JP2007262210A - A-type heavy oil composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an A-type heavy oil composition in which combustion equipment such as external combustion equipment, diesel engines and gas turbine engines can stably be operated without clogging filters due to sludge at the ordinary temperature and further without clogging the filters due to waxes at low temperature, and environmental loads is further reduced. <P>SOLUTION: The A-type heavy oil composition contains an FT wax having ≥360°C and produced by FT (Fischer-Tropsch) synthesis or a bottom component obtained by hydrocracking the FT wax having ≥360°C boiling point in an amount of ≥0.1 vol.% and ≤10 vol.% as a residual carbon-imparting base material. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an A heavy oil composition, and more particularly to an A heavy oil composition used as a fuel for combustion equipment such as boilers, diesel equipment, and gas turbines.

A heavy oil is widely used as fuel for external combustion equipment such as boilers, diesel engine equipment fuel other than for land transportation such as small fishing boats and construction machinery, and gas turbine equipment fuel.
Various combustion equipment using heavy fuel oil A is provided with a filter having an opening of 5 to 250 μm in the fuel system for the purpose of removing foreign substances in the fuel oil. However, when such a combustion device is used in winter, the filter is likely to be clogged with wax precipitated from A heavy oil.
On the other hand, the heavy carbon oil A contains a residual carbon content-imparting base so that the 10% residual carbon content is 0.2% by mass or more in the tax law. However, there has often been a problem that the fuel filter is clogged by sludge caused by the residual carbon-added base material, making it impossible to supply the fuel. It has become. For this reason, there is an increasing demand for heavy fuel oil A that does not block the fuel filter with sludge and has excellent filter oil permeability at room temperature.

Therefore, in order to solve such problems, studies are being made to improve low-temperature performance such as low-temperature fluidity of A heavy oil, such as blending heavy oil, increasing residual oil, adding low-temperature fluidity improvers, etc. Have been proposed (see, for example, Patent Documents 1 and 2 and Non-Patent Document 1).
However, the A heavy oil obtained by the above-described methods has room for improvement in the following points, and none of them is still sufficient to be put to practical use as A heavy oil. In other words, increased blending of heavy oil leads to a worsening of the wax precipitation point (cloud point), and an increase in residual oil can cause an increase in the amount of dust in the combustion gas, as well as a deterioration in solubility with other base materials. However, there is concern about filter oil permeability associated with sludge generation at room temperature. In addition, the performance of the low temperature fluidity improver depends largely on the compatibility with the base material used, and it is difficult to obtain sufficient low temperature performance as A heavy oil simply by adding.

  In addition, A heavy oil is added with a residual carbon content-imparting base from the viewpoint of tax law and combustibility. As the residual carbon content-providing substrate, in Patent Document 3, it is obtained from a normal pressure residual oil, a direct deoiled residue obtained from a direct heavy oil desulfurization apparatus, a depressurized residue obtained from a vacuum distillation apparatus, and a solvent refining apparatus for lubricating oil. In Patent Document 4 and Patent Document 5, such as an extract, direct dewatered residual oil obtained by hydrotreating normal pressure residual oil and / or residual pressure residual oil with a direct heavy oil desulfurization apparatus, in Patent Document 6, normal pressure residual oil, reduced pressure Residual oil, desulfurized residual oil, slurry oil, extract oil and the like are mentioned. However, these residual carbon content-providing substrates have not only a small amount of dust but also combustible problems such as generation of dust, and cannot be said to exhibit sufficient performance.

Patent Document 7 discloses that the oxygen content is 0.1% by mass or more, the ratio of the maximum absorbance at 1730 to 1750 cm ^{−1 and} the maximum absorbance at 1150 to 1170 cm ⁻¹ in infrared spectroscopy is 1 or more, A heavy oil composition characterized by having a burn-out temperature of less than 600 ° C. by differential thermal analysis is disclosed. However, these residual carbon content-imparting substrates have a problem with regard to burning out.

Japanese Patent Laid-Open No. 9-333583 JP-A-7-97581 JP 2003-342587 A JP 2000-239676 A Japanese Patent Laid-Open No. 2000-239677 JP-A-11-181453 JP 2006-52316 A Koji Nomura, “Science of Marine Fuel”, Naruyamado, 1994, p. 164-166

  The present invention has been made in view of such circumstances, does not cause filter clogging due to sludge at normal temperature, does not cause filter clogging due to wax at low temperature, and also has good combustibility and lubricity, An object of the present invention is to provide an A heavy oil composition capable of stably operating combustion equipment such as external combustion equipment, diesel equipment, and gas turbine equipment.

As a result of intensive studies to achieve the above object, the present inventors have found that the above problems can be solved by an A heavy oil composition having specific properties, and have completed the present invention.
That is, the present invention relates to a FT wax having a boiling point of 360 ° C. or higher produced by FT synthesis or a bottom component obtained by hydrocracking an FT wax having a boiling point of 360 ° C. or higher as a residual carbon-added base material and having a volume of 0.1% to 10% by volume. It is related with the A heavy oil composition characterized by containing below.
The present invention also relates to the A heavy oil composition as described above, wherein the burnout temperature by thermogravimetric-differential thermal analysis is less than 600 ° C.

  The A heavy oil composition of the present invention has enhanced performance such as filter oil permeability at normal temperature, low temperature performance, combustibility, lubricity, and safety in a well-balanced manner. Therefore, the A heavy oil composition of the present invention is very useful as a fuel for external combustion equipment such as boilers, diesel engine equipment other than land transportation such as small fishing boats and construction machinery, and gas turbine equipment.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

The present invention hydrocracks FT wax having a boiling point of 360 ° C. or higher or FT wax having a boiling point of 360 ° C. or higher, which is produced by FT synthesis as a residual carbon-providing base from the viewpoint of tax law and flammability, on A heavy oil base material The bottom component is contained in an amount of 0.1% by volume to 10% by volume. These substrates for imparting residual carbon content may be used singly or in combination of two or more.
The FT wax produced by FT synthesis in the present invention is obtained by applying a Fischer-Tropsch (FT) reaction to a mixed gas containing hydrogen and carbon monoxide as main components (sometimes referred to as synthesis gas). The paraffin wax to be used is shown.

In the present invention, the mixed gas used as the raw material for FT synthesis is a shift reaction in which a substance containing carbon is oxidized using oxygen and / or water and / or carbon dioxide as an oxidizing agent, and water is used as necessary. To obtain a predetermined hydrogen and carbon monoxide concentration.
Substances containing carbon include natural gas, petroleum liquefied gas, methane gas, etc., gas components consisting of hydrocarbons that are gaseous at room temperature, petroleum asphalt, biomass, coal, waste such as building materials and garbage, sludge, In addition, mixed gas obtained by exposing heavy crude oil, unconventional petroleum resources, etc. that are difficult to process by ordinary methods to high temperatures is common, but mixed gas mainly composed of hydrogen and carbon monoxide As long as is obtained, the raw material is not limited.

  A metal catalyst is used for the FT reaction in the present invention. Preferably a Group 8 metal of the periodic table, for example, cobalt, ruthenium, rhodium, palladium, nickel, iron, etc., more preferably a Group 8 Group 4 metal is used as the active catalyst component. Moreover, the metal group which mixed these metals in an appropriate amount can also be used. These active metals are generally used in the form of a catalyst obtained by being supported on a support such as silica, alumina, titania or silica alumina. Further, by using these catalysts in combination with a second metal in addition to the above active metal, the catalyst performance can be improved. Examples of the second metal include zirconium, hafnium, titanium, and the like in addition to alkali metals and alkaline earth metals such as sodium, lithium, and magnesium, and a chain that serves as an index for improving the conversion rate of carbon monoxide and generating wax. It is used appropriately according to the purpose, such as an increase in growth probability (α).

The bottom component obtained by hydrocracking the FT wax produced by FT synthesis in the present invention refers to a hydrocarbon mixture obtained by hydrocracking the paraffin wax produced by the FT reaction.
In the hydrocracking referred to in the present invention, a catalyst having a solid acid property on which a hydrogenation active metal is supported is generally used as a catalyst. is not.

  Supports having a solid acid property include amorphous and crystalline zeolites. Specific examples include amorphous silica-alumina, silica-magnesia, silica-zirconia, silica-titania and zeolite faujasite type, beta type, MFI type, and mordenite type. Preferred are faujasite type, beta type, MFI type, and mordenite type zeolite, and more preferred are Y type and beta type. The Y type is preferably ultra-stabilized.

As the active metal, the following two types (active metal A type and active metal B type) are preferably used.
The active metal A type is at least one metal selected from Group 6A and Group 8 metals in the periodic table. Preferably, it is at least one metal selected from Ni, Co, Mo, Pt, Pd and W. When using a noble metal catalyst composed of these metals, it can be used after pre-reduction treatment in a hydrogen stream. In general, when a gas containing hydrogen is circulated and heat of 200 ° C. or higher is applied according to a predetermined procedure, the active metal on the catalyst is reduced, and hydrogenation activity is exhibited.
The active metal B type may be a combination of these metals, and examples thereof include Pt—Pd, Co—Mo, Ni—Mo, Ni—W, and Ni—Co—Mo. Moreover, when using the catalyst which consists of these metals, it is preferable to use after pre-sulfiding.

  As the metal source, a general inorganic salt or a complex salt compound can be used, and as a supporting method, any method of a supporting method used in an ordinary hydrogenation catalyst such as an impregnation method or an ion exchange method can be used. When a plurality of metals are supported, they may be supported simultaneously using a mixed solution, or may be sequentially supported using a single solution. The metal solution may be an aqueous solution or an organic solvent.

  The reaction temperature when performing hydrocracking using a catalyst comprising an active metal A type and an active metal B type is preferably 200 ° C. or higher and 450 ° C. or lower, more preferably 250 ° C. or higher and 430 ° C. or lower. More preferably, the temperature is 300 ° C. or more and 400 ° C. or less. If the reaction temperature in the hydrocracking exceeds 450 ° C., side reactions that decompose into a naphtha fraction increase and the yield of the middle fraction is extremely reduced, which is not preferable. On the other hand, when the temperature is lower than 200 ° C., the activity of the catalyst is remarkably lowered, which is not preferable.

  The hydrogen pressure when hydrocracking using a catalyst comprising an active metal A type and an active metal B type is preferably 1 MPa or more and 20 MPa or less, more preferably 4 MPa or more and 16 MPa or less, and 6 MPa or more and 13 MPa. More preferably, it is as follows. The higher the hydrogen pressure is, the more hydrogenation reaction is promoted. However, the decomposition reaction rather slows down and the progress of the reaction needs to be adjusted by increasing the reaction temperature, leading to a decrease in catalyst life. For this reason, there is generally an economical optimum for the reaction temperature.

The liquid hourly space velocity which hydrocracking is carried out using a catalyst composed of the active metal A type (LHSV) is preferably at 0.1 h ^-1 or more ^{10h -1} or less, 0.3h ^-1 over 3.5h ^-More preferably, it is ¹ or less. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, an extremely large reaction tower volume is required, resulting in excessive capital investment, which is not economical.
The liquid hourly space velocity which hydrocracking is carried out using a catalyst composed of the active metal B type (LHSV) is preferably at 0.1 h ^-1 or more ^{2h -1} or less, 0.2 h ^-1 or more 1.7h more preferably ^{1 or} less, and more preferably 0.3h ^-1 or 1.5 h ^-1. The lower the LHSV, the more advantageous for the reaction. However, if the LHSV is too low, an extremely large reaction tower volume is required, resulting in excessive capital investment, which is not economical.

The hydrogen / oil ratio is preferably 50 NL / L or more and 1000 NL / L or less, more preferably 70 NL / L or more and 800 NL / L or less when hydrocracking using a catalyst composed of an active metal A type. Preferably, it is 400 NL / L or more and 1500 NL / L or less. The higher the hydrogen / oil ratio, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.
The hydrogen / oil ratio is preferably 150 NL / L or more and 2000 NL / L or less, more preferably 300 NL / L or more and 1700 NL / L or less when hydrocracking using a catalyst composed of an active metal B type. Preferably, it is 400 NL / L or more and 1500 NL / L or less. The higher the hydrogen / oil ratio, the more hydrogenation reaction is promoted, but generally there is an optimal point economically.

The hydrocracking apparatus may have any configuration, the reaction towers may be used singly or in combination, hydrogen may be additionally injected between the reaction towers, gas-liquid separation operation, hydrogen sulfide removal equipment, hydrogenation It may have a distillation column for fractionating the product and obtaining the desired fraction.
The reaction mode of the hydrocracking apparatus can take a fixed bed system. Hydrogen can take either a countercurrent or a cocurrent flow with respect to the feedstock, and may have a plurality of reaction towers and a combination of countercurrent and cocurrent flow. The general format is downflow, and there is a gas-liquid twin parallel flow format. Hydrogen gas may be injected into the middle stage of the reaction tower as a quench for the purpose of removing reaction heat or increasing the hydrogen partial pressure.

According to the present invention, the FT wax produced by FT synthesis and the properties of the bottom component obtained by hydrocracking the FT wax preferably have a density at 15 ° C. of 800 to 850 kg / m ³ and a kinematic viscosity at 100 ° C. of 4 It is preferable that it is-10mm < ² > / s.

  The bottom component obtained by hydrocracking FT wax having a boiling point of 360 ° C. or higher and FT wax having a boiling point of 360 ° C. or higher produced by FT synthesis has a distribution of about 16 to 90 carbon atoms, and has 16 to 80 carbon atoms. It is preferably a distribution, more preferably a distribution having 16 to 60 carbon atoms, and even more preferably a distribution having 16 to 40 carbon atoms.

  The content ratio of the bottom component obtained by hydrocracking FT wax having a boiling point of 360 ° C. or higher produced by FT synthesis or FT wax having a boiling point of 360 ° C. or higher should be 0.1% by volume or more based on the total amount of A heavy oil composition. And is preferably 0.5% by volume or more, more preferably 1% by volume or more. On the other hand, from the viewpoint of filter clogging at room temperature due to dry sludge and low temperature fluidity, it is necessary to be 10% by volume or less, preferably 5% by volume or less, and more preferably 3% by volume or less. preferable.

  In the present invention, conventional residual carbon application is achieved by using, as a base material for applying residual carbon, a bottom component obtained by hydrocracking FT wax having a boiling point of 360 ° C. or higher produced by FT synthesis or FT wax having a boiling point of 360 ° C. or higher. A heavy oil composition with reduced dust and superior flammability can be obtained.

  The A heavy oil composition of the present invention further comprises a residual carbon imparting base material other than a bottom component obtained by hydrocracking FT wax having a boiling point of 360 ° C. or higher or FT wax having a boiling point of 360 ° C. or higher produced by the above-described FT synthesis. May be. Examples of the residual carbon imparting base material include atmospheric residual oil, residual oil desulfurized heavy oil, vacuum residual oil, slurry oil, and extract oil. These substrates for imparting residual carbon content may be used singly or in combination of two or more. Here, the atmospheric residual oil is a residual oil obtained by distilling crude oil at atmospheric pressure with an atmospheric distillation apparatus. The residual oil desulfurized heavy oil is a heavy oil obtained when a normal pressure residual oil or a vacuum residual oil is desulfurized in a residual oil desulfurization apparatus. The vacuum residue is a residue obtained by distilling atmospheric residue under reduced pressure using a vacuum distillation apparatus. Slurry oil is residual oil obtained from a fluid catalytic cracker. Extract oil is an aromatic component that is not suitable for lubricating oil among the fractions extracted from the vacuum distillation apparatus for lubricating oil raw material by solvent extraction.

The A heavy oil composition of the present invention preferably has a burn-out temperature of less than 600 ° C., more preferably 585 ° C. or less, by thermogravimetric-differential thermal analysis. If the burnout temperature by thermogravimetric-differential thermal analysis is 600 ° C. or higher, unburned residue derived from heavy hydrocarbons increases during A heavy oil combustion, which is not preferable.
The thermogravimetric-differential thermal analysis referred to here means that the temperature of a sample is raised under a predetermined temperature condition, and the weight loss associated with vaporization / pyrolysis, etc. and the change in calorie associated with vaporization / oxidation / thermal decomposition, etc. are measured simultaneously. This is an analysis method. Specifically, about 5 mg of a sample is weighed on an aluminum pan having an inner diameter of 5 mm and set on a Thermoflex TAS300 manufactured by RIGAKU. Next, the sample is heated from room temperature to 1000 ° C. at 100 ° C./min. The temperature at which heat generation ends is defined as the burnout temperature.

The properties and blending ratio of the A heavy oil base constituting the A heavy oil composition of the present invention are not particularly limited as long as the burn-out temperature by thermogravimetric-differential thermal analysis is less than 600 ° C.
Preferred A heavy oil base materials include straight-run gas oil fraction or desulfurized gas oil fraction thereof, straight-run kerosene fraction or desulfurized kerosene fraction, hydrocracked light oil, hydrocracked kerosene, residual desulfurized gas oil fraction, hydrogen Desulfurized diesel oil fraction or hydrorefined diesel oil fraction, the residue obtained by removing normal paraffin fraction by extraction, denormalized paraffin diesel oil fraction, heavy diesel oil fraction, gas oil desulfurized vacuum gas oil, fluid catalytic cracking diesel oil, Examples include fluid catalytic cracking kerosene. These base materials may be used individually by 1 type, and may be used in combination of 2 or more type.

The A heavy oil composition of the present invention preferably contains a low temperature fluidity improver. The type of the low temperature fluidity improver is not particularly limited, but an ethylene-unsaturated ester copolymer, an ethylene-α-olefin copolymer, an alkyl fumarate-unsaturated ester copolymer represented by an ethylene-vinyl acetate copolymer, and the like. Polymers, polymer-type additives such as alkyl itaconate-unsaturated ester copolymers, oil-soluble dispersion-type additives, acids such as phthalic acid, ethylenediaminetetraacetic acid, nitriloacetic acid or acid anhydrides thereof and hydrocarbyl-substituted amines Examples include polar nitrogen compounds composed of reaction products, alkenyl succinic acid, and the like. These low temperature fluidity improvers may be used alone or in combination of two or more.
The content of the low temperature fluidity improver is preferably 1000 mg / L or less, more preferably 700 mg / L or less, and further preferably 500 mg / L or less. Even if the content of the low temperature fluidity improver is more than 1000 mg / L, a further improvement effect of the low temperature performance commensurate with the content cannot be obtained.

The heavy oil composition A of the present invention includes a cetane number improver, an antioxidant, a stabilizer, a dispersant, a metal deactivator, a microbial disinfectant, a combustion aid, a charge as an additive other than the low temperature fluidity improver. Various additives such as an inhibitor, a discriminating agent, and a coloring agent can also be contained.
As the above-mentioned additives (including a low-temperature fluidity improver), those synthesized according to a conventional method may be used, or commercially available additives may be used. In addition, the additive currently marketed may have diluted the active ingredient which contributes to the effect which the additive aimed at with the appropriate solvent. When using a commercially available additive in which the active ingredient is diluted, it is preferable to add the commercially available additive so as to satisfy the condition that the burning temperature of the A heavy oil composition is less than 600 ° C. The addition amount excluding the low temperature fluidity improver is arbitrary, but it is usually 0.5% by mass or less, preferably 0.2% by mass or less, based on the total amount of the A heavy oil composition.

  The A heavy oil composition of the present invention is not particularly limited as long as the burn-out temperature by thermogravimetric-differential thermal analysis is less than 600 ° C., but preferably has the following properties.

Although the density in 15 degreeC of A heavy oil composition of this invention is not specifically limited, From the point of the emitted-heat amount, it is preferable that it is 830 kg / m < ³ > or more.
The density at 15 ° C. referred to in the present invention is a value measured by JIS K 2249 “Crude oil and petroleum products—Density test method and density / mass / capacity conversion table”.

The flash point of the A heavy oil composition of the present invention is preferably 60 ° C. or higher, more preferably 62 ° C. or higher, from the viewpoint of safety in handling.
In addition, the flash point as used in the field of this invention means the value measured by JIS K 2265 "crude oil and petroleum products-flash point test method" by the Penschramlen closed type.

The kinematic viscosity of the A heavy oil composition of the present invention is not particularly limited, but the kinematic viscosity at 50 ° C. is from the viewpoint of supplying fuel from the tank to the combustion equipment without problems in the winter and performing good spraying and vaporization in burner combustion. It is preferable that it is 1.7-5.0 mm < ² > / s.
The kinematic viscosity at 50 ° C. in the present invention means a value measured by JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method”.

The distillation property of the A heavy oil composition of the present invention is not particularly limited, but the 10 vol% distillation temperature is 170 to 250 ° C, the 50 vol% distillation temperature is 230 to 320 ° C, and the 90 vol% distillation temperature is 280 to 380. It is preferable that it is ° C.
The 10 vol% distillation temperature (hereinafter referred to as “T10”) of the A heavy oil composition is preferably 170 ° C. or more, more preferably 173 ° C. or more, from the influence on safety due to the reduction in flash point. Preferably, it is 175 ° C. or higher. On the other hand, from the viewpoint of low-temperature performance, T10 is preferably 250 ° C. or lower, and more preferably 245 ° C. or lower.
The 50 vol% distillation temperature (hereinafter referred to as “T50”) of the A heavy oil composition is preferably 230 ° C. or higher, and more preferably 235 ° C. or higher. When T50 is less than 230 ° C., the calorific value tends to deteriorate. On the other hand, from the viewpoint of combustibility, T50 is preferably 320 ° C. or lower, and more preferably 315 ° C. or lower.
The 90 volume% distillation temperature (hereinafter referred to as “T90”) of the heavy oil composition A is preferably 380 ° C. or less, more preferably 375 ° C. or less, and further preferably 370 ° C. or less. . When the end point exceeds 380 ° C., vaporization is difficult to proceed and complete combustion tends to be difficult. In addition, the wax content is too high, and the effect of the low temperature fluidity improver is hardly exhibited. On the other hand, T90 is preferably 280 ° C. or higher, more preferably 285 ° C. or higher, and further preferably 290 ° C. or higher from the viewpoint of the amount of heat generated.
Furthermore, regarding the other distillation properties of the A heavy oil composition, the initial boiling point is preferably 150 ° C. or higher because of the influence on safety due to the reduction in flash point. The 95% by volume distillation temperature (hereinafter referred to as “T95”) is preferably 400 ° C. or less, more preferably 390 ° C. or less, from the viewpoint of combustibility.
The initial boiling point, T10, T50, T90 and T95 referred to in the present invention mean values measured by JIS K 2254 “Petroleum products—Distillation test method—Atmospheric pressure method”, respectively.

Moreover, it is preferable that the cetane index of the A heavy oil composition of this invention is 40 or more, More preferably, it is 42 or more. A cetane index of less than 40 is not preferable because the ignitability of the diesel engine is deteriorated.
In addition, the cetane index as used in the field of this invention means the value measured by JISK2280 "Petroleum product-fuel oil-octane number and cetane number test method and cetane index calculation method".

Further, the 10% residual carbon content of the A heavy oil composition of the present invention is preferably 0.2 to 1.0% by mass, more preferably 0.2 to 0.8% by mass, and still more preferably 0.00. 2 to 0.6% by mass. When the 10% residual carbon content is more than 1.0% by mass, the amount of dust in the combustion exhaust gas increases, and the burner tends to become dirty. On the other hand, the lower limit of the 10% residual carbon content is required to be 0.2% by mass or more in terms of tax exemption conditions for A heavy oil.
The 10% residual carbon content in the present invention means a value measured according to JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.

The sulfur content of the A heavy oil composition of the present invention is not particularly limited, but based on the total amount of the composition from the viewpoint of suppressing sulfur oxides in the combustion exhaust gas and the life of the exhaust gas aftertreatment catalyst installed in the equipment. 1.0 mass% or less, more preferably 0.8 mass% or less, still more preferably 0.5 mass% or less, and even more preferably 0.3 mass% or less. The content is preferably 0.1% by mass or less.
In addition, the sulfur content as used in the field of this invention means the value measured by JISK2541 "Crude oil and petroleum products-sulfur content test method".

Although the nitrogen content of A heavy oil composition of this invention is not specifically limited, From the point of nitrogen oxide suppression in combustion exhaust gas, it is preferable that it is 0.03 mass% or less on the basis of the composition whole quantity.
The nitrogen content in the present invention means a value measured according to JIS K 2609 “Crude oil and petroleum products—nitrogen content test method”.

The water content of the A heavy oil composition of the present invention is preferably 500 ppm by mass or less, and more preferably 400 ppm by mass or less. When the water content is higher than 500 ppm by mass, it is not preferable because it tends to precipitate as ice in winter and cause metal corrosion and filter clogging.
In addition, the water | moisture content said by this invention means the value measured by the Karl Fischer type | formula volumetric titration method of JISK2275 "Crude oil and petroleum products-moisture test method".

The cloud point of the heavy oil composition A of the present invention is preferably 0 ° C. or lower, more preferably −1 ° C. or lower, and further preferably −2 ° C. or lower. When the cloud point is higher than 0 ° C., wax is deposited in the tank in the winter, and the amount of wax in the supplied fuel in the line is increased, and line blockage is likely to occur.
In addition, the cloud point as used in the field of this invention means the value measured by JISK2269 "Pour point of crude oil and petroleum products, and petroleum product cloud point test method".

The clogging point of the A heavy oil composition of the present invention is preferably 0 ° C. or less, more preferably −3 ° C. or less, and further preferably −5 ° C. or less. When the clogging point is higher than 0 ° C., the filter clogging of the pump and the burner is likely to occur in winter, which is not preferable.
In addition, the clogging point as used in the field of this invention means the value measured by applying JISK2288 "light oil-clogging point test method" to A heavy oil.

The pour point of the heavy oil composition A of the present invention is preferably −5 ° C. or lower, more preferably −8 ° C. or lower, and further preferably −10 ° C. or lower. When the pour point is higher than −5 ° C., the fluidity of the fuel is lowered in the winter, and supply to the combustion equipment is delayed.
In addition, the pour point as used in the field of this invention means the value measured by JISK2269 "The pour point of crude oil and petroleum products, and the cloud point test method of petroleum products".

The corrected clogging point of the A heavy oil composition of the present invention is preferably 0 ° C. or lower, more preferably −3 ° C. or lower, and further preferably −5 ° C. or lower. If the corrected clogging point is higher than 0 ° C., the filter blockage of the pump or burner is likely to occur in winter, which is not preferable.
In addition, the correction clogging point as used in the field of this invention means the value measured by the correction method 4 described in the description of Petroleum Institute standard JPI-5S-47-96 "Low temperature fluidity test method of A heavy oil".

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

[Examples 1-4, Comparative Examples 1-2]
In Examples 1-4 and Comparative Examples 1-2, it has the composition shown in Table 3 using the base material shown in Tables 1 and 2, and the low temperature fluidity improver (ethylene-vinyl acetate copolymer), respectively. A heavy oil composition was prepared. Tables 1 and 2 show the properties of the base materials, and Table 3 shows the blending ratio of each base material and the properties of the A fuel oil composition.

Various properties shown in Tables 1, 2, and 3 were measured by the following analytical methods.
The density at 15 ° C. was measured according to JIS K 2249 “Crude oil and petroleum products—density test method and density / mass / capacity conversion table”.
The flash point (COC, PM) was measured by the Cleveland open type and the Penschemulten sealed type of JIS K 2265 "Crude oil and petroleum products-flash point test method", respectively.
The kinematic viscosity at 30 ° C., 50 ° C. and 100 ° C. was measured according to JIS K2283 “Crude oil and petroleum products—Kinematic viscosity test method”.
The initial boiling point, T10, T50, T90, and T95 were measured according to JIS K 2254 “Petroleum products—Distillation test method—Atmospheric pressure method”, respectively.
The cetane index was measured according to JIS K 2280 “Petroleum products—fuel oil—octane number and cetane number test method and cetane index calculation method”.
The cloud point and pour point were measured according to JIS K 2269 “Pour point of crude oil and petroleum product and cloud point test method of petroleum product”.
The clogging point was measured by applying JIS K 2288 “Light oil—clogging point test method” to heavy oil A.
The corrected clogging point was measured by the correction method 4 described in the explanation of JPI-5S-47-96 “Method for testing low temperature fluidity of A heavy oil”.

  Next, the low temperature performance evaluation test was implemented with the following method about the A heavy oil composition of Examples 1-4 and Comparative Examples 1-2.

(Normal temperature oil permeability evaluation test)
A 20 L pail can was prepared as a sample container, and a hole into which the sample suction tube was inserted was provided on the top surface of the pail can. The hole was formed at the midpoint of a straight line connecting the center of the upper surface and the point on the outer periphery. On the other hand, a copper tube having an outer diameter of 10 mm is prepared as a sample suction tube, and one end of the copper tube is filtered through a silicon rubber tube (a fuel filter manufactured by Nippon Filter Co., Ltd., model number 276237, oil passage area 2.0 ± 0.1 cm ^2. ) Connected to the entrance. Moreover, the outlet of the filter was connected to a suction pump through a copper tube. As the suction pump, a pump capable of adjusting the oil flow rate within a range of 1 to 10 L / hr was used.
Next, about 10 L of a sample (A heavy oil composition) having a temperature of 20 to 25 ° C. is put in the above-mentioned pail can. The pump was accommodated in a thermostat, the pump was driven, and the pump pressure was adjusted so that the oil flow rate was 5.0 ± 0.2 L / hr. As the low temperature thermostat, a thermostat equipped with a program temperature control function and adjustable within a temperature accuracy of ± 0.5 ° C. was used.
After the pail can and the filter were accommodated in the low-temperature thermostatic chamber, the inside of the low-temperature thermostatic chamber was cooled with a predetermined temperature profile, and the suction pump was driven. More specifically, after maintaining at an initial temperature of 20 ° C. for 2 hours, the pump is driven to start. The pressure was measured with a pressure gauge to determine the oil passage limit. The oil passage limit was determined by measuring the time required for the differential pressure to reach 26.6 kPa (200 mmHg) at the holding temperature.
When oil permeability is poor, filter clogging occurs and the differential pressure rises in a short time, whereas A heavy oil with good oil permeability has a long time until the differential pressure rises. The case where it did not reach 26.6 kPa even after 60 minutes passed was judged as good (◯), and the case where it reached 26.6 kPa in less than 60 minutes was judged as bad (x). Table 4 shows the obtained results.

(Low temperature oil permeability evaluation test)
A 20 L pail can was prepared as a sample container, and a hole into which the sample suction tube was inserted was provided on the top surface of the pail can. The hole was formed at the midpoint of a straight line connecting the center of the upper surface and the point on the outer periphery. On the other hand, a copper tube having an outer diameter of 10 mm was prepared as a sample suction tube, and one end of the copper tube was connected to the inlet of a filter (Nepon Corporation, code No. 120267) via a silicon rubber tube. Moreover, the outlet of the filter was connected to a suction pump through a copper tube. As the suction pump, a pump capable of adjusting the oil flow rate within a range of 1 to 10 L / hr was used.
Next, about 15 L of a sample (A heavy oil composition) having a temperature of 20 to 25 ° C. is put in the above-mentioned pail can, a lid with a sample suction tube is put in the hole on the top surface of the pail can, and then the pail can and the filter are cooled The pump was accommodated in a thermostat, the pump was driven, and the pump pressure was adjusted so that the oil flow rate was 9.5 ± 0.2 L / hr. As the low-temperature thermostatic bath, a thermostatic bath having a program temperature adjusting function and capable of cooling to −30 ° C. or less within a temperature system of ± 0.5 ° C. was used.
After the pail can and the filter were accommodated in the low-temperature thermostatic chamber, the inside of the low-temperature thermostatic chamber was cooled with a predetermined temperature profile, and the suction pump was driven. More specifically, the sample was cooled from a temperature 8 ° C. higher than the cloud point of the sample to a predetermined temperature at a cooling rate of 1 ° C./hr. The temperature was held for 3 hours, and the oil passage limit was determined by measuring the pressure with a pressure gauge. Judgment of the oil passage limit is accepted when the differential pressure is 33 kPa (250 mmHg) or less during oil passage for 60 minutes at the holding temperature, and is rejected when it exceeds 33 kPa, and held at 1 ° C intervals until it fails. The test was repeated at a lower temperature.
The highest temperature (clogging temperature) at which the judgment was rejected was used as an index for evaluating the low temperature performance. In addition, the sample was replaced with new oil for each test. A clogging temperature of −5 ° C. or lower was judged as good (◯), and a temperature of −4 ° C. or higher was judged as poor (×). Table 4 shows the obtained results.

(Flammability evaluation test)
The flammability was evaluated by the burnout temperature by thermogravimetric-differential thermal analysis.
About 5 mg of a sample is weighed on an aluminum pan having an inner diameter of 5 mm and set on a Thermoflex TAS300 manufactured by RIGAKU. Next, the sample is heated from room temperature to 1000 ° C. at 100 ° C./min. Then, the temperature at which the heat generation has ended is defined as the burnout temperature. A burn-out temperature of less than 600 ° C. was judged to be good (◯), and 600 ° C. or more was judged to be poor (×).

As shown in Table 4, the A heavy oil compositions of Examples 1 to 4 are all excellent in filter oil permeability at room temperature, and include low temperature performance, combustibility and safety as A heavy oil compositions. It was confirmed that the performance was sufficiently satisfied.
On the other hand, the heavy fuel oil compositions of Comparative Examples 1 and 2 were inferior in normal temperature oil permeability and resulted in a high burnout temperature.

Claims (2)

  A bottom component obtained by hydrocracking an FT wax having a boiling point of 360 ° C. or higher produced by FT synthesis or an FT wax having a boiling point of 360 ° C. or higher is contained as a residual carbon-added base material in an amount of 0.1% to 10% by volume. A heavy oil composition. The heavy fuel oil composition according to claim 1, wherein the burnout temperature by thermogravimetric-differential thermal analysis is less than 600 ° C.