JP7101021B2 - Manufacturing method of high calorific value light oil base material - Google Patents

Description

The present invention relates to a method for producing a light oil base material having a high calorific value.

Conventionally, as a light oil base material, a straight-run gas oil obtained from an atmospheric distillation apparatus for crude oil, which has been subjected to hydrorefining treatment or hydrodesulfurization treatment, is known. The conventional gas oil composition is produced by blending one or more of the above gas oil base material and kerosene base material.

On the other hand, the recent demand for petroleum products has been lightening, the demand for heavy oil has been sluggish, and the contact obtained from a fluid catalytic cracking device (FCC device) having a high content of aromatic hydrocarbons used as a base material for heavy oil. Decomposed gas oil such as cracked gas oil (LCO; Light Cycle Oil) and heat cracked gas oil obtained from a thermal cracking apparatus is becoming a surplus. Therefore, it is conceivable to mix these decomposed gas oils with the raw material oil for producing the gas oil and treat them.

Further, when a catalytically decomposed circulating oil or a thermally decomposed gas oil having a high content of aromatic hydrocarbons is hydrogenated, a compound having a naphthen ring is produced, so that the density of the distillate having the compound is increased and the calorific value is improved accordingly. There is expected.

Patent Document 1 describes the wear resistance of fuel injection pumps for engines of diesel vehicles and the like by hydrotreating raw material oil containing 70 to 90% by volume of straight-run gas oil and 10 to 30% by volume of catalytically decomposed circulating oil. It is disclosed that a diesel gas oil composition having excellent fuel consumption and low fuel consumption can be obtained.

On the other hand, when catalytically cracked gas oil and thermally cracked gas oil having a high content of olefins and aromatic hydrocarbons are hydrogenated, there is a problem that a large amount of cork is generated and the life of the catalyst is shortened, which is described in Patent Document 1. It is also necessary to reduce the content of catalytically cracked circulating oil in the raw material oil in the raw material oil.
Therefore, in the gas oil composition described in Patent Document 1, since the content of the compound having a naphthenic ring is low, there is a problem that the density of the gas oil composition is low and the calorific value is also low accordingly.

Japanese Unexamined Patent Publication No. 8-31462

An object of the present invention is to provide a method for producing a light oil base material having a high density and a high calorific value.

As a result of diligent studies to achieve the above object, the present inventors have divided a raw material oil having a 90% by volume distillation temperature of 320 to 360 ° C. and containing 37 to 65% by mass of aromatic hydrocarbons into hydrogen. By performing the hydrogenation treatment at 10 to 18 MPa, the sulfur content is 15 mass ppm or less, the 10% by volume distillation temperature is 240 to 300 ° C., and the 90% by volume distillation temperature is 310 to 360 ° C. The present invention was completed by finding that a light oil base material having a calorific value of 36,000 to 37,300 J / mL can be obtained.

That is, the present invention relates to a method for producing a light oil base material.
[1] It is characterized by comprising a step of hydrotreating a raw material oil having a 90% by volume distillation temperature of 320 to 360 ° C. and containing 37 to 65% by mass of aromatic hydrocarbons at a hydrogen partial pressure of 10 to 18 MPa. The sulfur content is 15 mass ppm or less, the 10% by volume distillation temperature is 240 to 300 ° C., the 90% by volume distillation temperature is 310 to 360 ° C., and the calorific value is 36,000. A method for producing a light oil base material having a temperature of ~ 37,300 J / mL.
[2] The raw material oil is selected from the group consisting of thermally cracked gas oil (LCGO), catalytically cracked gas oil (LCO), and light oil obtained by hydrogenating thermally cracked heavy oil (DS-LHCGO). The method for producing a diesel fuel substrate according to [1], which comprises at least one substrate.

According to the method for producing a light oil base material of the present invention, a light oil base material having a high calorific value can be obtained.

It is a schematic diagram of the manufacturing flow of the light oil base material which concerns on one Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described in detail, but the following description is an example of embodiments of the present invention, and the present invention is not limited to these contents, and is modified and implemented within the scope of the gist thereof. can do.

In the method for producing a gas oil base material according to the present invention, a raw material oil having a 90% by volume distillation temperature of 320 to 360 ° C. and containing 37 to 65% by mass of aromatic hydrocarbons is hydrogenated at a hydrogen partial pressure of 10 to 18 MPa. Including the step of performing the treatment, the gas oil base material has a sulfur content of 15% by mass or less, a 10% by volume distillation temperature of 240 to 300 ° C., and a 90% by volume distillation temperature of 310 to 360. The temperature is 36,000 to 37,300 J / mL and the calorific value is 36,000 to 37,300 J / mL.

<Raw oil>
The raw material oil used in the method for producing a light oil base material of the present embodiment is a raw material oil having a 90% by volume distillation temperature of 320 to 360 ° C. and containing 37 to 65% by mass of aromatic hydrocarbons.

The 90% by volume distillation temperature of the feedstock oil (hereinafter, also simply referred to as T90) is 320 to 360 ° C., preferably 330 to 360 ° C., more preferably 340 to 360 ° C. When T90 is at least the lower limit of the above range, the content of aromatic hydrocarbons in the raw material oil becomes high, and the hydrogenation treatment produces a large amount of compounds having a naphthen ring, and the calorific value of the obtained light oil base material is high. improves. When T90 is not more than the upper limit of the above range, the content of aromatic hydrocarbons in the raw material oil does not become too high, the generation of cork in the hydrogenation treatment reaction is suppressed, and the life of the hydrogenation treatment catalyst becomes long. ..
The 90% by volume distillation temperature, the 50% by volume distillation temperature described later, and the 10% by volume distillation temperature are measured in accordance with JIS K2254 "Petroleum products-Distillation test method-Atmospheric distillation test method", respectively. Means the value to be.

The content of aromatic hydrocarbons in the feedstock oil is 37 to 65% by mass, preferably 40 to 60% by mass, more preferably 45 to 60% by mass, and particularly preferably 50 to 60% by mass. When the content of the aromatic hydrocarbon is at least the lower limit of the above range, a large amount of the compound having a naphthenic ring is produced by the hydrogenation treatment, and the calorific value of the obtained light oil base material is improved. When the content of the aromatic hydrocarbon is not more than the upper limit of the above range, the generation of cork in the hydrogenation treatment reaction is suppressed, and the life of the hydrogenation treatment catalyst is extended.
The content of aromatic hydrocarbons means a value measured in accordance with IP 548 "Determination of aromatic hydrocarbon types in middle distillates --High performance liquid chromatography method with refractive index detection".

The sulfur content in the raw material oil is preferably 3% by mass or less, more preferably 2% by mass or less. When the sulfur content is not more than the upper limit value, it is not necessary to make the operating conditions of the hydrogenation treatment strict, so that the life of the catalyst is extended and it is economically advantageous.
The lower the sulfur content is, the more preferable it is. Therefore, the lower limit of the sulfur content is not particularly limited, but is usually 0.5 mass ppm or more.
The sulfur content means a value measured in accordance with JIS K 2541 "Crude oil and petroleum products-Sulfur content test method".

The nitrogen content in the feedstock is preferably 1,000 mass ppm or less, more preferably 800 mass ppm or less. When the nitrogen content is not more than the upper limit, it is not necessary to tighten the operating conditions of the hydrogenation treatment, so that the life of the catalyst is extended and it is economically advantageous. In addition, it does not adversely affect the hue of the manufactured gas oil base material.
Since the lower the nitrogen content is, the more preferable it is, the lower limit of the nitrogen content is not particularly limited, but it is usually 100 mass ppm or more.
The nitrogen content means a value measured in accordance with JIS K 2609 "Crude Oil and Petroleum Products-Nitrogen Content Test Method".

The density of the feedstock oil at 15 ° C. is preferably 0.86 to 0.91 g / mL, more preferably 0.865 to 0.905 g / mL. When the density at 15 ° C. is within the above range, cavitation of the feedstock pump for the feedstock oil used during the desulfurization reaction is prevented, and it is economically advantageous.
The density at 15 ° C. means a value measured in accordance with JIS K 2249 "Density test method for crude oil and petroleum products and density / mass / capacity conversion table".

The raw material oil of the present embodiment is selected from the group consisting of pyrolyzed gas oil (LCGO), catalytically cracked gas oil (LCO), and light oil obtained by hydrogenating the pyrolyzed gas oil (DS-LHCGO). It is preferable to contain at least one kind of substrate.
Hereinafter, each base material will be described with reference to FIG.

(Pyrolysis light oil)
Examples of the base material contained in the raw material oil of the present embodiment include pyrolyzed light oil (hereinafter, also referred to as “LCGO”). As shown in FIG. 1, LCGO is a light fraction of light oil obtained by thermally decomposing a vacuum distillation residue, and has a 10% by volume distillation temperature of 180 to 260 ° C. and a 90% by volume distillation temperature of 310. It is a distillate having a temperature of about 380 ° C.
Since LCGO is a fraction having a high aromatic content, it contributes to the improvement of the total calorific value of the obtained gas oil base material.
The content of LCGO with respect to the total volume of the feedstock is preferably 10 to 90% by volume, more preferably 20 to 80% by volume, still more preferably 30 to 70% by volume.
When the content of LCGO is not more than the lower limit of the above range, the content of aromatic hydrocarbons in the raw material oil becomes high, and a large amount of compounds having a naphthen ring are produced by hydrogenation treatment, and the obtained light oil base material The amount of heat generated is improved. When the content of LCGO is not more than the upper limit of the above range, the content of aromatic hydrocarbons in the raw material oil does not become too high, the generation of cork in the hydrogenation treatment reaction is suppressed, and the life of the hydrogenation treatment catalyst is suppressed. Becomes longer.

(Cracking light oil)
Examples of the base material contained in the raw material oil of the present embodiment include catalytically cracked gas oil (hereinafter, also referred to as “LCO”). As shown in FIG. 1, the LCO is a fraction distilled from the fluidized cracking apparatus, and for example, the 10% by volume distillation temperature is 185 to 250 ° C. and the 90% by volume distillation temperature is 270 to 370 ° C. There is a distillate.
Since LCO is a fraction having a high aromatic content, it contributes to the improvement of the total calorific value of the obtained gas oil base material.
The content of LCO with respect to the total volume of the feedstock is preferably 10 to 65% by volume, more preferably 20 to 65% by volume, still more preferably 22 to 63% by volume.
When the LCO content is at least the lower limit of the above range, the content of aromatic hydrocarbons in the raw material oil becomes high, and the hydrogenation treatment produces a large amount of compounds having a naphthen ring, so that the obtained gas oil base material can be used. The amount of heat generated is improved. When the LCO content is not more than the upper limit of the above range, the content of aromatic hydrocarbons in the raw material oil does not become too high, the generation of cork in the hydrogenation treatment reaction is suppressed, and the life of the hydrogenation treatment catalyst is suppressed. Becomes longer.

(Light gas oil obtained by hydrogenating pyrolyzed heavy light oil)
Examples of the base material contained in the raw material oil of the present embodiment include light gas oil (hereinafter, also referred to as “DS-LHCGO”) obtained by hydrogenating a thermally decomposed heavy light oil (HCGO). As shown in FIG. 1, DS-LHCGO is a gas oil obtained by hydrogenating HCGO, which is a heavier fraction than LCGO, among the gas oils obtained by thermally decomposing a vacuum distillation residue.
Since DS-LHCGO is a fraction having a high aromatic content, it contributes to the improvement of the total calorific value of the obtained gas oil base material.
DS-LHCGO has a 10% by volume distillation temperature of 200 to 260 ° C. Further, DS-LHCGO has a 90% by volume distillation temperature of 300 to 350 ° C.
The content of DS-LHCGO with respect to the total volume of the feedstock is preferably 3 to 10% by volume, more preferably 4 to 10% by volume, and even more preferably 5 to 10% by volume.
When the content of DS-LHCGO is at least the lower limit of the above range, the content of aromatic hydrocarbons in the raw material oil becomes high, and a large amount of compounds having a naphthenic ring are produced by hydrogenation treatment, and the obtained gas oil group is obtained. The calorific value of the material is improved. When the content of DS-LHCGO is not more than the upper limit of the above range, the content of aromatic hydrocarbons in the raw material oil does not become too high, the generation of cork in the hydrogenation treatment reaction is suppressed, and the hydrogenation treatment catalyst is used. Life will be longer.

Among the base materials contained in the raw material oil of the present embodiment described above, it is preferable to contain LCGO and LCO, which are fractions having a high aromatic content.
The total content of LCGO and LCO with respect to the total volume of the feedstock is preferably 30 to 100% by volume, more preferably 40 to 98% by volume, further preferably 50 to 95% by volume, and particularly preferably 60 to 95% by volume. preferable.
When the total content of LCGO and LCO is at least the lower limit of the above range, the content of aromatic hydrocarbons in the raw material oil becomes high, and the hydrogenation treatment produces a large amount of compounds having a naphthenic ring, resulting in light oil. The calorific value of the base material is improved. When the contents of LCGO and LCO are not more than the upper limit of the above range, the content of aromatic hydrocarbons in the raw material oil does not become too high, the generation of cork in the hydrogenation treatment reaction is suppressed, and the hydrogenation treatment catalyst is used. Life will be longer.
As one aspect of the present invention, the LCGO content is preferably 30 to 45% by volume and the LCO content is preferably 45 to 65% by volume with respect to the total volume of the raw material oil.
When the contents of LCGO and LCO are each above the lower limit of the above range, the content of aromatic hydrocarbons in the raw material oil becomes high, and a large amount of compounds having a naphthenic ring are produced by hydrogenation treatment, and the obtained light oil is obtained. The calorific value of the base material is improved. When the contents of LCGO and LCO are each below the upper limit of the above range, the content of aromatic hydrocarbons in the raw material oil does not become too high, the generation of cork in the hydrogenation treatment reaction is suppressed, and the hydrogenation treatment is performed. The life of the catalyst is extended.

<Other base materials>
The raw material oil of the present embodiment may contain other base materials other than the LCGO, LCO, and DS-LHCGO.
Examples of other base materials include gas oil distillate obtained by atmospheric distillation, gas oil distillate obtained from an indirect desulfurization apparatus, and gas oil distillate obtained from a direct desulfurization apparatus.
The content of the other base material with respect to the total volume of the feedstock is preferably 0 to 70% by volume, more preferably 2 to 60% by volume, still more preferably 5 to 50% by volume.

<Hydrogenation treatment>
The hydrogenation treatment in the method for producing a light oil base material according to the present invention is carried out at a hydrogen partial pressure of 10 to 18 MPa. Hereinafter, the details of the conditions for hydrogenation treatment will be described.

(Hydrogenation catalyst)
As the mixture constituting the carrier constituting the hydrogenation treatment catalyst, a porous inorganic oxide containing alumina can be used.
Examples of the active component constituting the hydrogenation treatment catalyst include at least one metal element selected from Group 6 of the Periodic Table and at least one metal element selected from Group 8 to 10 of the Periodic Table.
Molybdenum and tungsten are preferable as at least one metal element selected from Group 6 of the periodic table. As the molybdenum compound, molybdenum trioxide, ammonium molybdate and the like are preferable, and as the tungsten compound, tungsten trioxide, ammonium tungstate and the like are preferable. The amount of the Group 6 metal supported is preferably 8 to 20% by mass with respect to the total mass of the hydrogenation treatment catalyst in terms of oxide.
Cobalt and nickel are preferable as at least one metal element selected from the 8th to 10th groups of the periodic table. As the cobalt compound, cobalt carbonate, basic cobalt carbonate, cobalt nitrate and the like are preferable, and as the nickel compound, nickel carbonate, basic nickel carbonate, nickel nitrate and the like are preferable. The amount of the metal elements of Group 9 and Group 10 carried is preferably 2 to 6% by mass with respect to the total mass of the hydrogenation treatment catalyst in terms of oxide.
Among the above-mentioned active ingredients, a molybdenum nickel-based catalyst in which molybdenum and nickel are combined is preferable.
Further, it is preferable to use the above-mentioned hydrogenation treatment catalyst by hydrogen reduction treatment at 300 to 400 ° C. for 1 to 36 hours in a hydrogen atmosphere.

(Hydrogenation treatment conditions)
The partial pressure of hydrogen in the hydrogenation treatment is 10 to 18 MPa, preferably 11 to 16 MPa, more preferably 13 to 15 MPa. When the hydrogen partial pressure is equal to or higher than the lower limit of the above range, the generation of cork is suppressed even if the raw material oil having a high content of olefins and aromatic hydrocarbons as in the present embodiment is hydrogenated, and the hydrogenation treatment is performed. The life of the catalyst is extended. When the hydrogen partial pressure is not more than the upper limit of the above range, it is economically advantageous because the hydrogenation treatment equipment does not cost too much.

When the hydrogenation treatment is carried out in a flow reactor, the hydrogen / oil ratio at the reactor inlet (hereinafter referred to as “hydrogen / oil ratio”) is, for example, 100 to 800 Nm ³ / KL and 200 to 700 Nm ³ /. KL is preferable, and 300 to 650 Nm ³ / KL is more preferable.
When the hydrogen / oil ratio is at least the lower limit of the above range, the hydrogenation treatment reaction proceeds sufficiently. When the hydrogen / oil ratio is not more than the upper limit of the above range, the processing cost can be reduced without consuming excessive hydrogen. Further, quench hydrogen may be added according to the heat generated in the reactor.

When the hydrogenation treatment is carried out in a flow-type reactor, the liquid space velocity (LHSV) is, for example, 0.1 to 3 hr ^-1 , preferably 0.2 to 2 hr ^-1 , and 0.25 to 1 hr ^-1 . More preferred.
When the liquid space velocity is equal to or higher than the lower limit of the above range, the efficiency of the hydrogenation treatment is improved. When the liquid space velocity is not more than the upper limit of the above range, the contact time between the hydrogenation treatment catalyst and the raw material oil becomes sufficient, and the activity of the hydrogenation treatment catalyst is sufficiently exhibited.

The temperature of the catalyst layer is, for example, 300 to 420 ° C, preferably 310 to 400 ° C, and more preferably 310 to 390 ° C.
When the temperature of the catalyst layer is equal to or higher than the lower limit of the above range, the catalytic activity of the hydrogenation catalyst is improved. When the temperature of the catalyst layer is not more than the upper limit of the above range, coloring of the hydrotreated oil and shortening of the life of the hydrotreated catalyst are less likely to occur.

Examples of the reaction type include a fixed bed, a moving bed, and a fluidized bed, and the above-mentioned raw material oil may be introduced into this reactor and treated under the above-mentioned hydrogenation treatment conditions. Most commonly, the catalyst described above is maintained as a fixed bed in the above manner so that the feedstock oil passes downward through the fixed bed.

The substrate obtained by hydrogenation is distilled and separated, and the sulfur content is 15 mass ppm or less, the 10% by volume distillation temperature is 240 to 300 ° C., and the 90% by volume distillation temperature is A gas oil substrate having a calorific value of 36,000 to 37,300 J / mL at 310 to 360 ° C. is obtained.

It is preferable to use a distillation apparatus for the distillation separation. Here, the distillation apparatus is an apparatus for separating a liquid mixture by utilizing the difference in boiling point, and means an apparatus capable of separating a mixture of a liquid or a solid at normal temperature and pressure as a liquid mixture by controlling the temperature and pressure. ..

<Light oil base material>
The gas oil substrate according to the present invention has a sulfur content of 15% by mass or less, a 10% by mass distillation temperature of 240 to 300 ° C., and a 90% by mass distillation temperature of 310 to 360 ° C. It is a light oil base material having a calorific value of 36,000 to 37,300 J / mL.

The sulfur content of the light oil base material is 15% by mass or less, preferably 10% by mass or less, and more preferably 8% by mass or less. The lower the sulfur content is, the more preferable it is. Therefore, the lower limit of the sulfur content is not particularly limited, but is usually 1 mass ppm or more.

The 10% by volume distillation temperature of the light oil base material (hereinafter, also simply referred to as T10) is 240 to 300 ° C., preferably 250 to 300 ° C., more preferably 260 to 300 ° C.
When T10 is at least the lower limit of the above range, an appropriate flash point and kinematic viscosity can be maintained as light oil, the content of hydrocarbon per capacity increases, and the calorific value of the light oil base material improves. When T10 is not more than the upper limit of the above range, the wax precipitation temperature is limited, which is preferable in terms of maintaining low temperature fluidity.
The temperature of the light oil base material T90 is 310 to 360 ° C, preferably 320 to 360 ° C, and more preferably 330 to 360 ° C.
When T90 is at least the lower limit of the above range, an appropriate flash point and kinematic viscosity can be maintained as light oil, the content of hydrocarbon per capacity increases, and the calorific value of the light oil base material improves. When T90 is not more than the upper limit of the above range, it is preferable because it is possible to suppress contamination of the combustion chamber due to poor atomization at the time of fuel spraying, carbon adhesion to the nozzle, and the like.

The cetane number of the light oil base material is preferably 40 to 65, more preferably 45 to 60.
When the cetane index is within the above range, when the diesel fuel base material is used for the diesel engine, the startability at low temperature of the diesel engine is improved and the emission of CO and the like from the engine can be suppressed.
The cetane index means a value measured according to ASTM D613-84.

The cloud point of the light oil base material is preferably −10 to 6 ° C, more preferably −10 to 5 ° C.
When the cloud point is within the above range, the low temperature startability and low temperature operability of the diesel engine are improved when the light oil base material is used for the diesel engine.
The cloud point means a value measured in accordance with JIS K2269 "Pour point of crude oil and petroleum products and cloud point test method of petroleum products".

The pour point of the light oil base material is preferably −15 to 7.5 ° C, more preferably −15 to 5 ° C.
When the pour point is within the above range, it is possible to prevent the filter from clogging during low temperature operation when the diesel fuel base material is used in the diesel engine.
The pour point means a value measured in accordance with JIS K2269 "Pour point of crude oil and petroleum products and cloud point test method of petroleum products".

The content of the aromatic hydrocarbon of the light oil base material is preferably 11 to 30% by mass, more preferably 13 to 30% by mass. When the content of the aromatic hydrocarbon is at least the above lower limit value, the density becomes high and the calorific value can be increased. Further, when the content of aromatic hydrocarbons is not more than the above upper limit value, the amount of CO and the like emitted from the engine can be suppressed.

The calorific value of the light oil base material is 36,000 to 37,300 J / mL, preferably 36,300 to 37,100 J / mL, more preferably 36,500 to 37,000 J / mL, and 36,600 to 37. 000 J / mL is more preferable.
When the calorific value is not less than the lower limit of the above range, the fuel efficiency is improved when the diesel fuel is used as the light oil base material.
The calorific value means a value measured in accordance with JIS K2279 "Crude oil and petroleum products-calorific value test method and estimation method by calculation".

The density of the light oil substrate at 15 ° C. is preferably 0.82 to 0.875 g / mL, more preferably 0.83 to 0.87 g / mL. When the density at 15 ° C. is equal to or higher than the lower limit of the above range, the content of hydrocarbons per capacity increases, and the calorific value of the light oil substrate is improved.

The light oil base material of the present embodiment can be used as it is as a light oil product, but it may be used as a light oil base material for preparing a light oil product by mixing with other base materials.
Examples of other gas oil base materials mixed with the gas oil base material of the present embodiment include kerosene produced by refining crude oil, synthetic gas oil produced by Fischer-Tropsch synthesis, hydrolyzed gas oil, and the like. Is mentioned as. Further, vegetable oil methyl ester, ethers and the like may be blended as other light oil base materials. When the light oil base material obtained in the present embodiment is mixed with another light oil base material to produce a product light oil, the blending ratio can be appropriately selected so as to obtain the desired quality light oil. The blending ratio of the light oil base material is preferably 40% by mass or less, particularly preferably 30% by mass or less.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

The properties of the feedstock oil and the light oil base material were determined according to the following method.
[Density at 15 ° C]
Measurements were made in accordance with JIS K 2249 "Density test method for crude oil and petroleum products and density / mass / capacity conversion table".
[Sulfur content]
Measured according to JIS K 2541 "Crude oil and petroleum products-Sulfur content test method".
[Contents of aromatic hydrocarbons]
Measurements were made according to IP 548 "Determination of aromatic hydrocarbon types in middle distillates --High performance liquid chromatography method with refractive index detection".
[10% by volume distillation temperature, 50% by volume distillation temperature, 90% by volume distillation temperature]
Measurement was performed in accordance with JIS K2254 "Petroleum products-Distillation test method-Atmospheric distillation test method".
[Nitrogen]
Measured according to JIS K 2609 "Crude oil and petroleum products-Nitrogen content test method".
[Cetane index]
Measured according to ASTM D613-84.
[Cloud point and pour point]
The measurement was performed in accordance with JIS K2269 "Pour point test method for crude oil and petroleum products and cloud point test method for petroleum products".
[Calorific value]
Measurements were made in accordance with JIS K2279 "Crude oil and petroleum products-calorific value test method and calculation estimation method". The amount of water required to calculate the calorific value was measured according to JIS K2275, and the amount of ash was measured according to JIS K2272. The water content and ash content of the light oil base materials of Examples 1 to 8 and Comparative Examples 1 and 2 described later were 0% by mass.

Pyrolytic gas oil (LCGO), catalytic cracking gas oil (LCO), gas oil obtained by hydrogenation of pyrolysis gas oil (DS-LHCGO), and direct distillate gas oil (LGO) were prepared. Density of LCGO, LCO, DS-LHCGO, and LGO used at 15 ° C, sulfur content, nitrogen content, aromatic hydrocarbon content, T10, 50% by volume distillation temperature (hereinafter, simply (Also referred to as T50) and T90 are shown in Tables 1 to 4. Further, the oils were blended in the ratios shown in Table 5 to obtain raw material oils. Table 5 shows the densities of the feedstocks of Formulations 1 to 10 at 15 ° C., sulfur content, nitrogen content, aromatic hydrocarbon content, T10, T50, and T90.

(Hydrogenation catalyst)
A molybdenum nickel-based catalyst was used as the hydrogenation treatment catalyst.

Example 1
The raw material oil of Formulation 1 was hydrogenated at hydrogen / oil ratio: 400 Nm ³ / KL, hydrogen partial pressure: 14.2 MPa, liquid space velocity (LHSV): 0.54 hr ^-1 , reaction temperature: 340 ° C, and then fractionated. A light oil base material was obtained by distillation. Properties of the obtained gas oil base material (density at 15 ° C, sulfur content, nitrogen content, aromatic hydrocarbon content, T10, T50, T90, pour point, cloud point, cetan index, heat generation Amount) is shown in Table 6.

Example 2
The raw material oil of Formulation 2 is hydrogenated at hydrogen / oil ratio: 490 Nm ³ / KL, hydrogen partial pressure: 14.0 MPa, liquid space velocity (LHSV): 0.52 hr ^-1 , reaction temperature: 339 ° C., and then fractionated. A light oil base material was obtained by distillation. Table 6 shows the properties of the obtained gas oil base material.

Example 3
The raw material oil of Formulation 3 was hydrogenated at hydrogen / oil ratio: 410 Nm ³ / KL, hydrogen partial pressure: 14.2 MPa, liquid space velocity (LHSV): 0.49 hr ^-1 , reaction temperature: 337 ° C., and then fractionated. A light oil base material was obtained by distillation. Table 6 shows the properties of the obtained gas oil base material.

Example 4
The raw material oil of Formulation 4 is hydrogenated at hydrogen / oil ratio: 630 Nm ³ / KL, hydrogen partial pressure: 13.4 MPa, liquid space velocity (LHSV): 0.32 hr ^-1 , reaction temperature: 334 ° C., and then fractionated. A light oil base material was obtained by distillation. Table 6 shows the properties of the obtained gas oil base material.

Example 5
The raw material oil of Formulation 5 is hydrogenated at hydrogen / oil ratio: 520 Nm ³ / KL, hydrogen partial pressure: 14.0 MPa, liquid space velocity (LHSV): 0.39 hr ^-1 , reaction temperature: 334 ° C., and then fractionated. A light oil base material was obtained by distillation. Table 6 shows the properties of the obtained gas oil base material.

Example 6
The raw material oil of Formulation 6 was hydrogenated at hydrogen / oil ratio: 480 Nm ³ / KL, hydrogen partial pressure: 14.0 MPa, liquid space velocity (LHSV): 0.42 hr ^-1 , reaction temperature: 341 ° C., and then fractionated. A light oil base material was obtained by distillation. Table 6 shows the properties of the obtained gas oil base material.

Example 7
The raw material oil of Formulation 7 was hydrogenated at hydrogen / oil ratio: 570 Nm ³ / KL, hydrogen partial pressure: 13.5 MPa, liquid space velocity (LHSV): 0.37 hr ^-1 , reaction temperature: 342 ° C, and then fractionated. A light oil base material was obtained by distillation. Table 6 shows the properties of the obtained gas oil base material.

Example 8
The raw material oil of Formulation 8 is hydrogenated at hydrogen / oil ratio: 630 Nm ³ / KL, hydrogen partial pressure: 13.8 MPa, liquid space velocity (LHSV): 0.31 hr ^-1 , reaction temperature: 334 ° C., and then fractionated. A light oil base material was obtained by distillation. Table 6 shows the properties of the obtained gas oil base material.

Comparative Example 1
The raw material oil of Formulation 9 is hydrogenated at hydrogen / oil ratio: 510 Nm ³ / KL, hydrogen partial pressure: 13.9 MPa, liquid space velocity (LHSV): 0.40 hr ^-1 , reaction temperature: 336 ° C, and then fractionated. A light oil base material was obtained by distillation. Table 6 shows the properties of the obtained gas oil base material.

Comparative Example 2
The raw material oil of formulation 10 is hydrogenated at hydrogen / oil ratio: 610 Nm ³ / KL, hydrogen partial pressure: 12.8 MPa, liquid space velocity (LHSV): 0.33 hr ^-1 , reaction temperature: 335 ° C, and then fractionated. A light oil base material was obtained by distillation. Table 6 shows the properties of the obtained gas oil base material.

As shown in Table 6, it was found that the gas oil base material produced by the production method of the present invention had a very high calorific value.

Claims (2)

90% by volume distillation temperature is 320 to 360 ° C., raw material oil containing 37 to 65% by mass of aromatic hydrocarbons, hydrogen partial pressure 10 to 18 MPa , hydrogen / oil ratio 100 to 800 Nm ³ / KL, liquid space velocity. Production of a light oil base material including a step of performing a hydrogenation treatment at a temperature of 0.1 to 3 hr ^-1 and a catalyst layer temperature of 300 to 420 ° C. , and a step of distilling and separating the base material obtained by the hydrogenation treatment. It ’s a method ,
The raw material oil is at least one selected from the group consisting of pyrolyzed gas oil (LCGO), catalytically cracked gas oil (LCO), and light oil obtained by hydrogenating pyrolyzed gas oil (DS-LHCGO). Contains seed substrate,
The total content of LCGO and LCO with respect to the total volume of the raw material oil is 30 to 100% by volume.
The gas oil base material has a sulfur content of 15% by mass or less, a 10% by mass distillation temperature of 240 to 300 ° C., a 90% by mass distillation temperature of 310 to 360 ° C., and a calorific value. A method for producing a light oil base material having a temperature of 36,000 to 37,300 J / mL. The method for producing a gas oil base material according to claim 1, wherein the raw material oil contains the LCGO, the LCO, and the DS-LHCGO.

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