JP6084798B2 - Manufacturing method of base oil for lubricating oil - Google Patents

Description

The present invention relates to the production how the lubricant base oil.

  In the production of base oils for lubricants using petroleum as a raw material, for example, a vacuum distillation step, a solvent extraction step, a hydrodesulfurization step, an isomerization dewaxing step (hydroisomerization step), and a hydrofinishing step are performed. Perform in order. Hydrocarbon oils such as vacuum gas oil obtained by vacuum distillation contain aromatic hydrocarbons that impair the oxidative stability of the base oil for lubricating oil. The aromatic hydrocarbon is extracted with a solvent such as furfural and removed from the hydrocarbon oil. In hydrodesulfurization, sulfur, which is a catalyst poison of an isomerization dewaxing catalyst, is removed from a hydrocarbon oil. By isomerization and 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. Quality such as hue and oxidation stability of hydrocarbon oil is improved by hydrofinishing (see, for example, Patent Document 1 below).

JP-T-2001-525861

The present invention has been made in view of the aforesaid problems, to provide a manufacturing how the lubricant base oil can be produced in high yield with high lubricant base oil viscosity index For the purpose.

In one embodiment of the method for producing a lubricating base oil according to the present invention, a hydrogen-derived hydrocarbon oil is hydrotreated at a reaction temperature of 250 to 420 ° C. in an atmosphere having a hydrogen partial pressure of 11 to 20 MPa. The step of preparing the oil to be treated having an aromatic hydrocarbon content of 10 to 25% by mass and the hydroisomerization of the oil to be treated are performed using a zeolite having a 10-membered ring one-dimensional pore structure. Bei example a step, the performing, at least a zeolite having a 10 membered ring one-dimensional-like pore structure is selected from the group consisting of ZSM-22 zeolite, ZSM-23 zeolite, ZSM-48 zeolite, and SSZ-32 zeolite It is a type .

  In one embodiment of the present invention, it is preferable to perform hydroisomerization of the oil to be treated in an atmosphere having a hydrogen partial pressure of 11 to 20 MPa.

  In one embodiment of the present invention, it is preferable to hydroisomerize the oil to be treated at a reaction temperature of 200 to 450 ° C.

According to the present invention, prepared how the lubricant base oil can be produced in high yield with high lubricant base oil viscosity index is provided.

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

In the method for producing a base oil for lubricating oil according to the present embodiment, a vacuum distillation step, a solvent extraction step, a hydrotreating step, an isomerization dewaxing step (hydroisomerization step), a hydrofinishing step, and a purification step are performed. Perform in order. However, a lubricant base oil having a kinematic viscosity at 100 ° C. of 1.5 to 3.0 mm ² / s, and a lubricant base having a kinematic viscosity at 100 ° C. of 3.0 to 5.5 mm ² / s. When manufacturing oil, you may implement a hydrodesulfurization process and a hydroisomerization process after a vacuum distillation process, without implementing a solvent extraction process. In addition, when producing a lubricating base oil having a kinematic viscosity at 100 ° C. of 15.0 to 40.0 mm ² / s, an atmospheric distillation step, a vacuum distillation step, a solvent degassing step, a solvent extraction step, hydrogenation The treatment step, isomerization dewaxing step (hydroisomerization step), hydrofinishing step and purification step may be carried out in this order.

(Vacuum distillation process)
In the vacuum distillation step, petroleum-derived hydrocarbon oil (hereinafter referred to as “hydrocarbon oil”) such as vacuum gas oil (VGO) is obtained by vacuum distillation of petroleum-based raw material oil such as atmospheric residual oil.

(Solvent extraction process)
In the solvent extraction step, a part of the aromatic hydrocarbon in the hydrocarbon oil is extracted into the solvent and removed using an extraction tower. By the solvent extraction step, the hue, viscosity index and oxidation stability of the base oil for lubricating oil can be improved. As a solvent, if the component to be extracted (extracted component) is selectively dissolved, the extractable component has high solubility, is easily separated from the extractable component, and has low toxicity and corrosivity, There is no particular limitation. Specific examples of the solvent include furfural, phenol, N-methyl-2-pyrrolidinone and tetrahydrofuran. Among these solvents, it is preferable to use furfural for extraction of aromatic hydrocarbons. The operating conditions of the extraction tower using furfural are controlled by the solvent ratio (volume of the solvent when the volume of hydrocarbon oil is 100) and the extraction temperature. The solvent ratio may be about 100 to 400, and the extraction temperature may be about 30 to 150 ° C.

(Solvent removal process)
In the solvent degassing step, the asphalt content in the residual oil (vacuum residue) from the vacuum distillation tower is removed. The solvent degassing process separates heavy fraction and asphalt suitable for high-viscosity lubricants to produce lubricant raw materials. A common solvent desulfurization method is a propane desorption method (PDA). In the PDA method, the feed oil is supplied to the upper part of the deasphalting tower, and the solvent propane (liquid) is supplied to the lower part of the deasphalting tower. Since there is a specific gravity difference between the feedstock and propane, light propane rises in the tower while absorbing fractions suitable for lubricating oil, and asphalt that is not absorbed by propane falls. In the deasphalting tower, baffle plates and rotating disks are used to mix raw material oil and propane to efficiently degas. The solvent ratio (ratio of propane added to the raw material oil) in the solvent degassing step is 300 to 600%, and the temperature of the extraction tower is about 50 to 85 ° C. From the upper part of the deasphalting tower, defoamed oil absorbed by propane (suitable for high-viscosity lubricating oil) is extracted, and asphalt is extracted from the lower part of the deasphalting tower. By separating propane from the defoamed oil and asphalt extracted from the extraction tower in a solvent recovery system, the desired defoamed oil and asphalt are produced.

(Hydrogenation process)
<Properties of hydrocarbon oil>
In the hydrotreating step, hydrotreating of hydrocarbon oils having different properties is performed according to the standard of the target base oil for lubricating oil. A hydrocarbon oil having desired properties can be prepared by selecting a petroleum-based feedstock, a vacuum distillation step, a solvent extraction step, or the like.

  Base oils for lubricants that meet Group II standards defined by API (American Petroleum Institute) are as follows. Among the base oils for lubricants that satisfy this standard, for example, a lubricant base oil having the properties of the following lubricant base oil fractions 1 to 5 can be produced according to this embodiment.

[Classification of base oils by API (Group II)]
Viscosity index VI: 80 or more and less than 120 Saturation: 90% by mass or more Sulfur content: 0.03% by mass or less Note that VI means Visibility Index.

<< Lubricant fraction 1 >>
The kinematic viscosity at 100 ° C. of the lubricating oil fraction 1 is 1.5 to 3.0 mm ² / s, preferably 2.0 to 3.0 mm ² / s. The viscosity index VI of the lubricating oil fraction 1 is preferably 90 or more, more preferably 95 or more, and further 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 range of the lubricating oil fraction 1 is preferably 330 to 390 ° C.

<< Lubricant fraction 2 >>
The kinematic viscosity at 100 ° C. of the 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, more preferably 100 or more. The pour point of the lubricating oil fraction 2 is preferably −5.0 ° C. or lower, more preferably −10.0 ° C. or lower. The boiling range of the lubricating oil fraction 2 is preferably 390 to 450 ° C. Lubricating oil fraction 2 can meet the viscosity specification of SAE-10 fraction, which is an engine oil defined by the Society of Automotive Engineers (SAE).

<< Lubricant fraction 3 >>
The kinematic viscosity at 100 ° C. of the lubricating oil fraction 3 is 5.5 to 9.0 mm ² / s, preferably 6.0 to 8.5 mm ² / s. The viscosity index VI of the lubricating oil fraction 3 is preferably 90 or more, more preferably 100 or more. The pour point of the lubricating oil fraction 3 is preferably −5.0 ° C. or lower, more preferably −10.0 ° C. or lower. The boiling range of the lubricating oil fraction 3 is preferably 450 to 480 ° C. Lubricating oil fraction 3 can satisfy the SAE-20 fraction viscosity standard of engine oil determined by SAE.

<< Lubricating oil fraction 4 >>
The kinematic viscosity at 100 ° C. of the lubricating oil fraction 4 is 9.0 to 15.0 mm ² / s, preferably 9.5 to 13.0 mm ² / s. The viscosity index VI of the lubricating oil fraction 4 is preferably 90 or more, and more preferably 100 or more. The pour point of the lubricating oil fraction 4 is preferably −5.0 ° C. or lower, more preferably −10.0 ° C. or lower. The boiling point range of the lubricating oil fraction 4 is preferably 480 to 550 ° C. Lubricating oil fraction 4 can satisfy the SAE-30 fraction viscosity standard of engine oil determined by SAE.

<< Lubricant fraction 5 >>
<Kinematic viscosity at 100 ° C. of the lubricating oil fraction 5 15.0~40.0mm ² / s, preferably from 20.0~35.0mm ² / s. The viscosity index VI of the lubricating oil fraction 5 is preferably 90 or more, more preferably 100 or more. The pour point is preferably −5.0 ° C. or lower, more preferably −10.0 ° C. or lower. The boiling range is preferably 550 ° C. or higher.

(Hydrogenation process)
In the present embodiment, it is preferable to perform a hydrotreatment of a hydrocarbon oil having a boiling range of 310 to 680 ° C, and more preferably to perform a hydrotreatment of a hydrocarbon oil having a boiling range of 320 ° C to 650 ° C.

  For example, when producing a lubricating base oil corresponding to the above-described lubricating oil fractions 1 to 5, it is more preferable to perform a hydrotreating treatment of a hydrocarbon oil having the following properties.

When manufacturing the base oil for lubricating oil of the lubricating oil fraction 1, it is preferable to perform the hydrogenation process of the hydrocarbon oil having the following properties.
Boiling range: 310-490 ° C, preferably 320-480 ° C.
10% distillation temperature (T10): 345-385 ° C.
90% distillation temperature (T90): 415-455 ° C.
Kinematic viscosity at 100 ° C. Vis: 1.5 to 4.0 mm ² / s.
Viscosity index VI: 50-130.

When the base oil for lubricating oil of the lubricating oil fraction 2 is produced, it is preferable to perform a hydrogenation treatment of a hydrocarbon oil having the following properties.
Boiling range: 320-490 ° C, preferably 330-480 ° C.
10% distillation temperature (T10): 365-405 ° C.
90% distillation temperature (T90): 445-475 ° C.
Kinematic viscosity at 100 ° C. Vis: 3.0 to 6.5 mm ² / s.
Viscosity index VI: 50-130.

When the base oil for lubricating oil of the lubricating oil fraction 3 is produced, it is preferable to perform a hydrogenation treatment of a hydrocarbon oil having the following properties.
Boiling range: 340-530 ° C, preferably 350-520 ° C.
10% distillation temperature (T10): 410-450 ° C.
90% distillation temperature (T90): 475-505 ° C.
Kinematic viscosity at 100 ° C. Vis: 5.5 to 10.0 mm ² / s.
Viscosity index VI: 50-130.

When manufacturing the base oil for lubricating oil of the lubricating oil fraction 4, it is preferable to perform the hydrotreating of hydrocarbon oil having the following properties.
Boiling range: 360-600 ° C, preferably 370-590 ° C.
10% distillation temperature (T10): 435-475 ° C.
90% distillation temperature (T90): 545-575 ° C.
Kinematic viscosity at 100 ° C. Vis: 5.0 to 10.0 mm ² / s.
Viscosity index VI: 50-130.

When manufacturing the base oil for lubricating oil of the lubricating oil fraction 5, it is preferable to perform the hydrotreating of the hydrocarbon oil having the following properties.
Boiling range: 380-680 ° C, preferably 390-650 ° C.
10% distillation temperature (T10): 515-545 ° C.
90% distillation temperature (T90): 625-645 ° C.
Kinematic viscosity at 100 ° C. Vis: 15.0 to 41.0 mm ² / s.
Viscosity index VI: 50-130.

<Hydrotreating process conditions>
In the hydrotreating step, the hydrocarbon oil is brought into contact with the hydrotreating catalyst at a reaction temperature of 250 to 420 ° C. in an atmosphere having a hydrogen partial pressure of 11 to 20 MPa. Thereby, the to-be-processed oil whose content of aromatic hydrocarbon is 10-25 mass% is prepared. The content of aromatic hydrocarbons in the oil to be treated is preferably 10.0 to 18.0% by mass.

  The “hydrotreating” in the present embodiment is mainly intended to adjust the aromatic hydrocarbon content in the hydrocarbon oil within the above range by hydrogenating the aromatic hydrocarbon. . However, in the hydrotreating step, reactions such as desulfurization and denitrogenation may proceed. By these reactions, the sulfur content or nitrogen content that is the catalyst poison of the hydroisomerization catalyst is removed from the hydrocarbon oil, and the life of the hydroisomerization catalyst is improved. Further, in the hydrotreating step, hydrocracking and hydroisomerization of the wax component in the hydrocarbon oil may proceed in addition to the hydrogenation of the aromatic hydrocarbon.

  Naphthenes are produced by hydrogenation of aromatic hydrocarbons. Naphthene has a lower kinematic viscosity than aromatic hydrocarbons having the same carbon number. Accordingly, the lower the content of aromatic hydrocarbon in the hydrotreated hydrocarbon oil (treated oil), the higher the naphthene content in the treated oil and the lower the kinematic viscosity of the treated oil. There is. For the same reason, the kinematic viscosity of the lubricating base oil fraction finally obtained through the various steps after the hydrotreating step (hydroisomerization step, hydrofinishing step and refining step) also decreases. For example, when producing a base oil for lubricating oil having a high kinematic viscosity such as the above-mentioned lubricating oil fraction 4, the dynamic viscosity is reduced by incorporating a light oil having a low kinematic viscosity into the final lubricating oil base oil fraction. A base oil for lubricating oil adjusted to a value suitable for However, when the kinematic viscosity of the final lubricating base oil fraction is low, the kinematic viscosity of the lubricating base oil fraction tends to be lower than the standard value due to mixing with the light oil. Therefore, the lower the kinematic viscosity of the final lubricating base oil fraction, the smaller the amount of light oil that can be included with the lubricating base oil fraction, and the lower the yield of the target lubricating base oil. To do. In other words, the lower the content of aromatic hydrocarbons in the hydrotreated hydrocarbon oil (the oil to be treated), the lower the yield of the base oil for lubricating oil having a higher kinematic viscosity.

  However, in this embodiment, since the content of aromatic hydrocarbons in the oil to be treated obtained after the hydrotreating step is 10% by mass or more, the above problems are solved, and a desired high kinematic viscosity is obtained. It becomes possible to produce the base oil for lubricating oil having a high yield.

  Naphthenes produced by hydrogenation of aromatic hydrocarbons have a higher viscosity index than aromatic hydrocarbons having the same carbon number. Therefore, as the aromatic hydrocarbon content in the hydrotreated hydrocarbon oil (treated oil) increases, the naphthene content in the treated oil decreases and the VI of the treated oil tends to decrease. There is. Therefore, the higher the aromatic hydrocarbon content in the hydrotreated hydrocarbon oil (treated oil), the higher the VI of the lubricating base oil finally obtained through the various steps after the hydrotreating step. descend.

However, in this embodiment, since the content of aromatic hydrocarbons in the oil to be treated obtained after the hydrotreating step is 25 % by mass or less, the above problems are solved, and the desired high VI is obtained. It becomes possible to manufacture the base oil for lubricating oil with a high yield. In addition, the aromatic hydrocarbon becomes a catalyst poison of the hydroisomerization catalyst to be performed after the hydrotreating step. Therefore, when the aromatic hydrocarbon content in the oil to be treated is 25 % by mass or less, The poisoning of the isomerization catalyst can also be suppressed.

  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 hydrogen partial pressure 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 too low, the hydrogenation reaction of the aromatic hydrocarbon is difficult to occur, and the content of the aromatic hydrocarbon in the treated oil after the hydrotreating tends to exceed the above upper limit value. There is. Moreover, when the hydrogen partial pressure in a hydrotreating process is low, there exists a tendency for a desulfurization reaction and a denitrification reaction to become difficult to occur. On the other hand, when the hydrogen partial pressure is too high, hydrogenation of aromatic hydrocarbons is excessively promoted, and the content of aromatic hydrocarbons in the oil to be treated after hydrotreatment tends to be lower than the lower limit. is there.

  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 ° C, more preferably 270 to 410 ° C, and particularly preferably 280 to 400 ° C. The reaction temperature may be 300 to 365 ° C or 330 to 365 ° C. In addition, reaction temperature is the temperature of the catalyst layer comprised from the catalyst for hydrogenation processes, for example.

  When the reaction temperature in the hydrotreating process is too low, the hydrogenation reaction of the aromatic hydrocarbon is difficult to occur, and the content of the aromatic hydrocarbon in the oil to be treated after the hydrotreating tends to exceed the above upper limit value. is there. Moreover, when the reaction temperature in a hydroprocessing process is too low, there exists a tendency for a desulfurization reaction and a denitrification reaction to become difficult to occur. On the other hand, when the reaction temperature is too high, hydrogenation of aromatic hydrocarbons is excessively promoted, and the content of aromatic hydrocarbons in the oil to be treated after hydrotreatment tends to be lower than the lower limit value. . On the other hand, when the reaction temperature is too high, decomposition of the wax component in the hydrocarbon oil into light components proceeds excessively, and the yield of middle distillate and heavy components decreases.

  As described above, the kinematic viscosity and the yield of the base oil for lubricating oil are in a trade-off relationship with the increase or decrease in the content of aromatic hydrocarbons in the oil to be treated. In the present embodiment, a high VI and a high yield of lubricating base oil are achieved by preparing a to-be-treated oil having an aromatic hydrocarbon content of 10 to 25% by mass in the hydrotreating step. It becomes possible to make it. In the present embodiment, particularly when a base oil for lubricating oil of SAE-30 is produced, the production of the base oil for lubricating oil in which the product VI · Y of the viscosity index VI and the yield Y is in the range of 6000 to 7500 is achieved. It becomes possible. In this case, the viscosity index VI is preferably 100 to 150, and the yield Y is preferably 55 to 100% by mass.

In addition, the yield Y (unit: mass%) of the base oil for lubricating oil is defined by the following numerical formula, for example.
Y = (V _L / V _R ) × 100

In formula, _VL is the mass of the base oil for lubricating oil finally obtained. V _R is a mass of the treated oil obtained in the hydrotreating step, the mass of the treated oil before hydroisomerisation step. For example, when Y is the yield of the lubricating base oil in the lubricating base oil fraction 4, _VL is the hydrotreating process, hydroisomerization process, hydrofinishing process, and distillation process (refining process). Is the mass of the base oil fraction of the lubricating base oil fraction 4.

  The content of the aromatic hydrocarbon in the hydrocarbon oil before the hydrotreating step is preferably 25 to 50% by mass, more preferably 26 to 48% by mass. In this case, it becomes easy to adjust the content of the aromatic hydrocarbon in the oil to be treated obtained in the hydrotreating step within a range of 10 to 25% by mass. The content of the aromatic hydrocarbon in the hydrocarbon oil before the hydrotreating step is freely controlled by selecting the petroleum-based feedstock or various steps before the hydrotreating step (for example, a solvent extraction step).

  The sulfur content in the oil to be treated obtained in the hydrotreating step is preferably 1 to 100 ppm by mass, more preferably 3 to 80 ppm by mass, and particularly preferably 6 to 65 ppm by mass. . When the sulfur content is within the above range, the effect of the present invention becomes remarkable. When the sulfur content is within the above range, deactivation of the hydroisomerization catalyst is suppressed. When the sulfur content is within the above range, a lubricating base oil having a low sulfur content can be easily obtained. In addition, what is necessary is just to measure the content of the sulfur content in to-be-processed oil by the method defined by JISK2541 etc., for example.

  The sulfur content in the hydrocarbon oil before the hydrotreating step is preferably 50 to 30000 mass ppm, more preferably 100 to 25000 mass ppm. In this case, it becomes easy to adjust the sulfur content in the oil to be treated obtained in the hydrotreating step within the above numerical range. The sulfur content in the hydrocarbon oil before the hydrotreating process depends on the composition of the petroleum-based feedstock.

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

The liquid space velocity (LHSV) of the hydrocarbon oil in the hydrotreating process is about 0.1 to 4 h ⁻¹ , preferably 0.25 to 3 h ⁻¹ . When LHSV is less than 0.1 h ⁻¹ , the throughput is low, so the productivity is poor and impractical. On the other hand, when LHSV exceeds 4h ⁻¹ , it is necessary to increase the reaction temperature, and thus the hydrotreating catalyst tends to deteriorate.

The hydrogen / hydrocarbon oil ratio in the hydrotreating step 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 hydrotreating catalyst tends to decrease. On the other hand, when the hydrogen / oil ratio exceeds 2000 Nm ³ / m ³ , the desulfurization activity does not change greatly, but the operating cost increases.

  In the present embodiment, after the hydrotreating step, the pressure in the reactor subjected to the hydrotreating is adjusted to be equal to or lower than the pressure during the hydrotreating, and more preferably 1 MPa or more lower than the pressure during the hydrotreating. In this state, it is preferable to remove gaseous substances (hydrogen sulfide, ammonia, steam, etc.) from the oil to be treated in the reactor. It is preferable to carry out a hydroisomerization step after removing the gaseous substance.

  In order to obtain the lubricating base oil fractions 1 to 5, it is preferable to carry out the hydrotreating step under the following conditions.

<Conditions for hydrotreating process in case of lubricating base oil fraction 1>
Lubricant 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 a hydrocarbon oil obtained by solvent extraction of the vacuum gas oil obtained in the vacuum distillation step In order to obtain an oil base oil fraction, it is preferable to contact the hydrotreating catalyst at a reaction temperature of 280 to 420 ° C. in an atmosphere where the hydrogen partial pressure is 11 to 20 MPa in the hydrotreating step. More preferably, the partial pressure of hydrogen is 11 to 15 MPa, and the reaction temperature is 280 to 400 ° C. Thereby, the to-be-processed oil whose content of aromatic hydrocarbon is 10-25 mass%, Preferably it is 10-18 mass% can be prepared. LHSV is about 0.1 to 4 h ⁻¹ , preferably 0.5 to 2 h ⁻¹ . The hydrogen / hydrocarbon oil ratio in the hydrotreating step is about 100 to 2000 Nm ³ / m ³ , preferably 200 to 1000 Nm ³ / m ³ .

From hydrocarbon oil obtained by solvent extraction of vacuum gas oil obtained in vacuum distillation step without performing solvent extraction step, kinematic viscosity at 100 ° C. 1.5-3.0 mm ² / s, viscosity index 90 or more, sulfur content 0 In order to obtain a lubricating base oil fraction of 0.03% by mass or less, a hydrotreating catalyst is used in the hydrotreating step in an atmosphere having a hydrogen partial pressure of 11 to 20 MPa at a reaction temperature of 280 to 420 ° C. It is preferable to make it contact. More preferably, the partial pressure of hydrogen is 15 to 18 MPa, and the reaction temperature is 280 to 400 ° C. Thereby, the to-be-processed oil whose content of aromatic hydrocarbon is 10-25 mass%, Preferably it is 10-18 mass% can be prepared. LHSV is about 0.1 to 4 h ⁻¹ , preferably 0.5 to 2 h ⁻¹ . The hydrogen / hydrocarbon oil ratio in the hydrotreating step is about 100 to 2000 Nm ³ / m ³ , preferably 200 to 1000 Nm ³ / m ³ .

<Conditions of hydrotreating process in case of lubricating base oil fraction 2>
Lubricating oil having a kinematic viscosity of 3.0 to 5.5 mm ² / s at 100 ° C., a viscosity index of 90 or more, and a sulfur content of 0.03 mass% or less from hydrocarbon oil obtained by solvent extraction of vacuum gas oil obtained in the distillation step When obtaining a base oil fraction, it is preferable to contact the hydrotreating catalyst at a reaction temperature of 300 to 420 ° C. in an atmosphere where the hydrogen partial pressure is 11 to 20 MPa in the hydrotreating step. More preferably, the partial pressure of hydrogen is 11 to 15 MPa, and the reaction temperature is 310 to 360 ° C. Thereby, the to-be-processed oil whose content of aromatic hydrocarbon is 10-25 mass%, Preferably it is 10-18 mass% can be prepared. LHSV is about 0.1 to 4 h ⁻¹ , preferably 0.5 to 2 h ⁻¹ . The hydrogen / hydrocarbon oil ratio in the hydrotreating step is about 100 to 2000 Nm ³ / m ³ , preferably 200 to 1000 Nm ³ / m ³ .

From the hydrocarbon oil of the vacuum gas oil fraction obtained in the vacuum distillation step without performing the solvent extraction step, 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 0.00 When obtaining a lubricating base oil fraction of 03% by mass or less, in the hydrotreating step, contact with the hydrotreating catalyst at a reaction temperature of 300 to 420 ° C. in an atmosphere having a hydrogen partial pressure of 11 to 20 MPa. It is preferable to make it. More preferably, the partial pressure of hydrogen is 15 to 18 MPa, and the reaction temperature is 340 to 400 ° C. Thereby, the to-be-processed oil whose content of aromatic hydrocarbon is 10-25 mass%, Preferably it is 10-18 mass% can be prepared. LHSV is about 0.1 to 4 h ⁻¹ , preferably 0.5 to 2 h ⁻¹ . The hydrogen / hydrocarbon oil ratio in the hydrotreating step is about 100 to 2000 Nm ³ / m ³ , preferably 200 to 1000 Nm ³ / m ³ .

<Conditions for hydrotreating process in case of lubricating base oil fraction 3>
Lubricated oil 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 a hydrocarbon oil obtained by solvent extraction of the vacuum gas oil obtained in the vacuum distillation step In order to obtain an oil base oil fraction, it is preferable to contact the hydrotreating catalyst at a reaction temperature of 300 to 420 ° C. in an atmosphere where the hydrogen partial pressure is 11 to 20 MPa in the hydrotreating step. More preferably, the partial pressure of hydrogen is 11 to 15 MPa, and the reaction temperature is 310 to 360 ° C. Thereby, the to-be-processed oil whose content of aromatic hydrocarbon is 10-25 mass%, Preferably it is 10-18 mass% can be prepared. LHSV is about 0.1 to 4 h ⁻¹ , preferably 0.5 to 1.5 h ⁻¹ . The hydrogen / hydrocarbon oil ratio in the hydrotreating step is about 100 to 2000 Nm ³ / m ³ , preferably 200 to 1000 Nm ³ / m ³ .

<Conditions of hydrotreating process in case of lubricating base oil fraction 4>
Lubricant having a kinematic viscosity of 9.0 to 15.0 mm ² / s at 100 ° C., a viscosity index of 90 or more, and a sulfur content of 0.03 mass% or less from a hydrocarbon oil obtained by solvent extraction of the vacuum gas oil obtained in the vacuum distillation step In order to obtain an oil base oil fraction, it is preferable to contact the hydrotreating catalyst at a reaction temperature of 300 to 420 ° C. in an atmosphere where the hydrogen partial pressure is 11 to 20 MPa in the hydrotreating step. More preferably, the partial pressure of hydrogen is 11 to 17 MPa, and the reaction temperature is 320 to 370 ° C. Thereby, the to-be-processed oil whose content of aromatic hydrocarbon is 10-25 mass%, Preferably it is 10-18 mass% can be prepared. LHSV is about 0.1 to 4 h ⁻¹ , preferably 0.5 to 1.5 h ⁻¹ . The hydrogen / hydrocarbon oil ratio in the hydrotreating step is about 100 to 2000 Nm ³ / m ³ , preferably 200 to 1000 Nm ³ / m ³ .

<Conditions for hydrotreating process in case of lubricating base oil fraction 5>
The reduced-pressure distillation residue obtained in the reduced-pressure distillation step is converted into a kinematic viscosity at 100 ° C. of 15.0 to 40.0 mm ² / s and a viscosity index of 90 or more from a hydrocarbon oil obtained through a solvent degassing step and then a solvent extraction step. In order to obtain a lubricating base oil fraction having a sulfur content of 0.03% by mass or less, hydrogen is applied at a reaction temperature of 300 to 420 ° C. in an atmosphere having a hydrogen partial pressure of 11 to 20 MPa in the hydrotreatment step. It is preferable to make it contact with the catalyst for chemical conversion treatment. More preferably, the partial pressure of hydrogen is 11 to 19 MPa, and the reaction temperature is 350 to 400 ° C. Thereby, the to-be-processed oil whose content of aromatic hydrocarbon is 10-25 mass%, Preferably it is 10-18 mass% can be prepared. LHSV is about 0.1 to 4 h ⁻¹ , preferably 0.5 to 1.5 h ⁻¹ . The hydrogen / hydrocarbon oil ratio in the hydrotreating step is about 100 to 2000 Nm ³ / m ³ , preferably 200 to 1000 Nm ³ / m ³ .

<Hydroprocessing catalyst>
The catalyst for hydroprocessing is not particularly limited. Specific examples of the hydrotreating catalyst include a periodic table group 6 on a support made of a porous inorganic oxide containing two or more elements selected from aluminum, silicon, zirconium, boron, titanium, and magnesium. Examples thereof include a catalyst carrying a metal selected from Group 8, Group 9 and Group 10 elements.

  As the support for the hydrotreating catalyst, a porous inorganic oxide composed of two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium is preferably used. Generally, it is a porous inorganic oxide containing alumina, and other carrier constituents include silica, zirconia, boria, titania, magnesia and the like. Desirably, it is a complex oxide containing at least one kind selected from alumina and other constituents, and examples thereof include silica-alumina.

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

  It is desirable that the raw materials for the carrier constituents other than alumina be added in any step prior to the firing of the carrier. For example, it may be added to an aluminum aqueous solution in advance and then an aluminum hydroxide gel containing these components, may be added to a prepared aluminum hydroxide gel, or water or an acidic aqueous solution may be added to a commercially available alumina intermediate or boehmite powder. Although it may be added to the step of adding and kneading, a method of coexisting at the stage of preparing aluminum hydroxide gel is more desirable. Although the mechanism of the effect of these carrier constituents other than alumina has not been elucidated, it is thought that they form a complex oxide state with aluminum, which increases the surface area of the carrier and some interaction with the active metal. It is considered that the activity is affected by producing the action.

  The active metal of the hydrotreating catalyst preferably contains at least one metal selected from Group VIA (IUPAC Group 6) and Group VIII (IUPAC Group 8 to Group 10) of the Periodic Table, More preferably, it contains two or more kinds of metals selected from Group 6 and Groups 8-10. A hydrotreating catalyst containing at least one type of metal selected from Group 6 and at least one type of metal selected from Groups 8 to 10 as active metals is also suitable. Examples of the combination of active metals include Co-Mo, Ni-Mo, Ni-Co-Mo, Ni-W, and the like. In the hydrorefining treatment, these metals are converted into a sulfide state. use.

As a catalyst for hydrotreating, the total 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-ray diffraction analysis is used. A silica-titania-alumina support having an area of 1/4 or less with respect to the diffraction peak area showing the aluminum crystal structure attributed to the γ-alumina (400) plane, from groups VIA and VIII of the periodic table. A hydrodesulfurization catalyst for hydrocarbon oil carrying at least one selected metal component, wherein (a) specific surface area (SA) is 150 m ² / g or more, (b) total pore volume (PVo) Having a pore diameter of 0.30 ml / g or more, (c) an average pore diameter (PD) in the range of 6 to 15 nm (60 to 150 mm), and (d) an average pore diameter (PD) of ± 30%. volume The hydrotreating catalyst for hydrocarbon oil, wherein the proportion of PVP) is not less than 70% of the total pore volume (PVo) is particularly preferred. This catalyst is hereinafter referred to as “catalyst A”.

  Among the above hydrotreating catalysts, particularly when the catalyst A is used, hydrogenation of hydrocarbon oil easily proceeds at a relatively low reaction temperature in an atmosphere having a relatively high hydrogen partial pressure, and the content of aromatic hydrocarbons To be treated can be easily prepared.

<Specific embodiment of catalyst A>
The silica-titania-alumina carrier in the catalyst A preferably contains 1 to 10% by mass, more preferably 2 to 7% by mass, and more preferably 2 to 5% by mass of silica as SiO _{2 based} on the carrier. Is more preferable. When the silica content is less than 1% by mass, the specific surface area becomes low, and the titania particles tend to aggregate when the carrier is baked, and the crystal structures of anatase titania and rutile titania measured by X-ray diffraction analysis are obtained. The diffraction peak area shown increases. On the other hand, when the content of silica exceeds 10% by mass, the sharpness of the pore distribution of the obtained carrier is deteriorated and the desired desulfurization activity may not be obtained.

The silica-titania-alumina carrier of catalyst A preferably contains 3 to 40% by mass of titania as TiO _{2 on the} basis of the carrier, more preferably 15 to 35% by mass, and still more preferably 15 to 25% by mass. When the titania content is less than 3% by mass, the addition effect of the titania component is small, and the obtained catalyst may not obtain the desired desulfurization activity. Further, when the titania content is more than 40% by mass, the mechanical strength of the catalyst may be lowered, and the crystallization of titania particles is facilitated when the support is fired, so that the specific surface area is lowered. However, the desulfurization performance that meets the economic efficiency of the increased titania amount is not exhibited.

The silica-titania-alumina carrier of catalyst A preferably contains 50 to 96% by mass, more preferably 58 to 83% by mass, and further preferably 70 to 83% by mass of alumina as Al ₂ O _{3 based} on the carrier. To do. Here, when the content of alumina is less than 50% by mass, catalyst deterioration tends to increase, such being undesirable. Moreover, when there is more content of alumina than 96 mass%, since there exists a tendency for catalyst performance to fall, it is unpreferable.

  The catalyst A is obtained by supporting at least one metal component selected from Group VIA and Group VIII of the periodic table on the silica-titania-alumina support. Examples of the metal component of Group VIA of the periodic table include molybdenum (Mo) and tungsten (W). Examples of the metal component of Group VIII of the periodic table include cobalt (Co) and nickel (Ni). One of these metal components may be used alone, or two or more metal components may be used in combination. From the viewpoint of catalyst performance, the metal component is preferably a combination of nickel-molybdenum, cobalt-molybdenum, nickel-molybdenum-cobalt, nickel-tungsten, cobalt-tungsten, nickel-tungsten-cobalt, etc. A combination of cobalt-molybdenum and nickel-molybdenum-cobalt is more preferable.

  The supported amount of the metal component is preferably in the range of 1 to 35% by mass and more preferably in the range of 15 to 30% by mass as the oxide on the catalyst basis. In particular, the supported amount of the metal component of Group VIA of the periodic table is preferably in the range of 10 to 30% by mass, more preferably in the range of 13 to 24% by mass as the oxide. The supported amount of the metal component of Group VIII of the periodic table is preferably in the range of 1 to 10% by mass, more preferably in the range of 2 to 6% by mass as an oxide.

  When the catalyst A contains a metal component of Group VIA of the periodic table, it is preferable to dissolve the metal component using an acid. As the acid, it is preferable to use phosphoric acid and / or organic acid. When using phosphoric acid, phosphorus preferably supports 3 to 25% by mass of phosphoric acid, more preferably 10 to 15% by mass based on 100% by mass of the metal component of Group VIA of the periodic table. It is preferable to be carried in a range. If the loading amount exceeds 25% by mass, the catalyst performance tends to decrease, and this is not preferred. When an organic acid is used, the organic acid is preferably supported in the range of 35 to 75% by mass, more preferably 55 to 65% by mass with respect to the metal component of Group VIA of the periodic table. When the organic acid exceeds 75% by mass relative to the metal component of Group VIA of the periodic table, the viscosity of the solution containing the metal component (hereinafter also referred to as “supported metal-containing solution”) increases, and the impregnation step in the production is performed. It is not preferable because it becomes difficult, and if it is less than 35% by mass, the stability of the supported metal-containing solution is deteriorated and the catalyst performance tends to be deteriorated.

  The method for supporting and containing the metal component, phosphorus and / or organic acid in the carrier is not particularly limited. A known method such as an impregnation method (equilibrium adsorption method, pore filling method, initial wetting method) using a compound containing the above metal component, or a compound containing phosphorus and / or an organic acid, or an ion exchange method can be used. . Here, the impregnation method is a method of impregnating a support containing a solution containing an active metal, followed by drying and firing. In the impregnation method, it is preferable to simultaneously support a metal component of Group VIA of the periodic table and a metal component of Group VIII of the periodic table. If the metals are supported separately, the desulfurization activity or denitrification activity may be insufficient. When the loading is performed by the impregnation method, the dispersibility of the metal component of Group VIA of the periodic table on the support becomes high, and the desulfurization activity and denitrogenation activity of the resulting catalyst become higher. Therefore, the impregnation method is performed in the presence of an acid, preferably in the presence of phosphoric acid or an organic acid. In that case, it is preferable to add 3-25 mass% phosphoric acid or 35-75 mass% organic acid with respect to 100 mass% of periodic table VIA group metal components. As the organic acid, a carboxylic acid compound is preferable, and specific examples include citric acid, malic acid, tartaric acid, and gluconic acid.

The specific surface area of the catalyst A measured by the BET method is 150 m ² / g or more. More preferably, the specific surface area of the catalyst A is 170 m ² / g or more. If the specific surface area is less than 150 m ² / g, the active points of the desulfurization reaction are decreased, and the desulfurization performance may be deteriorated. On the other hand, since the catalyst strength when the specific surface area exceeds 250 meters ² / g tends to decrease, it is preferable that the specific surface area is 250 meters ² / g or less, more preferably 230 m ² / g.

  The total pore volume (PVo) of catalyst A measured by the mercury intrusion method (mercury contact angle: 135 degrees, surface tension: 480 dyn / cm) is 0.30 ml / g or more. Preferably, 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, and is 0.50 ml / g or less. It is more preferable.

  The average pore diameter (PD) of the catalyst A is in the range of 6 to 15 nm (60 to 150 mm). The PD is preferably in the range of 6.5 to 11 nm. When the average pore diameter (PD) is less than 6 nm, the pores are small and the reactivity with the raw material oil may be deteriorated. Moreover, when PD exceeds 15 nm, it is difficult to produce, and the specific surface area tends to be small and the catalyst performance tends to be poor. The total pore volume (PVo) represents pores having a pore diameter of 4.1 nm (41 cm) or more, which is the quantification limit in measurement, and the average pore diameter (PD) is the total pore volume (PVo). ) Represents the pore diameter corresponding to 50%.

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

  In the catalyst A carrier, the “titania diffraction peak area” measured by X-ray diffraction analysis is ¼ or less and preferably １ ／ or less of “alumina diffraction peak area”. It is more preferable that it is / 6 or less. 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 belonging 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 ¼, crystallization of titania proceeds and pores effective for the reaction decrease. Therefore, even if the amount of titania is increased, the desulfurization performance corresponding to the economic efficiency is not exhibited.

  The diffraction peak showing the crystal structure of the anatase type titania (101) plane is measured at 2θ = 25.5 °. The diffraction peak showing the crystal structure of the rutile-type titania (110) plane is measured at 2θ = 27.5 °. The diffraction peak showing the aluminum crystal structure attributed to the γ-alumina (400) plane is measured at 2θ = 45.9 °. In each method of calculating the diffraction peak area, a graph obtained by X-ray diffraction analysis with an X-ray diffractometer is fitted by the least square method to perform baseline correction. Then, the height (peak intensity W) from the maximum peak value of the graph to the baseline is obtained. A peak width (half-value width) at a half value (1/2 W) of the obtained peak intensity is obtained. The product of the half width and the peak intensity is defined as the diffraction peak area. From the obtained diffraction peak areas, “titania diffraction peak area / alumina diffraction peak area” is calculated.

  The manufacturing method of the catalyst A is manufactured by the following method. In the method for producing catalyst A, a mixed aqueous solution of titanium mineral acid salt and acidic aluminum salt (hereinafter also simply referred to as “mixed aqueous solution”) and a basic aluminum salt aqueous solution in the presence of silicate ions have a pH of 6 A first step of obtaining a hydrate by mixing to a degree of 0.5 to 9.5, a second step of obtaining a carrier by washing, molding, drying, and firing the hydrate sequentially, and And a third step of supporting at least one metal component selected from Group VIA (IUPAC Group 6) and Group VIII (IUPAC Group 8 to Group 10) of the periodic table. Hereinafter, each process will be described.

[First step]
In the presence of silicate ions, a mixed aqueous solution (acidic aqueous solution) of a titanium mineral salt and an acidic aluminum salt and a basic aqueous aluminum salt solution (alkaline aqueous solution) have a pH of 6.5 to 9.5, preferably It mixes so that it may become 6.5-8.5, More preferably, it is 6.5-7.5, The hydrate containing a silica, a titania, and an alumina is obtained.

  In the first step, (1) a mixed aqueous solution is added to a basic aluminum salt aqueous solution containing silicate ions, and (2) a basic aluminum salt aqueous solution is added to a mixed aqueous solution containing silicate ions. . In the case of (1), basic or neutral silicate ions contained in the basic aluminum salt aqueous solution can be used. As the basic silicate ion source, a silicate compound that generates silicate ions in water such as sodium silicate can be used. In the case of (2), the silicate ions contained in the mixed solution of the titanium mineral acid salt and the acidic aluminum salt aqueous solution can be acidic or neutral. As the acidic silicate ion source, a silicate compound that generates silicate ions in water such as silicic acid can be used.

  As the basic aluminum salt, sodium aluminate, potassium aluminate or the like is preferably used. Further, as the acidic aluminum salt, aluminum sulfate, aluminum chloride, aluminum nitrate and the like are preferably used, and as the titanium mineral acid salt, titanium tetrachloride, titanium trichloride, titanium sulfate, titanium nitrate and the like are exemplified. Titanium is preferably used because it is inexpensive.

  For example, a basic aluminum salt aqueous solution containing a predetermined amount of basic silicate ions is introduced into a tank with a stirrer and heated to 40 to 90 ° C., preferably 50 to 70 ° C., and held. A mixed aqueous solution of a predetermined amount of a titanium mineral acid salt and an acidic aluminum salt aqueous solution is heated to a temperature of the basic aluminum salt aqueous solution ± 5 ° C., preferably ± 2 ° C., more preferably ± 1 ° C. The heated mixed aqueous solution is continuously added to the basic aluminum salt aqueous solution for 5 to 20 minutes, preferably 7 to 15 minutes to form a precipitate, thereby obtaining a hydrate slurry. The mixed aqueous solution is changed to a basic aluminum salt aqueous solution so that the pH of the hydrate slurry is 6.5 to 9.5, preferably 6.5 to 8.5, more preferably 6.5 to 7.5. It is preferable to add. When the time of adding the mixed aqueous solution to the basic aluminum salt aqueous solution becomes longer, undesirable crystals such as bayerite and gibbsite may be formed in addition to pseudoboehmite. Bayerite and gibbsite are not preferred because their 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 hydrate slurry obtained in the first step is aged and then washed to remove by-product salts to obtain a hydrate slurry containing silica, titania and alumina. The obtained hydrate slurry is further heat-aged and then heat-kneaded to obtain a moldable kneaded product, which is then molded into a desired shape by extrusion molding or the like. The molded body is usually dried at 70 to 150 ° C., preferably 90 to 130 ° C., and further fired at 400 to 800 ° C., preferably 450 to 600 ° C., for 0.5 to 10 hours, preferably 2 to 5 hours. . By these steps, a silica-titania-alumina support containing silica, titania and alumina is obtained.

[Third step]
After at least one metal component selected from Group VIA and Group VIII of the periodic table is supported on the silica-titania-alumina support by the above method, it is usually 400 to 800 ° C., preferably 450 to 600. Baking is performed at a temperature of 0.5 to 10 hours, preferably 2 to 5 hours. The catalyst A is manufactured by the above process. As a raw material for the metal component, for example, nickel nitrate, nickel carbonate, cobalt nitrate, cobalt carbonate, molybdenum trioxide, ammonium molybdate, and ammonium paratungstate are preferably used.

(Hydroisomerization process)
The oil to be treated obtained in the hydrotreating step contains normal paraffin having 10 or more carbon atoms. In the hydroisomerization step, part or all of the oil to be treated containing normal paraffin is converted to isoparaffin by contact between the oil to be treated and the hydroisomerization catalyst.

  Hydroisomerization refers to a reaction in which only the molecular structure of the hydrocarbon oil is changed without changing the carbon number (molecular weight) of the hydrocarbon in the oil to be treated. Decomposition of hydrocarbon oil refers to a reaction accompanied by a decrease in the carbon number (molecular weight) of hydrocarbon oil. In the catalytic dewaxing reaction using a hydroisomerization catalyst, not only isomerization but also decomposition reaction of hydrocarbon oil and isomerization product may occur to some extent. There is no problem as long as the carbon number (molecular weight) of the product of the decomposition reaction falls within a predetermined range that allows the target base oil to be constituted. That is, the decomposition product may be a constituent component of the base oil.

  The reaction conditions for the hydroisomerization step are as follows.

  In the hydroisomerization step, it is preferable to perform hydroisomerization of the oil to be treated in an atmosphere having a hydrogen partial pressure of 11 to 20 MPa. Preferably, the hydrogen partial pressure in the hydroisomerization step is 11 to 19 MPa. When the reaction pressure is 11 MPa or more, coke formation is suppressed and the catalyst life tends to be long. When the reaction pressure is less than 11 MPa, the deterioration of the catalyst due to coke generation tends to be accelerated. On the other hand, when the reaction pressure exceeds 20 MPa, pressure resistance is required for the reaction apparatus, so that the cost for constructing the apparatus becomes high and it is difficult to realize an economical process. However, even when the hydrogen partial pressure is outside the above range, the effect of the present invention is achieved.

  The reaction temperature in the hydroisomerization step is preferably 200 to 450 ° C, more preferably 260 to 400 ° C. When the reaction temperature is equal to or higher than the lower limit, reduction and removal of the wax component by isomerization of normal paraffin contained in the oil to be treated is promoted. On the other hand, when the reaction temperature is not more than the above upper limit, excessive decomposition of the feedstock is suppressed, and the yield of the target hydrocarbon tends to be remarkably improved. However, even when the reaction temperature of the hydroisomerization reaction is out of the above range, the effect of the present invention is achieved.

Liquid hourly space velocity of the feedstock in the hydroisomerization reaction is preferably 0.1 to 10 ^-1, more preferably 0.5~5hr ^-1. When the liquid space velocity is equal to or higher than the lower limit, excessive decomposition of the raw material oil is suppressed, and the yield of the target base oil for lubricating oil tends to be remarkably improved. On the other hand, when the liquid space velocity is less than or equal to the above upper limit value, reduction and removal of the wax component by isomerization of normal paraffin contained in the raw material oil is promoted.

Supply ratio of hydrogen to be processed oil in the hydroisomerization reaction (ratio of hydrogen / treated oil) is more that is preferably 50 to 2000 nm ³ / ^{m 3,} a 100~1500Nm ³ / ^{m 3} preferable. Particularly preferably 200~800Nm ³ / ^{m 3.} When the supply ratio is less than 50 Nm ³ / m ³ , the hydrogen sulfide, ammonia gas, and water generated by the desulfurization, denitrogenation, and deoxygenation reactions that co-occur with the isomerization reaction are adsorbed by the active metal on the catalyst and the catalyst is Poisoned. Further, hydrogenation of a small amount of impurities such as olefin produced by the side reaction is insufficient, and catalyst deactivation due to coking tends to occur. On the other hand, when the supply ratio exceeds 2000 Nm ³ / m ³ , a high-capacity hydrogen supply facility is required, so that an economical process tends to be difficult to realize. However, even when the hydrogen supply ratio is out of the above range, the effects of the present invention are achieved.

  The conversion rate of normal paraffin by hydroisomerization reaction is freely controlled by adjusting reaction conditions such as reaction temperature according to the use of the obtained hydrocarbon.

  According to the hydroisomerization process described above, an isomer having a branched chain structure is obtained by allowing normal paraffin isomerization (that is, dewaxing) to proceed while sufficiently suppressing lightening of normal paraffin contained in the oil to be treated. A base oil having a high content of can be obtained in a high yield.

<Hydroisomerization catalyst>
Is a hydroisomerisation catalyst used in the hydroisomerization step (isomerization dewaxing catalysts), it is preferable to use a hydroisomerization catalyst following the feature is applied by being produced by a particular method . Hereinafter, the hydroisomerization catalyst will be described in accordance with its preferred production mode.

In the method for producing a hydroisomerization catalyst of the present embodiment, an organic template-containing zeolite containing an organic template and having a 10-membered ring one-dimensional pore structure is ion-exchanged in a solution containing ammonium ions and / or protons. A first step of obtaining a support precursor by heating a mixture containing an ion-exchanged zeolite and a binder obtained at a temperature of 250 to 350 ° C. in a N ₂ atmosphere, and a platinum salt and / or Alternatively, a hydroisomerization catalyst in which a catalyst precursor containing a palladium salt is calcined at a temperature of 350 to 400 ° C. in an atmosphere containing molecular oxygen and platinum and / or palladium is supported on a support containing zeolite. And a second step.

The organic template-containing zeolite used in the present embodiment is a one-dimensional fine particle consisting of a 10-membered ring from the viewpoint of achieving both high isomerization activity and suppressed decomposition activity in normal paraffin hydroisomerization reaction at a high level. Has a pore structure. Examples of such zeolite include AEL, EUO, FER, HEU, MEL, MFI, NES, TON, MTT, WEI, ^* MRE, and SSZ-32. The above three letters of the alphabet mean the skeletal structure codes given by the Structure Committee of The International Zeolite Association for each classified molecular sieve type structure. To do. In addition, zeolites having the same topology are collectively referred to by the same code.

As the above-mentioned organic template-containing zeolite, among the zeolites having the above-mentioned 10-membered ring one-dimensional pore structure, zeolites having a TON or MTT structure, and ^* MRE structures in terms of high isomerization activity and low decomposition activity ZSM-48 zeolite and SSZ-32 zeolite which are zeolites are preferred. ZSM-22 zeolite is more preferable as the zeolite having the TON structure, and ZSM-23 zeolite is more preferable as the zeolite having the MTT structure.

  The organic template-containing zeolite is hydrothermally synthesized by a known method from a silica source, an alumina source, and an organic template added to construct the predetermined pore structure.

  The organic template is an organic compound having an amino group, an ammonium group, etc., and is selected according to the structure of the zeolite to be synthesized, but is preferably an amine derivative. Specifically, at least one selected from the group consisting of alkylamine, alkyldiamine, alkyltriamine, alkyltetramine, pyrrolidine, piperazine, aminopiperazine, alkylpentamine, alkylhexamine and derivatives thereof is more preferable.

  The molar ratio ([Si] / [Al]) between silicon and aluminum constituting the organic template-containing zeolite having a 10-membered ring one-dimensional pore structure (hereinafter referred to as “Si / Al ratio”) is 10. It is preferable that it is -400, and it is more preferable that it is 20-350. When the Si / Al ratio is less than 10, the activity for the conversion of normal paraffin increases, but the isomerization selectivity to isoparaffin tends to decrease, and the increase in decomposition reaction accompanying the increase in reaction temperature tends to become rapid. Therefore, it is not preferable. On the other hand, when the Si / Al ratio exceeds 400, it is difficult to obtain the catalyst activity necessary for the conversion of normal paraffin, which is not preferable.

  The organic template-containing zeolite synthesized, preferably washed and dried usually has an alkali metal cation as a counter cation, and the organic template is included in the pore structure. The zeolite containing an organic template used in producing the hydroisomerization catalyst according to the present invention is in such a synthesized state, that is, calcination for removing the organic template included in the zeolite. It is preferable that the treatment is not performed.

  The organic template-containing zeolite is then ion exchanged in a solution containing ammonium ions and / or protons. By the ion exchange treatment, the counter cation contained in the organic template-containing zeolite is exchanged with ammonium ions and / or protons. At the same time, a part of the organic template included 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, and more preferably an aqueous solution. Examples of the compound that supplies ammonium ions 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, mineral acids such as hydrochloric acid, sulfuric acid and nitric acid are usually used as the compound for supplying protons into the solution. An ion-exchanged zeolite obtained by ion-exchange of an organic template-containing zeolite in the presence of ammonium ions (here, an ammonium-type zeolite) releases ammonia during subsequent calcination, and the counter cation serves as a proton as a brane. Stead acid point. As the cation species used for ion exchange, ammonium ions are preferred. The content of ammonium ions and / or protons contained in the solution is preferably set to be 10 to 1000 equivalents relative to the total amount of counter cation and organic template contained in the organic template-containing zeolite to be used. .

  The ion exchange treatment may be performed on the powdery organic template-containing zeolite alone, and prior to the ion exchange treatment, the organic template-containing zeolite is blended with an inorganic oxide as a binder, molded, and obtained. You may perform with respect to the molded object obtained. However, if the molded body is subjected to an ion exchange treatment without firing, the molded body is likely to collapse and pulverize, so the powdered organic template-containing zeolite can be subjected to an ion exchange treatment. preferable.

  The ion exchange treatment is preferably performed by an ordinary method, that is, a method in which a zeolite containing an organic template is immersed in a solution containing ammonium ions and / or protons, preferably an aqueous solution, and this is stirred or fluidized. Moreover, it is preferable to perform said stirring or a flow under a heating in order to improve the efficiency of ion exchange. In the present invention, a method of heating the aqueous solution and performing ion exchange under boiling and reflux is particularly preferable.

  Furthermore, from the viewpoint of increasing the efficiency of ion exchange, it is preferable to exchange the solution once or twice or more during the ion exchange of the zeolite with the solution, and exchange the solution once or twice. It is more preferable. In the case of changing the solution once, for example, the organic template-containing zeolite is immersed in a solution containing ammonium ions and / or protons, heated to reflux for 1 to 6 hours, and then replaced with a new one. By heating to reflux for ˜12 hours, the ion exchange efficiency can be increased.

  By the ion exchange treatment, almost all counter cations such as alkali metals in the zeolite can be exchanged for ammonium ions and / or protons. On the other hand, a part of the organic template included in the zeolite is removed by the above ion exchange treatment. However, it is generally difficult to remove all of the organic template even if the treatment is repeated. Part remains inside the zeolite.

  In this embodiment, a support precursor is obtained by heating a mixture containing ion-exchanged zeolite and a binder at a temperature of 250 to 350 ° C. in a nitrogen atmosphere.

  The mixture containing the ion exchange zeolite and the binder is preferably a mixture of the ion exchange zeolite obtained by the above method and an inorganic oxide as a binder and molding the resulting composition. The purpose of blending the inorganic oxide with the ion-exchanged zeolite is to improve the mechanical strength of the carrier (particularly, the particulate carrier) obtained by firing the molded body to such an extent that it can be practically used. The inventor has found that the choice of the inorganic oxide species affects the isomerization selectivity of the hydroisomerization catalyst. From such a viewpoint, the inorganic oxide is at least one selected from a composite oxide composed of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide, phosphorus oxide, and combinations of two or more thereof. Inorganic oxides are used. Among these, silica and alumina are preferable and alumina is more preferable from the viewpoint of further improving the isomerization selectivity of the hydroisomerization catalyst. The “composite oxide composed of a combination of two or more of these” is composed of at least two components of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide, and phosphorus oxide. The composite oxide is preferably a composite oxide mainly composed of alumina containing 50% by mass or more of an alumina component based on the composite oxide, and more preferably alumina-silica.

  The mixing ratio of the ion exchange zeolite and the inorganic oxide in the composition is preferably 10:90 to 90:10, more preferably 30:70 to 85, as a ratio of the mass of the ion exchange zeolite to the mass of the inorganic oxide. : 15. When this ratio is smaller than 10:90, it is not preferable because the activity of the hydroisomerization catalyst tends to be insufficient. On the other hand, when the ratio exceeds 90:10, the mechanical strength of the carrier obtained by molding and baking the composition tends to be insufficient, which is not preferable.

  The method of blending the above-mentioned inorganic oxide with the ion-exchanged zeolite is not particularly limited. For example, it is usual to add a suitable amount of liquid such as water to both powders to form a viscous fluid and knead this with a kneader or the like. The method performed can be adopted.

  A composition containing the ion-exchanged zeolite and the inorganic oxide or a viscous fluid containing the composition is molded by a method such as extrusion molding, and preferably dried to form a particulate molded body. The shape of the molded body is not particularly limited, and examples thereof include a cylindrical shape, a pellet shape, a spherical shape, and a modified cylindrical shape having a trefoil / four-leaf cross section. The size of the molded body is not particularly limited, but from the viewpoint of ease of handling, packing density into the reactor, and the like, for example, the major axis is preferably about 1 to 30 mm and the minor axis is about 1 to 20 mm.

In this embodiment, it is preferable to heat the molded body obtained as described above at a temperature of 250 to 350 ° C. in a N ₂ atmosphere to obtain a carrier precursor. About heating time, 0.5 to 10 hours are preferable and 1 to 5 hours are more preferable.

  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 blocked by the remaining template. It is considered that the isomerization active site is present near the pore pore mouse. In the above case, the reaction substrate cannot diffuse into the pore due to the clogging of the pore, and the active site is covered and the isomerization reaction does not proceed easily. The conversion rate of normal paraffin tends to be insufficient. On the other hand, when the heating temperature exceeds 350 ° C., the isomerization selectivity of the resulting hydroisomerization catalyst is not sufficiently improved.

  The lower limit temperature when the molded body is heated to form a carrier precursor is preferably 280 ° C. or higher. The upper limit temperature is preferably 330 ° C. or lower.

  In this embodiment, it is preferable to heat the mixture so that a part of the organic template contained in the molded body remains. Specifically, the micropore volume per unit mass of the hydroisomerization catalyst obtained through calcination after metal support described later is 0.02 to 0.12 cc / g, and the zeolite contained in the catalyst It is preferable to set the heating conditions so that the micropore volume per unit mass is 0.01 to 0.11 cc / g.

  Next, a catalyst precursor in which a platinum salt and / or a palladium salt is contained in the carrier precursor is 350 to 400 ° C., preferably 380 to 400 ° C., more preferably 400 ° C. in an atmosphere containing molecular oxygen. By calcining at a temperature, a hydroisomerization catalyst in which platinum and / or palladium is supported on a support containing zeolite is obtained. Note that “under an atmosphere containing molecular oxygen” means that the gas is in contact with a gas containing oxygen gas, preferably air. The firing time is preferably 0.5 to 10 hours, and more preferably 1 to 5 hours.

  Examples of the platinum salt include chloroplatinic acid, tetraamminedinitroplatinum, dinitroaminoplatinum, and tetraamminedichloroplatinum. Since the chloride salt generates hydrochloric acid during the reaction and may corrode the equipment, tetraamminedinitroplatinum, which is a platinum salt in which platinum is highly dispersed other than the chloride salt, is preferable.

  Examples of the palladium salt include palladium chloride, tetraamminepalladium nitrate, and diaminopalladium nitrate. Since the chloride salt generates hydrochloric acid during the reaction and may corrode the equipment, tetraamminepalladium nitrate, which is a palladium salt in which palladium is highly dispersed other than the chloride salt, is preferable.

  The supported amount of the active metal in the support containing zeolite according to the present embodiment is preferably 0.001 to 20% by mass, and more preferably 0.01 to 5% by mass based on the mass of the support. When the supported amount is less than 0.001% by mass, it is difficult to provide a predetermined hydrogenation / dehydrogenation function. On the other hand, when the supported amount exceeds 20% by mass, lightening by decomposition of hydrocarbons on the active metal tends to proceed, and the yield of the target fraction tends to decrease, This is not preferable because the catalyst cost tends to increase.

  Further, when the hydroisomerization catalyst according to the present embodiment is used for hydroisomerization of a hydrocarbon oil containing a large amount of sulfur-containing compounds and / or nitrogen-containing compounds, from the viewpoint of sustainability of the catalyst activity, as an active metal , Nickel-cobalt, nickel-molybdenum, cobalt-molybdenum, nickel-molybdenum-cobalt, nickel-tungsten-cobalt, and the like. The supported amount of these metals is preferably 0.001 to 50% by mass, and more preferably 0.01 to 30% by mass based on the mass of the carrier.

  In the present embodiment, the catalyst precursor is preferably calcined so that the organic template left on the support precursor remains. Specifically, the micropore volume per unit mass of the resulting hydroisomerization catalyst is 0.02 to 0.12 cc / g, and the micropore volume per unit mass of zeolite contained in the catalyst It is preferable to set the heating conditions so as to be 0.01 to 0.11 cc / g.

  The micropore volume per unit mass of the hydroisomerization catalyst is calculated by a method called nitrogen adsorption measurement. That is, for the catalyst, the physical adsorption / desorption isotherm of nitrogen measured at the liquid nitrogen temperature (−196 ° C.) is analyzed. Specifically, the adsorption isotherm of nitrogen measured at the liquid nitrogen temperature (−196 ° C.) is expressed as t. By analyzing by the -plot method, the micropore volume per unit mass of the catalyst is calculated. The micropore volume per unit mass of zeolite contained in the catalyst is also calculated by the above nitrogen adsorption measurement.

Micropore volume V _Z per unit mass of zeolite contained in the catalyst, for example, if the binder does not have a micropore volume, the value of the micropore volume per unit mass of the hydroisomerization catalyst It can be calculated according to the following formula from V _c and the content ratio M _z (mass%) of the zeolite in the catalyst.
V _Z = V _c / M _z × 100

  The hydroisomerization catalyst according to the present invention is preferably a catalyst that has been subjected to a reduction treatment after being charged into a reactor that preferably performs a hydroisomerization reaction following the above-described calcination treatment. Specifically, reduction treatment is performed for about 0.5 to 5 hours in an atmosphere containing molecular hydrogen, preferably in a hydrogen gas flow, preferably at 250 to 500 ° C., more preferably at 300 to 400 ° C. It is preferable that By such a process, the high activity with respect to dewaxing of hydrocarbon oil can be more reliably imparted to the catalyst.

  Another embodiment of the hydroisomerization catalyst according to the present invention comprises: a support having a zeolite having a 10-membered ring one-dimensional pore structure and a binder; and platinum and / or palladium supported on the support. And a hydroisomerization catalyst having a micropore volume per unit mass of the catalyst of 0.02 to 0.12 cc / g, wherein the zeolite contains an organic template and contains a 10-membered ring one-dimensional fine particle. The organic template-containing zeolite having a pore structure is derived from an ion-exchanged zeolite obtained by ion exchange in a solution containing ammonium ions and / or protons. The pore volume is 0.01 to 0.11 cc / g.

Said hydroisomerization catalyst can be manufactured by the method mentioned above. The micropore volume per unit mass of the catalyst and the micropore volume per unit mass of the zeolite contained in the catalyst are the blending amount of the ion exchange zeolite in the mixture containing the ion exchange zeolite and the binder, and the N of the mixture. The heating conditions under the _two atmospheres and the heating conditions under the atmosphere containing the molecular oxygen of the catalyst precursor can be appropriately adjusted to be within the above range.

(Hydrofinishing process)
In the present embodiment, hydrofinishing may be performed on the product oil obtained by the hydroisomerization step. In hydrofinishing, the product oil is contacted with a metal-supported hydrogenation catalyst in the presence of hydrogen. Examples of the hydrogenation catalyst include alumina and silica alumina on which platinum and / or palladium is supported. By the hydrofinishing, the hue, oxidation stability, etc. of the reaction product (product oil) obtained in the hydroisomerization step (dewaxing step) are improved, and the quality of the product can be improved. Even if a hydrofinishing catalyst layer is provided on the downstream side of the hydroisomerization catalyst catalyst layer provided in the reactor for performing the hydroisomerization process, the hydrofinishing may be performed following the dewaxing process. Good. Hydrofinishing may be performed in a reaction facility separate from the dewaxing step.

(Purification process)
In this embodiment, the base oil may be purified by performing vacuum distillation on the product oil obtained by the hydrofinishing step. You may perform vacuum distillation further with respect to the heavy fraction obtained by vacuum distillation. For example, the hydrorefining feedstock may be separated into a plurality of light fractions having a lower kinematic viscosity than the hydrorefining feedstock by a refining step. These base oils are mixed with a light oil having a low kinematic viscosity as necessary, and the properties such as kinematic viscosity and viscosity index (VI) of each fraction are adapted to each standard, thereby obtaining a desired lubricating oil. Base oil is prepared.

  The reaction equipment for carrying out the hydrotreating process and the reaction equipment for carrying out the hydroisomerization process are not particularly limited. A well-known thing can be used as each equipment. Each facility may be a continuous flow type, a batch type, or a semi-batch type, but is preferably a continuous flow type from the viewpoint of productivity and efficiency. The catalyst layer of each facility may be any of a fixed bed, a fluidized bed, and a stirring bed, but is preferably a fixed bed from the viewpoint of facility costs. The reaction phase is preferably a gas-liquid mixed phase.

  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.

<Manufacture of hydrotreating catalyst>
A tank with a capacity of 100 L and a steam jacket is charged with 8.16 kg of an aqueous solution of sodium aluminate having an Al ₂ O ₃ equivalent concentration of 22% by mass, diluted with 41 kg of ion-exchanged water, and an SiO ₂ equivalent concentration of 5 mass. % Sodium silicate solution 1.80 kg was added with stirring and heated to 60 ° C. to prepare a basic aluminum salt aqueous solution. Also, an acidic aluminum salt aqueous solution obtained by diluting 7.38 kg of an aluminum sulfate aqueous solution having a concentration in terms of Al ₂ O ₃ of 7% by mass with 13 kg of ion-exchanged water, and titanium sulfate 1 having a concentration in terms of TiO ₂ of 33% by mass. .82 kg was mixed with an aqueous solution of titanium mineral salt dissolved in 10 kg of ion exchange water, and heated to 60 ° C. to prepare a mixed aqueous solution. Hydrate slurry a containing silica, titania, and alumina is added to a tank containing a basic aluminum salt aqueous solution at a constant rate for 10 minutes using a roller pump until the pH is 7.2. Was prepared.

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

  X-ray diffraction analysis of the carrier a was performed using an R-ray diffraction apparatus RINT2100 manufactured by Rigaku Corporation. In the X-ray diffraction pattern of carrier a, the diffraction peak area showing the crystal structure of anatase titania and 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 at 95 ° C. for 5 hours with appropriate refluxing measures so as not to reduce the liquid volume. 68 g of phosphoric acid was added to the suspension after heating and dissolved to prepare an impregnation solution. The impregnation liquid was impregnated by spraying on 1000 g of carrier a, and then dried at 250 ° C. The dried carrier a was calcined in an electric furnace at 550 ° C. for 1 hour to obtain a hydrotreating catalyst a (hereinafter also referred to as “catalyst a”). The concentration of MoO ₃ with respect to the total mass of the catalyst a was 22% by mass. The concentration of CoO with respect to the total mass of the catalyst a was 3% by mass. The concentration of P ₂ O ₅ with respect to the total mass of the catalyst a was 3% by mass.

<Production of hydroisomerization catalyst>
A ZSM-22 zeolite composed of crystalline aluminosilicate having a Si / Al ratio of 45 (hereinafter sometimes referred to as “ZSM-22”) was produced by hydrothermal synthesis according to the following procedure.

First, the following four types of aqueous solutions were prepared.
Solution A: 1.94 g of potassium hydroxide dissolved in 6.75 mL of ion exchange water.
Solution B: A solution obtained by dissolving 1.33 g of aluminum sulfate 18-hydrate in 5 mL of ion-exchanged water.
Solution C: A solution obtained by diluting 4.18 g of 1,6-hexanediamine (organic template) 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, solution A was added to solution B and stirred until the aluminum component was completely dissolved. After adding the solution C to this mixed solution, the mixture of the solutions A, B and C was poured into the solution D with vigorous stirring at room temperature. 0.25 g of ZSM-22 powder, which was synthesized separately and not subjected to any special treatment after synthesis, was added to the mixture of solutions A, B, C and D as “seed crystals” to promote crystallization, A gel was obtained.

  The above gel-like material is transferred to a stainless steel autoclave reactor having an internal volume of 120 mL, and the autoclave reactor is rotated on a tumbling apparatus at a rotation speed of about 60 rpm in an oven at 150 ° C. for 60 hours, thereby hydrothermal synthesis reaction. Went. After completion of the reaction, the reactor was cooled and opened, and dried overnight in a dryer at 60 ° C. to obtain ZSM-22 having a Si / Al ratio of 45.

  The obtained ZSM-22 was subjected to ion exchange treatment with an aqueous solution containing ammonium ions by the following operation.

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

After heating reflux for 12 hours, the solid content was collected by filtration, washed with ion-exchanged water, and dried overnight in a dryer at 60 ° C. to obtain ion-exchanged NH ₄ type ZSM-22. This ZSM-22 is ion-exchanged in a state containing an organic template.

The 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 the mixture and kneaded. The obtained viscous fluid was filled into an extrusion molding machine and molded to obtain a cylindrical molded body having a diameter of about 1.6 mm and a length of about 10 mm. This molded body was heated at 300 ° C. for 3 hours under an N ₂ atmosphere to obtain a carrier precursor.

Tetraamminedinitroplatinum [Pt (NH ₃ ) ₄ ] (NO ₃ ) ₂ was dissolved in ion-exchanged water corresponding to the previously measured water absorption of the carrier precursor to obtain an impregnation solution. This solution is impregnated with the above-mentioned carrier precursor by the initial wet method, and platinum is supported on the ZSM-22 type zeolite so that the platinum content is 0.3% by mass with respect to the mass of the ZSM-22 type zeolite. It was. Next, the obtained impregnated product (catalyst precursor) was dried overnight at 60 ° C. and then calcined at 400 ° C. for 3 hours under air flow to obtain hydroisomerization catalyst b (hereinafter referred to as “catalyst”). b ").

Example 1
By extracting and removing a part of the aromatic hydrocarbon in the vacuum gas oil fraction into the furfural using an extraction tower, the hydrocarbon oil of Example 1 (hydrocarbon oil before hydrotreating) is removed. Obtained. Boiling range of hydrocarbon oil before hydrotreating of Example 1, T10, T90, content of aromatic hydrocarbon in hydrocarbon oil, content of sulfur in hydrocarbon oil, 100 ° C. of hydrocarbon oil Table 1 shows the kinematic viscosity and the viscosity index of the hydrocarbon oil. The density of the hydrocarbon oil before hydrotreatment of Example 1 at 15 ° C. was 0.8683 g / cm ³ . Content of the nitrogen content in the hydrocarbon oil before the hydrotreatment of 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 where the partial pressure of hydrogen was the value shown in Table 1. The oil to be treated of Example 1 was obtained. In the hydrotreating step, the ratio of hydrogen / hydrocarbon oil was adjusted to 253 Nm ³ / m ³ . In the hydrotreating step, the liquid space velocity of the hydrocarbon oil relative to the catalyst a was adjusted to the values shown in Table 1. The content of aromatic hydrocarbons in the oil to be treated obtained in the hydrotreating step of Example 1, the content of sulfur in the oil to be treated, the kinematic viscosity of the oil to be treated, and the viscosity index of the oil to be treated Each value of VI is shown in Table 1.

In the hydroisomerization step of Example 1, the oil to be treated of Example 1 was brought into contact with the catalyst b at the reaction temperature shown in Table 2 in an atmosphere where the partial pressure of hydrogen was the value shown in Table 2. The product oil of Example 1 was obtained. In the hydroisomerization step, the ratio of hydrogen / hydrocarbon oil was adjusted to 506 Nm ³ / m ³ . In the hydroisomerization step, the liquid space velocity of the hydrocarbon oil relative to the catalyst b was adjusted to the values shown in Table 2. The reaction temperature in the hydroisomerization step of Example 1 is the lowest at which the pour point of the following base oil fraction b for lubricating oil ("main base oil fraction" in Table 2) is -12.5 ° C or lower. Temperature. Table 2 shows the aromatic hydrocarbon content in the product oil of Example 1, the sulfur content in the product oil, and the yield X of Example 1. In addition, the yield X in Table 2 is a value represented by the following formula.
X = (V _L / V _R ) × 100
In formula, _VL is the sum total of the mass of each base oil fraction for lubricating oil (final base oil fraction). The final base oil fraction is obtained by distilling the product oil of the hydroisomerization step into naphtha, kerosene oil, and a heavy fraction having a target kinematic viscosity by distillation. V _R is a mass of the treated oil obtained in the hydrotreating step, the mass of the treated oil before hydroisomerisation step. The final base oil fractions of Example 1 and the following Examples and Comparative Examples are shown in Table 3.

  In the purification step (vacuum distillation step) of Example 1, the product oil obtained in the hydroisomerization step was fractionated into a naphtha, a kerosene oil fraction, and a heavy fraction. Furthermore, by fractionating the heavy fraction, the following base oil fraction a for lubricating oil (base oil fraction 1 in Table 3) and base oil fraction b for lubricating oil (base oil fraction in Table 3) Minute 2) was obtained. The base oil fraction b for lubricating oil of Example 1 corresponds to the “main base oil fraction” in Table 2.

[Base oil fraction a for lubricating oil a]
Kinematic viscosity at 100 ° C .: 2.71 mm ² / s.
Boiling range: 341-385 ° C.

[Base oil fraction b for lubricating oil]
Table 2 shows the yield Y, pour point, kinematic viscosity, viscosity index VI and (VI × Y) of the base oil fraction b (main base oil fraction) for lubricating oil. Note that the yield of the main base oil fraction, V _L is the mass of the main base oil fractions, V _R is a mass of the treated oil obtained in the hydrotreating step, hydroisomerisation step When it is the mass of the previous oil to be treated, it is a value represented by (V _L / V _R ) × 100. The boiling point range of the main base oil fraction of Example 1 was 395 to 421 ° C.

(Example 2)
In Example 2, the hydrotreating step was performed under the conditions shown in Table 1, and oil to be treated shown in Table 1 was obtained. In Example 2, the hydroisomerization process was implemented on the conditions shown in Table 2, and the product oil shown in Table 2 was obtained. In Example 2, the same purification process as in Example 1 was performed to obtain the base oil fractions shown in Table 2. Except for these matters, Example 1 and Example 2 are common.

(Example 3)
In Example 3, a hydrocarbon oil not subjected to the solvent extraction step (hydrocarbon oil before hydrotreatment) was used. Boiling range of hydrocarbon oil before hydrotreating of Example 3, T10, T90, content of aromatic hydrocarbon in hydrocarbon oil, content of sulfur in hydrocarbon oil, 100 ° C. of hydrocarbon oil Table 1 shows the kinematic viscosity and the viscosity index VI of the hydrocarbon oil. In addition, the density in 15 degreeC of the hydrocarbon oil before the hydrogenation process of Example 3 was 0.9150 g / cm < ³ >. The nitrogen content in the hydrocarbon oil before the hydrotreatment of 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 where the partial pressure of hydrogen was the value shown in Table 1. The oil to be treated of Example 3 was obtained. In the hydrotreating step, the ratio of hydrogen / hydrocarbon oil was adjusted to 844 Nm ³ / m ³ . In the hydrotreating step, the liquid space velocity of the hydrocarbon oil relative to the catalyst a was adjusted to the values shown in Table 1. The content of aromatic hydrocarbons in the oil to be treated obtained in the hydrotreating step of Example 3, the content of sulfur in the oil to be treated, the kinematic viscosity of the oil to be treated, and the viscosity index of the oil to be treated Each value of VI is shown in Table 1.

In the hydroisomerization step of Example 3, in the atmosphere where the partial pressure of hydrogen is the value shown in Table 2, the oil to be treated of Example 3 is brought into contact with the catalyst b at the reaction temperature shown in Table 2. The product oil of Example 3 was obtained. In the hydroisomerization step, the ratio of hydrogen / hydrocarbon oil was adjusted to 506 Nm ³ / m ³ . In the hydroisomerization step, the liquid space velocity of the hydrocarbon oil relative to the catalyst b was adjusted to the values shown in Table 2. The reaction temperature of the hydroisomerization step of Example 3 is the lowest at which the pour point of the following base oil fraction b for lubricating oil (“main base oil fraction” in Table 2) is −12.5 ° C. or lower. Temperature. Table 2 shows the aromatic hydrocarbon content in the product oil of Example 3, the sulfur content in the product oil, and the yield X of Example 3.

  In the purification step (vacuum distillation step) of Example 3, the product oil obtained in the hydroisomerization step was fractionated into a naphtha, a kerosene fraction, and a heavy fraction. Further, the heavy fraction was fractionated to obtain the following base oil fraction 1 for lubricating oil and base oil fraction b for lubricating oil. The base oil fraction b for lubricating oil in Example 3 corresponds to the “main base oil fraction” in Table 2.

[Base oil fraction a for lubricating oil a]
Kinematic viscosity at 100 ° C .: 2.70 mm ² / s.
Boiling range: 343-387 ° C.

[Base oil fraction b for lubricating oil]
Table 2 shows values of yield Y, pour point, kinematic viscosity, viscosity index VI and (VI × Y) of the base oil fraction b (main base oil fraction) for lubricating oil of Example 3. In addition, the boiling point range of the main base oil fraction of Example 3 was 392 to 447 ° C.

Example 4
By extracting a part of the aromatic hydrocarbon in the vacuum gas oil fraction into the furfural using an extraction tower and removing it, the hydrocarbon oil of Example 4 (hydrocarbon oil before hydrotreating) is removed. Obtained. Boiling range of hydrocarbon oil before hydrotreating in Example 4, T10, T90, aromatic hydrocarbon content in hydrocarbon oil, sulfur content in hydrocarbon oil, kinematic viscosity of hydrocarbon oil Each value of the viscosity index VI of the hydrocarbon oil is shown in Table 1. In addition, the density in 15 degreeC of the hydrocarbon oil before the hydrogenation process of Example 4 was 0.8724 g / cm < ³ >. Content of the nitrogen content in the hydrocarbon oil before the hydrotreatment of 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 where the partial pressure of hydrogen was the value shown in Table 1. The oil to be treated of Example 4 was obtained. In the hydrotreating step, the ratio of hydrogen / hydrocarbon oil was adjusted to 253 Nm ³ / m ³ . In the hydrotreating step, the liquid space velocity of the hydrocarbon oil relative to the catalyst a was adjusted to the values shown in Table 1. The content of aromatic hydrocarbons in the oil to be treated obtained in the hydrotreating step of Example 4, the content of sulfur in the oil to be treated, the kinematic viscosity of the oil to be treated, and the viscosity index of the oil to be treated Each value of VI is shown in Table 1.

In the hydroisomerization step of Example 4, in the atmosphere where the partial pressure of hydrogen is the value shown in Table 2, the oil to be treated of Example 4 is brought into contact with the catalyst b at the reaction temperature shown in Table 2. The product oil of Example 4 was obtained. In the hydroisomerization step, the ratio of hydrogen / hydrocarbon oil was adjusted to 506 Nm ³ / m ³ . In the hydroisomerization step, the liquid space velocity of the hydrocarbon oil relative to the catalyst b was adjusted to the values shown in Table 1. The reaction temperature of the hydroisomerization step of Example 4 is the most when the pour point of the following base oil fraction c for lubricating oil (“main base oil fraction” in Table 2) is −12.5 ° C. or less. The temperature is low. Table 2 shows the aromatic hydrocarbon content in the product oil of Example 4, the sulfur content in the product oil, and the yield X of Example 4.

  In the purification step (vacuum distillation step) of Example 4, the product oil obtained in the hydroisomerization step was fractionated into a naphtha, a kerosene fraction, and a heavy fraction. Further, by fractionating the heavy fraction, the following base oil fraction a for lubricating oil (base oil fraction 1 in Table 3) and base oil fraction b for lubricating oil (base oil fraction in Table 3) 2) and a base oil fraction c for lubricating oil (base oil fraction 3 in Table 3) were obtained. The base oil fraction c for lubricating oil of Example 4 corresponds to the “main base oil fraction” in Table 2.

[Base oil fraction a for lubricating oil a]
Kinematic viscosity at 100 ° C .: 2.70 mm ² / s.
Boiling range: 343-387 ° C.

[Base oil fraction b for lubricating oil]
Kinematic viscosity at 100 ° C .: 4.91 mm ² / s.
Boiling range: 395-445 ° C.

[Base oil fraction c for lubricating oil]
Table 2 shows the values of yield Y, pour point, kinematic viscosity, viscosity index VI and (VI × Y) of the base oil fraction c (main base oil fraction) for lubricating oil of Example 4. In addition, the boiling point range of the main base oil fraction of Example 4 was 455-472 degreeC.

(Example 5)
By using an extraction tower, a portion of the aromatic hydrocarbon in the vacuum gas oil fraction is extracted into furfural and removed, thereby removing the hydrocarbon oil of Example 5 (hydrocarbon oil before hydrotreating). Obtained. Boiling range of hydrocarbon oil before hydrotreating of Example 5, T10, T90, content of aromatic hydrocarbon in hydrocarbon oil, content of sulfur in hydrocarbon oil, 100 ° C. of hydrocarbon oil Table 1 shows the kinematic viscosity and the viscosity index VI of the hydrocarbon oil. In addition, the density in 15 degreeC of the hydrocarbon oil before the hydrogenation process of Example 5 was 0.8873 g / cm < ³ >. The nitrogen content in the hydrocarbon oil before hydrotreatment of Example 5 was 77 ppm by mass.

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 where the partial pressure of hydrogen was the value shown in Table 1. The oil to be treated of Example 5 was obtained. In the hydrotreating step, the ratio of hydrogen / hydrocarbon oil was adjusted to 253 Nm ³ / m ³ . In the hydrotreating step, the liquid space velocity of the hydrocarbon oil relative to the catalyst a was adjusted to the values shown in Table 1. The content of aromatic hydrocarbons in the oil to be treated obtained in the hydrotreating step of Example 5, the content of sulfur in the oil to be treated, the kinematic viscosity of the oil to be treated, and the viscosity index of the oil to be treated Each value of VI is shown in Table 1.

In the hydroisomerization step of Example 5, in the atmosphere where the partial pressure of hydrogen is the value shown in Table 2, the oil to be treated of Example 5 is brought into contact with the catalyst b at the reaction temperature shown in Table 2. The product oil of Example 5 was obtained. In the hydroisomerization step, the ratio of hydrogen / hydrocarbon oil was adjusted to 506 Nm ³ / m ³ . In the hydroisomerization step, the liquid space velocity of the hydrocarbon oil relative to the catalyst b was adjusted to the values shown in Table 1. The reaction temperature of the hydroisomerization step of Example 5 is the lowest at which the pour point of the following base oil fraction c for lubricating oil (“main base oil fraction” in Table 2) is −12.5 ° C. or lower. Temperature. Table 2 shows the aromatic hydrocarbon content in the product oil of Example 5, the sulfur content in the product oil, and the yield X of Example 5.

  In the purification step of Example 5 (vacuum distillation step), the product oil obtained in the hydroisomerization step was fractionated into a naphtha, a kerosene fraction, and a heavy fraction. Further, by fractionating heavy fractions, the following base oil fraction a for lubricating oil (base oil fraction 2 in Table 3) and base oil fraction b for lubricating oil (base oil fraction in Table 3) 3) and base oil fraction 3 for lubricating oil (base oil fraction 4 in Table 3) were obtained. The base oil fraction c for lubricating oil in Example 5 corresponds to the “main base oil fraction” in Table 2.

[Base oil fraction a for lubricating oil a]
Kinematic viscosity at 100 ° C .: 2.70 mm ² / s.
Boiling range: 395-447 ° C.

[Base oil fraction b for lubricating oil]
Kinematic viscosity at 100 ° C .: 4.93 mm ² / s.
Boiling range: 457-476 ° C.

[Base oil fraction c for lubricating oil]
Table 2 shows the values of yield Y, pour point, kinematic viscosity, viscosity index VI and (VI × Y) of the base oil fraction c (main base oil fraction) for lubricating oil of Example 5. In addition, the boiling point range of the main base oil fraction of Example 5 was 495-535 degreeC.

(Examples 6 to 9)
In Examples 6 to 9, the hydrotreating treatment of the hydrocarbon oil shown in Table 1 was performed under the conditions shown in Table 1, and the oil to be treated shown in Table 1 was obtained. In Examples 6-9, the hydroisomerization process with respect to the to-be-processed oil shown in Table 1 was implemented on the conditions shown in Table 2, and the product oil shown in Table 2 was obtained. Except for these matters, Examples 6 to 10 and Example 5 are common. Also in Examples 6 to 9, the same purification process as in Example 5 was performed to obtain the base oil fractions shown in Tables 2 and 3.

(Example 10)
By extracting a part of the aromatic hydrocarbon in the vacuum gas oil fraction into the furfural using an extraction tower and removing it, the hydrocarbon oil of Example 10 (hydrocarbon oil before hydrotreating) is removed. Obtained. Boiling range of hydrocarbon oil before hydrotreating of Example 10, T10, T90, content of aromatic hydrocarbon in hydrocarbon oil, content of sulfur in hydrocarbon oil, 100 ° C. of hydrocarbon oil Table 1 shows the kinematic viscosity and the viscosity index of the hydrocarbon oil. In addition, the density in 15 degreeC of the hydrocarbon oil before the hydrogenation process of Example 10 was 0.8589 g / cm < ³ >. The content of nitrogen content in the hydrocarbon oil before hydrotreatment of Example 10 was 25 ppm by mass.

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 where the partial pressure of hydrogen was the value shown in Table 1. The oil to be treated of Example 10 was obtained. In the hydrotreating step, the ratio of hydrogen / hydrocarbon oil was adjusted to 253 Nm ³ / m ³ . In the hydrotreating step, the liquid space velocity of the hydrocarbon oil relative to the catalyst a was adjusted to the values shown in Table 1. The content of aromatic hydrocarbons in the treated oil obtained in the hydrotreating step of Example 10, the content of sulfur in the treated oil, the kinematic viscosity of the treated oil, and the viscosity index of the treated oil Each value of VI is shown in Table 1.

In the hydroisomerization step of Example 10, the oil to be treated of Example 10 was brought into contact with the catalyst b at the reaction temperature shown in Table 2 in an atmosphere where the partial pressure of hydrogen was the value shown in Table 2. The product oil of Example 10 was obtained. In the hydroisomerization step, the ratio of hydrogen / hydrocarbon oil was adjusted to 506 Nm ³ / m ³ . In the hydroisomerization step, the liquid space velocity of the hydrocarbon oil relative to the catalyst b was adjusted to the values shown in Table 2. The reaction temperature in the hydroisomerization step of Example 10 is the lowest at which the pour point of the following base oil fraction a for lubricating oil (the “main base oil fraction” in Table 2) is −12.5 ° C. or lower. Temperature. Table 2 shows the aromatic hydrocarbon content in the product oil of Example 10, the sulfur content in the product oil, and the yield X of Example 10.

  The following base oil fraction a for lubricating oil (a base oil fraction 1 'in Table 3) was obtained through the purification step (vacuum distillation step) of Example 10.

[Base oil fraction a for lubricating oil a]
Kinematic viscosity at 100 ° C .: 2.702 mm ² / s.
Boiling range: 341-385 ° C.

  Table 2 shows the values of yield Y, pour point, kinematic viscosity, viscosity index VI and (VI × Y) of the base oil fraction a for lubricating oil (the main base oil fraction) of Example 10. The boiling point range of the main base oil fraction of Example 10 was 341 to 385 ° C.

(Example 11)
As the hydrocarbon oil of Example 11 (hydrocarbon oil before hydrotreatment), a vacuum gas oil fraction not subjected to the extraction step with furfural was used. Boiling range of hydrocarbon oil before hydrotreating of Example 11, T10, T90, content of aromatic hydrocarbon in hydrocarbon oil, content of sulfur in hydrocarbon oil, 100 ° C. of hydrocarbon oil Table 1 shows the kinematic viscosity and the viscosity index of the hydrocarbon oil. In addition, the density in 15 degreeC of the hydrocarbon oil before the hydrogenation process of Example 11 was 0.9054 g / cm < ³ >. The nitrogen content in the hydrocarbon oil before the hydrogenation treatment in Example 11 was 510 mass ppm.

The hydrotreating step of Example 11 was carried out by bringing the hydrocarbon oil of Example 11 into contact with the catalyst a at the reaction temperature shown in Table 1 in an atmosphere where the partial pressure of hydrogen was the value shown in Table 1. The oil to be treated of Example 11 was obtained. In the hydrotreating step, the ratio of hydrogen / hydrocarbon oil was adjusted to 253 Nm ³ / m ³ . In the hydrotreating step, the liquid space velocity of the hydrocarbon oil relative to the catalyst a was adjusted to the values shown in Table 1. The content of aromatic hydrocarbons in the oil to be treated obtained in the hydrotreating step of Example 11, the content of sulfur in the oil to be treated, the kinematic viscosity of the oil to be treated, and the viscosity index of the oil to be treated Each value of VI is shown in Table 1.

In the hydroisomerization step of Example 11, the oil to be treated of Example 11 was brought into contact with the catalyst b at the reaction temperature shown in Table 2 in an atmosphere where the partial pressure of hydrogen was the value shown in Table 2. The product oil of Example 11 was obtained. In the hydroisomerization step, the ratio of hydrogen / hydrocarbon oil was adjusted to 506 Nm ³ / m ³ . In the hydroisomerization step, the liquid space velocity of the hydrocarbon oil relative to the catalyst b was adjusted to the values shown in Table 2. The reaction temperature in the hydroisomerization step of Example 11 is the lowest at which the pour point of the following base oil fraction a for lubricating oil (“main base oil fraction” in Table 2) is −12.5 ° C. or lower. Temperature. Table 2 shows the aromatic hydrocarbon content in the product oil of Example 11, the sulfur content in the product oil, and the yield X of Example 11.

  The following base oil fraction a for lubricating oil (a base oil fraction 1 'in Table 3) was obtained through the purification step (vacuum distillation step) of Example 11.

[Base oil fraction a for lubricating oil a]
Kinematic viscosity at 100 ° C .: 2.702 mm ² / s.
Boiling range: 341-387 ° C.

  Table 2 shows values of yield Y, pour point, kinematic viscosity, viscosity index VI and (VI × Y) of the base oil fraction a for lubricating oil of Example 11 (main base oil fraction). The boiling point range of the main base oil fraction of Example 11 was 341 to 387 ° C.

(Example 12)
Using an extraction tower, a portion of the aromatic hydrocarbon in the vacuum gas oil fraction was extracted into furfural and removed, and then the solvent of the vacuum gas oil fraction was subjected to solvent degassing, whereby the hydrocarbon of Example 12 was obtained. An oil (hydrocarbon oil before hydrotreatment) was obtained. Boiling range of hydrocarbon oil before hydrotreating of Example 12, T10, T90, content of aromatic hydrocarbon in hydrocarbon oil, content of sulfur in hydrocarbon oil, 100 ° C. of hydrocarbon oil Table 1 shows the kinematic viscosity and the viscosity index VI of the hydrocarbon oil. The density of the hydrocarbon oil before hydrotreatment of Example 12 at 15 ° C. was 0.8831 g / cm ³ . The nitrogen content in the hydrocarbon oil before hydrotreatment of Example 12 was 18 ppm by mass.

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 where the partial pressure of hydrogen was the value shown in Table 1. The oil to be treated of Example 12 was obtained. In the hydrotreating step, the ratio of hydrogen / hydrocarbon oil was adjusted to 253 Nm ³ / m ³ . In the hydrotreating step, the liquid space velocity of the hydrocarbon oil relative to the catalyst a was adjusted to the values shown in Table 1. The content of aromatic hydrocarbons in the oil to be treated obtained in the hydrotreating step of Example 12, the content of sulfur in the oil to be treated, the kinematic viscosity of the oil to be treated, and the viscosity index of the oil to be treated Each value of VI is shown in Table 1.

In the hydroisomerization step of Example 12, the oil to be treated of Example 12 was brought into contact with the catalyst b at the reaction temperature shown in Table 2 in an atmosphere where the partial pressure of hydrogen was the value shown in Table 2. The product oil of Example 12 was obtained. In the hydroisomerization step, the ratio of hydrogen / hydrocarbon oil was adjusted to 506 Nm ³ / m ³ . In the hydroisomerization step, the liquid space velocity of the hydrocarbon oil relative to the catalyst b was adjusted to the values shown in Table 1. The reaction temperature in the hydroisomerization step of Example 12 is the lowest at which the pour point of the following base oil fraction c for lubricating oil ("main base oil fraction" in Table 2) is -12.5 ° C or lower. Temperature. Table 2 shows the aromatic hydrocarbon content in the product oil of Example 12, the sulfur content in the product oil, and the yield X of Example 12.

  In the purification step (vacuum distillation step) of Example 12, the product oil obtained in the hydroisomerization step was fractionated into a naphtha, a kerosene fraction, and a heavy fraction. Further, by fractionating the heavy fraction, the following base oil fraction a for lubricating oil (base oil fraction 3 in Table 3) and base oil fraction b for lubricating oil (base oil fraction in Table 3) 4) and a base oil fraction c for lubricating oil (base oil fraction 5 in Table 3) were obtained. The base oil fraction c for lubricating oil in Example 12 corresponds to the “main base oil fraction” in Table 2.

[Base oil fraction a for lubricating oil a]
Kinematic viscosity at 100 ° C .: 6.213 mm ² / s.
Boiling range: 457-476 ° C.

[Base oil fraction b for lubricating oil]
Kinematic viscosity at 100 ° C .: 10.50 mm ² / s.
Boiling range: 497-538 ° C.

[Base oil fraction c for lubricating oil]
Table 2 shows the values of yield Y, pour point, kinematic viscosity, viscosity index VI and (VI × Y) of the base oil fraction c (main base oil fraction) for lubricating oil of Example 12. The boiling point range of the main base oil fraction of Example 12 was 562 to 610 ° C.

(Comparative Example 1)
In Comparative Example 1, the hydrocarbon oil shown in Table 1 was hydrotreated under the conditions shown in Table 1 to obtain the oil to be treated shown in Table 1. In Comparative Example 1, the hydroisomerization step for the oil to be treated shown in Table 1 was performed under the conditions shown in Table 2 to obtain a product oil shown in Table 2. Except for these matters, Comparative Example 1 and Examples 1 and 2 are common. Also in the comparative example 1, the refinement | purification process similar to Example 1, 2 was implemented, and the base oil fraction shown to Table 2, 3 was obtained.

(Comparative Example 2)
In Comparative Example 2, the hydrocarbon oil shown in Table 1 was subjected to hydrogenation treatment under the conditions shown in Table 1 to obtain the oil to be treated shown in Table 1. In Comparative Example 2, the hydroisomerization step for the oil to be treated shown in Table 1 was performed under the conditions shown in Table 2 to obtain a product oil shown in Table 2. Except for these matters, Comparative Example 2 is common to Examples 1, 2 and Comparative Example 1. Also in the comparative example 2, the refinement | purification process similar to Example 1, 2 and the comparative example 1 was implemented, and the base oil fraction shown to Table 2, 3 was obtained.

(Comparative Example 3)
In Comparative Example 3, the hydrocarbon oil shown in Table 1 was subjected to hydrogenation treatment under the conditions shown in Table 1 to obtain an oil to be treated shown in Table 1. In Comparative Example 3, the hydroisomerization step for the oil to be treated shown in Table 1 was performed under the conditions shown in Table 2 to obtain a product oil shown in Table 2. Except for these matters, Comparative Example 3 and Example 3 are common. Also in the comparative example 3, the refinement | purification process similar to Example 3 was implemented, and the base oil fraction shown to Table 2, 3 was obtained.

(Comparative Example 4)
In Comparative Example 4, the hydrocarbon oil shown in Table 1 was hydrotreated under the conditions shown in Table 1 to obtain the oil to be treated shown in Table 1. In Comparative Example 4, the hydroisomerization process was performed on the oil to be treated shown in Table 1 under the conditions shown in Table 2 to obtain a product oil shown in Table 2. Except for these matters, Comparative Example 4, Example 3, and Comparative Example 3 are common. Also in the comparative example 4, the refinement | purification process similar to Example 3 and the comparative example 3 was implemented, and the base oil fraction shown to Table 2, 3 was obtained.

(Comparative Example 5)
In Comparative Example 5, the hydrocarbon oil shown in Table 1 was hydrotreated under the conditions shown in Table 1 to obtain the oil to be treated shown in Table 1. In Comparative Example 5, the hydroisomerization step for the oil to be treated shown in Table 1 was performed under the conditions shown in Table 2 to obtain a product oil shown in Table 2. Except for these matters, Comparative Example 5 and Example 4 are common. Also in the comparative example 5, the refinement | purification process similar to Example 4 was implemented, and the base oil fraction shown to Table 2, 3 was obtained.

(Comparative Example 6)
In Comparative Example 6, the hydrocarbon oil shown in Table 1 was subjected to hydrogenation treatment under the conditions shown in Table 1, and oil to be treated shown in Table 1 was obtained. In Comparative Example 6, the hydroisomerization step for the oil to be treated shown in Table 1 was performed under the conditions shown in Table 2 to obtain a product oil shown in Table 2. Except for these matters, Comparative Example 6 and Examples 5 to 9 are common. Also in the comparative example 6, the refinement | purification process similar to Examples 5-9 was implemented, and the base oil fraction shown to Table 2, 3 was obtained.

(Comparative Example 7)
In Comparative Example 7, the hydrocarbon oil shown in Table 1 was subjected to hydrogenation treatment under the conditions shown in Table 1 to obtain the oil to be treated shown in Table 1. In Comparative Example 7, the hydroisomerization process was performed on the oil to be treated shown in Table 1 under the conditions shown in Table 2 to obtain a product oil shown in Table 2. Except for these matters, Comparative Example 7 and Examples 5 to 9 are common. Also in the comparative example 7, the refinement | purification process similar to Examples 5-9 was implemented, and the base oil fraction shown to Table 2, 3 was obtained.

(Comparative Example 8)
In Comparative Example 8, the hydrocarbon oil shown in Table 1 was hydrotreated under the conditions shown in Table 1 to obtain the oil to be treated shown in Table 1. In Comparative Example 8, the hydroisomerization step was performed on the oil to be treated shown in Table 1 under the conditions shown in Table 2 to obtain a product oil shown in Table 2. Except for these matters, Comparative Example 8 and Examples 5 to 9 are common. Also in the comparative example 8, the refinement | purification process similar to Examples 5-9 was implemented, and the base oil fraction shown to Table 2, 3 was obtained.

(Comparative Example 9)
In Comparative Example 9, hydrotreating of the hydrocarbon oil shown in Table 1 was performed under the conditions shown in Table 1, and oil to be treated shown in Table 1 was obtained. In Comparative Example 9, the hydroisomerization step for the oil to be treated shown in Table 1 was performed under the conditions shown in Table 2 to obtain a product oil shown in Table 2. Except for these matters, Comparative Example 9 and Example 11 are common. Also in the comparative example 9, the refinement | purification process similar to Example 11 was implemented, and the base oil fraction shown to Table 2, 3 was obtained.

  In any of the examples, a main base oil fraction for a lubricating oil having a high viscosity index belonging to the group II lubricating base oil defined by API could be produced in a high yield.

  Since the base oil for lubricating oil obtained by the production method according to the present invention has excellent characteristics as described above, it can be suitably used as a base oil for various lubricating oils. Specifically, the lubricant base oil is used for lubricating oils used in internal combustion engines such as gasoline engines for passenger cars, gasoline engines for motorcycles, diesel engines, gas engines, gas heat pump engines, marine engines, and power generation engines. (Lubricating oil for internal combustion engines), automatic transmissions, manual transmissions, continuously variable transmissions, final reduction gears, etc. Lubricating oils (drive transmission device oils), shock absorbers, hydraulic equipment for construction machinery, etc. Hydraulic oil, compressor oil, turbine oil, gear oil, refrigerating machine oil, metalworking oil used in the above, and the like. By using the lubricating base oil of the present invention for these applications, the viscosity of each lubricating oil Improvements in temperature characteristics, thermal / oxidation stability, energy savings, fuel savings, etc., as well as extending the life of each lubricant and reducing environmentally hazardous substances at a high level Kill as to become.

Claims (3)

In an atmosphere having a hydrogen partial pressure of 11 to 20 MPa, the petroleum-derived hydrocarbon oil is hydrotreated at a reaction temperature of 250 to 420 ° C., and the content of the aromatic hydrocarbon is 10 to 25% by mass. Preparing a process oil;
Performing hydroisomerization of the oil to be treated using zeolite having a 10-membered ring one-dimensional pore structure ;
Equipped with a,
The zeolite having a 10-membered ring one-dimensional pore structure is at least one selected from the group consisting of ZSM-22 zeolite, ZSM-23 zeolite, ZSM-48 zeolite, and SSZ-32 zeolite. To
A method for producing a base oil for lubricating oil. The hydroisomerization of the oil to be treated is performed in an atmosphere having a hydrogen partial pressure of 11 to 20 MPa.
The manufacturing method of the base oil for lubricating oil of Claim 1. Performing the hydroisomerization of the oil to be treated at a reaction temperature of 200 to 450 ° C .;
The manufacturing method of the base oil for lubricating oil of Claim 1 or 2.