JPH10298566A - Heavy oil a composition good in storage stability, color tone stability and run - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heavy oil A composition using a considerably large amount of a light cycle oil as a base material without subjecting the light cycle oil to a special treatment, but excellent in storage stability, color tone stability and run, and suitable as a fuel for internal combustion engines. etc., by adding a directly desulfurized gas oil in a constant ratio or more. SOLUTION: This heavy oil A composition comprises 40-60 vol.% of a light cycled 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 0.900-0.985 g/cm<3> , 7-30 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 kerosene or another gas oil, and has a density of >0.8762 g/cm<2> (at 15 deg.C) and a cetane index of >=40.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a heavy oil A composition. More specifically, storage stability suitable for fuels of internal combustion engines and the like is obtained by mixing a fixed ratio of directly removed light oil and using no residual oil-based carbon base material and having a cetane index of 40 or more. Heavy oil composition suitable for use in internal combustion engines, which has good properties, hue stability and oil permeability.

[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 normal pressure 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. It was difficult to mix a certain amount or more as it was from the viewpoint of ensuring storage stability and oil permeability.

[0006] Further, it is known that browning of light cycle oil is liable to proceed during storage, and stabilization of hue has been demanded from the viewpoint of maintaining product quality. In addition, when a residual oil-based residual carbon base material generally used in heavy fuel oil A is added, storage stability, hue stability, and oil permeability are disadvantageously deteriorated. is necessary.

Light cycle oils improve the storage stability, hue stability and oil permeability by saturating diene and olefin compounds, which are considered to have an adverse effect on these compounds, and by increasing the reactivity of sulfur compounds and nitrogen compounds. It is effective to carry out a hydrogenation treatment to decompose and produce hydrocarbons, hydrogen sulfides and ammonia with low reactivity, but this is not desirable because the number of treatment steps increases and the cost increases.

To improve the storage stability, hue stability and oil permeability of the light cycle oil, in addition to the above, other impurities such as thiophenol, mercaptan, hydrogen sulfide, organic acids, and phenol by washing with caustic soda are used. There is also a method of adding additives such as body removal, a stabilizer, an antioxidant, a dispersant, and a metal deactivator that inactivates a metal (particularly copper) that catalyzes a contaminant formation reaction. All of these have led to increased costs.

[0009]

In general, hydrogenation is most effective in improving the storage stability, hue stability, and oil permeability of light cycle oil, but the cost of refining is large due to the increase in the number of processing steps. Affect. Furthermore, it cannot be easily adopted from the viewpoint of the processing capacity of the hydrotreating apparatus.

[0010] It is an object of the present invention to mix a directly removed light oil in a certain ratio or more so that the light cycle oil can be used in a considerably large amount as a base material without special treatment, and the storage stability and the hue stability can be improved. Another object of the present invention is to provide an A heavy oil composition which has excellent oil permeability and is suitable for a fuel such as an internal combustion engine.

[0011]

Means for Solving the Problems The present inventors have proposed a conventional A
In heavy fuel oil compositions, we have continued our research to overcome the drawbacks of storage stability, hue stability and oil permeability due to mixing of light cycle oils and to develop heavy oil A compositions that do not require hydrogenation of light cycle oils. As a result, it was found that by mixing a fixed ratio of the directly removed light oil with the light cycle oil, the storage stability, hue stability and oil permeability were improved even when the light cycle oil was used in a considerably large amount. 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 0.900-0.985g
/ Cm ³ of light cycle oil of 40% by volume or more and 60% by volume
Less than (B) boiling point range 130-500 ° C, 50% distillation point 250-400 ° C, 15 ° C density 0.860-0.95
0-30 g / cm ³ of directly removed gas oil and (C) other kerosene or gas oil, (D) and density (15
° C) exceeds 0.8762 g / cm ³ , and (E)
1. Fuel oil A composition having the above-mentioned cetane index, (C) Other kerosene or gas oil is (a) straight run kerosene or desulfurized kerosene, (b) straight run light gas or desulfurized light gas oil, (c) straight run heavy gas oil or desulfurized heavy 2. The A heavy oil composition according to the above 1, which is at least one selected from gas oil, (d) hydrocracked gas oil, and (e) hydrodesulfurized vacuum gas oil. The directly removed light 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 0.850 to 0.9.
3. The heavy oil composition A according to 1 or 2 above, which is a low-boiling fraction in the directly removed light oil of 00 g / cm ³ . The directly removed light oil has a boiling point range of 220 to 450 ° C, a 50% distillation point of 250 to 350 ° C, and a 15 ° C density of 0.860 to 0.9.
4. The A heavy oil composition according to the above 1 or 2, which is a medium-boiling fraction in the directly removed light oil of 20 g / cm ³ . 5. The heavy oil A composition according to the above 1 or 2, 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 gas oil is obtained directly from a heavy oil desulfurizing device. A fuel oil composition according to any one of the above.

[0013]

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 is a light cycle oil having a predetermined property of 40% by volume or more and less than 60% by volume, and a low-boiling fraction and / or a direct-run gas oil or a direct-run gas oil having a predetermined property.
Alternatively, the medium-boiling fraction is mixed at a rate of 7 to 30% by volume, and the remainder is other kerosene or light oil, and at this time, the density at 15 ° C. exceeds 0.8762 g / cm ^3, and the cetane index of 40 or more To have.

At this time, the other kerosene or light oil is (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 heavy gas oil, (d) hydrocracked gas oil, and (e) )
It is preferably at least one selected from hydrodesulfurized vacuum gas oils.

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 0.900 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 residual oil are added to the above feedstock and catalytically cracked in the presence of a solid 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.

The directly removed gas oil is a fraction having a boiling point of 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 0.860 to 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 0.850-0.900 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 0.860 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 is 60% by volume or more, it is difficult to maintain a cetane index of 40 or more. Further, when the mixing ratio of the directly removed gas oil is less than 7% by volume, the storage effect is insufficient due to the insufficient reforming effect of the directly removed gas oil.
A significant improvement in hue stability and oil permeability cannot be obtained.
When the mixing ratio of the light cycle oil is less than 40% by volume and / or when the mixing ratio of the directly removed gas oil exceeds 30% by volume, it is difficult to increase the 15 ° C. density beyond 0.8762, and the cost is reduced. In addition, if it is not practical due to the use of the residual carbonaceous material, and if it is not subject to the tax on light oil withdrawal, storage stability, hue stability, and oil permeability deteriorate.

Although the reason why the storage stability, hue stability and oil permeability are improved by mixing a fixed ratio of directly removed light oil with light cycle oil is not necessarily clear,
In the process where the feedstock oil is directly processed in a heavy oil desulfurization unit, some of the polycyclic aromatics and the like are hydrogenated to produce compounds with high reactivity (hydrogen donating ability). It is presumed to have an action of stabilizing an unstable compound having high potency. 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 Not in desulfurized vacuum gas oil,
When these straight-run fractions and the like alone were mixed with light cycle oil without using the directly removed gas oil specified in the present invention, storage stability, hue stability and oil permeability were not improved.

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, a flame retardant, Various additives such as an inhibitor and a discriminating agent can be appropriately added.

[0020]

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 ratios shown in Table 2 to prepare a fuel composition, and the change in sludge weight before and after storage was used as an index of storage stability. The change in ASTM color before and after storage was measured, and the filter passage time before and after storage was measured as an index of oil permeability.

[0022]

[Table 1]

[0023]

[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, a relatively large amount of light cycle oil is mixed. However, the amount of sludge produced was significantly reduced, and A heavy oil having excellent storage stability, hue stability and oil permeability 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.

* 4 ASTM color: JIS K258
0 was measured.

* 5 Oil permeability: A temperature of 20 ° C., a suction pressure of 500 mmHg, and a sample of 1,000 ml having a diameter of 47 m
m, the time required to pass through a 0.8 μm filter was measured.

[0031]

According to the present invention, a light cycle oil can be mixed in a considerably large amount 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. However, it is possible to produce heavy fuel oil A which is excellent in storage stability, hue stability and oil permeability and is suitable for fuels of internal combustion engines and the like, and light cycle oil can be effectively used.

Claims (6)

[Claims] (A) a boiling point range of 170 to 380 ° C., 50%
Distillation point 200-330 ° C, 15 ° C density 0.900-0.
985 g / cm ³ of light cycle oil at 40% by volume or more 6
0% by volume and (B) a boiling point range of 130 to 500 ° C., 5
0% distillation point 250-400 ° C, 15 ° C density 0.860-
0.950 g / cm ³ of directly removed light oil with 7 to 30% by volume,
(C) A fuel oil composition containing other kerosene or light oil, (D) having a density (15 ° C.) of more than 0.8762 g / cm ³ , and (E) further having a cetane index of 40 or more. Stuff. (C) another straight kerosene or desulfurized kerosene, (b) straight run light gas oil or desulfurized light gas oil, (c) straight run heavy gas oil or At least one selected from a desulfurized heavy gas oil, (d) hydrocracked gas oil, and (e) hydrodesulfurized vacuum gas oil
2. The fuel oil A composition according to claim 1, wherein (3) a directly removed light oil having a boiling point range of 130 to 330 ° C.
50% distillation point 200-300 ° C, 15 ° C density 0.850
The heavy oil A composition according to claim 1 or 2, which is a low-boiling fraction in the directly removed light oil of ０．９0.900 g / cm ³ . (4) a directly removed gas oil having a boiling point range of 220 to 450 ° C.
50% distillation point 250-350 ° C, 15 ° C density 0.860
The heavy oil A composition according to claim 1 or 2, which is a medium-boiling fraction in the directly removed light oil of ０．９0.920 g / cm ³ . 5. The heavy oil A composition according to claim 1, wherein the directly-oiled gas oil is a mixture of a low-boiling fraction and a medium-boiling fraction in the directly-oiled gas oil at an arbitrary ratio. . 6. 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 5, wherein the directly desulfurized gas oil is obtained from a direct heavy oil desulfurization apparatus.