JP2001019978A - A-fuel oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition high in combustibility, causing no filter cloggings due to wax in winter, and useful in high-performance engines by designing its naphthene fraction to fall within a specific range. SOLUTION: This A-fuel oil composition is obtained by designing its naphthene fraction at >=40 wt.%. Preferably, this composition is produced by mixing an A-fuel oil base with a residual carbon-imparting base followed by, as necessary, formulating the mixture with an additive; wherein the A-fuel oil base to be used comprises >=50 wt.% of hydrocracked light oil and >=0.5 vol.% of extracts; wherein the naphthene fraction comprises, for example, monocyclic naphthene fraction, bicyclic naphthene fraction and polycyclic naphthene fractions, in particular contains >=25 wt.% of the monocyclic naphthene based on the whole composition, and it is recommended that the above naphthene fractions including the monocyclic naphthene fraction is based on the total amount of A-heavy oil afforded in accordance with ASTM D-2786 'mass spectrometry'.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a fuel oil A composition. More specifically, the present invention relates to a fuel oil A composition having sufficient performance for a recent high-performance engine and having excellent low-temperature fluidity.

[0002]

2. Description of the Related Art Fuel oil A is used as boiler fuel and diesel engine fuel. However, in recent years, with the increase in output and fuel efficiency of engines used for fuel oil A, fuel oil A has been developed. As fuel oil, demands for higher performance are increasing year by year. When heavy fuel oil A is used as fuel for these high-performance engines, problems with flammability such as deterioration of ignitability and frequency of cleaning the burner and the furnace due to increased generation of soot may occur. on the other hand,
Heavy fuel oil A contains more heavy components than gasoline and kerosene, so that wax precipitation at low temperatures may become a problem. The deposition of wax at low temperatures may block the filter for preventing foreign substances in the fuel system, and in the worst case, make it impossible to supply fuel. As a method of suppressing wax deposition at low temperatures, a method of adding a fluidity improver is generally used, but at present, a sufficient effect cannot be exerted under actual severe winter use conditions. Conventionally, a test based on a clogging point has been used to determine filter clogging at low temperatures. In this test method, the low-temperature fluidity is improved by adding a fluidity improver. However, in this test method, the cooling rate of the sample oil is fast and rapid cooling (about 40 ° C./hour). Significantly different from below. It is known that the slower the cooling rate, the larger the amount of precipitated wax and clogging of the filter, and it has been found that the evaluation based on the clogging point is insufficient. In general, A fuel oil excellent in low-temperature performance often has poor flammability, and A fuel oil satisfying all these performances at the same time is desired. The object of the present invention is
An object of the present invention is to provide a fuel oil A composition that can withstand the use of recent high-performance engines and that does not cause clogging of filters by wax in winter.

[0003]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, when the naphthene content is in a specific range, the flammability is high, and the wax is used in winter. They found that clogging of the filter did not occur, and completed the present invention. That is, the heavy oil composition A of the present invention is characterized in that the naphthene content is 40% by mass or more. Further, the heavy oil composition A of the present invention is preferably obtained using a hydrocracked light oil and an extract.

[0004]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The heavy oil composition A of the present invention needs to have a naphthene content of 40% by mass or more. The naphthene component can simultaneously satisfy all aspects such as flammability and prevention of clogging of the filter by the wax in winter, and is more excellent by these effects. Therefore, the naphthene component is 40 mass% based on the total amount of the heavy oil A composition. % Or more, preferably 45% by mass or more, more preferably 50% by mass or more, and most preferably 55% by mass or more. The naphthene component includes a mononaphthene component, a bicyclic naphthene component, and a tricyclic or higher polycyclic naphthene component, and the content of these components is not particularly limited. However, all aspects such as combustibility and prevention of filter clogging due to wax in winter can be satisfied at the same time, and these effects are even more excellent. Is preferably 25% by mass or more, more preferably 30% by mass or more, and most preferably 35% by mass or more. In the present invention, the term “naphthene component” and “partial naphthene component” mean a value representing a value based on the total amount of heavy oil A obtained in accordance with ASTM D2786 “Mass Spectrometry”.

[0005] There is no particular limitation on the saturated content and aromatic content of the heavy oil A of the present invention. However, from the viewpoints of flammability, prevention of clogging of the filter by wax in winter, etc., the saturated content is preferably 55% by volume or more, more preferably 60% by volume or more, and 65% by volume or more.
Even more preferably, it is at least 70% by volume, particularly preferably at least 70% by volume, most preferably at least 75% by volume. Further, from the viewpoint of reducing flammability, the aromatic content is preferably 45% by volume or less,
More preferably 35% by volume or less, 30% by volume
Is still more preferred, and most preferably 25% by volume or less. In the present invention, the saturated component and the aromatic component refer to values measured in accordance with JPI-5S-49-97 "Test Method for Hydrocarbon Type-High Performance Liquid Chromatography". Further, normal paraffin is contained in the saturated component, but the amount is not particularly limited. However, normal paraffin is preferably 20% by mass or less, and more preferably 15% by mass or less, from the viewpoint of reducing wax precipitation at low temperatures. In the present invention, the normal paraffin content means a content representing a normal paraffin content based on the total amount of the heavy fuel oil composition A determined by the gas chromatography method described below. 1) Column: stainless steel, inner diameter 0.25 mm, length 2
5m 2) Injection temperature: 360 ° C 3) Carrier gas: helium 4) Detector: Flame ionization (FID) 5) Column temperature rate: 8 ° C / min (140-355)
In the present invention, the cetane index and the cetane number of the heavy oil composition A are not particularly limited, but from the viewpoint of excellent flammability, the cetane index is preferably 58 or more, and more preferably 60 or more. More preferably, the cetane number is 5
It is preferably 8 or more, more preferably 60 or more, and most preferably 62 or more. In the present invention, the cetane index is JIS K 2204-19.
92 means a value obtained based on “light oil”. That is, it is calculated by the following equation. Cetane index (C) = 0.49083 + 1.06577 (X)-0.001052
2 (X) ² X = 97.833 (logA) ² + 2.2088BlogA + 0.01247
B ² -423.51 log A-4.7808B + 419.59 A: (9/5) [50 at 101.3 kPa (760 mmHg)
% Distillation Temperature (° C.)] + 32 B: API Degree The 50% distilling temperature (° C.) at 101.3 kPa (760 mmHg) is measured according to JIS K2254 “Petroleum Product-Distillation Test Method”, and the API degree is JIS K 2249.
It is determined by converting from the density at 15 ° C according to “Crude oil and petroleum products-Density test method and density / mass / volume conversion table”. In addition, the cetane number means a value obtained according to JIS K 2280 "Petroleum products-fuel oil-Octane number and cetane number test method and cetane index calculation method". Further, in the present invention, the cloud point of the heavy fuel oil composition A is preferably -8 ° C or less from the viewpoint of reducing wax deposition at a low temperature that blocks a filter for preventing impurities in a fuel system, The temperature is more preferably -10C or lower, still more preferably -12C or lower, and most preferably -15C or lower. The heavy oil composition A of the present invention has no particular limitation on the pour point, but is preferably -15 ° C or lower from the viewpoint of reducing wax precipitation at low temperatures. In the present invention, the cloud point and the pour point refer to values obtained in accordance with JIS K 2269 "Test methods for pour point of crude oil and petroleum products and cloud point of petroleum products".

Further, CFPP of the heavy oil composition A of the present invention
The (clogging point) is not particularly limited, but is preferably -10 ° C or less, more preferably -12 ° C or less, because it is more excellent in preventing filter clogging with wax in winter. -15 ° C
It is most preferred that: In the present invention, CF
PP means a value obtained in accordance with JIS K 2288 "Diesel oil-clogging point test method". The wax content at -10 ° C of the heavy oil composition A of the present invention is not particularly limited, but is preferably 1.0% by mass or less because it is more excellent in preventing filter clogging with wax in winter. Is preferably 0.5% by mass or less, more preferably 0.5% by mass or less.
Most preferably, it is 3% by mass or less. In the present invention, the wax content at −10 ° C. means that a membrane filter, a methyl ethyl ketone-acetone mixed solvent and a sample are cooled to −10 ° C., and 17 g of the sample is suction-filtered through a 5.0 μm-aperture membrane filter. After washing the above wax with 30 ml of a mixed solvent of methyl ethyl ketone-acetone, the amount of wax collected on a filter is measured to indicate the amount of wax relative to the total amount of the sample. Further, the sulfur content and the nitrogen content of the heavy oil composition A of the present invention are not particularly limited. However, in order to reduce harmful substances in exhaust gas, the sulfur content is preferably 0.5% by mass or less. It is more preferably at most 0.3 mass%, most preferably at most 0.2 mass%. The nitrogen content is preferably 0.02% by mass or less, more preferably 0.015% by mass or less,
Most preferably, it is 0.01% by mass or less. In the present invention, the sulfur content and the nitrogen content refer to JIS K, respectively.
2541 "Crude oil and petroleum products-Test method for sulfur content", J
Means a value obtained in accordance with IS K 2609 "Crude oil and petroleum products-Test method for nitrogen content".
The 10% residual carbon content of the heavy oil composition A of the present invention is 0.2% by weight or more, preferably 0.2 to 1.0% by weight. If it is smaller than this range, the 10% residual carbon content is 0.1%.
2% by weight or more will not meet the tax exemption condition for Fuel Oil A. If the 10% residual carbon content exceeds the preferred range, the hue becomes worse and the image of the product becomes worse.
Dry sludge may increase, and the filter may be easily clogged at room temperature, and may adversely affect low-temperature fluidity. In the present invention, the 10% residual carbon content is J
It means a value obtained in accordance with IS K 2270 "Crude oil and petroleum products-Test methods for residual carbon content". The hue of the heavy oil A of the present invention is not particularly limited, but is preferably 7.0 or less from the viewpoint of image of the product and clogging of the filter at normal temperature and low temperature,
It is more preferably 6.0 or less, and most preferably 5.0 or less. In the present invention, the hue is J
It refers to an "ASTM color" obtained according to IS K 2580 "Petroleum products-Color test method".
The asphaltene content of the heavy oil composition A of the present invention is not particularly limited, but is preferably 0.01% by mass or less from the viewpoint of hue, filter clogging at room temperature due to dry sludge, low-temperature fluidity, and the like. The content is more preferably 0.005% by mass or less, and most preferably 0.002% by mass or less. In the present invention, the asphaltene content means a value that is obtained in accordance with IP143 “Asphaltene content test method”. The amount of dry sludge of the heavy oil composition A of the present invention is not particularly limited, but is preferably 2.0 mg / 100 ml or less, and is preferably 1.5 mg / 100 ml or less from the viewpoint that clogging of the filter at room temperature is unlikely to occur. Is more preferable, and most preferably 1.0 mg / 100 ml or less. In the present invention, the amount of dry sludge refers to the mass of a residue at normal temperature, which is obtained by suction-filtering a sample with a filter having an aperture of 1.2 μm, washing the filter after filtration and the residue on the filter with n-heptane, and drying. Means the value represented by the mass of the residue per 100 ml of the sample. The distillation properties of the heavy oil composition A of the present invention are not particularly limited, but usually those satisfying the following properties are used. Initial distillation point: 130 to 210 ° C. T10: 180 to 260 ° C. T50: 250 to 330 ° C. T90: 300 to 380 ° C. In the present invention, the above-mentioned distillation properties are JIS K225.
4 means a value obtained in accordance with "Petroleum products-distillation test method". The kinematic viscosity of the heavy oil composition A of the present invention is not particularly limited, but is usually 3 to 5 mm ² / s at 30 ° C.
Those having a temperature of 50 ° C. and ² to 3.5 mm ² / s are used. In the present invention, the kinematic viscosity means a value representing a value obtained in accordance with JIS K 2283 "Crude oil and petroleum products-Kinematic viscosity test method and viscosity index calculation method".
The flash point of the heavy oil composition A of the present invention is not particularly limited, but one having a temperature of 50 to 120 ° C is usually used. In the present invention, the flash point means a value obtained based on JIS K 2265 "Crude oil and petroleum products-flash point test method". The total calorific value of the heavy oil composition A of the present invention is not particularly limited, but is usually 35,000 to 5
0000 J / g is used. In the present invention,
The total calorific value means a value obtained based on JIS K 2279 "Crude oil and petroleum products-Calorific value test method and estimation method by calculation". The water content of the heavy oil composition A of the present invention is not particularly limited, but is usually 0.05% by volume or less. In the present invention, the term “water content” means a value obtained in accordance with JIS K 2275 “Crude Oil and Petroleum Products—Moisture Testing Method”. The density of the heavy oil composition A of the present invention is not particularly limited, but is usually 0.8 to 0.92 g /.
cm ³ is used. In the present invention, the density means a value obtained in accordance with JIS K 2249 "Crude oil and petroleum products-Density test method and density / mass / volume conversion table".

The method for producing the heavy oil A composition of the present invention is not particularly limited, and any conventionally known method can be used. Usually, a base material for imparting residual carbon is mixed with the heavy oil A base material, and if necessary, It is manufactured by blending additives. A heavy oil base material includes straight-run kerosene (or desulfurized kerosene), straight-run light gas oil (or desulfurized light gas oil), straight-run heavy gas oil (or desulfurized heavy oil) obtained from an atmospheric distillation unit. Gas oil), light cycle oil obtained from a fluid catalytic cracking unit and / or residue fluid catalytic cracking unit, hydrodesulfurized vacuum gas oil obtained by hydrodesulfurizing vacuum gas oil obtained from a vacuum distillation unit, hydrogenation obtained from a hydrocracking unit Crude gas oil, direct gas oil obtained from a direct A heavy oil desulfurization unit, and the like. One of these
Only a kind may be used and two or more kinds may be mixed.
Among them, it is preferable to use hydrocracked gas oil because it can simultaneously satisfy the flammability, prevention of clogging of the filter by wax in winter, and the like, and are more excellent in these effects. Here, the hydrocracked gas oil is a gas oil fraction obtained from the hydrocracking unit. Specifically, as the distillation properties, the 50% distillation point is 250 to 350 ° C., and the density at 15 ° C. is in the range of 0.810 to 0.880 g / cm ³ . Hydrocracking equipment converts heavy gas oil into amorphous N
Simultaneously with hydrocracking, under catalytic conditions such as i-Mo catalyst, under an operating hydrogen pressure of 8 to 15 MPa, an operating reaction temperature of 330 to 450 ° C., and a liquid hourly space velocity of 0.1 to 1.0 / h Perform desulfurization and denitrification. In addition, examples of the base material for imparting residual carbon include residual oil under normal pressure, residual oil directly removed, residual oil under reduced pressure, extract, and slurry oil. One of these may be used alone, or two or more thereof may be mixed. Among them, it is preferable to use an extract.
In particular, when a hydrocracked gas oil is used as the heavy oil A base, it is preferable to use an extract from the viewpoint of hue and filter clogging due to generation of dry sludge. The extract referred to here is a high aromatic oil produced as a by-product in the process of removing aromatic components in a lubricating oil using a solvent such as furfural, and specifically, as its properties,
The density at 15 ° C. is 0.95 to 1.05 g / cm ³ , 100
The kinematic viscosity at 5 ° C. is 5 to 100 mm ² / s, and the sulfur content is 0.5 to 5.0% by mass. As described above, the heavy oil composition A of the present invention preferably uses a hydrocracked gas oil and an extract, but there is no particular limitation on the blending amounts of both. However, in order to sufficiently exhibit the effect, it is preferable to use the hydrocracked gas oil in an amount of 50% or more, more preferably 75% or more, and more preferably 85% or more based on the total amount of the heavy fuel oil composition A. Is even more preferable, and 90% or more is most preferably used. Further, in order to satisfy the tax exemption condition for the residual carbon content, it is usually 99.5% by volume or less, preferably 99% by volume.
Used in: Further, in order to satisfy the tax exemption condition for the residual carbon content, the extract is generally used in an amount of 0.5% by volume or more, preferably 1% by volume or more based on the total amount of the heavy fuel oil composition A. Also, in consideration of filter clogging at room temperature due to dry sludge, low-temperature fluidity, and the like, it is preferably used at 5% by volume or less, more preferably at 3% by volume or less. Also, as an additive,
Various additives such as a cetane improver, an antioxidant, a stabilizer, a dispersant, a metal deactivator, a microbial bactericide, a flame retardant, an antistatic agent, a discriminating agent, a coloring agent, and the like. Can be added as appropriate. Among these, it is preferable to add a fluidity improver because it is more excellent in the effect of preventing clogging of the filter by wax in winter. As the fluidity improver, for example, a polymer type additive such as an ethylene-vinyl acetate copolymer and an ethylene-α-olefin copolymer, an oil-soluble dispersant type additive, and an alkyl succinic acid can be used. The amount of the fluidity improver is not particularly limited, but is preferably 0.001 to 0.1% by volume, preferably 0.01 to 0.03% by mass, based on the total weight of the heavy oil composition A. Is more preferable.

[0008]

The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the invention thereto. Examples 1 to 3 and Comparative Example 1 Each base material (hydrocracked gas oil, straight-run gas oil, cracked gas oil, extract) having the properties shown in Table 1 was mixed at a volume ratio as shown in each example of Table 2. A of Examples 1 to 3 and Comparative Example 1
The heavy oil compositions were prepared, and the properties of each of these adjusted compositions are shown in Table 2. For each sample oil (each composition), low-temperature fluidity performance evaluation and flammability performance evaluation were performed by the following methods. The results are shown in Table 2. Evaluation of low-temperature fluidity performance The low pressure fluidity performance was evaluated by measuring the magnitude of the negative pressure before and after the fuel filter at low temperatures by the following method. As a test device, a low-temperature fluidity test device including a burner portion of a heater used for heating greenhouse cultivation and a fuel filter (100 mesh) attached to the burner portion was used. The test conditions were based on severe outdoor temperature changes in winter, with a cooling rate of 0.5 ° C./h, a cooling start temperature of 5 ° C., and a soaking test temperature of 5 hours. The judgment was made by measuring the negative pressure for 1 hour before and after the fuel filter, and when the negative pressure was 700 mmHg or less during the measurement time, it was judged as pass, and when the negative pressure was sometimes larger than 700 mmHg during the measurement time, it was judged as reject. . Table 2 shows the minimum temperature at which the negative pressure measurement was accepted. Flammability performance evaluation The flammability performance was evaluated by measuring the ignition delay by the following method. The ignition delay adversely affects the engine performance and exhaust gas, and is a major cause of trouble particularly in recent high-performance engines. Using a fuel ignitability tester having a combustion chamber volume of 1 liter, a pressure of 45 barrels,
Fuel was injected into air at a temperature of 450 ° C., and the time from injection to ignition was measured. The results are shown in Table 2.

[0009]

[Table 1]

[0010]

[Table 2]

As is clear from the results shown in Table 2, the fuel oil compositions A of Examples 1 to 3 according to the present invention all have good ignitability and excellent flammability, and have sufficient performance for recent high-performance engines. It can be seen that it has excellent low-temperature fluidity. In contrast, Comparative Example 1 in which the naphthene content was less than the specified value
Has poor low-temperature fluidity and flammability.

[0012]

In summary, according to the present invention, there is provided a fuel oil A composition which has high flammability, can withstand the use in recent high-performance engines, and does not cause clogging of filters by wax in winter. Can be

Continued on the front page (72) Inventor Kazuo Shimizu 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Pref. Nishiishi Mitsui Co., Ltd. Central Research Laboratory (72) Inventor Atsushi Uehara 1-3-12 Nishishinbashi, Minato-ku, Tokyo Nishiishi Mitsubishi Co., Ltd. F-term (reference) 4H013 CB02

Claims (2)

[Claims] 1. A fuel oil A composition having a naphthene content of 40% by mass or more. 2. The heavy oil A composition according to claim 1, which is obtained by using a hydrocracked light oil and an extract.