KR20120040150A - Process for producing lube base oil, and lube base oil - Google Patents

Abstract

The manufacturing method of the lubricating oil base oil of this invention hydrogenates the hydrocracked oil obtained by hydrocracking the raw material oil containing at least 1 sort (s) chosen from the group which consists of a vacuum gas oil, an atmospheric pressure residual oil, and a vacuum residual oil in presence of molecular hydrogen. A process of contacting an isomerization catalyst to obtain dewaxed oil, a process of hydrofinishing the dewaxed oil to obtain a hydrogenated refined oil, and a process of distilling the hydrogenated refined oil to obtain a lubricating oil fraction, the carrier of the hydroisomerization catalyst, (a) calcined zeolite and (b) calcined inorganic oxide, and (a) calcined zeolite is characterized in that it is obtained by heating an ion exchange zeolite not heated to 350 ° C or higher within a range of 350 to 450 ° C.

Description

Process for producing lube base oil, and lube base oil

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

Among petroleum products, for example, lubricating oil, diesel oil, jet fuel and the like are products in which fluidity at low temperature is important. For this reason, the base oil used for these products is a wax component, such as normal paraffin and a slightly branched isoparaffin which are the cause of low-temperature fluidity, is completely or partially removed, or it converts into things other than a wax component. It is desirable to have.

As a dewaxing technique which removes a wax component from hydrocarbon oil, the method of extracting a wax component with solvents, such as liquefied propane and MEK, is known, for example. However, this method is problematic in that the operating cost is high, the applicable raw material varieties are limited, and the product yield is limited by the raw material varieties.

On the other hand, as a dewaxing technique for converting a wax component in a hydrocarbon oil into a non-wax component, for example, hydrocarbon oil is brought into contact with a hydroisomerization catalyst having a two-way function of hydrogenation-dehydrogenation and isomerization in the presence of hydrogen. Contact dewaxing that isomerizes normal paraffins in isoparaffins in water is known. Moreover, as a hydroisomerization catalyst used for a contact dewaxing, the catalyst containing a solid acid, especially a zeolite and the metal which belongs to group 8 to 10 or 6 of a periodic table is known.

Although contact dewaxing is effective as a method for improving the low temperature fluidity of hydrocarbon oil, in order to obtain an oil fraction suitable for base oil for lubricating oil, it is necessary to make the conversion ratio of normal paraffin high enough. However, since the hydroisomerization catalyst used in the catalytic dewaxing has an isomerization ability and also a hydrocarbon decomposition capability, hydrocarbon oil decomposition and hardening also progress with the increase of the normal paraffin conversion, and the yield of desired oil is reduced. In particular, when producing a high quality base oil for lubricating oil that requires a high viscosity index and a low flow point, it is necessary to improve the conversion rate to the extent that normal paraffin is not substantially contained, so that the target oil can be economically improved by contact dewaxing of hydrocarbon oil. It was very difficult to obtain.

In view of the above, in the field of manufacturing lubricating oil base oil and fuel base oil, especially lubricating oil base oil, in order to obtain a good yield of desired isoparaffin fraction from hydrocarbon oil containing wax component, suppressed decomposition activity and improved isomerization for hydrocarbon. There is a need for a hydroisomerization catalyst having activity, i.e. good isomerization selectivity.

Until now, attempts have been made to improve the isomerization selectivity of the hydroisomerization catalyst used in catalytic dewaxing. For example, the following Patent Document 1 has a medium sized one-dimensional pores such as ZSM-22, ZSM-23, ZSM-48, and the like containing metals such as Groups 8 to 10 of the Periodic Table. A process for producing a dewaxed lubricating oil is disclosed by contacting a hydrocarbon material having at least 10 linear or slightly branched carbonaceous carbon atoms under isomerization conditions with a catalyst composed of zeolite whose size does not exceed about 0.5 mu.

In addition, the zeolite constituting the hydroisomerization catalyst is produced by hydrothermal synthesis in the presence of an organic compound called an organic template having an amino group, an ammonium group or the like, in order to construct a predetermined pore structure. And the synthesized zeolite is described, for example, on page 453 of Non-Patent Document 1, "2. 1. Materials ", the last paragraph, the organic template to be contained is removed by baking at the temperature of about 550 degreeC or more in the atmosphere containing molecular oxygen. Next, the baked zeolite is described, for example, on page 453 of Non-Patent Document 1, "2.3. Catalytic experiments ", are typically ion exchanged to ammonium in an aqueous solution containing ammonium ions. In the zeolite after ion exchange, metal components such as group 8 to 10 of the periodic table are further supported. The zeolite loaded with the metal component is filled into the reactor through drying and, if necessary, molding and the like, and is typically calcined under an atmosphere containing molecular oxygen at a temperature of about 400 ° C. By performing a reduction treatment with hydrogen or the like at the temperature of, the catalytic activity as a binary functional catalyst is imparted.

The catalyst provided for commercial use is generally used in the form of a molded article for the purpose of improving the ease of handling, reducing the pressure loss of the reaction fluid on the catalyst, and the like. However, since the zeolite powder lacks the self caking property and the mechanical strength of the catalyst which consists of the molded object obtained by shaping | molding itself is small, it is difficult to put it into practical use. Therefore, in the catalyst using a zeolite, it is common to use in the form of the molded object shape | molded the composition which mix | blended the inorganic oxide powder called a binder with the zeolite powder.

Patent Document 1: US Patent Publication No. 5,282,958

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

As lubricating oil base oil, many petroleum lubricating oil base oils are used from the viewpoint of availability and cost. In particular, paraffin base oils are widely used for lubricating oils that require friction and wear reduction performance. This paraffin base oil has been improved in performance due to recent demands for fuel economy and long life. The engine oil base oil of the Group III standard of API is manufactured using the hydrocracking process of petroleum raw material oil, and is a high viscosity index base oil with the content of sulfur content and aromatic hydrocarbon components reduced. In recent years, it is required to further increase the productivity of such base oils.

An object of the present invention is to provide a method for producing a lubricating oil base oil capable of efficiently obtaining a lubricating oil base oil that satisfies the Group III standard of the API from petroleum-based raw oil and a lubricating oil base oil obtained thereby.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, this invention provides the molecular hydrogen for the hydrocracking oil obtained by hydrocracking the raw material oil containing at least 1 sort (s) chosen from the group which consists of a vacuum gas oil, an atmospheric pressure residual oil, and a vacuum residue. Present in contact with a hydroisomerization catalyst to obtain dewaxed oil, hydroprocessing dewaxed oil to obtain hydrogenated refined oil, and distilling hydrogenated refined oil to obtain lubricating oil fraction. The catalyst is at least one selected from the group consisting of a carrier which is a molded body subjected to a thermal history including heating at 350 ° C. or higher, and a metal, molybdenum and tungsten belonging to the Groups 8 to 10 of the periodic table supported on the carrier; 1 type of metal, and the carrier contains (a) an organic template and has a 10-membered ring one-dimensional pore structure Calcined zeolite obtained by calcining an ion-exchanged zeolite obtained by ion-exchanging a template-containing zeolite in a solution containing ammonium ions and / or protons under thermal history including heating at 350 ° C or higher, and (b) alumina, At least one inorganic oxide selected from the group consisting of silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide, and a composite oxide consisting of two or more of these combinations includes heating at 350 ° C or higher. The heat history received by the calcined zeolite, which contains a calcined inorganic oxide which is calcined by a heat history, is that the ion exchange zeolite which is not heated to 350 ° C. or higher is calcined by heating within a range of 350 to 450 ° C. First lubricant characterized in that it comprises It provides a method in mind.

In addition, in this specification, a periodic table refers to the table of the long-period form prescribed | regulated by IUPAC.

According to the manufacturing method of the 1st lube base oil of this invention, the hydroisomerization catalyst which concerns on the said invention containing the support which contains a specific zeolite and a specific inorganic oxide, and the specific active metal supported by the said support has sufficient mechanical strength. In addition, since it has a high isomerization selectivity, it becomes possible to efficiently obtain the lubricating oil base oil which meets the Group III specification of API from the said raw oil.

The present invention also provides a step of distilling a hydrocracked oil obtained by hydrocracking a crude oil containing at least one selected from the group consisting of vacuum gas oil, atmospheric pressure residue and vacuum residue, to obtain a lubricating oil fraction, and molecular hydrogen And the step of obtaining dewaxed oil by contacting the lubricating oil fraction with the hydroisomerization catalyst in the presence thereof, and the step of hydrofinishing the dewaxed oil, wherein the hydroisomerized catalyst is subjected to thermal history including heating at 350 ° C. or higher and fired. And a carrier which is a molded article and at least one metal selected from the group consisting of metals, molybdenum and tungsten belonging to the group 8 to 10 of the periodic table supported on the carrier, wherein the carrier is (a) organic An organic template-containing zeolite containing a template and having a 10-membered ring one-dimensional pore structure is prepared by ammonium ion and / or pro Calcined zeolite obtained by ion-exchanging zeolite obtained by ion exchange in a solution containing a calcined product having a thermal history including heating at 350 ° C. or higher, and (b) alumina, silica, titania, boria, zirconia, magnesia, At least one inorganic oxide selected from the group consisting of ceria, zinc oxide and phosphorus oxide, and a composite oxide composed of two or more kinds thereof is a calcined inorganic oxide obtained by calcining under thermal history including heating at 350 ° C or higher. The heat history received by the calcined zeolite is characterized in that the ion exchange zeolite which is not heated to 350 ° C. or more is calcined by heating within a range of 350 to 450 ° C. It provides a manufacturing method.

According to the method for producing the second lubricant base oil of the present invention, the hydroisomerization catalyst according to the present invention satisfies the Group III specification of API from the raw material oil in that it has sufficient mechanical strength and also has high isomerization selectivity. It is possible to efficiently obtain the lubricating oil base oil. In addition, the method for producing the second lubricant base oil of the present invention is hydrogenated under reaction conditions suitable for each of the oil fractions having different boiling ranges by contacting and delaminating the lubricating oil fraction obtained by distilling the hydrocracked oil to the hydroisomerization catalyst according to the present invention. Isomerization can be dewaxed to suppress undesirable decomposition reactions.

The present invention further provides a hydrocracked oil obtained by hydrocracking a crude oil containing at least one selected from the group consisting of vacuum gas oil, atmospheric residue and vacuum residue, in contact with a hydroisomerization catalyst in the presence of molecular hydrogen. A process of obtaining dewaxed oil, a process of distilling dewaxed oil to obtain a lubricating oil fraction, and a process of hydrofinishing the lubricating oil component, wherein the hydroisomerization catalyst receives a heat history including heating at 350 ° C. or higher. A carrier which is a fired molded body and at least one metal selected from the group consisting of metals, molybdenum and tungsten belonging to the group 8 to 10 of the periodic table supported on the carrier, wherein the carrier comprises (a) An organic template-containing zeolite containing an organic template and having a 10-membered ring one-dimensional pore structure is prepared by ammonium ion and / or pro Calcined zeolite obtained by ion-exchanging zeolite obtained by ion exchange in a solution containing a calcined product having a thermal history including heating at 350 ° C. or higher, and (b) alumina, silica, titania, boria, zirconia, magnesia, At least one inorganic oxide selected from the group consisting of ceria, zinc oxide and phosphorus oxide, and a composite oxide composed of two or more kinds thereof is a calcined inorganic oxide obtained by calcining under thermal history including heating at 350 ° C or higher. The heat history received by the calcined zeolite is characterized in that the ion exchange zeolite which is not heated to 350 ° C. or more is calcined by heating within a range of 350 to 450 ° C. It provides a manufacturing method.

According to the method for producing the third lubricant base oil of the present invention, the hydroisomerization catalyst according to the present invention satisfies the Group III specification of API from the raw material oil in that it has sufficient mechanical strength and also has high isomerization selectivity. It is possible to efficiently obtain the lubricating oil base oil. Further, in the method for producing the third lubricant base oil of the present invention, by hydrofinishing the lubricating oil fraction obtained by distillation of the dewaxed oil, hydrogenation can be completed under reaction conditions suitable for each fraction having a different boiling point range. It can be suppressed.

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

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

From the standpoint of further improving the mechanical strength of the catalyst while obtaining excellent isomerization selectivity, the carrier is preferably a molded body subjected to a thermal history including heating in the range of more than 450 ° C to 650 ° C or less.

In view of isomerization selectivity and reaction activity, it is preferred that the metal supported on the carrier is platinum and / or palladium.

From the standpoint of isomerization selectivity and reaction activity, the molar ratio ([Si] / [Al]) of silicon atoms and aluminum atoms in the organic template-containing zeolite is preferably 10 to 400.

In the method for producing the first to third lubricant base oils of the present invention, the hydroisomerization catalyst contains an organic template and an organic template-containing zeolite having a 10-membered ring one-dimensional pore structure, containing ammonium ions and / or protons. In a first step of obtaining an ion exchange zeolite by ion exchange in a solution, the ion exchange zeolite and alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide, and a combination of two or more thereof A second step of molding a composition containing at least one inorganic oxide selected from the group consisting of a complex oxide to obtain a molded body, and firing the molded body by heating it in at least 350 to 450 ° C. to obtain a carrier. 3rd process to make and the said support | carrier, periodic table group 8 th-th It is preferable that it is obtained by the manufacturing method of the hydroisomerization catalyst provided with the 4th process of supporting at least 1 sort (s) of metal chosen from the group which consists of a metal which belongs to group 10, molybdenum, and tungsten.

The hydroisomerization catalyst obtained by the above production method is capable of stably and efficiently obtaining a lubricating oil base oil satisfying the API Group III specification from the raw material oil in view of both excellent isomerization selectivity and mechanical strength.

From the viewpoint of further improving the mechanical strength of the catalyst to increase the productivity of the lubricating oil base oil, the third step is performed by heating the molded body within the range of 350 to 450 ° C and then heating within the range of more than 450 ° C and 650 ° C or less. It is preferable that it is a process of baking and obtaining the said support | carrier.

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

According to the present invention, it is possible to provide a process for producing lubricating oil base oil capable of efficiently obtaining lubricating oil base oil satisfying API Group III standard from petroleum-based raw oil, and the lubricating oil base oil obtained thereby.

BRIEF DESCRIPTION OF THE DRAWINGS It is a flowchart which shows an example of the lubricating oil base oil manufacturing apparatus in which the manufacturing method of the lubricating oil base oil of this invention is implemented.
It is a flowchart which shows the other example of the lubricating oil base oil manufacturing apparatus by which the manufacturing method of the lubricating oil base oil of this invention is implemented.
It is a flowchart which shows the other example of the lubricating oil base oil manufacturing apparatus by which the manufacturing method of the lubricating oil base oil of this invention is implemented.

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described in detail, referring an accompanying drawing. In addition, in description of drawing, the same code | symbol is attached | subjected to the same or equivalent element, and the overlapping description is abbreviate | omitted.

BRIEF DESCRIPTION OF THE DRAWINGS It is a flowchart which shows an example of the lubricating oil base oil manufacturing apparatus which implements the manufacturing method of the lubricating oil base oil of this invention. The lubricating oil base oil production apparatus 100 shown in FIG. 1 includes a flow path L1 into which raw material oil is introduced, a first reaction tower 10 for hydrocracking raw material oil introduced from the flow path L1, and a reaction tower 10. Hydroisomerizing (hydrogenation dewaxing) the first distillation tower 20 for atmospheric distillation of the hydrocracked oil supplied through the flow path L2 from the distillation column, and the hydrocracked bottom oil supplied from the distillation tower 20 through the flow path L5. A second reaction tower 30, a third reaction tower 40 for hydrofinishing (hydrogenation) the dewaxed oil supplied from the reaction tower 30 through the flow path L6, and a flow path from the reaction tower 40. And a second distillation column 50 for distilling under reduced pressure the hydrogenated refined oil supplied through L7) into a predetermined fraction. The first distillation column 20 is provided with a flow path L3 and a flow path L4 for taking out the hard oil to the outside of the system. In addition, each of the second distillation columns 50 is provided with flow paths L10 to L14 for taking out a predetermined oil content out of the system.

Hereinafter, the manufacturing method of the lubricating oil base oil of this invention is demonstrated in detail, referring the lubricating oil base oil manufacturing apparatus 100 of FIG.

As raw material oil to hydrocrack, what contains at least 1 sort (s) chosen from the group which consists of vacuum gas oil, atmospheric pressure residual oil, and vacuum residual oil is used. As a vacuum gas oil, the boiling point in normal pressure obtained from a vacuum distillation apparatus can use suitably 343 degreeC or more and 550 degrees C or less, for example. As the atmospheric residual oil, for example, an oil having a boiling point of 343 ° C or higher at atmospheric pressure obtained from an atmospheric distillation apparatus of crude oil can be suitably used. As a vacuum residual oil, the oil whose boiling point in normal pressure obtained from the vacuum distillation apparatus of an atmospheric residual oil is 550 degreeC or more can be used suitably. Since the raw material oil used by this invention obtains a lubricating oil base oil in high yield, it is preferable to contain 50 mass% or more of C20 or more hydrocarbons with respect to raw material oil whole quantity.

In the first reaction tower 10, the raw oil is hydrocracked. As the first reaction tower 10, a known fixed bed, fluidized bed, mobile bed, or boiling bed reaction tower can be used. In this embodiment, it is preferable to carry out hydrocracking by charging a predetermined hydrocracking catalyst in a fixed bed flow type reactor in the reaction column, and flowing molecular hydrogen and the raw material oil through the reactor. The hydrocracking here means the reaction which produces | generates low molecular weight hydrocarbon by paraffin decomposition and naphthenic ring opening, and desulfurization, denitrification, olefin hydrogenation, and aromatic hydrogenation of raw material oil 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, ultra-stabilized Y-type (USY) zeolite and β-zeolite, and the carrier And catalysts having at least one active metal selected from the group consisting of cobalt-molybdenum, nickel-molybdenum, nickel-tungsten and nickel-cobalt-molybdenum supported thereon.

The USY zeolite is a superstabilized Y-type zeolite by hydrothermal treatment and / or acid treatment, and is in the range of 20 to 100 GPa in addition to the micropore structure called the 20 pore or less micropore originally possessed by the Y-type zeolite. New pores are formed in the. When using a USY zeolite as a support | carrier of a hydrocracking catalyst, there is no restriction | limiting in particular in the average particle diameter, Preferably it is 1.0 micrometer or less, More preferably, it is 0.5 micrometer 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, It is still more preferable if it is 20-60.

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 of supporting nickel-molybdenum or the like which is an active metal on the carrier, a method used for producing a conventional desulfurization catalyst can be adopted. As the cobalt source, organic or inorganic cobalt salts such as cobalt nitrate, cobalt chloride or cobalt acetate can be used. As the nickel source, organic or inorganic cobalt salts such as nickel nitrate, nickel chloride or nickel acetate can be used. As the molybdenum source, ammonium molybdate or molybdenum oxide or the like, and as the tungsten source, ammonium tungstate or the like can be used. Moreover, about each metal, you may use organic salt or inorganic salt other than what is listed here. Moreover, you may make an organic compound coexist in the impregnation liquid containing an active metal. In addition to these active metals, phosphorus may be supported on the catalyst.

The supported amount of the active metal in the hydrocracking catalyst is preferably a supported amount of nickel, based on the total amount of the catalyst, of 3 to 15% by mass, with the catalyst being nickel-molybdenum catalyst or nickel-tungsten catalyst. In the case of the cobalt-molybdenum catalyst, the supported amount of nickel is preferably 0.1 to 5% by mass and the supported amount of cobalt is 3 to 15% by mass based on 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. If the average pore diameter is smaller than 6 nm, there is a tendency that sufficient catalytic activity is not obtained. If the average pore diameter exceeds 60 nm, the metal dispersion degree tends to be lowered and the catalyst activity tends to be lowered. The pore volume of the hydrocracking catalyst is preferably 0.2 mL / g or more. If the pore volume is smaller than 0.2 mL / g, the activity deterioration of the catalyst tends to be faster. The specific surface area of the hydrocracking catalyst is preferably 200 m 2 / 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 the 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 ° C., hydrogen partial pressure of 5 to 20 MPa, LHSV 0.1 to 2 h ⁻¹ , and hydrogen / ratio 2000 to 10000 scfb, and a reaction temperature of 370 to 430 ° C. More preferably, the partial pressure of hydrogen is 10 to 18 MPa, LHSV 0.1 to 1.0 h ⁻¹ , and hydrogen / ratio 2500 to 8000 scfb.

When raw material oil is vacuum gas oil, it is preferable to adjust reaction conditions so that sulfur content and nitrogen content concentration in hydrocracked oil may be 50 ppm or less and 5 ppm or less, respectively.

In addition, in this embodiment, when raw material oil is a vacuum gas oil, it is preferable to hydrodegrade raw material oil so that content of the oil content of boiling point 343 degreeC or less in hydrocracking oil may be 30-75 mass%.

In the first distillation column 20, by distilling hydrocracked oil under atmospheric pressure, fuel oil such as naphtha and kerosene can be taken out from the flow path L3 and the flow path L4. In this case, it is preferable to acquire the oil component of 343 degreeC or more as hydrocracking bottom oil. In addition, when the raw material oil is atmospheric pressure residual oil 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 tower 30, the hydrocracked bottom oil obtained above is dewaxed by hydroisomerization. As the second reaction tower 30, a known fixed bed reaction tower can be used. In this embodiment, it is preferable to carry out hydroisomerization by charging the hydroisomerization catalyst which concerns on this invention to a fixed bed flow type reactor, and circulating molecular hydrogen and hydrocracked bottom oil in this reactor.

Here, the hydroisomerization catalyst which concerns on this invention is demonstrated.

The hydroisomerization catalyst according to the present invention is endowed with its characteristics by being produced by a specific method. Hereinafter, the hydroisomerization catalyst which concerns on this invention is demonstrated according to the form of the preferable manufacture.

The organic template-containing zeolite serving as a starting material of the calcined zeolite (a) constituting the hydroisomerization catalyst according to the present invention has a high level of high isomerization activity and suppressed decomposition activity in the hydroisomerization reaction of normal paraffin to a high level. It is preferable to have a one-dimensional pore structure consisting of a 10-membered ring. Examples of such zeolites include AEL, EUO, FER, HEU, MEL, MFI, NES, TON, MTT, WEI, ZSM-48 and the like. In addition, each of the above three letters of the alphabet means a skeleton structure code assigned to the structure of the classified molecular zeolites by the Structure Commission of The International Zeolite Association. In addition, zeolites having the same topology are collectively called the same code.

As said organic template containing zeolite, the zeolite which has TON, MTT structure, and ZSM-48 type zeolite is preferable among the zeolite which has the said 10-membered ring one-dimensional pore structure from a point of high isomerization activity and low decomposition activity. . As a zeolite which has a TON structure, ZSM-22 zeolite is more preferable, and as a zeolite which has an MTT structure, ZSM-23 zeolite is more preferable.

The organic template containing zeolite which contains the organic template used as the starting material of the calcined zeolite (a) which comprises the hydroisomerization catalyst which concerns on this invention, and has a 10-membered ring one-dimensional pore structure is a silica source, an alumina source, and the said predetermined | prescribed pore. It is hydrothermally synthesized by a well-known method from the organic template added in order to build a structure.

An organic template is an organic compound which has an amino group, an ammonium group, etc., Although it is selected according to the structure of the zeolite to synthesize | combine, it is preferable that it is an amine derivative. Specifically, at least one selected from the group consisting of alkylamine, alkyldiamine, alkyltriamine, alkyltetraamine, pyrrolidine, piperazine, aminopiperazine, alkylpentamine, alkylhexamine and derivatives thereof More preferred.

The molar ratio ([Si] / [Al]) (hereinafter referred to as "Si / Al ratio") of the silicon and aluminum elements constituting the organic template-containing zeolite having a 10-membered ring one-dimensional pore structure is 10 to 400. It is preferable, and it is more preferable that it is 20-350. If the Si / Al ratio is less than 10, the activity for the conversion of normal paraffins is high, but the isomerization selectivity to isoparaffins is lowered, and the increase in decomposition reaction accompanying the increase in reaction temperature tends to be rapid. I can't. On the other hand, when the Si / Al ratio exceeds 400, the catalytic activity necessary for the conversion of normal paraffin becomes difficult to be obtained, which is not preferable.

The organic template-containing zeolite synthesized and preferably washed and dried usually has an alkali metal cation as a counter cation, and an organic template is included in the pore structure. It is preferable that the zeolite containing the organic template used when producing the hydroisomerization catalyst of this invention does not carry out the baking process for removing the thing of such a synthesized state, ie, the organic template contained in a zeolite.

The organic template-containing zeolite is then ion exchanged in a solution containing ammonium ions and / or protons. By ion exchange treatment, the counter 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.

It is preferable that it is a solution using the solvent containing at least 50 volume% of water, and, as for the solution used for the said ion exchange process, it is more preferable that it is an aqueous solution. Moreover, as a compound which supplies ammonium ion in a solution, various ammonium salts, inorganic and organic, such as ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium acetate, are mentioned. On the other hand, as a compound which supplies a proton in a solution, inorganic acids, such as hydrochloric acid, a sulfuric acid, nitric acid, are used normally. The ion exchange zeolite (here, ammonium zeolite) obtained by ion exchange of the organic template containing zeolite in the presence of ammonium ions releases ammonia at the time of later firing, and the cation becomes proton to become Bronsted acid point. As cationic species used for ion exchange, ammonium ion is preferable. It is preferable that content of ammonium ion and / or proton contained in a solution is set so that it may be 10-1000 equivalent with respect to the total amount of the large cation and organic template contained in the organic template containing zeolite to be used.

The ion exchange treatment may be performed on a powdery organic template-containing zeolite alone, or prior to ion exchange treatment, the organic oxide-containing zeolite may be blended with an inorganic oxide as a binder and molded to be obtained by molding. good. However, when the above-mentioned molded article is used for ion exchange treatment without firing, it is preferable to provide a powdery organic template-containing zeolite for ion exchange treatment, since the problem of collapse and powdering of the molded article is likely to occur.

The ion exchange treatment is preferably carried out by a method of immersing a zeolite containing an organic template in a normal method, that is, a solution containing ammonium ions and / or a proton, preferably an aqueous solution, and stirring or flowing the zeolite. In addition, it is preferable to perform said stirring or flow under heating, in order to raise the efficiency of ion exchange. In this invention, the method of heating the said aqueous solution and ion-exchanging under boiling and reflux is especially preferable.

In addition, from the viewpoint of increasing the efficiency of ion exchange, during the ion exchange of zeolite with the solution, it is preferable to replace the solution with a new one or more times, and it is more preferable to replace 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 ions and / or protons and heated to reflux for 1 to 6 hours, and then the solution is replaced with a new one. By further heating and refluxing for 6 to 12 hours, the ion exchange efficiency can be increased.

By ion exchange treatment, it is possible to exchange almost all of the large cations such as alkali metals in the zeolite with ammonium ions and / or protons. On the other hand, about the organic template contained in a zeolite, although the one part is removed by said ion exchange process, even if the same process is performed repeatedly, it is generally difficult to remove all the part inside the zeolite. Remaining.

Next, it is preferable to mix | blend the inorganic oxide which is a binder with the ion exchange zeolite obtained by said method, and to shape | mold the obtained composition, and to form a molded object. The purpose of blending the inorganic oxide with the ion exchange zeolite is to improve the mechanical strength of the carrier (particularly, the particulate carrier) obtained by firing of the molded body to the extent that it can be put to practical use. It has been found that the choice affects the isomerization selectivity of the hydroisomerization catalyst. In this respect, as the inorganic oxide, at least one inorganic oxide selected from alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide and a composite oxide composed of a combination of two or more thereof is Used. Among these, alumina is preferable from the viewpoint of further improving the isomerization selectivity of the hydroisomerization catalyst. In addition, said "composite oxide which consists of a combination of 2 or more of these" is a complex oxide which consists of at least 2 types of components of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide, and phosphorus oxide, The composite oxide which has alumina containing 50 mass% or more of alumina components on the basis of an oxide as a main component is preferable.

The blending ratio of the ion exchange zeolite and the inorganic oxide in the composition is a mass ratio of the mass of the ion exchange zeolite to the inorganic oxide, preferably 10:90 to 90:10, more preferably 30:70 to 85:15. to be. When this ratio is smaller than 10:90, since the activity of a hydroisomerization catalyst tends to become inadequate, it is unpreferable. On the other hand, when the said ratio exceeds 90:10, since the mechanical strength of the support | carrier obtained by shape | molding and baking a composition tends to become inadequate, it is unpreferable.

Although the method of mix | blending said inorganic oxide with an ion exchange zeolite is not specifically limited, For example, it is usual to make it into a viscous fluid by adding liquid, such as water, to both powders, and knead | mixing by kneader etc. The method implemented can be employ | adopted.

The composition containing the ion exchange zeolite and the inorganic oxide or the viscous fluid containing the same is molded by a method such as extrusion molding, and preferably dried to form a particulate shaped body. Although it does not specifically limit as a shape of a molded object, For example, mold release normal shape which has a cylindrical, a pellet form, a spherical form, and a trilobite-leaflet type cross section is mentioned. Although the size of a molded object is not specifically limited, From a viewpoint of ease of handling, the packing density to a reactor, etc., it is preferable that a major axis is 1-30 mm and a short axis is about 1-20 mm, for example.

The molded article obtained as described above is then calcined at a temperature of 350 to 450 캜, preferably 380 to 430 캜, more preferably 390 to 420 캜 in an atmosphere containing molecular oxygen. It is preferable to use a carrier calcined by receiving a thermal history including heating at 350 ° C or higher. "In the atmosphere containing molecular oxygen" means the gas containing oxygen gas, and also in contact with air preferably. Although the time of baking is not specifically limited, It is preferable that it is 1 to 24 hours.

By the said baking, the ion exchange zeolite which comprises a molded object turns into a calcination zeolite (a), and an inorganic oxide turns into a calcination inorganic oxide (b).

In the present embodiment, when the firing temperature is lower than 350 ° C., the removal of the organic template does not proceed sufficiently, or the removal of the organic template requires a long time, and the mechanical strength of the carrier does not tend to be sufficiently improved. It is not desirable because it exists. On the other hand, when the firing temperature exceeds 450 ° C, the isomerization selectivity of the obtained hydroisomerization catalyst tends not to be sufficiently improved, which is not preferable. Firing the ion exchange zeolite in which the organic template remains without heating above 350 ° C. at such a relatively low temperature is very important in improving the isomerization selectivity of the hydroisomerization catalyst according to the present invention.

As described above, the calcination may be performed in a state of a powdery ion exchange zeolite alone, in addition to being carried out in a state of a molded product obtained by molding a composition in which an inorganic oxide is mixed with an ion exchange zeolite. However, in that case, the molded object formed by shape | molding the composition which mix | blended the inorganic oxide with the obtained calcined zeolite is in the range of 350 degreeC or more, for example, 350-450 degreeC, and / or for the purpose of providing mechanical strength. It is necessary to perform baking at the temperature within the range of 450 degreeC or more and 650 degrees C or less.

The carrier is heated in a range of 350 to 450 ° C., preferably in an atmosphere containing molecular oxygen, more preferably in an air atmosphere, and heated and calcined in a range of more than 450 ° C. to 650 ° C. or less. It may be. In addition to heating at 350 to 450 ° C, by further heating to more than 450 ° C to 650 ° C and firing, it is possible to further improve the mechanical strength of the carrier without significantly affecting the hydroisomerization selectivity of the catalyst obtained. Therefore, when catalyst particles having higher mechanical strength are desired, it is preferable to perform firing by the above two-stage heating. When the heating temperature of the rear stage is 450 degrees C or less, it exists in the tendency which becomes difficult to improve the mechanical strength of a support further. On the other hand, when it exceeds 650 degreeC, since the environment of the aluminum atom which participates in formation of an active site on a zeolite changes, and there exists a tendency for decomposition activity to increase, it is unpreferable. Moreover, from the point which maintains isomerization selectivity, it is more preferable that the heating temperature of a rear | end stage is the temperature within the range of more than 450 degreeC and 600 degrees C or less.

In the present embodiment, at least one of metals, molybdenum, and tungsten belonging to Groups 8 to 10 of the Periodic Table are formed on a carrier which is a molded article which is thermally calcined and calcined by heating including 350 ° C or more. It is preferable to carry a metal (hereinafter, referred to as "active metal").

Examples of the metals belonging to Groups 8 to 10 of the periodic table include iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, and platinum. Among these, platinum and / or palladium are preferable, and platinum is especially preferable from a viewpoint of activity, isomerization selectivity, and the persistence of activity. Said active metal can be used individually by 1 type or in combination of 2 or more types. Moreover, when the hydroisomerization catalyst which concerns on this invention is used for the hydroisomerization of the hydrocracking oil which contains many sulfur-containing compounds and / or nitrogen-containing compounds, as an active metal, as an active metal, nickel-cobalt, nickel -A combination of molybdenum, cobalt-molybdenum, nickel-molybdenum-cobalt, nickel-tungsten-cobalt and the like.

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

As an example of an active metal precursor, hydrochloride, sulfate, nitrate, a complex compound, etc. of the said active metal are mentioned. When the active metal is platinum, platinum chloride acid, tetraammine dinitro platinum, dinitroamino platinum, tetraammine dichloro platinum, or the like is preferably used as the active metal precursor.

The total supported amount of the active metal supported on the carrier containing the calcined zeolite (a) and the calcined inorganic oxide (b) is preferably from 0.001 to 20 mass%, based on the mass of the support. When the supported amount is less than 0.001 mass%, it becomes difficult to give a predetermined hydrogenation / dehydrogenation function. On the other hand, when the supported amount exceeds 20% by mass, hardening due to decomposition of hydrocarbons on the active metal tends to proceed, and the yield of the target oil tends to decrease, which also leads to an increase in catalyst cost. It is not desirable because it tends to.

The active metal may be supported on any one or both of the calcined zeolite (a) and the calcined inorganic oxide (b) constituting the support. When the hydroisomerization catalyst according to the present invention is produced through a method in which an active metal is impregnated on a carrier by impregnation, etc., the distribution of the site on which the active metal is supported is mainly calcined with the active metal precursor used at the time of supporting. It is determined by the affinity of the zeolite (a) and the calcined inorganic oxide (b).

The support of the active metal is not limited to the embodiment to be carried out on the molded and calcined carrier. For example, an active metal may be supported on powdery ion exchange zeolite or calcined zeolite baked at a temperature of 350 to 450 ° C, may be supported on powdery inorganic oxide, or both.

The carrier on which the active metal component is supported is primarily 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. As baking temperature, 250-600 degreeC is preferable and 300-500 degreeC is more preferable. As an atmosphere containing molecular oxygen, air is preferable. The firing time is usually about 0.5 to 20 hours. Through this firing treatment, the active metal precursor is converted into a single metal, an oxide thereof or a species similar thereto.

As mentioned above, in the preferable aspect of manufacture of the hydroisomerization catalyst which concerns on this invention, "the ion exchange of an organic template containing zeolite", "the shaping | molding of the composition containing an ion exchange zeolite and an inorganic oxide", "at 350-450 degreeC Firing of the molded body by heating " or " firing of the molded body by heating at 350 to 450 ° C. followed by heating above 450 ° C. and below 650 ° C. ", " supporting the active metal to the carrier " Firing of carrier ”.

What is important in the hydroisomerization catalyst which concerns on this invention is that the said specific zeolite, the specific inorganic oxide, and the specific active metal are used, In addition, in the manufacturing process, it is "the organic contained in the organic template containing zeolite containing an organic template. Removing a portion of the template by ion exchange rather than firing ", " Ion exchange zeolite in which the organic template is partially heated without heating at 350 ° C. or above, is calcined at a relatively low temperature of 350 to 450 ° C. in the zeolite. Removing at least a part of the remaining organic template " and " carrier is a molded body that is calcined by thermal history including heating at 350 ° C or higher ". In the production of the hydroisomerization catalyst according to the present invention, the embodiments in which the above-described steps are performed and the order thereof are as long as the above three are secured, and furthermore, problems occur in each step of the catalyst production. In the range which does not cause an increase in the manufacturing cost due to the complicated process, the process may be different from those described in the above-described preferred mode of manufacture, and modification may be appropriately made.

The hydroisomerization catalyst according to the present invention is preferably subjected to reduction treatment after being charged into a reactor for carrying out the reaction of hydroisomerization, preferably after the firing treatment. Specifically, under a atmosphere containing molecular hydrogen, preferably under hydrogen gas flow, preferably at 250 to 500 ° C, more preferably at 300 to 400 ° C, reduction treatment of about 0.5 to 5 hours is performed. It is preferable. By such a process, the catalyst can be more reliably provided with activity capable of highly dewaxing hydrocracked oils such as vacuum gas oil, atmospheric residual oil, and vacuum residual oil.

In the hydroisomerization catalyst according to the present invention, metals other than molybdenum and tungsten belonging to Groups 8 to 10 of the Periodic Table on the calcined zeolite and / or the calcined inorganic oxide within a range in which the effects of the present invention are not impaired. This may also be supported.

The reaction conditions in the second reaction column 30 are preferably a reaction temperature of 250 to 400 ° C., a hydrogen partial pressure of 1 to 20 MPa, a LHSV of 0.1 to 5 h ⁻¹ , and a hydrogen / ratio of 1000 to 5000 scfb, and a reaction temperature of 300 to 360 ° C. More preferably, the partial pressure of hydrogen is 2 to 10 MPa, LHSV 1 to 4 h ^-1 and hydrogen / ratio 2000 to 4000 scfb.

In this embodiment, it is preferable to adjust reaction conditions so that the normal paraffin concentration in a dewaxed oil may be 1 mass% or less.

In the third reaction tower 40, dewaxed oil is hydrogenated (hydrogenated and purified). As the third reaction tower 40, a known fixed bed reaction tower can be used. In this embodiment, it is preferable to carry out hydrogenation purification by charging a predetermined | prescribed hydrorefining catalyst to a fixed bed flow type reactor, and circulating molecular hydrogen and the said dewaxed oil in this reactor. Hydrogenation refining here means improving the oxidative stability and color of lubricating oil, and olefin hydrogenation and aromatic hydrogenation of dewaxed oil are performed.

Examples of the hydrogenation purification catalyst include a carrier containing at least one inorganic solid acidic substance selected from alumina, silica, zirconia, titania, boria, magnesia and phosphorus, and platinum and palladium supported on the carrier. And catalysts having at least one active metal selected from the group consisting of nickel-molybdenum, nickel-tungsten and nickel-cobalt-molybdenum.

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

As a method of supporting the active metal on the carrier, conventional methods such as impregnation and ion exchange can be employed.

It is preferable that the total amount of metal of the active metal in a hydrogenation purification catalyst is 0.1-25 mass% with respect to a support | carrier.

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 smaller 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 decrease, which tends to decrease the catalytic activity. Moreover, the pore volume of a hydrogenation purification catalyst is preferable in it being 0.2 mL / g or more. If the pore volume is smaller than 0.2 mL / g, the active deterioration of the catalyst tends to be faster. Moreover, it is preferable that the specific surface area of a hydrorefining catalyst is 200 m <2> / g or more. When the specific surface area of a catalyst is less than 200 m <2> / g, there exists a tendency for the dispersibility of an active metal to become inadequate, and activity falls. The pore volume and specific surface area of such a catalyst can be measured and calculated by the method called BET method by nitrogen adsorption.

The reaction conditions in the third reaction column 40 are preferably reaction temperatures of 200 to 300 ° C, hydrogen partial pressure of 3 to 20 MPa, LHSV 0.5 to 5h ^-1 and hydrogen / ratio 1000 to 5000 scfb, and reaction temperatures of 200 to 300 ° C. It is more preferable if the partial pressure of hydrogen is 4 to 18 MPa, LHSV 0.5 to 4 h ⁻¹ , and hydrogen / ratio 2000 to 5000 scfb.

In this embodiment, it is preferable to adjust reaction conditions so that sulfur content and nitrogen content in hydrogenation refined oil may be 5 mass ppm or less and 1 mass ppm or less, respectively.

In the second distillation column 50, lubricating oil fraction is obtained by setting a plurality of cut points and distilling the hydrogenated refined oil under reduced pressure. In this embodiment, the 1st lubricating oil fraction of boiling point 343-390 degreeC, the 2nd lubricating oil fraction of boiling point 390-440 degreeC, the 3rd lubricating oil fraction of boiling point 440-510 degreeC, and boiling point 510 degreeC in normal pressure, for example. The above fourth lubricant oil fraction can be recovered as the lubricant base oil from the passages L11 to L14, respectively. The first lubricating oil fraction can be obtained as a lubricating oil base oil suitable for ATF or shock absorber. In this case, the kinematic viscosity at 100 ° C is preferably set to 2.7 ± 0.1 cSt. The second lubricating oil fraction can be obtained as a lubricating oil base oil according to the present invention suitable for engine oil base oils satisfying the API Group III standard. In this case, the kinematic viscosity at 100 ° C is set to 4.0 ± 0.1 cSt, It is preferable to set it as -22.5 degreeC or less. The third lubricating oil fraction can be obtained as a lubricating oil base oil suitable for industrial operating oil. In this case, the kinematic viscosity at 40 ° C is preferably 32 cSt or more. The fourth lubricating oil fraction can be obtained as a lubricating oil base oil suitable for industrial operating oil. In this case, the kinematic viscosity at 40 ° C is preferably 80 to 120 cSt. In addition, the 1st lubricating oil fraction can be acquired as lubricating oil base oil equivalent to 70 pallet, the 2nd lubricating oil fraction can be acquired as lubricating oil base oil equivalent to SAE-10, and the 3rd lubricating oil fraction is lubricating oil equivalent to SAE-20. It can acquire as a base oil, and a 4th lubricating oil fraction can be obtained as lubricating oil base oil corresponded to SAE-30.

In addition, the hydrogenated refined oil supplied from the 3rd reaction tower 40 of this embodiment contains light oil, such as naphtha and kerosene etc. which are by-produced by hydroisomerization and hydrofinishing (hydrogenation refinement). These can be recovered from the flow path L10 as an oil having a boiling point of 350 ° C. or lower, for example.

The manufacturing method of the lubricating oil base oil of this invention is not limited to said embodiment, It can change suitably. For example, the step of distilling the hydrocracked oil obtained by hydrocracking the raw material oil containing at least 1 sort (s) chosen from the group which consists of a vacuum gas oil, an atmospheric pressure residual oil, and a vacuum residual oil, and obtains a lubricating oil fraction, and the presence of molecular hydrogen Next, the step of obtaining dewaxed oil by contacting the lubricating oil fraction with a hydroisomerization catalyst and the step of hydrofinishing the dewaxed oil can be carried out in this order to produce a lubricating oil base oil. 2 is a flowchart showing an example of a lubricant base oil production apparatus for performing the above-described method for producing a lubricant base oil. The lubricating oil base oil manufacturing apparatus 110 of FIG. 2 is another embodiment after L5 in the lubricating oil base oil manufacturing apparatus of FIG. 1, and the second distillation column 50 distilling the hydrocracked bottom oil supplied through the flow path L5. ), A second reaction tower 30 for hydroisomerizing (hydrogenation dewaxing) the lubricating oil fraction supplied from the second distillation column 50 through the flow path L21, and a supply from the reaction tower 30 through the flow path L22. It is comprised by the 3rd reaction tower 40 which hydrogen-finishes (hydrogenation refining) the dewaxed oil to become. The third reaction column 40 is provided with a flow path L23 for taking out the hydrogenated refined oil out of the system.

Also in this embodiment, the same thing as said hydrocracking catalyst, hydroisomerization catalyst, and hydrorefining catalyst can be used.

In the second distillation column 50, it is preferable to distill the hydrocracked oil so that a lubricating oil fraction having a boiling point of 343 ° C or higher is obtained. It is preferable to collect the naphtha kerosene kerosene fraction whose boiling range in normal pressure is less than 343 degreeC from the other collection line provided in the 2nd distillation column 50. As shown in FIG. In the present embodiment, the second distillation column 50 may be classified into a plurality of lubricating oil fractions, and hydroisomerization and hydrogenation finishing may be performed on each fraction. These processes may be performed in the same line by switching the oil content from the 2nd distillation column 50, or may perform a some oil content from the 2nd distillation column 50 in a separate line. Examples of the plurality of oils include naphtha kerosene and kerosene oils having a boiling point range of 343 ° C. or lower, 70 fail oils of 343 to 390 ° C., SAE-10 oils of 390 to 440 ° C., and SAE of 440 to 510 ° C. SAE-30 oil etc. are mentioned as -20 oil and bottom oil exceeding 510 degreeC.

The reaction conditions for the hydroisomerization (hydrogenation dewaxing) of the lubricating oil fraction in the second reaction column 30 are reaction temperature 250 to 400 ° C, hydrogen partial pressure 1 to 20 Mpa, LHSV 1 to 4 h ^-1 , hydrogen / oil ratio 2000 to 4000 scfb is preferred.

In addition, in this embodiment, it is preferable to adjust reaction conditions so that the normal paraffin concentration in a dewaxed oil may be 1 mass% or less.

As for reaction conditions in the 3rd reaction tower 40, reaction temperature 200-300 degreeC, hydrogen partial pressure 4-18 MPa, LHSV 0.5-4h- ¹ , and hydrogen / oil ratio 2000-5000 sccfb are preferable.

In this embodiment, it is preferable to adjust reaction conditions so that sulfur content and nitrogen content in hydrogenation refined oil may be 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 base oil that satisfies the Group III standard of the API, but can be distilled to obtain a desired fraction as a lubricating oil base oil. . At this time, the hard oil by-produced by hydroisomerization and hydrogenation finishing (hydrogenation purification) can also be removed.

In the case of distilling hydrogenated refined oil, it is preferable to classify into plural fractions by vacuum distillation, for example, and as the plural fractions, for example, naphtha and kerosene oil fractions having a boiling point range at normal pressure of less than 343 ° C. And a 70-feil fraction of 343 to 390 ° C, a SAE-10 fraction of 390 to 440 ° C, a SAE-20 fraction of 440 to 510 ° C, and a SAE-30 fraction of the bottom fraction exceeding 510 ° C.

The manufacturing method of the lubricating oil base oil of this invention can be made into another form. For example, the hydrocracked oil obtained by hydrocracking the raw material oil containing at least 1 sort (s) chosen from the group which consists of a vacuum gas oil, an atmospheric pressure residual oil, and a vacuum residual oil is removed by contacting a hydroisomerization catalyst in molecular hydrogen presence. A lubricating oil base oil can be manufactured by carrying out the process of obtaining lobed oil, the process of distilling a dewaxed oil under reduced pressure, and obtaining a lubricating oil component, and the process of carrying out a hydrogenation finishing process of a lubricating oil component. 3 is a flowchart showing an example of a lubricating oil base oil production apparatus that performs the manufacturing method of the lubricating oil base oil described above. The lubricating oil base oil manufacturing apparatus 120 of FIG. 3 is another embodiment after L5 in the lubricating oil base oil manufacturing apparatus of FIG. 1, and hydroisomerizes (hydrogenation dewaxing) the hydrocracked bottom oil supplied through the flow path L5. The second reaction tower 30, the second distillation column 50 for distilling under reduced pressure the dewaxed oil supplied from the reaction tower 30 through the flow path L31, and the flow path L32 from the second distillation tower 50. It is comprised by the 3rd reaction tower 40 which hydrogen-finishes (hydrogenation | finishes) the lubricating oil component supplied. The third reaction tower 40 is provided with a flow path L33 for taking out the hydrogenated refined oil out of the system.

Also in this embodiment, the same thing as said hydrocracking catalyst, hydroisomerization catalyst, and hydrorefining catalyst can be used.

The reaction conditions for hydroisomerization (hydrogenation dewaxing) of hydrocracked oil in the second reaction column 30 are reaction temperature 300 to 360 ° C., hydrogen partial pressure 2 to 10 MPa, LHSV 1 to 4 h ⁻¹ , and hydrogen / oil ratio 2000 to 4000 scfb Is preferred.

In addition, in this embodiment, it is preferable to adjust reaction conditions so that the normal paraffin concentration in a dewaxed oil may be 1 mass% or less.

In the second distillation column 50, it is preferable to distill the dewaxed oil under reduced pressure so as to obtain a lubricating oil fraction having a boiling point of 343 ° C or higher. It is preferable to collect the naphtha kerosene kerosene fraction whose boiling range in normal pressure is less than 343 degreeC from the other collection line provided in the 2nd distillation column 50. As shown in FIG. In the present embodiment, the second distillation column 50 may be classified into a plurality of lubricating oil fractions, and hydrogenation finishing may be performed on each fraction. These processes may be performed in the same line by switching the oil content from the 2nd distillation column 50, or may perform a some oil content from the 2nd distillation column 50 in a separate line. Examples of the plurality of oils include naphtha kerosene and kerosene oils having a boiling point range of 343 ° C. or lower, 70 fail oils of 343 to 390 ° C., SAE-10 oils of 390 to 440 ° C., and SAE of 440 to 510 ° C. SAE-30 oil etc. are mentioned as -20 oil and bottom oil exceeding 510 degreeC.

As for reaction conditions in the 3rd reaction tower 40, reaction temperature 200-300 degreeC, hydrogen partial pressure 4-18 MPa, LHSV 0.5-4h- ¹ , and hydrogen / oil ratio 2000-5000 sccfb are preferable.

In this embodiment, it is preferable to adjust reaction conditions so that sulfur content and nitrogen content in hydrogenation refined oil may be 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 base oil that satisfies the Group III standard of the API, but can be distilled to obtain a desired fraction as a lubricating oil base oil. . At this time, the hard oil by-produced by hydroisomerization and hydrogenation finishing (hydrogenation purification) can also be removed.

In the case of distilling hydrogenated refined oil, it is preferable to classify into plural fractions by vacuum distillation, for example, and as the plural fractions, for example, naphtha and kerosene oil fractions having a boiling point range at normal pressure of less than 343 ° C. And a 70-feil fraction of 343 to 390 ° C, a SAE-10 fraction of 390 to 440 ° C, a SAE-20 fraction of 440 to 510 ° C, and a SAE-30 fraction of the bottom fraction exceeding 510 ° C.

According to the manufacturing method of the lubricating oil base oil which concerns on this invention demonstrated above, the lubricating oil base oil whose sulfur content is 0.03 mass% or less, and the viscosity index is 120 or more can be produced efficiently.

Example

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

[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 1/16 cylindrical pellets. The molded product obtained was calcined at 550 ° C. for 3 hours under air circulation. The extrusion support was impregnated with 12 mass% and 22 mass% of nickel and tungsten as active metals, respectively, and then calcined at 550 ° C. under air flow for 3 hours to obtain a hydrocracking catalyst.

[Production of Hydrogen Isomerization Catalyst]

(Hydroisomerization Catalyst A)

<Synthesis of ZSM-22 Zeolite>

ZSM-22 zeolite composed of crystalline aluminosilicate having a Si / Al ratio of 30 was prepared by Chem. Eur. J, 2007, vol. 13, p. 10070, was prepared by hydrothermal synthesis in the following procedure in accordance with the method described in "Experimental Section".

First, the following four types of aqueous solution were prepared.

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

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

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

Solution D: diluting 18 g of colloidal silica (Ludox AS-40, manufactured by Grace Davison) 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 solution C to this mixed solution, the mixture of solution A, B, C was injected into solution D, stirring vigorously at room temperature. Further, 0.25 grams of ZSM-22 powder, which was separately synthesized and had no special treatment after synthesis, was added as a "seed crystal" for promoting crystallization, thereby obtaining a gelled product.

The gel product obtained by the above operation was transferred to an internal volume 120 ml stainless steel autoclave reactor, and the hydrothermal synthesis reaction was advanced by rotating the autoclave reactor at a rotational speed of 30 rpm on a tumbling apparatus for 60 hours in an oven at 150 ° C. . After completion of the hydrothermal synthesis reaction, the reactor was cooled, the solids generated from each reactor were collected by filtration, washed with ion-exchanged water, dried overnight in a dryer at 60 ° C, and an organic template having a Si / Al ratio of 30. A ZSM-22 zeolite (hereinafter sometimes referred to as "ZSM-22") containing was obtained.

<Production of Ion Exchange ZSM-22>

ZSM-22 containing the organic template obtained above was taken in a flask, and 100 ml of 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 portion was washed with ion-exchanged water. To this, the same amount of 0.5N-ammonium chloride aqueous solution was added again and heated to reflux for 12 hours.

Thereafter, the solids were collected by filtration, washed with ion-exchanged water, and dried in a drier at 60 ° C. overnight to obtain ion-exchanged NH ₄ ZSM-22.

<Binder blending, molding, firing>

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

<Platinum support, firing>

Tetraamminedichloro platinum (II) (Pt (NH ₃ ) ₄ Cl ₂ ) was dissolved in ion-exchanged water corresponding to the absorption (pre-measured amount) of the molded and fired carrier particles to obtain an impregnation solution. This solution was impregnated into the above-mentioned shaped and calcined carrier particles by the initial wet method, and carried so that the amount of platinum was 0.5 mass% with respect to the mass of ZSM-22 type zeolite. Next, the obtained impregnated product was dried overnight in a dryer at 60 ° C, and then calcined at 400 ° C for 3 hours under air circulation to obtain a hydroisomerization catalyst A. In addition, the crush strength of the obtained catalyst particles was 12.4 N / mm. The crush strength of the catalyst particles was measured in accordance with JIS R2206 "Test Method for Compressive Strength of Refractory Bricks".

(Hydroisomerization Catalyst B)

By the same operation as the hydroisomerization catalyst A, an ion-exchanged NH ₄ type ZSM-22 is obtained, and also by the same operation as the hydroisomerization catalyst A, a molded product such as the hydroisomerization catalyst A by extrusion molding method using alumina as a binder. Obtained.

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

The formed molded-fired carrier particles were supported, dried, and calcined with platinum in the same manner as the hydroisomerization catalyst A to obtain a hydroisomerization catalyst B. In addition, the crush strength of the obtained catalyst particles was 13.0 N / mm.

(Hydroisomerization Catalyst C)

Except for changing the binder from alumina to silica, by the same operation as the hydroisomerization catalyst B, molded and calcined carrier particles were obtained.

The carrier particles thus obtained were supported, dried and calcined with platinum in the same manner as the hydroisomerization catalyst A to obtain a hydroisomerization catalyst C. In addition, the crush strength of the obtained catalyst particles was 9.0 N / mm.

(Hydroisomerization Catalyst D)

By the same operation as the hydroisomerization catalyst A, the same molded product as the hydroisomerization catalyst A using alumina as a binder was obtained. The molded body is dried for 3 hours under air flow in a dryer at 120 ° C, heated at 440 ° C for 3 hours under air flow, and then calcined by heating at 550 ° C for 3 hours under air flow, thereby forming Obtained carrier particles.

The formed molded-fired carrier particles were supported, dried, and calcined with platinum in the same manner as the hydroisomerization catalyst A to obtain a hydroisomerization catalyst D. In addition, the crush strength of the obtained catalyst particles was 13.0 N / mm.

(Hydroisomerization Catalyst E)

<Synthesis of ZSM-23 Zeolite>

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

First, Diquat-7 (N, N, N, N ', N', N'-hexamethyl-1,7-diaminoheptanedibromide), which is an organic template, was prepared in U.S. Patent Publication No. 4,490,342, Example A It synthesize | combined by changing and using the method described in some. That is, 50 g of 1,7-dibromoheptane and 100 ml of ethanol were mixed in a branch flask, and 70 g of triethylamine (33 mass% ethanol solution) was added thereto under stirring, followed by heating to reflux overnight. The reaction product was cooled to -21 ° C and the crystals were collected by filtration. This was washed with diethyl ether cooled to −21 ° C. and dried at room temperature to obtain the desired Diquat-7 (dibromide salt).

ZSM-23 was synthesized by the following operation using Diquat-7 obtained above.

First, the following two types 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: A mixture of 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.

Next, solution F was injected into solution E with stirring. The obtained gelled material was transferred to an internal volume 120 ml stainless steel autoclave reactor, and the reaction proceeded while rotating the autoclave reactor itself at a rotational speed of about 60 rpm for 72 hours in an oven at 160 ° C. After the completion of the reaction, the reactor was cooled, the resulting solids were collected by filtration, washed with ion-exchanged water, dried overnight in a dryer at 60 ° C, and contained an ZSM-23 organic template having a Si / Al ratio of 30. Obtained.

<Production of Ion Exchange ZSM-23>

NH ₄ ZSM ion-exchanged by an operation such as ion exchange of ZSM-22 of the hydroisomerization catalyst A, except that ZSM-23 containing the organic template obtained above was used instead of ZSM-22 containing the organic template. -23 was obtained.

<Binder blending, molding, firing>

From the ion-exchanged ZSM-23 obtained above and the alumina as a binder, a molded product is obtained by the same operation as the hydroisomerization catalyst B, and further by the same operation as the hydroisomerization catalyst B at 400 ° C and 550 ° C. Firing was carried out to obtain molded and fired carrier particles.

<Platinum support, firing>

Platinum supported, dried and calcined by the same operation as the hydroisomerization catalyst B, except that molded and fired carrier particles containing ZSM-23 obtained above were used instead of molded and fired carrier particles containing ZSM-22. Was carried out to obtain a hydroisomerization catalyst E. In addition, the crush strength of the obtained catalyst particles was 13.0 N / mm.

(Hydroisomerization Catalyst F)

<Synthesis of ZSM-48 Zeolite>

A ZSM-48 zeolite having a Si / Al ratio of 30 containing an organic template (hereinafter sometimes referred to as "ZSM-48") is based on Applied Catalysis A: General vol. 299 (2006) 167-174. Synthesized. Specifically, 5.1 g of aluminum sulfate 18-hydrate 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%) were first dissolved, and 26.2 g of hexanediamine was added thereto at room temperature. Stirred. 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 gel obtained was introduced into a stainless autoclave and kept stirred at 160 ° C. for 3 days. Thereafter, after the autoclave contents were cooled to room temperature, ZSM-48 zeolite crystals were obtained by washing the solid on the filter paper with suction filtration and ion-exchanged water.

<Production of Ion Exchange ZSM-48>

NH ₄ ZSM ion-exchanged by an operation such as ion exchange of ZSM-22 of the hydroisomerization catalyst A, except that ZSM-48 containing the organic template obtained above was used instead of ZSM-22 containing the organic template. -48 was obtained.

<Binder blending, molding, firing>

From the ion-exchanged ZSM-48 obtained above and the alumina as a binder, a molded product is obtained by the same operation as the hydroisomerization catalyst B, and further by the same operation as the hydroisomerization catalyst B at 400 ° C and 550 ° C. Firing was carried out to obtain molded and fired carrier particles.

<Platinum support, firing>

Platinum supported, dried and calcined by the same operation as the hydroisomerization catalyst B, except that molded and fired carrier particles containing ZSM-48 obtained above were used instead of molded and fired carrier particles containing ZSM-22. Was carried out to obtain a hydroisomerization catalyst F. In addition, the crush strength of the obtained catalyst particles was 13.0 N / mm.

(Hydroisomerization Catalyst G)

Except having changed the baking temperature of the molded object from 400 degreeC to 470 degreeC, the carrier particle shape | molded and baked by the operation similar to hydroisomerization catalyst A was obtained.

The carrier particles thus obtained were supported, dried and calcined in the same manner as in the hydroisomerization catalyst A to obtain a hydroisomerization catalyst G. In addition, the crush strength of the obtained catalyst particles was 13.0 N / mm.

(Hydroisomerization Catalyst H)

The powdered ZSM-22 containing the organic template obtained by synthesis in the same manner as the hydroisomerization catalyst A was calcined at 550 ° C. for 6 hours under air circulation.

The calcined ZSM-22 obtained above was taken in a flask and subjected to ion exchange and drying with an aqueous solution of ammonium chloride by the same operation as the hydroisomerization catalyst A to obtain NH ₄ type ZSM-22.

From the NH ₄ type ZSM-22 obtained above and the alumina which is a binder, the molded object was obtained by operation similar to the hydroisomerization catalyst A. Thereafter, by the same operation as in the hydroisomerization catalyst A, drying, firing, platinum carrying and firing were carried out to obtain a hydroisomerization catalyst H. In addition, the crush strength of the obtained catalyst particles was 12.0 N / mm.

(Hydroisomerization Catalyst I)

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

From the NH ₄ type ZSM-22 obtained above and the alumina which is a binder, the molded object was obtained by operation similar to the hydroisomerization catalyst A. Then, the obtained molded product was calcined at 470 ° C. under air circulation, and then platinum supported and calcined by an operation similar to the hydroisomerization catalyst A to obtain a hydroisomerization catalyst I. In addition, the crush strength of the obtained catalyst particles was 13.0 N / mm.

(Hydroisomerization Catalyst J)

The hydroisomerization catalyst J was obtained by the same operation as the hydroisomerization catalyst E, except that the temperature of the first step of firing the molded product obtained from the ion exchange ZSM-23 and the alumina was changed to 470 ° C instead of 400 ° C. In addition, the crush strength of the obtained catalyst particles was 13.0 N / mm.

(Hydroisomerization Catalyst K)

The hydroisomerization catalyst K was obtained by the same operation as the hydroisomerization catalyst F, except that the temperature of the first step of firing the molded product obtained from the ion exchange ZSM-48 and the alumina was changed to 470 ° C instead of 400 ° C. In addition, the crush strength of the obtained catalyst particles was 13.0 N / mm.

[Preparation of Hydrogenation Refining Catalyst]

A commercially available amorphous silica alumina carrier was extruded into a 1/16 cylindrical shape and calcined at 550 ° C. for 3 hours under air circulation to obtain a catalyst carrier. The obtained carrier was impregnated with 0.2 mass% and 0.3 mass% of platinum and palladium as active metals, respectively, and calcined at 550 ° C. for 3 hours under air circulation to obtain a hydrogenation purification catalyst.

<Production of Lubricant Base Oil>

(Example 1)

<Preparation of raw oil>

As the crude oil, a general vacuum gas oil obtained from crude oil from the Middle East was used. The boiling point range of the vacuum gas oil was 343-550 degreeC, and sulfur content and nitrogen content were 2.41 mass% and 0.2 mass%, respectively.

<Hydrolysis of Raw Oil>

The hydrocracking reaction of raw material oil was performed on condition of the following. A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was charged with 200 ml of the hydrocracking catalyst prepared above, and the catalyst was sulfided with raw material oil for 24 hours under a catalyst bed average temperature of 300 ° C. and hydrogen flow (10 MPa of hydrogen partial pressure). Thereafter, the reaction temperature was raised to 385 ° C. and maintained at LHSV 0.3 h ⁻¹ and hydrogen / oil ratio 5000 scfb, and hydrocracking was carried out under reduced pressure. As a result of distilling the obtained hydrocracked oil, the yield (decomposition rate) of the oil content below 343 degreeC was 57 mass%, and the yield of the lubricating oil content of 343 degreeC or more was 43 mass%.

<Hydroisomerization of Hydrocracked Oil>

A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was charged with 200 ml of the catalyst A obtained above, and subjected to a reduction treatment for 12 hours under a catalyst bed average temperature of 350 ° C. and hydrogen flow (5 MPa). Thereafter, the hydrocracked oil having a boiling point of 343 ° C. or more obtained as a raw material oil was passed through under conditions of a reaction temperature of 320 ° C., a hydrogen partial pressure of 3 MPa, LHSV 2h ⁻¹ , and a hydrogen / oil ratio of 3000 sccfb, and hydroisomerized. The normal paraffin concentration of the obtained dewaxed oil A was less than 0.01 mass%.

<Hydrogenation of dewaxed oil>

A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was charged with 200 ml of the hydrogenated purification catalyst obtained above, and subjected to a reduction treatment for 12 hours under a catalyst bed average temperature of 350 ° C. and hydrogen flow (5 MPa). Thereafter, the dewaxed oil A after the hydroisomerization treatment was passed as a raw material oil under the conditions of a reaction temperature of 320 ° C., a hydrogen partial pressure of 5 MPa, LHSV 2h ⁻¹ , and a hydrogen / oil ratio of 3000 sccfb and hydrorefined. The yield of the hydrogenated refined oil A with respect to the obtained dewaxed oil A was 99 mass% or more, the seybolt 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>

The hydrogenated refined oil A obtained by the hydrogenation finish was further subjected to distillation under reduced pressure, and in terms of atmospheric distillation, a 70-peel fraction having a boiling point of 343 to 390 ° C., a SAE-10 fraction having a boiling point of 390 to 440 ° C. and a SAE-20 having a boiling point of 440 to 510 ° C. By classifying the oil and the SAE-30 oil having a boiling point of 510 ° C or higher, the 70-base lubricating oil, the SAE-10 lubricating oil, the SAE-20 lubricating oil, and the SAE-30 lubricating oil (bottom oil) Obtained.

Yields of the obtained 70-fail equivalent lubricant base oil, the SAE-10 equivalent lubricant base oil, the SAE-20 equivalent lubricant base oil, and the SAE-30 equivalent lubricant base oil were 14.4 mass%, 38.2 mass%, 33.0 mass%, and 8.5, respectively. Mass%. In addition, the viscosity index, pour point, sulfur content, and nitrogen content of lubricating oil base oil equivalent to 70 fail are 108, -27.5 degreeC, 0.1 mass ppm, 0.1 mass ppm, and the viscosity index of lubricating oil base oil equivalent to SAE-10, pour point, sulfur powder, and nitrogen powder, respectively. Silver, 122, -17.5 degreeC, 0.2 mass ppm, 0.2 mass ppm, and the viscosity index, pour point, sulfur content, and nitrogen content of lubricating oil base oil equivalent to SAE-20 are 130, -12.5 degreeC, 0.2 mass ppm, 0.2 mass ppm, respectively The viscosity index, pour point, sulfur content, and nitrogen content of lubricating oil base oil of SAE-30 were 129, -12.5 degreeC, 0.3 mass ppm, and 0.5 mass ppm, respectively.

The results obtained above are shown in Table 1. In addition, Seybolt color was measured based on JIS K2580, sulfur content JIS K2541, nitrogen content JIS K2609, viscosity index JIS K2283, and pour point JIS K2269. In addition, a yield shows the yield (mass%) of each lube base oil when the oil content of 343 degreeC or more of hydrocracking oil is 100.

(Example 2)

A dewaxed oil B was obtained by carrying out hydroisomerization treatment of hydrocracked oil at 343 ° C or higher as in Example 1 except that the catalyst B was charged in the reaction tube instead of the catalyst A. The normal paraffin concentration of the obtained dewaxed oil B was less than 0.01 mass%.

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

(Example 3)

A dewaxed oil C was obtained by carrying out hydroisomerization of hydrocracked oil at 343 ° C or higher as in Example 1 except that the catalyst C was charged to the reaction tube instead of the catalyst A. The normal paraffin concentration of the obtained dewaxed oil C was less than 0.01 mass%.

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

(Example 4)

A dewaxed oil D was obtained by carrying out hydroisomerization of hydrocracked oil at 343 ° C or higher as in Example 1 except that the catalyst D was charged in the reaction tube instead of the catalyst A. The normal paraffin concentration of the obtained dewaxed oil D was less than 0.01 mass%.

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

(Example 5)

A dewaxed oil E was obtained by carrying out hydroisomerization of hydrocracked oil at 343 ° C or higher as in Example 1 except that the catalyst E was charged in the reaction tube instead of the catalyst A. The normal paraffin concentration of the obtained dewaxed oil E was less than 0.01 mass%.

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

(Example 6)

A dewaxed oil F was obtained by carrying out hydroisomerization of hydrocracked oil at 343 ° C or higher as in Example 1 except that the catalyst F was charged in the reaction tube instead of the catalyst A. The normal paraffin concentration of the obtained dewaxed oil F was less than 0.01 mass%.

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

(Comparative Example 1)

A dewaxed oil G was obtained by carrying out hydroisomerization of hydrocracked oil at 343 ° C or higher as in Example 1 except that the catalyst G was charged in the reaction tube instead of the catalyst A. The normal paraffin concentration of the obtained dewaxed oil G was less than 0.01 mass%.

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

(Comparative Example 2)

A dewaxed oil H was obtained by carrying out hydroisomerization of hydrocracked oil at 343 ° C. or higher in the same manner as in Example 1 except that the catalyst H was charged in the reaction tube instead of the catalyst A. The normal paraffin concentration of the obtained dewaxed oil H was less than 0.01 mass%.

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

(Comparative Example 3)

A dewaxed oil I was obtained by carrying out hydroisomerization of hydrocracked oil at 343 ° C or higher as in Example 1, except that the catalyst I was charged to the reaction tube instead of the catalyst A. The normal paraffin concentration of the obtained dewaxed oil I was less than 0.01 mass%.

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

(Comparative Example 4)

A dewaxed oil J was obtained by carrying out hydroisomerization of hydrocracked oil at 343 ° C or higher as in Example 1 except that the catalyst J was charged in the reaction tube instead of the catalyst A. The normal paraffin concentration of the obtained dewaxed oil J was less than 0.01 mass%.

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

(Comparative Example 5)

A dewaxed oil K was obtained by carrying out hydroisomerization of hydrocracked oil at 343 ° C or higher as in Example 1 except that the catalyst K was charged in the reaction tube instead of the catalyst A. The normal paraffin concentration of the obtained dewaxed oil K was less than 0.01 mass%.

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

When using the hydroisomerization catalysts A to F that satisfy the predetermined conditions according to the present application, compared to the case when using the hydroisomerization catalysts G to K that do not satisfy the predetermined conditions, the lubricant base oil (70 fail) which satisfies the group III standard Equivalent lubricating oil base oil, lubricating oil base oil equivalent to SAE-10, lubricating oil base oil equivalent to SAE-20 and lubricating oil base oil equivalent to SAE-30 were found to be efficiently obtained.

(Example 7)

<Preparation of raw oil>

As the crude oil, a general vacuum gas oil obtained from crude oil from the Middle East was used. The boiling point range of the vacuum gas oil was 343-550 degreeC, and sulfur content and nitrogen content were 2.41 mass% and 0.2 mass%, respectively.

<Hydrolysis of Raw Oil>

The hydrocracking reaction was performed under the conditions described below. A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was charged with 200 ml of the hydrocracking catalyst prepared above, and the catalyst was sulfided with raw material oil for 24 hours under a catalyst bed average temperature of 300 ° C. and hydrogen flow (10 MPa of hydrogen partial pressure). Thereafter, the reaction temperature was raised to 385 ° C. and maintained at LHSV 0.3 h ⁻¹ and hydrogen / oil ratio 5000 scfb, and hydrocracking was carried out under reduced pressure. As a result of distilling the obtained hydrocracked oil, the yield (decomposition rate) of the oil content below 343 degreeC was 57 mass%, and the yield of the lubricating oil content of 343 degreeC or more was 43 mass%. Further, as a result of distillation under reduced pressure of a lubricant oil at 343 ° C or higher, a 70-peil fraction (boiling point of 343 to 390 ° C in terms of atmospheric distillation), SAE-10 fraction (boiling point of 390 to 440 ° C in terms of atmospheric distillation, SAE-20 fraction (atmospheric distillation) The yield of boiling point 440-510 degreeC in conversion, and SAE-30 fraction (boiling point 510 degreeC or more in conversion of atmospheric pressure distillation) was 15 mass%, 40 mass%, 35 mass%, and 10 mass%, respectively.

<Hydroisomerization of Hydrocracked Oil>

A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was charged with 200 ml of the catalyst A obtained above, and subjected to a reduction treatment for 12 hours under a catalyst bed average temperature of 350 ° C. and hydrogen flow (5 MPa). Subsequently, each of the 70-peel, SAE-10, SAE-20, and SAE-30 obtained above as raw material oil was subjected to reaction temperature of 320 DEG C, hydrogen partial pressure 3 MPa, LHSV 2h- ¹ , and hydrogen / oil ratio 3000 scfb. Via and hydroisomerize. The yield of the dewaxed oil of each obtained fraction was 96.1 mass%, 95.5 mass%, 94.2 mass%, and 90.0 mass% in 70 fail, SAE-10, SAE-20, and SAE-30, respectively. In addition, each viscosity index, a pour point, a sulfur content, and a nitrogen content are 108, -27.5 degreeC, 0.1 mass ppm, 0.1 mass ppm in 70 fail, 122, -17.5 degreeC, 0.2 mass ppm, 0.2 mass ppm, and SAE in SAE-10 It was 130 at -20, -12.5 degreeC, 0.2 mass ppm, 0.2 mass ppm, and SAE-30 was 128, -12.5 degreeC, 0.3 mass ppm, and 0.3 mass ppm.

<Hydrogenation of dewaxed oil>

A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was charged with 200 ml of the hydrogenated purification catalyst obtained above, and subjected to a reduction treatment for 12 hours under a catalyst bed average temperature of 350 ° C. and hydrogen flow (5 MPa). Subsequently, each of the 70 fail, SAE-10, SAE-20, and SAE-30 fractions after the hydroisomerization treatment were subjected to reaction temperature of 320 ° C., hydrogen partial pressure of 5 MPa, LHSV 2h ⁻¹ , and hydrogen / oil ratio of 3000 sccfb as raw material oils. Via oil and purify hydrogen. The yield of the hydrogenated refined oil of each obtained fraction was 99 volume% or more, and the Seybolt color was +30 or more.

(Example 8)

<Preparation of raw oil>

As the crude oil, a general vacuum gas oil obtained from crude oil from the Middle East was used. The boiling point range of the vacuum gas oil was 343-550 degreeC, and sulfur content and nitrogen content were 2.41 mass% and 0.2 mass%, respectively.

<Hydrolysis of Raw Oil>

The hydrocracking reaction was performed under the conditions described below. A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was charged with 200 ml of the hydrocracking catalyst prepared above, and the catalyst was sulfided with raw material oil for 24 hours under a catalyst bed average temperature of 300 ° C. and hydrogen flow (10 MPa of hydrogen partial pressure). Thereafter, the reaction temperature was raised to 385 ° C. and maintained at LHSV 0.3 h ⁻¹ and hydrogen / oil ratio 5000 scfb, and hydrocracking reaction was performed under reduced pressure. As a result of distilling the obtained hydrocracked oil, the yield (decomposition rate) of the oil content below 343 degreeC was 57 mass%, and the yield of the lubricating oil content of 343 degreeC or more was 43 mass%.

<Hydroisomerization of Hydrocracked Oil>

A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was charged with 200 ml of the catalyst A obtained above, and subjected to a reduction treatment for 12 hours under a catalyst bed average temperature of 350 ° C. and hydrogen flow (5 MPa). Thereafter, 343 ° C. or more of the hydrocracked oil obtained above was passed through the conditions of a reaction temperature of 320 ° C., hydrogen partial pressure of 3 MPa, LHSV 2h ⁻¹ , and hydrogen / oil ratio 3000 scfb, and hydroisomerized. The normal paraffin concentration of the obtained dewaxed oil A was less than 0.01 mass%.

<Distillation of Wax Oil>

The obtained dewaxed oil A was distilled under reduced pressure, and in terms of atmospheric distillation, a 70-peil fraction having a boiling point of 343 to 390 ° C, a SAE-10 fraction having a boiling point of 390 to 440 ° C, a SAE-20 fraction having a boiling point of 440 to 510 ° C and a boiling point of 510 ° C or higher By classifying each of the SAE-30 fractions, 70 base oil equivalents of lubricating oil, SAE-10 equivalents of lubricating oil, SAE-20 equivalents of lubricating oil, and SAE-30 equivalent of lubricating oil base (bottom oil) were obtained.

Yields of the obtained 70-fail equivalent lubricant base oil, the SAE-10 equivalent lubricant base oil, the SAE-20 equivalent lubricant base oil, and the SAE-30 equivalent lubricant base oil were 15 mass%, 40 mass%, 35 mass%, and 10, respectively. Mass%. In addition, the viscosity index, pour point, sulfur content, and nitrogen content of lubricating oil base oil equivalent to 70 fail are 108, -27.5 degreeC, 0.1 mass ppm, 0.1 mass ppm, and the viscosity index of lubricating oil base oil equivalent to SAE-10, pour point, sulfur powder, and nitrogen powder, respectively. Silver, 122, -17.5 degreeC, 0.2 mass ppm, 0.2 mass ppm, and the viscosity index, pour point, sulfur content, and nitrogen content of lubricating oil base oil equivalent to SAE-20 are 130, -12.5 degreeC, 0.2 mass ppm, 0.2 mass ppm, respectively The viscosity index, pour point, sulfur content, and nitrogen content of the lubricating oil base oil equivalent to SAE-30 were 128, -12.5 degreeC, 0.3 mass ppm, and 0.3 mass ppm, respectively.

<Hydrogenation of dewaxed oil>

A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was charged with 200 ml of the hydrogenated purification catalyst obtained above, and subjected to a reduction treatment for 12 hours under a catalyst bed average temperature of 350 ° C. and hydrogen flow (5 MPa). Subsequently, as raw material oil, a 70-peil equivalent lubricant base oil, a SAE-10 equivalent lubricant base oil, a SAE-20 equivalent lubricant base oil, and a SAE-30 equivalent lubricant base oil obtained by fractionation after the hydroisomerization treatment, respectively, were subjected to a reaction temperature of 320. The mixture was subjected to hydrogenation and hydrogenation under the conditions of 占 폚, partial pressure of hydrogen of 5 MPa, LHSV 2h ^-1 and hydrogen / ratio 3000 sccfb. The yield of the hydrogenated refined oil of each obtained lubricating oil base oil was 99 volume% or more, and the seybolt color was +30 or more.

According to the present invention, it is possible to provide a method for producing a lubricating oil base oil capable of efficiently obtaining a lubricating oil base oil that satisfies the Group III standard of the API from a petroleum-based raw oil and a lubricating oil base oil obtained thereby.

10... Reaction tower, 20. Distillation column, 30... Reaction tower, 40... Reaction tower, 50... Distillation column, 100, 110, 120... Lubricant base oil manufacturing device.

Claims (11)

The hydrocracked oil obtained by hydrocracking the raw material oil containing at least 1 sort (s) chosen from the group which consists of a vacuum gas oil, an atmospheric pressure residual oil, and a vacuum residual oil is removed by contacting a hydroisomerization catalyst in molecular hydrogen presence. A process of obtaining rapeseed oil,
Hydrofinishing the dewaxed oil to obtain a hydrogenated refined oil;
Distilling the hydrogenated refined oil to obtain a lubricating oil fraction
And
The hydroisomerization catalyst,
At least one member selected from the group consisting of a carrier which is a molded body subjected to a thermal history including heating at 350 ° C. or higher, and a metal, molybdenum, and tungsten belonging to the group 8 to 10 of the periodic table supported on the carrier; Contains metal,
The carrier,
(a) The ion exchange zeolite obtained by ion-exchanging the organic template containing zeolite which contains an organic template and has a 10-membered ring one-dimensional pore structure in the solution containing ammonium ion and / or proton, contains 350 degreeC or more heating. A calcined zeolite formed by being calcined by receiving a thermal history,
(b) at least one inorganic oxide selected from the group consisting of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide and a composite oxide composed of two or more of these compounds is 350 ° C. Calcined inorganic oxide formed by receiving a thermal history including the above heating
Containing,
The thermal history received by the calcined zeolite includes calcination of the ion exchange zeolite not heated to 350 ° C. or higher by heating in a range of 350 to 450 ° C. Manufacturing method. Distilling the hydrocracked oil obtained by hydrocracking the crude oil containing at least one selected from the group consisting of vacuum gas oil, atmospheric pressure residue and vacuum residue, to obtain a lubricating oil fraction;
Contacting the lubricating oil fraction with a hydroisomerization catalyst in the presence of molecular hydrogen to obtain dewaxed oil,
Process of hydrofinishing the dewaxed oil
And
The hydroisomerization catalyst,
At least one member selected from the group consisting of a carrier which is a molded body subjected to a thermal history including heating at 350 ° C. or higher, and a metal, molybdenum, and tungsten belonging to the group 8 to 10 of the periodic table supported on the carrier; Contains metal,
The carrier,
(a) The ion exchange zeolite obtained by ion-exchanging the organic template containing zeolite which contains an organic template and has a 10-membered ring one-dimensional pore structure in the solution containing ammonium ion and / or proton, contains 350 degreeC or more heating. A calcined zeolite formed by being calcined by receiving a thermal history,
(b) at least one inorganic oxide selected from the group consisting of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide and a composite oxide composed of two or more of these compounds is 350 ° C. Calcined inorganic oxide formed by receiving a thermal history including the above heating
Containing,
The thermal history received by the calcined zeolite is a method for producing a lubricating oil base oil, characterized in that the ion exchange zeolite not heated to 350 ° C or more is calcined by heating within a range of 350 to 450 ° C. The hydrocracked oil obtained by hydrocracking the crude oil containing at least 1 sort (s) chosen from the group which consists of a vacuum gas oil, an atmospheric pressure residual oil, and a vacuum residual oil is contacted with a hydroisomerization catalyst in molecular hydrogen presence, and a dewaxed oil is obtained. Fair,
Distilling the dewaxed oil to obtain a lubricating oil fraction;
Process for hydrofinishing the lubricating oil fraction
And
The hydroisomerization catalyst,
At least one member selected from the group consisting of a carrier which is a molded body subjected to a thermal history including heating at 350 ° C. or higher, and a metal, molybdenum, and tungsten belonging to the group 8 to 10 of the periodic table supported on the carrier; Contains metal,
The carrier,
(a) The ion exchange zeolite obtained by ion-exchanging the organic template containing zeolite which contains an organic template and has a 10-membered ring one-dimensional pore structure in the solution containing ammonium ion and / or proton, contains 350 degreeC or more heating. A calcined zeolite formed by being calcined by receiving a thermal history,
(b) at least one inorganic oxide selected from the group consisting of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide and a composite oxide composed of two or more of these compounds is 350 ° C. Calcined inorganic oxide formed by receiving a thermal history including the above heating
Containing,
The thermal history received by the calcined zeolite is a method for producing a lubricating oil base oil, characterized in that the ion exchange zeolite not heated to 350 ° C or more is calcined by heating within a range of 350 to 450 ° C. The lubricating oil base oil according to any one of claims 1 to 3, wherein the organic template-containing zeolite is at least one member selected from the group consisting of ZSM-22, ZSM-23 and ZSM-48 zeolites. Manufacturing method. The method for producing a lubricating oil base oil according to any one of claims 1 to 4, wherein the inorganic oxide is alumina. The method for producing a lubricating oil base oil according to any one of claims 1 to 5, wherein the carrier is a molded body subjected to a thermal history including heating within a range of more than 450 ° C and 650 ° C or less. . The method for producing a lubricating oil base oil according to any one of claims 1 to 6, wherein the metal supported on the carrier is platinum and / or palladium. The lubricating oil base oil according to any one of claims 1 to 7, wherein a molar ratio ([Si] / [Al]) of silicon atoms and aluminum atoms in the organic template-containing zeolite is 10 to 400. Manufacturing method. The hydroisomerization catalyst according to any one of claims 1 to 3, wherein
A first step of obtaining an ion exchange zeolite by ion-exchanging an organic template-containing zeolite containing an organic template and having a 10-membered ring one-dimensional pore structure in a solution containing ammonium ions and / or protons,
At least one inorganic oxide selected from the group consisting of the ion exchange zeolite and a composite oxide composed of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide and a combination of two or more thereof A second step of molding the composition to be obtained to obtain a molded article,
A third step of calcining by heating the formed body within a range of at least 350 to 450 ° C. to obtain a carrier, and
A fourth step of supporting the carrier with at least one metal selected from the group consisting of metals, molybdenum, and tungsten belonging to groups 8 to 10 of the periodic table;
A process for producing a lubricating oil base oil, characterized in that obtained by the process for producing a hydroisomerization catalyst having a. The said 3rd process is a process of baking the said molded object in the range of 350-450 degreeC, and then heating by heating in the range of more than 450 degreeC and 650 degreeC or less, and obtaining the said carrier. A method for producing a lubricating oil base oil. The lubricant base oil obtained by the manufacturing method of the lubricating oil base oil in any one of Claims 1-10 is 0.03 mass% or less, and the viscosity index is 120 or more, The lubricating oil base oil characterized by the above-mentioned.

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