JP2019182919A - Fuel oil composition for internal combustion engine and method for producing the same - Google Patents

Abstract

To provide the fuel oil composition for the internal combustion engine and the method for producing the same in that the fuel oil composition can suppress sulfur content, can also suppress a generation amount of dry sludge, and has an excellent fuel oil filter blockage suppressing effect.SOLUTION: Provided are the fuel oil composition for the internal combustion engine and the method for producing the same in that the fuel oil composition comprises at least a cracked light oil fraction, and at least one heavy oil fraction selected from a desulfurized heavy oil, a cracked heavy oil, and a C heavy oil, and the fuel oil composition satisfies that (1) a sulfur content based on a total amount of the composition is 0.50 mass% or less, (2) a real dry sludge reduction ratio is 50% or more, (3) real dry sludge is 0.05 mass% or less, and (4) density at 15°C is 0.9850 g/cmor less, (5) kinematic viscosity at 50°C is 10.0 mm/s or more to 180.0 mm/s or less, and (6)a pour point is 30.0°C or less.SELECTED DRAWING: None

Description

  The present invention relates to a fuel oil composition for an internal combustion engine and a method for producing the same.

  JIS K2205: 2006 type 3 heavy oil (hereinafter also referred to as “C heavy oil”) has a higher calorific value per unit volume compared to kerosene, light oil, type A heavy oil (JIS K2205: 2006 type 1 heavy oil), etc. Since the amount (volume) of fuel oil can be reduced and it is inexpensive, it is widely used as a fuel oil for internal combustion engines such as marine diesel engines and as a fuel oil for external combustion machines such as power generation boilers. Yes. When sludge is produced in C heavy oil, it is known that the fuel oil filter is clogged. On the other hand, 15 ° C density, 50 ° C kinematic viscosity, residual carbon content, asphaltene content, sulfur content, aromatics A C heavy oil composition having a minute content within a predetermined range has been proposed (see, for example, Patent Document 1).

  Further, as fuel oil for ships, a fuel oil that satisfies ISO 8217 “Petoleum products-Fuels (class F) -Specification of marine fuels” is known. Since this marine fuel oil may cause clogging of the fuel oil filter, predetermined properties such as sulfur content, residual carbon content, asphaltene content, 15 ° C. density, and total sediment by hot filtration (ISO 10307-1). Has been proposed (see, for example, Patent Document 2).

JP2013-203802A JP 2014-028977 A

  In recent years, the prevention of environmental pollution has been cited as one of the most important issues in the world. The International Maritime Organization (IMO) has been using fuel oil for all ships since 2020 as part of measures to prevent air pollution. It was decided that the sulfur content concentration should be strengthened from the current 3.5% by mass or less to 0.5% by mass or less. For this reason, there is an urgent need to set the sulfur content concentration of marine fuel oil to 0.5% by mass or less. However, the C heavy oil composition described in Patent Document 1 has a sulfur content of 3.5% by mass or less, and is allowed to be 0.5% by mass or more, so it complies with the required performance of 0.5% by mass or less. It becomes impossible. Moreover, the heavy oil composition described in Patent Document 2 has a sulfur content of 0.05 to 0.4 mass%, and can be said to be a composition that can comply with 0.5 mass% or less.

  By the way, in recent years, fuel oil filters have a relatively high molecular weight, such as asphaltenes and resins, contained in fuel oil compositions. Occlusion occurs. This phenomenon is remarkable when a heavy oil fraction such as desulfurized heavy oil is used directly so that the sulfur content in the fuel oil is 0.5% by mass or less, such as the heavy oil composition described in Patent Document 2 above. Become. Direct desulfurized heavy oil has a high calorific value and low sulfur content, so it can reduce the amount of fuel oil used (volume) and is a suitable fraction for reducing the sulfur content in fuel oil. On the other hand, it has the characteristic that it is easy to generate dry sludge. There is a demand for a fuel oil composition that has both the performance of having an excellent fuel oil filter clogging suppression effect that suppresses the sulfur content and also reduces the amount of dry sludge generated. The oil composition is not found.

  As a result of intensive studies in view of the above problems, the present inventor has found that the problem can be solved by the following invention. That is, this invention provides the fuel oil composition for internal combustion engines which has the following structure, and its manufacturing method.

[1] A fuel oil composition for an internal combustion engine comprising at least a cracked light oil fraction and at least one heavy oil fraction selected from desulfurized heavy oil, cracked heavy oil and C heavy oil, and satisfying any of the following (1) to (6): .
(1) Sulfur content based on the total amount of the composition is 0.50% by mass or less (2) Real dry sludge reduction ratio is 50% or more (3) Real dry sludge is 0.05% by mass or less (4) Pour point 30.0 ° C. or less (5) density at 15 ℃ is 0.9850g / cm ³ or less (6) 50 kinematic viscosity at ° C. is 10.0 mm ² / s or more 180.0mm ² / s or less [2] at least cracked gas oil fraction And a fuel oil composition for an internal combustion engine that satisfies all of the above (1) to (6), wherein at least one heavy oil fraction selected from desulfurized heavy oil, cracked heavy oil and C heavy oil is mixed.

  According to the present invention, it is possible to provide a fuel oil composition for an internal combustion engine having an excellent effect of suppressing the blockage of a fuel oil filter while suppressing the amount of dry sludge while suppressing the sulfur content, and a method for producing the same. .

[Fuel oil composition for internal combustion engine]
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 “this embodiment”) and a method for producing the same will be described more specifically.
The fuel oil composition for an internal combustion engine of the present embodiment includes at least a cracked gas oil fraction and at least one heavy oil fraction selected from desulfurized heavy oil, cracked heavy oil and C heavy oil, and (1) a sulfur content based on the total amount of the composition The content is 0.50% by mass or less, (2) the real dry sludge reduction ratio is 50% or more, (3) the real dry sludge is 0.05% by mass or less, and (4) the density at 15 ° C. is 0.9850 g / cm. ³ below, one of (5) 50 kinematic viscosity at ° C. is 10.0 mm ² / s or more 180.0mm ² / s or less, and (6) a pour point of 30.0 ° C. or less, (1) to (6) Is a satisfactory fuel oil composition. Hereinafter, it demonstrates from the property of (1)-(6) which the fuel oil composition of this embodiment has.

(1) Sulfur content The sulfur content of the fuel oil composition for an internal combustion engine of the present embodiment is required to be 0.50 mass% or less based on the total amount of the composition. If the sulfur content is greater than 0.50% by mass, it will not be possible to meet the requirements of the International Maritime Organization (IMO), the environmental load due to sulfur oxides in the exhaust gas will not be reduced, and the flue due to a decrease in the acid dew point of the exhaust gas Corrosion tends to occur, and stable engine operation becomes difficult. From the viewpoint of excellent environmental performance and stable engine operation, the sulfur content is preferably 0.48% by mass or less, more preferably 0.46% by mass or less, and further preferably 0.45% by mass or less.
In the present specification, the sulfur content is measured by selecting a measurement method according to the content. 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: Values measured according to the radiation excitation method).

(2) Real dry sludge reduction ratio The real dry sludge reduction ratio of the fuel oil composition for internal combustion engines of this embodiment needs to be 50% or more. When the actual dry sludge reduction ratio is less than 50%, the fuel oil filter is likely to be blocked due to the generation of dry sludge. From the viewpoint of suppressing the generation amount of dry sludge and obtaining a better fuel oil filter clogging suppression effect, the actual dry sludge reduction ratio is preferably 60% or more, more preferably 70% or more, and even more preferably 80% or more. is there.
In the present specification, the actual dry sludge reduction ratio is a value measured and calculated based on the method described in the examples.

(3) Real dry sludge The real dry sludge of the fuel oil composition for internal combustion engines of this embodiment needs to be 0.05 mass% or less. When the actual dry sludge is larger than 0.05% by mass, the fuel oil filter is likely to be clogged due to the generation of dry sludge. From the viewpoint of suppressing the amount of dry sludge generated and obtaining a more excellent fuel oil filter blockage suppression effect, the actual dry sludge is preferably 0.04 mass% or less, more preferably 0.03% mass% or less.
In the present specification, the actual dry sludge of the fuel oil composition for an internal combustion engine is a value calculated according to (i) to (ix) of the calculation method of “(2) Real dry sludge reduction ratio” described in the examples. .

(4) Density at 15 ° C. The density at 15 ° C. of the fuel oil composition for an internal combustion engine of the present embodiment needs to be 0.9850 g / cm ³ or less. When the density at 15 ° C. is larger than 0.9850 g / cm ³ , the fuel oil filter is likely to be blocked due to the generation of dry sludge. The density at 15 ° C. is preferably 0.9750 g / cm ³ or less, more preferably 0.9700 g / cm ³ or less, from the viewpoint of suppressing the generation amount of dry sludge and obtaining a better fuel oil filter blockage suppressing effect. is there. Moreover, although there is no restriction | limiting in particular as a minimum, When the total calorific value of the fuel oil composition for internal combustion engines is considered, Preferably it is 0.9310 g / cm < ³ > or more, More preferably, it is 0.9350 g / cm < ³ > or more.
In this 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).

(5) a kinematic viscosity at 50 ° C. for an internal combustion engine fuel oil composition kinematic viscosity present embodiment at 50 ° C. is required to be 10.0 mm ² / s or more 180.0mm at ² / s or less. If the kinematic viscosity at 50 ° C. is larger than 180.0 mm ² / s, the same level of performance as ISO 8217 grade RME cannot be maintained, and the handleability deteriorates, and if it is less than 10.0 mm ² / s, existing equipment (Pump, flow meter) and the like are difficult to use as they are, and the spray state of the fuel oil composition in the internal combustion engine tends to become unstable. The kinematic viscosity at 50 ° C. of the fuel oil composition for an internal combustion engine is preferably 11.1 from the viewpoint of maintaining at least the same level of performance as ISO 8217 grade RME, easily using existing equipment, and obtaining a more stable spray state. 0 mm ² / s or more, more preferably 11.5 mm ² / s or more, preferably the upper limit is 140.0mm ² / s or less, more preferably 100.0 mm ² / s or less, more preferably 80.0 mm ² / s or less, particularly preferably 50.0 mm ² / s or less.
In this specification, the kinematic viscosity at 50 ° C. is a value measured according to JIS K 2283: 2000 (kinematic viscosity test method for crude oil and petroleum products).

(6) Pour point The pour point of the fuel oil composition for internal combustion engines of this embodiment needs to be 30.0 degrees C or less. When the pour point is higher than 30.0 ° C., the same level of performance as ISO 8217 grade RME cannot be maintained, and the handleability deteriorates. From the viewpoint of maintaining at least the same level of performance as ISO 8217 grade RME and improving the handleability, the pour point is preferably 20.0 ° C. or lower, more preferably 10.0 ° C. or lower, and further preferably 5.0 ° C. or lower. is there. 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.
In this specification, the pour point is a value measured according to JIS K 2269: 1987 (pour point of crude oil and petroleum products and petroleum product cloud point test method).

(7) Residual carbon content The fuel oil composition for an internal combustion engine of the present embodiment preferably has a residual carbon content of 10.0% by mass or less. When the residual carbon content is 10.0% by mass or less, it becomes easy to maintain the combustion performance of the fuel oil composition for internal combustion engines, and the effect of reducing soot generation due to poor combustion is improved, so that stable engine operation is easier. It becomes. From the same viewpoint, the residual carbon content of the fuel oil composition for an internal combustion engine is preferably 5.5% by mass or less, more preferably 5.0% by mass or less, and further preferably 4.7% by mass or less. Moreover, although there is no restriction | limiting in particular as a minimum, Usually, it is 0.1 mass% or more.
In the present specification, the residual carbon content is a value measured in accordance with JIS K 2270-1: 2009 (crude oil and petroleum products—how to obtain residual carbon content—Part 1: Conradson method). The residual carbon content of the oil is a value measured using 10% residual oil prepared according to Annex A.

(Base material)
The fuel oil composition for an internal combustion engine of the present embodiment needs to contain at least a cracked light oil fraction and at least one heavy oil fraction selected from desulfurized heavy oil, cracked heavy oil and C heavy oil. By including these light oil fraction and heavy oil fraction, the properties (1) to (6), more preferably (7), can be easily obtained.

(Light oil fraction)
The fuel oil composition for an internal combustion engine of the present embodiment includes a cracked light oil fraction as a light oil fraction. If the cracked light oil fraction is not included as the light oil fraction, the sulfur content cannot be suppressed, and an excellent fuel oil filter blockage suppressing effect with reduced dry sludge generation cannot be obtained. ) To (6), more preferably the property (7) cannot be obtained.

(Decomposed gas oil fraction)
The cracked light oil fraction is a light oil fraction obtained by fluid catalytic cracking of atmospheric distillation residue oil and / or vacuum distillation residue oil, and preferably has the following properties (A1) to (A5) It is.

(A1) Sulfur content The sulfur content of the cracked gas oil fraction is preferably 0.45 mass% or less, more preferably 0.35 mass% or less, and still more preferably 0.30 mass% or less. Moreover, although there is no restriction | limiting in particular as a minimum, Preferably it is 0.15 mass% or more, More preferably, it is 0.20 mass% or more, More preferably, it is 0.25 mass% or more. When the sulfur content of the cracked light oil fraction is within the above range, the sulfur content of the fuel oil composition for an internal combustion engine of the present embodiment is particularly easily set to 0.50% by mass or less.

(A2) Density at 15 ° C. The density of the cracked gas oil fraction at 15 ° C. is preferably 0.9050 g / cm ³ or more, more preferably 0.9150 g / cm ³ or more, and further preferably 0.9250 g / cm ³ or more. The upper limit is preferably 0.9530 g / cm ³ or less, more preferably 0.9430 g / cm ³ or less, and still more preferably 0.9350 g / cm ³ or less. When the density of the cracked light oil fraction at 15 ° C. is within the above range, the amount of dry sludge generated can be suppressed, and a better fuel oil filter blockage suppressing effect can be easily obtained. The density at 15 ° C. of the composition tends to be 0.9850 g / cm ³ or less. In addition, a calorific value sufficient as a fuel oil composition for an internal combustion engine can be obtained.

(A3) Kinematic viscosity at 50 ° C. The kinematic viscosity at 50 ° C. of the cracked gas oil fraction is preferably 1.80 mm ² / s or more, more preferably 2.30 mm ² / s or more, and further preferably 2.80 mm ² / s. or more, preferably the upper limit is 3.50 mm ² / s or less, more preferably 3.40 mm ² / s or less, more preferably 3.30 mm ² / s or less. When the kinematic viscosity at 50 ° C. of the cracked light oil fraction is within the above range, the fuel oil composition for an internal combustion engine of the present embodiment maintains at least the same performance as ISO 8217 grade RME, and it is easy to use existing equipment. and it is assumed that more easily obtained a stable spray state and easily with a kinematic viscosity at 50 ℃ 10.0mm ² / s or more 180.0mm ² / s or less.

(A4) Pour point The pour point of the cracked gas oil fraction is preferably 0.0 ° C. or lower, more preferably −2.5 ° C. or lower, still more preferably −5.0 ° C. or lower. However, it is usually −35.0 ° C. or higher, preferably −25.0 ° C. or higher, more preferably −10.0 ° C. or higher. When the pour point of the cracked light oil fraction is within the above range, the fuel oil composition for an internal combustion engine of the present embodiment should maintain at least the same performance as ISO 8217 grade RME, improve the handleability, and flow It becomes easy to make a point into 30.0 degrees C or less.

(A5) Aromatic content The aromatic content of the cracked gas oil fraction is preferably 60.0% by volume or more, more preferably 62.5% by volume or more, and even more preferably 65.0% by volume or more. The upper limit is preferably 85.0% by volume or less, more preferably 80.0% by volume or less, and still more preferably 75.0% by volume or less. When the aromatic content of the cracked light oil fraction is within the above range, the amount of dry sludge generated is suppressed, and a more excellent blocking effect of the fuel oil filter can be easily obtained.
In the present specification, the aromatic content of the gas oil fraction is determined by the petroleum product-hydrocarbon type test method-high performance liquid chromatography method (High Performance Liquid Chromatography method) defined in JPI-5S-49-2007. The value to be measured.

(A6) CCAI: Calculated Carbon Aromaticity Index
The cracked light oil fraction preferably has a property of (A6) CCAI of 980 or less as properties other than the properties (A1) to (A5). When the CCAI of the cracked light oil fraction is 980 or less, more excellent combustion performance as a fuel oil composition can be obtained. From the same viewpoint, the CCAI of the cracked light oil fraction is more preferably 950 or less, and still more preferably 900 or less.
In this specification, CCAI is a value calculated from a calculation formula described in Annex F of ISO 8217-2012.

(Other light oil fractions)
The fuel oil composition for an internal combustion engine of the present embodiment includes light oils such as the above-mentioned cracked light oil fraction, straight-run light oil fraction, reduced-pressure light oil fraction, desulfurized light oil fraction, desulfurized cracked light oil fraction, and directly degasified light oil fraction. A fraction can also be contained.
・ Direct-run gas oil fraction (light oil fraction obtained by atmospheric distillation of crude oil with atmospheric distillation equipment)
-Vacuum gas oil fraction (a gas oil fraction obtained by vacuum distillation of atmospheric distillation residue oil with a vacuum distillation device)
・ Desulfurized gas oil fraction (a gas oil fraction obtained by desulfurizing a straight gas oil fraction and / or a vacuum gas oil fraction)
・ Desulfurized cracked diesel oil fraction (gas oil fraction obtained by desulfurizing cracked diesel oil fraction)
・ Direct degassing light oil fraction (light oil fraction obtained by desulfurizing atmospheric distillation residue oil and / or vacuum distillation residue oil directly with desulfurization equipment)

(Properties of other diesel oil fractions)
The properties of the other light oil fractions that can be used in the present embodiment preferably have the following properties. When the other light oil fraction has the following properties, the amount of dry sludge is suppressed while suppressing the sulfur content, and an excellent fuel oil filter blockage suppressing effect is easily obtained.
The sulfur content is preferably 0.30% by mass or less, more preferably 0.28% by mass or less, and further preferably 0.26% by mass or less.
Density at 15 ℃ is preferably 0.8300g / cm ³ or more, more preferably 0.8750g / cm ³ or more, more preferably 0.9000g / cm ³ or more and the upper limit is 0.9250g / cm ³ or less preferable.
Kinematic viscosity at 50 ° C. is preferably below 2.70 mm ² / s, more preferably not more than 2.30 mm ² / s, more preferably less 2.00 mm ² / s, also 1.80 mm ² / s or more as a lower limit Is preferred.
The pour point is preferably -10.0 ° C or lower, more preferably -15.0 ° C or lower, and further preferably -20.0 ° C or lower.
The aromatic content is preferably 20.0% by volume or more, more preferably 40.0% by volume or more, still more preferably 60.0% by volume or more, and particularly preferably 70.0% by volume or more.
Further, the residual carbon content of the 10% residual oil is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less.

(Heavy oil fraction)
The fuel oil composition for an internal combustion engine of the present embodiment includes at least one heavy oil fraction selected from desulfurized heavy oil, cracked heavy oil and C heavy oil as the heavy oil fraction. If these heavy oils are not included as a heavy oil fraction, the sulfur content cannot be suppressed, and an excellent fuel oil filter clogging suppression effect with reduced dry sludge generation cannot be obtained. To (6), more preferably, the property (7) cannot be obtained.

(Desulfurized heavy oil)
The desulfurized heavy oil is a heavy oil fraction obtained by directly desulfurizing an atmospheric distillation residue oil and / or a vacuum distillation residue oil with a desulfurization apparatus, and preferably a fraction preferably having the following properties (B1) to (B6): It is.

(B1) Sulfur Content The sulfur content of the desulfurized heavy oil is preferably 1.85% by mass or less, more preferably 1.00% by mass or less, and further preferably 0.50% by mass or less. Moreover, although there is no restriction | limiting in particular as a minimum, Preferably it is 0.09 mass% or more, More preferably, it is 0.15 mass% or more, More preferably, it is 0.25 mass% or more. When the sulfur content of the desulfurized heavy oil is within the above range, the sulfur content of the fuel oil composition for an internal combustion engine of the present embodiment is particularly easily set to 0.50% by mass or less. In addition, the heavy oil direct desulfurization apparatus can be operated under milder conditions.

(B2) Real dry sludge The real dry sludge of desulfurized heavy oil is preferably 0.10% by mass or more, more preferably 0.20% by mass or more, still more preferably 0.30% by mass or more, and the upper limit is preferably 0. .50% by mass or less, more preferably 0.45% by mass or less, and still more preferably 0.40% by mass or less. When the actual dry sludge of desulfurized heavy oil is within the above range, the amount of dry sludge generated is suppressed, and a more excellent fuel oil filter blockage suppressing effect can be easily obtained, and the fuel oil composition for an internal combustion engine of the present embodiment can be obtained. It becomes easy to make real dry sludge 0.05 mass% or less, and it becomes easy to make a real dry sludge reduction ratio 50% or more.

(B3) Density at 15 ° C. The density of desulfurized heavy oil at 15 ° C. is preferably 0.8370 g / cm ³ or more, more preferably 0.8700 g / cm ³ or more, still more preferably 0.9000 g / cm ³ or more, The upper limit is preferably 0.9875 g / cm ³ or less, more preferably 0.9600 g / cm ³ or less, still more preferably 0.9500 g / cm ³ or less. When the density of desulfurized heavy oil at 15 ° C. is within the above range, the amount of dry sludge generated can be suppressed, and a more excellent fuel oil filter blockage suppressing effect can be easily obtained, and the fuel oil composition for an internal combustion engine of the present embodiment It becomes easy to make the density in 15 degreeC into 0.9850 g / cm < ³ > or less.

(B4) a kinematic viscosity at 50 ° C. kinematic viscosity desulfurized fuel oil at 50 ° C. is preferably 63.5 mm ² / s or more, more preferably 68.5mm ² / s or higher, more preferably at 70.0 mm ² / s or more There, upper limit is preferably 135.0mm ² / s or less, more preferably 100.0 mm ² / s or less, more preferably 85.0mm ² / s or less. When the kinematic viscosity at 50 ° C. of the desulfurized heavy oil is within the above range, the fuel oil composition for an internal combustion engine of the present embodiment maintains at least the same performance as ISO 8217 grade RME, and it is easy to use existing equipment, and We shall easily obtained a more stable spray state and easily the kinematic viscosity at 50 ° C. or less 10.0 mm ² / s or more 180.0mm ² / s.

(B5) Pour point The pour point of desulfurized heavy oil is preferably 32.5 ° C. or less, more preferably 25.0 ° C. or less, and further preferably 15.0 ° C. or less. -10.0 ° C or higher. When the pour point of desulfurized heavy oil is within the above range, the fuel oil composition for an internal combustion engine of the present embodiment should have at least the same level of performance as ISO 8217 grade RME, and handleability should be improved. It becomes easy to set it as 30.0 degrees C or less.

(B6) Residual carbon content The residual carbon content of the desulfurized heavy oil is preferably 14.0% by mass or less, more preferably 10.0% by mass or less, still more preferably 5.0% by mass or less, and the lower limit is particularly limited. However, it is usually 0.1% by mass or more. When the residual carbon content of the desulfurized heavy oil is within the above range, the combustion performance of the fuel oil composition for the internal combustion engine can be easily maintained, and the effect of reducing soot generation due to poor combustion is improved, so that stable engine operation is easier. It becomes.

(B7) CCAI
The desulfurized heavy oil preferably has a property (B7) CCAI of 830 or less as properties other than the properties (B1) to (B6). When the CCAI of the desulfurized heavy oil is 830 or less, more excellent combustion performance as a fuel oil composition can be obtained. From the same viewpoint, the CCAI of the desulfurized heavy oil is more preferably 820 or less, and still more preferably 810 or less.

(Decomposed heavy oil)
The cracked heavy oil is a heavy oil fraction obtained by fluid catalytic cracking of desulfurized heavy oil, and preferably a fraction preferably having the following properties (C1) to (C6).

(C1) Sulfur content The sulfur content of the cracked heavy oil is preferably 0.96% by mass or less, more preferably 0.80% by mass or less, and still more preferably 0.70% by mass or less. Moreover, although there is no restriction | limiting in particular as a minimum, Preferably it is 0.50 mass% or more, More preferably, it is 0.55 mass% or more, More preferably, it is 0.60 mass% or more. When the sulfur content of cracked heavy oil is within the above range, the sulfur content of the fuel for the internal combustion engine of the present embodiment is particularly easily set to 0.50% by mass or less. In addition, the heavy oil direct desulfurization apparatus can be operated under milder conditions.

(C2) Real dry sludge The real dry sludge of cracked heavy oil is preferably 0.45% by mass or less, more preferably 0.20% by mass or less, and still more preferably 0.10% by mass or less. If the actual dry sludge of cracked heavy oil is within the above range, the amount of dry sludge generated can be suppressed, and a more excellent fuel oil filter blockage suppression effect can be easily obtained, and the fuel oil composition for an internal combustion engine of the present embodiment can be obtained. It becomes easy to make real dry sludge 0.05 mass% or less, and it becomes easy to make a real dry sludge reduction ratio 50% or more.

(C3) Density at 15 ° C. The density of cracked heavy oil at 15 ° C. is preferably 0.8950 g / cm ³ or more, more preferably 0.9450 g / cm ³ or more, and further preferably 0.9900 g / cm ³ or more. The upper limit is preferably 1.0700 g / cm ³ or less, more preferably 1.0500 g / cm ³ or less, and still more preferably 1.0350 g / cm ³ or less. If the density of the cracked heavy oil at 15 ° C. is within the above range, the amount of dry sludge generated can be suppressed, and a more excellent fuel oil filter blockage suppressing effect can be easily obtained, and the fuel oil composition for an internal combustion engine of the present embodiment It becomes easy to make the density in 15 degreeC into 0.9850 g / cm < ³ > or less.

(C4) a kinematic viscosity at 50 ° C. kinematic viscosity degradation heavy oil at 50 ° C. is preferably 57.5 mm ² / s or more, more preferably 100.0 mm ² / s or higher, more preferably at 150.0 ² / s or more The upper limit is preferably 385.0 mm ² / s or less, more preferably 285.0 mm ² / s or less, and still more preferably 200.0 mm ² / s or less. When the kinematic viscosity at 50 ° C. of the cracked heavy oil is within the above range, the fuel oil composition for an internal combustion engine of the present embodiment maintains at least the same performance as ISO 8217 grade RME, and it is easy to use existing equipment, and We shall easily obtained a more stable spray state and easily the kinematic viscosity at 50 ° C. or less 10.0 mm ² / s or more 180.0mm ² / s.

(C5) Pour point The pour point of cracked heavy oil is preferably 32.5 ° C. or less, more preferably 20.0 ° C. or less, and still more preferably 5.0 ° C. or less. -10.0 ° C or higher. When the pour point of cracked heavy oil is within the above range, the fuel oil composition for an internal combustion engine of the present embodiment has at least the same performance as ISO 8217 grade RME, and has improved handling properties, and the pour point is It becomes easy to set it as 30.0 degrees C or less.

(C6) Residual carbon content The residual carbon content of cracked heavy oil is preferably 9.0% by mass or less, more preferably 8.0% by mass or less, still more preferably 7.0% by mass or less, and the lower limit is particularly limited. However, it is usually 0.1% by mass or more. When the residual carbon content of the cracked heavy oil is within the above range, it becomes easy to maintain the combustion performance of the fuel oil composition for an internal combustion engine of the present embodiment, and the effect of reducing soot generation due to poor combustion is improved. Driving becomes easier.

(C7) CCAI
The cracked heavy oil preferably has a property of (C7) CCAI of 980 or less as properties other than the properties (C1) to (C6). When CCAI of cracked heavy oil is 980 or less, more excellent combustion performance as a fuel oil composition can be obtained. From the same viewpoint, the CCAI of the cracked light oil fraction is more preferably 950 or less, and still more preferably 900 or less.

(Other heavy oil fractions)
In addition to the C heavy oil, desulfurized heavy oil and cracked heavy oil, the fuel oil composition for an internal combustion engine of the present embodiment can also contain heavy oil fractions such as atmospheric distillation residue oil and vacuum distillation residue oil.
・ Atmospheric distillation residue oil (residual oil obtained by normal pressure distillation of crude oil with an atmospheric distillation device)
-Vacuum distillation residue oil (residual oil obtained by vacuum distillation of atmospheric distillation residue oil with a vacuum distillation device)

(Properties of other heavy oil fractions)
The properties of the other heavy oil fractions that can be used in the present embodiment preferably have the following properties. When other heavy oil fractions have the following properties, the amount of dry sludge generated is suppressed while the sulfur content is suppressed, and an excellent fuel oil filter blockage suppressing effect is easily obtained.
The sulfur content is preferably 0.60% by mass or less, and more preferably 0.55% by mass or less. Moreover, as a lower limit, it is 0.51 mass% or more normally.
Density at 15 ℃ is preferably 0.8800g / cm ³ or more, more preferably 0.9000g / cm ³ or more, more preferably 0.9200g / cm ³ or more and the upper limit is 0.9500g / cm ³ or less preferable.
Kinematic viscosity at 50 ° C. is preferably less 190.0mm ² / s, more preferably not more than 180.0mm ² / s, more preferably less 160.0mm ² / s, also 30.0 mm ² / s or more as a lower limit The degree, preferably 50.0 mm ² / s or more.
The pour point is preferably 15.0 ° C or lower, more preferably 12.5 ° C or lower, and still more preferably 10.0 ° C or lower.
The residual carbon content is preferably 8.0% by mass or less, more preferably 6.0% by mass or less, and still more preferably 5.0% by mass or less.
The aromatic content is preferably 40.0% by mass or more, more preferably 50.0% by mass or more, and still more preferably 55.0% by mass or more.
CCAI is preferably 830 or less, more preferably 820 or less, and even more preferably 810 or less.

The fuel oil composition for an internal combustion engine of the present embodiment is composed of at least a cracked gas oil fraction, a desulfurized heavy oil, a cracked heavy oil and a C heavy oil so as to satisfy the properties (1) to (6) and (7) above. It is obtained by preparing at least one selected heavy oil fraction in an arbitrary content. In this case, in addition to the cracked light oil fraction as the light oil fraction, the other light oil fractions described above, that is, the straight light gas oil fraction, the vacuum gas oil fraction, the desulfurized light oil fraction, the desulfurized cracked light oil fraction, and the direct degasified light oil fraction. In addition to desulfurized heavy oil, cracked heavy oil and C heavy oil, other heavy oil fractions mentioned above, that is, heavy oil such as atmospheric distillation residue oil, vacuum distillation residue oil, etc. A fraction may be used.
In the present embodiment, the properties (1) to (6) and (7) are easily satisfied, and the amount of dry sludge is suppressed while the sulfur content is further suppressed, and the fuel oil is more excellent. From the viewpoint of obtaining the filter blockage suppression effect, the above-mentioned light oil fraction and heavy oil fraction are combined with a cracked light oil fraction, desulfurized heavy oil, cracked heavy oil and C heavy oil, a cracked light oil fraction, desulfurized heavy oil and cracked heavy oil. A combination of desulfurized heavy oil and cracked heavy oil is preferable, a combination of cracked light oil fraction, desulfurized heavy oil and cracked heavy oil, a combination of desulfurized heavy oil and cracked heavy oil is more preferable, a light oil fraction, desulfurized heavy oil and cracked heavy oil The combination with is more preferable.

  In the present embodiment, the content of the composition based on the total amount of the cracked gas oil fraction is appropriately determined so that the obtained fuel oil composition for an internal combustion engine satisfies the properties (1) to (6) and further (7). There is no particular limitation, but from the viewpoint of further reducing the amount of dry sludge while further suppressing the sulfur content, and obtaining a better fuel oil filter blockage suppression effect, preferably 0.0% by volume. Above, more preferably 5.0% by volume or more, still more preferably 10.0% by volume or more, still more preferably 25.0% by volume or more, and the upper limit is preferably 80.0% by volume or less, more preferably 65% by volume. 0.0% by volume or less, more preferably 50.0% by volume or less, and particularly preferably 35.0% by volume or less. Moreover, when using another light oil fraction, the total content of a cracked light oil fraction and another light oil fraction should just be in the said range.

  In the present embodiment, the content of the desulfurized heavy oil composition based on the total amount may be appropriately adjusted so as to satisfy the properties (1) to (6) and (7), and is not particularly limited. From the viewpoint of further reducing the amount of dry sludge while suppressing the sulfur content, and obtaining a better fuel oil filter blockage suppression effect, it is preferably at least 15.0% by volume, more preferably at least 20.0% by volume. More preferably, it is 25.0% by volume or more, and the upper limit is preferably 80.0% by volume or less, more preferably 70.0% by volume or less, still more preferably 60.0% by volume or less, particularly preferably 55.0%. The capacity is less than%.

  In the present embodiment, the content of the composition basis of the cracked heavy oil may be appropriately adjusted so as to satisfy the properties (1) to (6), and further (7), and is not particularly limited. From the viewpoint of suppressing the generation amount of dry sludge while further suppressing the sulfur content, and obtaining a better fuel oil filter blockage suppressing effect, preferably 10.0% by volume or more, more preferably 15.0% by volume or more. More preferably, it is 20.0% by volume or more, and the upper limit is preferably 70.0% by volume or less, more preferably 60.0% by volume or less, still more preferably 50.0% by volume or less. Moreover, when using heavy oil fractions other than desulfurized heavy oil and cracked heavy oil, the total content of desulfurized heavy oil, cracked heavy oil and other light oil fractions may be within the range of the content of the desulfurized heavy oil.

(Other additives)
Various additives such as pour point depressants, combustion accelerators, detergents, sludge dispersants and the like are appropriately added to the fuel oil composition for an internal combustion engine of the present embodiment as long as the above properties can be maintained. Can be selected and blended.

(Use of fuel oil composition for internal combustion engines)
The fuel oil composition of the present embodiment is used in an internal combustion engine, and is a fuel oil composition that has an excellent effect of suppressing clogging of a fuel oil filter by suppressing the amount of dry sludge while further suppressing the sulfur content. Therefore, it is suitably used particularly for an internal combustion engine such as a marine diesel engine, and particularly suitable for a large diesel engine such as a large marine diesel engine having a pretreatment device including a centrifugal separator.

[Method for producing fuel oil composition for internal combustion engine]
The method for producing a fuel oil composition for an internal combustion engine of the present embodiment mixes at least the above-mentioned cracked light oil fraction, and at least one heavy oil fraction selected from the above desulfurized heavy oil, the above cracked heavy oil and the above C heavy oil (1 ) To (6). The fuel oil composition for internal combustion engines of this embodiment can be manufactured by the manufacturing method of the fuel oil composition for internal combustion engines of this embodiment mentioned above, for example.
In the production method of the present embodiment, the cracked gas oil fraction, desulfurized heavy oil, cracked heavy oil, C heavy oil, and the properties (1) to (6) of the fuel oil composition for an internal combustion engine have the properties of the fuel oil composition for an internal combustion engine described above. Same as described. Further, in the production method of the present embodiment, for example, the fuel oil composition for an internal combustion engine preferably includes the property (7), the light oil fraction, each light oil fraction other than the heavy oil fraction, and each heavy oil fraction. In addition, other preferred embodiments are the same as those described for the fuel oil composition for an internal combustion engine.

  In the production method of the present embodiment, cracked gas oil fraction, desulfurized heavy oil, cracked heavy oil, C heavy oil, other gas oil fractions and the content of each heavy oil fraction are the contents of these components in the fuel oil composition for internal combustion engines. It is the same as described for the quantity. In particular, when the content of cracked gas oil fraction, desulfurized heavy oil, and cracked heavy oil is within the above preferred ranges, the properties (1) to (6) and (7) are obtained as the properties of the fuel oil composition for an internal combustion engine. It becomes easy to be done.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited at all by these examples.

(Measurement of properties of fuel oil composition for internal combustion engines)
About the property of the fuel oil composition of each Example and a comparative example, it measured with the following method.
(1) Sulfur content: Measured according to JIS K2541-4: 2003 (Part 4).
(2) Real dry sludge reduction ratio The real dry sludge reduction ratio is a value calculated by the following method.
(I) First, put a filter paper (Whatman No. 50, pore diameter: 1.0 μm, thickness: 0.12 mm) in a glass petri dish, and slightly dry the lid with a dryer (110 ° C.) for 20 minutes. It was allowed to cool to a constant weight (1 hour), the filter paper was taken out from the glass petri dish and weighed in units of 0.1 mg, and this was defined as the mass M ₁ (mg) of the filter paper.
(Ii) The vacuum bottle was attached to a pressure filter (Shell Hot Filtration method, “SMS 742-76“ Determination of Existent and Dry Sledge Content of Residual Fuel Oil ”) using a rubber stopper. An eye plate was attached to the funnel of the pressure filter, a felt disk and the above-mentioned weighed filter paper were placed on the eye plate, and the inside of the vacuum bottle was depressurized with a vacuum pump. The inner wall of the jacket of the pressure filter was washed with an organic solvent (xylene, toluene, etc.), and after fixing the jacket to the pressure filter, the reduced pressure was released and the jacket was kept at 99-100 ° C. A pressure medium was heated by circulating a heat medium (hot water, silicone oil, etc.) with a circulation pump.
(Iii) Separately, a sample for measurement was prepared by the following procedure. The fuel oil composition for internal combustion engines and C heavy oil of this embodiment were weighed to a 0.01 g unit in a glass container (beaker or the like), and 10 g ± 0.5 g was collected. In addition, various fractions such as cracked gas oil fraction, desulfurized heavy oil, cracked heavy oil, and direct desulfurized oil that are process-controlled at the time of production are weighed to a unit of 0.01 g in a glass container (beaker, etc.), and 50 g ± 0 .5 g was collected. Samples obtained by heating C heavy oil and various fractions collected in a glass container to 100 ± 3 ° C. using a heat medium (hot water, silicone oil, etc.) or a hot plate were used.
(Iv) The obtained sample is poured from a glass container onto a filter paper, a lid is attached to the filter to form a sample chamber, and the sample chamber is pressurized to 490 kPaG with gas (air or nitrogen). When the glass container containing the sample has cooled, the glass container after pouring the sample onto the filter paper is weighed to determine the mass M (g) of the sample amount used for filtration.
(V) When the inlet pressure has dropped, stop pressurizing with gas (air or nitrogen), confirm that the sample chamber has returned to normal pressure, remove the lid, and check whether the surface of the filter paper is dry ( Check if oil remains. When the sample is not dried, the sample amount is reduced to 5 g when 10 g is collected, and when 50 g is collected, the sample amount is decreased to 25 g, 10 g, and 5 g until the sample is dried. The same operation was repeated from collecting to checking whether the surface of the filter paper was dry. If the filtration time takes 25 minutes or more even if the sample amount is reduced to 5 g, the amount is reduced to an arbitrary amount that can be filtered within 25 minutes.
After confirming that the surface of the filter paper is dry, remove the jacket of the filter and visually inspect the periphery of the filter paper. If the periphery is not soiled (not colored), apply 20 mL of n-heptane twice. Use a pipette to wash the sludge on the filter paper. On the other hand, when the peripheral part of the filter paper is visually observed and the peripheral part is dirty (colored), the sample is leaked and accurate measurement cannot be performed. Repeated.
(Vi) Next, the decompression is released, the pressure in the decompression bottle is returned to normal pressure, the filter paper is removed from the pressure filter, the filter paper is placed in a glass petri dish, the lid is slightly shifted, and the dryer (110 ° C.) And then allowed to cool for 1 hour, and then the filter paper was taken out and weighed to the nearest 0.1 mg to obtain the total mass M ₂ (mg) of the filter paper and dry sludge.
(Vii) For the blank test, the prepared new filter paper is weighed to the nearest 0.1 mg to obtain the mass M ₃ (mg) of the filter paper before the blank test, the pressure inside the vacuum bottle is reduced, and the filter paper is placed on the eye plate. Then, 20 mL of n-heptane was divided into two portions using a pipette, and the surface of the filter paper was washed and sucked. Then, the filter paper was weighed to obtain the mass M ₄ (mg) of the filter paper after the blank test.
(Viii) Using the mass M and the masses M _{1 to} M ₄ measured by the above (i) to (vii), the dry sludge amount is calculated by the following formula (1), and the actual dry sludge DS ₁ (mass%) It was.
DS = (M ₂ −M ₁ ) − (M ₂ −M ₁ ) / {(M ₄ −M ₃ ) / (10 × M)} (1)
M: Mass of sample amount (g)
M ₁ : Mass of filter paper (mg)
M ₂ : Total mass of filter paper and dry sludge (mg)
M ₃ : Mass of filter paper before blank test (mg)
M ₄ : Mass of filter paper after blank test (mg)
(Ix) The above operations (i) to (viii) are performed once again, the actual dry sludge DS ₂ (mass%) is calculated, and the average value of DS ₁ and DS ₂ is determined as the fuel oil composition for the internal combustion engine of the present embodiment. Real dry sludge of products, C heavy oil and various fractions. If the difference between DS ₁ and DS ₂ is not the indoor concurrent tolerance shown in Table 1, the operations (i) to (viii) are repeated until the indoor concurrent tolerance is reached.

(X) The dry sludge reduction ratio of the fuel oil composition for an internal combustion engine is calculated by the following formula using the fuel oil composition for an internal combustion engine, the C heavy oil, and the actual dry sludge of various fractions calculated by the above (i) to (ix). The value calculated by (2).
R _DS = (DS _FU− DS _FR ) / DS _FR × 100 (2)
R _DS : Dry sludge reduction ratio (%)
DS _FU : Real dry sludge of fuel oil composition
DS _FR : Weighted average value of actual dry sludge of various fractions contained in the fuel oil composition

In the above-mentioned (i) to (vii) actual dry sludge and reduction ratio measurement methods, the manufacturer name, model number, etc. are described for the equipment used, etc., but these are limited to the manufacturer name, model number, etc. Instead, it may be measured with an equivalent product.
(3) Real dry sludge The real dry sludge is a value calculated according to (i) to (ix) in the calculation method of “(2) Real dry sludge reduction ratio”.
(4) Density at 15 ° C .: Measured according to JIS K 2249-1: 2011 (Part 1).
(5) Kinematic viscosity at 50 ° C .: measured according to JIS K 2283: 2000.
(6) Pour point: Measured according to JIS K 2269: 1987.
(7) Residual carbon content: Measured according to JIS K 2270-1: 2009 (Part 1).

(Measurement of substrate properties)
The properties of the cracked light oil fraction, desulfurized heavy oil, and cracked heavy oil used in each Example and Comparative Example were measured by the following methods.
(A) Sulfur content: Measured according to JIS K2541-4: 2003 (crude oil and petroleum products-sulfur content test method-part 4: radiation excitation method).
(B) Real dry sludge: a value calculated according to (i) to (ix) of the calculation method of “(2) Real dry sludge reduction ratio” in “(Measurement of properties of fuel oil composition for internal combustion engine)” above. is there.
(C) Density at 15 ° C .: Measured according to JIS K 2249-1: 2011 (Part 1).
(D) Kinematic viscosity at 50 ° C .: Measured according to JIS K 2283: 2000.
(E) Pour point: Measured according to JIS K 2269: 1987.
(F) Residual carbon content: Measured according to JIS K 2270-1: 2009 (Part 1). Further, when measuring the residual carbon content of 10% residual oil, 10% residual oil prepared according to Annex A was used.
(G) Aromatic content: The aromatic content of the gas oil fraction is defined by JPI-5S-49-2007, petroleum product-hydrocarbon type test method-high performance liquid chromatography method (High Performance Liquid). Chromatography method).
(H) CCAI: Calculated from the calculation formula described in Annex F of ISO 8217-2012.

(Evaluation of dry sludge generation suppression performance of fuel oil compositions for internal combustion engines)
About the fuel oil composition for internal combustion engines of each Example and a comparative example, the reduction ratio of the actual dry sludge was evaluated as O when less than 50% and less than 50% as x. The evaluation results are shown in Table 3. If the reduction rate of the actual dry sludge is 50% or more, it can be said that the dry sludge generation suppression performance is excellent.

(Production of fuel oil compositions of Examples 1 to 3 and Comparative Examples 1 to 5)
Base oils (decomposed gas oil fraction, desulfurized heavy oil, decomposed heavy oil) having the properties shown in Table 2 below were mixed at a mixing ratio shown in Table 3, and fuel oils for internal combustion engines of Examples 1 to 3 and Comparative Examples 1 to 3 were used. A composition was prepared. Table 3 shows the evaluation results of the respective performances of the obtained fuel oil compositions for internal combustion engines by the above method.

From the results in Table 3, the fuel oil composition of the present embodiment has a sulfur content of 0.50% by mass or less, and also suppresses the amount of dry sludge generated, and has an excellent fuel oil filter blocking effect. It was confirmed that it had.
On the other hand, since the fuel oil compositions of Comparative Examples 1 and 2 have a large amount of actual dry sludge and a small ratio of actual dry sludge, the amount of dry sludge is suppressed and the fuel oil filter has an excellent blocking effect on the fuel oil filter. It couldn't be said.

Claims (6)

A fuel oil composition for an internal combustion engine comprising at least a cracked light oil fraction and at least one heavy oil fraction selected from desulfurized heavy oil, cracked heavy oil and C heavy oil, and satisfying any of the following (1) to (6):
(1) Sulfur content based on the total amount of the composition is 0.50% by mass or less (2) Real dry sludge reduction ratio is 50% or more (3) Real dry sludge is 0.05% by mass or less (4) At 15 ° C. density 0.9850g / cm ³ or less (5) a kinematic viscosity at 50 ° C. is 10.0 mm ² / s or more 180.0mm ² / s or less (6) pour point 30.0 ° C. or less   The content of cracked gas oil fraction based on the total amount of the composition is 0.0 volume% or more and 80.0 volume% or less, the content of desulfurized heavy oil is 15.0 volume% or more and 80.0 volume% or less, the content of cracked heavy oil 2. The fuel oil composition for an internal combustion engine according to claim 1, wherein is 10.0 vol% or more and 70.0 vol% or less. The fuel oil composition for an internal combustion engine according to claim 1 or 2, wherein the cracked light oil fraction is a fraction that satisfies all of the following (A1) to (A5).
(A1) Sulfur content is 0.15 mass% or more and 0.45 mass% or less (A2) Density at 15 ° C. is 0.9050 g / cm ³ or more and 0.9530 g / cm ³ or less (A3) Kinematic viscosity at 50 ° C. There 1.80 mm ² / s or more 3.50 mm ² / s or less (A4) pour point -35.0 ° C. or higher 0.0 ° C. or less (A5) aromatic content 60.0 vol% 85.0 Capacity% or less The fuel oil composition for an internal combustion engine according to any one of claims 1 to 3, wherein the desulfurized heavy oil is a fraction that satisfies all of the following (B1) to (B6).
(B1) Sulfur content is 0.09% by mass or more and 1.85% by mass or less (B2) Real dry sludge is 0.10% by mass or more and 0.50% by mass or less (B3) The density at 15 ° C. is 0.8370 g. / cm ³ or more 0.9875G / cm ³ or less (B4) a kinematic viscosity at 50 ° C. is 63.5 mm ² / s or more 135.0mm ² / s or less (B5) a pour point of 32.5 ° C. or less (B6) residual carbon 14.0% by mass or less The fuel oil composition for an internal combustion engine according to any one of claims 1 to 4, wherein the cracked heavy oil is a fraction that satisfies all of the following (C1) to (C6).
(C1) Sulfur content is 0.50 mass% or more and 0.96 mass% or less (C2) Real dry sludge is 0.45 mass% or less (C3) The density at 15 ° C. is 0.8950 g / cm ³ or more. 0700g / cm ³ or less (C4) kinematic viscosity at 50 ° C. is 57.5 mm ² / s or more 385.0mm ² / s or less (C5) a pour point of 32.5 ° C. or less (C6) carbon residue 9.0 weight %Less than A method for producing a fuel oil composition for an internal combustion engine, wherein at least one cracked gas oil fraction and at least one heavy oil fraction selected from desulfurized heavy oil, cracked heavy oil and C heavy oil are mixed and satisfy all of the following (1) to (6): .
(1) Sulfur content based on the total amount of the composition is 0.50% by mass or less (2) Real dry sludge reduction ratio is 50% or more (3) Real dry sludge is 0.05% by mass or less (4) At 15 ° C. density 0.9850g / cm ³ or less (5) a kinematic viscosity at 50 ° C. is 10.0 mm ² / s or more 180.0mm ² / s or less (6) pour point 30.0 ° C. or less