JP2021031624A - Fuel oil composition for internal combustion engine - Google Patents

Abstract

To provide a fuel oil composition for an internal combustion engine having excellent storage stability and environmental performance and also excellent thermal stability performance.SOLUTION: The fuel oil composition for an internal combustion engine includes 50.0 volume% or more and less than 90.0 volume% of a direct-desulfurized heavy oil fraction based on a composition total amount, which satisfies all of (a1) a sulfur content of 0.450 mass% or less, (a2) an asphaltene content of 1.5 mass% or less and (a3) a carbon/hydrogen (molar ratio) of the asphaltene content of 1.10 or more and 1.20 or less: and satisfies all of (1) a sulfur content of 0.500 mass % or less and (2) a kinematic viscosity at 50°C of 10.00 mm2/s or more and 100.0 mm2/s or less.SELECTED DRAWING: None

Description

The present invention relates to a fuel oil composition for an internal combustion engine.

JIS K2205: 2006 type 3 heavy oil (hereinafter, also referred to as "C heavy oil") has a higher calorific value per unit volume than kerosene, light oil, A heavy oil (JIS K2205: 2006 type 1 heavy oil) and the like. Since the amount (volume) of fuel oil used can be reduced and it is inexpensive, it is widely used as fuel oil for internal combustion engines such as marine diesel engines and as fuel oil for external fuel oils such as power generation boilers. There is.
On the other hand, C heavy oil generally has a higher sulfur content and residual carbon content than kerosene, light oil, A heavy oil, etc., has a large environmental load, and is prone to sludge generation, and the fuel oil filter is clogged due to sludge generation. It is known to be more likely to occur. On the other hand, a C heavy oil composition having a density of 15 ° C., a kinematic viscosity of 50 ° C., a residual carbon content, an asphaltene content, a sulfur content, and an aromatic content within a predetermined range has been proposed (see, for example, Patent Document 1). ..

Further, as a fuel oil for ships, a fuel oil satisfying ISO8217 "Petroleum products-Fuels (class F) -Specification of marine fuels" is known. Since this fuel oil for ships may cause clogging of the fuel oil filter, predetermined sulfur content, residual carbon content, asphaltene content, 15 ° C. density, patent by hot filtration (ISO 10307-1), etc. A heavy oil composition containing a predetermined amount of directly desulfurized heavy oil having properties has been proposed (see, for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 2013-203802 Japanese Unexamined Patent Publication No. 2014-028977

However, even if the fuel oil composition for an internal combustion engine having improved oil permeability is used, especially when the fuel oil composition for an internal combustion engine is used for a large diesel engine such as a diesel engine of a large ship, the fuel oil filter is blocked during normal use. The frequency tends to increase, and when used after long-term storage in a fuel oil tank or the like in a ship, the frequency of blockage tends to increase. Therefore, fuel oil compositions for internal combustion engines are required to have storage stability performance that maintains normal temperature oil flow performance even after long-term storage, and the required performance is becoming more stringent.

Therefore, the present inventor has proposed a fuel oil composition for an internal combustion engine containing a high aromatic content of 80.0% by volume or more and 99.0% by volume or more as a fuel oil composition having a low sulfur content (for example). Japanese Patent Application No. 2018-0367665, Japanese Patent Application No. 2018-0367661, etc.). These fuel oil compositions for internal combustion engines have filtration performance such as normal temperature oil flow performance and storage stability performance, environmental performance that can reduce the sulfur oxide concentration in exhaust gas, and fluidity is significantly reduced in low temperature environments in the piping. It is excellent in ease of handling and does not exhibit remarkable behavior in response to changes in the environment such as temperature, such as staying in the air.

By the way, some diesel engines of various ships such as large ships are supplied after being heated to a temperature of about 100 to 150 ° C. at the engine inlet. It wasn't done. The fuel oil composition for internal combustion engines used for diesel engines of various ships such as large ships has not only stable storage performance and environmental performance, but also a stable fuel oil composition even when heated to the above temperature range. Thermal stability performance that can demonstrate the performance as a vehicle is required. However, the fuel oil composition described in the above patent document has room for improvement, especially in terms of thermal stability performance.

As a result of diligent studies in view of the above problems, the present inventors have found that the following invention can solve the problem. That is, the present invention provides a fuel oil composition for an internal combustion engine having the following configuration.

[1] The following ( ₁ ) to (a ₃ ), which satisfies all of the following (a 1) to (a 3), is contained in a content of 50.0% by volume or more and less than 90.0% by volume based on the total amount of the composition. A fuel oil composition for an internal combustion engine that satisfies both 1) and (2).
(A ₁ ) Sulfur content is 0.450% by mass or less (a ₂ ) Asphaltene content is 1.5% by mass or less (a ₃ ) Carbon / hydrogen (molar ratio) of asphaltene is 1.10 or more 1 .20 or less (1) sulfur content of 0.500 wt% or less (2) 50 kinematic viscosity at ℃ is 10.00 mm ² / s or more 100.0 mm ² / s or less [2] in addition, the carbon / hydrogen (molar The fuel oil composition for an internal combustion engine according to claim 1, which comprises a distillate having a ratio) of 0.60 or more.
[3] The fuel oil composition for an internal combustion engine according to the above [2], which contains the fraction in an amount of 10.0% by volume or more as the content based on the total amount of the composition.
[4] The fuel for an internal combustion engine according to any one of [1] to [3] above, wherein the content of the direct-removed heavy oil fraction based on the total amount of the composition is 50.0% by volume or more and 75.0% by volume or less. Oil composition.
[5] The fuel oil composition for an internal combustion engine according to the above [4], wherein the content of the distillate based on the total amount of the composition is 25.0% by volume or more and 50.0% by volume or less.
[6] The fuel for an internal combustion engine according to any one of the above [1] to [5], which is used as a pretreatment device for a diesel engine having a heating device having an inlet temperature of a fuel oil composition for an internal combustion engine of 100 ° C. or higher. Oil composition.

According to the present invention, it is possible to provide a fuel oil composition for an internal combustion engine having excellent thermal stability performance as well as excellent storage stability performance and environmental performance.

Hereinafter, a fuel oil composition for an internal combustion engine according to an embodiment of the present invention (hereinafter, may be simply referred to as “the present embodiment”) will be specifically described. In addition, in this specification, the numerical values relating to "below", "greater than or equal to" and "~" regarding the description of a numerical range are numerical values that can be arbitrarily combined, and the numerical values of Examples are used as upper limit values or lower limit values. It is a numerical value to be obtained.

[Fuel oil composition for internal combustion engine]
The fuel oil composition for an internal combustion engine of the present embodiment contains _{a directly removed heavy oil fraction that satisfies all of the following (a 1} ) to (a ₃ ) as a content of 50.0% by volume or more based on the total amount of the composition 90. A fuel oil composition for an internal combustion engine, which comprises less than 0% by volume and satisfies both the following (1) and (2).
(A ₁ ) Sulfur content is 0.450% by mass or less (a ₂ ) Asphaltene content is 1.5% by mass or less (a ₃ ) Carbon / hydrogen (molar ratio) of asphaltene is 1.10 or more 1 .20 or less (1) sulfur content of 0.500 wt% or less (2) 50 kinematic viscosity at ℃ is 10.00 mm ² / s or more 100.0 mm ² / s or less

(Composition and properties of fuel oil composition for internal combustion engine)
The fuel oil composition for an internal combustion engine of the present embodiment satisfies all of the compositions and properties defined in the following (1) and (2).
(1) Sulfur content The sulfur content of the fuel oil composition for an internal combustion engine of the present embodiment is 0.500% by mass or less. If the sulfur content is not within the above range, corrosion may occur due to the rise of sulfur oxides in the exhaust gas, which may increase the burden on the environment and reduce the environmental performance. Considering the suppression of the occurrence of corrosion and the improvement of environmental performance, the sulfur content is preferably 0.450% by mass or less, more preferably 0.405% by mass or less. Further, the smaller the sulfur content is, the more preferable it is, and the lower limit is not particularly limited, but it is usually 0.01% by mass or more from the viewpoint of improving storage stability and lubricity.
In the present specification, the sulfur content is measured by selecting a measuring method according to the content, and when the content is 0.01 to 5% by mass, JIS K 2541-4: 2003 (crude oil and petroleum). Product-Sulfur content test method-Part 4: Radial excitation method).

(2) a kinematic viscosity at 50 ° C. for an internal combustion engine fuel oil composition kinematic viscosity present embodiment at 50 ° C. is not more than 10.00 mm ² / s or more 100.0 mm ² / s. If the kinematic viscosity at 50 ° C. is not within the above range, it becomes difficult to meet the usage range of various devices such as pumps and flow meters, lubricity cannot be ensured, and it can be used as a fuel oil composition for internal combustion engines. It may disappear.
From the viewpoint of easily adapting to the range of use of the above-mentioned various devices and improving lubricity, the kinematic viscosity at 50 ° C. is preferably 15.00 mm ² / s or more, more preferably 25.00 mm ² / s or more, and further. It is preferably 50.00 mm ² / s or more, and the upper limit is preferably 90.00 mm ² / s or less, more preferably 85.00 mm ² / s or less, and further preferably 75.00 mm ² / s or less.
In the present specification, the kinematic viscosity at 50 ° C. is a value measured according to JIS K 2283: 2000 (kinetic viscosity test method for crude oil and petroleum products).

Further, the fuel oil composition for an internal combustion engine of the present embodiment includes at least one selected from the following properties (3) to (8) in addition to the above-mentioned properties (1) and (2). It is preferable to be satisfied, and it is particularly preferable to satisfy all of the properties and compositions (3) to (8) below.

(3) Density at 15 ° C. The density of the fuel oil composition for an internal combustion engine of the present embodiment at 15 ° C. is preferably 0.9850 g / cm ³ or less, more preferably 0.9750 g / cm ³ or less, still more preferably 0. It is 9650 g / cm ³ or less, and the lower limit is preferably 0.8600 g / cm ³ or more, more preferably 0.8800 g / cm ³ or more, and further preferably 0.9100 g / cm ³ or more. When the density at 15 ° C. is within the above range, it becomes difficult to reduce the sludge separation performance by the centrifuge attached in front of the diesel engine for ships such as large ships, so that the storage stability performance is improved. ..
In the present specification, the density at 15 ° C. is a value measured according to JIS K 2249-1: 2011 (crude oil and petroleum products-how to obtain density-Part 1: vibration method).

(4) Flash Point The flash point of the fuel oil composition for an internal combustion engine of the present embodiment is preferably 70.0 ° C. or higher, more preferably 95.0 ° C. or higher, still more preferably 130, from the viewpoint of handling safety. It is 0.0 ° C. or higher, more preferably 165.5 ° C. or higher.
In the present specification, the flash point is a value measured according to JIS K 2265-3: 2007 (crude oil and petroleum products-flash point test method-Part 3: Penschee Quartense sealing method).

(5) Pour point The pour point of the fuel oil composition for an internal combustion engine of the present embodiment is preferably 30.0 ° C. or lower. When the pour point is 30.0 ° C. or lower, the handleability is improved. From the same viewpoint as this, the pour point is preferably 20.0 ° C. or lower, more preferably 15.0 ° C. or lower, still more preferably 10.0 ° C. or lower. The lower limit of the pour point is preferably as low as possible, and there is no particular limitation, but it is usually about -10.0 ° C. or higher.
In the present specification, the pour point is a value measured according to JIS K 2269: 1987 (pour point of crude oil and petroleum products and cloud point test method of petroleum products). Here, regarding the fuel oil composition and the direct deweighted oil fraction, as a sample used for measurement, 500 mL thereof is left at room temperature (10 to 20 ° C.) for 168 hours (7 days) and then heated to 45 ° C. for preliminary treatment. It is decided to use the one that did not perform.

(6) Residual carbon content The residual carbon content of the fuel oil composition for an internal combustion engine of the present embodiment is preferably 3.5% by mass or less, more preferably 3.0% by mass or less, still more preferably 2.5% by mass or less. The lower limit is not particularly limited, but is usually 0.1% by mass or more. When the residual carbon content is within the above range, it becomes easy to maintain the combustion performance of the fuel oil composition for the internal combustion engine, and the effect of reducing soot generation due to poor combustion is improved, so that the internal combustion engine can be operated more stably. ..
In the present specification, the residual carbon content is a value measured according to JIS K 2270-1: 2009 (crude oil and petroleum products-method for determining residual carbon content-Part 1: Conradson method). As for the lightly decomposed gas oil, 10% residual oil prepared in accordance with Annex A was used.

(7) Total calorific value The total calorific value of the fuel oil composition for an internal combustion engine of the present embodiment is preferably 40,500 (kJ / L) or more, more preferably 40,800 (from the viewpoint of improving fuel efficiency performance). It is kJ / L) or more, more preferably 42,200 (kJ / L) or more.
In the present specification, the total calorific value is measured and estimated according to JIS K2279: 2003 (crude oil and petroleum products-calorific value test method and calculation method-) for heavy cracked gas oil and light cracked gas oil. Estimated by the calculation formula for crude oil, kerosene, light oil, A heavy oil and B heavy oil specified in "6. Total calorific value estimation method, 6.3 e) 1)". The fuel oil composition and the direct deweighted oil fraction are measured and estimated according to JIS K2279: 2003 (crude oil and petroleum products-calorific value test method and estimation method by calculation-) ("6. Total calorific value"). Estimating method, estimated by the calculation formula for C heavy oil specified in 6.3 e) 1) ”.

(8) Latent Sedge The latent sediment of the fuel oil composition for an internal combustion engine of the present embodiment is preferably 0.10% by mass or less, more preferably 0.05% by mass or less, still more preferably 0.03% by mass or less, and more. More preferably, it is 0.02% by mass or less. When the latent segment is within the above range, the oil permeability of the fuel oil filter after the fuel oil is stored is ensured, and better storage stability performance can be obtained.
In the present specification, the latent sediment can be measured according to JPI-5S-60-2000 (crude oil and petroleum products-sediment test method-).

(Direct de-heavy oil fraction)
The fuel oil composition for an internal combustion engine of the present embodiment contains _{a direct-removed heavy oil fraction that satisfies all of the following (a 1} ) to (a ₃ ) as a content based on the total amount of the composition, which is 50.0% by volume or more and 90.0. Included in less than% volume. In the present embodiment, the direct decarburized oil fraction is a heavy oil fraction obtained by directly desulfurizing atmospheric distillation residual oil and / or vacuum distillation residual oil with a desulfurization apparatus, and in the present embodiment, the heavy oil fraction. A distillate _{that satisfies all of the following (a 1} ) to (a ₃ ) is defined as a direct fuel oil distillate.
(A ₁ ) Sulfur content is 0.450% by mass or less (a ₂ ) Asphaltene content is 1.5% by mass or less (a ₃ ) Carbon / hydrogen (molar ratio) of asphaltene is 1.10 or more 1 .20 or less

(A ₁ ) Sulfur content The sulfur content of the direct fuel oil distillate is 0.450% by mass or less. If the sulfur content is more than 0.450% by mass, it becomes difficult to reduce the sulfur content of the fuel oil composition for an internal combustion engine of the present embodiment to 0.500% by mass or less, so that the sulfur oxide in the exhaust gas increases. Corrosion may occur due to this, which may increase the load on the environment and reduce the environmental performance. From the viewpoint of suppressing the occurrence of corrosion and improving the environmental performance, the sulfur content of the directly removed heavy oil fraction is preferably 0.350% by mass or less, more preferably 0.300% by mass or less, still more preferably. It is 0.285% by mass or less.

(A ₂ ) Asphaltene content The asphaltene content of the direct fuel oil distillate is 1.5% by mass or less. If the asphaltene content is more than 1.5% by mass, the storage stability is lowered. From the viewpoint of improving storage stability, the asphaltene content is preferably 1.4% by mass or less, more preferably 1.3% by mass or less, and even more preferably 1.25% by mass or less.
In the present specification, the asphaltene content is determined by weighing 50 g of a sample (directly removed heavy oil distillate), adding 1500 cc of n-heptane (special grade) to the sample, and performing reflux treatment for 1 hour to obtain a circular quantitative filter paper (No. After filtering with 5C), the residue is put into a cylindrical filter paper, soxhlet is extracted with n-heptane (special grade) using a Soxhlet extractor together with the cylindrical filter paper, and then soxhlet is further extracted with toluene (special grade), and then a solvent. The n-heptane insoluble and toluene-soluble component obtained by removing the above was weighed and used as the asphaltene content.

(A ₃ ) Carbon / hydrogen (molar ratio) of asphaltene
The carbon / hydrogen (molar ratio) of the asphaltene content of the direct fuel oil fraction is 1.10 or more and 1.20 or less. If the carbon / hydrogen (molar ratio) is more than 1.20, the thermal stability performance deteriorates, and if it is less than 1.10, the storage stability deteriorates. From the viewpoint of improving the thermal stability performance as well as the storage stability, the carbon / hydrogen (molar ratio) of the asphaltene content of the direct fuel oil fraction is preferably 1.11 or more, more preferably 1.13 or more, still more preferably 1. It is .15 or more, and the upper limit is preferably 1.19 or less, more preferably 1.17 or less.
In the present specification, the carbon / hydrogen (molar ratio) of the asphaltene content is the asphaltene content (n-heptane insoluble and toluene-soluble component) obtained by the _{above-mentioned measurement method of “(a 2) asphaltene content”.} It is a value obtained by measuring the carbon and hydrogen contents (mass%) of asphaltene by the CHN coder method and calculating the molar ratio. The measurement by the CHN coder method may be performed using, for example, an elemental analyzer such as a carbon / hydrogen / nitrogen simultaneous quantifier.

Further, the direct fuel oil fraction satisfies at least one selected from the following properties _{(a 4} ) to (a ₁₄ ) in addition to _{the above-mentioned properties and compositions (a 1} ) to (a _3). It is preferable that all of the following _{properties and compositions (a 4} ) to (a ₁₄ ) are satisfied.

(A ₄ ) Density at 15 ° C. The density of the direct deweighted oil distillate at 15 ° C. is preferably 0.9150 g / cm ³ or more, more preferably 0.9175 g / cm ³ or more, ^{still more preferably 0.9200 g / cm 3} As described above, the upper limit is preferably 0.9350 g / cm ³ or less, more preferably 0.9300 g / cm ³ or less, and further preferably 0.9280 g / cm ³ or less. When the density of the directly removed heavy oil fraction at 15 ° C. is within the above range, the sludge separation performance of the fuel oil composition in the centrifuge is improved.

_(A 5) the kinematic viscosity at 50 ° C. kinematic viscosity direct desulfurization of heavy oil fractions at 50 ° C. is preferably 50.00 mm ² / s or more, more preferably 75.00mm ² / s or more, more preferably 100.0 mm ² It is / s or more, and the upper limit is preferably 150.0 mm ² / s or less, more preferably 125.0 mm ² / s or less, and further preferably 115.0 mm ² / s or less. When the kinematic viscosity at 50 ° C. is within the above range, since the kinematic viscosity at 50 ° C. for an internal combustion engine fuel oil composition of the present embodiment easily than 10.00 mm ² / s or more 100.0 mm ² / s, the pump In addition, it becomes easier to adapt to the range of use of various devices such as flow meters, and the lubricity is improved.

(A ₆ ) Flash point The flash point of the directly removed heavy oil fraction is preferably 70.0 ° C. or higher, more preferably 120.0 ° C. or higher, still more preferably 155.0 ° C. or higher from the viewpoint of handling safety. , Even more preferably 180.0 ° C.

(A ₇ ) Pour point The pour point of the directly removed heavy oil fraction is preferably 25.0 ° C. or lower, more preferably 20.0 ° C. or lower, still more preferably 17.5 ° C. or lower. When the pour point is within the above range, the handleability is improved. The lower limit of the pour point is preferably as low as possible, and there is no particular limitation, but it is usually about -10.0 ° C. or higher.

(A ₈ ) Residual carbon content The residual carbon content of the direct deweighted oil fraction is preferably 6.0% by mass or less, more preferably 5.0% by mass or less, still more preferably 4.0% by mass or less, and the lower limit. Although there is no particular limitation, it is usually 0.1% by mass or more, preferably 1.0% by mass or more. When the residual carbon content is within the above range, it becomes easy to maintain the combustion performance of the fuel oil composition for the internal combustion engine, and the effect of reducing soot generation due to poor combustion is improved, so that the internal combustion engine can be operated more stably. ..

(A ₉ ) Existing Sedge The actual Sedge of the direct deweighted oil fraction is preferably 0.05% by mass or less, more preferably 0.03% by mass or less, and further preferably 0.02% by mass or less. When the actual sediment is within the above range, the storage stability is improved.
In the present specification, the actual sediment is a value measured according to JPI-5S-60-2000 (crude oil and petroleum products-sediment test method-).

(A ₁₀ ) Latent Sedge The latent sediment of the direct deweighted oil fraction is preferably 0.10% by mass or less, more preferably 0.05% by mass or less, still more preferably 0.03% by mass or less, still more preferably 0. It is 0.02% by mass or less. When the latent segment is within the above range, the oil permeability of the fuel oil filter after the fuel oil is stored is ensured, and better storage stability performance can be obtained.

(A ₁₁ ) Moisture content The water content of the directly removed heavy oil fraction is preferably 0.10% by volume or less, more preferably 0.05% by volume or less, still more preferably 0.01% by volume based on the total amount of the composition. % Or less. When the water content is within the above range, it is possible to suppress a decrease in storage stability (sludge formation due to an emulsion of asphaltene and water) and prevent clogging due to sludge.
In the present specification, the water content is a value measured according to JIS K 2275-3: 2015 (crude oil and petroleum products-how to obtain water-Part 3: Karl Fischer titration method).

(A ₁₂ ) Aromatic content The aromatic content of the direct fuel oil fraction is preferably 50.0% by mass or more, more preferably 52.5% by mass or more, and the upper limit is preferably 70.0. It is 55.5% by mass or less, more preferably 55.5% by mass or less. When the aromatic content is within the above range, the fuel oil filter blockage due to sludge generation is further suppressed, so that the storage stability is improved and the combustion performance is also improved.
In the present specification, the aromatic content of the directly desorbed heavy oil fraction and the heavily decomposed gas oil is measured by the TLC / FID method specified in IP-469 (International Standard Test Method (IP Test Methods)). The value. The lightly decomposed gas oil was measured by a petroleum product-hydrocarbon type test method-high performance liquid chromatography method specified in JPI-5S-49-2007.

(A ₁₃ ) Saturation content and resin content The saturation content of the direct deweighted oil fraction is preferably 20.0% by mass or more, more preferably 30.0% by mass or more, still more preferably 35.0. It is mass% or more, and the upper limit is preferably 50.0 mass% or less, more preferably 40.0 mass% or less. The resin content is preferably 2.0% by mass or more, more preferably 3.0% by mass or more, and the upper limit is preferably 10.0% by mass or less, more preferably 6.0% by mass or less, still more preferably. Is 4.0% by mass or less. When the saturation content is within the above range, the combustion performance is improved, and when the resin content is within the above range, the fuel oil filter blockage due to the generation of sludge is further suppressed, so that the storage stability is improved and combustion is performed. Performance is also improved.
In the present specification, the saturated content and the resin content are values measured by the same method as the above-mentioned method for measuring the aromatic content.

(A ₁₄ ) Total calorific value The total calorific value of the direct fuel oil distillate is preferably 40,500 (kJ / L) or more, more 40,800 (kJ / L) or more, and more preferably 41,000 (kJ / kJ /). L) That's all. When the total calorific value is within the above range, excellent fuel efficiency can be obtained.

(Content of direct fuel oil fraction)
In the fuel oil composition for an internal combustion engine of the present embodiment, the content of the direct-removed heavy oil fraction based on the total amount of the composition is 50.0% by volume or more and less than 90.0% by volume. If it is not within the above range, excellent storage stability performance, environmental performance and thermal stability performance cannot be obtained in a well-balanced manner, and if it is 90.0% by volume or more, the storage stability is lowered. Environmental performance and thermal stability performance cannot be obtained in a well-balanced manner.
From the viewpoint of obtaining more excellent storage stability performance, environmental performance and thermal stability performance in a well-balanced manner, the content of the directly deducted heavy oil fraction is preferably 52.5% by volume or more, more preferably 55.0% by volume or more. The upper limit is preferably 75.0% by volume or less, more preferably 65.0% by volume or less.

(Distillate with carbon / hydrogen (molar ratio) of 0.60 or more)
The fuel oil composition for an internal combustion engine of the present embodiment preferably contains a fraction having a carbon / hydrogen (molar ratio) of 0.60 or more. By containing this distillate, more excellent storage stability performance, environmental performance and heat stability performance can be obtained in a well-balanced manner, and the heat stability performance is particularly improved. The carbon / hydrogen (molar ratio) is more preferably 0.65 or more, still more preferably 0.70 or more, still more preferably 0.70 or more, from the viewpoint of improving storage stability, environmental performance and thermal stability, especially thermal stability. Is 0.75 or more. The upper limit is not particularly limited, and is, for example, about 0.85 or less.
As the fraction having such properties, a fraction having a carbon / hydrogen (molar ratio) of 0.60 or more can be appropriately selected and used from the light oil fraction and the heavy oil fraction described later.
In the present specification, the carbon / hydrogen (molar ratio) of the distillate is a value obtained by measuring the carbon and hydrogen contents (mass%) of the distillate by the CHN coder method and calculating the molar ratio. The measurement by the CHN coder method may be performed using, for example, an elemental analyzer such as a carbon / hydrogen / nitrogen simultaneous quantifier.

(Content of fraction with carbon / hydrogen (molar ratio) of 0.60 or more)
In the fuel oil composition for an internal combustion engine of the present embodiment, the content of a fraction having a carbon / hydrogen (molar ratio) of 0.60 or more based on the total amount of the composition is preferably 10.0% by volume or more, more preferably 25. It is 0.0% by volume or more, more preferably 35.0% by volume or more, and the upper limit is preferably 50.0% by volume or less, more preferably 45.0% by volume or less. When the content of the distillate is within the above range, more excellent storage stability performance, environmental performance and heat stability performance can be obtained in a well-balanced manner, and above all, the heat stability performance can be improved.

(Light oil fraction)
The fuel oil composition for an internal combustion engine of the present embodiment contains a gas oil fraction such as a straight gas gas distillate, a vacuum gas oil distillate, a desulfurized gas oil distillate, a decomposed gas oil distillate, a desulfurized gas oil fraction, and a direct gas oil distillate. Can be contained. Further, as described above, it is preferable to use a fraction having a carbon / hydrogen (molar ratio) of 0.60 or more among these gas oil fractions.
・ Direct distillate gas oil fraction (light oil distillate obtained by atmospheric distillation of crude oil with an atmospheric distillation unit)
・ Reduced gas oil fraction (light oil fraction obtained by vacuum distillation of atmospheric distillation residual oil with a vacuum distillation apparatus)
・ Desulfurized gas oil fraction (direct gas oil fraction and / or gas oil fraction obtained by desulfurizing vacuum gas oil fraction)
Light or heavy cracked gas oil fraction (light or heavy gas oil fraction obtained by fluid cracking of atmospheric distillation residual oil and / or vacuum distillation residual oil)
・ Desulfurization cracked gas oil fraction (light oil fraction obtained by desulfurizing the cracked gas oil fraction)
Direct desulfurization gas oil fraction (light oil fraction obtained by directly desulfurizing atmospheric distillation residual oil and / or vacuum distillation residual oil with a desulfurization apparatus)

(Characteristics of light oil fraction)
As the properties of the gas oil fraction that can be used in the present embodiment, it is preferable that the light oil fraction has the following properties, for example, in addition to the carbon / hydrogen (molar ratio) described above. When the gas oil fraction has the following properties, excellent storage stability performance, environmental performance and thermal stability performance can be easily obtained.
The sulfur content is preferably 0.65% by mass or less, more preferably 0.60% by mass or less, still more preferably 0.55% by mass or less.
The density at 15 ° C. is preferably 0.8900 g / cm ³ or more, more preferably 1.000 g / cm ³ or more, and the upper limit is preferably 1.0400 g / cm ³ or less, more preferably 1.0300 g / cm ^3. It is as follows.
The kinematic viscosity at 50 ° C. is preferably 50.00 mm ² / s or less, more preferably 45.00 mm ² / s or less, and the lower limit is preferably 2.000 mm ² / s or more, more preferably 2.500 mm ² / s or more. Is.
The pour point is preferably 15.0 ° C. or lower, more preferably 12.5 ° C. or lower.
The flash point is preferably 65.0 ° C. or higher, more preferably 70.0 ° C. or higher.
The total calorific value is preferably 40,000 (kJ / L) or more, more preferably 43,000 (kJ / L) or more.
As for the distillation properties, the initial distillation point is preferably 170.0 ° C. or higher, more preferably 180.0 ° C. or higher, and the 10% by volume distillation temperature is preferably 210.0 ° C. or higher, more preferably 225.0 ° C. As described above, the 50% by volume distillation temperature is preferably 270.0 ° C. or higher, more preferably 280.0 ° C. or higher. When the initial distillation point, 10% by volume distillation temperature and 50% by volume distillation temperature are within the above range, the combustion performance is improved, the flash point is easily set within the above range, and the handling safety is improved. Stable operation of the engine becomes easy. It is also advantageous in terms of reducing odor.
In the present specification, the initial distillation point of the distillation properties, the 10% by volume distillation temperature and the 50% by volume distillation temperature are values measured according to JIS K2254: 1998 (Petroleum products-distillation test method-).

(Other heavy oil fractions)
The fuel oil composition for an internal combustion engine of the present embodiment may contain C heavy oil, atmospheric distillation residual oil, vacuum distillation residual oil and cracked heavy oil in addition to the above direct deheavy oil fraction. Further, as described above, it is preferable to use a fraction having a carbon / hydrogen (molar ratio) of 0.60 or more among these heavy oil fractions.
-C heavy oil / atmospheric distillation residual oil (residual oil obtained by atmospheric distillation of crude oil with an atmospheric distillation apparatus)
-Remaining oil for vacuum distillation (residual oil obtained by vacuum distillation of atmospheric distillation residual oil with a vacuum distillation apparatus)
・ Decomposed heavy oil (heavy oil obtained by cracking direct decompression of heavy oil fraction)

(Characteristics of other heavy oil fractions)
As the properties of the above-mentioned other heavy oil fractions that can be used in the present embodiment, it is preferable that they have, for example, the following properties other than the above-mentioned carbon / hydrogen (molar ratio). When other heavy oil fractions have the following properties, excellent storage stability performance, environmental performance and thermal stability performance can be easily obtained.
The sulfur content is preferably 1.2% by mass or less, more preferably 1.0% by mass or less, and even more preferably 0.6% by mass or less. The lower limit is usually 0.51% by mass or more.
The aromatic content is preferably 40% by volume or more, more preferably 50% by volume or more, and even more preferably 55% by volume or more.
Density at 15 ℃ is preferably 0.9000g / cm ³ or more, more preferably 0.9600g / cm ³ or more, more preferably 1.0100g / cm ³ or more and the upper limit is 1.3000g / cm ³ or less preferable.
Kinematic viscosity at 50 ° C. is preferably less 190.0mm ² / s, more preferably not more than 160.0mm ² / s, also the extent 30.00 mm ² / s or more as a lower limit, preferably 50.00 mm ² / s or more Is.
The pour point is preferably 15.0 ° C. or lower, more preferably 12.5 ° C. or lower, and even more preferably 10.0 ° C. or lower.
The total calorific value 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.
The residual carbon content is preferably 8.0% by mass or less, more preferably 6.0% by mass or less, and further preferably 5.0% by mass or less.

(Various additives)
The fuel oil composition for an internal combustion engine of the present embodiment has an antioxidant, a low-temperature fluidity improver, a lubricity improver, and a cetane number as various additives as necessary within a range in which the above properties can be maintained. Various additives such as improvers, combustion accelerators, cleaning agents, sludge dispersants, and fungicides can be appropriately selected and blended. In addition, coumarin may be blended from the viewpoint of light oil take-back tax.

(Use)
The fuel oil composition for an internal combustion engine of the present embodiment is a fuel oil composition that is used for an internal combustion engine and has excellent thermal stability as well as excellent storage stability and environmental performance. Therefore, it is particularly preferably used for internal combustion engines such as diesel engines for ships, and among them, as a pretreatment device, a large ship having a heating device having an inlet temperature of a fuel oil composition for an internal combustion engine preferably about 100 ° C. or higher and 150 ° C. or lower. It is suitably used for diesel engines of various ships such as.

[Manufacturing method of fuel oil composition for internal combustion engine]
The fuel oil composition for an internal combustion engine of the present embodiment contains the above-mentioned direct deheavy oil fraction, preferably a distillate having a carbon / hydrogen (molar ratio) of 0.60 or more, and other light oil distillates and heavy oil distillates. The content of the fraction is 50.0% by volume or more and less than 90.0% by volume, and preferably the content of the fraction having a carbon / hydrogen (molar ratio) of 0.60 or more is 25.0% by volume. It can be produced by blending so as to be% or more.

There are no particular restrictions on the order in which the direct de-heavy oil fraction, the preferably used carbon / hydrogen (molar ratio) of 0.60 or more, various other light oil fractions, heavy oil fractions, and various additives are blended, for example. , A fraction having a carbon / hydrogen (molar ratio) of 0.60 or more, various other light oil fractions, a heavy oil fraction, and various additives may be sequentially added and mixed with the direct deweighted heavy oil fraction. , After mixing various additives in advance, even if the direct de-heavy oil fraction, the fraction with carbon / hydrogen (molar ratio) of 0.60 or more, and various other light oil fractions and heavy oil fractions are mixed. Good.

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 base material were determined according to the following method as described above.

[Measurement of properties and composition]
The properties and compositions of the various substrates of the direct-depleted heavy oil fraction, the heavy cracked gas oil fraction and the lightly decomposed gas oil fraction used in Examples and Comparative Examples, and the properties and composition of the fuel oil compositions of Examples and Comparative Examples It was measured by the following method. Table 1 shows the properties and compositions of various base materials. Table 2 shows the properties and composition of the fuel oil composition.
-Sulfur content: Measured according to JIS K 2541-4: 2003 (crude oil and petroleum products-sulfur content test method-Part 4: radiation excitation method).
-Kinematic viscosity at 50 ° C.: Measured according to JIS K 2283: 2000 (kinematic viscosity test method for crude oil and petroleum products).
-Density at 15 ° C.: Measured according to JIS K 2249-1: 2011 (crude oil and petroleum products-how to determine density-Part 1: vibration method).
-Flash point: Measured according to JIS K 2265-3: 2007 (crude oil and petroleum products-flash point test method-Part 3: Pencil Stainless Sealing Method).
-Fluid point: Lightly decomposed gas oil fraction and heavy fuel oil gas oil distillate are measured according to JIS K2269: 1987 (flow point of crude oil and petroleum products and clouding point test method of petroleum products), and fuel oil composition and direct removal. For heavy oil distillates, 500 mL of the distillate was left at room temperature (10 to 20 ° C.) for 168 hours (7 days) and then heated to 45 ° C. without pretreatment. JIS K2269: 1987 (crude oil and petroleum products) Flow point and petroleum product clouding point test method).
-Residual carbon content: For fuel oil composition, direct fuel oil fraction, and heavy cracked gas oil, JIS K 2270-1: 2009 (crude oil and petroleum products-how to obtain residual carbon content-Part 1: Conradson method) It was measured according to. As for the lightly decomposed gas oil, 10% residual oil was used.
-Latent segmentation: Measured according to JPI-5S-60-2000 (crude oil and petroleum products-sediment test method-).
-Existing sediment: Measured according to JPI-5S-60-2000 (crude oil and petroleum products-sediment test method-).
Moisture content: Measured according to JIS K 2275-3: 2015 (crude oil and petroleum products-how to determine water-Part 3: Karl Fischer titration method).
-Saturation content, aromatic content and resin content: The content of the above-mentioned various components of the direct-removed heavy oil fraction and the heavy-decomposition gas oil is as follows in IP-469 (International Standard Test Method (IP Test Methods)). It was measured by the specified TLC / FID method. The lightly decomposed gas oil was measured by a petroleum product-hydrocarbon type test method-high performance liquid chromatography method specified in JPI-5S-49-2007.
-Distillation properties (initial distillation point, end point, 90% by volume distillation temperature, etc.): Measured according to JIS K2254: 1998 (Petroleum products-distillation test method-).
-Asphaltene content: After weighing 50 g of direct deweighted heavy oil residue, add 1500 cc of n-heptane (special grade) to the sample, perform reflux treatment for 1 hour, filter with a circular quantitative filter paper (No. 5C), and residue. Was put into a cylindrical filter paper, soxhlet was extracted with n-heptane (special grade) using a Soxhlet extractor together with the cylindrical filter paper, and then soxhlet was further extracted with toluene (special grade), and then the solvent was removed. The n-heptane insoluble and toluene-soluble components were weighed to obtain the asphaltene content.
-Carbon / hydrogen (molar ratio) of asphaltene content: For the asphaltene content (n-heptane insoluble and toluene-soluble component) obtained by the measurement of the above "asphaltene content", an elemental analyzer ("vario EL cube (model)" ) ”, Manufactured by Elemental Japan Co., Ltd.), the carbon and hydrogen contents (mass%) of asphaltene were measured by the CHN coder method, and the molar ratio was calculated.
-Carbon / hydrogen (molar ratio) of fractions: For heavy cracked gas oil and light cracked gas oil, use an elemental analyzer ("vario EL cube (model)", manufactured by Elementer Japan Co., Ltd.) by the CHN coder method. The carbon and hydrogen contents (mass%) of these decomposed gas oil fractions were measured and the molar ratio was calculated.
-Total calorific value: For heavy cracked gas oil and light cracked gas oil, measure and estimate according to JIS K2279: 2003 (crude oil and petroleum products-calorific value test method and estimation method by calculation-) ("6. Total calorific value". Estimated by the formula for crude oil, kerosene, light oil, A heavy oil and B heavy oil specified in "Amount estimation method, 6.3 e) 1)"). The fuel oil composition and the direct deweighted oil fraction are measured and estimated according to JIS K2279: 2003 (crude oil and petroleum products-calorific value test method and calculation method-) ("6. Total calorific value". Estimating method, estimated by the calculation formula for C heavy oil specified in 6.3 e) 1) ”.

[Performance evaluation criteria]
Each of the following performances 1 to 3 was evaluated, and the worst evaluation was evaluated as a comprehensive evaluation. If it is a C evaluation, it fails. The evaluation of each performance is shown in Table 2.

1. 1. Evaluation of storage stability performance Regarding the storage stability performance of the fuel oil compositions of each Example and Comparative Example, the above-mentioned composition deteriorated according to JPI-5S-60-2000: Crude Oil and Petroleum Products-Segment Test Method. Based on the latent segment measured by the method, it was evaluated according to the following criteria.
A. The latent sediment was 0.05% by mass or less.
B. The latent sediment was more than 0.05% by mass and less than 0.10% by mass.
C. The latent sediment was greater than 0.10% by weight.
2. Evaluation of environmental performance The environmental performance of the fuel oil compositions of Examples and Comparative Examples was evaluated based on the sulfur content according to the following criteria.
A. The sulfur content was 0.30% by mass or less.
B. The sulfur content was more than 0.30% by mass and 0.45% by mass or less.
C. The sulfur content was more than 0.45% by mass.
3. 3. Evaluation of thermal stability performance A thermal stability performance test was conducted in accordance with ASTM D1661: 1964. Specifically, regarding the thermal stability performance of the fuel oil compositions of each Example and Comparative Example, the surface of a steel heating tube is circulated by convection in a glass heating device using the composition as a sample. Was contacted for 6 hours. The temperature of the heater and the heating tube in the heating tube is maintained at 177 ° C. After 6 hours of contact, the heating tube is pulled out, the heating tube on which the sample adhering to the surface of the heating tube is dropped by its own weight is dipped in toluene for cleaning, and then the discoloration and deposition state of the surface are observed. Evaluation was performed based on the criteria of A (stable), B (limit) and C (unstable) shown in Table 1.

[Examples 1 and 2, Comparative Examples 1 and 3]
Various base materials having the properties and compositions shown in Table 2 were mixed at the ratios shown in Table 3 to prepare fuel oil compositions of Examples 1 and 2 and Comparative Examples 1 to 3.
The storage stability performance, environmental performance and thermal stability performance of each of the obtained fuel oil compositions were evaluated by the above methods. The results are shown in Table 3.

[Performance evaluation result]
As shown in Table 3, the fuel oil composition for an internal combustion engine of the present embodiment has good evaluations of storage stability, environmental performance and thermal stability performance, and in consideration of these performances, it is particularly for ships. Diesel of various ships such as large ships, which is preferably used for internal combustion engines such as diesel engines and has a heating device as a pretreatment device for which the inlet temperature of the fuel oil composition for internal combustion engines is preferably about 100 ° C. or higher and 150 ° C. or lower. It was confirmed that it can withstand use in engines and the like.
On the other hand, the fuel oil compositions of Comparative Examples 1 and 2 which do not contain a specific direct-removed heavy oil fraction are inferior in terms of thermal stability performance and environmental performance, respectively, and also contain an excess of a specific direct-removed heavy oil fraction. The fuel oil composition of Comparative Example 3 was inferior in terms of storage stability performance.

The fuel oil composition for an internal combustion engine of the present embodiment is excellent in thermal stability performance as well as excellent storage stability performance and environmental performance, and is suitably used for an internal combustion engine, particularly an internal combustion engine such as a marine diesel engine, and above all, pretreatment. As a device, it is suitably used for a diesel engine or the like for a ship such as a large ship having a heating device of 100 ° C. or higher.

Claims (6)

The following _(a 1) ~ a direct desulfurization heavy oil fraction which satisfies both the _{(a 3),} comprising less than 50.0% by volume or more 90.0 volume percent content of the total amount of the composition below (1) and A fuel oil composition for an internal combustion engine that satisfies all of (2).
(A ₁ ) Sulfur content is 0.450% by mass or less (a ₂ ) Asphaltene content is 1.5% by mass or less (a ₃ ) Carbon / hydrogen (molar ratio) of asphaltene is 1.10 or more 1 .20 or less (1) sulfur content of 0.500 wt% or less (2) 50 kinematic viscosity at ℃ is 10.00 mm ² / s or more 100.0 mm ² / s or less The fuel oil composition for an internal combustion engine according to claim 1, further comprising a fraction having a carbon / hydrogen (molar ratio) of 0.60 or more. The fuel oil composition for an internal combustion engine according to claim 2, wherein the fraction is contained in an amount of 10.0% by volume or more as the content based on the total amount of the composition. The fuel oil composition for an internal combustion engine according to any one of claims 1 to 3, wherein the content of the direct-removed heavy oil fraction based on the total amount of the composition is 50.0% by volume or more and 75.0% by volume or less. The fuel oil composition for an internal combustion engine according to claim 4, wherein the content of the distillate based on the total amount of the composition is 25.0% by volume or more and 50.0% by volume or less. The fuel oil composition for an internal combustion engine according to any one of claims 1 to 5, which is used as a pretreatment device for a diesel engine having a heating device having an inlet temperature of the fuel oil composition for an internal combustion engine of 100 ° C. or higher.