JP2015074695A - A heavy oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an A heavy oil composition good in ignitability, excellent in filter oil-permeability, good in fuel consumption and easy in manufacturing, and to provide a manufacturing method therefor.SOLUTION: There is provided an A heavy oil composition containing a FT synthetic oil, decomposed light oil and residual coal adjustment member and having density of 0.820 to 0.890 g/cm, carbon/hydrogen ratio of a residual oil after 95% cut by an ASTM distillate of 6.4 or less and the residual carbon content of 10% residual oil of over 0.20 mass%.

Description

  The present invention corresponds to JIS K 2205, No. 1, No. 2, No. 2 heavy oil, has good ignitability, excellent filter oil permeability, good fuel consumption, and easy production, and its production It is about the method.

  Since Fischer-Tropsch synthetic oil (hereinafter referred to as FT synthetic oil) is synthesized using natural gas, coal, biomass, or the like as a raw material, it does not contain sulfur or aromatics. Therefore, it is expected to be used as an environmentally friendly fuel that suppresses the emission of sulfur oxides and particulate matter (PM) during combustion. In recent years, use as an A heavy oil base material has been attempted.

  When producing and selling A heavy oil, the residual carbon content of 10% residual oil exceeds 0.20 mass% so that it can be distinguished from the light oil composition from the viewpoint of tax law (light oil collection tax). Therefore, it is necessary to add a small amount of heavy fraction such as residual oil containing residual carbon (hereinafter referred to as residual coal modifier) to the kerosene / light oil fraction. Therefore, compared with kerosene and light oil, there is a concern that a specific component in the residual coal adjuster may block a filter installed in a fuel supply system such as a combustion device. Similarly, when FT synthetic oil is used as the base material of the A heavy oil composition, there is a concern about deterioration of filter oil permeability caused by the residual coal modifier. Therefore, attempts have been made to improve the filter oil permeability of the A heavy oil composition in which FT synthetic oil is used as a base material.

  For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2007-269926) proposes mixing an extract oil as a residual carbon adjuster of an A heavy oil composition in which an FT synthetic oil is used as a base material. .

JP 2007-269926 A

  However, when extract oil is used as a residual coal adjuster, it can be produced only in a production facility equipped with a lubricating oil production plant or a production facility where extract oil can be brought in, and it is difficult to put it to practical use. Moreover, even if other residual coal modifiers are used, when FT synthetic oil is used as the base material of the A heavy oil composition, the influence of the properties of the residual coal modifier on the filter oil permeability of the A heavy oil is unknown. .

  When using FT synthetic oil as a base material for A heavy oil composition, one of the reasons for concern about deterioration of filter oil permeability caused by residual coal modifier is that FT synthetic oil does not contain aromatic components. Is considered. Therefore, in order to improve the problem of filter oil permeability, a method of blending aromatic components may be considered, but it is not clear what aromatic components are effective for improving filter oil permeability among aromatic components. Absent.

  On the other hand, since FT synthetic oil does not contain an aromatic component, it has a high cetane index and thus has good ignitability and environmental friendliness. On the other hand, there is a concern that the calorific value is low and fuel consumption is deteriorated.

  By the way, in recent years when fuel conversion from A heavy oil to natural gas and the like is proceeding rapidly, A heavy oil and cracked light oil which is one of its base materials are surplus. Therefore, in order to solve problems such as filter clogging of A heavy oil fuel while sufficiently responding to the actual circumstances of society, it is necessary to effectively utilize decomposed light oil that is surplus in many manufacturing facilities. In addition, since cracked light oil has a characteristic of containing a large amount of aromatic components, there is a possibility that degradation of filter oil permeability due to the use of FT synthetic oil may be improved. There is concern over problems such as poor ignition and start-up congestion of combustion equipment such as diesel engines and boilers, as the index falls and ignitability deteriorates.

  Accordingly, an object of the present invention is to provide an A heavy oil composition having good ignitability, excellent filter oil permeability, good fuel consumption, and easy production, and a method for producing the same.

In order to achieve the above object, the present inventors consider the characteristics of FT synthetic oil, cracked light oil, and the residual coal modifier used, and the effects of these properties on the filter oil passing performance of A heavy oil. As a result of intensive research, the inventors have found that it is possible to provide an A heavy oil composition having good ignitability, excellent filter oil permeability, good fuel efficiency, and easy manufacture. That is, the present invention includes FT synthetic oil, cracked light oil, and residual coal modifier, the density is 0.820 to 0.890 g / cm ³ , and the carbon / hydrogen ratio of the residual oil after 95% cut by ASTM distillation is 6 A heavy oil composition having a carbon content of not more than 4 and a residual carbon content of 10% residual oil exceeding 0.20% by mass. The present invention also relates to an FT synthetic oil having a density (15 ° C.) of 0.770 g / cm ³ or more and a normal paraffin having 21 or more carbon atoms of 2.0 to 10.0% by mass; Production of A heavy oil composition comprising a step of mixing 860 g / cm ³ or more, a cracked light oil having an aromatic content of 50.0% by volume or more, and a bicyclic or higher aromatic content of 40.0% by volume or more. Is the method.

  As described above, according to the present invention, it is possible to provide an A heavy oil composition having good ignitability, excellent filter oil permeability, good fuel consumption, and easy manufacture.

[A heavy oil composition]
The A heavy oil composition according to the present invention contains FT synthetic oil and cracked light oil as a base material. FT synthetic oil is obtained by Fischer-Tropsch synthesis using natural gas, coal, biomass, or the like as a raw material. The FT synthetic oil is preferably GTL whose raw material is natural gas from the viewpoint of economy and availability. The base material may contain other base materials, for example, light oil fractions such as desulfurized light oil, straight-run light oil, direct de-light gas oil, and intermediate de-light oil, and kerosene such as desulfurized kerosene and straight-run kerosene. Fractions.

  In addition to the base material, the heavy fuel oil composition A according to the present invention includes a residual charcoal adjusting material. As the residual coal modifier, it is obtained by subjecting the atmospheric residue oil or the vacuum residue oil to atmospheric pressure residue oil obtained by atmospheric distillation or the vacuum residue oil obtained by distillation under reduced pressure. Deasphalted asphalt or residual oil (slurry oil) obtained from a fluid catalytic cracking apparatus can be used. In accordance with recent social demands, the mixing ratio is preferably as high as possible. When using a C heavy oil base material with low added value, the residual carbon adjusting material preferably has a high residual carbon content. An extract oil obtained by dissolving an aromatic component in a solvent and extracting it from a normal pressure residue oil or a vacuum residue oil is unsuitable from the viewpoint of ease of production as described above.

  Furthermore, the heavy fuel oil composition A according to the present invention may contain an additive. Examples of the additive include a low temperature fluidity improver, a cetane number improver, a surfactant, a rust inhibitor, a detergent, a lubricity improver, and a discriminating agent. These may be used alone or in combination. You may use it in combination.

  What is necessary is just to let the kind and content of the base material to be used be the range which satisfy | fills the structure of A heavy oil composition which concerns on this invention. For example, the FT synthetic oil is preferably contained in the A heavy oil composition in an amount of 1.0 to 50.0% by volume, more preferably 10.0 to 45.0% by volume, and more preferably 25.0 to 35%. More preferably, the content is 0.0%. The cracked light oil is preferably contained in the A heavy oil composition in an amount of 5.0 to 50.0% by volume, and more preferably 10.0 to 40.0% by volume. When desulfurized light oil is included, it can be included, for example, 20.0 to 50.0% by volume. The residual coal modifier is preferably 0.2% by volume or more, and more preferably 0.3 to 3.0% by volume in the heavy fuel oil composition A.

  The heavy fuel oil composition A according to the present invention preferably contains 15.0% by volume or more of an aromatic component. As the aromatic component, for example, a monocyclic aromatic component having an alkyl group or naphthene ring in benzene, a bicyclic aromatic component having an alkyl group or naphthene ring in naphthalene, and an alkyl group or naphthene ring in phenanthrene or anthracene. A tricyclic aromatic component is mentioned. The aromatic content is more preferably 20.0% by volume or more, and further preferably 23.0% by volume or more in order to increase the solubility of sludge and improve the oil permeation performance. However, if the aromatic content is too large, the cetane index will decrease, causing problems such as poor engine startability, and is preferably 50.0% by volume or less, and preferably 45.0% by volume or less. More preferred is 43.0% by volume or less. The aromatic content can be adjusted as appropriate by, for example, changing the properties of the cracked light oil or the ratio of the cracked light oil in the A heavy oil composition.

  The A heavy oil composition according to the present invention preferably contains 5.0% by volume or more, more preferably 15.0% by volume or more, and more preferably 25.0% by volume, of an aromatic content of two or more rings as the aromatic content. It is more preferable to include the above. In order to adjust the aromatic content of two or more rings, for example, the operating conditions of a fluid catalytic cracking device when producing cracked light oil are adjusted, or the blending ratio of FT synthetic oil and cracked light oil is adjusted. Just do it. In order to prevent filter clogging, carbon / hydrogen of residual oil after 95% cut by ASTM distillation (to be described later) is used for aromatic content of two or more rings, considering the balance between 10% residual carbon and cetane index. It is preferable to adjust based on the ratio (hereinafter sometimes simply referred to as carbon / hydrogen ratio).

  In the A heavy oil composition according to the present invention, the normal paraffin having 21 or more carbon atoms is preferably 0.1 to 4.0% by mass, more preferably 0.5 to 4.0% by mass. It is more preferable that it is 0.0-3.5 mass%, and it is especially preferable that it is 2.0-3.0 mass%. If the number of normal paraffins having 21 or more carbon atoms is too large, the oil permeability of the filter may be deteriorated, and if it is too small, the cetane index may be too low. The content of the normal paraffin having 21 or more carbon atoms is, for example, adjusting the production conditions of the FT synthetic oil so that the normal paraffin having 21 or more carbon atoms in the FT synthetic oil is 10.0% by mass or less, or It can adjust by adjusting the mixing ratio of FT synthetic oil and decomposition | disassembly light oil suitably.

In the heavy oil composition A according to the present invention, the carbon / hydrogen ratio of the residual oil after 95% cut by ASTM distillation is 6.4 or less, preferably 6.0 to 6.3, and 6.2 to 6.2. More preferably, it is 6.3. If the carbon / hydrogen ratio is out of the above range, the filter may be clogged, and the oil permeability of the filter may not be sufficiently improved. The carbon / hydrogen ratio can be adjusted, for example, by adjusting the operating conditions of a distillation apparatus such as a crude oil atmospheric distillation apparatus so that the density of the residual coal adjusting material is 0.931 g / cm ³ or more, The mixing ratio can be adjusted as appropriate.

  The A heavy oil composition according to the present invention preferably has a sulfur content of 0.15% by mass or less from the viewpoint of reducing sulfur oxides in the exhaust gas.

The A heavy oil composition according to the present invention has a density of 0.820 to 0.890 g / cm ³ and preferably 0.850 to 0.880 g / cm ³ . If the density is too small, the fuel efficiency is deteriorated. If the density is too large, the cetane index may be lowered, and the ignitability and combustibility may be deteriorated.

The A heavy oil composition according to the present invention preferably has a kinematic viscosity (50 ° C.) of 2.0 to 4.5 mm ² / s, and more preferably 2.0 to ^2.5 mm ² / s. When the kinematic viscosity is small, the lubricating performance is deteriorated. When the kinematic viscosity is large, the spray state in the combustor is deteriorated, and the exhaust gas properties may be deteriorated.

  The A heavy oil composition according to the present invention may have a clogging point of −2 ° C. or lower.

  In the distillation properties of the A heavy oil composition according to the present invention, the 10% distillation temperature is preferably 195 to 260 ° C, more preferably 230 to 250 ° C. If the 10% distillation temperature is low, white smoke tends to be generated during combustion, and if it is too high, the low-temperature fluidity may be deteriorated. The 50% distillation temperature is preferably 260 to 310 ° C, more preferably 270 to 300 ° C, further preferably 280 to 290 ° C. If the 50% distillation temperature is too low, fuel efficiency and ignitability may be affected. If it is too high, low temperature fluidity may be deteriorated. The 90% distillation temperature is preferably 315 to 370 ° C, more preferably 320 to 350 ° C, and further preferably 320 to 340 ° C. If the 90% distillation temperature is too low, the ignitability may be affected. If it is too high, the low-temperature fluidity may be deteriorated or the black smoke in the combustion exhaust gas may increase.

In the fuel oil A composition according to the present invention, the ignitability can be determined by using the cetane index as an index, and the cetane index (new) can be, for example, 40 or more, preferably 45 or more. A higher cetane index is preferable from the viewpoint of ignitability, but if it is too high, the exhaust gas properties may be deteriorated, so 70 or less is preferable, and 60 or less is more preferable. The filter oil permeability can be, for example, such that the differential pressure before and after the filter after passing through the membrane filter for 1 hour under the condition of a flow rate of 1.0 L / h is 0.7 kg / cm ² or less. For fuel consumption, the amount of heat generated can be used as an index. For example, it can be determined that the amount of heat generated is 37500 kJ / L or more. The A heavy oil composition according to the present invention can easily produce an A heavy oil composition having good ignitability, excellent filter oil permeability, and good fuel efficiency without using extract oil.

[Method for producing A heavy oil composition]
Although the manufacturing method of A heavy oil composition which concerns on this invention is not specifically limited, For example, it can manufacture as follows.

Density (15 ℃) 0.770g / cm ³ or more, and the FT synthetic oil number 21 or more normal paraffins carbon is 2.0 to 10.0 wt%, a density (15 ℃) 0.860g / cm ³ or more The cracked light oil having an aromatic content of 50.0% by volume or more and an aromatic content of two or more rings of 40.0% by volume or more is mixed with the residual coal modifier. You may mix and mix desulfurized light oil.

  The FT synthetic oil can be obtained, for example, by gasifying natural gas to obtain synthetic gas (carbon monoxide and hydrogen), FT synthesis, and hydrocracking and distilling the obtained synthesized product. The cracked light oil can be obtained, for example, by a distillation operation after cracking with a fluid catalytic cracking apparatus using a direct dehydrated residue oil, an indirect desulfurized residue oil, a vacuum gas oil or the like as a raw material.

(Examples 1-5, Comparative Examples 1-4)
GTL diesel oil (density (15 ° C.) 0.782 g / cm ³ , initial boiling point 202 ° C., 10% distillation temperature 239 ° C., 50% distillation temperature 285 ° C., 90% distillation temperature 328 ° C. listed in Table 1 , End point 342 ° C., flash point 92 ° C., cetane index 89.2, kinematic viscosity (30 ° C.) 3.966 mm ² / s, sulfur content 1 mass ppm or less, aromatic content 1 vol% or less, carbon number 8-20 Normal paraffin 29.80% by mass, C21 or more normal paraffin 9.15% by mass), catalytic cracking gas oil (density (15 ° C.) 0.946 g / cm ³ , 1-ring aromatic content 17.7% by volume, 2 Table 1 shows the composition of ring aromatics 49.3 vol%, aromatic rings 29.5 vol%, aromatic rings 10.2 vol% tricyclic or higher, desulfurized diesel oil and residual coal modifier A according to Examples 1 to 5 and Comparative Examples 1 to 4 mixed in an amount (volume%) To give an oil composition. In addition, the said property etc. were measured and calculated | required similarly to the obtained A heavy oil composition.

The following materials were used as the residual coal adjuster.
"Remaining coal adjuster 1"
A slurry oil having a density (15 ° C.) of 1.033 g / cm ³ , distilled from a fluid catalytic cracker and having a sulfur content of 0.79% by mass and a residual carbon content of 5.91% by mass.
"Remaining coal adjustment material 2"
A density (15 ° C.) of 0.939 g / cm ³ and a sulfur content of 1.00% by mass were obtained by treating a Middle Eastern crude oil with an atmospheric distillation apparatus, a sulfur content of 2.15% by mass, and a residual carbon content of 5. 95 mass% atmospheric residue oil.
"Remaining coal adjuster 3"
A density (15 ° C.) of 0.993 g / cm ³ and a sulfur content of 2.92 mass% were obtained by treating a Middle Eastern crude oil with an atmospheric distillation apparatus, and a sulfur content of 3.55 mass% and a residual carbon content of 12. 0 mass% atmospheric residue oil.

  About A heavy oil composition which concerns on Examples 1-5 and Comparative Examples 1-4, a composition and a property were measured as follows. The results are shown in Tables 2 and 3.

Kinematic viscosity (50 ° C):
Measured according to JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.
Residual carbon content of 10% residual oil:
It was measured according to JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.
Clogging point:
Measured according to JIS K 2288 “Petroleum products—fuel oil—clogging point test method”.

Density (15 ° C):
Measured according to JIS K 2249 “Crude oil and petroleum products—Density test method and density / mass / volume conversion table”.
ASTM distillation:
Measured according to JIS K 2254 “Petroleum products—Distillation test method 4. Atmospheric pressure distillation test method”.

“Carbon”, “Hydrogen”, “Carbon / hydrogen ratio”
These are carbon content, hydrogen content, and mass ratio of carbon to hydrogen measured by JPI-5S-65-2004 “Testing method for carbon, hydrogen, nitrogen, sulfur content of petroleum products”. However, the measurement object is residual oil after 95% cut by ASTM distillation.

Normal paraffin having 21 or more carbon atoms:
ASTM D 2887 “Standard Test Method for Boiling Range Distribution of Petroleum Fractionation by Gas Chromatography” was used to calculate the carbon content of each carbon from the obtained chromatogram using the gas chromatographic method. That is, the retention time was examined using a mixture of normal paraffins having different carbon numbers as a standard, and the normal paraffin content was determined from the total area value of the normal paraffin peaks.
The type of column in the gas chromatographic method is HP5 (length: 30 m, inner diameter: 0.32 mm, liquid layer thickness: 0.25 μm), and each analysis condition is as follows.
Column tank temperature rising condition: 35 ° C. (5 minutes) → 10 ° C./minute (temperature rising) → 320 ° C. (11.5 minutes)
Sample vaporization chamber conditions; 320 ° C constant Split ratio 150: 1
Detector section: 320 ° C

Sulfur content:
Measured according to JIS K 2541-4 “Crude oil and petroleum products—Sulfur content test method Part 4: Radiation excitation method”.
Aromatic content:
Measured according to JPI-5S-49-97 “Petroleum products—Hydrocarbon type test method—High performance liquid chromatograph method”.
Cetane index (new):
Measured according to JIS K 2280 “Petroleum products—fuel oil—octane number and cetane number test method and cetane index calculation method 8. Method for calculating cetane index using four-variable equation”.
Cetane index (old):
It means the cetane index obtained according to JIS K 2204-1992 “Diesel”.

Oil permeability:
The test apparatus referred to IP387 / 07 and used a filter unit having a diameter of 90 mm. The filter used was a membrane filter LSWP09025 (product name: manufactured by Merck & Co., Inc.). The test fuel was passed for 1 hour under conditions of an oil temperature of 13 ° C. and a flow rate of 1.0 L / h, and the pressure value after passing was measured. However, when the pressure difference after oil passing exceeded 0.7 kg / cm ² , “> 0.7” was set. The determination of oil permeability is 0 based on this value because the measurement result of the A heavy oil composition prepared by imitating a product that clogged in actual use exceeded 0.7 kg / cm ^2. 0.7 kg / cm ² or less was accepted.

Calorific value:
It was calculated according to JIS K 2279 “Crude oil and petroleum products—heat generation test method and calculation estimation method”. Since the ash and moisture required for the calculation were very small as a result of the measurement, the calculation was made with 0 mass%.

Claims (6)

Including FT synthetic oil, cracked light oil and residual coal modifier, density is 0.820-0.890 g / cm ³ , carbon / hydrogen ratio of residual oil after 95% cut by ASTM distillation is 6.4 or less, and 10 A heavy oil composition, wherein the residual carbon content of the% residual oil exceeds 0.20% by mass.   The heavy fuel oil composition according to claim 1, wherein the aromatic content is 15.0% by volume or more, and the aromatic content of two or more rings is 5.0% by volume or more.   The heavy fuel oil composition according to claim 1 or 2, wherein the normal paraffin having 21 or more carbon atoms is 0.1 to 4.0% by mass.   The A heavy oil composition according to any one of claims 1 to 3, wherein 1.0 to 50.0% by volume of the FT synthetic oil and 5.0 to 50.0% by volume of the cracked light oil are contained. The heavy fuel oil composition according to any one of claims 1 to 4, wherein the differential pressure before and after the filter after passing through the membrane filter for 1 hour at a flow rate of 1.0 L / h is 0.7 kg / cm ² or less. . Density (15 ℃) 0.770g / cm ³ or more, and the FT synthetic oil number 21 or more normal paraffins carbon is 2.0 to 10.0 wt%, a density (15 ℃) 0.860g / cm ³ or more And a cracked gas oil having an aromatic content of 50.0% by volume or more and a bicyclic or higher aromatic content of 40.0% by volume or more. A method for producing a heavy oil composition according to claim 1.