JP7227868B2 - Fuel oil composition for external combustion engine and method for producing the same - Google Patents

Description

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

As fuel oil compositions for external combustion engines such as boilers, hot air heaters, and industrial furnaces, mainly kerosene (JIS K 2203), A heavy oil (JIS K 2205 class 1 heavy oil) and C heavy oil (JIS K 2205 3 types of heavy oil) are used.

Kerosene has extremely low contents of sulfur, nitrogen, and residual carbon, and has the characteristic of having a small environmental load due to its combustion. In addition, due to its excellent low-temperature fluidity and combustibility, it is excellent even when used in an external combustion engine equipped with a hydraulic spray burner with a low rated combustion volume and low spray oil pressure in cold regions during the severe cold season. Exhibits combustibility. However, in cold regions in winter, there is a large demand for kerosene for indoor heating, etc., and special consideration is required for stable supply. In addition, since the calorific value per unit volume is smaller than that of A heavy oil and C heavy oil, there is a tendency to demand improvement in the calorific value.
Heavy oil A is generally excellent in supply stability and has the advantage of having a higher calorific value than kerosene. However, A-heavy oil sometimes needs consideration such as facility measures in order to prevent filter clogging due to deposition of wax during the severe cold season in cold regions. Further, A heavy oil needs to be improved in combustibility when it is used in an external combustion engine equipped with a hydraulic atomizing burner having a small rated combustion amount and a low atomizing oil pressure.
C heavy oil has a higher calorific value than A heavy oil. However, due to its high viscosity, it is inconvenient to handle, such as the need for heating equipment when used. In addition, C heavy oil has low combustibility, so it cannot be used for external combustion engines equipped with hydraulic spray burners with low rated combustion and low spray pressure. However, many of them have the drawback of having a large environmental load.

For the purpose of contributing to the stable supply of fuel oil compositions for external combustion engines in winter, the present inventors have so far demonstrated excellent stability in long-term storage and excellent in cold regions during the severe cold season. A fuel oil composition for an external combustion engine that exhibits low-temperature fluidity, exhibits excellent combustibility even in an external combustion engine equipped with a hydraulic atomizing burner with a small rated combustion volume and a low spray oil pressure, and can be obtained at a high yield. have been proposed (see Patent Documents 1 to 3).

JP 2004-182744 A JP 2004-182745 A JP 2017-114948 A

However, there is a growing demand for further stabilization of the supply of the fuel oil composition for external combustion engines, especially in winter, and improvement in fuel consumption by increasing the calorific value. It is no longer adequate.

Therefore, the present invention is equipped with a hydraulic spray burner that has excellent stability even in long-term storage, exhibits excellent low-temperature fluidity even in cold regions during the severe cold season, and has a small rated combustion amount and a low spray oil pressure. Provided is a fuel oil composition for an external combustion engine that exhibits excellent combustibility even in an external combustion engine with a high yield rate, can be stably supplied, and has a high calorific value that can contribute to improving fuel efficiency. intended to

As a result of intensive studies in view of the above problems, the inventors have found that the problems can be solved by the following inventions. That is, the present invention provides a fuel oil composition for an external combustion engine having the following constitutions and a method for producing the same.

[1] A fuel oil composition for an external combustion engine containing 50% by volume or more of hydrocracked kerosene obtained by hydrocracking a feedstock containing catalytically cracked gas oil and heavy gas oil, wherein The content of catalytically cracked light oil is 20% by volume or more and 40% by volume or less, and the content of antioxidant is 20 mass ppm or more and 100 mass ppm or less, and all of the following conditions (1) to (6) are satisfied. A fuel oil composition for a combustion engine.
(1) Initial boiling point of 140.0°C or higher (2) 95% by volume distillation temperature of 271.0°C or higher and 300.0°C or lower (3) Flash point of 45.0°C or higher (4) Sulfur content is 3 mass ppm or more and 10 mass ppm or less (5) Cloud point is -20.0 ° C. or less (6) Total calorific value is 37,200 (kJ / L) or more [2] Catalytic cracking light oil 20% by volume or more 40 volumes % or less and blending hydrocracked kerosene obtained by hydrocracking a raw material oil containing heavy gas oil and an antioxidant, wherein the hydrogenation Contains 50% by volume or more of cracked kerosene, and the content of the antioxidant based on the total amount of the composition is 20 ppm by mass or more and 100 ppm by mass or less. A method for producing a fuel oil composition for a combustion engine.
(1) Initial boiling point of 140.0°C or higher (2) 95% by volume distillation temperature of 271.0°C or higher and 300.0°C or lower (3) Flash point of 45.0°C or higher (4) Sulfur content is 3 mass ppm or more and 10 mass ppm or less (5) Cloud point is -20.0 ° C. or less (6) Total calorific value is 37,200 (kJ / L) or more

According to the present invention, it has excellent stability even in long-term storage, exhibits excellent low-temperature fluidity even in cold regions during the severe cold season, and is equipped with a hydraulic spray burner with a small rated combustion amount and low spray oil pressure. Provided is a fuel oil composition for an external combustion engine that exhibits excellent combustibility even in an external combustion engine with a high yield rate, can be stably supplied, and has a high calorific value to contribute to improvement of fuel consumption. be able to. The fuel oil composition for an external combustion engine can be suitably used particularly in an external combustion engine equipped with a hydraulic spray burner having a rated combustion rate of 10.0 L/hr or less and a spray pressure of 0.9 MPa or less.

Hereinafter, a fuel oil composition for an external combustion engine and a method for producing the same according to an embodiment of the present invention (hereinafter sometimes simply referred to as "this embodiment") will be specifically described. In this specification, the numerical values related to “less than”, “more than” and “to” regarding the description of numerical ranges are numerical values that can be arbitrarily combined, and the numerical values in the examples are used as the upper limit or lower limit. It is a numerical value that can be

[Fuel oil composition for external combustion engine]
The fuel oil composition for an external combustion engine of the present embodiment contains 50% by volume or more of hydrocracked kerosene obtained by hydrocracking a feedstock containing catalytically cracked gas oil and heavy gas oil, and contains 20% antioxidant. Contains mass ppm or more and 100 mass ppm or less. Further, the content of catalytically cracked light oil in the raw material oil is 20% by volume or more and 40% by volume or less, and the fuel oil composition for an external combustion engine satisfies all of the following conditions (1) to (6). do.
(1) Initial boiling point of 140.0°C or higher (2) 95% by volume distillation temperature of 271.0°C or higher and 300.0°C or lower (3) Flash point of 45.0°C or higher (4) Sulfur content is 3 mass ppm or more and 10 mass ppm or less (5) Cloud point is -20.0 ° C. or less (6) Total calorific value is 37,200 (kJ / L) or more

(Composition and properties of fuel oil composition for external combustion engine)
The fuel oil composition for an external combustion engine of the present embodiment satisfies all of the composition and properties specified in (1) to (6) above. Each provision of (1) to (6) will be described in detail below.
(1) Initial boiling point The initial boiling point of the fuel oil composition for an external combustion engine of the present embodiment is 140.0°C or higher. If the initial boiling point is less than 140°C, the handling safety is lowered. From the viewpoint of improving safety in handling, it is preferably 143.0° C. or higher, more preferably 145.0° C. or higher, and the upper limit is preferably 160.0° C. or lower from the viewpoint of improving the yield. and more preferably 155.0° C. or less.
In the present specification, the initial boiling point and the 95% by volume distillation temperature described below are values measured according to JIS K2254: 1998 (petroleum products-distillation test method-).

(2) 95% by volume distillation temperature The 95% by volume distillation temperature of the fuel oil composition for an external combustion engine of the present embodiment is 271.0°C or higher and 300.0°C or lower. If the 95% by volume distillation temperature is not within the above range, excellent yield cannot be obtained. When the 95% by volume distillation temperature of the fuel oil composition for an external combustion engine is 271.0 ° C. or higher, it is higher than the 95% by volume distillation temperature of No. 1 kerosene (270 ° C. or lower), so the boiling point range is Since the boiling point range is wider than that of No. 1 kerosene, an excellent yield can be obtained.
The 95% by volume distillation temperature of the fuel oil composition for an external combustion engine of the present embodiment depends on the 95% by volume distillation temperature of the constituent fraction. Since the % distillation temperature is 271.0° C. or more and 300.0° C. or less, the boiling point range is wider than that of No. 1 kerosene, and the yield from crude oil is higher than that of No. 1 kerosene.
From the viewpoint of improving the yield, the 95% by volume distillation temperature is preferably 275.0° C. or higher, more preferably 280.0° C. or higher, and the upper limit is preferably 295.0° C. or lower, more preferably 290.0°C or less.

(3) Flash point The flash point of the fuel oil composition for an external combustion engine of the present embodiment is 45.0°C or higher. If the flash point is less than 45.0°C, safety in handling is lowered. From the viewpoint of improving safety in handling, the flash point is preferably 48.0°C or higher.
As used herein, the flash point is a value measured according to JIS K 2265-1:2007 (Crude oil and petroleum products-Flash point test method-Part 1: Tag sealing method).

(4) Sulfur Content The sulfur content of the fuel oil composition for an external combustion engine of the present embodiment is 3 mass ppm or more and 10 mass ppm or less. If the sulfur content is not within the above range, it may become difficult to maintain storage stability, and corrosion may occur due to an increase in sulfur oxides in the exhaust gas. From the viewpoint of improving storage stability and suppressing the occurrence of corrosion, the sulfur content is preferably 6 mass ppm or less, and preferably 4 mass ppm or more as a lower limit.
As used herein, the sulfur content is a value measured according to JIS K2541-7:2003 (Crude oil and petroleum products-Sulfur content test method-Part 7: Wavelength dispersive X-ray fluorescence method).

(5) Cloud Point The cloud point of the fuel oil composition for an external combustion engine of the present embodiment is −20.0° C. or less. If the cloud point exceeds −20.0° C., the low-temperature fluidity is lowered and the filter is likely to be clogged by precipitated wax, requiring equipment such as heat insulation. It is preferably -23.0°C or less, more preferably -25.0°C, from the viewpoint of suppressing filter clogging by improving low-temperature fluidity in the harsh winter of cold regions and eliminating the need for equipment such as heat retention. It is below. On the other hand, the lower limit is not particularly limited, but is usually -40.0°C or higher.
As used herein, the cloud point is a value measured according to JIS K2269:1987 (Determination of pour points and cloud points of crude oil and petroleum products).

(6) Total Calorific Value The total calorific value of the fuel oil composition for an external combustion engine of the present embodiment is 37,200 (kJ/L) or more. If the total calorific value is less than 37,200 (kJ/L), the fuel consumption will decrease, making it difficult to improve the fuel consumption. From the viewpoint of further improving fuel economy, the total calorific value is preferably 37,400 (kJ/L) or more, more preferably 37,500 (kJ/L) or more.
In this specification, the total calorific value is measured according to JIS K2279: 2003 (Crude oil and petroleum products-calorific value test method and calculation estimation method-) and estimated ("6. Total calorific value estimation method, 6. 3 e) It is a value estimated by the calculation formula for crude oil, kerosene, light oil, A heavy oil and B heavy oil specified in 1).

Further, the fuel oil composition for an external combustion engine of the present embodiment satisfies at least one selected from the following (7) to (13) in addition to the properties and compositions of (1) to (6) above. In particular, it is preferable to satisfy all of the following (7) to (13).
(7) The result of the petroleum product reaction test is neutral (8) The water content is 0.01% by volume or less (9) The ash content is 0.001% by mass or less (10) The residual carbon content of 10% residual oil is 0 (11) Kinematic viscosity at 30°C of 1.300 mm ² /s or more and 1.700 mm ² /s or less (12) Density at 15°C of 0.8100 g/cm ^{3 or} more (13) Based on the total amount of the composition Saturated content of 75.0% by volume or more, olefin content of 0.3% by volume or less, 1-ring aromatic content of 25.0% by volume or less, 2-ring aromatic content of 3.0% by volume or less, and 3-ring The above aromatic content is 0.5% by volume or less.

(7) Petroleum Product Reaction Test It is preferable that the fuel oil composition for an external combustion engine of the present embodiment is neutral as a result of a petroleum product-reaction test according to JIS K 2252:1998. By being neutral, it prevents corrosion of various equipment that the fuel oil composition for an external combustion engine of the present embodiment comes into contact with, such as fuel oil tanks, pipes, diesel engines, and auxiliary equipment such as equipped pumps. Therefore, the stable operation of the external combustion engine becomes possible more easily.

(8) Moisture Content The moisture content of the fuel oil composition for an external combustion engine of the present embodiment is preferably 0.01% by volume or less. When the water content is within the above range, deterioration of storage stability (sludge formation due to emulsion of asphaltene and water), freezing, etc. can be suppressed, and clogging of the filter can be prevented.
As used herein, the moisture content is a value measured according to JIS K 2275-3:2015 (Crude oil and petroleum products-Determination of moisture content-Part 3: Karl Fischer coulometric titration method).

(9) Ash Content The ash content of the fuel oil composition for an external combustion engine of the present embodiment is preferably 0.001% by mass or less. When the ash content is within the above range, the wear of the burner tip can be further suppressed, and the environmental load due to the exhaust gas can be reduced.
As used herein, the ash content is a value measured according to JIS K 2272:1998 (crude oil and petroleum products-ash and sulfated ash test methods-).

(10) Residual carbon content of 10% residual oil It is preferable that the residual carbon content of 10% residual oil of the fuel oil composition for an external combustion engine of the present embodiment is 0.01% by mass or less. When the residual carbon content is within the above range, it becomes easy to maintain the combustion performance, and generation of soot due to poor combustion is suppressed.
In this specification, the residual carbon content is JIS K 2270-1: 2009 (Crude oil and petroleum products-Determination of residual carbon content-Part 1: Conradson method), Annex A Prepared in accordance with 10 It is a value measured using % residual oil.

(11) Kinematic viscosity at 30° C. The kinematic viscosity at 30° C. of the fuel oil composition for an external combustion engine of the present embodiment is preferably 1.300 mm ² /s or more, more preferably 1.350 mm ² /s or more, and further It is preferably 1.375 mm ² /s or more, and the upper limit is preferably 1.700 mm ² /s or less, more preferably 1.600 mm ² /s or less, still more preferably 1.500 mm ² /s or less. When the kinematic viscosity at 30°C is within the above range, the fuel oil composition for an external combustion engine is easily adapted to the specifications of various devices such as pumps and flow meters, and the combustibility is improved.
As used herein, the kinematic viscosity at 30° C. is a value measured according to JIS K 2283:2000 (testing method for kinematic viscosity of crude oil and petroleum products).

(12) Density at 15°C The density at 15°C of the fuel oil composition for an external combustion engine of the present embodiment is preferably 0.8100 g/cm ³ or more. This is because a sufficient amount of heat is ensured.
As used herein, the density at 15° C. is a value measured according to JIS K 2249-1:2011 (Crude oil and petroleum products-Determination of density-Part 1: Vibration method).

(13) Composition The saturated content of the fuel oil composition for an external combustion engine of the present embodiment is preferably 75.0% by volume or more, more preferably 80.0% by volume or more, based on the total amount of the composition. The olefin content is preferably 0.3% by volume or less, more preferably 0.1% by volume or less. The monocyclic aromatic content is preferably 25.0% by volume or less, more preferably 20.0% by volume or less. The bicyclic aromatic content is preferably 3.0% by volume or less, more preferably 2.0% by volume or less. Also, the aromatic content of 3 or more rings is preferably 0.5% by volume or less, more preferably 0.3% by volume or less. When the content of these components is within the above range, the combustibility is particularly improved.
In the present specification, the above saturated content, olefinic content, 1-ring aromatic content, 2-ring aromatic content and 3- or more ring aromatic content are specified in JPI-5S-49-2007, petroleum products - carbonization Hydrogen type test method—value measured by High Performance Liquid Chromatography method.

The hydrocracking kerosene, which is the main component of the fuel oil composition for an external combustion engine of the present embodiment, is obtained by hydrocracking a feed oil containing catalytically cracked gas oil and heavy gas oil.
(a) Catalytically cracked gas oil Catalytically cracked gas oil is a fraction obtained from a catalytic cracking unit, and the 90% by volume distillation temperature in distillation properties is usually in the range of 280 ° C. or higher and 390 ° C. or lower, preferably 300 ° C. or higher. 370°C or less. Also, the density at 15° C. is usually 0.800 g/cm ³ or more and 1.000 g/cm ³ or less, preferably 0.820 g/cm ³ or more and 0.980 g/cm ³ or less. The sulfur content is preferably 0.1% by mass or more and 0.8% by mass or less, and preferably 0.2% by mass or more and 0.7% by mass or less.

(b) Heavy gas oil Heavy gas oil is a fraction from an atmospheric distillation apparatus or a vacuum distillation apparatus, or a mixture of these fractions, and the temperature at the end point in distillation properties is usually 400 ° C. or higher and 600 ° C. It is in the following range, preferably 420° C. or higher and 580° C. or lower. Also, the density at 15° C. is usually 0.800 g/cm ³ or more and 1.000 g/cm ³ or less, preferably 0.820 g/cm ³ or more and 0.950 g/cm ³ or less. The sulfur content is preferably 1.0% by mass or more and 3.0% by mass or less, and preferably 1.5% by mass or more and 2.8% by mass or less.

(c) Feedstock and hydrocracking conditions The feedstock to be hydrocracked contains (a) catalytically cracked gas oil and (b) heavy gas oil, and the content of catalytically cracked gas oil in the feedstock is 20% by volume or more and 40% by volume or less. If the content of catalytic cracking light oil is 20% by volume or more, it is advantageous in terms of calorific value, and if it exceeds 40% by volume, it is disadvantageous in terms of combustibility.
From the above point of view, the content of catalytically cracked light oil in the raw material oil is preferably 25% by volume or more and 35% by volume or less.
Next, as conditions for hydrogenolysis, the reaction temperature is usually 300 to 450°C, preferably 360 to 420°C. The hydrogen partial pressure is usually in the range of 3.0-20.0 MPa, preferably in the range of 10.0-18.0 MPa. The hydrogen/feedstock ratio is usually in the range of 300-2,000 Nm ³ /kL, preferably in the range of 500-1000 Nm ³ /kL. The liquid hourly space velocity is usually in the range of 0.1 to 10.0 hr ^-1 , preferably in the range of 0.3 to 5.0 hr ^-1 .
The hydrocracking catalyst is not particularly limited as long as it has both decomposability and hydrogenation ability, but an amorphous or zeolite catalyst is preferably used.

(d) Fuel Oil Composition for External Combustion Engine The fuel oil composition for an external combustion engine of the present embodiment contains at least 50% by volume of hydrocracked kerosene obtained by hydrocracking the raw material oil. The fraction other than hydrocracked kerosene is not particularly limited as long as it can maintain suitable properties as the final fuel oil composition for external combustion engines. Desulfurized desulfurized kerosene is preferably used. The content of desulfurized kerosene is preferably 30% by volume or more.
Here, desulfurized kerosene is a fraction obtained by desulfurizing straight-run kerosene. Here, straight-run kerosene is a fraction obtained from an atmospheric distillation apparatus, and usually has an initial boiling point of 140°C or higher and a 95% distillation temperature of 271°C or higher and 305°C or lower, preferably 280°C. It is a fraction having a temperature of 300°C or higher.

As conditions for desulfurization, the reaction temperature is usually 250 to 390°C, preferably 290 to 350°C. The hydrogen partial pressure is usually in the range of 1.0-10.0 MPa, preferably in the range of 2.0-5.0 MPa. The hydrogen/feedstock ratio is usually in the range of 50-500 Nm ³ /kL, preferably in the range of 70-200 Nm ³ /kL. The liquid hourly space velocity is usually in the range of 0.1 to 10.0 hr ^-1 , preferably in the range of 1.0 to 8.0 hr ^-1 .
As the catalyst, a commonly used hydrodesulfurization catalyst can be used. For example, a catalyst in which molybdenum is supported on an alumina carrier is used as the main catalyst, and cobalt or cobalt-nickel supported as a promoter metal is preferably used. Used.

In addition, the fuel oil composition for an external combustion engine of the present embodiment may contain other fractions in addition to hydrocracked kerosene and desulfurized kerosene. Other fractions include, for example, the following fractions.
(i) A fraction obtained by hydrocracking a gas oil fraction (also referred to as a "straight-run gas oil fraction") obtained by atmospheric distillation of crude oil in an atmospheric distillation apparatus (ii) Crude oil is subjected to atmospheric distillation in an atmospheric distillation apparatus Hydrocracking the gas oil fraction (also referred to as "vacuum gas oil fraction") obtained by vacuum distillation of the residue fraction obtained by pressure distillation (also referred to as "atmospheric distillation residue") with a vacuum distillation apparatus The fraction (iii) obtained by desulfurizing the atmospheric distillation residue and/or the vacuum distillation residue with a direct desulfurization unit (also referred to as a "directly desulfurized gas oil fraction") is hydrocracked. Among isoparaffinic solvents or aromatic solvents produced in the obtained fraction (iv) petrochemical plant, the sulfur content is 10 ppm by mass or less and the boiling point range is 140.0 ° C. or higher and 320.0 ° C. or lower. fraction of

(Antioxidant)
The fuel oil composition for an external combustion engine of the present embodiment contains an antioxidant in a range of 20 ppm by mass or more and 100 ppm by mass or less based on the total amount of the composition. If the above antioxidant is not contained in the above content, the storage stability may be lowered and the combustibility may be lowered. As for the upper limit, even if the content exceeds the upper limit, the addition effect is poor and it is economically disadvantageous.
The content of the antioxidant based on the total amount of the composition is preferably 25 mass ppm or more, more preferably 30 mass ppm or more, from the viewpoint of efficiently improving storage stability and improving combustibility. The value is preferably 80 mass ppm or less, more preferably 60 mass ppm or less.

The antioxidant used in the present embodiment can be used without particular limitation as long as it is commonly used in fuel oil compositions. For example, antioxidants such as phenolic antioxidants and amine antioxidants are preferably mentioned. Moreover, in this embodiment, an antioxidant can be used individually by 1 type or in combination of multiple types.

Phenolic antioxidants include 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,4,6 monocyclic tert-alkylphenol antioxidants such as -tri-tert-butylphenol, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol; 4,4'-methylenebis(2 ,6-di-tert-butylphenol), 4,4′-isopropylidenebis(2,6-di-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-tert-butylphenol), 4, 4'-bis(2,6-di-tert-butylphenol), 4,4'-bis(2-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol ), polycyclic tert-alkylphenol antioxidants such as 4,4′-butylidenebis(3-methyl-6-tert-butylphenol), and the like.

Amine-based antioxidants include monoalkyldiphenylamine-based antioxidants such as monooctyldiphenylamine and monononyldiphenylamine; ,4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, 4,4'-dinonyldiphenylamine and other dialkyldiphenylamine antioxidants; tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, tetranonyldiphenylamine polyalkyldiphenylamine-based antioxidants; naphthylamine-based antioxidants such as α-naphthylamine, phenyl-α-naphthylamine and butylphenyl-α-naphthylamine;

In the present embodiment, a phenolic antioxidant having a tert-alkyl group is preferred, and a monocyclic phenolic antioxidant having a tert-alkyl group is more preferred. Among them, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol and 2,6-di-tert-butyl-4-methylphenol are preferred.

(other additives)
The fuel oil composition for an external combustion engine of the present embodiment may optionally contain other additives other than the antioxidants, such as a low-temperature fluidity improver and a lubricating agent, as long as the above properties can be maintained. Various additives such as a property improver, a cetane number improver, a combustion accelerator, a detergent, a sludge dispersant, and an antifungal agent can be appropriately selected and blended. In addition, coumarin may be blended from the viewpoint of light oil collection tax.

(Application)
The fuel oil composition for an external combustion engine of the present embodiment has high storage stability, exhibits excellent low-temperature fluidity even in cold climates during the severe cold season, exhibits excellent oxidation stability, and is also excellent in combustibility. Therefore, even in an external combustion engine equipped with a hydraulic atomizing burner with a small rated combustion volume and low atomizing oil pressure, it exhibits excellent combustibility. It has a characteristic that it can contribute to fuel efficiency improvement by having Specifically, it is suitably used for external combustion engines such as steam boilers, hot water boilers, hot air heaters, absorption chiller heaters, and hot water generators.
Further, the fuel oil composition for an external combustion engine of the present embodiment has a rated combustion amount of 10.0 L/hour or less and a spray oil pressure of 0.90 MPa or less, preferably a rated combustion amount of 7 .0 L/hour or less and spray oil pressure of 0.80 MPa or less, more preferably 5.0 L/hour or less of rated combustion amount and spray oil pressure of 0.70 MPa or less for an external combustion engine equipped with a hydraulic spray burner. , the above characteristics are particularly exhibited.

[Method for producing fuel oil composition for external combustion engine]
The method for producing a fuel oil composition for an external combustion engine of the present embodiment is a method for producing a fuel oil composition for an external combustion engine that satisfies all of the above (1) to (6), and has the following steps: .
(A) Step of obtaining hydrocracked kerosene by hydrocracking feedstock oil containing 20% by volume or more and 40% by volume or less of catalytically cracked light oil and containing heavy diesel oil (B) Hydrocracked kerosene obtained in the previous step A step of adding an antioxidant to a fuel oil composition containing 50% by volume or more of

Further, as a preferred embodiment, the hydrocracked kerosene and desulfurized kerosene obtained in the step (A) are mixed so that the content of each is 50% by volume or more and 30% by volume or more. A manufacturing method including a step of blending an antioxidant so that the content of the composition based on the total amount is 20 mass ppm or more and 100 mass ppm or less.
The fuel oil composition for an external combustion engine of this embodiment can be easily produced by the production method of this embodiment.

In the method for producing a fuel oil composition for an external combustion engine of the present embodiment, the properties and composition of the obtained fuel oil composition for an external combustion engine, hydrocracked kerosene, desulfurized kerosene, antioxidants, etc. are the above-mentioned It is the same as the aspect of the fuel oil composition for external combustion engines.
There are no particular restrictions on the order in which hydrocracked kerosene, desulfurized kerosene, antioxidants, and various additives used as necessary are added. For example, hydrocracked kerosene, desulfurized kerosene, antioxidants, and various additives They may be added successively and mixed, or after premixing the antioxidant and various additives, the mixture, hydrocracked kerosene, and desulfurized kerosene may be mixed.

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

[Measurement of properties and composition]
Various properties and compositions of the fuel oil composition of this embodiment were measured by the following methods.
Distillation properties (initial boiling point, end point and 95% by volume distillation temperature): Measured according to JIS K2254: 1998 (petroleum products-distillation test method-).
Flash point: Measured according to JIS K 2265-1:2007 (Crude oil and petroleum products-Flash point test method-Part 3: Tag sealing method).
Sulfur content: Measured according to JIS K2541-7:2003 (Crude oil and petroleum products-Sulfur content test method-Part 7: Wavelength dispersive fluorescent X-ray method).
- Cloud point: Measured according to JIS K2269: 1987 (Testing methods for pour point and cloud point of crude oil and petroleum products).
・ Gross calorific value: Measured and estimated according to JIS K2279: 2003 (crude oil and petroleum products-calorific value test method and calculation-based estimation method-) ("6. Total calorific value estimation method, 6.3 e) 1) Estimated by the calculation formula for crude oil, kerosene, light oil, A heavy oil and B heavy oil specified in ".
• Petroleum product reaction test: Measured by a petroleum product-reaction test according to JIS K 2252:1998.
Moisture content: Measured according to JIS K 2275-3: 2015 (Crude oil and petroleum products-Method for determining moisture content-Part 3: Karl Fischer coulometric titration method).
Ash content: Measured according to JIS K 2272: 1998 (Crude oil and petroleum products-Ash and sulfated ash test methods-).
・ 10% residual carbon residue: JIS K 2270-1: 2009 (Crude oil and petroleum products-Determination of carbon residue-Part 1: Conradson method) Prepared in accordance with Annex A 10 % residual oil Kinematic viscosity at 30°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-Determination of density-Part 1: Vibration method).
・ Composition: Saturated content, olefin content, 1-ring aromatic content, 2-ring aromatic content and 3- or more ring aromatic content are specified in JPI-5S-49-2007, petroleum products-Hydrocarbon type test method- It was measured by a high performance liquid chromatography method (High Performance Liquid Chromatography method).

[Evaluation criteria for performance]
Each of the following performances 1 to 4 was evaluated. If there was an x evaluation in any of the items, the comprehensive evaluation was x evaluation (failed).
1. Combustibility (1) Evaluation model, conditions/evaluation model; hot air warmer ("House Kaonki HK-1527", manufactured by Nepon Co., Ltd., rated combustion volume 4.9 L / hour, on-off control)
・Fuel spray pressure: 0.69 MPa (hydraulic spray burner)
・Band shutter opening: adjust exhaust gas oxygen concentration to 3.0 ± 0.2% ・Heater in front of burner for heating fuel: OFF , after burning for 500 hours, the following items were evaluated.
・Ignition: Visually no ignition delay ・Combustibility: Measure soot concentration in exhaust gas (Baccaraca smoke number; SN) with a Baccaracca smoke tester (3) Evaluation criteria 〇: Visually no ignition delay, soot Density (SN) is 1.0 or less ×: Other than the above

2. Storage stability (1) Evaluation item According to ASTM D4625, after storing in the dark for 8 weeks at 43 ° C. (equivalent to storage at room temperature for about 8 months), peroxidation according to JPI-5S-71 I measured the price.
(2) Evaluation criteria ○: Peroxide value is less than 1 ppm ×: Other than the above

3. Low-temperature fluidity (1) Evaluation item The oil flow limit temperature was measured according to JPI-5S-47-96 Low-temperature fluidity test method standard for heavy oil A (actual machine simulation method). The oil flow limit temperature is the lowest oil temperature at which the filter is not clogged by wax that precipitates at low temperatures. If the oil temperature is lowered below the oil passage limit temperature, the possibility of filter blockage due to wax becomes very high.
(2) Evaluation criteria ◯: Oil flow limit temperature ≤ -20.0 ° C
×: Other than the above

4. Fuel efficiency (1) Evaluation items Based on JIS K 2279 (JIS K 2279 6. Total calorific value estimation method “Crude oil, kerosene, light oil, A heavy oil”), the total calorific value is determined by density, sulfur content, water content, and ash content. was calculated.
(2) Evaluation Criteria Based on the total calorific value, evaluation was made according to the following criteria.
○: Total calorific value is 37,200 kJ/L or more ×: Total calorific value is less than 37,200 kJ/L

[Production of hydrocracked kerosene]
Catalytically cracked gas oil and heavy gas oil having the properties shown in Table 1 are mixed to 30% by volume and 70% by volume respectively, hydrocracked under the following conditions, and then distilled to adjust the flash point. was removed to obtain hydrocracked kerosene. The properties are shown in Table 2.
(Conditions for hydrocracking)
Reaction temperature: 380° C., Hydrogen partial pressure: 16.0 MPa, Hydrogen/raw oil ratio: 800 Nm ³ /kL, Liquid hourly space velocity: 3.0 hr ⁻¹ , Catalyst: Hydrocracking catalyst (zeolitic)

[Production of desulfurized kerosene]
Straight-run kerosene having the properties shown in Table 1 was hydrocracked under the following conditions, and then light components were removed by distillation to adjust the flash point to obtain desulfurized kerosene. The properties are shown in Table 2.
(Conditions for hydrodesulfurization)
Reaction temperature: 310° C., Hydrogen partial pressure: 5.0 MPa, Hydrogen/raw oil ratio: 90 Nm ³ /kL, Liquid hourly space velocity: 7.0 hr ⁻¹ , Catalyst: Hydrodesulfurization catalyst (cobalt-molybdenum system)

[Example 1]
Hydrocracked kerosene and desulfurized kerosene whose properties are shown in Table 2 are each mixed at 50% by volume, and 2,6-di-tert-butyl-4-methylphenol is added as an antioxidant to 100 parts by mass of the above mixed oil. A fuel oil composition was obtained by blending 40 ppm by mass. Table 3 shows the properties and evaluation results of the fuel oil composition.

[Example 2]
A fuel oil composition was obtained in the same manner as in Example 1, except that the blending amounts of hydrocracked kerosene and desulfurized kerosene were 60% by volume and 40% by volume, respectively. Table 3 shows the properties and evaluation results of the fuel oil composition.

[Comparative Example 1]
A fuel oil composition was obtained in the same manner as in Example 1, except that no antioxidant was added. Table 3 shows the properties and evaluation results of the fuel oil composition.

[Comparative Examples 2 and 3]
A fuel oil composition was obtained in the same manner as in Example 1, except that 100% by volume of desulfurized kerosene alone was used (Comparative Example 2), and 100% by volume of hydrocracked kerosene alone was used (Comparative Example 3). Table 3 shows the properties and evaluation results of the fuel oil composition.

[Results of performance evaluation]
As shown in Table 3, the fuel oil composition for an external combustion engine of the present embodiment has good combustibility, storage stability, low-temperature fluidity, and fuel efficiency, and even in cold regions during the severe cold season. It exhibits excellent low-temperature fluidity and exhibits excellent combustibility even in an external combustion engine equipped with a hydraulic atomizing burner with a low rated combustion volume and low atomizing oil pressure. It was confirmed that the presence of heat and a higher calorific value can contribute to the improvement of fuel efficiency.
In contrast, Comparative Example 1 containing no antioxidant had insufficient storage stability. Further, the fuel oil composition of Comparative Example 2, which uses only desulfurized kerosene, has poor fuel efficiency due to its low total calorific value, and the fuel oil composition of Comparative Example 3, which uses only hydrocracked kerosene, is storage stable. was inadequate.

The fuel oil composition for an external combustion engine of the present embodiment has excellent long-term storage stability, exhibits excellent low-temperature fluidity even in cold regions during the severe cold season, and is used in a hydraulic spray burner with a small rated combustion amount and a low spray oil pressure. It also exhibits excellent combustibility in the external combustion engine it is installed in, and is capable of more stable supply due to its high yield. It can solve the shortage of supply of kerosene and kerosene fractions, which are in great demand in winter.
The fuel oil composition for an external combustion engine of the present embodiment is suitably used for external combustion engines such as steam boilers, hot water boilers, hot air heaters, absorption chiller heaters, and hot water generators. When used in a steam external combustion engine equipped with a hydraulic atomizing burner having a flow rate of 10.0 L/hour or less and an atomizing oil pressure of 0.90 MPa or less, the above characteristics are exhibited, and thus it is particularly preferably used.

Claims (5)

A fuel oil composition for an external combustion engine containing 50% by volume or more of hydrocracked kerosene obtained by hydrocracking a feedstock containing catalytically cracked gas oil and heavy gas oil, wherein the catalytically cracked gas oil in the feedstock oil content is 20% by volume or more and 40% by volume or less, further contains 20 mass ppm or more and 100 mass ppm or less of an antioxidant, and satisfies all of the following conditions (1) to (6). Fuel oil composition.
(1) Initial boiling point of 140.0°C or higher (2) 95% by volume distillation temperature of 271.0°C or higher and 300.0°C or lower (3) Flash point of 45.0°C or higher (4) Sulfur content is 3 mass ppm or more and 10 mass ppm or less (5) Cloud point is -20.0 ° C. or less (6) Total calorific value is 37,200 (kJ / L) or more The fuel oil composition for an external combustion engine according to claim 1, further satisfying at least one selected from the following (7) to (13).
(7) The result of the petroleum product reaction test is neutral (8) The water content is 0.01% by volume or less (9) The ash content is 0.001% by mass or less (10) The residual carbon content of 10% residual oil is 0 (11) Kinematic viscosity at 30°C of 1.300 mm ² /s or more and 1.700 mm ² /s or less (12) Density at 15°C of 0.8100 g/cm ^{3 or} more (13) Based on the total amount of the composition Saturated content of 75.0% by volume or more, olefin content of 0.3% by volume or less, 1-ring aromatic content of 25.0% by volume or less, 2-ring aromatic content of 3.0% by volume or less, and 3-ring 0.5% by volume or less of the aromatic content of 3. The fuel oil composition for an external combustion engine according to claim 1, which is used in an external combustion engine equipped with a hydraulic atomizing burner having a rated combustion rate of 10.0 L/hour or less and an atomizing oil pressure of 0.9 MPa or less. The fuel oil composition for an external combustion engine according to any one of claims 1 to 3, further comprising 30% by volume or more of desulfurized kerosene. A fuel oil composition for an external combustion engine containing 20% by volume or more and 40% by volume or less of catalytically cracked gas oil and containing hydrocracked kerosene obtained by hydrocracking a feedstock oil containing heavy gas oil and an antioxidant. The following (1) that contains 50% by volume or more of the hydrocracked kerosene and that the content of the antioxidant based on the total amount of the composition is 20 mass ppm or more and 100 mass ppm or less A method for producing a fuel oil composition for an external combustion engine that satisfies all of (6).
(1) Initial boiling point of 140.0°C or higher (2) 95% by volume distillation temperature of 271.0°C or higher and 300.0°C or lower (3) Flash point of 45.0°C or higher (4) Sulfur content is 3 mass ppm or more and 10 mass ppm or less (5) Cloud point is -20.0 ° C. or less (6) Total calorific value is 37,200 (kJ / L) or more