JPH10298567A - Heavy oil a composition good in storage stability and used for heating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heavy oil A composition using a light cycle oil as a base material without subjecting the light cycle oil to a special treatment, excellent in storage stability, and suitable as a fuel for internal combustion engines. SOLUTION: This heavy oil A composition comprises 60-92.5 vol.% of a light cycle oil having a boiling point range of 170-380 deg.C, a 50% recovery point of 200-330 deg.C, and a 15 deg.C density of 0.860-0.985 g/cm<3> , 7-40 vol.% of a directly desulfurized gas oil having a boiling point range of 130-500 deg.C, a 50% recovery point of 250-400 deg.C, and a 15 deg.C density of 0.860-0.950 g/cm<3> , and further a base material for imparting a residual carbon content, and has a residual carbon content of >0.2 wt.% in 10% of a residual oil.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a heavy oil A composition. More specifically, by mixing a fixed ratio of directly removed light oil, good storage stability suitable for fuel for combustion equipment,
The present invention relates to a fuel oil A composition suitable for heating.

[0002]

2. Description of the Related Art Fuel oil A has a suitable quality as a fuel for internal combustion engines such as diesel engines and fuels for combustion equipment such as boilers and various furnaces which comply with the provisions of JIS K 2205 Type 1 or No. 2. Mineral oil. In general, for heavy fuel oil A, among the four items (density, fractionation properties, residual carbon content, and flash point) that are not subject to the taxation of light oil collection tax stipulated in Article 700 of the Local Tax Law, the residual carbon content item is applied. ing. For this reason, A fuel oil is usually straight kerosene (or desulfurized kerosene), straight light gas oil (or desulfurized light gas oil), straight straight heavy gas oil (or desulfurized heavy gas oil) obtained from an atmospheric distillation unit. Hydrodesulfurized vacuum gas oil obtained by hydrodesulfurizing a light cycle oil obtained from a fluid catalytic cracking unit and / or a residual fluid catalytic cracking unit and a vacuum gas oil obtained from a vacuum distillation unit , Mixing the hydrocracked gas oil obtained from the hydrocracking unit, the directly desulfurized gas oil obtained from the direct heavy oil desulfurization unit, etc., and further mixing the atmospheric residual oil, the direct residual oil, the vacuum residual oil, etc. Thus, the residual carbon content of the 10% residual oil exceeds 0.2% by weight.

[0003] In recent years, the demand trend of fuel oils has been toward white oil, and cracking apparatuses (fluid catalytic cracking apparatus, residual fluid catalytic cracking apparatus, direct heavy oil desulfurizing apparatus, etc.) for decomposing heavy oil and increasing the production of white oil. Hydrocrackers, etc.) are expected to have higher operating rates.

[0004] At present, a distillate equivalent to light oil (cracked gas oil) produced in a cracking unit is mainly used as a blend base material for heavy fuel oil A, and is used as a substitute for straight-run gas oil or kerosene obtained from an atmospheric distillation unit. In view of the increase in white oil production, there is an urgent need to further increase the mixing ratio of cracked gas oil to Fuel Oil A.

[0005] However, among the cracked gas oils, light cycle oils are known to have poor storage stability, and are liable to generate contaminants during storage that contribute to clogging of filters and burner nozzles of combustion equipment. Therefore, it was difficult to mix a certain amount or more as it was from the viewpoint of ensuring storage stability.

[0006] Light cycle oils improve the storage stability by saturating diene and olefin compounds, which are considered to have an adverse effect on them, decomposing highly reactive sulfur and nitrogen compounds, It is effective to carry out hydrotreatment to generate low hydrocarbons, hydrogen sulfide, and ammonia, but this is not desirable because the number of treatment steps increases and the cost increases.

To improve the storage stability of light cycle oils, in addition to the above, removal of contaminant precursors such as thiophenol, mercaptan, hydrogen sulfide, organic acids and phenol by washing with caustic soda, There are also methods to add additives such as antioxidants, dispersants, and metal deactivators that inactivate metals (particularly copper) that catalyze the contaminant formation reaction, all of which lead to increased costs. Met.

[0008]

In general, hydrotreating is most effective for improving the storage stability of light cycle oil, but it greatly affects the refining cost due to the increase in the number of treatment steps. Furthermore, it cannot be easily adopted from the viewpoint of the processing capacity of the hydrotreating apparatus.

An object of the present invention is to use a light cycle oil as a base material without any special treatment, to provide excellent storage stability,
An object of the present invention is to provide a fuel oil A composition suitable for a fuel for combustion equipment.

[0010]

Means for Solving the Problems The present inventors have proposed a conventional A
In heavy oil compositions, as a result of intensive research to overcome the above-mentioned disadvantages of storage stability due to mixing of light cycle oils and to develop a heavy oil A composition that does not require hydrotreating of light cycle oils, the direct removal gas oil By mixing a certain ratio with light cycle oil, an effect of improving storage stability was found, and the present invention was completed.

That is, the objects of the present invention are: (A) Boiling point range 170-380 ° C, 50% distillation point 2
00-330 ° C, 15 ° C density 0.860-0.985g
/ Cm ³ of light cycle oil of 60 to 92.5% by volume,
(B) Boiling range 130-500 ° C., 50% distillation point 250
~ 400 ° C, 15 ° C Density 0.840 ~ 0.950g / c
and 7-40 volume% of direct desulfurization gas oil m ^3, (C) residue containing carbon component substrate for imparting, (D) and that more than 0.2 wt% carbon residue of the 10% residual oil 1. A heavy oil composition, The base material for imparting residual carbon is selected from atmospheric residual oil, direct residual oil obtained from a direct heavy oil desulfurization unit, vacuum residual oil obtained from a vacuum distillation unit, and extract obtained from a solvent refining unit for lubricating oil. 2. The heavy oil composition A according to the above 1, wherein the composition is at least one selected from the group consisting of: In addition to the above components (A) to (C), (a) straight run kerosene or desulfurized kerosene, (b) straight run light gas oil or desulfurized light gas oil, (c) straight run heavy gas oil or desulfurized process 3. The A heavy oil composition according to the above 1 or 2, comprising at least one selected from heavy gas oil, (d) hydrocracked gas oil, and (e) reduced pressure gas oil hydrodesulfurized. 4. The directly removed gas oil has a boiling point range of 130 to 330 ° C, a 50% distillation point of 200 to 300 ° C, and a 15 ° C density of 0.840 to 0.9.
4. The heavy oil composition A according to the above 1, 2, or 3, which is a low-boiling fraction in the directly removed light oil of 00 g / cm ³ . The directly removed gas oil has a boiling point range of 220 to 450 ° C, a 50% distillation point of 250 to 350 ° C, and a density of 15 ° C of 0.850 to 0.9.
5. The heavy oil composition A according to the above 1, 2, or 3, which is a medium-boiling fraction in the directly removed light oil of 20 g / cm ³ . 6. The heavy oil composition A according to the above 1, 2, or 3, wherein the directly removed gas oil is a mixture of a low-boiling fraction and a medium-boiling fraction in the directly removed gas oil at an arbitrary ratio. The light cycle oil is obtained from a fluid catalytic cracking device and / or a residual fluid catalytic cracking device, and the directly removed light oil is obtained directly from a heavy oil desulfurization device. The composition is achieved by each of the heavy oil compositions A according to any one of the above.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The heavy fuel oil A of the present invention comprises 60 to 92.5% by volume of a light cycle oil having a predetermined property, and a low-boiling fraction and / or a medium-boiling fraction among the direct-removed gas oil or the direct-removed gas oil having the predetermined property. 7 to 40% by volume, and mixed therewith with a base material for imparting residual carbon (normal pressure residual oil, direct residual oil obtained from a direct heavy oil desulfurization unit, vacuum residual oil obtained from a vacuum distillation unit, lubricating oil 10% by adding at least one selected from extracts obtained from a solvent refining device).
The residual carbon content of the residual oil exceeds 0.2% by mass.

The light cycle oil is obtained from a fluidized catalytic cracking unit and / or a residual fluidized catalytic cracking unit and has a boiling point of 170.
It is a fraction within the range of ３380 ° C. Specifically, as its distillation properties, the 50% distillation point is 200 to 330 ° C,
Those having a density at 15 ° C. in the range of 0.860 to 0.985 g / cm ³ can be appropriately used. The fluidized catalytic cracking device is used to convert heavy gas oil and reduced pressure gas oil using a hydrodesulfurization device in the presence of a catalyst such as an alumina-supported Co-Mo catalyst and an alumina-supported Ni-Mo catalyst, in the range of 5 to 10MP, preferably 5 to 8MP. Under a pressure of 350 to 450 ° C, preferably 360 to 420 ° C
At a temperature of 0.5 to 4.0 / h, preferably 1.0 to 3.0 / h, a desulfurized vacuum gas oil or the like, which has been subjected to a hydrogenation treatment, at a temperature of 0.5 to 4.0 / h. In the case of (1), a direct-residue oil obtained from a direct heavy oil desulfurization unit and a low-sulfur atmospheric residue are added to the above-mentioned feedstock and catalytically cracked in the presence of a solid catalyst, usually a silica-alumina catalyst or a zeolite catalyst. And the reaction conditions are generally at a reaction temperature of 4
The reaction pressure is about 70 to 550 ° C. and the reaction pressure is about 0.08 to 0.3 MP, but these conditions are not particularly limited.

[0014] The directly removed gas oil is a fraction having a boiling point of from 130 to 500 ° C obtained from a direct heavy oil desulfurization unit. Specifically, as the distillation property, the 50% distillation point is 250 to
400 ° C. and the density at 15 ° C. is 0.840-0.95
Those having a range of 0 g / cm ³ can be appropriately used. The low-boiling fraction of the directly desulfurized gas oil is obtained directly from the heavy oil desulfurization unit.
It is a fraction having a boiling point in the range of 130 to 330 ° C. Specifically, as a distillation property, a 50% distillation point is 200 to 30.
0 ° C, and the density at 15 ° C is 0.840-0.900 g
/ Cm ³ can be appropriately used. The medium-boiling fraction of the directly-desulfurized gas oil is a fraction having a boiling point of 220 to 450 ° C. obtained from a direct heavy oil desulfurization unit. In particular,
As a distillation property, the 50% distillation point is 250-350 ° C.
And the density at 15 ° C. is 0.850 to 0.920 g / c.
Those having a range of m ³ can be used as appropriate. In addition, the direct heavy oil desulfurization unit converts the residual oil under normal pressure and / or the residual pressure under reduced pressure into alumina-supported C.
In the presence of a catalyst such as an o-Mo catalyst or an alumina-supported Ni-Mo catalyst, at a pressure of 10 to 25MP, preferably 14 to 20MP, 350 to 450 ° C, preferably 360 to 420 ° C.
This is an apparatus for performing hydrogenation at a temperature of 0 ° C. and a LHSV of 0.1 to 1.0 / h, preferably 0.2 to 0.5 / h, but these conditions are not particularly limited. .

When the mixing ratio of the light cycle oil exceeds 92.5% by volume and / or when the mixing ratio of the directly removed gas oil is less than 7% by volume, the storage effect is insufficient due to insufficient reforming effect of the directly removed gas oil. No significant improvement effect can be obtained. When the mixing ratio of the light cycle oil is less than 60% by volume and / or when the mixing ratio of the directly removed gas oil exceeds 40% by volume, it is disadvantageous in terms of cost and is not practical.

The reason why the storage stability is improved by mixing a fixed ratio of the directly desulfurized light oil with the light cycle oil is not necessarily clear, but it is not clear in the process in which the raw oil is directly processed by the heavy oil desulfurization unit. , A part of the polycyclic aromatic compound is hydrogenated to produce a compound having high reactivity (hydrogen donating ability),
It is presumed that these compounds have the effect of stabilizing unstable compounds having high reactivity of light cycle oil.
This effect is achieved by straight kerosene (or desulfurized kerosene), straight light gas oil (or desulfurized light gas oil), straight heavy gas oil (or desulfurized heavy gas oil), hydrocracked gas oil, and hydrogenated The storage stability was not improved when only these straight-run fractions were mixed with the light cycle oil without using the desulfurized gas oil specified in the present invention but in the desulfurized vacuum gas oil.

The heavy oil A of the present invention may contain, if necessary, a cetane number improver, an antioxidant, a stabilizer, a dispersant, a fluidity improver, a metal deactivator, a microbial bactericide, an auxiliary agent, Various additives such as an inhibitor and a discriminating agent can be appropriately added.

[0018]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.

Examples 1, 2, 3, 4, 5 and Comparative Examples 1,
2, 3 Base materials having the properties shown in Table 1 were mixed at the volume ratio shown in Table 2 to prepare a fuel composition, and the change in sludge weight before and after storage was measured as an index of its storage stability.

[0020]

[Table 1]

[0021]

[Table 2]

As is evident from Table 2, by mixing a low-boiling fraction and / or a medium-boiling fraction among a certain percentage of directly-oiled gas oil or directly-oiled gas oil, even if a large amount of light cycle oil is mixed, A fuel oil A having significantly reduced sludge generation and excellent storage stability was obtained.

The properties and storage stability of the fuel oil were determined by the following methods.

* 1 Density: JIS K224
9 was measured.

* 2 Distillation properties: JIS K225
4 was measured.

* 3 Sludge weight: Pyrex bottle with screw cap (Corningl 372)
Drill a 6mm hole in the cap of
After storage at 0 ° C. for 1 week, 100 ml was filtered with a filter having an aperture of 0.8 μm, and the weight of the sludge captured on the paper after drying was measured.

[0027]

According to the present invention, by mixing a low-boiling fraction and / or a medium-boiling fraction among a certain percentage of directly-oiled gas oil or directly-oiled gas oil, even if a large amount of light cycle oil is mixed, Fuel oil A excellent in storage stability and suitable as a fuel for heating (for example, for boilers) can be produced, and light cycle oil can be effectively used.

Claims (7)

[Claims] (A) a boiling point range of 170 to 380 ° C., 50%
Distillation point 200-330 ° C, 15 ° C density 0.860-0.
985 g / cm ³ of light cycle oil of 60 to 92.5% by volume, (B) boiling point range of 130 to 500 ° C, 50% distillation point of 250 to 400 ° C, and 15 ° C density of 0.840 to 0.95
0 to 40% by volume of the directly removed light oil of 0 g / cm ³ and (C) a base material for imparting residual carbon content, and (D) a residual carbon content of 10% residual oil is 0.2% by mass. A heavy oil composition comprising: 2. A base material for imparting a residual carbon content is obtained from an atmospheric residual oil, a direct residual oil obtained from a direct heavy oil desulfurization apparatus, a vacuum residual oil obtained from a vacuum distillation apparatus, and a solvent refining apparatus for lubricating oil. The heavy oil A composition according to claim 1, wherein the composition is at least one selected from extracts. 3. In addition to the above components (A) to (C), (a) straight kerosene or desulfurized kerosene, (b) straight run light gas oil or desulfurized light gas oil, (c) straight run weight At least one selected from high-quality gas oil or desulfurized heavy gas oil, (d) hydrocracked gas oil, and (e) hydrodesulfurized vacuum gas oil
3. A according to claim 1 or 2, wherein
Heavy oil composition. (4) a directly removed gas oil having a boiling point range of 130 to 330 ° C.
50% distillation point 200-300 ° C, 15 ° C density 0.840
The heavy oil A composition according to claim 1, 2 or 3, which is a low-boiling fraction in the directly removed light oil of ０．９0.900 g / cm ³ . 5. The gas oil according to claim 1, which has a boiling point range of 220 to 450 ° C.
50% distillation point 250-350 ° C, 15 ° C density 0.850
~0.920g / cm claim 1, 2 or 3 A fuel oil composition, wherein the a-boiling fraction of the ^three straight de gas oil. 6. The heavy oil A according to claim 1, wherein the directly removed gas oil is a mixture of a low-boiling fraction and a medium-boiling fraction in the directly removed gas oil at an arbitrary ratio. Composition. 7. A light cycle oil obtained from a fluidized catalytic cracking device and / or a residual fluidized catalytic cracking device,
The heavy oil A composition according to any one of claims 1 to 6, wherein the directly desulfurized gas oil is obtained from a direct heavy oil desulfurization apparatus.