KR20150063492A - Method for producing lubricant base oil and lubricant base oil - Google Patents

Abstract

Provided is a method for producing a base oil for a lubricating oil capable of producing a base oil for a lubricating oil having a high viscosity index with a high yield. One aspect of the method for producing a base oil for a lubricating oil according to the present invention is a process for hydrogenating a hydrocarbon-derived hydrocarbon oil at a reaction temperature of 250 to 420 DEG C in an atmosphere having a partial pressure of hydrogen of 11 to 20 MPa to obtain a base oil having a content of aromatic hydrocarbons of 10 By mass to 25% by mass, and a step of performing hydrogenation isomerization of the to-be-treated oil.

Description

METHOD FOR PRODUCING LUBRICANT BASE OIL AND LUBRICANT BASE OIL BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a process for producing a base oil for a lubricating oil and a base oil for a lubricating oil.

In the production of a base oil for a lubricating oil made of petroleum as a raw material, for example, a vacuum distillation step, a solvent extraction step, a hydrodesulfurization step, an isomerization desorption step (hydrogenation isomerization step), a hydrogenation finishing step, Conduct. The hydrocarbon oil such as reduced pressure diesel oil obtained by the reduced pressure distillation contains aromatic hydrocarbons that impair the oxidation stability of the base oil for lubricating oil. The aromatic hydrocarbon is extracted with a solvent such as furfural to remove it from the hydrocarbon flow path. In the hydrodesulfurization, sulfur, which is the catalyst poison of the catalyst for isomerization and desorption, is removed from the hydrocarbon flow path. By isomerization dewaxing, the wax component (normal paraffin) in the hydrocarbon oil is converted to isoparaffin or the like to improve the low-temperature fluidity of the hydrocarbon oil. The hydrogenation finish improves the color quality of the hydrocarbon oil, oxidation stability, and the like (see, for example, Patent Document 1 below).

Japanese Patent Publication No. 2001-525861

The present invention has been made in view of the above problems of the prior art, and an object of the present invention is to provide a process for producing a base oil for a lubricating oil capable of producing a base oil for a lubricating oil having a high viscosity index at a high yield and a process for producing a base oil for a lubricating oil, The purpose is to provide.

One aspect of the method for producing a base oil for a lubricating oil according to the present invention is a process for hydrogenating a hydrocarbon-derived hydrocarbon oil at a reaction temperature of 250 to 420 DEG C in an atmosphere having a partial pressure of hydrogen of 11 to 20 MPa to obtain a base oil having a content of aromatic hydrocarbons of 10 To 25% by mass, and a step of performing hydrogenation isomerization of the to-be-treated oil.

In one aspect of the present invention, it is preferable to carry out the hydrogenation isomerization of the crude oil to be treated in an atmosphere having a hydrogen partial pressure of 11 to 20 MPa.

In one aspect of the present invention, it is preferable to carry out the hydrogenation isomerization of the treated product at a reaction temperature of 200 to 450 ° C.

One form of base oil for a lubricating oil according to the present invention is produced by the above production method.

According to the present invention, there is provided a process for producing a base oil for a lubricating oil capable of producing a base oil for a lubricating oil having a high viscosity index at a high yield and a base oil for a lubricating oil obtained by the production process.

Hereinafter, preferred embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments.

In the method for producing a base oil for lubricating oil according to this embodiment, a vacuum distillation step, a solvent extraction step, a hydrogenation step, an isomerization step (hydrogenation isomerization step), a hydrogenation finishing step and a purification step are carried out in this order. However, in the case of producing a lubricating base oil having a kinematic viscosity at 100 DEG C of 1.5 to 3.0 mm < 2 > / s and a base oil for a lubricating oil having a kinematic viscosity at 3.0 DEG C of 5.5 to 5.5 mm2 / s, After the process, the hydrodesulfurization process and the hydrogenation isomerization process may be carried out. In the case of producing a lubricating base oil having a kinematic viscosity at 100 ° C of 15.0 to 40.0 mm 2 / s, it is also possible to carry out an atmospheric distillation step, a vacuum distillation step, a solvent deasphalting step, a solvent extraction step, a hydrogenation step, ), A hydrogenation finishing step and a purification step may be carried out in this order.

(Reduced pressure distillation step)

In the vacuum distillation step, a petroleum-derived hydrocarbon oil (hereinafter referred to as " hydrocarbon oil ") such as vacuum gas oil (VGO) is obtained by distillation under reduced pressure of a petroleum raw oil such as an atmospheric residue do.

(Solvent extraction process)

In the solvent extraction step, a part of the aromatic hydrocarbons in the hydrocarbon oil is extracted into the solvent and removed using the extraction tower. By the solvent extraction step, the hue, viscosity index and oxidation stability of the base oil for lubricating oil can be improved. The solvent is not particularly limited as long as it selectively dissolves components to be extracted (components to be extracted), solubility of a component to be extracted is high, separation from a component to be extracted is easy, and toxicity and corrosiveness are low. Specific examples of the solvent include furfural, phenol, N-methyl-2-pyrrolidinone, and tetrahydrofuran. Of these solvents, furfural is preferably used for extraction of aromatic hydrocarbons. The operation conditions of the extraction column using furfural are controlled by the ratio of the solvent (the volume of the solvent when the volume of the hydrocarbon oil is 100) and the extraction temperature. The volume ratio of the solvent may be about 100 to 400, and the extraction temperature may be about 30 to 150 占 폚.

(Solvent deasphalting process)

In the solvent deasphalting process, the asphalt component (minute) in the residue (decompression residue) from the reduced pressure distillation column is removed. By a solvent deasphalting process, a heavy oil fraction and an asphalt oil fraction suitable for a high viscosity lubricant oil are separated to prepare a lubricant oil raw material. A general solvent deasphalting method is a propane deasphalting process (PDA). In the PDA method, the raw oil is supplied to the upper portion of the deasphalting tower, and the propane (liquid) of the solvent is supplied to the lower portion of the deasphalting tower. Since there is a specific gravity difference between the feed oil and propane, the light propane rises in the tower while absorbing the oil suitable for the lubricating oil, and the asphalt powder which is not absorbed by the propane falls. In the deasphalting tower, a raw material oil and propane are mixed using an obstruction plate or a rotary disk to efficiently perform deasphalting. In the solvent deasphalting step, the molar ratio (ratio of propane to the raw oil) is 300 to 600%, and the temperature of the extraction column is about 50 to 85 ° C. From the upper part of the deasphalting tower, deasphalted oil absorbed in propane (suitable for high viscosity lubricating oil) is extracted, and asphalt is extracted from the bottom of the deasphalting tower. By separating propane from each of the deasphalted oil and the asphalt extracted from the extraction tower in the solvent absorption system, the desired deasphalted oil and asphalt are produced.

(Hydrogenation treatment step)

≪ Properties of Hydrocarbon < RTI ID = 0.0 >

In the hydrotreating step, the hydrotreating of hydrocarbon oils having different properties is carried out according to the standard of the base oil for the lubricating oil. A hydrocarbon oil having a desired property can be prepared by selecting a petroleum-based raw material oil, a reduced pressure distillation process, or a solvent extraction process.

The base oils for lubricants conforming to the Group II standards set by the American Petroleum Institute (API) are as follows. Of the base oils for lubricating oils meeting this specification, for example, the lubricating base oils having the properties of the following lubricating base oil fractions 1 to 5 can be produced by this embodiment.

[Classification of base oils by API (Group II)]

Viscosity Index (VI): 80 or more and less than 120

Saturated content: 90% by mass or more

Content of sulfur: 0.03 mass% or less

Further, VI means Viscosity Index.

<< Lubricating oil 1 >>

The kinematic viscosity at 100 캜 of the lubricating oil fraction 1 is 1.5 to 3.0 mm 2 / s, preferably 2.0 to 3.0 mm 2 / s. Further, the viscosity index (VI) of the lubricating oil fraction 1 is preferably 90 or more, more preferably 95 or more, and particularly preferably 100 or more. The pour point of the lubricating oil fraction 1 is preferably -10.0 ° C or lower, more preferably -15.0 ° C or lower. The boiling point range of the lubricating oil fraction 1 is preferably 330 to 390 ° C.

<< Lubricating oil 2 >>

The kinematic viscosity at 100 캜 of lubricating oil fraction 2 is 3.0 to 5.5 mm 2 / s, preferably 3.5 to 5.0 mm 2 / s. The viscosity index (VI) of the lubricating oil fraction 2 is preferably 90 or more, and more preferably 100 or more. The pour point of the lubricating oil fraction 2 is preferably -5.0 DEG C or lower, more preferably -10.0 DEG C or lower. The boiling point range of the lubricating oil fraction 2 is preferably 390 to 450 ° C. Lubricating oil 2 can meet the viscosity specification of SAE-10 oil fraction of engine oil as stipulated by the Society of Automotive Engineers SAE (SAE).

<< Lubricating oil 3 >>

The kinematic viscosity at 100 占 폚 of the lubricating oil fraction 3 is 5.5 to 9.0 mm2 / s, preferably 6.0 to 8.5 mm2 / s. The viscosity index VI of the lubricating oil fraction 3 is preferably 90 or more, and more preferably 100 or more. The pour point of the lubricating oil fraction 3 is preferably -5.0 DEG C or lower, more preferably -10.0 DEG C or lower. The boiling point range of the lubricating oil fraction 3 is preferably 450 to 480 캜. Lubricating oil fraction 3 can meet the SAE-20 oil viscosity specification, which is engine-driven, as stipulated by SAE.

<< Lubricating oil 4 >>

The kinematic viscosity at 100 캜 of lubricating oil fraction 4 is 9.0 to 15.0 mm 2 / s, preferably 9.5 to 13.0 mm 2 / s. Further, the viscosity index (VI) of the lubricating oil fraction 4 is preferably 90 or more, more preferably 100 or more. The pour point of the lubricating oil fraction 4 is preferably -5.0 DEG C or lower, more preferably -10.0 DEG C or lower. The boiling point range of the lubricating oil fraction 4 is preferably 480 to 550 ° C. Lube oil 4 can meet the SAE-30 oil viscosity specification, which is the engine lubricant specified by SAE.

<< Lubricating oil 5 >>

The kinematic viscosity of the lubricating oil fraction 5 at 100 캜 is 15.0 to 40.0 mm 2 / s, preferably 20.0 to 35.0 mm 2 / s. Further, the viscosity index (VI) of the lubricating oil fraction 5 is preferably 90 or more, and more preferably 100 or more. The pour point is preferably -5.0 DEG C or lower, more preferably -10.0 DEG C or lower. The boiling point range is preferably 550 DEG C or higher.

(Hydrogenation treatment step)

In the present embodiment, it is preferable to carry out hydrogenation treatment of hydrocarbon oil having a boiling point range of 310 to 680 DEG C, and more preferably to carry out hydrogenation treatment of hydrocarbon oil having a boiling point range of 320 to 650 DEG C.

For example, in the case of producing a lubricating base oil corresponding to lubricating oil fractions 1 to 5, it is more preferable to carry out hydrogenation treatment of hydrocarbon oils having the following characteristics.

In the case of producing a base oil for lubricating oil of lubricating oil fraction 1, it is preferable to perform hydrogenation treatment of hydrocarbon oil having the following characteristics.

Boiling range: 310 to 490 캜, preferably 320 to 480 캜.

10% distillation temperature (T10): 345 to 385 &lt; 0 &gt; C.

90% outflow temperature (T 90): 415 to 455 ° C.

Viscosity at 100 캜 (Vis): 1.5 to 4.0 mm 2 / s.

Viscosity Index (VI): 50 to 130.

In the case of producing a base oil for lubricating oil of lubricating oil fraction 2, it is preferable to perform hydrogenation treatment of hydrocarbon oil having the following characteristics.

Boiling range: 320 to 490 캜, preferably 330 to 480 캜.

10% outflow temperature (T10): 365 to 405 占 폚.

90% outflow temperature (T 90): 445 to 475 ° C.

Viscosity at 100 캜 (Vis): 3.0 to 6.5 mm 2 / s.

Viscosity Index (VI): 50 to 130.

In the case of producing a base oil for lubricating oil of lubricating oil fraction 3, it is preferable to carry out the hydrogenation treatment of hydrocarbon oil having the following characteristics.

Boiling range: 340 to 530 캜, preferably 350 to 520 캜.

10% outflow temperature (T10): 410 to 450 占 폚.

90% outflow temperature (T 90): 475 to 505 ° C.

Viscosity at 100 캜 (Vis): 5.5 to 10.0 mm 2 / s.

Viscosity Index (VI): 50 to 130.

In the case of producing a base oil for lubricating oil of lubricating oil fraction 4, it is preferable to perform hydrogenation treatment of hydrocarbon oil having the following characteristics.

Boiling range: 360 to 600 占 폚, preferably 370 to 590 占 폚.

10% outflow temperature (T10): 435 to 475 &lt; 0 &gt; C.

90% outflow temperature (T90): 545 to 575 &lt; 0 &gt; C.

Viscosity at 100 캜 (Vis): 5.0 to 10.0 mm 2 / s.

Viscosity Index (VI): 50 to 130.

In the case of producing a base oil for a lubricating oil of lubricating oil fraction 5, it is preferable to perform the hydrogenation treatment of the hydrocarbon oil having the following characteristics.

Boiling range: 380 to 680 캜, preferably 390 to 650 캜.

10% outflow temperature (T10): 515 to 545 &lt; 0 &gt; C.

90% outflow temperature (T90): 625 to 645 &lt; 0 &gt; C.

Viscosity at 100 캜 (Vis): 15.0 to 41.0 mm 2 / s.

Viscosity Index (VI): 50 to 130.

<Various Conditions of Hydrotreating Process>

In the hydrotreating step, the hydrocarbon oil is brought into contact with the hydrotreating catalyst at a reaction temperature of 250 to 420 DEG C in an atmosphere having a hydrogen partial pressure of 11 to 20 MPa. As a result, a crude oil having an aromatic hydrocarbon content of 10 to 25 mass% is prepared. The content of aromatic hydrocarbons in the treated oil is preferably 10.0 to 18.0 mass%.

The main purpose of the &quot; hydrogenation treatment &quot; in the present embodiment is to adjust the content of aromatic hydrocarbons in the hydrocarbon oil to within the above range by hydrogenating the aromatic hydrocarbons. However, in the hydrotreating step, the reaction such as desulfurization and denitrification may proceed. By such a reaction, the sulfur or nitrogen component, which is a catalyst poison of the hydrogenation isomerization catalyst, is removed from the hydrocarbon flow path, and the lifetime of the hydrogenation isomerization catalyst is improved. Further, in the hydrotreating step, in addition to the hydrogenation of aromatic hydrocarbons, the hydrocracking and hydrogenation isomerization of the wax component in the hydrocarbon oil may proceed.

Naphthene is produced by hydrogenation of aromatic hydrocarbons. Naphthenes have a lower kinematic viscosity than aromatic hydrocarbons having the same number of carbon atoms. Therefore, as the content of aromatic hydrocarbons in the hydrocarbon oil (the treated oil) after the hydrogenation treatment is lowered, the content of naphthene in the oil to be treated tends to be higher, and the kinematic viscosity of the oil to be treated tends to decrease. For the same reason, the kinematic viscosity of the lubricating oil base oil finally obtained through various steps after the hydrotreating step (hydrogenation isomerization step, hydrogenation finishing step and purification step) is also lowered. For example, in the case of producing a base oil for a lubricating oil having a high kinematic viscosity such as the above lubricating oil fraction 4, a base oil for lubricating oil whose kinematic viscosity is adjusted to a value suitable for the standard is prepared by introducing light oil having a low kinematic viscosity to the final lubricating oil base oil There is a case. However, when the kinematic viscosity of the final lubricating oil base oil is low, the kinematic viscosity of the lubricating oil base oil tends to be lower than the standard value by mixing with light oil. Therefore, the lower the kinematic viscosity of the final lubricating oil base oil, the lower the amount of light oil that can be contained in the lubricating base oil oil, thereby reducing the yield of the desired base oil for the lubricating oil. In other words, the lower the content of aromatic hydrocarbons in the hydrocarbon oil (the treated oil) after the hydrogenation treatment, the lower the yield of base oil for lubricating oil having a higher kinematic viscosity.

However, in the present embodiment, since the content of aromatic hydrocarbons in the processing oil obtained after the hydrotreating process is 10 mass% or more, the above-mentioned problem is solved and a base oil for a lubricating oil having a desired high kinematic viscosity is produced at a high yield Lt; / RTI &gt;

Naphthenes produced by hydrogenation of aromatic hydrocarbons have a higher viscosity index than aromatic hydrocarbons having the same number of carbon atoms. Therefore, as the content of aromatic hydrocarbons in the hydrocarbon oil (the treating oil) after the hydrogenation treatment is increased, the content of naphthene in the treating oil is lowered and the oil to be treated VI tends to be lowered. Therefore, the higher the content of aromatic hydrocarbon in the hydrocarbon oil (the treated oil) after the hydrogenation treatment, the lower the VI of the base oil for lubricating oil finally obtained through various steps after the hydrotreating step.

However, in the present embodiment, since the content of aromatic hydrocarbons in the treated oil obtained after the hydrotreating process is 40 mass% or less, the above-mentioned problem is solved and a base oil for a lubricating oil having a desired high VI is produced at a high yield Lt; / RTI &gt; Further, since the aromatic hydrocarbon is a catalyst poison of the hydrogenation isomerization catalyst to be carried out after the hydrotreating step, the poisoning of the hydrogenation isomerization catalyst can be suppressed by making the content of aromatic hydrocarbons in the treated oil 40 mass% or less.

In the hydrotreating step, the hydrocarbon oil is brought into contact with the hydrotreating catalyst in an atmosphere having a hydrogen partial pressure of 11 to 20 MPa. The partial pressure of the hydrogen is preferably 11.1 to 19.5 MPa, more preferably 11.1 to 19 MPa.

When the hydrogen partial pressure in the hydrotreating process is excessively low, the hydrogenation reaction of the aromatic hydrocarbon hardly occurs, and the content of the aromatic hydrocarbons in the treated oil after the hydrogenation treatment tends to exceed the upper limit value. In addition, when the hydrogen partial pressure in the hydrotreating step is low, the desulfurization reaction and the denitrification reaction tend to be difficult to occur. On the other hand, when the hydrogen partial pressure is excessively high, the hydrogenation of the aromatic hydrocarbon is excessively promoted, and the content of aromatic hydrocarbons in the treated oil after the hydrogenation treatment tends to be lower than the above lower limit value.

In the hydrotreating step, the hydrocarbon oil is brought into contact with the hydrotreating catalyst at a reaction temperature of 250 to 420 ° C. The reaction temperature is preferably 260 to 420 占 폚, more preferably 270 to 410 占 폚, and particularly preferably 280 to 400 占 폚. The reaction temperature may be 300 to 365 캜 or 330 to 365 캜. On the other hand, the reaction temperature is, for example, the temperature of the catalyst layer composed of the catalyst for hydrotreating.

When the reaction temperature in the hydrotreating step is too low, the hydrogenation reaction of the aromatic hydrocarbon hardly occurs, and the content of aromatic hydrocarbons in the treated oil after the hydrogenation treatment tends to exceed the upper limit value. In addition, when the reaction temperature in the hydrotreating step is excessively low, the desulfurization reaction and the denitrification reaction tend to be difficult to occur. On the other hand, when the reaction temperature is excessively high, the hydrogenation of the aromatic hydrocarbon is excessively promoted, and the content of aromatic hydrocarbons in the treated oil after the hydrogenation treatment tends to be lower than the above lower limit value. In addition, when the reaction temperature is too high, the decomposition of the wax component into the hard component in the hydrocarbon oil proceeds excessively, and the yield of the middle oil component and the heavy component is decreased.

As described above, the kinematic viscosity and the yield of the base oil for lubricating oil are in a trade-off relationship with respect to the increase or decrease of the content of aromatic hydrocarbons in the processing oil. In the present embodiment, by using a hydrotreating step, a high-yield VI of the base oil for lubricating oil can be made compatible with the high yield of the base oil for lubricating oil by preparing a treating oil having an aromatic hydrocarbon content of 10 to 25 mass%. In the present embodiment, it is possible to manufacture a base oil for lubricating oil in which the product (VI · Y) of the viscosity index (VI) and yield (Y) is in the range of 6000 to 7500, particularly when producing the base oil for lubricating oil of SAE- It becomes. In this case, the viscosity index (VI) is preferably 100 to 150, and the yield (Y) is preferably 55 to 100% by mass.

The yield Y (unit: mass%) of the base oil for lubricating oil is defined, for example, by the following equation.

Y = (V _L / V _R ) x 100

In the above equation, V _L is the mass of the finally obtained base oil for lubricating oil. V _R is the mass of the oil to be treated obtained in the hydrotreating step and the mass of the oil to be treated before the hydrogenation isomerization step. For example, when Y is the yield of the base oil for lubricating oil of lubricating oil base oil fraction 4, V _L is the oil content of the lubricating oil base oil in the oil fraction obtained by the hydrogenation treatment step, hydrogenation isomerization step, hydrogenation finishing step and distillation step (refining step) It is the mass of the base oil of the oil 4.

The content of the aromatic hydrocarbon in the hydrocarbon oil before the hydrotreatment step is preferably 25 to 50 mass%, and more preferably 26 to 48 mass%. In this case, it is easy to adjust the content of the aromatic hydrocarbons in the treated oil obtained in the hydrotreating step to within the range of 10 to 25 mass%. The content of the aromatic hydrocarbon in the hydrocarbon oil before the hydrotreatment process is freely controlled by the selection of the petroleum raw material oil or various steps before the hydrotreatment step (for example, a solvent extraction step).

The content of the sulfur content in the treated oil obtained in the hydrotreating process is preferably 1 to 100 mass ppm, more preferably 3 to 80 mass ppm, and particularly preferably 6 to 65 mass ppm. When the content of sulfur is within the above range, the effect of the present invention becomes remarkable. When the sulfur content is within the above range, the deactivation of the hydrogenation isomerization catalyst is inhibited. When the content of sulfur is within the above range, it is easy to obtain a base oil for lubricating oil having a low sulfur content. On the other hand, the content of the sulfur content in the oil to be treated may be measured by, for example, a method prescribed in JIS K2541.

The content of sulfur in the hydrocarbon oil before the hydrotreatment step is preferably 50 to 30000 ppm by mass, and more preferably 100 to 25000 ppm by mass. In this case, it becomes easy to adjust the content of the sulfur content in the object oil obtained in the hydrotreating process to the above-mentioned numerical range. The content of the sulfur content in the hydrocarbon oil before the hydrotreating process depends on the composition of the petroleum raw material oil.

The kinetic viscosity at 100 캜 of the oil to be treated obtained in the hydrotreating step is preferably about 1.5 to 40.0 mm 2 / s, and more preferably 2.0 to 38.0 mm 2 / s. The viscosity index (VI) of the treated oil is preferably 85 to 140, more preferably 90 to 130. [ When the kinematic viscosity and viscosity index of the oil to be treated are within the above-mentioned numerical ranges, it is easy to obtain a base oil for lubricating oil having a desired kinematic viscosity and viscosity index at a high yield.

Note that the liquid hydrocarbon space velocity (LHSV) in the hydrogenation step is from 0.1 to about 4h ^-1, and preferably from 0.25 to 3h ^-1. When the LHSV is less than 0.1 h &lt; ^-1 &gt;, the throughput is low and the productivity is poor, which is not practical. On the other hand, when the LHSV exceeds 4 h ^-1 , it is necessary to increase the reaction temperature, so that the catalyst for hydrogenation treatment is liable to be deteriorated.

Hydrogen / hydrocarbon ratio in the hydrotreating process is about 100 to 2000 Nm 3 / m 3, preferably 200 to 1000 Nm 3 / m 3. When the hydrogen / oil ratio is less than 100 Nm 3 / m 3, the desulfurization activity of the catalyst for hydrotreating tends to decrease. On the other hand, when the hydrogen / oil ratio exceeds 2000 Nm 3 / m 3, the desulfurizing activity does not change much, but the operation cost increases.

In the present embodiment, in the state where the pressure in the reactor subjected to the hydrogenation treatment is adjusted to be equal to or lower than the pressure in the hydrogenation treatment after the hydrogenation treatment, more preferably, the pressure in the reactor is lowered by 1 MPa or more, It is desirable to remove gaseous substances (hydrogen sulfide, ammonia, steam, etc.) from the oil. After removal of the gaseous material, it is preferable to carry out the hydrogenation isomerization process.

On the other hand, in order to obtain the lubricating base oil fraction 1 to 5, it is preferable to carry out the hydrogenation treatment step under the following conditions.

&Lt; Condition of Hydrotreating Process in Case of Lubricating Oil Base Oil 1 >

In order to obtain a lubricating base oil fraction having a kinematic viscosity at 100 ° C of 1.5 to 3.0 mm 2 / s, a viscosity index of 90 or more, and a sulfur content of 0.03 mass% or less from the hydrocarbon oil obtained by solvent extraction of the reduced pressure diesel oil obtained in the reduced pressure distillation step, It is preferable to bring the hydrocarbon oil at a reaction temperature of 280 to 420 占 폚 into contact with the hydrotreating catalyst in an atmosphere having a hydrogen partial pressure of 11 to 20 MPa. More preferably, the partial pressure of hydrogen is 11 to 15 MPa and the reaction temperature is 280 to 400 ° C. Thus, a treating oil having an aromatic hydrocarbon content of 10 to 25 mass%, preferably 10 to 18 mass%, can be prepared. The LHSV is about 0.1 to 4 h ^-1 , preferably 0.5 to 2 h ^-1 . Hydrogen / hydrocarbon ratio in the hydrotreating process is about 100 to 2000 Nm 3 / m 3, preferably 200 to 1000 Nm 3 / m 3.

A lubricating base oil fraction having a kinematic viscosity at 100 ° C of 1.5 to 3.0 mm 2 / s, a viscosity index of 90 or more, and a sulfur content of 0.03% by mass or less was obtained from hydrocarbon oils obtained by solvent extraction of reduced pressure light oil obtained in the vacuum distillation step without performing the solvent extraction step It is preferable that the hydrocarbon oil is brought into contact with the hydrotreating catalyst at a reaction temperature of 280 to 420 占 폚 in an atmosphere having a hydrogen partial pressure of 11 to 20 MPa in the hydrotreating step. More preferably, the hydrogen partial pressure is 15 to 18 MPa and the reaction temperature is 280 to 400 ° C. Thus, a treating oil having an aromatic hydrocarbon content of 10 to 25 mass%, preferably 10 to 18 mass%, can be prepared. The LHSV is about 0.1 to 4 h ^-1 , preferably 0.5 to 2 h ^-1 . Hydrogen / hydrocarbon ratio in the hydrotreating process is about 100 to 2000 Nm 3 / m 3, preferably 200 to 1000 Nm 3 / m 3.

&Lt; Condition of Hydrotreating Process in Case of Lubricating Oil Base Oil 2 >

When obtaining a lubricating base oil fraction having a kinematic viscosity at 100 DEG C of 3.0 to 5.5 mm &lt; 2 &gt; / s, a viscosity index of 90 or more, and a sulfur content of 0.03 mass% or less from the hydrocarbon oil obtained by solvent extraction of the reduced pressure diesel oil obtained in the distillation step, In the atmosphere having a partial pressure of 11 to 20 MPa, the hydrocarbon oil is contacted with the catalyst for hydrotreating at a reaction temperature of 300 to 420 deg. More preferably, the hydrogen partial pressure is 11 to 15 MPa and the reaction temperature is 310 to 360 ° C. Thus, a treating oil having an aromatic hydrocarbon content of 10 to 25 mass%, preferably 10 to 18 mass%, can be prepared. The LHSV is about 0.1 to 4 h ^-1 , preferably 0.5 to 2 h ^-1 . Hydrogen / hydrocarbon ratio in the hydrotreating process is about 100 to 2000 Nm 3 / m 3, preferably 200 to 1000 Nm 3 / m 3.

In the case of obtaining a lubricating base oil fraction having a kinematic viscosity at 100 ° C of 3.0 to 5.5 mm 2 / s, a viscosity index of 90 or more and a sulfur content of 0.03 mass% or less from the hydrocarbon flow path of the reduced pressure light oil fraction obtained in the reduced pressure distillation step without performing the solvent extraction step , It is preferable to bring the hydrocarbon oil into contact with the hydrotreating catalyst at a reaction temperature of 300 to 420 占 폚 in an atmosphere having a hydrogen partial pressure of 11 to 20 MPa in the hydrotreating step. More preferably, the partial pressure of hydrogen is 15 to 18 MPa and the reaction temperature is 340 to 400 ° C. Thus, a treating oil having an aromatic hydrocarbon content of 10 to 25 mass%, preferably 10 to 18 mass%, can be prepared. The LHSV is about 0.1 to 4 h ^-1 , preferably 0.5 to 2 h ^-1 . Hydrogen / hydrocarbon ratio in the hydrotreating process is about 100 to 2000 Nm 3 / m 3, preferably 200 to 1000 Nm 3 / m 3.

&Lt; Condition of Hydrotreating Process in Case of Lubricating Oil Base Oil 3 >

In order to obtain a lubricating base oil fraction having a kinematic viscosity at 100 ° C of 5.5 to 9.0 mm 2 / s, a viscosity index of 90 or more, and a sulfur content of 0.03 mass% or less from the hydrocarbon oil obtained by solvent extraction of the reduced pressure diesel oil obtained in the reduced pressure distillation step, It is preferable that the hydrocarbon oil is brought into contact with the hydrotreating catalyst at a reaction temperature of 300 to 420 占 폚 in an atmosphere having a partial pressure of hydrogen of 11 to 20 MPa. More preferably, the hydrogen partial pressure is 11 to 15 MPa and the reaction temperature is 310 to 360 ° C. Thus, a treating oil having an aromatic hydrocarbon content of 10 to 25 mass%, preferably 10 to 18 mass%, can be prepared. LHSV is from 0.1 to about 4h ^-1, and preferably between 0.5 and 1.5h ^-1. Hydrogen / hydrocarbon ratio in the hydrotreating process is about 100 to 2000 Nm 3 / m 3, preferably 200 to 1000 Nm 3 / m 3.

&Lt; Condition of Hydrotreating Process in Case of Lube Oil Base Oil 4 >

In order to obtain a lubricating base oil fraction having a kinematic viscosity at 100 ° C of 9.0 to 15.0 mm 2 / s, a viscosity index of 90 or more, and a sulfur content of 0.03 mass% or less from the hydrocarbon oil obtained by solvent extraction of the reduced pressure diesel oil obtained in the reduced pressure distillation step, It is preferable that the hydrocarbon oil is brought into contact with the hydrotreating catalyst at a reaction temperature of 300 to 420 占 폚 in an atmosphere having a partial pressure of hydrogen of 11 to 20 MPa. More preferably, the partial pressure of hydrogen is 11 to 17 MPa and the reaction temperature is 320 to 370 ° C. Thus, a treating oil having an aromatic hydrocarbon content of 10 to 25 mass%, preferably 10 to 18 mass%, can be prepared. LHSV is from 0.1 to about 4h ^-1, and preferably between 0.5 and 1.5h ^-1. Hydrogen / hydrocarbon ratio in the hydrotreating process is about 100 to 2000 Nm 3 / m 3, preferably 200 to 1000 Nm 3 / m 3.

&Lt; Condition of Hydrotreating Process in Case of Lubricating Oil Base Oil 5 >

The reduced-pressure distillation residue obtained in the vacuum distillation step is subjected to a solvent deasphalting step and then a solvent extraction step to obtain a lubricating oil having a kinematic viscosity at 100 ° C of 15.0 to 40.0 mm 2 / s, a viscosity index of 90 or more, and a sulfur content of 0.03 mass% In order to obtain the base oil fraction, it is preferable that in the hydrotreating step, the hydrocarbon oil is brought into contact with the hydrotreating catalyst at a reaction temperature of 300 to 420 占 폚 in an atmosphere having a hydrogen partial pressure of 11 to 20 MPa. More preferably, the hydrogen partial pressure is 11 to 19 MPa and the reaction temperature is 350 to 400 ° C. Thus, a treating oil having an aromatic hydrocarbon content of 10 to 25 mass%, preferably 10 to 18 mass%, can be prepared. LHSV is from 0.1 to about 4h ^-1, and preferably between 0.5 and 1.5h ^-1. Hydrogen / hydrocarbon ratio in the hydrotreating process is about 100 to 2000 Nm 3 / m 3, preferably 200 to 1000 Nm 3 / m 3.

<Catalyst for Hydrotreating Process>

The catalyst for hydrotreating is not particularly limited. Specific examples of the catalyst for hydrotreating include a catalyst comprising a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, 9 &lt; th &gt; and 10 &lt; th &gt; elements.

As the carrier of the catalyst for hydrotreating treatment, a porous inorganic oxide comprising two or more kinds of elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium is suitably used. The carrier is generally a porous inorganic oxide containing alumina, and other carrier components include silica, zirconia, boria, titania, magnesia and the like. A preferred carrier is a composite oxide containing at least one kind selected from alumina and other constituent components, and examples thereof include silica-alumina and the like.

The raw material to be a precursor of silica, zirconia, boria, titania or magnesia as a carrier constituent component other than alumina is not particularly limited and a solution containing ordinary silicon, zirconium, boron, titanium or magnesium can be used. For example, silicic acid, water glass, silica sol and the like can be used as a raw material containing silicon. As a raw material containing titanium, titanium sulfate, titanium tetrachloride, various alkoxide salts, and the like can be used. As the raw material containing zirconium, zirconium sulfate, various alkoxide salts and the like can be used. As the raw material containing boron, boric acid and the like can be used. Magnesium nitrate and the like can be used as a raw material containing magnesium. As the raw material containing phosphorus, an alkali metal salt of phosphoric acid or phosphoric acid can be used.

It is preferable that the raw material of the carrier component other than alumina is added to the raw material (alumina) of the carrier in any one of the steps before the calcination of the carrier. For example, after the carrier component is added to the aluminum solution in advance, an aluminum hydroxide gel containing these carrier components may be prepared. The carrier component may be added to the prepared aluminum hydroxide gel. Alternatively, the carrier component may be added to commercially available alumina intermediate or boehmite powder together with water or an acidic aqueous solution, and these may be kneaded. Preferably, the carrier constituents are co-present in the step of preparing the aluminum hydroxide gel. Although the mechanisms for manifesting the effect of the carrier component other than alumina have not been elucidated, it is considered that the carrier component other than alumina forms a complex oxide state with aluminum. This is considered to be m, which affects the activity, either by increasing the surface area of the support, or by generating any interaction with the active metal.

The active metal of the catalyst for hydrotreating is preferably at least one metal selected from group VIA (IUPAC group VI) and group VIII (IUPAC group 8 to group 10), more preferably Is at least two kinds of metals selected from Groups 6 and 8 to 10. A hydrotreating catalyst containing at least one kind of metal selected from group 6 and at least one kind of metal selected from group 8 to group 10 as an active metal is also suitable. Examples of the combination of the active metals include Co-Mo, Ni-Mo, Ni-Co-Mo and Ni-W. In the hydrogenation treatment, these metals may be converted into a sulfide state and used.

As the catalyst for the hydrogenation treatment, the total area of the diffraction peak area showing the crystal structure of the anatase type titania (101) plane and the diffraction peak area showing the crystal structure of the rutile type titania (110) plane measured by X- a silica-titania-alumina support having a ¼ or less diffraction peak area showing an aluminum crystal structure attributed to the γ-alumina (400) plane, at least one kind of metal selected from Group VIA and Group VIII (B) a total pore volume (PVo) of not less than 0.30 ml / g, (c) an average pore diameter (g) of not less than 100 m 2 / g, Wherein the ratio of the pore volume (PVp) of the pore diameter (PD) ± 30% to the total pore volume (PVo) in the range of 6 to 15 nm (60 to 150 Å) Catalysts for the hydrotreating of hydrocarbon oils desirable. This catalyst is hereinafter referred to as &quot; catalyst A &quot;.

Among the above catalysts for hydrotreating, when the catalyst A is used, the hydrogenation of the hydrocarbon is easy to proceed especially at a relatively low reaction temperature in an atmosphere having a relatively high hydrogen partial pressure, so that the oil having a content of aromatic hydrocarbons of 10 to 25 mass% .

&Lt; Specific Form of Catalyst A >

Titania-silica in the catalyst A-alumina carrier, a silica, preferably 1 to 10% by mass of the carrier reference as SiO _2, and more preferably 2 to 7% by weight, particularly preferably 2 to 5% by weight . When the content of silica is less than 1% by mass, the specific surface area is lowered, and the titania particles tend to agglomerate when the carrier is baked, and the crystal structure of anatase type titania and rutile type titania measured by X- The diffraction peak area becomes large. When the content of silica is more than 10% by mass, the sharpness of the pore distribution of the obtained carrier is deteriorated, and the desired desulfurization activity may not be obtained in some cases.

The silica-titania-alumina carrier of the catalyst A contains titania in an amount of preferably 3 to 40 mass%, more preferably 15 to 35 mass%, and particularly preferably 15 to 25 mass%, based on the carrier as TiO ₂ . When the content of the titania is less than 3% by mass, the effect of addition of the titania component is small, and the desired desulfurization activity may not be obtained with the resulting catalyst. When the content of titania is more than 40% by mass, the mechanical strength of the catalyst may be lowered, and crystallization of the titania particles tends to proceed when the carrier is calcined, so that the specific surface area is lowered and the amount of titania The desulfurization performance sufficient for the following cost is not exhibited.

The silica-titania-alumina carrier of the catalyst A preferably contains alumina in an amount of 50 to 96 mass%, more preferably 58 to 83 mass%, particularly preferably 70 to 83 mass%, based on the carrier as Al ₂ O ₃ , . When the content of alumina is less than 50% by mass, deterioration of the catalyst tends to increase, which is not preferable. When the alumina content is more than 96% by mass, the catalyst performance tends to be lowered, which is not preferable.

The catalyst A is supported on the above-mentioned silica-titania-alumina carrier with at least one metal component selected from Group VIA and Group VIII of the periodic table. Examples of the metal component of the VIA group of the periodic table include molybdenum (Mo), tungsten (W), and the like. Examples of the metal component of Group VIII of the periodic table include cobalt (Co), nickel (Ni) and the like. One of these metal components may be used alone, or two or more metal components may be used in combination. Nickel-molybdenum, nickel-molybdenum-cobalt, nickel-tungsten, cobalt-tungsten, nickel-tungsten-cobalt and the like are preferable as the combination of metals in view of catalyst performance, -Molybdenum, and nickel-molybdenum-cobalt are more preferable.

The amount of the metal component supported as the metal oxide is preferably 1 to 35 mass%, more preferably 15 to 30 mass%, based on the catalyst. In particular, the loading amount of the metal component of the periodic table VIA group as the metal oxide is preferably 10 to 30 mass%, and more preferably 13 to 24 mass%. The loading amount of the metal component of Group VIII of the Periodic Table as the metal oxide is preferably 1 to 10 mass%, more preferably 2 to 6 mass%.

When the catalyst A contains a metal component of the periodic table VIA group, it is preferable to use an acid to dissolve the metal component. As the acid, phosphoric acid and / or organic acid is preferably used. When phosphoric acid is used, phosphoric acid is preferably supported in an amount of 3 to 25 mass% (converted value as oxide of phosphorus), more preferably 10 to 15 mass%, based on 100 mass% of the metal component of the group VIA of the periodic table. If the amount is more than 25 mass%, the catalyst performance tends to be lowered, and if it is less than 3 mass%, the stability of the supported metal solution becomes poor, which is not preferable. In the case of using an organic acid, 35 to 75% by weight of an organic acid, more preferably 55 to 65% by weight of an organic acid is supported on the metal component of the periodic table VIA group. If the amount of the organic acid to be supported exceeds 75 mass% with respect to the metal component of the VIA group of the periodic table, the viscosity of the solution containing the metal component (hereinafter also referred to as &quot; supported metal-containing solution &quot;) becomes high, Which is undesirable because the process becomes difficult. If the loading amount of the organic acid is less than 35 mass%, the stability of the supported metal-containing solution is deteriorated, and the catalyst performance tends to be lowered.

The method for supporting and containing the metal component, phosphorus and / or organic acid on the carrier is not particularly limited. Known methods such as an impregnation method (equilibrium adsorption method, forefilling method, initial wetting method) and ion exchange method using a compound containing the metal component or a compound containing phosphorus and / or an organic acid may be used. Here, the impregnation method refers to a method in which a carrier is impregnated with a solution containing an active metal, followed by drying and firing. In the impregnation method, it is preferable to simultaneously carry the metal component of the VIA group of the periodic table and the metal component of the periodic table VIII group. If the metals are individually supported, the desulfurization activity or the denitrification activity may become insufficient. When the impregnation is carried out by the impregnation method, the dispersibility of the metal component of the VIA group of the periodic table on the support becomes high, and the obtained catalyst becomes higher in desulfurization activity and denitrification activity. Therefore, impregnation is carried out in the presence of an acid, preferably in the presence of a phosphoric acid or an organic acid. At this time, it is preferable to add 3 to 25 mass% of phosphoric acid or 35 to 75 mass% of organic acid to 100 mass% of the metal component of the VIA group of the periodic table. As the organic acid, a carboxylic acid compound is preferable, and specific examples thereof include citric acid, malic acid, tartaric acid, gluconic acid and the like.

The specific surface area of the catalyst A measured by the BET method is 150 m2 / g or more. More preferably, the specific surface area of the catalyst A is at least 170 m2 / g. If the specific surface area is less than 150 m &lt; 2 &gt; / g, the active site of the desulfurization reaction is reduced and the desulfurization performance may be lowered. On the other hand, if the specific surface area exceeds 250 m &lt; 2 &gt; / g, the mechanical strength of the catalyst tends to be lowered. Therefore, the specific surface area is preferably 250 m & The specific surface area of the catalyst A is calculated in the following manner. First, pretreatment for removing moisture adsorbed on the catalyst A is performed. In the pretreatment, for example, the interior of the closed container in which the catalyst A is placed is heated while the inside of the container is evacuated, so that the catalyst A is maintained in a vacuum of 300 캜 for 5 hours. The adsorption / desorption isotherm of the gas in the catalyst A after the pretreatment is automatically measured by the constant capacity method. As the gas, nitrogen may be used. The temperature of the nitrogen may be the liquid nitrogen temperature (-196 DEG C). As the measuring apparatus, BELSORP-max manufactured by Nippon Bell Co., Ltd. may be used. For the analysis of the measurement data, the analysis software (BELMaster ^TM ) attached to the apparatus may be used. The adsorption / desorption isotherm of the measured nitrogen is automatically analyzed by the equation of BET, and the surface area per unit mass of the catalyst A (m 2 / g) is calculated.

The total pore volume (PVo) of the catalyst A measured by the mercury infiltration method (contact angle of mercury: 135 degrees, surface tension: 480 dyn / cm) is 0.30 ml / g or more. Preferably, the PVo is 0.35 ml / g or more. On the other hand, when the total pore volume (PVo) exceeds 0.60 ml / g, the catalyst strength tends to decrease. Therefore, PVo is preferably 0.60 ml / g or less, more preferably 0.50 ml / g or less.

Catalyst A has an average pore diameter (PD) of 6 to 15 nm (60 to 150 ANGSTROM). Preferably, the PD is 6.5 to 11 nm. When the average pore diameter (PD) is less than 6 nm, the reactivity with the raw oil may deteriorate because of small pores. In addition, a catalyst having a PD exceeding 15 nm is difficult to produce, and the specific surface area of the catalyst becomes small, and the catalyst performance tends to deteriorate. On the other hand, the total pore volume (PVo) represents pores having a pore diameter of 4.1 nm (41 ANGSTROM) or more, which is the measurement limit of measurement, and the average pore diameter (PD) is a pore diameter .

In the catalyst A, the ratio (PVp / PVo) to the total pore volume (PVo) of the pore volume (PVp) having the pore diameter of the average pore diameter (PD) ± 30% is 70% or more. Its pore distribution is sharp. PVp / PVo is preferably 80% or more. When the PVp / PVo is less than 70%, the pore distribution of the catalyst becomes broad and the desired desulfurization performance may not be obtained in some cases.

In the carrier of the catalyst A, the "titania diffraction peak area" measured by X-ray diffraction analysis is preferably 1/4 or less, preferably 1/5 or less, more preferably 1/6 or less of the "alumina diffraction peak area" More preferable. The "titania diffraction peak area" is the total area of the diffraction peak area showing the crystal structure of the anatase-type titania (101) plane and the diffraction peak area showing the crystal structure of the rutile-type titania (110) plane. The "alumina diffraction peak area" is a diffraction peak area showing an aluminum crystal structure attributed to the γ-alumina (400) plane. When the ratio of the titania diffraction peak area to the alumina diffraction peak area (titania diffraction peak area / alumina diffraction peak area) is larger than 1/4, the crystallization of titania proceeds and the pores effective for the reaction are reduced. The desulfurization performance sufficient for the cost accompanying the increase of the titania amount is not exhibited. On the other hand, RINT2500 manufactured by Rigaku Corporation may be used as a measuring apparatus for X-ray diffraction analysis. A Cu-K? Line (50 kV, 200 mA) may be used as the source of the electric power.

The diffraction peak showing the crystal structure of the anatase type titania (101) plane was measured at 2? = 25.5 占. The diffraction peak showing the crystal structure of the rutile type titania (110) plane is measured at 2? = 27.5 占. Further, the diffraction peak indicating the aluminum crystal structure attributed to the? -Alumina (400) plane was measured at 2? = 45.9 占. In the calculation method of each diffraction peak area, a graph obtained by X-ray diffraction analysis by an X-ray diffraction apparatus is fitted by a least squares method to perform a base line correction. Then, the height from the maximum peak value of the graph to the base line (peak intensity W) is obtained. And the peak width (half width) at a half value (W / 2) of the obtained peak intensity is obtained. The product of half width and peak intensity is the diffraction peak area. From the obtained diffraction peak areas, the &quot; titania diffraction peak area / alumina diffraction peak area &quot; is calculated.

Catalyst A is prepared by the following method. The method for producing the catalyst A is a method in which a mixed aqueous solution of a titanium salt of a mineral acid and an acidic aluminum salt (hereinafter, simply referred to as a "mixed aqueous solution") and an aqueous solution of a basic aluminum salt are mixed to a pH of 6.5 to 9.5 A second step of obtaining a carrier by sequentially carrying out washing, molding, drying, and firing of the hydrate; and a second step of obtaining a carrier, wherein the carrier is a carrier of a VIA group (IUPAC group 6) And at least one metal component selected from Group VIII (IUPAC Group 8 to Group 10). Hereinafter, each step will be described.

[First Step]

(Acidic aqueous solution) and a basic aluminum salt aqueous solution (alkaline aqueous solution) at a pH of 6.5 to 9.5, preferably 6.5 to 8.5, more preferably 6.5 to 8.5, in the presence of a silicate ion, 6.5 to 7.5, thereby obtaining a hydrate containing silica, titania and alumina.

In the first step, a basic aqueous aluminum salt solution may be added to a mixed aqueous solution containing (1) a silicate ion-containing basic aluminum salt aqueous solution and (2) a silicate ion-containing aqueous solution. In the case of (1), as the silicate ion contained in the basic aluminum salt aqueous solution, a basic or neutral one can be used. As a basic silicate ion source, a silicate compound capable of generating silicate ion in water such as sodium silicate can be used. In the case of (2), as the silicate ion contained in the mixed solution of the titanium salt of the inorganic acid and the aqueous solution of the acidic aluminum salt, an acidic or neutral one may be used. As the acidic silicate ion source, a silicate compound capable of generating silicate ion in water such as silicic acid can be used.

As the basic aluminum salt, sodium aluminate, potassium aluminate and the like are suitably used. As the acidic aluminum salt, aluminum sulfate, aluminum chloride, aluminum nitrate and the like are suitably used. Examples of the titanium salt of inorganic acid include titanium tetrachloride, titanium trichloride, titanium sulfate, titanium nitrate and the like, and titanium sulfate is suitably used because it is inexpensive.

For example, a basic aluminum salt aqueous solution containing a predetermined amount of basic silicate ion is introduced into a tank equipped with a stirrer and maintained at 40 to 90 캜, preferably 50 to 70 캜, for holding. A mixed aqueous solution of a predetermined amount of a titanium salt of an inorganic salt and an aqueous solution of an aqueous solution of an aluminum salt is heated to a temperature of ± 5 ° C, preferably ± 2 ° C, more preferably ± 1 ° C of an aqueous solution of a basic aluminum salt. The warmed mixed aqueous solution is continuously added to the aqueous basic aluminum salt solution for 5 to 20 minutes, preferably 7 to 15 minutes to form a precipitate to obtain a slurry of the hydrate. A mixed aqueous solution is added to the aqueous basic aluminum salt solution so that the pH of the slurry of the hydrate is 6.5 to 9.5, preferably 6.5 to 8.5, more preferably 6.5 to 7.5. If the addition time of the aqueous solution of the basic aluminum salt solution is prolonged, undesirable crystalline substances such as bayerite and gibbsite may be produced in addition to pseudo-boehmite. Bayerite or gibbsite is undesirable because the specific surface area decreases when fired. Therefore, the addition time is preferably 15 minutes or less, and more preferably 13 minutes or less.

[Second Step]

The slurry of the hydrate obtained in the first step is aged and then washed to remove the by-product salt to obtain a slurry of hydrate containing silica, titania and alumina. The slurry of the obtained hydrate is further subjected to heat aging, followed by heat kneading to obtain a kneadable product which can be molded. The kneaded product is formed into a desired shape by extrusion molding or the like. The molded body is usually dried at 70 to 150 ° C, preferably at 90 to 130 ° C and then calcined at 400 to 800 ° C, preferably at 450 to 600 ° C for 0.5 to 10 hours, preferably 2 to 5 hours. By these processes, a silica-titania-alumina support containing silica, titania and alumina is obtained.

[Third Step]

The carrier supporting the metal component is supported on the above-mentioned silica-titania-alumina carrier by at least one kind of metal component selected from Group VIA and Group VIII of the periodic table by the above- , Preferably 450 to 600 ° C, for 0.5 to 10 hours, preferably 2 to 5 hours. By the above process, the catalyst A is produced. As a preferable raw material for the metal component, for example, nickel nitrate, nickel carbonate, cobalt nitrate, cobalt carbonate, molybdenum trioxide, molybdic acid ammonium, paratungstic acid and the like are used.

(Hydrogenation isomerization step)

The crude oil obtained in the hydrotreating process contains normal paraffin having 10 or more carbon atoms. In the hydrogenation isomerization process, normal paraffin is partly or wholly converted to isoparaffin by the contact of the untreated oil with the hydrogenation isomerization catalyst.

On the other hand, hydrogenation isomerization refers to a reaction in which only the molecular structure of a hydrocarbon oil is changed without changing the carbon number (molecular weight) of the hydrocarbon in the processing oil. The decomposition of hydrocarbon oil refers to a reaction accompanied by a decrease in the carbon number (molecular weight) of the hydrocarbon. In the contact dewaxing reaction using a hydrogenation isomerization catalyst, not only isomerization but also decomposition reaction of the hydrocarbon oil and the isomerization product occur to some extent. There is no problem if the number of carbon atoms (molecular weight) of the product of the decomposition reaction falls within a predetermined range that can constitute the desired base oil. That is, the decomposition product may be a constituent component of the base oil.

The reaction conditions of the hydrogenation isomerization process are as follows.

In the hydrogenation isomerization step, the hydrogenation isomerization of the crude oil to be treated is preferably carried out in an atmosphere having a hydrogen partial pressure of 11 to 20 MPa. Preferably, the partial pressure of hydrogen in the hydrogenation isomerization step is 11 to 19 MPa. When the reaction pressure is at least 11 MPa, generation of coke is suppressed, and the catalyst life tends to be prolonged. When the reaction pressure is lower than 11 MPa (lower), the deterioration of the catalyst due to the formation of coke tends to be accelerated. On the other hand, when the reaction pressure exceeds 20 MPa, since the pressure resistance is required in the reaction apparatus, the cost for constructing the apparatus is increased and an economical process tends to be difficult to be realized. However, even when the partial pressure of hydrogen is out of the above range, the effect of the present invention is achieved.

The reaction temperature of the hydrogenation isomerization step is preferably 200 to 450 ° C, more preferably 260 to 400 ° C. When the reaction temperature is not lower than the lower limit, the reduction and removal of the wax component due to the isomerization of the normal paraffin contained in the processing oil are promoted. On the other hand, when the reaction temperature is lower than the upper limit value, excessive decomposition of the raw material oil is suppressed, and the yield of the desired hydrocarbon tends to be remarkably improved. However, even when the reaction temperature of the hydrogenation isomerization reaction is out of the above range, the effect of the present invention is achieved.

Note that the raw material liquid space velocity in the hydrogenation-isomerization reaction, the it is preferred from 0.1 to 10h ^-1, more preferably from 0.5 to 5h ^-1. When the liquid space velocity is above the lower limit value, excessive decomposition of the raw material oil is suppressed, and the yield of the desired base oil for lubricating oil tends to be remarkably improved. On the other hand, when the liquid space velocity is lower than or equal to the upper limit value, reduction and removal of the wax component due to isomerization of normal paraffin contained in the raw oil are promoted.

The hydrogen supply ratio (ratio of hydrogen / untreated oil) to the treated oil in the hydrogenation isomerization reaction is preferably 50 to 2000 Nm 3 / m 3, more preferably 100 to 1500 Nm 3 / m 3. Particularly preferably 200 to 800 Nm 3 / m 3. When the feed rate is less than 50 Nm 3 / m 3, hydrogen sulfide, ammonia gas, and water generated by the desulfurization, denitrification, and deoxygenation reactions associated with the isomerization reaction are adsorbed on the active metal on the catalyst to poison the catalyst. The hydrogenation of the impurities such as a small amount of olefin produced by the side reaction tends to be insufficient, and catalyst deactivation due to caulking tends to occur. On the other hand, when the supply rate exceeds 2000 Nm 3 / m 3, an economical process tends to be difficult to be realized because a hydrogen supply facility with high capability is required. However, even when the supply rate of hydrogen is out of the above range, the effect of the present invention is achieved.

The conversion rate of normal paraffins by the hydrogenation isomerization reaction is freely controlled by adjusting the reaction conditions such as the reaction temperature depending on the use of the obtained hydrocarbons.

The hydrogenation isomerization process described above promotes the isomerization (that is, desorption) of the normal paraffins while sufficiently suppressing the hardening of the normal paraffins contained in the processed oil, thereby obtaining a base oil having a high content of isomers having a branched chain Can be obtained in high yield.

&Lt; Hydrogenation isomerization catalyst &

The hydrogenation isomerization catalyst (isomerization catalyst) used in the hydrogenation isomerization step is not particularly limited, and a known catalyst may be used in the present embodiment. However, as the hydrogenation isomerization catalyst, it is preferable to use the following hydrogenation isomerization catalyst, which is characterized by being produced by a specific method. Hereinafter, the hydrogenation isomerization catalyst will be described in accordance with its preferred form of production.

The method for producing a hydrogenation isomerization catalyst of the present embodiment is a method for producing a hydrogenation isomerization catalyst in which a zeolite having a one-dimensional pore structure containing an organic template and containing a 10-membered ring (organic template-containing zeolite) is mixed with a solution containing ammonium ions and / by ion exchange from the obtained ion-exchanged zeolites, and platinum a mixture containing the ion-exchanged zeolite and a binder, in a first step, a carrier precursor at the heating temperature of N ₂ atmosphere at a temperature of 250 to 350 ℃ obtain a support precursor A catalyst precursor containing a salt and / or a palladium salt is calcined at a temperature of from 350 to 400 캜 in an atmosphere containing molecular oxygen to obtain a catalyst precursor containing a support containing zeolite and platinum and / And a second step of obtaining a hydrogenation isomerization catalyst.

The organic template-containing zeolite used in the present embodiment has a one-dimensional pore structure composed of a 10-membered ring from the viewpoint of achieving a high level of high isomerization activity and suppressed decomposition activity in the hydrogenation isomerization reaction of normal paraffin. Examples of such zeolites include AEL, EUO, FER, HEU, MEL, MFI, NES, TON, MTT, WEI, * MRE and SSZ-32. Each of the three alphabetic characters represents a skeleton structure code given by the Structure Committee of the International Zeolite Association for each structure of the classified molecular sieve type zeolite. In addition, zeolites with the same topology are collectively referred to as the same code.

Among the zeolites having the 10-membered ring one-dimensional phase structure, zeolite having a TON, MTT structure, zeolite having a * MRE structure (ZSM-48 Zeolite), and SSZ-32 zeolite are preferred. As the zeolite having the TON structure, ZSM-22 zeolite is more preferable, and as the zeolite having the MTT structure, ZSM-23 zeolite is more preferable.

The organic template-containing zeolite is obtained by hydrothermal synthesis using a silica source, an alumina source, and an organic template added as a raw material to add the desired pore structure.

The organic template is an organic compound having an amino group, an ammonium group or the like and is selected according to the structure of the zeolite to be synthesized. The organic template is preferably an amine derivative. Specifically, the organic template is selected from the group consisting of alkylamines, alkyldiamines, alkyltriamines, alkyltetramines, pyrrolidines, piperazines, aminopiperazines, alkylpentamines, alkylhexamines, and derivatives thereof More preferably at least one species.

The molar ratio ([Si] / [Al]) (hereinafter referred to as Si / Al ratio) of silicon and aluminum elements constituting the organic template-containing zeolite having a 10- And more preferably from 20 to 350. [ When the Si / Al ratio is less than 10, the activity toward conversion of normal paraffin is increased, but the isomerization selectivity to isoparaffin is lowered, and the increase in the decomposition reaction accompanying the increase in the reaction temperature tends to be abrupt I can not. On the other hand, when the Si / Al ratio exceeds 400, the catalytic activity required for conversion of normal paraffin becomes difficult to obtain, which is not preferable.

The organic template-containing zeolite synthesized, preferably washed and dried has usually an alkali metal cation as a counter cation and the organic template is contained in the pore structure. The zeolite containing the organic template used in the production of the hydrogenation isomerization catalyst according to the present embodiment is a zeolite containing such synthetic state that the sintering treatment for removing the organic template contained in the zeolite is not carried out desirable.

The organic template-containing zeolite is then ion-exchanged in a solution containing ammonium ions and / or protons. By the ion exchange treatment, the cations contained in the organic template-containing zeolite are exchanged with ammonium ions and / or protons. At the same time, a part of the organic template contained in the organic template-containing zeolite is removed.

The solution used for the ion exchange treatment is preferably a solution using a solvent containing at least 50% by volume of water, more preferably an aqueous solution. Examples of the compound for supplying the ammonium ion into the solution include various inorganic and organic ammonium salts such as ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, and ammonium acetate. On the other hand, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and the like are generally used as a compound for supplying proton into a solution. An ion-exchanged zeolite (here, ammonium type zeolite) obtained by ion-exchanging an organic template-containing zeolite in the presence of ammonium ion releases ammonia at the time of subsequent calcination, and the biantite becomes a proton and becomes a Bronsted acid point. As cationic species used for ion exchange, ammonium ion is preferable. It is preferable that the content of the ammonium ion and / or proton contained in the solution is set to be 10 to 1000 equivalents relative to the total amount of the counter anion and the organic template contained in the organic template-containing zeolite to be used.

The ion exchange treatment may be performed on a powdery organic template-containing zeolite carrier. In addition, prior to the ion exchange treatment, an inorganic oxide as a binder may be blended with the organic template-containing zeolite, and the resulting molded article may be subjected to ion exchange treatment. However, it is preferable to provide the powdery organic template-containing zeolite for the ion exchange treatment because the above-mentioned molded body is not subjected to firing and is provided for ion exchange treatment, the problem of collapsing and differentiation of the molded body tends to occur.

The ion exchange treatment is preferably carried out by a method of immersing a solution containing a ammonium ion and / or a proton, preferably a zeolite containing an organic template in an aqueous solution, and stirring or flowing the solution. In addition, the above stirring or flow is preferably carried out under heating in order to increase the efficiency of ion exchange. In the present embodiment, a method in which the aqueous solution is heated and subjected to ion exchange in boiling or reflux is particularly preferable.

It is also preferable to exchange the solution with a new one or two or more times during the ion exchange of the zeolite with the solution in order to increase the efficiency of the ion exchange and to exchange the solution once or twice with a new one desirable. When the solution is exchanged once, for example, the organic template-containing zeolite is immersed in a solution containing ammonium ions and / or protons, refluxed for 1 to 6 hours, and then the solution is exchanged for a new one, And then refluxed by heating for 6 to 12 hours again, it becomes possible to increase the ion exchange efficiency.

By virtue of the ion exchange treatment, it is possible to exchange almost all of the countercations such as alkali metals in the zeolite with ammonium ions and / or protons. On the other hand, regarding the organic template contained in the zeolite, a part of the organic template contained in the zeolite is removed by the above ion exchange treatment. However, even if the treatment is repeatedly performed, it is generally difficult to remove all of the organic template. Remains.

In the present embodiment, the mixture containing the ion-exchanged zeolite and the binder is heated at a temperature of 250 to 350 占 폚 in a nitrogen atmosphere to obtain a carrier precursor.

The mixture containing the ion-exchange zeolite and the binder is preferably formed by molding the composition obtained by mixing the ion-exchanged zeolite obtained by the above-mentioned method with the inorganic oxide as the binder. The object of blending an inorganic oxide in an ion-exchange zeolite is to improve the mechanical strength of a carrier (particularly, a particulate carrier) obtained by calcining the formed body to such an extent that it can withstand practical use. Has an effect on the isomerization selectivity of the hydrogenation isomerization catalyst. From this viewpoint, at least one kind of inorganic oxide selected from the group consisting of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide, do. Of these, silica or alumina is preferable, and alumina is more preferable in view of further improving the isomerization selectivity of the hydrogenation isomerization catalyst. The composite oxide comprising two or more of these is a composite oxide comprising at least two components selected from the group consisting of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide. A composite oxide (composite oxide comprising alumina as a main component) containing an alumina component of 50 mass% or more based on the composite oxide is preferable, and among these, alumina-silica is more preferable.

The mixing ratio of the ion-exchanged zeolite to the inorganic oxide in the composition is preferably 10:90 to 90:10, more preferably 30:70 to 85:10, as a ratio of the mass of the ion-exchanged zeolite to the mass of the inorganic oxide : 15. When the ratio is smaller than 10: 90, the activity of the hydrogenation isomerization catalyst tends to become insufficient, which is not preferable. On the other hand, when the ratio exceeds 90:10, the mechanical strength of the carrier obtained by the molding and firing of the composition tends to become insufficient, which is not preferable.

The method of compounding the above-mentioned inorganic oxide with the ion-exchange zeolite is not particularly limited. For example, it is possible to prepare a viscous fluid by adding a liquid such as an appropriate amount of water to both powders and kneading the fluid with a kneader or the like May be adopted.

The composition containing the ion-exchanged zeolite and the inorganic oxide or the viscous fluid containing the ion-exchanged zeolite is molded by a method such as extrusion molding, and is preferably dried to form a particulate molded body. The shape of the molded body is not particularly limited, and examples thereof include cylindrical, pellet-shaped, spherical, three-leaf and four-leaf-shaped cross-sectional shapes and the like. The size of the molded body is not particularly limited. It is preferable that the long axis of the molded article is 1 to 30 mm and the minor axis of the molded article is approximately 1 to 20 mm from the viewpoints of ease of handling and packing density into the reactor.

In the present embodiment, the molded article obtained as described above, by heating in N ₂ atmosphere at a temperature of 250 to 350 ℃ it is preferable that the support precursor. The heating time is preferably 0.5 to 10 hours, more preferably 1 to 5 hours.

In the present embodiment, when the heating temperature is lower than 250 ° C, a large amount of the organic template remains, and the zeolite pores are closed by the remaining template. It is considered that the isomerization active site exists in the vicinity of the pore pore mouse. In such a case, the reaction substrate is not diffused into the pores due to the pore clogging, and the active site is covered thereby making the isomerization reaction difficult. It tends to be difficult to obtain sufficiently. On the other hand, when the heating temperature exceeds 350 ° C, the isomerization selectivity of the obtained hydrogenation isomerization catalyst is not sufficiently improved.

The lower limit temperature when the formed body is heated to be a carrier precursor is preferably 280 DEG C or more. The upper limit temperature is preferably 330 DEG C or less.

In the present embodiment, it is preferable to heat the mixture so that a part of the organic template contained in the formed body remains. Concretely, the micropore volume per unit mass of the hydrogenation isomerization catalyst obtained through firing after metal-supporting described later is 0.02 to 0.12 cc / g, and the micropore volume per unit mass of the zeolite contained in the catalyst is 0.01 - It is preferable to set the heating conditions so as to be 0.11 cc / g.

Next, the catalyst precursor containing the platinum salt and / or the palladium salt in the carrier precursor is heated in an atmosphere containing molecular oxygen at 350 to 400 ° C, preferably 380 to 400 ° C, more preferably 400 ° C Temperature to obtain a hydrogenated isomerization catalyst carrying platinum and / or palladium on a carrier containing zeolite. On the other hand, "an atmosphere containing molecular oxygen" means a gas containing oxygen gas, preferably air. The baking time is preferably 0.5 to 10 hours, more preferably 1 to 5 hours.

Examples of the platinum salt include chloroplatinic acid, tetraammine dinitroplatinum, dinitroaminoplatinum, tetramethyldichloroplatinum and the like. The chloride salt is preferably a tetraammine dinitroplatinum which is a platinum salt in which platinum is highly dispersed in addition to a chloride salt because hydrochloric acid is generated during the reaction and hydrochloric acid may corrode the apparatus.

Examples of the palladium salt include palladium chloride, tetraammine palladium nitrate, diaminopalladium nitrate and the like. Tetraammine palladium nitrate, which is a palladium salt in which palladium is highly dispersed in addition to a chloride salt, is preferable because a chloride salt generates hydrochloric acid during the reaction and hydrochloric acid may corrode the apparatus.

The loading amount of the active metal in the zeolite-containing support according to the present embodiment is preferably 0.001 to 20 mass%, more preferably 0.01 to 5 mass%, based on the mass of the support. When the amount is less than 0.001 mass%, it becomes difficult to impart a predetermined hydrogenation / dehydrogenation function to the catalyst. On the other hand, when the loading amount exceeds 20 mass%, hardening due to decomposition of hydrocarbons on the active metal tends to proceed, and the yield of the intended oil tends to be lowered, resulting in an increase in catalyst cost Which is undesirable.

In addition, when the hydrogenation isomerization catalyst according to this embodiment is used for hydrogenation isomerization of a hydrocarbon oil containing a large amount of a sulfur compound and / or a nitrogen compound, in view of the persistence of the catalytic activity, the catalyst may be nickel- , Nickel-molybdenum, cobalt-molybdenum, nickel-molybdenum-cobalt, nickel-tungsten-cobalt and the like. The amount of these metals to be supported is preferably 0.001 to 50 mass%, more preferably 0.01 to 30 mass%, based on the mass of the carrier.

In the present embodiment, it is preferable that the catalyst precursor is baked so that the organic template remaining in the carrier precursor remains. Specifically, it is preferable that the hydrogenation isomerization catalyst obtained has a micropore volume per unit mass of 0.02 to 0.12 cc / g and a micropore volume per unit mass of the zeolite contained in the catalyst is 0.01 to 0.11 cc / g. It is desirable to set the conditions.

The micropore volume per unit mass of the hydrogenation isomerization catalyst is calculated by the following method called nitrogen adsorption measurement. First, pretreatment for removing water adsorbed to the hydrogenation isomerization catalyst is carried out. In the pretreatment, for example, the hydrogenation isomerization catalyst may be kept in a vacuum of 300 캜 for 5 hours by evacuating the inside of the container while heating the inside of the closed container in which the hydrogenation isomerization catalyst is disposed. The adsorption / desorption isotherm of the gas in the hydrogenation isomerization catalyst after this pretreatment is automatically measured by the constant capacity method. As the gas, nitrogen may be used. The temperature of the nitrogen may be the liquid nitrogen temperature (-196 DEG C). As the measuring apparatus, BELSORP-max manufactured by Nippon Bell Co., Ltd. may be used. For the analysis of the measurement data, the analysis software (BELMaster ^TM ) attached to the apparatus may be used. The adsorption / desorption isotherm of the measured nitrogen is automatically analyzed by the t-plot method, and the micropore volume per unit mass of the catalyst is calculated. The micropore volume per unit mass of the zeolite contained in the catalyst is also calculated by the above nitrogen adsorption measurement.

The micropore volume (V _z ) per unit mass of zeolite contained in the catalyst can be calculated, for example, by multiplying the value (V _c ) of the micropore volume per unit mass of the hydrogenation isomerization catalyst to, from the content of the zeolite (M _z) (% by mass) of the catalyst it can be calculated according to the following equation.

[Mathematical Expression]

V _z = V _c / M _z x 100

It is preferable that the hydrogenation isomerization catalyst according to the present invention is subjected to a reduction treatment following the above-mentioned firing treatment (preferably after being filled with a reactor that performs a hydrogenation isomerization reaction). Concretely, hydrogenation is carried out in an atmosphere containing molecular hydrogen (preferably, hydrogen gas flow), preferably 250 to 500 ° C (more preferably 300 to 400 ° C) for about 0.5 to 5 hours, Is subjected to a reduction treatment. By such a process, a high activity for the dewaxing of the hydrocarbon oil can be more reliably given to the catalyst.

Another embodiment of the hydrogenation isomerization catalyst comprises a support containing a zeolite having a one-dimensional pore structure containing a 10-membered ring and a binder, platinum and / or palladium supported on the support, Wherein the zeolite has a pore volume of 0.02 to 0.12 cc / g, wherein the zeolite comprises an organic template-containing zeolite containing an organic template and having a 10-membered ring one-dimensional pore structure in a solution containing an ammonium ion and / Exchanged zeolite obtained by ion exchange, and the micropore volume per unit mass of the zeolite contained in the catalyst is 0.01 to 0.11 cc / g.

The above hydrogenation isomerization catalyst can be produced by the above-mentioned method. The micropore volume per unit mass of the catalyst and the micropore volume per unit mass of the zeolite contained in the catalyst are determined by the amount of the ion-exchanged zeolite in the mixture containing the ion-exchanged zeolite and the binder, the heating conditions under the N ₂ atmosphere , And the heating conditions in an atmosphere containing the molecular oxygen of the catalyst precursor are suitably adjusted to fall within the above range.

(Hydrogenation finishing process)

In the present embodiment, the product oil obtained by the hydrogenation isomerization step may be hydrofinished. In the hydrogenation finish, the product oil is contacted with the metal-supported hydrogenation catalyst in the presence of hydrogen. As the hydrogenation catalyst, for example, alumina or silica alumina carrying platinum and / or palladium may be mentioned. The hydrogenation finish improves the hue, oxidation stability, and the like of the reaction product (product oil) obtained in the hydrogenation isomerization step (dewetting step), thereby improving the quality of the product. The hydrogenation-finishing catalyst layer may be provided on the downstream side of the catalyst layer of the hydrogenation isomerization catalyst provided in the reactor for carrying out the hydrogenation isomerization process, and the hydrogenation may be performed subsequent to the dewaxing step. The hydrogenation may be performed in a reaction facility different from the dewaxing process.

(Purification process)

In the present embodiment, the product oil obtained by the hydrogenation finishing step may be subjected to reduced pressure distillation to refine the base oil. The heavy oil fraction obtained by vacuum distillation may be further subjected to reduced pressure distillation. For example, the crude oil for the hydrogenation purification may be separated into a plurality of light oil fractions having a kinematic viscosity lower than the raw oil for the hydrogenation purification by a purification process. These base oils are mixed with light oils having a low kinematic viscosity as necessary to make the kinematic viscosity of each oil and the properties such as viscosity index (VI) conform to each standard, thereby preparing a base oil for a desired lubricating oil.

The reaction equipment for carrying out the above hydrogenation treatment step and the reaction equipment for carrying out the hydrogenation isomerization step are not particularly limited. As each facility, known ones can be used. Each facility may be of a continuous flow type, a batch type or a semi-batch type, but from the viewpoint of productivity and efficiency, it is preferable to use a continuous flow type. The catalyst layer of each facility may be a stationary phase, a fluidized bed, or a stirred phase, but is preferably a stationary phase in terms of facility cost and the like. The reaction phase is preferably vapor-liquid mixed phase.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following Examples without departing from the technical idea of the present invention.

&Lt; Production of Catalyst for Hydrotreatment >

A steam jacket mounted in the tank a capacity of 100L, into the Al ₂ O ₃ in terms of sodium aluminate aqueous solution of 8.16kg a concentration of 22% by mass of, after dilution with ion-exchanged water 41kg, the concentration of SiO ₂ in terms of 5% by weight silicic acid Sodium salt solution was added with stirring, and the mixture was heated to 60 占 폚 to prepare a basic aluminum salt aqueous solution. Further, an aqueous solution of an acidic aluminum salt in which 7.38 kg of an aqueous aluminum sulfate solution having a concentration of 7% by mass in terms of Al ₂ O ₃ was diluted with 13 kg of ion-exchanged water and 1.82 kg of titanium sulfate having a concentration of 33% by mass in terms of TiO ₂ , , And the mixture was heated to 60 占 폚 to prepare a mixed aqueous solution. A mixed aqueous solution was added to a tank containing a basic aluminum salt aqueous solution at a constant speed for 10 minutes until a pH of 7.2 was reached using a roller pump to prepare a hydrate slurry a containing silica, titania and alumina.

The hydrate slurry a was aged at 60 캜 for 1 hour while stirring, dehydrated using a flat plate filter, and further washed with 150 L of a 0.3% by mass aqueous ammonia solution. The slurry on the cake after washing was diluted with ion-exchanged water so that the concentration of Al ₂ O ₃ was 10 mass%, and the pH was adjusted to 10.5 with 15 mass% ammonia water. This was transferred to an aging tank equipped with a reflux condenser and aged at 95 DEG C for 10 hours while stirring. The aged slurry was dewatered, kneaded with a twin arm kneader equipped with a steam jacket, and kneaded to a predetermined water content. The resulting kneaded product was shaped into a cylindrical shape having a diameter of 1.8 mm by a press molding machine and dried at 110 캜. The dried molded article was fired in an electric furnace at a temperature of 550 DEG C for 3 hours to obtain a carrier a. The concentration of silica relative to the total mass of the carrier a was 3 mass% in terms of SiO ₂ . The concentration of titania with respect to the total mass of the carrier a was 20 mass% in terms of TiO ₂ . The concentration of aluminum relative to the total mass of the carrier a was 77 mass% in terms of Al ₂ O ₃ .

X-ray diffraction analysis of the carrier a was carried out using an X-ray diffraction device RINT2500 manufactured by Rigaku Corporation. Cu-K? Ray (50 kV, 200 mA) was used as the source of the water. In the X-ray diffraction pattern of the carrier a, the diffraction peak area showing the crystal structure of the anatase type titania and the rutile type titania was 1/8 of the diffraction peak area showing the crystal structure attributed to aluminum. That is, the value of (titania diffraction peak area / alumina diffraction peak area) was 1/8.

306 g of molybdenum trioxide and 68 g of cobalt carbonate were suspended in 500 ml of ion-exchanged water, and this suspension was heated under proper refluxing treatment so that the liquid amount was not reduced at 95 캜 for 5 hours. To the suspension after heating, 68 g of phosphoric acid was added and dissolved to prepare an impregnation solution. This impregnation solution was sprayed on 1000 g of carrier a and impregnated, followed by drying at 250 캜. The dried support a was calcined in an electric furnace at 550 ° C for 1 hour to obtain a catalyst a for hydrotreating treatment (hereinafter also referred to as "catalyst a"). The concentration of MoO ₃ with respect to the total mass of the catalyst a was 22 mass%. The concentration of CoO with respect to the total mass of the catalyst a was 3 mass%. The concentration of P ₂ O ₅ with respect to the total mass of the catalyst a was 3 mass%.

&Lt; Production of hydrogenation isomerization catalyst &

ZSM-22 zeolite (hereinafter sometimes referred to as "ZSM-22") composed of crystalline aluminosilicate having Si / Al ratio of 45 was produced by hydrothermal synthesis in the following procedure.

First, the following four kinds of aqueous solutions were prepared.

Solution A: 1.94 g of potassium hydroxide dissolved in 6.75 mL of ion-exchanged water.

Solution B: 1.33 g of aluminum sulfate 18 hydrate dissolved in 5 mL of ion-exchanged water.

Solution C: 4.18 g of 1,6-hexanediamine (organic template) diluted with 32.5 mL of ion-exchanged water.

Solution D: 18 g of colloidal silica (Ludox AS-40 manufactured by Grace Davison) diluted with 31 mL of ion-exchanged water.

Next, the mixed solution obtained by adding the solution A to the solution B was stirred until the aluminum component completely dissolved. Solution C was added to this mixed solution. The mixture of solutions A, B and C was injected into solution D in this mixture with vigorous stirring at room temperature. 0.25 g of ZSM-22 powder separately synthesized and not subjected to any special treatment after synthesis was added to the mixture of Solutions A, B, C and D as &quot; seed crystals &quot; .

The gel was transferred to a stainless steel autoclave reactor having an internal volume of 120 mL, and the autoclave reactor was rotated on the tumbling apparatus at a rotation speed of about 60 rpm for 60 hours in an oven at 150 캜 to perform a hydrothermal synthesis reaction. After completion of the reaction, the reactor was cooled, opened, and dried overnight in a drier at 60 占 폚 to obtain ZSM-22 having a Si / Al ratio of 45.

With respect to the obtained ZSM-22, an ion exchange treatment was carried out with an aqueous solution containing ammonium ions by the following procedure.

The above ZSM-22 was placed in a flask, and 100 mL of a 0.5 N ammonium chloride aqueous solution per 1 g of ZSM-22 zeolite was added to ZSM-22, and this liquid was refluxed for 6 hours. After refluxing the liquid to room temperature, the supernatant was removed, and the crystalline aluminosilicate was washed with ion-exchanged water. To this, 0.5N aqueous ammonium chloride solution equivalent to the above amount was added again, and the mixture was refluxed for 12 hours.

After heating under reflux for 12 hours, the solid collected by filtration, washed with ion-exchanged water, which was dried overnight in a 60 ℃ dryer, the ion-exchanged NH ₄ type ZSM-22 was obtained. This ZSM-22 was ion-exchanged with an organic template.

The above NH ₄ type ZSM-22 and alumina as a binder were mixed at a mass ratio of 7: 3, and a small amount of ion-exchanged water was added to this mixture and kneaded. The obtained viscous fluid was filled in an extruder and molded to obtain a cylindrical molded body having a diameter of about 1.6 mm and a length of about 10 mm. The formed body was heated at 300 캜 for 3 hours under N ₂ atmosphere to obtain a carrier precursor.

The tetra arm Mindy.Mindy nitro platinum _{[Pt (NH 3) 4]} (NO 3) 2, was dissolved in ion exchange corresponding to the amount of water absorption of the support precursor was measured in advance to obtain an impregnating solution. This solution was impregnated into the carrier precursor by the initial wetting method, and platinum was supported on ZSM-22 type zeolite so that the content of platinum relative to the mass of ZSM-22 type zeolite was 0.3 mass%. Next, the obtained impregnated material (catalyst precursor) was dried in a drier at 60 ° C. overnight, and then calcined at 400 ° C. for 3 hours under air flow to obtain a hydrogenation isomerization catalyst b (hereinafter also referred to as "catalyst b") .

(Example 1)

A portion of the aromatic hydrocarbons in the reduced-pressure diesel oil fraction was extracted into furfural by using an extraction tower and removed to obtain the hydrocarbon oil of Example 1 (hydrocarbon oil before the hydrogenation treatment). The values of boiling range, T10, T90, content of aromatic hydrocarbons in hydrocarbon oil, content of sulfur in hydrocarbon oil, kinematic viscosity at 100 DEG C of hydrocarbon oil and viscosity index of hydrocarbon before hydrotreating in Example 1 are shown in Table 1 . On the other hand, the density of the hydrocarbon oil before hydrotreating in Example 1 at 15 캜 was 0.8683 g / cm 3. The content of nitrogen in the hydrocarbon oil before the hydrogenation treatment in Example 1 was 23 mass ppm.

In the hydrotreating step of Example 1, the hydrocarbon oil of Example 1 was brought into contact with the catalyst a at the reaction temperature shown in Table 1 in an atmosphere in which the partial pressure of hydrogen was the value shown in Table 1, To give a crude oil. On the other hand, in the hydrogenation step, the hydrogen / hydrocarbon ratio was adjusted to 253 Nm 3 / m 3. In the hydrotreating step, the liquid space velocity of the hydrocarbon oil with respect to the catalyst a was adjusted to the values shown in Table 1. Table 1 shows the contents of aromatic hydrocarbons in the treated oil obtained in the hydrotreating step of Example 1, the content of sulfur in the treated oil, the kinematic viscosity of the oil to be treated, and the viscosity index (VI) of the oil to be treated.

The hydrogenation isomerization step of Example 1 was carried out in the same manner as in Example 1 except that the reaction product of Example 1 was contacted with the catalyst b at the reaction temperature shown in Table 2 in an atmosphere having a hydrogen partial pressure as shown in Table 2, A product oil was obtained. On the other hand, in the hydrogenation isomerization step, the hydrogen / hydrocarbon ratio was adjusted to 506 Nm 3 / m 3. In the hydrogenation isomerization step, the liquid space velocity of the hydrocarbon oil relative to the catalyst b was adjusted to the value shown in Table 2. [ The reaction temperature in the hydrogenation isomerization process of Example 1 is the lowest temperature at which the pour point of the following lubricating oil base oil fraction b ("main base oil fraction" in Table 2) becomes -12.5 ° C or lower. Table 2 shows the content of aromatic hydrocarbons in the produced oil of Example 1, the content of sulfur in the produced oil, and the yield (X) of Example 1. On the other hand, the yield (X) in Table 2 is a value expressed by the following formula.

[Mathematical Expression]

X = (V _L / V _R ) x 100

In the above equation, V _L is the sum of masses of base oil fractions (final base oil fractions) for each lubricating oil. The final base oil fraction is obtained by distilling the product oil of the hydrogenation isomerization process into naphtha, isoparaffin, and heavy oil fraction having the target kinematic viscosity. V _R is the mass of the oil to be treated obtained in the hydrotreating step and the mass of the oil to be treated before the hydrogenation isomerization step. The final boiling oil fractions of Example 1 and the following Examples and Comparative Examples are shown in Table 3.

In the purification step (reduced pressure distillation step) of Example 1, the product oil obtained in the hydrogenation isomerization step was classified into naphtha, isobut oil, and heavy oil. By further classifying the heavy oil fraction, the following base oil fraction a (base oil fraction 1 in Table 3) and base oil fraction b (base oil fraction 2 in Table 3) for lubricating oil were obtained. The base oil fraction b of the lubricating oil of Example 1 corresponds to &quot; main base oil fraction &quot;

[Base oil for lubricating oil a]

Kinematic viscosity at 100 캜: 2.71 mm 2 / s.

Boiling range: 341 to 385 ° C.

[Base oil for lubricating oil b]

The yield (Y), pour point, kinematic viscosity, viscosity index (VI) and (VI x Y) of base oil b (main base oil fraction) for lubricating oil are shown in Table 2. The yield (Y) of the main base oil fraction is the mass of the base oil fraction in which V _L is the main mass oil fraction and V _R is the mass of the target oil to be obtained in the hydrotreating process, V _L / V _R ) × 100. The boiling range of the main base oil fraction of Example 1 was 395 to 421 占 폚.

(Example 2)

In Example 2, a hydrotreating process was carried out under the conditions shown in Table 1 to obtain a treating oil as shown in Table 1. [ In Example 2, a hydrogenation isomerization step was carried out under the conditions shown in Table 2 to obtain a product oil as shown in Table 2. In Example 2, the same refining process as in Example 1 was carried out to obtain the base oil fraction shown in Table 2. [ Except for these points, Embodiment 1 and Embodiment 2 are common.

(Example 3)

In Example 3, hydrocarbon oil (hydrocarbon oil before hydrogenation treatment) not subjected to the solvent extraction step was used. T10, T90, the content of aromatic hydrocarbons in the hydrocarbon oil, the content of sulfur in the hydrocarbon oil, the kinematic viscosity at 100 DEG C of the hydrocarbon oil, and the viscosity index (VI) of the hydrocarbon oil before the hydrogenation treatment in Example 3 Lt; tb &gt; On the other hand, the density of the hydrocarbon oil before hydrotreating in Example 3 at 15 캜 was 0.9150 g / cm 3. The content of nitrogen in the hydrocarbon oil before hydrotreating in Example 3 was 630 mass ppm.

In the hydrotreating step of Example 3, the hydrocarbon oil of Example 3 was brought into contact with the catalyst a at the reaction temperature shown in Table 1 in an atmosphere in which the partial pressure of hydrogen was the value shown in Table 1, To give a crude oil. On the other hand, in the hydrogenation step, the hydrogen / hydrocarbon ratio was adjusted to 844 Nm 3 / m 3. In the hydrotreating step, the liquid space velocity of the hydrocarbon oil with respect to the catalyst a was adjusted to the values shown in Table 1. Table 1 shows the values of the content of aromatic hydrocarbons in the treated oil obtained in the hydrotreating step of Example 3, the content of sulfur in the treated oil, the kinematic viscosity of the oil to be treated and the viscosity index (VI) of the oil to be treated.

In the hydrogenation isomerization step of Example 3, the treated oil of Example 3 was brought into contact with the catalyst b at the reaction temperature shown in Table 2 in an atmosphere in which the partial pressure of hydrogen was the value shown in Table 2, A product oil was obtained. On the other hand, in the hydrogenation isomerization step, the hydrogen / hydrocarbon ratio was adjusted to 506 Nm 3 / m 3. In the hydrogenation isomerization step, the liquid space velocity of the hydrocarbon oil relative to the catalyst b was adjusted to the value shown in Table 2. [ The reaction temperature in the hydrogenation isomerization step of Example 3 is the lowest temperature at which the pour point of the following lubricating oil base oil fraction b ("main base oil fraction" in Table 2) becomes -12.5 ° C or lower. Table 2 shows the content of aromatic hydrocarbons in the produced oil of Example 3, the content of sulfur in the produced oil, and the yield (X) of Example 3.

In the purification step (reduced pressure distillation step) of Example 3, the product oil obtained in the hydrogenation isomerization step was classified into naphtha, isobut oil, and heavy oil. By further classifying the heavy oil fraction, the following base oil fraction a (base oil fraction 1 in Table 3) and base oil fraction b (base oil fraction 2 in Table 3) for lubricating oil were obtained. The base oil fraction b of the lubricating oil of Example 3 corresponds to &quot; main base oil fraction &quot;

[Base oil for lubricating oil a]

Kinematic viscosity at 100 캜: 2.70 mm 2 / s.

Boiling range: 343 to 387 ° C.

[Base oil for lubricating oil b]

(Y), pour point, kinematic viscosity, viscosity index (VI) and (VI x Y) of the base oil fraction b (main base oil fraction) for lubricant of Example 3 are shown in Table 2. On the other hand, the boiling point range of the main base oil fraction of Example 3 was 392 to 447 占 폚.

(Example 4)

A portion of the aromatic hydrocarbons in the reduced-pressure light oil fraction was extracted into furfural using an extraction tower and removed to obtain a hydrocarbon oil (hydrocarbon oil before hydrogenation treatment) of Example 4. The values of boiling range, T10, T90, content of aromatic hydrocarbons in hydrocarbon oil, content of sulfur in hydrocarbon oil, kinetic viscosity of hydrocarbon and viscosity index (VI) of hydrocarbon oil before hydrotreating in Example 4 are shown in Table 1 do. On the other hand, the density of the hydrocarbon oil before hydrotreating in Example 4 at 15 캜 was 0.8724 g / cm 3. The content of nitrogen in the hydrocarbon oil before the hydrogenation treatment in Example 4 was 58 mass ppm.

In the hydrotreating step of Example 4, the hydrocarbon oil of Example 4 was brought into contact with the catalyst a at the reaction temperature shown in Table 1 in an atmosphere in which the partial pressure of hydrogen was the value shown in Table 1, To give a crude oil. On the other hand, in the hydrogenation step, the hydrogen / hydrocarbon ratio was adjusted to 253 Nm 3 / m 3. In the hydrotreating step, the liquid space velocity of the hydrocarbon oil with respect to the catalyst a was adjusted to the values shown in Table 1. Table 1 shows the contents of the aromatic hydrocarbon, the content of sulfur in the treated oil, the kinematic viscosity of the oil to be treated, and the viscosity index (VI) of the oil to be treated in the hydrotreating oil obtained in the hydrotreating step of Example 4.

The hydrogenation isomerization step of Example 4 was carried out in the same manner as in Example 4 except that the hydrogenation isomerization step of Example 4 was brought into contact with the catalyst b at the reaction temperature shown in Table 2 in an atmosphere in which the hydrogen partial pressure was the value shown in Table 2, A product oil was obtained. On the other hand, in the hydrogenation isomerization step, the hydrogen / hydrocarbon ratio was adjusted to 506 Nm 3 / m 3. In the hydrogenation isomerization step, the liquid space velocity of the hydrocarbon oil with respect to the catalyst b was adjusted to the values shown in Table 1. [ The reaction temperature in the hydrogenation isomerization step of Example 4 is the lowest temperature at which the pour point of the following base oil fraction c (main base oil fraction) of lubricating oil is -12.5 DEG C or less. Table 2 shows the content of aromatic hydrocarbons in the produced oil, the content of sulfur in the produced oil, and the yield (X) of Example 4 in Example 4.

In the purification step (reduced pressure distillation step) of Example 4, the product oil obtained in the hydrogenation isomerization step was classified into naphtha, isobut oil, and heavy oil. (Base oil fraction 1 in Table 3), base oil fraction b (lubricant base oil fraction 2 in Table 3), and base oil fraction c (lubricant base oil fraction 3 in Table 3) in the following lubricant base oil a &Lt; / RTI &gt; The base oil fraction c of the lubricating oil of Example 4 corresponds to &quot; main base oil fraction &quot;

[Base oil for lubricating oil a]

Kinematic viscosity at 100 캜: 2.70 mm 2 / s.

Boiling range: 343 to 387 ° C.

[Base oil for lubricating oil b]

Kinematic viscosity at 100 캜: 4.91 mm 2 / s.

Boiling range: 395 to 445 ° C.

[Base oil for lubricant oil c]

(Y), pour point, kinematic viscosity, viscosity index (VI) and (VI x Y) of the base oil fraction c (main base oil fraction) for lubricating oil of Example 4 are shown in Table 2. On the other hand, the boiling point range of the main base oil fraction of Example 4 was 455 to 472 ° C.

(Example 5)

A portion of the aromatic hydrocarbons in the reduced-pressure light oil fraction was extracted into furfural and removed by using an extraction tower to obtain a hydrocarbon oil (hydrocarbon oil before the hydrogenation treatment) of Example 5. T10, T90, the content of aromatic hydrocarbons in the hydrocarbon oil, the content of sulfur in the hydrocarbon oil, the kinematic viscosity at 100 DEG C of the hydrocarbon oil, and the viscosity index (VI) of the hydrocarbon oil before the hydrogenation treatment in Example 5 Lt; tb &gt; On the other hand, the density of the hydrocarbon oil before hydrotreating in Example 5 at 15 캜 was 0.8873 g / cm 3. The content of nitrogen in the hydrocarbon oil before the hydrogenation treatment in Example 5 was 77 mass ppm.

In the hydrotreating step of Example 5, the hydrocarbon oil of Example 5 was brought into contact with the catalyst a at the reaction temperature shown in Table 1 in an atmosphere in which the partial pressure of hydrogen was the value shown in Table 1, To give a crude oil. On the other hand, in the hydrogenation step, the hydrogen / hydrocarbon ratio was adjusted to 253 Nm 3 / m 3. In the hydrotreating step, the liquid space velocity of the hydrocarbon oil with respect to the catalyst a was adjusted to the values shown in Table 1. Table 1 shows the content of aromatic hydrocarbons in the treated oil obtained in the hydrotreating step of Example 5, the content of sulfur in the treated oil, the kinematic viscosity of the oil to be treated, and the viscosity index (VI) of the oil to be treated.

The hydrogenation isomerization step of Example 5 was carried out in the same manner as in Example 5 except that the treatment liquid of Example 5 was brought into contact with the catalyst b at the reaction temperature shown in Table 2 in an atmosphere in which the partial pressure of hydrogen was the value shown in Table 2, A product oil was obtained. On the other hand, in the hydrogenation isomerization step, the hydrogen / hydrocarbon ratio was adjusted to 506 Nm 3 / m 3. In the hydrogenation isomerization step, the liquid space velocity of the hydrocarbon oil with respect to the catalyst b was adjusted to the values shown in Table 1. [ The reaction temperature in the hydrogenation isomerization step of Example 5 is the lowest temperature at which the pour point of the following base oil fraction c (main base oil fraction in Table 2) is below -12.5 占 폚. Table 2 shows the content of aromatic hydrocarbons in the produced oil of Example 5, the content of sulfur in the produced oil, and the yield (X) of Example 5.

In the purification step (reduced pressure distillation step) of Example 5, the product oil obtained in the hydrogenation isomerization step was classified into naphtha, isotactic oil fraction and heavy oil fraction. (Base oil fraction 2 in Table 3), base oil fraction b (lubricant base oil fraction 3 in Table 3), and base oil fraction 3 (lubricant base oil fraction 4 in Table 3) in the following lubricating oil, &Lt; / RTI &gt; The base oil fraction c for lubricating oil of Example 5 corresponds to &quot; main base oil fraction &quot;

[Base oil for lubricating oil a]

Kinematic viscosity at 100 캜: 2.70 mm 2 / s.

Boiling range: 395 to 447 ° C.

[Base oil for lubricating oil b]

Kinematic viscosity at 100 캜: 4.93 mm 2 / s.

Boiling range: 457 to 476 ° C.

[Base oil for lubricant oil c]

(Y), pour point, kinematic viscosity, viscosity index (VI) and (VI 占 Y) of the base oil fraction c (main base oil fraction) for lubricating oil of Example 5 are shown in Table 2. On the other hand, the boiling point range of the main base oil fraction in Example 5 was 495 to 535 ° C.

(Examples 6 to 9)

In Examples 6 to 9, hydrocarbon oils described in Table 1 were hydrogenated under the conditions shown in Table 1 to obtain a coating oil as shown in Table 1. In Examples 6 to 9, the hydrogenation isomerization process was carried out on the processed oils listed in Table 1 under the conditions shown in Table 2 to obtain the product oils listed in Table 2. Except for these points, the sixth to tenth embodiments and the fifth embodiment are common. Also in Examples 6 to 9, purification steps similar to those in Example 5 were carried out to obtain base oil fractions shown in Tables 2 and 3.

(Example 10)

A part of the aromatic hydrocarbons in the reduced-pressure light oil fraction was extracted into furfural and removed by using an extraction tower to obtain a hydrocarbon oil (hydrocarbon oil before the hydrogenation treatment) of Example 10. T10, T90, the content of aromatic hydrocarbons in the hydrocarbon oil, the content of sulfur in the hydrocarbon oil, the kinematic viscosity at 100 DEG C of the hydrocarbon oil, and the viscosity index (VI) of the hydrocarbon oil before the hydrogenation treatment in Example 10 Lt; tb &gt; On the other hand, the density of the hydrocarbon oil before hydrotreating in Example 10 at 15 캜 was 0.8589 g / cm 3. The content of nitrogen in the hydrocarbon oil before hydrotreating in Example 10 was 25 mass ppm.

In the hydrotreating step of Example 10, the hydrocarbon oil of Example 10 was brought into contact with the catalyst a at the reaction temperature shown in Table 1 in an atmosphere in which the partial pressure of hydrogen was the value shown in Table 1, To give a crude oil. On the other hand, in the hydrogenation step, the hydrogen / hydrocarbon ratio was adjusted to 253 Nm 3 / m 3. In the hydrotreating step, the liquid space velocity of the hydrocarbon oil with respect to the catalyst a was adjusted to the values shown in Table 1. Table 1 shows the values of the aromatic hydrocarbon content, the sulfur content in the treated oil, the kinematic viscosity of the oil to be treated, and the viscosity index (VI) of the oil to be treated in the hydrotreating oil obtained in the hydrotreating step of Example 10.

The hydrogenation isomerization step of Example 10 was carried out in the same manner as in Example 10 except that the reaction product of Example 10 was contacted with the catalyst b at the reaction temperature shown in Table 2 in an atmosphere in which the partial pressure of hydrogen was the value shown in Table 2, A product oil was obtained. On the other hand, in the hydrogenation isomerization step, the hydrogen / hydrocarbon ratio was adjusted to 506 Nm 3 / m 3. In the hydrogenation isomerization step, the liquid space velocity of the hydrocarbon oil relative to the catalyst b was adjusted to the value shown in Table 2. [ The reaction temperature in the hydrogenation isomerization step of Example 10 is the lowest temperature at which the pour point of the base oil fraction a (main base oil fraction in Table 2) below is -12.5 DEG C or less. Table 2 shows the content of aromatic hydrocarbons in the produced oil of Example 10, the content of sulfur in the produced oil, and the yield (X) of Example 10.

(Base oil fraction 1 'in Table 3) was obtained through the purification step (reduced pressure distillation step) of Example 10.

[Base oil for lubricating oil a]

Kinematic viscosity at 100 캜: 2.702 mm 2 / s.

Boiling range: 341 to 385 ° C.

(Y), pour point, kinematic viscosity, viscosity index (VI) and (VI 占 Y) of base oil fraction a (main base oil fraction) for lubricating oil of Example 10 are shown in Table 2. The boiling range of the main base oil fraction of Example 10 was 341 to 385 占 폚.

(Example 11)

As the hydrocarbon oil (hydrocarbon oil before the hydrogenation treatment) of Example 11, a reduced pressure light oil fraction not subjected to the extraction process by furfural was used. T10, T90, the content of aromatic hydrocarbons in the hydrocarbon oil, the content of sulfur in the hydrocarbon oil, the kinematic viscosity at 100 DEG C of the hydrocarbon oil and the viscosity index (VI) of the hydrocarbon oil before the hydrogenation treatment in Example 11 Lt; tb &gt; On the other hand, the density of the hydrocarbon oil before hydrotreating in Example 11 at 15 캜 was 0.9054 g / cm 3. The content of nitrogen in the hydrocarbon oil before hydrotreating in Example 11 was 510 ppm by mass.

In the hydrotreating step of Example 11, the hydrocarbon oil of Example 11 was brought into contact with the catalyst a at the reaction temperature shown in Table 1 in an atmosphere in which the partial pressure of hydrogen was the value shown in Table 1, To give a crude oil. On the other hand, in the hydrogenation step, the hydrogen / hydrocarbon ratio was adjusted to 253 Nm 3 / m 3. In the hydrotreating step, the liquid space velocity of the hydrocarbon oil with respect to the catalyst a was adjusted to the values shown in Table 1. Table 1 shows the contents of the aromatic hydrocarbon, the content of sulfur in the treated oil, the kinematic viscosity of the oil to be treated and the viscosity index (VI) of the oil to be treated in the hydrotreating oil obtained in the hydrotreating step of Example 11.

The hydrogenation isomerization step of Example 11 was carried out in the same manner as in Example 11 except that the above-mentioned distillate of Example 11 was contacted with the catalyst b at the reaction temperature shown in Table 2 in an atmosphere having a hydrogen partial pressure as shown in Table 2, A product oil was obtained. On the other hand, in the hydrogenation isomerization step, the hydrogen / hydrocarbon ratio was adjusted to 506 Nm 3 / m 3. In the hydrogenation isomerization step, the liquid space velocity of the hydrocarbon oil relative to the catalyst b was adjusted to the value shown in Table 2. [ The reaction temperature in the hydrogenation isomerization step of Example 11 is the lowest temperature at which the pour point of the base oil fraction a (main base oil fraction in Table 2) below is -12.5 DEG C or less. Table 2 shows the content of aromatic hydrocarbons in the produced oil of Example 11, the content of sulfur in the produced oil, and the yield (X) of Example 11.

(Base oil fraction 1 'in Table 3) was obtained through the purification step (reduced pressure distillation step) of Example 11.

[Base oil for lubricating oil a]

Kinematic viscosity at 100 캜: 2.702 mm 2 / s.

Boiling range: 341 to 387 ° C.

(Y), pour point, kinematic viscosity, viscosity index (VI) and (VI 占 Y) of base oil fraction a (main base oil fraction) for lubricating oil of Example 11 are shown in Table 2. On the other hand, the boiling point range of the main base oil fraction of Example 11 was 341 to 387 占 폚.

(Example 12)

A part of the aromatic hydrocarbons in the reduced-pressure light oil fraction was extracted into furfural by using an extraction tower, and then subjected to solvent deasphalting of reduced-pressure light oil fraction to obtain a hydrocarbon oil (hydrocarbon oil before hydrotreating) of Example 12 Respectively. T10, T90, the content of aromatic hydrocarbons in the hydrocarbon oil, the content of sulfur in the hydrocarbon oil, the kinematic viscosity at 100 DEG C of the hydrocarbon oil, and the viscosity index (VI) of the hydrocarbon oil before hydrotreating in Example 12, Lt; tb &gt; On the other hand, the density of the hydrocarbon oil before hydrotreating in Example 12 at 15 캜 was 0.8831 g / cm 3. The content of nitrogen in the hydrocarbon oil before hydrotreating in Example 12 was 18 mass ppm.

In the hydrotreating step of Example 12, the hydrocarbon oil of Example 12 was brought into contact with the catalyst a at the reaction temperature shown in Table 1 in an atmosphere in which the partial pressure of hydrogen was the value shown in Table 1, To give a crude oil. On the other hand, in the hydrogenation step, the hydrogen / hydrocarbon ratio was adjusted to 253 Nm 3 / m 3. In the hydrotreating step, the liquid space velocity of the hydrocarbon oil with respect to the catalyst a was adjusted to the values shown in Table 1. Table 1 shows the contents of the aromatic hydrocarbon, the content of sulfur in the treated oil, the kinematic viscosity of the oil to be treated and the viscosity index (VI) of the oil to be treated in the hydrotreating oil obtained in the hydrotreating step of Example 12.

In the hydrogenation isomerization step of Example 12, the above-mentioned distillate of Example 12 was brought into contact with the catalyst b at the reaction temperature shown in Table 2 in an atmosphere in which the partial pressure of hydrogen was the value shown in Table 2, A product oil was obtained. On the other hand, in the hydrogenation isomerization step, the hydrogen / hydrocarbon ratio was adjusted to 506 Nm 3 / m 3. In the hydrogenation isomerization step, the liquid space velocity of the hydrocarbon oil with respect to the catalyst b was adjusted to the values shown in Table 1. [ The reaction temperature in the hydrogenation isomerization process of Example 12 is the lowest temperature at which the pour point of the following base oil fraction c (main base oil fraction in Table 2) is below -12.5 ° C. Table 2 shows the content of aromatic hydrocarbons in the oil produced in Example 12, the content of sulfur in the oil produced, and the yield (X) in Example 12.

In the purification step (reduced pressure distillation step) of Example 12, the product oil obtained in the hydrogenation isomerization step was classified into naphtha, isotactic oil fraction and heavy fraction. Further, by classifying the heavy oil fraction, the following base oil fraction a (the base oil fraction 3 in Table 3), the base oil fraction b (lubricant base oil fraction 4 in Table 3) and the base oil fraction c (lubricant base oil fraction 5 in Table 3) ). The base oil fraction c for lubricating oil of Example 12 corresponds to &quot; main base oil fraction &quot;

[Base oil for lubricating oil a]

Kinematic viscosity at 100 캜: 6.213 mm 2 / s.

Boiling range: 457 to 476 ° C.

[Base oil for lubricating oil b]

Kinematic viscosity at 100 캜: 10.50 mm &lt; 2 &gt; / s.

Boiling range: 497 to 538 占 폚.

[Base oil for lubricant oil c]

(Y), pour point, kinematic viscosity, viscosity index (VI) and (VI x Y) of the base oil fraction c (main base oil fraction) for lubricant of Example 12 are shown in Table 2. On the other hand, the boiling point range of the main base oil fraction of Example 12 was 562 to 610 占 폚.

(Comparative Example 1)

In Comparative Example 1, the hydrogenation treatment of the hydrocarbon oil shown in Table 1 was carried out under the conditions shown in Table 1 to obtain a treatment oil shown in Table 1. In Comparative Example 1, the hydrogenation isomerization process for the target oil shown in Table 1 was carried out under the conditions shown in Table 2 to obtain a product oil as shown in Table 2. Except for these points, Comparative Example 1 and Examples 1 and 2 are common. Also in Comparative Example 1, purification steps similar to those of Examples 1 and 2 were carried out to obtain base oil fractions shown in Tables 2 and 3.

(Comparative Example 2)

In Comparative Example 2, hydrogenation treatment of the hydrocarbon oil shown in Table 1 was carried out under the conditions shown in Table 1 to obtain a treating oil as shown in Table 1. [ In Comparative Example 2, the hydrogenation isomerization process for the target oil shown in Table 1 was carried out under the conditions shown in Table 2 to obtain a product oil as shown in Table 2. Except for these points, Comparative Example 2, Examples 1 and 2, and Comparative Example 1 are common. Also in Comparative Example 2, purification steps similar to those of Examples 1 and 2 and Comparative Example 1 were carried out to obtain base oil fractions shown in Tables 2 and 3.

(Comparative Example 3)

In Comparative Example 3, the hydrogenation treatment of the hydrocarbon oil shown in Table 1 was carried out under the conditions shown in Table 1 to obtain a treating oil described in Table 1. [ In Comparative Example 3, the hydrogenation isomerization process for the treated oil shown in Table 1 was carried out under the conditions shown in Table 2 to obtain a product oil as shown in Table 2. Except for these points, Comparative Example 3 and Example 3 are common. Also in Comparative Example 3, the same refining process as in Example 3 was carried out to obtain the base oil fraction shown in Tables 2 and 3.

(Comparative Example 4)

In Comparative Example 4, the hydrogenation treatment of the hydrocarbon oil shown in Table 1 was carried out under the conditions shown in Table 1 to obtain a treating oil shown in Table 1. [ In Comparative Example 4, the hydrogenation isomerization process for the target oil shown in Table 1 was carried out under the conditions shown in Table 2 to obtain a product oil as shown in Table 2. Except these items, Comparative Example 4, Example 3 and Comparative Example 3 are common. Also in Comparative Example 4, purification steps similar to those of Example 3 and Comparative Example 3 were carried out to obtain a base oil fraction shown in Tables 2 and 3.

(Comparative Example 5)

In Comparative Example 5, the hydrogenation treatment of the hydrocarbon oil shown in Table 1 was carried out under the conditions shown in Table 1 to obtain a treatment oil shown in Table 1. [ In Comparative Example 5, the hydrogenation isomerization process for the target oil described in Table 1 was carried out under the conditions shown in Table 2 to obtain the product oil shown in Table 2. [ With the exception of these points, Comparative Example 5 and Example 4 are common. Also in Comparative Example 5, the same refining process as in Example 4 was carried out to obtain the base oil fraction shown in Tables 2 and 3.

(Comparative Example 6)

In Comparative Example 6, the hydrogenation treatment of the hydrocarbon oil shown in Table 1 was carried out under the conditions shown in Table 1 to obtain a treatment oil shown in Table 1. In Comparative Example 6, the hydrogenation isomerization process for the treated oil shown in Table 1 was carried out under the conditions shown in Table 2 to obtain a product oil shown in Table 2. Except for these points, Comparative Example 6 and Examples 5 to 9 are common. Also in Comparative Example 6, purification steps as in Examples 5 to 9 were carried out to obtain base oil fractions shown in Tables 2 and 3.

(Comparative Example 7)

In Comparative Example 7, the hydrogenation treatment of the hydrocarbon oil shown in Table 1 was carried out under the conditions shown in Table 1 to obtain a treatment oil shown in Table 1. [ In Comparative Example 7, the hydrogenation isomerization process was carried out on the treated oil shown in Table 1 under the conditions shown in Table 2 to obtain a product oil as shown in Table 2. Except for these points, Comparative Example 7 and Examples 5 to 9 are common. Also in Comparative Example 7, purification steps similar to those in Examples 5 to 9 were carried out to obtain base oil fractions shown in Tables 2 and 3.

(Comparative Example 8)

In Comparative Example 8, the hydrogenation treatment of the hydrocarbon oil shown in Table 1 was carried out under the conditions shown in Table 1 to obtain a treatment oil shown in Table 1. In Comparative Example 8, the hydrogenation isomerization process for the processed oil listed in Table 1 was carried out under the conditions shown in Table 2 to obtain a product oil as shown in Table 2. Except for these matters, Comparative Example 8 and Examples 5 to 9 are common. Also in Comparative Example 8, purification steps similar to those in Examples 5 to 9 were carried out to obtain base oil fractions shown in Tables 2 and 3.

(Comparative Example 9)

In Comparative Example 9, the hydrogenation treatment of the hydrocarbon oil shown in Table 1 was carried out under the conditions shown in Table 1 to obtain a treatment oil as shown in Table 1. In Comparative Example 9, the hydrogenation isomerization process was carried out on the treated oil shown in Table 1 under the conditions shown in Table 2 to obtain a product oil as shown in Table 2. [ Except for these points, Comparative Example 9 and Example 11 are common. Also in Comparative Example 9, the same refining process as in Example 11 was carried out to obtain a base oil fraction shown in Tables 2 and 3.

In any of the examples, the main base oil fraction for the lubricating oil belonging to the group II lubricant base oil defined by the API was produced at a high yield.

Since the base oil for lubricating oil obtained by the production method according to the present invention has excellent properties as described above, it can be suitably used as a base oil for various lubricating oils. Specific examples of the use of the lubricating oil base oil include lubricating oil (lubricating oil for internal combustion engine) used in an internal combustion engine such as a gasoline engine for passenger cars, a gasoline engine for a motorcycle, a diesel engine, a gas engine, an engine for a gas heat pump, , Hydraulic oil, compressor oil, turbine oil, and gears used in hydraulic devices such as lubricating oils (drive transmission oil), shock absorbers, and construction machinery used in drive transmission devices such as automatic transmissions, manual transmissions, continuously variable transmissions, Oil, refrigerator oil, and oil for metal processing. By using the lubricating base oil of the present invention for these applications, it is possible to improve the characteristics such as viscosity-temperature characteristics, heat and oxidation stability, energy saving, fuel economy saving, and longevity of each lubricating oil, Can be achieved at a high level.

Claims (4)

Hydrogenation treatment of petroleum hydrocarbon is carried out at a reaction temperature of 250 to 420 DEG C in an atmosphere having a hydrogen partial pressure of 11 to 20 MPa to prepare a treating oil having an aromatic hydrocarbon content of 10 to 25 mass% The process,
Step of performing hydrogenation isomerization of the to-be-treated oil
, &Lt; / RTI &
A method for producing a base oil for lubricating oil. The process according to claim 1, wherein the hydrogenation is carried out in an atmosphere having a hydrogen partial pressure of 11 to 20 MPa,
Method for manufacturing base oil for lubricating oil. 3. The process according to claim 1 or 2, wherein the hydrogenation is carried out at a reaction temperature of 200 to 450 DEG C,
Method for manufacturing base oil for lubricating oil. A base oil for a lubricating oil produced by the method for producing a base oil for a lubricating oil according to any one of claims 1 to 3.