KR20140145594A - Method for producing lubricant base oil - Google Patents

Abstract

A process for producing a lubricating base oil according to the present invention comprises a step of bringing a raw oil containing hydrocarbons having 21 or more carbon atoms into contact with a first catalyst and a second catalyst in this order in the presence of hydrogen, A zeolite having a primary pore structure, and a binder, and platinum and / or palladium supported on the support, wherein the zeolite contains an organic template containing a 10-membered ring primary primary pore structure Wherein the catalyst is derived from an ion-exchange zeolite obtained by ion-exchanging zeolite in a solution containing ammonium ion and / or proton, wherein the amount of carbon contained in the catalyst is 0.4 to 3.5% by mass and the second catalyst is a 10- Structure and a platinum and / or palladium supported on the support, wherein the platinum and / or palladium And a ratio V1 / V2 of the volume V1 of the first catalyst to the volume V2 of the second catalyst is 70/30 to 90/10, in terms of metal atoms, in terms of metal atoms, relative to 100 parts by mass of the carrier. do.

Description

METHOD FOR PRODUCING LUBRICANT BASE OIL

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

Among petroleum products, for example, lubricating oil and the like are products in which fluidity at low temperatures is important. Therefore, the base oil used in these products is preferably a wax component that has been sufficiently removed from wax components such as normal paraffin or isoparaffin having a slight branching . In recent years, since hydrocarbons (hereinafter abbreviated as " FT synthetic oil ") obtained by the Fischer-Tropsch synthesis method do not contain environmental load substances such as sulfur compounds, they have attracted attention as a raw material oil in the production of lubricating oil The hydrocarbon oil is composed of a wax component.

As a dewaxing technique for converting a wax component in a hydrocarbon oil into a non-wax component, for example, a process in which a hydrocarbon oil is contacted with a so-called two-function catalyst having hydrogenation-dehydrogenating ability and isomerization ability in the presence of hydrogen, Contact desorption is known in which normal paraffin in a hydrocarbon is isomerized to isoparaffin (see, for example, Patent Document 1).

Japanese Patent Publication No. 2006-502297

When the raw material oil to be contact dewatered becomes heavy, the cloud point sometimes does not satisfy the target value even when the pouring point of generated oil satisfies a predetermined value. This phenomenon is problematic in the production of heavy oil base oils such as bright stock, for example. As the causative substance, hydrocarbons having a very small amount of a long chain portion in the molecule have been widely used. As a method for removing a causative substance, there are methods such as solvent dehydration, centrifugal separation, adsorption separation, etc. None of them can be said to be an efficient method and is not practical in terms of cost.

An object of the present invention is to provide a process for producing a lubricating base oil capable of efficiently obtaining a heavy lubricant base oil having a sufficiently low pour point and a cloud point.

In one aspect of the present invention, there is provided a process for producing a carbonaceous material, comprising the steps of bringing a raw oil containing hydrocarbons having 21 or more carbon atoms into contact with a first catalyst and a second catalyst in this order in the presence of hydrogen, A zeolite having a pore structure, and a binder, and a hydrogenation isomerization catalyst containing platinum and / or palladium supported on the support, wherein the zeolite is a catalyst containing an organic template and having a 10-membered ring primary pore structure Wherein the catalyst is derived from an ion-exchange zeolite obtained by ion-exchanging the template-containing zeolite in a solution containing ammonium ion and / or proton, wherein the amount of carbon contained in the catalyst is 0.4 to 3.5 mass% A support comprising zeolite having a circular pore structure and platinum and / or palladium carried on the support, wherein the platinum and / or And the ratio V1 / V2 of the volume V1 of the first catalyst to the volume V2 of the second catalyst is 70/30 to 90/10 in terms of metal atoms, The present invention also provides a method for producing a lubricating base oil.

In the present specification, the amount of carbon in the hydrogenation isomerization catalyst is calculated by analyzing the oxygen-air current by the combustion-infrared absorption method. Specifically, a catalyst is burned in an oxygen stream using a carbon-sulfur analyzer (for example, EMIA-920V manufactured by Horiba Seisakusho Co., Ltd.), and the amount of carbon is quantitatively determined by the infrared absorption method.

According to the method for producing a lubricating base oil of the present invention, it is possible to efficiently obtain a heavy lubricating base oil having a sufficiently low pour point and a cloud point.

The inventors of the present invention presume the reason why the above effect can be obtained as follows. That is, since the zeolite contained in the first catalyst and the second catalyst has a 10-membered ring primary pore structure, it is possible to selectively adsorb hydrocarbons having a long chain paraffin structure in the molecule, which is considered to be a cause of deteriorating the carrier, In the hydrocarbon having the long-chain paraffin structure in which the hydrogenation isomerization is efficiently carried out by the first catalyst having the specific amount of carbon and the hydrogenation isomerization remains, the specific active metal is added in the above- It is considered that the improvement of both the pour point and the cloud point can be considered while maintaining the yield of the lubricant base oil sufficiently.

It is preferable that the first catalyst has a micropore volume per unit mass of the catalyst of 0.02 to 0.12 cc / g and a micropore volume per unit mass of zeolite contained in the catalyst of 0.01 to 0.12 cc / g.

In the present specification, the micropore volume per unit mass of the hydrogenation isomerization catalyst is calculated by a method called nitrogen adsorption measurement. Namely, the adsorption isotherm of nitrogen adsorbed by nitrogen adsorption isotherms measured at liquid nitrogen temperature (-196 ° C), specifically at the liquid nitrogen temperature (-196 ° C) , The micropore volume per unit mass of the catalyst is calculated. The micropore volume per unit mass of the zeolite contained in the catalyst is also calculated by the above nitrogen adsorption measurement.

In this specification, micro-pores refer to "pores having a diameter of 2 nm or less" defined by International Union of Pure and Applied Chemistry (IUPAC).

According to another aspect of the present invention, there is provided a process for producing a catalyst comprising the steps of contacting raw oil containing hydrocarbons having 21 or more carbon atoms in the presence of hydrogen in this order to a first catalyst and a second catalyst, containing and 10-membered ring primary circle an organic template-containing zeolite having a pore structure, and ion-exchanged zeolite obtained by ion-exchange in a solution containing ammonium ions and / or protons, the mixture which contains a binder, under a N ₂ atmosphere, 250 And a catalyst precursor containing a platinum salt and / or a palladium salt in a carrier precursor under an atmosphere containing molecular oxygen at a temperature of 350 to 400 占 폚 And a second step of obtaining a hydrogenation isomerization catalyst in which platinum and / or palladium is supported on a carrier containing zeolite, Wherein the second catalyst comprises a support comprising zeolite having a 10-membered ring primary pore structure, platinum and / or palladium supported on the support, platinum and / or palladium supported on the support, And the ratio V1 / V2 of the volume V1 of the first catalyst to the volume V2 of the second catalyst is 70/30 to 90/10 in terms of metal atoms, The present invention also provides a method for producing a lubricating base oil.

According to the present invention, it is possible to provide a method for producing a lubricating base oil, which can efficiently obtain a heavy lubricant base oil having a sufficiently low pour point and a cloud point.

Fig. 1 is a flowchart showing an example of a lubricating base oil producing apparatus for carrying out the method for producing a lubricating base oil according to the present invention.
Fig. 2 is a flowchart showing another example of the apparatus for producing a lubricating base oil according to the present invention.

Best Mode for Carrying Out the Invention 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 flowchart showing an example of a lubricating base oil producing apparatus for carrying out the method for producing a lubricating base oil according to the present invention. The apparatus 100 for producing a lubricating base oil shown in Fig. 1 is a device for producing a hydrocarbon oil containing a component useful as a lubricant base oil from a raw material containing a paraffinic hydrocarbon.

The hydrocarbon oil production apparatus 100 shown in Fig. 1 comprises a reaction tower 10 for hydrotreating a raw material (raw oil) containing a paraffinic hydrocarbon and a reaction column 10 for producing a product oil obtained from the reaction column 10, And a first distillation column 15 and a second distillation column 20 for classifying the distillate as a distillate. A feed line L1 for feeding the raw material oil to the reaction tower 10 is connected to the column top of the reaction tower 10, and a line L2 through which hydrogen is introduced is connected to this line L1. Raw material oil and hydrogen are supplied to the reaction tower 10 through these lines. The bottom of the reaction tower 10 and the distillation column 20 are connected to each other at the transfer line L3 and the product oil obtained from the reaction column 10 is sent to the first distillation column 15 through the line L3. The first distillation tower 15 is connected to lines L4, L5 and L6 for extracting naphtha oil fraction, uneven oil fraction and lubricant oil fraction classified by the first distillation tower 15. [ The line L6 is connected to the second distillation column 20 and can supply the lubricating oil fraction to the second distillation column 20. Lines L8, L9, and L10 for extracting various kinds of lubricant base oil classified by the second distillation tower 20 are connected to the second distillation tower 20.

In the present embodiment, the reaction tower 10 comprises a first catalyst layer 12 comprising a first catalyst and a second catalyst layer 14 comprising a second catalyst from the top of the column in this order I have.

The paraffinic hydrocarbon provided for the hydrogenation treatment is not particularly limited as far as the number of carbon atoms is concerned, and examples thereof include hydrocarbons having 21 to 100 carbon atoms. In the present embodiment, a raw material oil containing a hydrocarbon having 30 or more carbon atoms, preferably a raw material oil containing 50% by mass or more of a hydrocarbon oil having 40 or more carbon atoms is provided for the hydrogenation treatment.

As the raw material oil, oil obtained by classifying FT synthetic oil, reduced pressure light oil, reduced pressure light oil hydrocracking column low oil and reduced pressure residual oil deasphalted oil may be used.

As the first catalyst of this embodiment, an ion exchange zeolite obtained by ion-exchanging an organic template-containing zeolite containing an organic template and having a 10-membered ring primary pore structure in a solution containing ammonium ion and / or proton, the mixture is contained, N ₂ in an atmosphere, a first in which the catalyst precursor comprises the step of, platinum salts and / or palladium salt on the support precursor to obtain a support precursor is heated to a temperature of 250 to 350 ℃, molecular oxygen And a second step of obtaining a hydrogenation isomerization catalyst in which platinum and / or palladium is supported on a support containing zeolite, at a temperature of 350 to 400 ° C in an atmosphere containing The obtained hydrogenation isomerization catalyst can be used.

The organic template-containing zeolite used in the present embodiment has a primary pore structure composed of a 10-membered ring from the viewpoint of achieving a high level of high isomerization activity and suppressed decomposition activity in the hydrogenation isomerization reaction of normal paraffin at a high level. Examples of such zeolites include AEL, EUO, FER, HEU, MEL, MFI, NES, TON, MTT, WEI, * MRE and SSZ-32. In addition, each of the three alphabetic characters 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.

Among the zeolites having the 10-membered ring primary pore structure, zeolite having TON, MTT structure, ZSM-48 zeolite having a * MRE structure, in view of high isomerization activity and low decomposition activity, , And SSZ-32 zeolite are preferred. As the zeolite having the TON structure, ZSM-22 zeolite is more preferable, and as the zeolite having an MTT structure, ZSM-23 zeolite is more preferable.

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

The organic template is an organic compound having an amino group, an ammonium group or the like and is selected depending on the structure of the zeolite to be synthesized, but it is preferably an amine derivative. Specifically, it is at least one selected from the group consisting of alkylamine, alkyldiamine, alkyltriamine, alkyltetramine, pyrrolidine, piperazine, aminopiperazine, alkylpentamine, alkylhexamine and derivatives thereof More preferable. The number of carbon atoms of the alkyl may be 4 to 10, preferably 6 to 8. Representative examples of the alkyldiamine include 1,6-hexanediamine, 1,8-diaminooctane, and the like.

(Si / Al) (hereinafter referred to as " Si / Al ratio ") of silicon and aluminum elements constituting the organic template-containing zeolite having a 10-membered circular primary pore structure is preferably 10-400 , 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 with increasing reaction temperature tends to be abrupt, not. On the other hand, when the Si / Al ratio exceeds 400, the catalytic activity necessary for conversion of normal paraffin becomes difficult to obtain, which is not preferable.

The organic template-containing zeolite synthesized, preferably washed and dried has usually an alkali metal cation as a counter cation, and the organic template is contained in the pore structure. The zeolite containing the organic template used in the production of the hydrogenation isomerization catalyst according to the present invention is 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 comprising ammonium ions and / or protons. By the ion exchange treatment, 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, as a compound for supplying proton into a solution, a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid and the like is usually used. The ion-exchanged zeolite (here, ammonium type zeolite) obtained by ion-exchanging the zeolite containing the organic template in the presence of ammonium ion releases ammonia at the subsequent calcination, and the large cation becomes a proton and becomes a Bronsted acid point. As the cationic species used for ion exchange, ammonium ion is preferable. It is preferable that the content of the ammonium ion and / or proton contained in the solution is set to be 10 to 1000 equivalents relative to the total amount of the large cation and the organic template contained in the organic template-containing zeolite to be used.

The ion exchange treatment may be carried out with respect to a zeolite carrier containing a powdery organic template, and before the ion exchange treatment, an inorganic oxide which is a binder is added to the organic template-containing zeolite and molded, . However, it is preferable to provide the zeolite containing a powdery organic template in the ion exchange treatment, since the above-mentioned molded body is not subjected to firing and is provided for ion exchange treatment, problems such as collapse and differentiation (powdering) of the molded body tend to occur.

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

It is also preferable to exchange the solution with a new one or two or more times during the ion exchange of the zeolite with the solution in order to increase the efficiency of the ion exchange and to exchange the solution once or twice with a new one More preferable. 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 for 1 to 6 hours under reflux, and then the solution is exchanged for a new one, And further refluxed for 6 to 12 hours, it becomes 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, the organic template contained in the zeolite is partially removed by the above-mentioned ion exchange treatment, but even if the same treatment is repeatedly performed, it is generally difficult to remove all of the organic template, do.

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

The mixture containing the ion-exchanged zeolite and the binder is preferably obtained by compounding an inorganic oxide as a binder in the ion-exchanged zeolite obtained by the above-mentioned method, and shaping the obtained composition. The object of blending an inorganic oxide in an ion-exchange zeolite is to improve the mechanical strength of a carrier (particularly, a particulate carrier) obtained by calcining the formed body to such an extent that it can withstand practical use. Has been found to influence 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 phosphorus oxide, Is used. Among them, silica and alumina are preferable, and alumina is more preferable from the viewpoint that the isomerization selectivity of the hydrogenation isomerization catalyst is further improved. The above-mentioned " composite oxide comprising two or more of these compounds " is a complex oxide consisting of at least two components selected from alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide, A composite oxide containing alumina as a main component containing an alumina component of 50 mass% or more based on the complex oxide is preferable, and alumina-silica is more preferable.

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

The method of compounding the above-mentioned inorganic oxide with an ion-exchange zeolite is not particularly limited. For example, a suitable amount of water such as water is added to both powders to make a viscous fluid, which is kneaded with a kneader or the like And the like can be employed.

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, three-leaf and four-leaf type cross-sectional shapes, and the like. The size of the molded body is not particularly limited, but it is preferable that the long axis is 1 to 30 mm and the short axis is 1 to 20 mm, for example, from the viewpoints of ease of handling and packing density into the reactor.

In this embodiment, a molded shaped body obtained as described above, under a N ₂ atmosphere and heated to a temperature of 250 to 350 ℃ it is preferable that the support precursor. The heating time is preferably 0.5 to 10 hours, more preferably 1 to 5 hours.

In the present embodiment, when the heating temperature is lower than 250 ° C, a large amount of the organic template remains, and the zeolite pores are occluded by the remaining template. It is believed that the isomerization active site is present near the pore pore mouse. In this case, the reaction substrate becomes unable to diffuse into the pores due to the pore clogging, and the active site is covered and the isomerization reaction becomes difficult to proceed. Conversion rate) tends to be difficult to obtain sufficiently. On the other hand, when the heating temperature exceeds 350 ° C, the isomerization selectivity of the obtained hydrogenation isomerization catalyst is not sufficiently improved.

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

In the present embodiment, it is preferable to heat the mixture so that a part of the organic template contained in the formed body remains. Concretely, the amount of carbon contained in the hydrogenation isomerization catalyst obtained through firing after metal-supporting described later is 0.4 to 3.5 mass%, preferably 0.4 to 3.0 mass%, more preferably 0.4 to 2.5 mass% Is set to 0.4 to 1.5% by mass. The microporous volume per unit mass of the hydrogenation isomerization catalyst obtained through firing after metal-supporting described later is 0.02 to 0.12 cc / g, and the micropore volume per unit mass of the zeolite contained in the catalyst is 0.01 to 0.12 cc / lt; RTI ID = 0.0 > g. < / RTI >

Next, the catalyst precursor containing the platinum salt and / or the palladium salt in the carrier precursor is heated at a temperature of 350 to 400 캜, preferably 380 to 400 캜, more preferably 400 캜 Temperature to obtain a hydrogenation isomerization catalyst in which platinum and / or palladium is supported on a support containing zeolite. The term "in an atmosphere containing molecular oxygen" means a gas containing oxygen gas, particularly preferably in contact with air. The firing time is preferably 0.5 to 10 hours, more preferably 1 to 5 hours.

Examples of the platinum salt include chloroplatinic acid, tetraammine dinitro platinum, dinitroamine platinum, tetraammine dichloroplatinum and the like. The chloride salt is preferably a tetraammine ditnitroplatinum, which is a platinum salt in which platinum is highly dispersed in addition to a chloride salt, since hydrochloric acid is generated during the reaction and there is a risk of corrosion of the apparatus.

Examples of the palladium salt include palladium chloride, tetraammine palladium nitrate, diaminopalladium nitrate and the like. The chloride salt is preferably tetraammine palladium nitrate, which is a palladium salt in which palladium is highly dispersed in addition to the chloride salt, since hydrochloric acid is generated during the reaction and there is a risk of corrosion of the apparatus.

The loading amount of the active metal in the carrier containing the zeolite according to the present embodiment is preferably 0.001 to 20 mass%, more preferably 0.01 to 5 mass%, based on the mass of the 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 amount is more than 20% by mass, hardening (smoothing) due to decomposition of hydrocarbons on the active metal tends to proceed, and the yield of the intended oil tends to decrease, Which tends to cause an increase in the catalyst cost.

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

In the present embodiment, it is preferable that the catalyst precursor is baked so that the organic template remaining in the carrier precursor remains. Specifically, the amount of carbon contained in the hydrogenation isomerization catalyst to be obtained is preferably 0.4 to 3.5 mass%, preferably 0.4 to 3.0 mass%, more preferably 0.4 to 2.5 mass%, and still more preferably 0.4 to 1.5 mass% It is desirable to set heating conditions. The heating conditions are set so that the micropore volume per unit mass of the obtained hydrogenation isomerization catalyst is 0.02 to 0.12 cc / g and the micropore volume per unit mass of the zeolite contained in the catalyst is 0.01 to 0.12 cc / g .

The carbon content of the hydrogenation isomerization catalyst is calculated by analyzing the oxygen-containing stream by the combustion-infrared absorption method. Specifically, a carbon-sulfur analyzer (for example, EMIA-920V manufactured by Horiba Seisakusho Co., Ltd.) is used, the catalyst is burned in an oxygen stream, and the amount of carbon is quantitatively determined by the infrared absorption method.

The micropore volume per unit mass of the hydrogenation isomerization catalyst is calculated by a method called nitrogen adsorption measurement. Namely, the adsorption isotherm of nitrogen adsorbed by nitrogen adsorption isotherms measured at liquid nitrogen temperature (-196 ° C), specifically at the liquid nitrogen temperature (-196 ° C) , The micropore volume per unit mass of the catalyst is calculated. The micropore volume per unit mass of the zeolite contained in the catalyst is also calculated by the above nitrogen adsorption measurement.

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

V _z = V _c / M _z × 100

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, a reduction treatment is carried out under an atmosphere containing molecular hydrogen, preferably under hydrogen gas circulation, preferably at 250 to 500 ° C, more preferably at 300 to 400 ° C for about 0.5 to 5 hours . By such a process, high activity for dehydration of hydrocarbon oil can be more reliably given to the catalyst.

In addition, in the present embodiment, as the first catalyst, a zeolite having a 10-membered ring primary pore structure and a carrier containing a binder, and platinum and / or palladium supported on the carrier, Containing zeolite having a 10-membered ring primary pore structure in an ion-exchange solution obtained by ion-exchange in a solution containing an ammonium ion and / or a proton, and the amount of carbon contained in the catalyst is 0.4 to 3.5 % By mass. It is also possible to use a hydrogenation isomerization catalyst having a micropore volume per unit mass of zeolite contained in the catalyst of 0.01 to 0.12 cc / g as a hydrogenation isomerization catalyst having a micropore volume per unit mass of catalyst of 0.02 to 0.12 cc / g More preferable.

The amount of carbon contained in the catalyst is preferably 0.4 to 3.0% by mass, more preferably 0.4 to 2.5% by mass, still more preferably 0.4 to 1.5% by mass.

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

The second catalyst of the present embodiment is a catalyst comprising a support containing zeolite having a 10-membered ring primary pore structure and platinum and / or palladium supported on the support, wherein the total amount of supported platinum and / A catalyst is used in an amount of 0.05 to 0.4 parts by mass based on 100 parts by mass of the carrier.

In this embodiment, for the purpose of preventing the stability of the unstable substance produced during the reaction by hydrogenation to become insufficient and preventing the catalyst from being inactivated faster by increasing the coke production rate, the total amount of platinum and / or palladium Is 0.05 part by mass or more, preferably 0.08 part by mass or more, based on 100 parts by mass of the support in terms of metal atoms. On the other hand, the total amount of platinum and / or palladium to be supported is not more than 0.4 part by mass, preferably not more than 0.2 part by mass, based on 100 parts by mass of the support in terms of metal atoms, for the purpose of preventing the reaction of removing the fogging material.

The zeolite constituting the above catalyst is obtained by firing the hydrothermally synthesized zeolite at a temperature of, for example, about 550 ° C or higher in an atmosphere containing molecular oxygen. This temperature is selected to sufficiently burn and remove the organic template. After the calcination, the second catalyst can be obtained by carrying out ion exchange, carrying of a metal component, and activation by firing.

The carrier of the second catalyst may contain a binder. Specific examples of the binder include inorganic oxides such as alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide, and at least one Of inorganic oxides can be used. Among them, silica and alumina are preferable and alumina is more preferable from the viewpoint of suppressing paraffin decomposition activity. From the viewpoint of preserving the crushing strength of the catalyst, a composite oxide containing alumina as a main component containing an alumina component of 50 mass% or more based on the composite oxide is preferable, and alumina-silica is more preferable.

The ratio of the zeolite to the inorganic oxide in the carrier of the second catalyst according to the present embodiment is preferably 10:90 to 90:10, more preferably 30: 70 to 85:15. When the ratio is smaller than 10: 90, the catalyst activity tends to become insufficient, which is not preferable. On the other hand, when the ratio exceeds 90:10, the mechanical strength of the carrier tends to become insufficient, which is not preferable.

In the present embodiment, the ratio V1 / V2 of the volume V1 of the first catalyst constituting the first catalyst layer to the volume V2 of the second catalyst constituting the second catalyst layer is 70/30 to 90/10. If the ratio is less than 70/30, that is, if the volume V1 of the first catalyst is too small, the pour point of the lubricating oil can not be sufficiently lowered. On the other hand, if the ratio is larger than 90/10, Is too small, the removal of the deteriorating material at the spot becomes insufficient. V1 / V2 is preferably 2.6 to 7.3, more preferably 3.0 to 5.7 from the viewpoint of maintaining the yield of the lubricating oil at the same time as the predetermined pour point.

In the present embodiment, for example, when the cross-sectional area of the first catalyst layer and the second catalyst layer of the reaction tower 10 when cut into a plane perpendicular to the flow direction is constant regardless of the cutting position, The ratio [D1 / D2] of the thickness D1 of the first catalyst layer to the thickness D2 of the second catalyst layer can be set within the range of 70/30 to 90/10, preferably within the range of 2.6 to 7.3, And more preferably within the range of < RTI ID = 0.0 >

The hydrogenation treatment in the reaction tower 10 can be carried out under the following reaction conditions. The hydrogen partial pressure may be 1 to 20 MPa, preferably 3 to 15 MPa. The liquidus space velocity (LHSV) of the raw material oil may be 0.1 to 5 h ^-1 , preferably 1 to 3 h ^-1 . The hydrogen / oil ratio may be 100 to 1500 NL / L, preferably 200 to 1000 NL / L.

The reaction temperature in the hydrogenation treatment may be 200 to 400 占 폚, preferably 250 to 380 占 폚, and more preferably 300 to 350 占 폚.

In this embodiment, from the viewpoint of obtaining a lubricating base oil excellent in viscosity index and pour point, it is preferable to hydrogenate the raw material oil under the condition that the conversion rate of normal paraffin defined by the following formula (I) is 100% by mass.

(%) Of normal paraffin = [1 - (the total amount of the normal paraffins having 21 or more carbon atoms contained in 100 parts by mass of the product oil obtained after the hydrogenation treatment) / (the number of carbon atoms contained in 100 parts by mass of the raw material oil before hydrotreatment The total mass of normal paraffin part))] x 100 ... (I)

In this specification, isomerization refers to a reaction in which the number of carbon atoms (molecular weight) does not change but changes in molecular structure, and decomposition refers to a reaction accompanied by a decrease in the number of carbon atoms (molecular weight). In the contact dewaxing reaction using an isomerization reaction, even if the decomposition of the hydrocarbon and the isomerization product of the raw material oil occurs to some extent, the number of carbon atoms (molecular weight) of the product may be within a predetermined range that allows the desired base oil to constitute, The product may be a component of the base oil.

In the reaction tower 10 shown in FIG. 1, the object to be treated is supplied as a downflow. If necessary, the first catalyst layer 12 and the second catalyst layer 14 may be supplied in an upflow order. In this case, the generated oil is transferred from the top of the reaction tower 10 to the first distillation tower 15.

Further, in the present embodiment, a hydrogenation treatment may be carried out using a reaction tower having three or more catalyst layers instead of the reaction tower 10 having two catalyst layers. In this case, each catalyst layer may be filled so that the total volume of the first catalyst and the total volume of the second catalyst satisfy the above-described ratio.

The hydrogenation treatment conducted in the reaction tower 10 includes both hydrocracking and hydrogenation isomerization. Also, the case where both reactions of hydrocracking and hydrogenation isomerization proceed intricately intertwining each other. In addition, decomposition refers to a chemical reaction accompanied by a decrease in molecular weight, and isomerization refers to conversion to other compounds having different carbon skeletons while maintaining the molecular weight and the carbon number constituting the molecule.

As the first distillation column 15 and the second distillation column 20, a known distillation column may be used.

In the first distillation tower 15, the product oil obtained from the reaction tower 10 by distillation is classified into, for example, light oil fractions (naphtha and oil race oil) and lubricating oil fractions. The light oil fractions (naphtha, rudder oil fraction) can be recovered from the lines L4 and L5 connected to the first distillation tower 15, respectively. The lubricating oil fraction is supplied from the line L6 connected to the bottom of the first distillation tower 15 to the second distillation tower 20 and distilled under reduced pressure in the second distillation tower 20. [ Further, in the present embodiment, it is possible to separate the generated oil using a separation tower instead of the first distillation tower.

In the distillation column 20, the lubricating oil fraction is, for example, 70 Pale (oil of boiling point 330 to 410 캜), SAE-10 (oil of boiling point 410 to 470 캜), SAE-20 (oil of boiling point 470 to 520 캜) , SAE-30 (oil of boiling point 520 to 560 ° C), and brightstock (oil of boiling point 560 ° C or more). These oil fractions can be recovered, for example, from the lines L8 to L10 connected to the second distillation column 20. [

According to the above apparatus 100 for producing a lubricating base oil, it is possible to obtain a heavy lubricating base oil in which the cloud point is sufficiently improved.

Fig. 2 is a flowchart showing another example of a hydrocarbon oil producing apparatus in which a method for producing a lubricating base oil according to the present invention is practiced. 2 includes two reaction columns 30 and 30 connected in series via a transfer line L8 in place of the reaction column 10 in the apparatus 100 for producing a lubricating base oil, 40 of the present invention is provided with the same construction as the apparatus 100 for producing a lubricating base oil. The apparatus 110 for producing a lubricating base oil is characterized in that the reaction tower 30 has the same catalyst layer 16 as the first catalyst layer and the reaction tower 40 has the same catalyst layer 18 as the second catalyst layer And hydrogenation treatment of the raw material oil is carried out by these two reaction columns 30 and 40.

The hydrogenation treatment in the reaction tower (30) and the reaction tower (40) can be carried out under the following reaction conditions. The hydrogen partial pressure may be 1 to 20 MPa, preferably 3 to 15 MPa. 0.1 to 5h As the raw material liquid significant space velocity (LHSV) ^- there can be ^one, preferably 0.5 to 3h ^-1. The hydrogen / oil ratio may be 100 to 1500 NL / L, preferably 200 to 1000 NL / L.

In the present embodiment, the ratio V1 / V2 of the volume V1 of the first catalyst constituting the catalyst layer 16 to the volume V2 of the second catalyst constituting the catalyst layer 18 is 70/30 to 90/10. For the same reason as in the manufacturing apparatus 100, V1 / V2 is preferably 2.6 to 7.3, more preferably 3.0 to 5.7.

In this embodiment, for example, the cross-sectional area when the first catalyst layer of the reaction tower 30 and the second catalyst layer of the reaction tower 40 are cut in a plane perpendicular to the flow direction is determined by the cutting position The ratio [D3 / D4] of the thickness D3 of the first catalyst layer and the thickness D4 of the second catalyst layer shown in Fig. 2 can be set in the range of 70/30 to 90/10 and in the range of 2.6 to 7.3 , And more preferably in the range of 3.0 to 5.7.

In the method for producing a lubricating base oil according to the present embodiment, the product oil obtained through the hydrogenation treatment can be further treated, for example, by hydrofinishing. Hydrofinishing can generally be carried out by contacting the workpiece with a supported metal hydrogenation catalyst (e.g., alumina bearing platinum and / or palladium) in the presence of hydrogen. By performing such hydrogenation finishing, the color of the produced oil, the oxidation stability and the like are improved, and the quality of the product can be improved. The hydrogenation finishing may be carried out in a reaction facility different from the line in which the first catalyst and the second catalyst are contained. However, the hydrogenation finishing may be carried out at the downstream side of the second catalyst layer comprising the second catalyst according to the present invention, Of the catalyst layer may be formed.

Example

[Production of catalyst]

(Production Example 1)

≪ Preparation of ZSM-22 zeolite >

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

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

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

Solution B: 1.33 g of aluminum sulfate 18 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 was 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 to obtain a gel product.

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 autoclave reactor was rotated on the tumbling apparatus at a rotation speed of about 60 rpm for 60 hours in an oven at 150 캜 to perform a hydrothermal synthesis reaction Respectively. After completion of the reaction, the reactor was cooled, opened, and dried overnight in a drier at 60 DEG C to obtain ZSM-22 having a Si / Al ratio of 45.

≪ Ion exchange of ZSM-22 containing organic template >

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

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

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

≪ 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 shaped body having a diameter of about 1.6 mm and a length of about 10 mm. The formed body was heated at 300 캜 for 3 hours under an N ₂ atmosphere to obtain a carrier precursor.

<Supporting platinum, plastic>

Tetra nitro cancer Mindy.Mindy the platinum _{[Pt (NH 3) 4]} (NO 3) 2, was dissolved in ion exchange water which corresponds to the pre-measured amount of water absorption of the support precursor to yield the impregnating solution. This solution was impregnated with the above carrier precursor by the initial wetting method, and carried so as to have a platinum content of 0.3 mass% with respect to the mass of the ZSM-22 zeolite. Next, the obtained impregnated product (catalyst precursor) was dried in a drier at 60 占 폚 overnight and then calcined at 400 占 폚 under air circulation for 3 hours to obtain a hydrogenation isomerization catalyst E-1 having a carbon content of 0.56 mass%. In addition, the amount of carbon was measured by the combustion-infrared absorption method in oxygen flow using EMIA-920V manufactured by Horiba Seisakusho.

The micropore volume per unit mass of the hydrogenation isomerization catalyst thus obtained was calculated by the following method. First, in order to remove moisture adsorbed by the hydrogenation isomerization catalyst, pretreatment was performed by vacuum exhausting at 150 DEG C for 5 hours. The hydrogenation isomerization catalyst after this pretreatment was subjected to nitrogen adsorption measurement at a liquid nitrogen temperature (-196 DEG C) using BELSORP-max manufactured by Nippon Berry Co., Ltd. Then, the adsorption isotherm of the measured nitrogen was analyzed by t-plot method to calculate the micropore volume (cc / g) per unit mass of the hydrogenation isomerization catalyst.

Further, the micropore volume V _z per unit mass of the zeolite contained in the catalyst was calculated according to the following equation. Further, nitrogen adsorption measurement was performed on the alumina used as the binder as described above, and it was confirmed that the alumina had no micropores.

V _z = V _c / M _z × 100

In the above equation, V _c represents the micropore volume per unit mass of the hydrogenation isomerization catalyst, and M _z represents the content ratio (mass%) of the zeolite contained in the catalyst.

The micropore volume per unit mass of the hydrogenation isomerization catalyst E-1 was 0.055 cc / g, and the micropore volume per unit mass of the zeolite contained in the catalyst was 0.079 cc / g.

(Production Example 2)

First, as in Production Example 1, ZSM-22 having a Si / Al ratio of 45 was obtained. ZSM-22 was charged in a quartz tube and heated to 400 캜 at a rate of 5 캜 / minute under a nitrogen stream, and maintained at that temperature for 6 hours. Thereafter, the flowing gas was changed to oxygen gas, and the temperature was further raised to 550 DEG C at a rate of 5 DEG C / minute, and the temperature was maintained at 550 DEG C overnight.

The fired ZSM-22 was cooled to room temperature, transferred to a flask, and a 0.5 M ammonium chloride aqueous solution was added thereto, and the mixture was refluxed for one night and ion-exchanged. After completion of the ion exchange, the solid content was collected by filtration, washed with ion-exchanged water, and dried in a dryer at 60 캜 overnight to obtain NH ₄ type ZSM-22.

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 shaped body having a diameter of about 1.6 mm and a length of about 10 mm. The formed body was heated at 300 캜 for 3 hours under an N ₂ atmosphere to obtain a carrier precursor.

Platinum and palladium were supported on the support precursor obtained as described above by the following method.

First, tetraammine MindiNitroplatinum (II) and tetraammine ditnitropalladium were dissolved in a minimal amount of ion-exchanged water. This solution was impregnated into the carrier precursor by the initial wetting method and supported so as to have a platinum amount of 0.1 mass% and a palladium amount of 0.3 mass% with respect to the mass of ZSM-22. Next, these were dried in a drier at 60 占 폚 overnight, and then calcined at 400 占 폚 for 3 hours under air circulation. Then, they were molded into a disk by a tablet molding and further coarsely pulverized, Thereby forming a granular irregular shape of 250 mu m. Thus, catalyst E-2 was obtained.

(Production Example 3)

Catalyst E-3 was obtained in the same manner as in Production Example 2 except that the amounts of platinum and palladium supported were changed to 0.1 mass% and 0.1 mass%, respectively.

(Production Example 4)

Catalyst E-4 was obtained in the same manner as in Production Example 2 except that the amounts of platinum and palladium supported were changed to 0.1 mass% and 0.2 mass%, respectively.

(Production Example 5)

Catalyst E-5 was obtained in the same manner as in Production Example 2 except that the amount of platinum and palladium supported was changed to 0.01 mass% and 0.01 mass%, respectively.

[Raw material oil]

The following raw materials were prepared.

R-1: Vacuum distillation column bottom oil (boiling point: 560 占 폚 or higher, content ratio of hydrocarbons having 21 or more carbon atoms: 100 mass%) of FT synthetic oil

R-2: Deasphalted distillation column of Middle East crude oil Deasphalted oil (content ratio of hydrocarbons having a boiling point of 550 ° C or higher and a carbon number of 21 or more: 100% by mass) in which asphalt is removed by a propane dewaxing process,

R-3: Mixture of R-1 and R-2 mixed at a volume ratio R-1 / R-2 = 50/50.

[Production of lubricant base oil]

(Example 1)

The catalyst E-1 was charged 80 ml on the upstream side (upper layer) of the fixed-bed reactor and 20 ml of the catalyst E-2 on the downstream side (lower layer), respectively.

Then, R-1 as a raw material oil was supplied from the column top of the reactor (upper side of the catalyst layer) at an LHSV of 1.0 h ^-1 and subjected to a hydrogenation treatment under a hydrogen atmosphere at a hydrogen pressure of 5 MPa and a reaction temperature of 331 占 폚.

The resulting oil was distilled to obtain an oil having a boiling point of 550 DEG C or higher. The viscosity index of this fraction was 159, the pour point was -15 ° C, and the cloud point was -10 ° C. The yield of this oil relative to the feed oil was 80 mass%.

The viscosity index, the pour point and the light spot were measured according to the viscosity index calculation method prescribed in JIS K2283, the pour point test method prescribed in JIS K2269, and the spot test method prescribed in JIS K2269.

(Example 2)

90 ml of the catalyst E-1 was placed on the upstream side (upper layer) of the fixed bed reactor, and 10 ml of the catalyst E-3 was placed on the downstream side (lower layer).

Then, R-1 as a raw material oil was supplied from an overhead of the reactor (upper side of the catalyst layer) at an LHSV of 1.0 h ^-1 and subjected to a hydrogenation treatment under a hydrogen atmosphere at a hydrogen pressure of 5 MPa and a reaction temperature of 321 캜.

The resulting oil was distilled to obtain an oil having a boiling point of 550 DEG C or higher. The viscosity index of this fraction was 159, the pour point was -15 ° C, and the cloud point was -4 ° C. The yield of this oil relative to the feed oil was 78 mass%.

(Example 3)

The catalyst E-1 was charged in an amount of 70 ml on the upstream side (upper layer) of the fixed-bed reactor, and the downstream side (lower layer) was charged with 30 ml of the catalyst E-4 to form a two-layer catalyst layer in the reactor.

Then, R-1 as a raw material oil was supplied from an overhead of the reactor (upper side of the catalyst layer) at an LHSV of 1.0 h ^-1 and hydrogenated at a hydrogen pressure of 5 MPa and a reaction temperature of 318 캜 under a hydrogen stream.

The resulting oil was distilled to obtain an oil having a boiling point of 550 DEG C or higher. The viscosity index of this fraction was 158, the pour point was -15 ° C, and the cloud point was -13 ° C. The yield of this oil relative to the feed oil was 74 mass%.

(Example 4)

The catalyst E-1 was charged 80 ml on the upstream side (upper layer) of the fixed-bed reactor and 20 ml of the catalyst E-2 on the downstream side (lower layer), respectively.

Next, R-2 as raw material oil was supplied from the column top (upper side of the catalyst layer) of the reactor at an LHSV of 1.0 h ^-1 and subjected to a hydrogenation treatment under a hydrogen pressure of 10 MPa and a reaction temperature of 341 캜.

The resulting oil was distilled to obtain an oil having a boiling point of 550 DEG C or higher. The viscosity index of this fraction was 110, the pour point was -12.5 ° C, and the cloud point was -10 ° C. The yield of this oil relative to the feed oil was 79 mass%.

(Example 5)

The catalyst E-1 was charged 80 ml on the upstream side (upper layer) of the fixed-bed reactor and 20 ml of the catalyst E-2 on the downstream side (lower layer), respectively.

Next, R-3 as a raw material oil was supplied from the top of the reactor (upper side of the catalyst layer) at an LHSV of 1.5 h ^-1 and subjected to a hydrogenation treatment under a hydrogen atmosphere at a hydrogen pressure of 10 MPa and a reaction temperature of 345 占 폚.

The resulting oil was distilled to obtain an oil having a boiling point of 550 DEG C or higher. The viscosity index of this fraction was 131, the pour point was -15 ° C, and the cloud point was -81 ° C. The yield of this oil relative to the feed oil was 82 mass%.

(Comparative Example 1)

Only 100 ml of the catalyst E-1 was filled in the fixed bed reactor to form a single-layer catalyst bed in the reactor.

Then, R-1 as a raw material oil was supplied from the top of the reactor (upper side of the catalyst layer) at an LHSV of 1.0 h ^-1 and subjected to hydrogenation treatment at a hydrogen pressure of 5 MPa and a reaction temperature of 330 캜 under a hydrogen stream.

The resulting oil was distilled to obtain an oil having a boiling point of 550 DEG C or higher. The viscosity index of this fraction was 159, the pour point was -15 ° C, and the cloud point was 15 ° C. The yield of this oil relative to the feed oil was 68 mass%.

(Comparative Example 2)

Only 100 ml of the catalyst E-1 was filled in the fixed bed reactor to form a single-layer catalyst bed in the reactor.

Next, R-2 as a raw material oil was supplied from the top of the reactor (upper layer side of the catalyst layer) at an LHSV of 1.0 h ^-1 and subjected to a hydrogenation treatment under a hydrogen atmosphere at a hydrogen pressure of 5 MPa and a reaction temperature of 331 占 폚.

The resulting oil was distilled to obtain an oil having a boiling point of 550 DEG C or higher. The viscosity index of this fraction was 108, the pour point was -12.5 ° C, and the cloud point was 6 ° C. The yield of this oil relative to the feed oil was 62 mass%.

(Comparative Example 3)

95 ml of the catalyst E-1 was placed on the upstream side (upper layer) of the fixed bed reactor, and 5 ml of the catalyst E-2 was placed on the downstream side (lower layer).

Then, R-1 as a raw material oil was supplied from an overhead of the reactor (upper side of the catalyst layer) at an LHSV of 1.0 h ^-1 and hydrogenated at a hydrogen pressure of 5 MPa and a reaction temperature of 318 캜 under a hydrogen stream.

The resulting oil was distilled to obtain an oil having a boiling point of 550 DEG C or higher. The viscosity index of this fraction was 159, the pour point was -15 ° C, and the cloud point was 10 ° C. The yield of this oil relative to the feed oil was 76 mass%.

(Comparative Example 4)

Catalyst E-1 was charged in an amount of 80 ml on the upstream side (upper layer) of the fixed bed reactor, and 20 ml of Catalyst E-5 was charged on the downstream side (lower layer).

Then, R-1 as a raw material oil was fed from the top of the reactor (upper side of the catalyst layer) at an LHSV of 1.0 h ^-1 and subjected to a hydrogenation treatment under a hydrogen atmosphere at a hydrogen pressure of 10 MPa and a reaction temperature of 345 占 폚.

The resulting oil was distilled to obtain an oil having a boiling point of 550 DEG C or higher. The viscosity index of this fraction was 157, the pour point was -15 ° C, and the cloud point was 14 ° C. The yield of this oil relative to the raw oil was 81 mass%.

As shown in the table, the raw material oil is passed through the catalyst layer obtained by laminating the first catalyst and the second catalyst according to the present invention at a predetermined ratio, and hydrogenation treatment is carried out to obtain a catalyst having a high viscosity index and a low pour point, A lubricating oil base oil can be obtained.

Wherein the first catalyst bed comprises a first catalyst bed and the second catalyst bed comprises a first catalyst bed and a second catalyst bed, , 100, 110: Lubricating oil base oil producing apparatus.

Claims (3)

In the presence of hydrogen, a raw oil containing hydrocarbons having 21 or more carbon atoms in this order to the first catalyst and the second catalyst,
Wherein the first catalyst is a hydrogenation isomerization catalyst containing a carrier comprising a zeolite having a 10-membered ring primary pore structure and a binder, and platinum and / or palladium supported on the carrier, wherein the zeolite contains an organic template Exchanged zeolite obtained by ion-exchanging an organic template-containing zeolite having a 10-membered ring primary pore structure in a solution containing ammonium ion and / or proton, and the amount of carbon contained in the catalyst is 0.4 to 3.5 mass% ego,
Wherein the second catalyst comprises a support comprising zeolite having a 10-membered ring primary pore structure and platinum and / or palladium supported on the support, wherein the total amount of platinum and / or palladium supported is 100 Wherein the ratio V1 / V2 of the volume V1 of the first catalyst to the volume V2 of the second catalyst is 70/30 to 90/10, Oil) The catalyst according to claim 1, wherein the first catalyst has a micropore volume per unit mass of catalyst of 0.02 to 0.12 cc / g and a micropore volume per unit mass of zeolite contained in the catalyst of 0.01 to 0.12 cc / g Wherein the lubricant base oil is produced by a method comprising the steps of: In the presence of hydrogen, a raw oil containing hydrocarbons having 21 or more carbon atoms in this order to the first catalyst and the second catalyst,
Wherein the first catalyst comprises an ion-exchange zeolite obtained by ion-exchanging an organic template-containing zeolite containing an organic template and having a 10-membered ring primary pore structure in a solution containing ammonium ion and / or proton, the mixture, N ₂ comprises a first step, the platinum salt and / or a catalyst which comprises a palladium salt precursor to the support precursor, molecular oxygen in an atmosphere, by heating to a temperature of 250 to 350 ℃ obtain a support precursor And a second step of obtaining a hydrogenation isomerization catalyst in which platinum and / or palladium is supported on a support containing zeolite by calcination at a temperature of 350 to 400 ° C. A hydrogenation isomerization catalyst,
Wherein the second catalyst comprises a support comprising zeolite having a 10-membered ring primary pore structure and platinum and / or palladium supported on the support, wherein the total amount of platinum and / or palladium supported is 100 And 0.05 to 0.4 parts by mass relative to the mass part,
Wherein the ratio V1 / V2 of the volume V1 of the first catalyst to the volume V2 of the second catalyst is 70/30 to 90/10.

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