds). Weigh the beaker after use, and define the weighed mass as M2 (g). (v) After stopping the vacuum pump, repeat the same procedure as for the first sample above for the second and third samples. During this time, do not perform any actions that change the measurement conditions, such as removing the tester or cleaning the equipment. Also, if the sample cannot be filtered due to blockage of the filter paper, end the filtration process and proceed to the next step. Specifically, if filtration is not complete within 6 minutes of starting filtration, end the filtration process. If the filter paper is clogged, dissolve the remaining sample in toluene and remove it with a pipette or similar. Then, after washing the funnel and filter paper with n-heptane, remove the upper funnel and check the edge of the filter paper. If the color is visible up to the edge of the filter paper, the sample has leaked, so retest should be performed. (vi) The filtration time per unit volume of fuel oil composition for each measurement was calculated using the following formula (1). T n =t n / (M / d) (1) (vii) In the above formula (1), n is the number of measurements, which is 3. n is the filtration time per unit volume of the fuel oil composition (seconds / cm) calculated from the time required for filtration in the nth measurement. 3 ), t nis the time (seconds) required for the nth measurement of filtration, M is the mass (M1-M2) (g) of the filtered fuel oil composition, and d is the density (g / cm) of the fuel oil composition at 15°C. 3 ) If filtration is not possible due to blockage of the filter paper, the result will be "not calculable." The vertical axis represents the filtration time per unit volume of the fuel oil composition, and the horizontal axis represents the number of measurements of the time required for filtration. From these plotted points, the slope of the approximate line was calculated by the least squares method, and this was taken as the slope of the filtration time (sec / cm 3 )

[0124] 2.Storage stability The storage stability of the fuel oil compositions of each of the Examples and Comparative Examples was evaluated according to the following criteria based on the potential sediment measured by the above-mentioned method. A. The potential sediment content was 0.08% by mass or less. B. The potential sediment content was greater than 0.08 mass% and less than 0.10 mass%. C. The potential sediment content was more than 0.10% by mass. 3. Combustion performance The combustion performance of the fuel oil compositions of each of the Examples and Comparative Examples was evaluated according to the following criteria based on the CCAI measured by the above method. A. CCAI is 825 or less, residual carbon content is 5.0 mass% or less, and kinematic viscosity at 50°C is 90.0mm 2 / s or less. B. CCAI is 835 or less, residual carbon content is 5.0 mass% or less, and kinematic viscosity at 50°C is 100.0 mm 2 / s or less. C. CCAI is greater than 835, residual carbon content is greater than 5.0% by mass, or kinematic viscosity at 50°C is less than 100.0mm 2 / s. 4.Environmental performance The environmental performance of the fuel oil compositions of the Examples and Comparative Examples was evaluated based on the sulfur content according to the following criteria. A. The sulfur content was 0.38 mass% or less. B. The sulfur content was more than 0.38 mass% and not more than 0.40 mass%. C. The sulfur content was more than 0.40% by mass. 5. Lubrication performance The viscosity suitability of the fuel oil compositions of the Examples and Comparative Examples was evaluated based on the kinematic viscosity at 50°C according to the following criteria. A. Kinematic viscosity at 50°C is 60.0 mm 2 / s or more. B. The kinematic viscosity at 50°C is 50.0 mm 2 / s or more 60.0mm 2 / s. C. The kinematic viscosity at 50°C is 50.0 mm 2 / s.

[0125] [Table 1]

[0126] [Examples 1 to 8, Comparative Examples 1 to 9] Various base materials having the properties and compositions shown in Table 1 were mixed in the proportions shown in Tables 2 and 3 to prepare the fuel oil compositions of Examples 1 to 8 and Comparative Examples 1 to 9. The composition and properties of each fuel oil composition obtained, measured by the above-mentioned methods, are shown in Tables 2 and 3. Furthermore, each fuel oil composition obtained was evaluated for oil passing performance, storage stability, combustion performance, environmental performance, and viscosity suitability by the above-mentioned methods. The results are shown in Tables 2 and 3.

[0127] [Table 2]

[0128] [Table 3]

[0129] As shown in Table 2, it was confirmed that the fuel oil composition for internal combustion engines of this embodiment effectively utilizes ethylene bottom oil and is excellent in the evaluations of oil passing performance, storage stability, combustion performance, environmental performance, and lubrication performance. Furthermore, since the storage stability was rated A, it is clear that the composition can meet the extremely strict storage stability requirements that can withstand use in internal combustion engines such as marine diesel engines, particularly diesel engines of various ships such as large ships equipped with centrifugal separators as pretreatment devices. On the other hand, as shown in Table 3, the fuel oil compositions of Comparative Examples 1 and 3, in which the animal and vegetable oil content was outside the range of 15.0 to 35.0% by volume, were confirmed to have poor combustion performance and storage stability. Also, the fuel oil composition of Comparative Example 2, which contained 35.0% by volume of animal and vegetable oil but did not contain ethylene bottom oil in a content of 0.14 times the animal and vegetable oil ratio, or 0.20 times or more, was confirmed to have poor storage stability. Furthermore, it was confirmed that the fuel oil compositions of Comparative Examples 4 to 9, which contained vegetable oil in an amount of 15.0 to 35.0% by volume but did not contain ethylene bottom oil, were inferior in at least one of storage stability, combustion performance, environmental friendliness, and lubrication performance. [Industrial Applicability]

[0130] The fuel oil composition for internal combustion engines of this embodiment is a fuel oil composition that effectively utilizes ethylene bottom oil and meets extremely strict requirements for oil passing performance and storage stability while also satisfying other performance requirements, namely, combustion performance, environmental performance, and lubrication performance, and is suitably used in internal combustion engines, particularly internal combustion engines such as marine diesel engines, and particularly suitably used in marine diesel engines, such as large ships, that are equipped with a centrifugal separator as a pretreatment device.

Claims

1. The following (a １ ) and (a ２ ) and the following animal and vegetable oils that satisfy all of the above (b １ ) to (b ３ ), wherein the content of the animal and vegetable oils in the composition is 15.0% by volume or more and 35.0% by volume or less, based on the total volume of the composition, and the content of the ethylene bottom oil in the composition is 0.20 times or more the content of the animal and vegetable oils in the composition, based on the total volume of the composition, and the fuel oil composition satisfies all of the following (1) to (4): (a １ ) Sulfur content is 0.02% by mass or less (a ２ ) Kinematic viscosity at 50 ° C. is 20.0 mm ２ / s or more 50.0mm ２ / s or less (b １ ) Sulfur content is less than 0.30% by mass (b ２ ) Kinematic viscosity at 50 ° C. is 10.0 mm ２ / s or more 50.0mm ２ / s or less (b ３ ) Aromatic content is 80.0% by volume or more (1) Sulfur content is 0.400% by mass or less (2) Kinematic viscosity at 50 ° C. is 50.0 mm ２ / s or more 100.0mm ２ / s or less (3) CCAI is 835 or less (4) Potential sediment is 0.10% by mass or less

2. Furthermore, the following (c １ ) and (c ２ 2. The fuel oil composition for internal combustion engines according to claim 1, comprising a directly desiccant heavy oil fraction satisfying all of the above criteria, and the content of the directly desiccant heavy oil fraction based on the total amount of the components is 50.0% by volume or more and 70.0% by volume or less. (c １ )Sulfur content is 0.50 mass% or more and 0.60 mass% or less (c ２ ) Kinematic viscosity at 50 ° C. is 100.0 mm ２ / s or more 200.0mm ２ / s or less

3. 3. The fuel oil composition for internal combustion engines according to claim 1, which is used in a marine diesel engine equipped with a centrifugal separator as a pretreatment device.

4. The following (a １ ) and (a ２ ) and animal and vegetable oils that satisfy all of the above. The following (b １ ) to (b ３ ) an ethylene bottom oil satisfying all of the above requirements, The content of the animal and vegetable oil based on the total amount of the composition is 15.0% by volume or more and 35.0% by volume or less, The ethylene bottom oil is mixed so that the content of the ethylene bottom oil based on the total amount of the composition is 0.20 times or more the content of the animal and vegetable oil based on the total amount of the composition. A method for producing a fuel oil composition for internal combustion engines, which satisfies all of the following (1) to (4): (a １ ) Sulfur content is 0.02% by mass or less (a ２ ) Kinematic viscosity at 50 ° C. is 20.0 mm ２ / s or more 50.0mm ２ / s or less (b １ ) Sulfur content is less than 0.30% by mass (b ２ ) Kinematic viscosity at 50 ° C. is 10.0 mm ２ / s or more 50.0mm ２ / s or less (b ３ ) Aromatic content is 80.0% by volume or more (1) Sulfur content is 0.400% by mass or less (2) Kinematic viscosity at 50 ° C. is 50.0 mm ２ / s or more 100.0mm ２ / s or less (3) CCAI is 835 or less (4) Potential sediment is 0.10% by mass or less

5. Furthermore, the following (c １ ) and (c ２ 5. A method for producing a fuel oil composition for internal combustion engines according to claim 4, wherein directly decomposed heavy oil fractions satisfying all of the above criteria are mixed so that the content of the directly decomposed heavy oil fractions based on the total amount of the components is 50.0% by volume or more and 70.0% by volume or less. (c １ )Sulfur content is 0.50 mass% or more and 0.60 mass% or less (c ２ ) Kinematic viscosity at 50 ° C. is 100.0 mm ２ / s or more 200.0mm ２ / s or less

Images