JP3218785B2 - Diesel diesel composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel diesel light oil composition, and more particularly, to the effective use of catalytic cracking light oil, which has not been effectively used in the past, and the generation of particulate matter (particulates) during combustion. The present invention relates to a diesel light oil composition which generates a small amount of heat, generates a large amount of heat, and generates little sludge during storage.

[0002]

2. Description of the Related Art Conventionally, gas oil for diesel engines (diesel gas oil) is obtained by hydrorefining a straight-run gas oil obtained from an atmospheric distillation unit of crude oil, or a hydro-refined straight-run gas oil. For example, straight kerosene obtained from a pressure distillation apparatus or a mixture of hydrogenated products thereof has been used.

On the other hand, in order to produce high octane gasoline,
Catalytic cracking of straight-run heavy oil obtained from a crude oil atmospheric distillation unit or vacuum gas oil obtained by vacuum distillation of an atmospheric distillation residue is often used to obtain cracked gasoline, which is a high-octane gasoline base material. At that time, it is known that a heavy fraction called catalytic cracking gas oil is by-produced as a high boiling fraction of the catalytic cracking product.

[0004] However, this catalytic cracking gas oil has a low cetane number, generates a large amount of particulate matter when burned in a diesel engine, and has poor thermal and oxidative stability. It is not used for diesel light oil because of clogging, etc., and has been used as a heavy oil cutter material until now.

[0005] To cope with an increase in demand for light oil, it is necessary to effectively use middle distillates. If catalytic cracking light oil can be used, it will greatly contribute to the stable supply of energy. However, for that purpose, it is important not to have an adverse effect on the environment such as generation of particulate matter during combustion, and at the same time, a technique for preventing sludge generation during storage has been required.

It has been proposed to improve the cetane number by adding a nitrate ester or an organic peroxide in order to effectively use the catalytic cracking gas oil thus far. However, even with the addition of these compounds, there is a problem that there is no significant improvement effect on the tendency of particulate matter generation during combustion and sludge formation during storage. It has not been found yet.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to reduce the generation of particulate matter (particulates) during combustion even when a catalytic cracking gas oil, which has not been effectively used, is blended with a diesel gas oil base material. Another object of the present invention is to provide a diesel light oil composition which has a high calorific value and generates little sludge during storage.

[0008]

[Means for Solving the Problems] Under such circumstances,
The present inventors have conducted detailed studies from a new viewpoint on catalytic cracking gas oil, which was considered to be impossible to use for diesel gas oil, and as a result, have established a technology for effective use thereof.

A first aspect of the present invention is that the catalytic cracking gas oil produced as a by-product from the catalytic cracking device has a boiling point in the range of 180 to 320 ° C. and a boiling point of 180 ° C.
Not containing fractions less than or less than 320 ° C., containing from 19 to 70% by volume of saturated component, 39 to 60% by volume of aromatic component , 1 to 20% by volume of olefin component, and having a density of 0.85 at 15 ° C. The present invention relates to a diesel light oil composition characterized in that a fraction of ０．９0.90 g / cm ³ is contained as an essential component and 5 to 30% by volume based on the total amount of the composition. A second aspect of the present invention is the diesel gas oil composition according to the first aspect, wherein the catalytic cracking gas oil has a boiling point range of 180 to 180.
It is characterized by a temperature of 300 ° C. Claim 3 of the present invention
Has a density of 0.86 to 0.89 g / cm ³ in the diesel light oil composition according to claim 1 or 2. Claim 4 of the present invention is Claim 1
The diesel gas oil composition according to any one of claims 1 to 3, wherein the amount of the catalytic cracking gas oil is 5 to 20% by volume. Claim 5 of the present invention relates to the diesel gas oil composition according to any one of claims 1 to 4, wherein the diesel gas oil composition has a boiling point of 160 to 380.
° C. Claim 6 of the present invention is the diesel gas oil composition according to any one of claims 1 to 4, wherein the diesel gas oil composition has a boiling point of 180 to
It is characterized by a temperature of 360 ° C. Claim 7 of the present invention
Is a diesel gas oil composition according to any one of claims 1 to 6, characterized in that the diesel gas oil composition has a cetane number of 50 to 60. According to claim 8 of the present invention, in the diesel gas oil composition according to any one of claims 1 to 6, the cetane number of the diesel gas oil composition is 55 to 60. A ninth aspect of the present invention is the diesel gas oil composition according to any one of the first to eighth aspects, wherein the catalytic cracking gas oil has a saturated content of 39 to 60% by volume.

According to the present invention, the catalytic cracking gas oil can be effectively utilized by blending a catalytic cracking gas oil having a specific boiling range and a specific density range with a diesel gas base material in a specific amount, and the amount of heat generated during combustion is high. In addition, a diesel light oil composition having excellent performance, such as a small amount of particulate matter generated during combustion and no generation of sludge during storage, can be obtained.

Hereinafter, the contents of the present invention will be described in more detail. The diesel gas oil base material as referred to in the present invention is, as described above, a petroleum product used as ordinary diesel gas oil, and is obtained by hydrorefining a straight gas oil obtained from an atmospheric distillation unit of crude oil, or a straight gas oil. A straight-run kerosene obtained from an atmospheric distillation unit for crude oil may be mixed and hydrorefined, or a mixture of these straight-run gas oil and straight-run kerosene after hydrorefining may be used. Further, a mixture of these and a hydrocracked gas oil can also be used.

It is to be noted that the diesel gas base material used herein generally has a cetane number of 50, preferably 55 or more and a sulfur content of 0.2% by weight or less within a range of a boiling point of 160 to 380 ° C. Desirably, specifically, for example, JI
Special No. 1, No. 2 specified in SK 2204 "Light Oil"
No. 3, No. 3 or No. 3 can be preferably used.

[0013] The catalytic cracking gas oil, which is an essential component of the present invention, refers to a boiling point of 180 to 38, which has a higher boiling point than the cracked gasoline fraction and is by-produced from a catalytic cracking unit for producing cracked gasoline.
It is a fraction within the range of 0 ° C.

The catalytic cracking unit referred to here is a device for catalytically cracking a high-boiling fraction of light oil or higher in the presence of a solid catalyst to obtain a gasoline base material having a high octane number. Usually, an amorphous silica alumina catalyst or a zeolite catalyst is used. The catalytic cracking apparatus basically comprises a reaction tower and a catalyst regeneration tower, and the reaction conditions are usually 470 to 550 ° C. in the reaction tower, and 650 to 650 ° C. in the regeneration tower.
The reaction pressure is about 750 ° C., the reaction tower pressure is about 0.8 to 1.5 g / cm ² , and the regeneration tower pressure is about 0.9 to 1.6 g / cm ² . The main catalytic cracking processes are air lift thermophor method, food reflow method, UOP method, shell two-stage method, flexi cracking method, ortho flow method, Texaco method, Gulf method, ultra cat cracking method, alco cracking method, HOC cracking method, HOC And RCC methods. However, in the present invention, the process and operating conditions of the catalytic cracking device are not particularly limited, and any known catalytic cracking device can be used.

The catalytic cracking gas oil used in the present invention includes not only catalytic cracking gas oil itself produced as a by-product from the catalytic cracking unit, but also hydrorefining the purified catalytic cracking gas in which the content of impurities such as sulfur is reduced. Light oil can also be used.

In the present invention, the catalytic cracking gas oil produced as a by-product from the catalytic cracking unit is cut to fractions, and the boiling point is from 180 to 3
A fraction within the range of 20 ° C, preferably 180-300 ° C, and having a density at 15 ° C of 0.85-0.9.
0 g / cm ³ , preferably 0.86 to 0.89 g / cm
Use a fraction that is ³ .

In the present invention, when a fraction cracked in the whole boiling range of the catalytic cracking gas oil is used, and when a fraction exceeding a boiling point of 320 ° C. is contained even when the fraction is cut, generation of particulate matter during combustion or It is not preferable because sludge generation during storage increases. When a fraction whose density does not reach the above range is used, the calorific value of the composition is reduced.On the other hand, when a fraction whose density exceeds the above range is used, generation of particulate matter during combustion or storage Each is not preferable because sludge generation increases. The fraction of the catalytic cracking gas oil having a boiling point exceeding 320 ° C., which is not used in the present invention, can be effectively used by mixing it into Fuel Oil A or using it directly as Fuel Oil A.

In the present invention, the composition of the fraction having a boiling point in the range of 180 to 320 ° C. and a density at 15 ° C. of 0.85 to 0.90 g / cm ³ is arbitrary, In terms of the amount of heat generated by combustion, the generation of particulate matter during combustion, and the effect on sludge formation during storage, the saturation
It is preferred to have a hydrocarbon composition of 9-70% by volume, 29-80% by volume of aromatics and 1-20% by volume of olefins, 39-60% by volume of saturated components, 39-6% of aromatics.
More preferably, it has a hydrocarbon composition of 0% by volume and an olefin content of 1 to 10% by volume. In addition, the hydrocarbon composition referred to here is a value measured by applying this test method as it is to the above-mentioned boiling point fraction of catalytic cracking gas oil according to “Test Method of Fuel Oil Hydrocarbon Components” specified in JIS K 2536. Means.

In the diesel gas oil composition of the present invention, the blending amount of the catalytic cracking gas oil in the specific boiling point range and the specific density range is 5 to 30% by volume, preferably 5 to 20% by volume, based on the total amount of the composition. . Even if the amount is less than 5% by volume, there is no problem in performance, but there is a problem from the viewpoint of actively utilizing catalytic cracking gas oil. On the other hand, when the compounding amount exceeds 30% by volume, the resulting diesel gas oil composition has a large adverse effect due to a decrease in cetane number, and further increases the generation of particulate matter during combustion and generation of sludge during storage. Absent.

In the present invention, as described above, the catalytic cracking gas oil can be effectively utilized only by blending a specific amount of catalytic cracking gas oil having a specific boiling range and a specific density range with the diesel gas oil base material. As compared with the case where all the fractions are blended, a diesel light oil composition having excellent performances such as no generation of particulate matter during combustion and no generation of sludge during storage is obtained. The properties of the gas oil composition obtained by the present invention are not particularly limited, but the boiling point is usually in the range of 160 to 380 ° C, preferably 180 to 360 ° C, and 50 to 360 ° C.
It is desirable to have a cetane number of 60, preferably 55-60.

In the light oil composition of the present invention, a known fuel oil additive is used alone for the purpose of further enhancing its performance.
Alternatively, they can be added in combination of several types. Specific examples of these additives include a cetane number improver such as a nitrate ester and an organic peroxide; a low-temperature fluidity improver such as an ethylene-vinyl acetate copolymer and an alkenyl succinamide; -Based antioxidants: metal deactivators such as salicylidene derivatives; detergents and dispersants such as alkenyl succinimides and polyalkylamines; anti-freezing agents such as polyglycol ethers; corrosion of fatty acid amines and alkenyl succinates Antistatic agents such as anionic, cationic and amphoteric surfactants; coloring agents such as azo dyes;

The amount of these additives to be added is also optional, but usually, the amount of each additive is 0.1% based on the total amount of the composition.
It is at most 5% by weight, preferably at most 0.2% by weight.

[0023]

Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. (Examples 1 to 6) Diesel diesel base oil (the properties of which are shown in Table 1) obtained by hydrorefining a straight-run diesel obtained from an atmospheric distillation unit of Middle Eastern crude oil (paraffin type) is also used. The catalytic cracking gas oil shown in Table 1 was blended in the amount shown in Table 2 to obtain a gas oil composition according to the present invention. In addition, this catalytic cracking light oil A
Is obtained when a vacuum gas oil obtained by vacuum distillation of an atmospheric distillation residue of paraffinic crude oil is treated by a fluid catalytic cracking apparatus for producing cracked gasoline. Further, the catalytic cracking gas oil E is a fraction having a boiling point of 180 to 280 ° C of the catalytic cracking gas oil obtained by treating the atmospheric distillation residue of another paraffinic crude oil in the same manner. The following evaluation tests were performed on the diesel light oil composition according to the present invention, and the results are also shown in Table 2.

(Comparative Examples 1 to 6) For comparison, gas oil compositions of Comparative Examples were prepared according to the compositions shown in Table 2, and similar evaluation tests were conducted. The results are also shown in Table 2.

[0025]

[Table 1]

[0026]

[Table 2]

"Exhaust gas test" An engine test was conducted using a 7.1-liter direct injection naturally aspirated diesel engine (for a 4t class vehicle) under the following conditions and modes. The amount of particulate matter was measured. The unit kWh is a value obtained by converting PSh. Output: 195PS / 2900rpm Torque: 51.0kg ・ m / 1800rpm Mode: Diesel 13 mode (Related to Article 31 of the Road Transport Vehicle Law Enforcement Regulations described in the official gazette of March 27, 1991, extra page 38, page 14) Mode)

"Thermal stability test" ASTM D 873 "Standard
Test Method Oxidation Stability of AviationFuels
According to the method described in “Iron plate (2 cm × 2
cm) and a copper plate (1 cm × 1 cm), an oxidation test was performed under the conditions of an oxygen pressure of 5 kg / cm ² and a test time of 6 hours. After the test, the diesel light oil composition was
And the amount of generated sludge was measured.

"True calorific value" After measuring the total calorific value of the sample in accordance with "Test method for calorific value of crude oil and fuel oil" of JIS K 2279, the value was calculated as the true calorific value (cal / cm ³ ).
Was converted to

As is clear from Table 2, the diesel gas oil compositions of the examples according to the present invention show the same or higher performance evaluation results as the diesel gas oil of Comparative Example 1 in which no catalytic cracking gas oil is blended. In other words, by combining the catalytic cracking gas oil, the generation of particulate matter during combustion is reduced, and the excellent effect of increasing the true calorific value is exhibited, and the stability during storage is not adversely affected. In addition, the catalytic cracking gas oil can be used effectively. On the other hand, Comparative Example 2 was a case where the whole fraction was used as the catalytic cracking gas oil, Comparative Example 3 was a case where the catalytic cracking gas oil was fractionated to a higher boiling point than the present invention, and Comparative Example 4 was a catalytic cracking gas oil. In this case, a light oil which falls within the boiling point range of the present invention but has a low density is used as a light oil. In Comparative Examples 5 and 6, the amount of the catalytic cracking gas oil was increased, but even if the catalytic cracking gas oil within the boiling range or the density range of the present invention was used, the adverse effect due to the increase in the blending amount was observed. Is remarkable.

[0031]

As described above, the catalytic cracking gas oil can be effectively utilized by blending the catalytic cracking gas oil having a specific boiling range and a specific density range with the diesel gas base material in a specific amount, and the calorific value generated during combustion can be achieved. The present invention can provide a diesel light oil composition having excellent performances, such as high fuel efficiency, a small amount of particulate matter generated during combustion, and no generation of sludge during storage. In order to cope with the increase in demand for gas oil, it is necessary to effectively use middle distillates. However, the diesel gas oil composition of the present invention makes it possible to use catalytically cracked gas oil, which greatly contributes to a stable energy supply. It has a great industrial value.

Continuation of the front page (56) References JP-A-5-140567 (JP, A) JP-A-5-59376 (JP, A) JP-A-63-54496 (JP, A) (58) Fields investigated (Int) .Cl. ⁷ , DB name) C10L 1/04 C10L 1/08

Claims (9)

(57) [Claims] 1. A catalytic cracking gas oil produced as a by-product from a catalytic cracking device has a boiling point of 180 to 320 with respect to a diesel gas oil base material.
° C and a boiling point below 180 ° C and 3
It does not contain a distillate exceeding 20 ° C., a saturated content of 19 to 70% by volume, an aromatic content of 39 to 60 % by volume, and an olefin content of 1 to 20%.
% At 15 ° C. and a density of 0.85 to 0.5% at 15 ° C.
A diesel light oil composition comprising 90 to 90% by volume of a 90 g / cm ³ fraction as an essential component, based on the total amount of the composition. 2. The catalytic cracking gas oil has a boiling range of 180 to 30.
The diesel gas oil composition according to claim 1, which is at 0 ° C. 3. The diesel composition according to claim 1, which has a density of 0.86 to 0.89 g / cm ³ . 4. The amount of the catalytic cracking gas oil is 5 to 20% by volume.
The diesel light oil composition according to any one of claims 1 to 3, wherein 5. The diesel gas oil composition having a boiling point of 160 to
The diesel gas oil composition according to any one of claims 1 to 4, which has a temperature of 380 ° C. 6. The diesel gas oil composition having a boiling point of 180 to
The diesel gas oil composition according to any one of claims 1 to 4, which has a temperature of 360 ° C. 7. The diesel gas oil composition having a cetane number of 50
The diesel gas oil composition according to any one of claims 1 to 6, wherein 8. The diesel gas oil composition having a cetane number of 55
The diesel gas oil composition according to any one of claims 1 to 6, wherein 9. The diesel gas oil composition according to claim 1, wherein the catalytic cracking gas oil has a saturated content of 39 to 60% by volume.