KR101810827B1 - Process for producing lube base oil, and lube base oil - Google Patents

Abstract

A process for producing a lubricating base oil according to the present invention is a process for producing a lubricating base oil which comprises subjecting a hydrocracked oil obtained by hydrogenolysis of a raw material oil containing at least one selected from the group consisting of reduced pressure light oil, And a step of distilling the hydrogenated refined oil to obtain a lubricating oil fraction, wherein the carrier of the hydrogenation isomerization catalyst is obtained by a process comprising the steps of: (a) a calcined zeolite and (b) a calcined inorganic oxide, wherein (a) the calcined zeolite is obtained by heating an ion-exchanged zeolite not heated to 350 ° C or higher within a range of 350 to 450 ° C.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a process for producing a lube base oil and a lube base oil,

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

Among petroleum products, for example, lubricating oil, light oil, jet fuel and the like are products in which fluidity at low temperatures is important. As a result, the base oil used in these products is either completely or partially removed from wax components such as normal paraffin or isoparaffin having a small branch which cause low temperature fluidity, or is converted to a component other than the wax component .

As a technique for removing the wax component from the hydrocarbon flow path, for example, a method of extracting the wax component by a solvent such as liquefied propane or MEK is known. However, this method has a problem that the operation cost is large, the applicable raw oil species are limited, and further, the yield of the product is limited by raw oil species.

On the other hand, as a bleaching technique for converting a wax component in a hydrocarbon oil into a non-wax component, for example, a method in which a hydrocarbon oil is contacted with a hydrogenation isomerization catalyst having a bifunctional function of hydrogenation- Contact dropping is known for isomerizing normal paraffin in oil to isoparaffin. As the hydrogenation isomerization catalyst used for contact dewaxing, there is known a catalyst containing a solid acid, among which zeolite and a metal belonging to Group 8 to Group 10 or Group 6 of the periodic table.

Contact dewatering is effective as a method for improving low-temperature fluidity of hydrocarbon oil, but in order to obtain oil fractions suitable for base oil for lubricating oil, it is necessary to sufficiently increase the conversion rate of normal paraffin. However, since the hydrogenation isomerization catalyst used in the contact dewatering has the ability to decompose hydrocarbons together with the isomerization ability, the decomposition and hardening of the hydrocarbon oil proceeds with the increase of the normal paraffin conversion rate, and the yield of the desired oil is lowered. Particularly, when producing a base oil for a high-quality lubricating oil which requires a high viscosity index and a low pour point, it is necessary to improve the conversion rate to such an extent that the normal paraffin is substantially not contained. Therefore, the objective oil is economically It was very difficult to obtain.

By virtue of the above circumstances, in order to obtain a desired yield of the desired isoparaffin oil fraction from the hydrocarbon oil channel containing the wax component in the field of the production of a lubricating oil base oil and a fuel base oil, in particular, a lubricant base oil, There is a demand for a hydrogenation isomerization catalyst having an activity, that is, a superior isomerization selectivity.

Up to now, attempts have been made to improve the isomerization selectivity of the hydrogenation isomerization catalysts used in contact stripping. For example, Patent Document 1 has a one-dimensional pore size of medium size such as ZSM-22, ZSM-23 and ZSM-48 containing metals such as Group 8 to Group 10 of the periodic table, Is contacted with a catalyst composed of a zeolite having a size of not more than about 0.5 mu m, under a isomerization condition, with a linear or slightly branched hydrocarbon raw material having a carbon number of 10 or more and producing a waxed lubricating oil.

The zeolite constituting the hydrogenation isomerization catalyst is prepared by hydrothermal synthesis in the presence of an organic compound usually called an organic template having an amino group, an ammonium group or the like, in order to construct a predetermined pore structure. The synthesized zeolite is, for example, described in Non-Patent Document 1, page 453, " 2. As described in "1. Materials", the final paragraph, the organic template contained is removed by being fired at a temperature of about 550 ° C. or higher in an atmosphere containing molecular oxygen. Next, the fired zeolite is, for example, described in Non-Patent Document 1, page 453, "2.3. Quot; Catalytic experiments ", typically ion exchanged in ammonium form in an aqueous solution containing ammonium ions. The zeolite after the ion exchange also carries a metal component such as Group 8 to Group 10 of the periodic table. The zeolite carrying the metal component is filled in the reactor through the steps of drying and, if necessary, shaping and the like, and is typically fired in an atmosphere containing molecular oxygen at a temperature of about 400 ° C., Is subjected to a reduction treatment with hydrogen or the like to give a catalytic activity as a binary functional catalyst.

The catalyst provided for commercial use is generally used in the form of a molded article for the purpose of improving ease of handling and reducing pressure loss of the reaction fluid on the catalyst. However, the zeolite powder lacks the self-tightness, and since the mechanical strength of the catalyst composed of the molded body obtained by molding itself is small, it is difficult to put the zeolite powder to practical use. Thus, in the case of a catalyst using zeolite, a zeolite powder is generally used in the form of a molded article obtained by molding a composition containing an inorganic oxide powder called a binder.

Patent Document 1: U.S. Patent No. 5,282,958

Non-Patent Document 1: J. A. Martens et al., J. Catal. 239 (2006) 451

As a lubricant base oil, a petroleum base oil base oil is widely used in terms of availability and cost. Particularly, paraffin base oils are widely used for lubricating oils that require performance to reduce friction and wear. This paraffin base oil has been made more sophisticated due to recent fuel economy saving and longevity demand. The API III Group III engine oil is manufactured using a hydrocracking process of petroleum-based feedstock and is a high viscosity index base with reduced content of sulfur or aromatic hydrocarbons. In recent years, it has been desired to further increase the productivity of such base oils.

It is an object of the present invention to provide a process for producing a lubricant base oil that can efficiently obtain a lubricant base oil that meets the group III standard of API from a petroleum-based raw material channel, and a lubricant base oil obtained thereby.

In order to solve the above problems, the present invention provides a process for producing a hydrocracked oil obtained by hydrocracking a raw material oil containing at least one selected from the group consisting of reduced pressure gas oil, atmospheric pressure residue (residual oil) In the presence of a hydrogenating isomerization catalyst to obtain a deasphalted oil, a step of hydrogenating and finishing the deasphalted oil to obtain a hydrogenated purified oil, and a step of distilling the hydrogenated and purified oil to obtain a lubricating oil fraction, Wherein the catalyst is at least one selected from the group consisting of a fired casting carrier subjected to a thermal history including heating at 350 DEG C or higher and a metal belonging to Group 8 to Group 10 of the periodic table carried on the carrier, molybdenum and tungsten (A) an organic template containing a 10-membered ring one-dimensional pore structure; and Wherein the ion exchange zeolite obtained by ion-exchanging the template-containing zeolite in a solution containing ammonium ion and / or proton is subjected to a thermal history including heating at 350 DEG C or higher to obtain a calcined zeolite; and (b) At least one kind of inorganic oxide selected from the group consisting of silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and oxidized phosphorus and a composite oxide composed of two or more of these is heated at 350 ° C or higher And the calcined zeolite contains the calcined zeolite. The thermal history of the calcined zeolite is such that the ion-exchanged zeolite not heated to 350 ° C or higher is calcined by heating in the range of 350 to 450 ° C Wherein the first lubricant It provides a method in mind.

Also, in the present specification, the periodic table refers to a long-term periodic table defined by the International Association of Pure and Applied Chemistry (IUPAC).

According to the first process for producing a lubricating base oil of the present invention, the hydrogenation isomerization catalyst according to the present invention containing a carrier containing a specific zeolite and a specific inorganic oxide and a specific active metal carried on the carrier has a sufficient mechanical strength And also has a high isomerization selectivity, it becomes possible to efficiently obtain a lubricating base oil that satisfies the group III standard of the API from the raw material flow path.

The present invention also provides a process for producing a lubricating oil composition comprising the steps of distilling a hydrogenated oil obtained by hydrogenolysis of a raw oil containing at least one selected from the group consisting of reduced pressure diesel oil, A step of bringing the lubricating oil fraction into contact with a hydrogenation isomerization catalyst to obtain an oil extraction oil and a step of subjecting the oil extraction oil to a hydrogenation treatment, wherein the hydrogenation isomerization catalyst is subjected to a thermal history including heating at 350 DEG C or higher, Wherein the carrier comprises at least one metal selected from the group consisting of metals belonging to Group 8 to Group 10 of Periodic Table, molybdenum and tungsten supported on the carrier, A zeolite containing an organic template containing a template and having a 10-membered ring one-dimensional pore structure is reacted with an ammonium ion and / Exchanged zeolite obtained by ion exchange in a solution containing alumina, silica, titania, boria, zirconia, magnesia, and zirconia, and calcined zeolite obtained by calcination under a thermal history including heating at 350 DEG C or higher, At least one kind of inorganic oxide selected from the group consisting of ceria, zinc oxide, and oxidized phosphorus and a composite oxide comprising at least two of these is mixed with a fired inorganic oxide obtained by firing under a thermal history including heating at 350 DEG C or higher Wherein the thermal history of the fired zeolite is that the ion-exchanged zeolite not heated to 350 DEG C or higher is fired by heating in a range of 350 to 450 DEG C. And a manufacturing method thereof.

According to the second process for producing a lubricating base oil of the present invention, the hydrogenation isomerization catalyst according to the present invention has sufficient mechanical strength and high isomerization selectivity, It is possible to efficiently obtain a lubricating oil base oil. The method for producing the second lubricating base oil of the present invention is characterized in that the lubricating oil fraction obtained by distilling the hydrocracked oil is brought into contact with the hydrogenation isomerization catalyst according to the present invention and dripped, Isomerization can be carried out and an undesirable decomposition reaction can be suppressed.

The present invention also provides a process for producing a hydrogenated oil obtained by contacting a hydrocracked oil obtained by hydrocracking a raw material oil containing at least one selected from the group consisting of reduced pressure diesel oil, atmospheric pressure residual oil and reduced pressure residual oil to a hydrogenation isomerization catalyst in the presence of molecular hydrogen A step of distilling the deasphalted oil to obtain a lubricating oil fraction; and a step of finishing the hydrotreatment of the lubricating oil fraction, wherein the hydrogenation isomerization catalyst receives a thermal history including heating at 350 ° C. or higher (A) at least one metal selected from the group consisting of metals belonging to groups 8 to 10 of the periodic table, molybdenum and tungsten supported on the carrier, A zeolite containing an organic template and an organic template having a ten-membered one-dimensional pore structure is reacted with an ammonium ion and / Exchanged zeolite obtained by ion exchange in a solution containing alumina, silica, titania, boria, zirconia, magnesia, and zirconia, and calcined zeolite obtained by calcination under a thermal history including heating at 350 DEG C or higher, At least one kind of inorganic oxide selected from the group consisting of ceria, zinc oxide, and oxidized phosphorus and a composite oxide comprising at least two of these is mixed with a fired inorganic oxide obtained by firing under a thermal history including heating at 350 DEG C or higher Wherein the thermal history of the calcined zeolite is such that the ion exchange zeolite not heated to 350 DEG C or higher is calcined by heating in the range of 350 to 450 DEG C. And a manufacturing method thereof.

According to the process for producing the third lubricating base oil of the present invention, since the hydrogenation isomerization catalyst according to the present invention has sufficient mechanical strength and high isomerization selectivity, It is possible to efficiently obtain a lubricating oil base oil. In addition, the third process for producing a lubricating base oil of the present invention can finish hydrogenation under a reaction condition suitable for each oil having a different boiling range by finishing the lubricating oil obtained by distilling the lubricating oil, .

In the first to third lubricant base oil producing methods of the present invention, it is preferable that the organic template-containing zeolite is at least one selected from the group consisting of ZSM-22, ZSM-23 and ZSM-48 type zeolite.

From the viewpoint of further improving the isomerization selectivity and mechanical strength of the catalyst, it is preferable that the inorganic oxide is alumina.

From the standpoint of further enhancing the mechanical strength of the catalyst while obtaining excellent isomerization selectivity, it is preferable that the carrier is a fired body subjected to a thermal history including heating within a range of 450 占 폚 to 650 占 폚.

From the standpoint of isomerization selectivity and reaction activity, it is preferable that the metal supported on the support is platinum and / or palladium.

From the viewpoint of isomerization selectivity and reaction activity, it is preferable that the mole ratio (Si / Al) of silicon atoms to aluminum atoms in the organic template-containing zeolite is 10-400.

In the first to third lubricant base oil producing methods of the present invention, it is preferable that the hydrogenation isomerization catalyst comprises an organic template-containing zeolite containing an organic template and having a 10-membered ring one- A first step of obtaining an ion-exchange zeolite by ion-exchange in a solution in which the ion-exchanged zeolite is obtained; And at least one kind of inorganic oxides selected from the group consisting of a composite oxide comprising a metal oxide and a metal oxide; and a step of calcining the formed body by heating in a range of at least 350 to 450 ° C to obtain a carrier , And a third step of applying a carrier to the carrier, And a fourth step of supporting at least one metal selected from the group consisting of a metal belonging to Group 10, molybdenum and tungsten.

The hydrogenation isomerization catalyst obtained by the above production method is excellent in isomerization selectivity and mechanical strength, and it is possible to obtain a lubricating base oil satisfying the group III standard of API from the raw material channel stably and efficiently.

From the viewpoint of further enhancing the mechanical strength of the catalyst to increase the productivity of the lubricating base oil, the third step is a step of heating the molded body in the range of 350 to 450 占 폚 and then in the range of 450 占 폚 to 650 占 폚 Followed by calcination to obtain the carrier.

The present invention also provides a lubricating base oil obtained by the method for producing a lubricating base oil according to the present invention, wherein the sulfur content is 0.03 mass% or less and the viscosity index is 120 or more.

According to the present invention, it is possible to provide a process for producing a lubricating base oil that can efficiently obtain a lubricating base oil satisfying the group III standard of API from a petroleum-based raw material channel, and a lubricating base oil obtained thereby.

1 is a flowchart showing an example of a lube oil base oil producing apparatus in which a method for manufacturing a lube oil base oil of the present invention is practiced.
Fig. 2 is a flowchart showing another example of a lube base oil producing apparatus in which a method for manufacturing a lube oil base oil of the present invention is implemented.
3 is a flowchart showing another example of the apparatus for producing a lubricating base oil in which the method for producing the lubricating base oil of the present invention is practiced.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the description of the drawings, the same or equivalent elements are denoted by the same reference numerals, and redundant explanations are omitted.

Fig. 1 is a flow chart showing an example of a lube oil base oil producing apparatus that implements the method for producing a lube oil base oil of the present invention. The apparatus 100 for producing a lubricating base oil shown in Fig. 1 comprises a flow path L1 for introducing a raw material oil, a first reaction tower 10 for hydrogenating and decomposing raw material oil introduced from the flow path L1, A first distillation column 20 for distilling hydrocracked oil supplied from a distillation column 20 through a flow passage L2 and a hydrocracking bottom oil supplied from a distillation column 20 through a flow passage L5 to hydrogenation A third reaction tower 40 for hydrogenating (hydrogenating and purifying) the deasphalted oil supplied through the flow path L6 from the reaction tower 30; And a second distillation tower 50 for distilling off the hydrogenated refined oil supplied through the second distillation column L7 to a predetermined oil fraction. The first distillation column 20 is provided with a flow passage L3 and a flow passage L4 for taking out the hard oil from outside the system. The second distillation column 50 is provided with a flow passage L10 and a flow passage L14 for taking out predetermined oil fractions from the outside of the system.

Hereinafter, a method of producing the lubricating base oil of the present invention will be described in detail with reference to the lubricating base oil producing apparatus 100 of FIG.

The raw material flow path for hydrocracking includes at least one selected from the group consisting of reduced pressure light oil, atmospheric pressure residual gas and reduced pressure residual flow path. As the reduced-pressure light oil, for example, oil fractions having a boiling point of 343 DEG C or higher and 550 DEG C or lower at normal pressure obtained from a vacuum distillation apparatus can be suitably used. For the normal pressure residual flow, for example, oil fractions having a boiling point of 343 DEG C or higher at normal pressure obtained from an atmospheric distillation apparatus of crude oil can be suitably used. As the reduced pressure residual flow path, an oil fraction having a boiling point of 550 ° C or higher at normal pressure obtained from a vacuum distillation apparatus of atmospheric pressure residual can be suitably used. The raw material oil used in the present invention preferably contains hydrocarbons having 20 or more carbon atoms in an amount of 50 mass% or more with respect to the raw material flow rate, in view of obtaining a lubricating base oil at a high yield.

In the first reaction column (10), the raw oil is subjected to hydrogenolysis. As the first reaction column 10, a well-known stationary phase, fluidized bed, mobile phase, or boiling phase reaction column may be used. In the present embodiment, it is preferable that the hydrogenolysis is carried out in a reaction column by charging a fixed hydrogenolysis catalyst into a stationary-phase flow reactor and allowing the molecular hydrogen and the raw oil to flow through the reactor. Hydrogenolysis as used herein refers to a reaction in which paraffin decomposition and naphthenic ring opening generate low molecular weight hydrocarbons, and desulfurization, denitrification, olefin hydrogenation, and aromatic hydrogenation are also performed.

Examples of the hydrocracking catalyst include a carrier comprising at least one solid acidic substance selected from alumina, silica, zirconia, titania, boria, zeolite of superstabilized Y type (USY) and beta zeolite, A catalyst comprising at least one active metal selected from the group consisting of cobalt-molybdenum, nickel-molybdenum, nickel-tungsten and nickel-cobalt-molybdenum.

The USY zeolite is a Y-type zeolite which is superstabilized by hydrothermal treatment and / or acid treatment. In addition to the fine pore structure called the micropores of 20 Å or less inherent to the Y-type zeolite, A new pore has been formed. When USY zeolite is used as the carrier of the hydrocracking catalyst, the average particle diameter is not particularly limited, but is preferably 1.0 占 퐉 or less, and more preferably 0.5 占 퐉 or less. In the USY zeolite, the molar ratio of silica / alumina (molar ratio of silica to alumina; hereinafter referred to as " silica / alumina ratio ") is preferably 10 to 200, more preferably 15 to 100, Even more preferably from 20 to 60. [

As a suitable carrier, an inorganic oxide containing at least one kind of alumina, magnesia, silica, titania, boria, phosphorus, or zirconia is preferable.

As a method for supporting nickel-molybdenum or the like, which is an active metal, on a carrier, a method used for producing a conventional desulfurization catalyst can be employed. As the cobalt source, an organic or inorganic cobalt salt such as cobalt nitrate, cobalt chloride or cobalt acetate can be used. As the nickel source, an organic or inorganic cobalt salt such as nickel nitrate, nickel chloride or nickel acetate can be used. As the molybdenum source, ammonium molybdate or molybdenum oxide may be used. As the tungsten source, ammonium tungstate and the like may be used. As for each metal, an organic salt or an inorganic salt other than the metal salt may be used. The organic compound may be coexistent with the impregnation solution containing the active metal. In addition to these active metals, phosphorus may be supported on the catalyst.

When the catalyst is a nickel-molybdenum catalyst or a nickel-tungsten catalyst, the loading amount of the active metal in the hydrocracking catalyst is preferably 3 to 15 mass% based on the total amount of the catalyst, In the case of a cobalt-molybdenum catalyst, it is preferable that the loading amount of nickel is 0.1 to 5 mass% and the loading amount of cobalt is 3 to 15 mass% with respect to the total amount of the catalyst.

The average pore diameter of the hydrocracking catalyst is preferably 6 to 60 nm, more preferably 7 to 30 nm. When the average pore diameter is less than 6 nm, sufficient catalytic activity tends not to be obtained. When the average pore diameter exceeds 60 nm, the metal dispersibility is lowered, and the catalytic activity tends to be lowered. The pore volume of the hydrocracking catalyst is preferably 0.2 mL / g or more. When the pore volume is less than 0.2 mL / g, the activity of the catalyst tends to decrease rapidly. The specific surface area of the hydrocracking catalyst is preferably 200 m2 / g or more. If the specific surface area of the catalyst is less than 200 m < 2 > / g, the active metal tends not to be sufficiently dispersed. The pore volume and specific surface area of these catalysts can be measured and calculated by a method called BET method by nitrogen adsorption.

The reaction conditions in the first reaction column 10 are preferably a reaction temperature of 350 to 450 DEG C, a hydrogen partial pressure of 5 to 20 MPa, an LHSV of 0.1 to 2 h < ^-1 >, a hydrogen / oil ratio of 2000 to 10000 scfb, , Hydrogen partial pressure of 10 to 18 MPa, LHSV of 0.1 to 1.0 h ^-1 , and hydrogen / oil ratio of 2500 to 8000 scfb.

It is preferable to adjust the reaction conditions so that the concentrations of sulfur and nitrogen in the hydrocracked oil become 50 ppm or less and 5 ppm or less, respectively.

Further, in the present embodiment, it is preferable to hydrocrack the raw oil so that the content of oil having a boiling point of 343 DEG C or lower in the hydrogenated oil is 30 to 75% by mass when the raw oil is a reduced-pressure gas oil.

In the first distillation column 20, fuel oil such as naphtha or light oil can be taken out from the flow path L3 and the flow path L4 by atmospheric distillation of the hydrogenated cracked oil. In this case, it is preferable to obtain the oil fraction of 343 占 폚 or higher as the hydrocracked bottom oil. When the raw oil is an atmospheric residue or the like, the distillation column 20 may be omitted and the hydrocracked oil from the first reaction column 10 may be supplied to the second reaction column 30 as it is.

In the second reaction column 30, the hydrocracked bottom oil obtained in this manner is tapped by hydrogenation isomerization. As the second reaction tower 30, a well-known fixed bed reaction tower can be used. In this embodiment, it is preferable that the hydrogenation isomerization is carried out by charging the stationary phase flow reactor of the hydrogenation isomerization catalyst according to the present invention in the reaction column, and passing the molecular hydrogen and the hydrocracked bottom oil through the reactor.

Here, the hydrogenation isomerization catalyst according to the present invention will be described.

The hydrogenation isomerization catalyst according to the present invention is characterized by being produced by a specific method. Hereinafter, the hydrogenation isomerization catalyst according to the present invention will be described in accordance with its preferred production form.

The organic template-containing zeolite as the starting material of the calcined zeolite (a) constituting the hydrogenation isomerization catalyst according to the present invention has a high degree of isomerization activity in the hydrogenation isomerization reaction of normal paraffin and a high decomposition activity , And a one-dimensional perforated structure composed of a 10-membered ring. Examples of such zeolites include AEL, EUO, FER, HEU, MEL, MFI, NES, TON, MTT, WEI and ZSM-48. In addition, each of the three alphabetic characters mentioned above means a skeleton structure code given by the Structure Committee of the International Zeolite Association for each structure of the classified molecular sieve type zeolite. In addition, zeolites with the same topology are collectively referred to as the same code.

As the zeolite containing the organic template, among the zeolites having the above-mentioned 10-membered ring one-dimensional pore structure, zeolite having TON, MTT structure and ZSM-48 type zeolite are preferable in view of high isomerization activity and low decomposition activity . As the zeolite having the TON structure, ZSM-22 type zeolite is more preferable, and as the zeolite having the MTT structure, ZSM-23 type zeolite is more preferable.

The organic template-containing zeolite containing the organic template serving as the starting material of the fired zeolite (a) constituting the hydrogenation isomerization catalyst according to the present invention and having the 10-membered ring one-dimensional pore structure is composed of silica source, alumina source, Hydrothermally synthesized from an organic template added for constructing a structure by a known method.

The organic template is an organic compound having an amino group, an ammonium group or the like and is selected in accordance with the structure of the zeolite to be synthesized, but it is preferably an amine derivative. Specifically, it is at least one member selected from the group consisting of alkylamine, alkyldiamine, alkyltriamine, alkyltetraamine, pyrrolidine, piperazine, aminopiperazine, alkylpentamine, alkylhexamine and derivatives thereof More preferable.

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

The organic template-containing zeolite synthesized, preferably washed and dried has usually an alkali metal cation as a counter cation, and the organic template is contained in the pore structure. The zeolite containing the organic template used in the production of the hydrogenation isomerization catalyst of the present invention is preferably such a zeolite in the synthesized state, that is, it is not subjected to the calcination treatment for removing the organic template contained in the zeolite.

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

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

The ion exchange treatment may be carried out on a single zeolite containing a powdery organic template or may be carried out on a molded body obtained by mixing an inorganic oxide as a binder with an organic template containing zeolite prior to the ion exchange treatment good. However, it is preferable to provide the powdery organic template-containing zeolite to the ion exchange treatment because the above-mentioned molded article is provided to the ion exchange treatment without being baked, since the problem of collapsing and powdering of the formed article tends to occur.

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

In addition, in order to increase the efficiency of ion exchange, it is preferable to exchange the solution with a new one or more times while the zeolite is ion-exchanged with the solution, and it is preferable to exchange the solution with a new one or two times desirable. When the solution is exchanged once, for example, the organic template-containing zeolite is immersed in a solution containing ammonium ion and / or proton, heated to reflux for 1 to 6 hours, , And heating and refluxing for 6 to 12 hours again makes it possible to increase the ion exchange efficiency.

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

Next, it is preferable that an inorganic oxide which is a binder is added to the ion-exchanged zeolite obtained by the above-mentioned method, and the obtained composition is molded to form a formed body. The objective of blending an inorganic oxide in an ion-exchange zeolite is to improve the mechanical strength of a carrier (particularly, a particulate carrier) obtained by calcining the formed body to such an extent that it can be practically used. The choice affects the isomerization selectivity of the hydrogenation isomerization catalyst. From this viewpoint, it is preferable that at least one kind of inorganic oxide selected from the group consisting of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and oxidized phosphorus, Is used. Of these, alumina is preferable from the viewpoint that the isomerization selectivity of the hydrogenation isomerization catalyst is further improved. The composite oxide consisting of at least two of these compounds is a composite oxide composed of at least two components selected from alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide. A composite oxide containing alumina as a main component containing an alumina component of 50 mass% or more based on the oxide is preferable.

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

The method of compounding the above-mentioned inorganic oxide with an ion-exchange zeolite is not particularly limited, but a method in which an appropriate amount of water such as water is added to both powders to make a viscous fluid and kneading the same with a kneader or the like A method of practicing the present invention can be adopted.

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

Next, the molded article thus obtained is sintered in an atmosphere containing molecular oxygen at a temperature of 350 to 450 캜, preferably 380 to 430 캜, more preferably 390 to 420 캜 , And it is preferable that the carrier is fired under a thermal history including heating at 350 DEG C or higher. The phrase " in an atmosphere containing molecular oxygen " means that a gas containing oxygen gas, among these, preferably comes into contact with air. The firing time is not particularly limited, but is preferably 1 to 24 hours.

By the above firing, the ion-exchange zeolite constituting the formed body becomes fired zeolite (a), and the inorganic oxide becomes fired inorganic oxide (b).

In the present embodiment, when the firing temperature is lower than 350 占 폚, the removal of the organic template does not sufficiently proceed, the removal thereof takes a long time, and the mechanical strength of the carrier tends not to be sufficiently improved It is not desirable. On the other hand, when the calcination temperature exceeds 450 ° C, the isomerization selectivity of the obtained hydrogenation isomerization catalyst tends not to be sufficiently improved, which is not preferable. It is very important to increase the isomerization selectivity of the hydrogenation isomerization catalyst according to the present invention by calcining the ion exchange zeolite in which the organic template is not heated to 350 DEG C or more at the relatively low temperature.

The firing may be carried out in the form of a powdery ion-exchange zeolite as a single body, in addition to the above-mentioned operation in the form of a compact obtained by molding a composition containing an inorganic oxide in an ion-exchange zeolite as described above. However, in that case, the molded product obtained by molding the composition containing the inorganic oxide in the obtained fired zeolite may be heated at a temperature of 350 ° C or more, for example, in the range of 350 to 450 ° C and / It is necessary to perform firing at a temperature in the range of more than 450 DEG C to 650 DEG C or less.

The carrier is preferably heated in an atmosphere containing molecular oxygen, more preferably in the range of 350 to 450 DEG C under an air atmosphere, and heated to a temperature of more than 450 DEG C and not more than 650 DEG C, It may be good. It is possible to further improve the mechanical strength of the support without significantly affecting the hydrogenation isomerization selectivity of the obtained catalyst by further heating and firing at a temperature higher than 450 DEG C but not higher than 650 DEG C in addition to heating at 350 to 450 DEG C. Therefore, when catalyst particles having higher mechanical strength are desired, it is preferable to carry out the calcination by the above two-step heating. When the heating temperature at the rear end is 450 DEG C or less, the mechanical strength of the carrier tends to be more difficult to be improved. On the other hand, if it exceeds 650 ° C, the environment of the aluminum atom involved in the formation of active sites on the zeolite tends to be changed and the decomposition activity tends to increase, which is not preferable. Further, from the viewpoint of maintaining the isomerization selectivity, it is more preferable that the heating temperature at the subsequent stage is a temperature within a range from 450 deg. C to 600 deg.

In this embodiment, at least one kind of metal belonging to groups 8 to 10 of the periodic table, molybdenum, and tungsten is added to the carrier, which is a mold that has been fired under a thermal history including heating at 350 DEG C or higher, (Hereinafter also referred to as " active metal ").

Examples of metals belonging to groups 8 to 10 of the periodic table include iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium and platinum. Among them, platinum and / or palladium are preferable, and platinum is particularly preferable in view of activity, isomerization selectivity and continuity of activity. The above-mentioned active metals may be used singly or in combination of two or more. When the hydrogenation isomerization catalyst according to the present invention is used for isomerization of hydrocracking oils containing a large amount of a sulfur-containing compound and / or a nitrogen-containing compound, from the viewpoint of the persistence of catalytic activity, the active metals include nickel-cobalt, nickel -Molybdenum, cobalt-molybdenum, nickel-molybdenum-cobalt, nickel-tungsten-cobalt and the like are preferable.

The method of supporting the active metal on the carrier is not particularly limited and the impregnation method using a compound containing the active metal element (hereinafter, sometimes referred to as an "active metal precursor") (equilibrium adsorption method, Method, an initial wetting method), and an ion exchange method.

Examples of the active metal precursor include a hydrochloride, a sulfate, a nitrate, and a complex of the active metal. When the active metal is platinum, examples of the active metal precursor include chloroplatinic acid, tetraammine dinitroplatinum, dinitroaminoplatinum, tetramethyldichloroplatinum and the like.

The total amount of the active metals supported on the carrier containing the fired zeolite (a) and the fired inorganic oxide (b) is preferably 0.001 to 20 mass% based on the mass of the carrier. When the amount is less than 0.001 mass%, it becomes difficult to impart a predetermined hydrogenation / dehydrogenation function. On the other hand, when the loading amount exceeds 20 mass%, hardening due to decomposition of hydrocarbons on the active metal tends to proceed, and the yield of the intended oil tends to be lowered, It is not preferable because there is a tendency.

The active metal may be supported on one or both of the fired zeolite (a) and the fired inorganic oxide (b) constituting the carrier. In the case where the hydrogenation isomerization catalyst according to the present invention is produced by a method in which an active metal is supported on a support by impregnation or the like, the distribution of the site where the active metal is supported is mainly controlled by the active metal precursor, Is determined by the affinity of the zeolite (a) and the fired inorganic oxide (b).

Carrying of the active metal is not limited to the form to be carried out for the shaped and sintered carrier. For example, an active metal may be supported on an ion-exchange zeolite in powder form or in a calcined zeolite calcined at a temperature of 350 to 450 ° C, or may be carried in a powdered inorganic oxide, or both.

The support on which the active metal component is supported is mainly intended to remove the anion component or the ligand component contained in the active metal precursor, and is preferably fired in an atmosphere containing molecular oxygen. The firing temperature is preferably 250 to 600 占 폚, more preferably 300 to 500 占 폚. As the atmosphere containing molecular oxygen, air is preferable. The baking time is usually about 0.5 to 20 hours. After the calcination treatment, the active metal precursor is converted into a metal single crystal, an oxide thereof or a similar species.

As described above, in a preferred embodiment of the production of the hydrogenation isomerization catalyst according to the present invention, "ion exchange of organic template-containing zeolite", "molding of a composition containing ion-exchanged zeolite and inorganic oxide" Firing of a molded article by heating "or" firing of a molded article by heating at a temperature of 450 ° C or more and 650 ° C or less after heating at 350 to 450 ° C "," carrying of an active metal to a carrier " Calcining the carrier ".

What is important in the hydrogenation isomerization catalyst according to the present invention is that, in addition to the use of the specific zeolite, the specific inorganic oxide, and the specific active metal, in the production process thereof, the " organosiloxane containing organic template-containing zeolite A part of the template is removed by ion exchange not by firing "," an ion-exchange zeolite in which the organic template is partially left without being heated to 350 ° C or higher is fired at a relatively low temperature of 350 to 450 ° C, Removing at least a part of the residual organic template " and " carrier is a molded article subjected to heat history including heating at 350 DEG C or higher ". In the production of the hydrogenation isomerization catalyst according to the present invention, the above-described respective steps and the order of these steps are not limited as long as the above-mentioned three are secured, and the problems And may be different from those described in the above-described preferred embodiments in the range not causing an increase in manufacturing cost due to the complicated process, and can be suitably changed.

The hydrogenation isomerization catalyst according to the present invention is preferably subjected to a reduction treatment after being charged in a reactor for carrying out a hydrogenation isomerization reaction, preferably following the above firing treatment. Concretely, reduction treatment is carried out in an atmosphere containing molecular hydrogen, preferably hydrogen gas flow, preferably at 250 to 500 ° C, more preferably at 300 to 400 ° C for about 0.5 to 5 hours . By such a process, it is possible to more reliably impart to the catalyst the activity capable of highly debinding the hydrocracked oil such as reduced-pressure gas oil, atmospheric pressure residue and reduced pressure residue.

In the hydrogenation isomerization catalyst according to the present invention, a metal belonging to group 8 to group 10 of the periodic table, molybdenum, and metals other than tungsten are added to the fired zeolite and / or fired inorganic oxide, This may also be carried.

The reaction conditions in the second reaction tower 30 are preferably a reaction temperature of 250 to 400 캜, a hydrogen partial pressure of 1 to 20 MPa, an LHSV of 0.1 to 5 h ^-1 and a hydrogen / anhydrous ratio of 1000 to 5000 scfb, , Hydrogen partial pressure of 2 to 10 MPa, LHSV of 1 to 4 h ^-1 , and hydrogen / oil ratio of 2000 to 4000 scfb.

In the present embodiment, it is preferable to adjust the reaction conditions so that the normal paraffin concentration in the descaling oil is 1% by mass or less.

In the third reaction tower (40), the dewaxing oil is hydrogenated (hydrogenated). As the third reaction column 40, a known stationary phase reaction column may be used. In the present embodiment, it is preferable that the hydrogenation purification is carried out in a reaction column by charging a fixed hydrogenation purification catalyst in a stationary phase flow reactor and circulating the molecular hydrogen and the de-lube in this reactor. The hydrogenation purification referred to herein means improvement of the oxidation stability and color of the lubricating oil, and olefin hydrogenation and aromatics hydrogenation of the terephthalic acid are carried out.

Examples of the hydrogenation purification catalyst include a carrier comprising at least one inorganic solid acidic substance selected from alumina, silica, zirconia, titania, boria, magnesia and phosphorus, , Nickel-molybdenum, nickel-tungsten, and nickel-cobalt-molybdenum.

Suitable carriers are inorganic solid acidic materials containing at least two kinds of alumina, silica, zirconia, or titania.

As a method for supporting the active metal on the carrier, a conventional method such as impregnation or ion exchange may be employed.

The amount of the active metal supported in the hydrogenation purification catalyst is preferably 0.1 to 25% by mass based on the total amount of the metal.

The average pore diameter of the hydrogenation purification catalyst is preferably 6 to 60 nm, more preferably 7 to 30 nm. When the average pore diameter is less than 6 nm, sufficient catalytic activity tends not to be obtained. When the average pore diameter exceeds 60 nm, the dispersibility of the active metal tends to be lowered, and the catalytic activity tends to decrease. The pore volume of the hydrogenation purification catalyst is preferably 0.2 mL / g or more. When the pore volume is less than 0.2 mL / g, the catalyst activity tends to accelerate deterioration. The specific surface area of the hydrogenation purification catalyst is preferably 200 m2 / g or more. If the specific surface area of the catalyst is less than 200 m < 2 > / g, the dispersibility of the active metal tends to be insufficient and the activity tends to decrease. The pore volume and specific surface area of such a catalyst can be measured and calculated by a method called BET method by nitrogen adsorption.

The reaction conditions in the third reaction column 40 are preferably a reaction temperature of 200 to 300 캜, a hydrogen partial pressure of 3 to 20 MPa, an LHSV of 0.5 to 5 h ^-1 and a hydrogen / anhydrous ratio of 1000 to 5000 scfb, , A hydrogen partial pressure of 4 to 18 MPa, an LHSV of 0.5 to 4 h ^-1 and a hydrogen / oil ratio of 2000 to 5000 scfb.

In the present embodiment, it is preferable to adjust the reaction conditions so that the sulfur content and the nitrogen content in the hydrogenated refined oil are 5 mass ppm or less and 1 mass ppm or less, respectively.

In the second distillation tower 50, lubricating oil fractions are obtained by setting a plurality of cut points and subjecting the hydrogenated refined oil to distillation under reduced pressure. In this embodiment, for example, a first lubricating oil fraction having a boiling point of 343 to 390 占 폚 at normal pressure, a second lubricating oil fraction having a boiling point of 390 to 440 占 폚, a third lubricating oil fraction having a boiling point of 440 to 510 占 폚, The fourth lubricating oil fraction can be recovered from the oil lines L11 to L14 as lubricating oil. The first lubricating oil fraction can be obtained as a lubricating base oil suitable for ATF or a shock absorber. In this case, it is preferable to set the kinematic viscosity at 100 占 폚 to 2.7 占 0.1 cSt. The second lubricating oil fraction can be obtained as a lubricating oil base oil according to the present invention which is suitable for engine oil based oils satisfying the group III standard of the API. In this case, the kinematic viscosity at 100 占 폚 is 4.0 ± 0.1 cSt, -22.5 DEG C or lower. The third lubricating oil fraction can be obtained as a lubricating base oil suitable for industrial working oil. In this case, the kinematic viscosity at 40 占 폚 is preferably 32 cSt or more. The fourth lubricating oil fraction can be obtained as a lubricating oil suitable for industrial working oil. In this case, the kinematic viscosity at 40 캜 is preferably 80 to 120 cSt. Further, the first lubricating oil fraction can be obtained as the lubricating base oil equivalent to 70 Pale, the second lubricating oil fraction can be obtained as the lubricating base oil corresponding to SAE-10, the third lubricating oil fraction can be obtained as SAE-20 , And the fourth lubricating oil fraction can be obtained as a lubricating oil equivalent to SAE-30.

The hydrogenated refined oil fed from the third reaction column 40 of the present embodiment contains a hard oil such as naphtha or light oil which is by-produced by hydrogenation isomerization or hydrogenation finishing (hydrogenation refining). These can be recovered from the flow path L10 as an oil fraction having a boiling point of 350 DEG C or less, for example.

The method of manufacturing the lubricating base oil of the present invention is not limited to the above-described embodiment, but can be changed appropriately. For example, a step of distilling a hydrocracked oil obtained by hydrocracking a raw oil containing at least one kind selected from the group consisting of a reduced pressure gas oil, an atmospheric pressure residue and a reduced pressure residual oil to obtain a lubricating oil fraction, A step of contacting the lubricating oil fraction with a hydrogenation isomerization catalyst to obtain a deasphalted oil and a step of finishing the deasphalted oil in this order can be carried out in this order to produce a lubricant base oil. Fig. 2 is a flow chart showing an example of a lubricating base oil producing apparatus that carries out the above-described method for producing a lubricating base oil. The lubricating oil base oil producing apparatus 110 of FIG. 2 is another embodiment after L5 in the lubricating oil base oil producing apparatus of FIG. 1, and includes a second distillation tower 50 for distilling the hydrocracking bottom oil supplied through the oil passage L5 A second reaction tower 30 for hydrogenating and desulfurizing the lubricating oil fraction supplied from the second distillation tower 50 through the flow path L21 and a second reaction tower 30 for supplying the oil via the flow passage L22 from the reaction tower 30 And a third reaction tower (40) for hydrogenating (hydrogenating and refining) the deasphalted oil. The third reaction column (40) is provided with a flow path (L23) for taking hydrogenated refined oil out of the system.

Also in the present embodiment, the same hydrocracking catalyst, hydrogenation isomerization catalyst and hydrogenation purification catalyst can be used.

In the second distillation column 50, it is preferable to distill the hydrocracked oil so as to obtain a lubricating oil fraction having a boiling point of 343 DEG C or higher. The naphtha isotonic oil fraction having a boiling point at normal pressure of lower than 343 DEG C is preferably recovered from another recovery line installed in the second distillation column 50. [ In the present embodiment, the second distillation tower 50 can be divided into a plurality of lubricating oil fractions, and hydrogenation isomerization and hydrogenation finishing can be performed for each oil fraction. These processes may be carried out in the same line by switching the oil from the second distillation column 50 or a plurality of oil fractions from the second distillation column 50 may be carried out in separate lines. Examples of the plurality of oil fractions include naphtha and isopara oil fractions having a boiling point at normal pressure lower than 343 DEG C, 70-fold oil fractions at 343 to 390 DEG C, SAE-10 oil fractions at 390 to 440 DEG C, SAE -20 oil fraction, and the bottom oil fraction exceeding 510 캜, SAE-30 oil fraction and the like.

The hydrogenation isomerization (hydrogenation desorption) of the lubricating oil fraction in the second reaction tower 30 is carried out under the conditions of a reaction temperature of 250 to 400 ° C., a partial pressure of hydrogen of 1 to 20 MPa, an LHSV of 1 to 4 h ^-1 , a hydrogen / 4000 scfb is preferable.

Further, in the present embodiment, it is preferable to adjust the reaction conditions so that the normal paraffin concentration in the descaling oil is 1% by mass or less.

The reaction conditions in the third reaction column 40 are preferably a reaction temperature of 200 to 300 캜, a hydrogen partial pressure of 4 to 18 MPa, an LHSV of 0.5 to 4 h ^-1 and a hydrogen / anhydrous ratio of 2000 to 5000 scfb.

In the present embodiment, it is preferable to adjust the reaction conditions so that the sulfur content and the nitrogen content in the hydrogenated refined oil are 5 mass ppm or less and 1 mass ppm or less, respectively.

The hydrogenated refined oil supplied from the third reaction column 40 of the present embodiment can be used as a lubricating oil satisfying the group III standard of the API but can also be distilled to obtain a desired oil as a lubricating oil . At this time, it is also possible to remove light oil fractions produced as a result of hydrogenation isomerization or hydrogenation finishing (hydrogenation purification).

When the hydrogenated refined oil is distilled, it is preferable to classify the refined oil into a plurality of oil fractions by, for example, vacuum distillation. As the plurality of oil fractions, for example, naphtha and isobutylene oils having a boiling point at normal pressure of less than 343 DEG C SAE-20 oil fractions of 440 to 510 DEG C, and SAE-30 oil fractions of more than 510 DEG C as the bottom oil fraction.

The method of manufacturing the lubricating base oil of the present invention may be another form. For example, the hydrocracked oil obtained by hydrocracking a raw oil containing at least one member selected from the group consisting of reduced pressure light oil, atmospheric pressure residue and reduced pressure residual oil is contacted with a hydrogenation isomerization catalyst in the presence of molecular hydrogen, A lubricating base oil can be produced by carrying out a step of obtaining a lubricating oil, a step of distilling off the lubricating oil to obtain a lubricating oil fraction by distillation under reduced pressure, and a step of finishing the hydrogenation of the lubricating oil fraction in this order. Fig. 3 is a flowchart showing an example of a lubricating base oil producing apparatus for carrying out the above-mentioned method for producing a lubricating base oil. The lubricating oil base oil producing apparatus 120 of Fig. 3 is another embodiment after L5 in the lubricating oil base oil producing apparatus of Fig. 1, and the hydrogenating and decomposing bottom oil supplied through the oil line L5 is hydrogenated and isomerized A second distillation column 50 for distilling off the deasphalted oil supplied from the reaction column 30 through the flow passage L31 and a second distillation column 50 for passing the distillation column 50 from the second distillation column 50 through a passage L32 And a third reaction tower 40 for hydrogenating (hydrogenating and refining) the supplied lubricating oil fraction. The third reaction column 40 is provided with a flow passage L33 for taking hydrogenated refined oil out of the system.

Also in the present embodiment, the same hydrocracking catalyst, hydrogenation isomerization catalyst and hydrogenation purification catalyst can be used.

The hydrogenation isomerization (hydrogenation desorption) of the hydrogenation product in the second reaction column 30 is carried out at a reaction temperature of 300 to 360 캜, a hydrogen partial pressure of 2 to 10 MPa, an LHSV of 1 to 4 h ^-1 , a hydrogen / .

Further, in the present embodiment, it is preferable to adjust the reaction conditions so that the normal paraffin concentration in the descaling oil is 1% by mass or less.

In the second distillation tower 50, it is preferable to distill off the de-oiled oil so as to obtain a lubricating oil fraction having a boiling point of 343 DEG C or higher. The naphtha isotonic oil fraction having a boiling point at normal pressure of lower than 343 DEG C is preferably recovered from another recovery line installed in the second distillation column 50. [ Further, in the present embodiment, the second distillation tower 50 can be divided into a plurality of lubricating oil fractions, and hydrogenation can be performed for each oil fraction. These processes may be carried out in the same line by switching the oil from the second distillation column 50 or a plurality of oil fractions from the second distillation column 50 may be carried out in separate lines. Examples of the plurality of oil fractions include naphtha and isopara oil fractions having a boiling point at normal pressure lower than 343 DEG C, 70-fold oil fractions at 343 to 390 DEG C, SAE-10 oil fractions at 390 to 440 DEG C, SAE -20 oil fraction, and the bottom oil fraction exceeding 510 캜, SAE-30 oil fraction.

The reaction conditions in the third reaction column 40 are preferably a reaction temperature of 200 to 300 캜, a hydrogen partial pressure of 4 to 18 MPa, an LHSV of 0.5 to 4 h ^-1 and a hydrogen / anhydrous ratio of 2000 to 5000 scfb.

In the present embodiment, it is preferable to adjust the reaction conditions so that the sulfur content and the nitrogen content in the hydrogenated refined oil are 5 mass ppm or less and 1 mass ppm or less, respectively.

The hydrogenated refined oil supplied from the third reaction column 40 of the present embodiment can be used as a lubricating oil satisfying the group III standard of the API but can also be distilled to obtain a desired oil as a lubricating oil . At this time, it is also possible to remove the light oil fraction produced as a result of hydrogenation isomerization or hydrogenation finish (hydrogenation purification).

When the hydrogenated refined oil is distilled, it is preferable to classify the refined oil into a plurality of oil fractions by, for example, vacuum distillation. As the plurality of oil fractions, for example, naphtha and isobutylene oils having a boiling point at normal pressure of less than 343 DEG C SAE-20 oil fractions of 440 to 510 DEG C, and SAE-30 oil fractions of more than 510 DEG C as the bottom oil fraction.

According to the method for producing a lubricating base oil according to the present invention described above, it is possible to efficiently produce a lubricating base oil having a sulfur content of 0.03 mass% or less and a viscosity index of 120 or more.

Example

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

[Production of hydrocracking catalyst]

A catalyst carrier containing 90% by mass of commercially available amorphous silica-alumina and 10% by mass of commercially available USY zeolite was prepared, and extruded into a 1/16 cylinder pellet. The obtained molded body was fired at 550 캜 for 3 hours under air flow. 12% by mass and 22% by mass of nickel and tungsten were impregnated and impregnated into the extruded carrier as active metals, respectively, and then calcined at 550 ° C for 3 hours under air flow to obtain a hydrocracking catalyst.

[Production of hydrogenation isomerization catalyst]

(Hydrogenation isomerization catalyst A)

≪ Synthesis of ZSM-22 type zeolite >

ZSM-22 type zeolite comprising a crystalline aluminosilicate having a Si / Al ratio of 30 was prepared according to Chem. Eur. J, 2007, vol.13, page 10070, "Experimental Section" by hydrothermal synthesis in the following sequence.

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

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

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

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

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

Next, Solution A was added to Solution B and stirred until the aluminum component completely dissolved. After adding the solution C to the mixed solution, a mixture of the solutions A, B and C was injected into the solution D while vigorously stirring at room temperature. Further, as the " seed crystal " for promoting crystallization, 0.25 g of ZSM-22 powder separately synthesized and not subjected to any special treatment after synthesis was added, and a gel product was obtained.

The gel product obtained by the above operation was transferred to a stainless steel autoclave reactor having an internal volume of 120 ml and the hydrothermal synthesis reaction was carried out by rotating the autoclave reactor in an oven at 150 ° C for 60 hours at a rotation speed of 30 rpm on a tumbling device . After completion of the hydrothermal synthesis reaction, the reactor was cooled, and solid components produced from the respective reactors were collected by filtration, washed with ion-exchanged water, and dried in a drier at 60 캜 overnight to obtain an organic template having a Si / Al ratio of 30 ZSM-22 type zeolite (hereinafter sometimes referred to as " ZSM-22 ").

≪ Preparation of ion exchange ZSM-22 >

ZSM-22 containing the organic template obtained above was placed in a flask, and 100 ml of a 0.5N-ammonium chloride aqueous solution per 1 g of the ZSM-22 was added and heated to reflux for 6 hours. After cooling to room temperature, the supernatant was removed, and the fixed component was washed with ion-exchanged water. To this, 0.5N aqueous ammonium chloride solution of the same amount as above was added again, and the mixture was heated to reflux for 12 hours.

Thereafter, the solid component was collected by filtration, washed with ion-exchanged water, and dried in a drier at 60 캜 overnight to obtain ion-exchanged NH ₄ -type ZSM-22.

≪ Binder formulation, molding, firing >

The NH ₄ type ZSM-22 obtained above and alumina as a binder were mixed at a mass ratio of 7: 3, and a small amount of ion-exchanged water was added thereto and kneaded. The obtained viscous fluid was filled in an extrusion molding machine and molded to obtain a cylindrical molded body having a diameter of about 1.5 mm and a length of about 5 mm. The formed body was dried in a dryer at 120 캜 for 3 hours under air circulation and then calcined at 400 캜 for 3 hours under air circulation to obtain molded and calcined carrier particles.

<Supporting platinum, plastic>

Tetra-aminodichloroplatinum (II) (Pt (NH ₃ ) ₄ Cl ₂ ) was dissolved in ion-exchanged water corresponding to the amount of absorption (preliminarily measured amount) of the formed and sintered carrier particles to obtain an impregnation solution. This solution was impregnated into the above molded and calcined carrier particles by the initial wetting method, and carried so as to have a platinum content of 0.5% by mass with respect to the mass of the ZSM-22 type zeolite. Next, the obtained impregnated material was dried in a drier at 60 ° C. overnight, and then calcined at 400 ° C. for 3 hours under air flow to obtain a hydrogenation isomerization catalyst A. The crushing strength of the obtained catalyst particles was 12.4 N / mm. The crushing strength of the catalyst particles was measured in accordance with JIS R2206 &quot; Test Method for Compressive Strength of Refractory Bricks &quot;.

(Hydrogenation isomerization catalyst B)

The catalyst was subjected to an operation similar to that of the hydrogenation isomerization catalyst A to obtain an ion-exchanged NH ₄ ZSM-22. Further, by the same operation as the hydrogenation isomerization catalyst A, alumina was used as a binder, &Lt; / RTI &gt;

The obtained molded article was dried in a dryer at 120 ° C for 3 hours under air circulation, heated at 400 ° C for 3 hours under air flow, then fired by heating at 550 ° C for 3 hours under air flow, The calcined carrier particles were obtained.

The formed and calcined carrier particles were subjected to platinum loading, drying and firing by the same operation as the hydrogenation isomerization catalyst A to obtain a hydrogenation isomerization catalyst B. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Hydrogenation isomerization catalyst C)

The shaped and calcined carrier particles were obtained by the same operation as the hydrogenation isomerization catalyst B except that the binder was changed from alumina to silica.

The obtained carrier particles were subjected to platinum loading, drying and firing by an operation similar to that of the hydrogenation isomerization catalyst A to obtain a hydrogenation isomerization catalyst C. The crushing strength of the obtained catalyst particles was 9.0 N / mm.

(Hydrogenation isomerization catalyst D)

By the same operation as the hydrogenation isomerization catalyst A, a molded article identical to that of the hydrogenation isomerization catalyst A containing alumina as a binder was obtained. This molded body was dried in a dryer at 120 캜 for 3 hours under air circulation, heated at 440 캜 for 3 hours under air circulation, and then fired by heating at 550 캜 for 3 hours under air circulation, To obtain carrier particles.

The formed and calcined carrier particles thus obtained were subjected to platinum loading, drying and firing by an operation similar to that of the hydrogenation isomerization catalyst A to obtain a hydrogenation isomerization catalyst D. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Hydrogenation isomerization catalyst E)

<Synthesis of ZSM-23 type zeolite>

ZSM-23 type zeolite (hereinafter sometimes referred to as "ZSM-23") having a Si / Al ratio of 30 was produced by hydrothermal synthesis according to the method described in US Pat. No. 4,490,342 and Example 2.

First, the organic template Diquat-7 (N, N, N, N ', N', N'-hexamethyl-1,7-diaminoheptane dibromide) Was partially modified and used. That is, 50 g of 1,7-dibromoheptane and 100 ml of ethanol were mixed in an eggplant-shaped flask, and 70 g of triethylamine (33 mass% of ethanol solution) was added to the flask with stirring, and the mixture was heated under reflux for one night. The reaction product was cooled to-21 C and crystals were collected by filtration. This was washed with diethyl ether cooled to -21 占 폚 and dried at room temperature to obtain the desired Diquat-7 (2 bromate salt).

Using Diquat-7 obtained above, ZSM-23 was synthesized by the following procedure.

First, the following two kinds of solutions were prepared.

Solution E: 15 g of colloidal silica (Ludox HS-40 manufactured by Grace Davison) diluted with 31.6 ml of ion-exchanged water.

Solution F: 48.3 ml of ion-exchanged water, 0.327 g of sodium aluminate, 1.22 g of sodium hydroxide, 0.9 g of sulfuric acid, and 2.74 g of Diquat-7 salt mixed well.

Next, Solution F was injected into Solution E while stirring. The resulting gel was transferred to a stainless steel autoclave reactor having an internal volume of 120 ml and the reaction was carried out while rotating the autoclave reactor itself at 160 ° C in an oven at a rotation speed of about 60 rpm for 72 hours. After completion of the reaction, the reactor was cooled, and the resulting solid was collected by filtration, washed with ion-exchanged water, and dried in a drier at 60 캜 overnight to obtain ZSM-23 containing an organic template having a Si / Al ratio of 30 &Lt; / RTI &gt;

&Lt; Preparation of ion exchange ZSM-23 >

Except that ZSM-23 containing the organic template obtained above was used in place of ZSM-22 containing an organic template, ion-exchanged NH ₄ -type ZSM -23. &Lt; / RTI &gt;

&Lt; Binder formulation, molding, firing >

A molded article was obtained from the ion-exchanged ZSM-23 obtained above and alumina as a binder by the same operation as that of the hydrogenation isomerization catalyst B, and thereafter, the same operation as that of the hydrogenation isomerization catalyst B was carried out. And firing was carried out to obtain molded and calcined carrier particles.

<Supporting platinum, plastic>

Drying and sintering were carried out by the same operation as the hydrogenation isomerization catalyst B except that the molded and fired carrier particles containing the ZSM-23 obtained above were used in place of the molded and fired carrier particles containing ZSM-22 Was carried out to obtain a hydrogenation isomerization catalyst E. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Hydrogenation isomerization catalyst F)

<Synthesis of ZSM-48 type zeolite>

ZSM-48 type zeolite (hereinafter sometimes referred to as &quot; ZSM-48 &quot;) having an Si / Al ratio of 30 containing an organic template was prepared according to Applied Catalysis A: General vol.299 (2006) 167-174 Were synthesized. Concretely, 5.1 g of aluminum sulfate octahydrate was added to 180 g of ion-exchanged water in which 2.97 g of sodium hydroxide and 0.9 ml of concentrated sulfuric acid (98%) had been dissolved in advance, 26.2 g of hexanediamine was added thereto, Lt; / RTI &gt; To this aqueous solution, 75 g of colloidal silica Ludox HS-40 was added and stirred at room temperature for 2 hours to obtain a zeolite raw gel. The obtained gel was introduced into an autoclave made of stainless steel, and maintained in a stirred state at 160 캜 for 3 days. Thereafter, the autoclave content was cooled to room temperature, and then the solid matter on the filter paper was washed with suction filtration and ion exchange water to obtain ZSM-48 type zeolite crystals.

&Lt; Preparation of ion exchange ZSM-48 >

Except that ZSM-48 containing the above-obtained organic template was used in place of ZSM-22 containing an organic template, ion-exchanged NH ₄ type ZSM -48. &Lt; / RTI &gt;

&Lt; Binder formulation, molding, firing >

A molded article was obtained from the ion-exchanged ZSM-48 obtained above and alumina as a binder by the same operation as that of the hydrogenation isomerization catalyst B, and thereafter, the same operation as that of the hydrogenation isomerization catalyst B was conducted And firing was carried out to obtain molded and calcined carrier particles.

<Supporting platinum, plastic>

Drying and sintering were carried out by the same operation as the hydrogenation isomerization catalyst B except that the molded and fired carrier particles containing the ZSM-48 obtained above were used in place of the molded and fired carrier particles containing ZSM-22 Was carried out to obtain a hydrogenation isomerization catalyst F. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Hydrogenation isomerization catalyst G)

The shaped and calcined carrier particles were obtained by an operation similar to that of the hydrogenation isomerization catalyst A except that the calcination temperature of the compact was changed from 400 ° C to 470 ° C.

Platinum was supported on the resulting carrier particles by the same operation as the hydrogenation isomerization catalyst A, followed by drying and firing, thereby obtaining a hydrogenation isomerization catalyst G. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Hydrogenation isomerization catalyst H)

The powdery ZSM-22 containing the organic template obtained by synthesis in the same manner as the hydrogenation isomerization catalyst A was calcined at 550 캜 for 6 hours under air flow.

The fired ZSM-22 obtained above was placed in a flask and subjected to ion exchange with an ammonium chloride aqueous solution and drying by an operation similar to the hydrogenation isomerization catalyst A to obtain NH ₄ type ZSM-22.

A shaped body was obtained from the NH ₄ type ZSM-22 obtained above and alumina as a binder by the same operation as the hydrogenation isomerization catalyst A. Subsequently, the hydrogenation isomerization catalyst A was subjected to drying, calcination, platinum deposition and calcination by an operation similar to that of the hydrogenation isomerization catalyst A to obtain a hydrogenation isomerization catalyst H. The crushing strength of the obtained catalyst particles was 12.0 N / mm.

(Hydrogenation isomerization catalyst I)

The powdery ZSM-22 containing the organic template obtained by synthesis in the same manner as the hydrogenation isomerization catalyst A was calcined by the same operation as the hydrogenation isomerization catalyst H and ion-exchanged.

A molded article was obtained from the alumina as a binder and the hydrogenation isomerization catalyst A by the operation of the NH ₄ type ZSM-22 obtained above. Then, the obtained molded body was subjected to air calcination at 470 캜 for 3 hours, and then platinum supported and calcined by an operation similar to the hydrogenation isomerization catalyst A to obtain a hydrogenation isomerization catalyst I. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Hydrogenation isomerization catalyst J)

A hydrogenation isomerization catalyst J was obtained by an operation similar to that of the hydrogenation isomerization catalyst E except that the temperature of the first step of calcining the formed body obtained from the ion-exchange ZSM-23 and alumina was changed to 470 캜 instead of 400 캜. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Hydrogenation isomerization catalyst K)

A hydrogenation isomerization catalyst K was obtained by the same operation as that of the hydrogenation isomerization catalyst F except that the temperature of the first step of calcining the formed body obtained from ion exchange ZSM-48 and alumina was changed to 470 캜 instead of 400 캜. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

[Preparation of hydrogenation purification catalyst]

A commercially available amorphous silica-alumina carrier was extruded into a 1/16 cylinder type and calcined at 550 캜 for 3 hours under air flow to obtain a catalyst carrier. The resulting carrier was impregnated with 0.2 mass% and 0.3 mass% of platinum and palladium as active metals respectively, and calcined at 550 캜 for 3 hours under air flow to obtain a hydrogenation purification catalyst.

&Lt; Production of lubricating oil base oil &

(Example 1)

<Preparation of raw oil>

As the raw material oil, a general reduced pressure light oil obtained from the Middle Eastern crude oil was used. The boiling point range of the reduced pressure light oil was 343 to 550 캜, and the sulfur content and the nitrogen content were 2.41% by mass and 0.2% by mass respectively.

<Hydrogenolysis of raw material oil>

The hydrocracking reaction of the raw oil was carried out under the following conditions. 200 ml of the hydrocracking catalyst prepared above was charged in a reaction tube made of stainless steel having an inner diameter of 15 mm and a length of 380 mm and the catalyst was sulfided by raw oil for 24 hours under the hydrogen atmosphere (hydrogen partial pressure: 10 MPa). Thereafter, the reaction temperature was raised to 385 DEG C, and LHSV of 0.3 h &lt; ^-1 &gt; and a hydrogen / oil ratio of 5000 scfb were maintained. The obtained hydrocracked oil was distilled, and as a result, the yield of the oil fraction (decomposition ratio) of less than 343 占 폚 was 57 mass%, and the yield of the lubricating oil fraction of 343 占 폚 or higher was 43 mass%.

&Lt; Hydrogenation Isomerization of Hydrocracking Oil &

200 ml of the catalyst A obtained above was charged in a stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm and subjected to a reduction treatment at an average temperature of the catalyst layer of 350 DEG C and hydrogen flow (5 MPa) for 12 hours. Thereafter, hydrogenated oil having a boiling point of 343 DEG C or higher obtained as described above was passed through (oil passing) at a reaction temperature of 320 DEG C, a hydrogen partial pressure of 3 MPa, an LHSV of 2 h &lt; ^-1 &gt;, and a hydrogen / The normal paraffin concentration of the obtained deasphalted oil A was less than 0.01% by mass.

&Lt; Hydrogenation finish of rape oil >

200 ml of the hydrogenation purification catalyst obtained above was charged in a stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm and subjected to reduction treatment at an average temperature of the catalyst layer of 350 占 폚 and hydrogen flow (5 MPa) for 12 hours. Thereafter, as the raw material oil, the above-described dehydrochemical dehydrogenating oil A was subjected to hydrogenation and refining at a reaction temperature of 320 DEG C, hydrogen partial pressure of 5 MPa, LHSV of 2 h &lt; ^-1 &gt; and hydrogen / oil ratio of 3000 scfb. The yield of the hydrogenated refined oil A relative to the obtained deasphalted oil A was 99 mass% or more, the Sabolite color was +30 or more, the sulfur content was 0.1 mass ppm, and the nitrogen content was 0.1 mass ppm.

<Distillation of hydrogenated refined oil>

Hydrogenated refined oil A obtained by hydrogenation was subjected to further distillation under reduced pressure to obtain a 70-fold oil fraction having a boiling point of 343 to 390 DEG C, an SAE-10 oil fraction having a boiling point of 390 to 440 DEG C and an SAE-20 SAE-20 equivalent lubricant base oil, and SAE-30 equivalent lubricant base oil (bottom oil) by classifying lubricant base oil equivalent to 70 pails, SAE-10 equivalent lubricant base oil, SAE- .

The yields of the obtained 70 pails equivalent lubricant base oil, SAE-10 equivalent lubricant base oil, SAE-20 equivalent lubricant base oil and SAE-30 equivalent lubricant base oil were respectively 14.4 mass%, 38.2 mass%, 33.0 mass%, 8.5 Mass%. The viscosity index, pour point, sulfur content and nitrogen content of the lubricant base oil corresponding to 70 pails were 108, -27.5 캜, 0.1 mass ppm and 0.1 mass ppm, respectively. The viscosity index, pour point, sulfur content and nitrogen content of the lubricant base oil corresponding to SAE- The viscosity index, the pour point, the sulfur content and the nitrogen content of the lubricating oil base oil corresponding to SAE-20 were respectively 130, -12.5 DEG C, 0.2 mass ppm and 0.2 mass ppm, respectively, of 122, -17.5 DEG C, The viscosity index, pour point, sulfur content, and nitrogen content of the lubricant base oil corresponding to SAE-30 were 129, -12.5 DEG C, 0.3 mass ppm, and 0.5 mass ppm, respectively.

The results obtained above are shown in Table 1. In addition, the measurement was carried out on the basis of JIS K2580 for the Sabolvite color, JIS K2541 for the sulfur content, JIS K2609 for the nitrogen content, JIS K2283 for the viscosity index, and JIS K2269 for the pour point. In addition, the yield represents the yield (mass%) of each lubricant base oil when the oil fraction of 343 占 폚 or higher of hydrocracking oil is taken as 100.

(Example 2)

Except that the catalyst B was charged into the reaction tube instead of the catalyst A, the hydrogenation isomerization treatment of the hydrogenolysis-decomposing agent at 343 占 폚 or higher was carried out as in Example 1 to obtain the deasphalting oil B. The normal paraffin concentration of the obtained deasphalted oil B was less than 0.01% by mass.

Thereafter, the same operation as in Example 1 was carried out. The results are shown in Table 1.

(Example 3)

The hydrogenation isomerization treatment of the hydrogenolytic decomposition product of 343 DEG C or higher was carried out in the same manner as in Example 1 except that the catalyst C was charged in the reaction tube instead of the catalyst A, The normal paraffin concentration of the obtained de-Lumpy C was less than 0.01% by mass.

Thereafter, the same operation as in Example 1 was carried out. The results are shown in Table 1.

(Example 4)

Except that catalyst D instead of catalyst A was charged in a reaction tube, hydrolysis isomerization treatment of hydrogenolysis with a temperature of 343 占 폚 or higher was carried out in the same manner as in Example 1, The normal paraffin concentration of the obtained de-Lumpy D was less than 0.01% by mass.

Thereafter, the same operation as in Example 1 was carried out. The results are shown in Table 1.

(Example 5)

Except that catalyst E was charged in a reaction tube instead of catalyst A, hydrolysis isomerization of hydrogenolysing oil at 343 DEG C or higher was carried out as in Example 1 to obtain deasphalted oil E. [ The normal paraffin concentration of the obtained de-oiled oil E was less than 0.01% by mass.

Thereafter, the same operation as in Example 1 was carried out. The results are shown in Table 1.

(Example 6)

Except that the catalyst F was charged in the reaction tube instead of the catalyst A, the hydrogenation isomerization treatment of the hydrogenolytic decomposition product of 343 DEG C or higher was carried out as in Example 1 to obtain the deasphalted oil F. [ The normal paraffin concentration of the obtained degummed oil F was less than 0.01% by mass.

Thereafter, the same operation as in Example 1 was carried out. The results are shown in Table 1.

(Comparative Example 1)

Except that the catalyst G was charged in the reaction tube instead of the catalyst A, the hydrogenation isomerization treatment of the hydrogenolytic decomposition product of 343 DEG C or higher was carried out in the same manner as in Example 1 to obtain the degumming oil G. [ The normal paraffin concentration of the obtained degummed oil G was less than 0.01% by mass.

Thereafter, the same operation as in Example 1 was carried out. The results are shown in Table 1.

(Comparative Example 2)

Except that the catalyst H was charged in the reaction tube instead of the catalyst A, the hydroisomerization treatment of the hydrogenated product of 343 占 폚 or higher was carried out in the same manner as in Example 1, The normal paraffin concentration of the obtained de-oiled oil H was less than 0.01% by mass.

Thereafter, the same operation as in Example 1 was carried out. The results are shown in Table 1.

(Comparative Example 3)

The hydrogenation isomerization treatment of hydrogenolysis with a degree of hydrogenation of at least 343 占 폚 was carried out in the same manner as in Example 1 except that the catalyst I was charged into the reaction tube instead of the catalyst A, The normal paraffin concentration of the obtained deasphalted oil I was less than 0.01% by mass.

Thereafter, the same operation as in Example 1 was carried out. The results are shown in Table 1.

(Comparative Example 4)

The hydrogenation isomerization of the hydrogenolysis-decomposing oil at 343 DEG C or higher was carried out in the same manner as in Example 1 except that the catalyst J was charged into the reaction tube instead of the catalyst A, The normal paraffin concentration of the obtained deasphalted oil J was less than 0.01% by mass.

Thereafter, the same operation as in Example 1 was carried out. The results are shown in Table 1.

(Comparative Example 5)

Except that the catalyst K was charged in the reaction tube in place of the catalyst A, the hydroisomerization treatment of the hydrogenolytic decomposition product of 343 占 폚 or higher was carried out in the same manner as in Example 1 to obtain the deasphalting oil K. The normal paraffin concentration of the obtained deasphalted oil K was less than 0.01% by mass.

Thereafter, the same operation as in Example 1 was carried out. The results are shown in Table 1.

In the case of using the hydrogenation isomerization catalysts A to F satisfying the predetermined conditions according to the present invention, compared with the case where the hydrogenation isomerization catalysts G to K which do not satisfy the predetermined conditions are used, A lubricating base oil equivalent to SAE-10, a lubricating base oil equivalent to SAE-20, and a lubricating base oil equivalent to SAE-30) were efficiently obtained.

(Example 7)

<Preparation of raw oil>

As the raw material oil, a general reduced pressure light oil obtained from the Middle Eastern crude oil was used. The boiling point range of the reduced pressure light oil was 343 to 550 ° C, and the sulfur content and the nitrogen content were 2.41 mass% and 0.2 mass%, respectively.

<Hydrogenolysis of raw material oil>

The hydrocracking reaction was carried out under the conditions described below. 200 ml of the hydrocracking catalyst prepared above was charged in a reaction tube made of stainless steel having an inner diameter of 15 mm and a length of 380 mm and the catalyst was sulfided by raw oil for 24 hours under the hydrogen atmosphere (hydrogen partial pressure: 10 MPa). Thereafter, the reaction temperature was raised to 385 DEG C, and LHSV of 0.3 h &lt; ^-1 &gt; and a hydrogen / oil ratio of 5000 scfb were maintained. The obtained hydrocracked oil was distilled, and as a result, the yield of the oil fraction (decomposition ratio) of less than 343 占 폚 was 57 mass%, and the yield of the lubricating oil fraction of 343 占 폚 or higher was 43 mass%. Further, as a result of distillation of the lubricating oil having a temperature of 343 DEG C or higher by vacuum distillation, a 70-fold oil fraction (boiling point 343 to 390 DEG C in terms of normal pressure distillation), SAE-10 oil fraction (boiling point 390 to 440 DEG C in terms of normal pressure distillation, (Boiling point 440 to 510 ° C in terms of conversion) and SAE-30 oil fractions (boiling point 510 ° C or more in terms of normal pressure distillation) were 15 mass%, 40 mass%, 35 mass% and 10 mass%, respectively.

&Lt; Hydrogenation Isomerization of Hydrocracking Oil &

200 ml of the catalyst A obtained above was charged in a stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm and subjected to a reduction treatment at an average temperature of the catalyst layer of 350 DEG C and hydrogen flow (5 MPa) for 12 hours. Thereafter, the oil fractions of the 70-pale, SAE-10, SAE-20 and SAE-30 obtained as the raw oil were subjected to the reaction at a reaction temperature of 320 ° C, a hydrogen partial pressure of 3 MPa, an LHSV of 2 h ^-1 and a hydrogen / Flowed and hydrogenated and isomerized. The yields of the oil droplets obtained in the oil fractions were 96.1 mass%, 95.5 mass%, 94.2 mass%, and 90.0 mass% in the 70th fail, SAE-10, SAE-20 and SAE-30, respectively. 0.1, ppm, 0.1 mass ppm in SAE-10, 0.2 mass ppm in ppm, 0.2 mass ppm in SAE-10, 0.2 mass ppm in SAE-10, -20 to 130, -12.5 DEG C, 0.2 mass ppm and 0.2 mass ppm, SAE-30 to 128, -12.5 DEG C, 0.3 mass ppm and 0.3 mass ppm, respectively.

&Lt; Hydrogenation finish of rape oil >

200 ml of the hydrogenation purification catalyst obtained above was charged in a stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm and subjected to reduction treatment at an average temperature of the catalyst layer of 350 占 폚 and hydrogen flow (5 MPa) for 12 hours. Thereafter, the hydrogenation-isomerization each fail-70, SAE-10, SAE-20 , SAE-30 oil for each reaction temperature 320 ℃, a hydrogen partial pressure of 5MPa, 2h ^-1 LHSV, the conditions of a hydrogen / UB 3000scfb after treatment as a raw oil with Flowed and hydrogenated and purified. The yield of the hydrogenated refined oil of each oil obtained was 99% by volume or more, and the Sabolite color was +30 or more.

(Example 8)

<Preparation of raw oil>

As the raw material oil, a general reduced pressure light oil obtained from the Middle Eastern crude oil was used. The boiling point range of the reduced pressure light oil was 343 to 550 ° C, and the sulfur content and the nitrogen content were 2.41 mass% and 0.2 mass%, respectively.

<Hydrogenolysis of raw material oil>

The hydrocracking reaction was carried out under the conditions described below. 200 ml of the hydrocracking catalyst prepared above was charged in a reaction tube made of stainless steel having an inner diameter of 15 mm and a length of 380 mm and the catalyst was sulfided by raw oil for 24 hours under the hydrogen atmosphere (hydrogen partial pressure: 10 MPa). Thereafter, the reaction temperature was raised to 385 DEG C, and LHSV of 0.3 h &lt; ^-1 &gt; and hydrogen / oil ratio of 5000 scfb were maintained, and hydrocracking reaction of diesel light oil was carried out. The obtained hydrocracked oil was distilled, and as a result, the yield of the oil fraction (decomposition ratio) of less than 343 占 폚 was 57 mass%, and the yield of the lubricating oil fraction of 343 占 폚 or higher was 43 mass%.

&Lt; Hydrogenation Isomerization of Hydrocracking Oil &

200 ml of the catalyst A obtained above was charged in a stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm and subjected to a reduction treatment at an average temperature of the catalyst layer of 350 DEG C and hydrogen flow (5 MPa) for 12 hours. Thereafter, the hydrocracked oil having a temperature of 343 DEG C or higher obtained as above was flowed and hydrogenated and isomerized under the conditions of a reaction temperature of 320 DEG C, a hydrogen partial pressure of 3 MPa, an LHSV of 2 h &lt; ^-1 &gt; and a hydrogen / The normal paraffin concentration of the obtained deasphalted oil A was less than 0.01% by mass.

&Lt; Distillation of oil droplets &

Distillation of the obtained deasphalted oil A under reduced pressure yielded 70 oil fractions having a boiling point of 343 to 390 占 폚, SAE-10 oil fractions having a boiling point of 390 to 440 占 폚, SAE-20 oil fractions having a boiling point of 440 to 510 占 폚, SAE-30 oil equivalent, SAE-20 equivalent lubricating oil base oil and SAE-30 equivalent lubricating oil base oil (bottom oil) were obtained.

The yields of the obtained 70 oil-equivalent lubricant base oils, SAE-10 equivalent lubricant base oils, SAE-20 equivalent lubricant base oils and SAE-30 equivalent lubricant base oils were 15 mass%, 40 mass%, 35 mass%, 10 mass% Mass%. The viscosity index, pour point, sulfur content and nitrogen content of the lubricant base oil corresponding to 70 pails were 108, -27.5 캜, 0.1 mass ppm and 0.1 mass ppm, respectively. The viscosity index, pour point, sulfur content and nitrogen content of the lubricant base oil corresponding to SAE- The viscosity index, the pour point, the sulfur content and the nitrogen content of the lubricating oil base oil corresponding to SAE-20 were respectively 130, -12.5 DEG C, 0.2 mass ppm and 0.2 mass ppm, respectively, of 122, -17.5 DEG C, The viscosity index, pour point, sulfur content, and nitrogen content of the lubricant base oil corresponding to SAE-30 were 128, -12.5 DEG C, 0.3 mass ppm, and 0.3 mass ppm, respectively.

&Lt; Hydrogenation finish of rape oil >

200 ml of the hydrogenation purification catalyst obtained above was charged in a stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm and subjected to reduction treatment at an average temperature of the catalyst layer of 350 占 폚 and hydrogen flow (5 MPa) for 12 hours. Then, the lubricant base oil equivalent to 70 pails, the lubricant base oil equivalent to SAE-10, the lubricant base oil equivalent to SAE-20, and the lubricant base oil equivalent to SAE-30 obtained by classification after the hydrogenation isomerization treatment, Hydrogen partial pressure of 5 MPa, LHSV of 2 h ^-1 , and hydrogen / oil ratio of 3000 scfb. The yield of hydrogenated refined oil of each obtained lubricating base oil was 99% by volume or more, and the Sabolite color was +30 or more.

According to the present invention, it is possible to provide a method for producing a lubricating base oil that can efficiently obtain a lubricating base oil satisfying the group III standard of API from a petroleum-based raw material channel, and a lubricating base oil obtained by the method.

10 ... Reaction tower, 20 ... Distillation tower, 30 ... Reaction tower, 40 ... Reaction tower, 50 ... Distillation tower, 100, 110, 120 ... Lubricating oil base oil manufacturing equipment.

Claims (11)

A hydrocracked oil obtained by hydrocracking a raw material oil containing at least one member selected from the group consisting of reduced pressure diesel oil, atmospheric pressure residue (residual oil) and reduced pressure residual oil is contacted with a hydrogenation isomerization catalyst in the presence of molecular hydrogen, A step of obtaining a degumming oil,
Subjecting the de-lapping oil to hydrogenation treatment to obtain a hydrogenated refined oil,
A step of distilling the hydrogenated refined oil to obtain a lubricating oil fraction
And,
Wherein the hydrogenation isomerization catalyst comprises
A first step of obtaining an ion-exchange zeolite by ion-exchanging an organic template-containing zeolite containing an organic template and a 10-membered ring one-dimensional pore structure in a solution containing an ammonium ion and / or a proton,
Wherein said ion exchange zeolite which is not heated to 350 DEG C or more and a complex oxide composed of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide and a combination of two or more of these A second step of molding a composition containing at least one kind of inorganic oxide to obtain a molded article,
A third step of firing the formed body by heating in a range of at least 350 to 450 DEG C to obtain a carrier,
A fourth step of supporting at least one kind of metal selected from the group consisting of metals belonging to groups 8 to 10 in the periodic table, molybdenum and tungsten to the carrier
Wherein the hydrogenation isomerization catalyst is obtained by a process for producing a hydrogenation isomerization catalyst. A step of distilling the hydrocracked oil obtained by hydrocracking a raw oil containing at least one selected from the group consisting of a reduced pressure gas oil, an atmospheric pressure residue and a reduced pressure residual oil to obtain a lubricating oil fraction;
Contacting the lubricating oil fraction with a hydrogenation isomerization catalyst in the presence of molecular hydrogen to obtain an oil extracting oil;
A step of subjecting the de-lapping oil to hydrogenation treatment
And,
Wherein the hydrogenation isomerization catalyst comprises
A first step of obtaining an ion-exchange zeolite by ion-exchanging an organic template-containing zeolite containing an organic template and a 10-membered ring one-dimensional pore structure in a solution containing an ammonium ion and / or a proton,
Wherein said ion exchange zeolite which is not heated to 350 DEG C or more and a complex oxide composed of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide and a combination of two or more of these A second step of molding a composition containing at least one kind of inorganic oxide to obtain a molded article,
A third step of firing the formed body by heating in a range of at least 350 to 450 DEG C to obtain a carrier,
A fourth step of supporting at least one kind of metal selected from the group consisting of metals belonging to groups 8 to 10 in the periodic table, molybdenum and tungsten to the carrier
Wherein the hydrogenation isomerization catalyst is obtained by a process for producing a hydrogenation isomerization catalyst. Contacting a hydrocracked oil obtained by hydrocracking a raw material oil containing at least one member selected from the group consisting of reduced pressure diesel oil, atmospheric pressure residue and reduced pressure residual oil with a hydrogenation isomerization catalyst in the presence of molecular hydrogen to obtain a de- The process,
Distilling the deasphalted oil to obtain a lubricating oil fraction;
A step of hydrogenating the lubricating oil fraction
And,
Wherein the hydrogenation isomerization catalyst comprises
A first step of obtaining an ion-exchange zeolite by ion-exchanging an organic template-containing zeolite containing an organic template and a 10-membered ring one-dimensional pore structure in a solution containing an ammonium ion and / or a proton,
Wherein said ion exchange zeolite which is not heated to 350 DEG C or more and a complex oxide composed of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide and a combination of two or more of these A second step of molding a composition containing at least one kind of inorganic oxide to obtain a molded article,
A third step of firing the formed body by heating in a range of at least 350 to 450 DEG C to obtain a carrier,
A fourth step of supporting at least one kind of metal selected from the group consisting of metals belonging to groups 8 to 10 in the periodic table, molybdenum and tungsten to the carrier
Wherein the hydrogenation isomerization catalyst is obtained by a process for producing a hydrogenation isomerization catalyst. The lubricating base oil according to any one of claims 1 to 3, wherein the organic template-containing zeolite is at least one selected from the group consisting of ZSM-22, ZSM-23 and ZSM-48 type zeolite Gt; The method for producing a lubricating base oil according to any one of claims 1 to 3, wherein the inorganic oxide is alumina. The production method of a lubricating base oil according to any one of claims 1 to 3, wherein the carrier is a molding subjected to a thermal history including heating within a range of from 450 占 폚 to 650 占 폚 or less . The method for producing a lubricating base oil according to any one of claims 1 to 3, wherein the metal supported on the carrier is platinum and / or palladium. 4. The lubricating base oil according to any one of claims 1 to 3, wherein the molar ratio (Si / Al) of silicon atoms to aluminum atoms in the organic template-containing zeolite is 10-400 Gt; The method according to any one of claims 1 to 3, wherein in the third step, the molded body is heated by heating within a range of 350 to 450 占 폚 and then by heating within a range of 450 占 폚 to 650 占 폚 , And a step of obtaining the carrier. A lubricating oil base oil obtained by the method for producing a lubricating base oil according to any one of claims 1 to 3, wherein the sulfur content is 0.03 mass% or less and the viscosity index is 120 or more.
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