JP5411864B2 - Lubricating base oil manufacturing method and lubricating base oil - Google Patents

Description

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

  Among petroleum products, for example, lubricating oil, light oil, jet fuel and the like are products in which fluidity at low temperatures is regarded as important. Therefore, the base oils used in these products have wax components such as normal paraffins and slightly branched isoparaffins that cause a decrease in low-temperature fluidity completely or partially removed, or waxes. It is desirable to be converted to something other than ingredients.

  As a dewaxing technique for removing the wax component from the hydrocarbon oil, for example, a method of extracting the wax component with a solvent such as liquefied propane or MEK is known. However, this method has problems such as high operating costs, limited applicable feedstock types, and product yields limited by feedstock types.

  On the other hand, as a dewaxing technique for converting a wax component in a hydrocarbon oil into a non-wax component, for example, a hydrocarbon oil can have a dual function of hydrogenation-dehydrogenation ability and isomerization ability in the presence of hydrogen. Catalytic dewaxing is known in which a normal paraffin in a hydrocarbon oil is isomerized into an isoparaffin by contacting with a hydroisomerization catalyst. As hydroisomerization catalysts used for catalytic dewaxing, catalysts containing solid acids, especially zeolites and metals belonging to Groups 8 to 10 or Group 6 of the periodic table are known.

  Catalytic dewaxing is effective as a method for improving the low temperature fluidity of hydrocarbon oils, but in order to obtain a fraction suitable for a base oil for lubricating oil, it is necessary to sufficiently increase the conversion rate of normal paraffin. However, since hydroisomerization catalysts used in catalytic dewaxing have both isomerization ability and hydrocarbon resolution, hydrocarbon oils are increasingly decomposed and lightened as normal paraffin conversion increases. As a result, the yield of the desired fraction decreases. In particular, when producing a high-quality base oil for lubricating oil that requires a high viscosity index and a low pour point, it is necessary to increase the conversion rate to such an extent that normal paraffin is not substantially contained, and contact with hydrocarbon oil. It was very difficult to obtain the target fraction with good economic efficiency by dewaxing.

  Due to the above circumstances, in order to obtain a desired isoparaffin fraction from a hydrocarbon oil containing a wax component in the field of production of a lubricant base oil and a fuel base oil, in particular, a lubricant base oil, it was suppressed against hydrocarbons. There is a need for hydroisomerization catalysts having cracking activity and increased isomerization activity, ie, excellent isomerization selectivity.

  Until now, attempts have been made to improve the isomerization selectivity of the hydroisomerization catalyst used in catalytic dewaxing. For example, Patent Document 1 below has medium-sized one-dimensional pores such as ZSM-22, ZSM-23, and ZSM-48 containing metals such as Groups 8 to 10 of the periodic table, and crystals. A dewaxed lubricating oil obtained by contacting a linear or slightly branched hydrocarbon raw material having a carbon number of 10 or more with a catalyst comprising a zeolite whose size does not exceed about 0.5 μm under isomerization conditions A process for manufacturing is disclosed.

  Incidentally, the zeolite constituting the hydroisomerization catalyst is usually 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. Is done. The synthesized zeolite is, for example, about 550 ° C. in an atmosphere containing molecular oxygen as described in the following Non-Patent Document 1, page 453, “2.1. Materials”, the last paragraph. By baking at the above temperature, the organic template contained is removed. Next, the calcined zeolite is typically ammonium in an aqueous solution containing ammonium ions, as described in, for example, the following Non-Patent Document 1, page 453, section “2.3. Catalytic experiments”. Ion exchanged into mold. The zeolite after the ion exchange further carries metal components such as groups 8 to 10 of the periodic table. Then, the zeolite carrying the metal component is filled into the reactor through steps such as drying and, if necessary, molding, and is typically fired in an atmosphere containing molecular oxygen at a temperature of about 400 ° C. By performing a reduction treatment with hydrogen or the like at a temperature of about a degree, catalytic activity as a dual function catalyst is imparted.

  The catalyst used for commercial use is generally used in the form of a molded product for the purpose of improving the ease of handling and reducing the pressure loss of the reaction fluid in the catalyst bed. However, zeolite powder is poor in self-caking property, and it is difficult to put it to practical use because the mechanical strength of a catalyst comprising a molded product obtained by molding only itself is small. Therefore, a catalyst using zeolite is usually used in the form of a molded body obtained by molding a composition in which an inorganic oxide powder called a binder is blended with zeolite powder.

US Pat. No. 5,282,958

J. et al. A. Martens et al. , J .; Catal. 239 (2006) 451

  As the lubricating base oil, many petroleum-based lubricating base oils are used in terms of availability and cost. In particular, paraffinic base oils are widely used for lubricating oils that require performance to reduce friction and wear. This paraffinic base oil has been improved in performance due to recent demands for fuel saving and longer life. API Group III standard engine oil base oil is manufactured using a hydrocracking process of petroleum-based feedstock, and has a high viscosity index base with reduced sulfur content and aromatic hydrocarbon content. Oil. Recently, it has been demanded to further increase the productivity of such base oil.

  The present invention provides a method for producing a lubricating base oil that can efficiently obtain a lubricating base oil that satisfies API Group III standards from petroleum-based feedstock, and a lubricating base oil obtained thereby. Objective.

  In order to solve the above problems, the present invention provides a hydrocracked oil obtained by hydrocracking a raw material oil containing at least one selected from the group consisting of a vacuum gas oil, an atmospheric residue and a vacuum residue. In the presence of gaseous hydrogen, contacting a hydroisomerization catalyst to obtain a dewaxed oil, hydrofinishing the dewaxed oil to obtain a hydrorefined oil, and distilling the hydrorefined oil to lubricate A step of obtaining an oil fraction, wherein the hydroisomerization catalyst is a molded body fired by receiving a thermal history including heating at 350 ° C. or higher, and a periodic table supported on the carrier. A metal belonging to Group 8 to 10 and at least one metal selected from the group consisting of molybdenum and tungsten, and the carrier contains (a) an organic template and a 10-membered ring one-dimensional pore structure. Having an organic template-containing zeolite, A calcined zeolite obtained by calcining an ion exchange zeolite obtained by ion exchange in a solution containing muon and / or protons under a thermal history including heating at 350 ° C. or higher, and (b) alumina, silica, At least one inorganic oxide selected from the group consisting of titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide and a composite oxide composed of a combination of two or more thereof includes heating at 350 ° C. or higher. The thermal history received by the calcined zeolite, including the calcined inorganic oxide that is calcined in response to the thermal history, is that the ion-exchanged zeolite not heated at 350 ° C. or higher is in the range of 350 ° C. to 450 ° C. There is provided a method for producing a first lubricating base oil characterized by including firing by heating.

  In the present specification, the periodic table refers to a long-period table defined by the International Pure and Applied Chemical Association (IUPAC).

  According to the first method for producing a lubricating base oil of the present invention, the present invention comprises a carrier comprising a specific zeolite and a specific inorganic oxide, and a specific active metal supported on the carrier. Since the hydroisomerization catalyst according to the present invention has sufficient mechanical strength and high isomerization selectivity, it is possible to efficiently obtain a lubricating base oil satisfying the API Group III standard from the above raw material oil. Is possible.

  The present invention also provides a lubricating oil fraction obtained by distilling hydrocracked oil obtained by hydrocracking a feedstock containing at least one selected from the group consisting of vacuum gas oil, atmospheric residue and vacuum residue. A dewaxed oil by contacting a lubricating oil fraction with a hydroisomerization catalyst in the presence of molecular hydrogen, and a hydrofinishing treatment of the dewaxed oil. From the support | carrier which is a molded object which the isomerization catalyst received the heat history including the heating of 350 degreeC or more, and was baked, and the metal which belongs to the periodic table group 8-10 carried by this support | carrier, molybdenum, and tungsten At least one metal selected from the group consisting of: (a) an organic template-containing zeolite containing an organic template and having a 10-membered ring one-dimensional pore structure; ammonium ions and / or protons In solution containing An ion exchange zeolite obtained by ion exchange is calcined zeolite that is calcined by receiving a heat history including heating at 350 ° C. or higher, and (b) alumina, silica, titania, boria, zirconia, magnesia, ceria, Firing in which at least one inorganic oxide selected from the group consisting of zinc oxide, phosphorus oxide and a composite oxide composed of a combination of two or more thereof is fired by receiving a thermal history including heating at 350 ° C. or higher. The thermal history received by the calcined zeolite containing the inorganic oxide includes that the ion-exchanged zeolite not heated at 350 ° C. or higher is calcined by heating within the range of 350 ° C. to 450 ° C. A method for producing a second lubricating base oil is provided.

  According to the second lubricating base oil production method of the present invention, the hydroisomerization catalyst according to the present invention has sufficient mechanical strength and high isomerization selectivity. It is possible to efficiently obtain a lubricating base oil satisfying the API Group III standard from the above raw material oil. Moreover, the second method for producing a lubricating base oil of the present invention comprises dewaxing a lubricating oil fraction obtained by distilling hydrocracked oil by contacting the hydroisomerization catalyst according to the present invention. In addition, hydroisomerization dewaxing can be performed under reaction conditions suitable for each fraction having different boiling ranges, and undesirable decomposition reactions can be suppressed.

  The present invention also provides a hydrocracked oil obtained by hydrocracking a feedstock containing at least one selected from the group consisting of vacuum gas oil, atmospheric residue and vacuum residue, in the presence of molecular hydrogen, A step of obtaining a dewaxed oil by contacting with a hydroisomerization catalyst, a step of distilling the dewaxed oil to obtain a lubricating oil fraction, and a step of hydrofinishing the lubricating oil fraction. A carrier in which the hydroisomerization catalyst is a molded body fired by receiving a thermal history including heating at 350 ° C. or higher, a metal belonging to Groups 8 to 10 of the periodic table, molybdenum and tungsten carried on the carrier. At least one metal selected from the group consisting of: and (a) an organic template-containing zeolite containing an organic template and having a 10-membered ring one-dimensional pore structure, ammonium ions and / or Proton-containing solution An ion-exchanged zeolite obtained by ion-exchange in the above, a calcined zeolite that is calcined by receiving a heat history including heating at 350 ° C. or higher, and (b) alumina, silica, titania, boria, zirconia, magnesia, ceria In addition, at least one inorganic oxide selected from the group consisting of zinc oxide, phosphorus oxide, and composite oxides composed of a combination of two or more thereof is fired by receiving a thermal history including heating at 350 ° C. or higher. The thermal history received by the calcined zeolite, including the calcined inorganic oxide, includes that the ion-exchanged zeolite not heated at 350 ° C. or higher is calcined by heating within the range of 350 ° C. to 450 ° C. A third method for producing a lubricating base oil is provided.

  According to the third lubricating base oil production method of the present invention, the hydroisomerization catalyst according to the present invention has sufficient mechanical strength and high isomerization selectivity. It is possible to efficiently obtain a lubricating base oil satisfying the API Group III standard from the above raw material oil. Further, the third method for producing a lubricating base oil of the present invention is such that the lubricating oil fraction obtained by distilling the dewaxed oil is subjected to hydrofinishing, whereby reaction conditions suitable for each fraction having different boiling ranges. Underwater hydrofinishing can be performed, and undesirable decomposition reactions can be suppressed.

  In the first to third lubricating base oil production methods of the present invention, the organic template-containing zeolite is at least one selected from the group consisting of ZSM-22, ZSM-23, and ZSM-48 type zeolites. Is preferred.

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

  From the viewpoint of further improving the mechanical strength of the catalyst while obtaining excellent isomerization selectivity, the carrier is molded by being subjected to a thermal history including heating in the range of more than 450 ° C. and not more than 650 ° C. It is preferable that it is a body.

  From the viewpoint of isomerization selectivity and reaction activity, the metal supported on the carrier is preferably platinum and / or palladium.

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

  In the first to third lubricating base oil production methods 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, ammonium ions and 1st step of obtaining ion exchange zeolite by ion exchange in a solution containing protons, the above ion exchange zeolite, alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide and these A second step of obtaining a molded body by molding a composition containing at least one inorganic oxide selected from the group consisting of composite oxides composed of two or more combinations, and at least 350 ° C. A third step of obtaining a carrier by calcining by heating within a range of 450 ° C .; Metals belonging to 10 group, it is preferably obtained by the fourth step, the manufacturing method of the hydroisomerization catalyst comprises a for supporting the at least one metal selected from the group consisting of molybdenum and tungsten.

  Since the hydroisomerization catalyst obtained by the above production method is excellent in both isomerization selectivity and mechanical strength, a lubricating base oil satisfying API Group III standard can be stably and efficiently obtained from the above raw material oil. Can be obtained.

  From the viewpoint of further improving the mechanical strength of the catalyst and increasing the productivity of the lubricating base oil, the third step is to heat the molded body within a range of 350 ° C. to 450 ° C. and then exceed 450 ° C. to 650 It is preferable to be a step of obtaining the above-mentioned carrier by baking within a range of not higher than ° C.

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

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the lubricating base oil which can obtain efficiently the lubricating base oil which satisfy | fills API group III specification from petroleum-type raw material oil, and the lubricating base oil obtained by it are provided. be able to.

It is a flowchart which shows an example of the lubricating base oil manufacturing apparatus with which the manufacturing method of the lubricating base oil of this invention is implemented. It is a flowchart which shows the other example of the lubricating base oil manufacturing apparatus with which the manufacturing method of the lubricating base oil of this invention is implemented. It is a flowchart which shows the other example of the lubricating base oil manufacturing apparatus with which the manufacturing method of the lubricating base oil of this invention is implemented.

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

  FIG. 1 is a flow chart showing an example of a lubricating base oil production apparatus for carrying out the lubricating base oil production method of the present invention. A lubricating 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 the raw material oil introduced from the flow path L1, and a reaction tower 10 From the first distillation column 20 for atmospheric distillation of the hydrocracked oil supplied through the flow path L2 and the hydrocracked bottom oil supplied from the distillation tower 20 through the flow path L5 to hydroisomerization (hydrodehydration). A second reaction tower 30 that waxes, a third reaction tower 40 that hydrofinishes (hydrorefining) dewaxed oil supplied from the reaction tower 30 through the flow path L6, and a flow path L7 from the reaction tower 40. And a second distillation column 50 for vacuum-distilling the hydrorefined oil supplied through a predetermined fraction. The first distillation column 20 is provided with flow paths L3 and L4 for taking out the light fraction out of the system. The second distillation column 50 is provided with flow paths L10 to L14 for taking out predetermined fractions out of the system.

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

  As the feedstock to be hydrocracked, one containing at least one selected from the group consisting of vacuum gas oil, atmospheric residue and vacuum residue is used. As the vacuum gas oil, for example, a fraction having a boiling point of 343 ° C. or higher and 550 ° C. or lower at normal pressure obtained from a vacuum distillation apparatus can be suitably used. As the atmospheric residual oil, for example, a fraction having a boiling point of 343 ° C. or higher at normal pressure obtained from a crude oil atmospheric distillation apparatus can be suitably used. As the vacuum residue, a fraction having a boiling point of 550 ° C. or higher at normal pressure obtained from a vacuum distillation apparatus for atmospheric residue can be suitably used. The raw material oil used in the present invention preferably contains 50% by mass or more of hydrocarbons having 20 or more carbon atoms with respect to the total amount of the raw material oil from the viewpoint of obtaining a lubricating base oil with high yield.

  In the first reaction tower 10, the feedstock is hydrocracked. As the first reaction tower 10, a known fixed bed, fluidized bed, moving bed, or ebullated bed reaction tower can be used. In the present embodiment, in a reaction tower, hydrocracking is carried out by charging a predetermined hydrocracking catalyst into a fixed bed flow-type reactor and circulating molecular hydrogen and the above-mentioned feedstock in this reactor. Is preferred. The hydrocracking here means a reaction for producing low molecular weight hydrocarbons by paraffin cracking or naphthene ring opening, and desulfurization, denitrogenation, olefin hydrogenation and aromatic hydrogenation of the feedstock oil are also performed.

  As the hydrocracking catalyst, for example, a carrier comprising one or more solid acidic substances selected from alumina, silica, zirconia, titania, boria, ultra-stabilized Y-type (USY) zeolite and β zeolite, And a catalyst having one or more active metals selected from the group consisting of cobalt-molybdenum, nickel-molybdenum, nickel-tungsten and nickel-cobalt-molybdenum supported on the carrier.

  USY zeolite is obtained by ultra-stabilizing Y-type zeolite by hydrothermal treatment and / or acid treatment, and in addition to the fine pore structure of 20 pores or less originally possessed by Y-type zeolite, New pores are formed in the area. When USY zeolite is used as the carrier for the hydrocracking catalyst, the average particle size is not particularly limited, but is preferably 1.0 μm or less, more preferably 0.5 μm or less. In the USY zeolite, the silica / alumina molar ratio (molar ratio of silica to alumina; hereinafter referred to as “silica / alumina ratio”) is preferably 10 to 200, more preferably 15 to 100, and 20 It is still more preferable that it is -60.

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

  As a method for supporting nickel-molybdenum, which is an active metal, on the support, a method used for producing a normal desulfurization catalyst can be employed. As the cobalt source, an organic or inorganic cobalt salt such as cobalt nitrate, cobalt chloride or cobalt acetate can be used. As the nickel source, an organic or inorganic cobalt salt such as nickel nitrate, nickel chloride or nickel acetate can be used. As the molybdenum source, ammonium molybdate or molybdenum oxide can be used, and as the tungsten source, ammonium tungstate can be used. For each metal, organic salts or inorganic salts other than those listed here may be used. Furthermore, an organic compound may coexist in the impregnation liquid containing the active metal. In addition to these active metals, phosphorus may be supported on the catalyst.

  When the catalyst is a nickel-molybdenum catalyst or a nickel-tungsten catalyst, the supported amount of active metal in the hydrocracking catalyst is preferably 3-15% by mass of nickel supported with respect to the total amount of the catalyst, When the catalyst is a nickel-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 with respect to the total amount of the catalyst.

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

The reaction conditions in the first reaction column 10 are preferably a reaction temperature of 350 to 450 ° C., a hydrogen partial pressure of 5 to 20 MPa, an LHSV of 0.1 to 2 h ⁻¹ , and a hydrogen / oil ratio of 2000 to 10,000 scfb, and a reaction temperature of 370 ° C. to It is more preferable that they are 430 degreeC, hydrogen partial pressure 10-18MPa, LHSV0.1-1.0h < ^-1 >, and hydrogen / oil ratio 2500-8000scfb.

  When the feedstock oil is a vacuum gas oil, it is preferable to adjust the reaction conditions so that the sulfur content and the nitrogen content concentration in the hydrocracked oil are 50 ppm or less and 5 ppm or less, respectively.

  In the present embodiment, when the feedstock oil is a vacuum gas oil, the feedstock oil is hydrocracked so that the content of the fraction having a boiling point of 343 ° C. or less in the hydrocracked oil is 30 to 75% by mass. Is preferred.

  In the first distillation column 20, fuel oil such as naphtha or kerosene oil can be taken out from the flow paths L3 and L4 by subjecting the hydrocracked oil to atmospheric distillation. In this case, it is preferable to obtain a fraction of 343 ° C. or higher as a hydrocracked bottom oil. When the raw material oil is atmospheric residual oil or the like, the distillation tower 20 may be omitted and the hydrocracked oil from the first reaction tower 10 may be supplied to the second reaction tower 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 the present embodiment, in the reaction tower, the hydroisomerization catalyst according to the present invention is packed in a fixed bed flow type reactor, and molecular hydrogen and hydrocracked bottom oil are circulated through this reactor. It is preferred to carry out the isomerization.

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

  The hydroisomerization catalyst according to the present invention is characterized by being produced by a specific method. Hereinafter, the hydroisomerization catalyst according to the present invention will be described in accordance with its preferable production mode.

  The organic template-containing zeolite used as a starting material for the calcined zeolite (a) constituting the hydroisomerization catalyst according to the present invention has high isomerization activity and suppressed decomposition activity in the hydroisomerization reaction of normal paraffin. From the viewpoint of achieving both levels, it is preferable to have a one-dimensional pore structure consisting of a 10-membered ring. Examples of such zeolite include AEL, EUO, FER, HEU, MEL, MFI, NES, TON, MTT, WEI, and ZSM-48. The above three letters of the alphabet mean the skeletal structure codes given by the Structure Committee of The International Zeolite Association for each classified molecular sieve type structure. To do. In addition, zeolites having the same topology are collectively referred to by the same code.

  Among the zeolites having the 10-membered ring one-dimensional pore structure, the organic template-containing zeolite includes TON, zeolite having an MTT structure, and ZSM-48 in terms of high isomerization activity and low decomposition activity. Type zeolite is preferred. As a zeolite having a TON structure, a ZSM-22 type zeolite is more preferable, and as a zeolite having an MTT structure, a ZSM-23 type zeolite is more preferable.

  An organic template-containing zeolite containing an organic template serving as a starting material for the calcined zeolite (a) constituting the hydroisomerization catalyst according to the present invention and having a 10-membered ring one-dimensional pore structure includes a silica source, an alumina source, Hydrothermal synthesis is performed by a known method from the organic template added to construct the predetermined pore structure.

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

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

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

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

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

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

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

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

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

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

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

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

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

  Next, the molded article obtained as described above is fired at 350 to 450 ° C., preferably 380 to 430 ° C., more preferably 390 to 420 ° C. in an atmosphere containing molecular oxygen. And it is preferable to make the support | carrier baked by receiving the heat history including the heating of 350 degreeC or more. “In an atmosphere containing molecular oxygen” means contacting with a gas containing oxygen gas, preferably air. The firing time is not particularly limited, but is preferably 1 to 24 hours.

  By the calcination, the ion exchange zeolite constituting the molded body becomes the calcined zeolite (a), and the inorganic oxide becomes the calcined inorganic oxide (b).

  In the present embodiment, when the baking temperature is lower than 350 ° C., the removal of the organic template does not proceed sufficiently, or it takes a long time to remove, and further, the mechanical strength of the carrier does not tend to be sufficiently improved. This is not preferable. On the other hand, when the calcination temperature exceeds 450 ° C., the isomerization selectivity of the resulting hydroisomerization catalyst tends not to be sufficiently improved, which is not preferable. Firing an ion-exchanged zeolite that is not heated at 350 ° C. or higher and has an organic template remaining at a relatively low temperature as described above improves the isomerization selectivity of the hydroisomerization catalyst according to the present invention. Very important.

  As described above, the calcination may be performed in the state of a powdery ion-exchanged zeolite as well as in the form of a molded body obtained by molding a composition in which an inorganic oxide is mixed with ion-exchanged zeolite. Good. However, in that case, a molded body obtained by molding a composition in which the obtained calcined zeolite is blended with an inorganic oxide is molded at a temperature of 350 ° C. or higher, for example, in the range of 350 to 450 ° C. for the purpose of imparting mechanical strength. It is necessary to perform firing at a temperature within the range of 650 ° C. or higher and / or higher than 450 ° C.

  The carrier is heated in the range of 350 to 450 ° C., preferably in an atmosphere containing molecular oxygen, more preferably in an air atmosphere, and further heated and calcined in the range of more than 450 ° C. and not more than 650 ° C. It may be. In addition to heating at 350 to 450 ° C., further heating at 450 ° C. or lower and calcination at 650 ° C. or lower does not greatly affect the hydroisomerization selectivity of the resulting catalyst, and the support machine It is possible to further improve the mechanical strength. Therefore, when catalyst particles having higher mechanical strength are desired, it is preferable to perform firing by the two-stage heating described above. When the subsequent heating temperature is 450 ° C. or lower, it tends to be difficult to further improve the mechanical strength of the carrier. On the other hand, when the temperature exceeds 650 ° C., the environment of aluminum atoms involved in the formation of active sites on the zeolite tends to change and the decomposition activity tends to increase, such being undesirable. Furthermore, the heating temperature in the latter stage is more preferably in the range of more than 450 ° C. and 600 ° C. or less from the viewpoint of maintaining isomerization selectivity.

  In the present embodiment, at least one of metals belonging to Groups 8 to 10 of the periodic table, molybdenum and tungsten is added to the support, which is a molded body fired by receiving a thermal history including heating at 350 ° C. or higher, obtained as described above. It is preferable to support a metal (hereinafter sometimes referred to as “active metal”).

  Examples of metals belonging to Groups 8 to 10 of the periodic table include iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, and platinum. Among these, platinum and / or palladium are preferable from the viewpoint of activity, isomerization selectivity, and activity sustainability, and platinum is particularly preferable. Said active metal can be used individually by 1 type or in combination of 2 or more types. Further, when the hydroisomerization catalyst according to the present invention is used for hydroisomerization of hydrocracked oil containing a large amount of sulfur-containing compounds and / or nitrogen-containing compounds, from the viewpoint of sustainability of catalyst activity, as an active metal Is preferably a combination of nickel-cobalt, nickel-molybdenum, cobalt-molybdenum, nickel-molybdenum-cobalt, nickel-tungsten-cobalt and the like.

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

  Examples of the active metal precursor include hydrochloride, sulfate, nitrate, complex compound and the like of the above active metal. When the active metal is platinum, chloroplatinic acid, tetraamminedinitroplatinum, dinitroaminoplatinum, tetraamminedichloroplatinum or the like is preferably used as the active metal precursor.

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

  The active metal may be supported on 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 manufactured through a method in which an active metal is supported on a support by an impregnation method or the like, the distribution of the site where the active metal is supported is mainly used for the support. It is determined by the affinity between the active metal precursor to be calcined, the calcined zeolite (a) and the calcined inorganic oxide (b).

  The support of the active metal is not limited to the mode performed on the molded and fired carrier. For example, powdered ion-exchanged zeolite, or calcined zeolite calcined at 350 to 450 ° C. may be loaded with active metal, powdered inorganic oxide, or both. It may be.

  The support on which the active metal component is supported is preferably fired in an atmosphere containing molecular oxygen, mainly for the purpose of removing the anion component or the ligand component contained in the active metal precursor. . As a calcination temperature, 250 to 600 degreeC is preferable and 300 to 500 degreeC is more preferable. Air is preferable as the atmosphere containing molecular oxygen. The firing time is usually about 0.5 to 20 hours. Through such a baking treatment, the active metal precursor is converted into a metal simple substance, an oxide thereof, or a similar species.

  As described above, in a preferred embodiment of the production of the hydroisomerization catalyst according to the present invention, “ion exchange of an organic template-containing zeolite”, “molding of a composition containing an ion exchange zeolite and an inorganic oxide”, “350 Calcination of the molded body by heating at ˜450 ° C. ”or“ heating at 350 to 450 ° C. and then calcination of the molded body by heating at higher than 450 ° C. and 650 ° C. ”,“ supporting of active metal on the carrier ”, In addition, each step of “calcination of a carrier on which an active metal is supported” is included.

  What is important in the hydroisomerization catalyst according to the present invention is that in addition to the use of the specific zeolite, the specific inorganic oxide, and the specific active metal, in the process of production thereof, “containing an organic template containing an organic template” “Part of the organic template included in the zeolite is removed by ion exchange instead of calcination”, “Ion-exchanged zeolite that is not heated at 350 ° C. or higher and that part of the organic template remains is 350-450 ° C. Calcination at a relatively low temperature to remove at least a part of the organic template remaining in the zeolite ”and“ The carrier is a molded body that has been baked by receiving a thermal history including heating at 350 ° C. or higher. There are three points. In the production of the hydroisomerization catalyst according to the present invention, the embodiment in which the above-described steps are performed and the order thereof, as long as the above three points are ensured, and the occurrence of problems in each step of the catalyst production, As long as the manufacturing cost is not increased due to complicated processes, the manufacturing cost may be different from that described in the above-described preferable manufacturing mode, and can be appropriately changed.

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

  In the hydroisomerization catalyst according to the present invention, other than the metals belonging to Groups 8 to 10 of the periodic table, molybdenum and tungsten on the calcined zeolite and / or calcined inorganic oxide as long as the effects of the present invention are not impaired. These metals may be further supported.

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

  In the present embodiment, the reaction conditions are preferably adjusted so that the normal paraffin concentration in the dewaxed oil is 1% by mass or less.

  In the third reaction tower 40, the dewaxed oil is hydrofinished (hydrorefined). As the third reaction tower 40, a known fixed bed reaction tower can be used. In the present embodiment, hydrorefining is carried out by charging a predetermined hydrorefining catalyst in a fixed bed flow-type reactor in the reaction tower and circulating molecular hydrogen and the dewaxed oil in the reactor. It is preferable. Hydrorefining here means improving the oxidation stability and hue of lubricating oil, and olefin hydrogenation and aromatic hydrogenation of dewaxed oil are performed.

  As the hydrorefining catalyst, for example, a support comprising one or more inorganic solid acidic substances selected from alumina, silica, zirconia, titania, boria, magnesia and phosphorus, and supported on the support, Examples thereof include a catalyst provided with one or more active metals selected from the group consisting of platinum, palladium, nickel-molybdenum, nickel-tungsten and nickel-cobalt-molybdenum.

  A suitable carrier is an inorganic solid acidic substance containing at least two kinds of alumina, silica, zirconia, or titania.

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

  The supported amount of active metal in the hydrotreating catalyst is preferably such that the total amount of metal is 0.1 to 25% by mass with respect to the support.

The average pore diameter of the hydrorefining catalyst is preferably 6 to 60 nm, and more preferably 7 to 30 nm. When the average pore diameter is smaller than 6 nm, sufficient catalytic activity tends to be not obtained, and when the average pore diameter exceeds 60 nm, the catalytic activity tends to decrease due to a decrease in the degree of dispersion of the active metal. The pore volume of the hydrotreating catalyst is preferably 0.2 mL / g or more. When the pore volume is less than 0.2 mL / g, the catalyst activity tends to be rapidly deteriorated. Furthermore, the specific surface area of the hydrotreating catalyst is preferably 200 m ² / g or more. When the specific surface area of the catalyst is less than 200 m ² / g, the dispersibility of the active metal is insufficient and the activity tends to decrease. The pore volume and specific surface area of these catalysts can be measured and calculated by a method called the BET method based on nitrogen adsorption.

The reaction conditions in the third reaction tower 40 are preferably a reaction temperature of 200 to 300 ° C., a hydrogen partial pressure of 3 to 20 MPa, an LHSV of 0.5 to 5 h ⁻¹ , a hydrogen / oil ratio of 1000 to 5000 scfb, and a reaction temperature of 200 ° C. to More preferably, it is 300 ° C., hydrogen partial pressure 4-18 MPa, LHSV 0.5-4 h ⁻¹ , and hydrogen / oil ratio 2000-5000 scfb.

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

  In the second distillation column 50, a lubricating oil fraction is obtained by setting a plurality of cut points and distilling the hydrorefined oil under reduced pressure. In the present embodiment, for example, a first lubricating oil fraction having a boiling point of 343 to 390 ° C., a second lubricating oil fraction having a boiling point of 390 to 440 ° C., and a third lubricating oil having a boiling point of 440 to 510 ° C. at normal pressure. The oil fraction and the fourth lubricating oil fraction having a boiling point of 510 ° C. or higher can be recovered as the lubricating base oil from the flow paths L11-14, respectively. The first lubricating oil fraction can be obtained as a lubricating base oil suitable for ATF or shock absorber. In this case, the kinematic viscosity at 100 ° C. is preferably 2.7 ± 0.1 cSt. The second lubricating oil fraction can be obtained as a lubricating base oil according to the present invention suitable for an engine base oil that satisfies the API Group III standard. In this case, the kinematic viscosity at 100 ° C. is 4.0. It is preferable that the difference is ± 0.1 cSt and the pour point is −22.5 ° C. or lower. The third lubricating oil fraction can be obtained as a lubricating base oil suitable for industrial hydraulic 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 base oil suitable for industrial hydraulic oil. In this case, the kinematic viscosity at 40 ° C. is preferably 80 to 120 cSt. Furthermore, the first lubricating oil fraction can be obtained as a lubricating base oil corresponding to 70 Pale, and the second lubricating oil fraction can be obtained as a lubricating base oil corresponding to SAE-10, The third lubricating oil fraction can be obtained as a lubricating base oil corresponding to SAE-20, and the fourth lubricating oil fraction can be obtained as a lubricating base oil corresponding to SAE-30.

  In addition, the hydrorefined oil supplied from the third reaction tower 40 of the present embodiment includes light fractions such as naphtha and kerosene oil that are by-produced by hydroisomerization or hydrofinishing (hydrorefining). included. These can be recovered from the flow path L10 as a fraction having a boiling point of 350 ° C. or less, for example.

  The manufacturing method of the lubricating base oil of the present invention is not limited to the above-described embodiment, and can be changed as appropriate. For example, a step of obtaining a lubricating oil fraction by distilling hydrocracked oil obtained by hydrocracking a raw oil containing at least one selected from the group consisting of vacuum gas oil, atmospheric residue and vacuum residue And in the presence of molecular hydrogen, a step of contacting a lubricating oil fraction with a hydroisomerization catalyst to obtain a dewaxed oil, and a step of hydrofinishing the dewaxed oil in this order, Oil can be produced. FIG. 2 is a flowchart showing an example of a lubricating base oil production apparatus that implements the above lubricating base oil production method. The lubricating base oil production apparatus 110 of FIG. 2 is another embodiment after L5 in the lubricating base oil production apparatus of FIG. 1, and is a second method for distilling hydrocracked bottom oil supplied through the flow path L5. Distillation tower 50, second reaction tower 30 for hydroisomerizing (hydrodewaxing) the lubricating oil fraction supplied from second distillation tower 50 through passage L21, and passage L22 from reaction tower 30 And a third reaction tower 40 for hydrofinishing (hydrorefining) of the dewaxed oil supplied through the second degassing oil. The third reaction tower 40 is provided with a flow path L23 for taking out hydrorefined oil out of the system.

  In the present embodiment, the same hydrocracking catalyst, hydroisomerization catalyst, and hydrorefining catalyst described above can be used.

  In the second distillation column 50, it is preferable to distill hydrocracked oil so that a lubricating oil fraction having a boiling point of 343 ° C. or higher can be obtained. The naphtha / kerosene oil fraction having a boiling point range of less than 343 ° C. at normal pressure is preferably recovered from another recovery line provided in the second distillation column 50. In the present embodiment, the second distillation column 50 can be fractionated into a plurality of lubricating oil fractions, and hydroisomerization and hydrofinishing can be performed on each fraction. These steps can be performed in the same line by switching the fraction from the second distillation column 50, or a plurality of fractions from the second distillation column 50 can be performed in separate lines. . Examples of the plurality of fractions include, for example, a naphtha / kerosene oil fraction having a boiling point range of less than 343 ° C. at normal pressure, a 70-pale fraction having a temperature of 343 to 390 ° C., and a SAE-10 fraction having a temperature of 390 to 440 ° C. Minute, SAE-20 fraction having a temperature of 440 to 510 ° C., and bottom fraction exceeding 510 ° C. include SAE-30 fraction.

The reaction conditions for hydroisomerization (hydrodewaxing) of the lubricating oil fraction in the second reaction tower 30 are as follows: reaction temperature 250 ° C. to 400 ° C., hydrogen partial pressure ^{1 to} 20 MPa, LHSV ^{1 to} 4 h ⁻¹ , hydrogen An oil ratio of 2000 to 4000 scfb is preferred.

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

The reaction conditions in the third reaction tower 40 are preferably a reaction temperature of 200 ° C. to 300 ° C., a hydrogen partial pressure of 4 to 18 MPa, LHSV of 0.5 to 4 h ⁻¹ , and a hydrogen / oil ratio of 2000 to 5000 scfb.

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

  Further, the hydrorefined oil supplied from the third reaction tower 40 of the present embodiment can be used as a lubricating base oil satisfying API Group III standards, but further distillation is performed to obtain a desired fraction. It can be obtained as a lubricating base oil. At this time, the light fraction produced as a by-product by hydroisomerization or hydrofinishing (hydrorefining) can also be removed.

  In the case of distilling hydrorefined oil, it is preferable to fractionate into a plurality of fractions by, for example, vacuum distillation, and the plurality of fractions, for example, have a boiling range of less than 343 ° C. at normal pressure. As a naphtha / kerosene oil fraction, a 70-pale fraction at 343-390 ° C., an SAE-10 fraction at 390-440 ° C., an SAE-20 fraction at 440-510 ° C., and a bottom fraction above 510 ° C. Examples include SAE-30 fraction.

  The manufacturing method of the lubricating base oil of the present invention can be further changed. For example, hydrocracked oil obtained by hydrocracking a feedstock containing at least one selected from the group consisting of vacuum gas oil, atmospheric residue, and vacuum residue is hydroisomerized in the presence of molecular hydrogen. The process of obtaining a dewaxed oil by contacting it with a hydroforming catalyst, the process of obtaining a lube oil fraction by distilling the dewaxed oil under reduced pressure, and the process of hydrofinishing the lube oil fraction in this order for lubrication. An oil base oil can be produced. FIG. 3 is a flowchart showing an example of a lubricating base oil production apparatus that implements the above lubricating base oil production method. The lubricating base oil production apparatus 120 of FIG. 3 is another embodiment after L5 in the lubricating base oil production apparatus of FIG. 1, and hydroisomerizes the hydrocracked bottom oil supplied through the flow path L5 ( A second reaction tower 30 for hydrodewaxing), a second distillation tower 50 for distilling dewaxed oil supplied from the reaction tower 30 through the flow path L31, and a flow path L32 from the second distillation tower 50. And a third reaction tower 40 for hydrofinishing (hydrorefining) the lubricating oil fraction fed through The third reaction tower 40 is provided with a flow path L33 for taking out hydrorefined oil out of the system.

  In the present embodiment, the same hydrocracking catalyst, hydroisomerization catalyst, and hydrorefining catalyst described above can be used.

The reaction conditions for hydroisomerization (hydrodewaxing) of hydrocracked oil in the second reaction tower 30 are as follows: reaction temperature 300 ° C. to 360 ° C., hydrogen partial pressure 2 to 10 MPa, LHSV ^{1 to} 4 h ⁻¹ , hydrogen / An oil ratio of 2000 to 4000 scfb is preferred.

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

  In the second distillation column 50, the dewaxed oil is preferably distilled under reduced pressure so that a lubricating oil fraction having a boiling point of 343 ° C. or higher can be obtained. The naphtha / kerosene oil fraction having a boiling point range of less than 343 ° C. at normal pressure is preferably recovered from another recovery line provided in the second distillation column 50. In the present embodiment, it is possible to fractionate into a plurality of lubricating oil fractions in the second distillation column 50 and perform hydrofinishing on each fraction. These steps can be performed in the same line by switching the fraction from the second distillation column 50, or a plurality of fractions from the second distillation column 50 can be performed in separate lines. . Examples of the plurality of fractions include, for example, a naphtha / kerosene oil fraction having a boiling point range of less than 343 ° C. at normal pressure, a 70-pale fraction having a temperature of 343 to 390 ° C., and a SAE-10 fraction having a temperature of 390 to 440 ° C. Minute, SAE-20 fraction having a temperature of 440 to 510 ° C., and bottom fraction exceeding 510 ° C. include SAE-30 fraction.

The reaction conditions in the third reaction tower 40 are preferably a reaction temperature of 200 ° C. to 300 ° C., a hydrogen partial pressure of 4 to 18 MPa, LHSV of 0.5 to 4 h ⁻¹ , and a hydrogen / oil ratio of 2000 to 5000 scfb.

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

  Further, the hydrorefined oil supplied from the third reaction tower 40 of the present embodiment can be used as a lubricating base oil satisfying API Group III standards, but further distillation is performed to obtain a desired fraction. It can be obtained as a lubricating base oil. At this time, the light fraction produced as a by-product by hydroisomerization or hydrofinishing (hydrorefining) can also be removed.

  In the case of distilling hydrorefined oil, it is preferable to fractionate into a plurality of fractions by, for example, vacuum distillation, and the plurality of fractions, for example, have a boiling range of less than 343 ° C. As a naphtha / kerosene oil fraction, a 70-pale fraction at 343-390 ° C., an SAE-10 fraction at 390-440 ° C., an SAE-20 fraction at 440-510 ° C., and a bottom fraction above 510 ° C. Examples include SAE-30 fraction.

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

  EXAMPLES 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 this was extruded into 1/16 cylinder type pellets. The obtained molded body was fired at 550 ° C. for 3 hours under air flow. This extruded carrier was impregnated with 12% by mass and 22% by mass of nickel and tungsten as active metals, respectively, and then calcined at 550 ° C. for 3 hours under air flow to obtain a hydrocracking catalyst.

[Production of hydroisomerization catalyst]
(Hydroisomerization catalyst A)
<Synthesis of ZSM-22 type zeolite>
A ZSM-22 type zeolite composed of crystalline aluminosilicate having a Si / Al ratio of 30 was obtained from Chem. Eur. J, 2007, vol. In accordance with the method described in “Experimental Section” on page 13,10070, it was produced by hydrothermal synthesis according to the following procedure.

First, the following four types of aqueous solutions were prepared.
Solution A: 1.94 g of potassium hydroxide dissolved in 6.75 mL of ion exchange water.
Solution B: A solution obtained by dissolving 1.33 g of aluminum sulfate 18-hydrate in 5 mL of ion-exchanged water.
Solution C: A solution obtained by diluting 4.18 g of 1,6-hexanediamine (organic template) with 32.5 ml of ion-exchanged water.
Solution D: 18 g of colloidal silica (Ludox AS-40 manufactured by Grace Davison) diluted with 31 ml of ion-exchanged water.

  Next, solution A was added to solution B and stirred until the aluminum component was completely dissolved. After adding the solution C to this mixed solution, the mixture of the solutions A, B and C was poured into the solution D with vigorous stirring at room temperature. Further, 0.25 g of ZSM-22 powder synthesized separately and not subjected to any special treatment after synthesis was added as a “seed crystal” for promoting crystallization, thereby obtaining a gel-like product.

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

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

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

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

<Platinum support, firing>
Tetraamminedichloroplatinum (II) (Pt (NH ₃ ) ₄ Cl ₂ ) was dissolved in ion-exchanged water corresponding to the amount of water absorption (preliminarily measured) of the molded and calcined carrier particles to obtain an impregnation solution. This solution was impregnated with the above-molded and calcined carrier particles by an initial wetting method, and supported so that the amount of platinum was 0.5 mass% with respect to the mass of the ZSM-22 type zeolite. Next, the impregnated material thus obtained was dried overnight in a dryer at 60 ° C., and then calcined at 400 ° C. for 3 hours under an air stream to obtain a hydroisomerization catalyst A. The crushing strength of the obtained catalyst particles was 12.4 N / mm. The crushing strength of the catalyst particles was measured according to JIS R2206 “Testing method for compressive strength of refractory bricks”.

(Hydroisomerization catalyst B)
By the same operation as hydroisomerization catalyst A, ion-exchanged NH ₄ type ZSM-22 is obtained, and further by the same operation as hydroisomerization catalyst A, hydroisomerization is performed by extrusion molding using alumina as a binder. A molded product similar to catalyst A was obtained.

  The obtained molded body is dried in a 120 ° C. dryer for 3 hours under air flow, heated at 400 ° C. for 3 hours under air flow, and then heated at 550 ° C. for 3 hours under air flow. To obtain carrier particles molded and fired.

  The obtained molded and calcined carrier particles were loaded with platinum, dried and calcined in the same manner as in the hydroisomerization catalyst A to obtain a hydroisomerization catalyst B. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Hydroisomerization catalyst C)
Molded and calcined carrier particles were obtained by the same operation as the hydroisomerization catalyst B except that the binder was changed from alumina to silica.

  The obtained carrier particles were loaded with platinum, dried and calcined in the same manner as in the hydroisomerization catalyst A to obtain a hydroisomerization catalyst C. The crushing 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 body as the hydroisomerization catalyst A using alumina as a binder was obtained. The molded body is dried in a 120 ° C drier for 3 hours under air flow, heated at 440 ° C for 3 hours under air flow, and then heated at 550 ° C for 3 hours under air flow. Thus, molded and fired carrier particles were obtained.

  The obtained carrier particles thus molded and calcined were loaded with platinum, dried and calcined in the same manner as in the hydroisomerization catalyst A to obtain a hydroisomerization catalyst D. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Hydroisomerization catalyst E)
<Synthesis of ZSM-23 type zeolite>
Hydrothermal synthesis of a ZSM-23 type zeolite having a Si / Al ratio of 30 (hereinafter sometimes referred to as “ZSM-23”) according to the method described in US Pat. No. 4,490,342 and Example 2. Manufactured by.

  First, Diquat-7 (N, N, N, N ′, N ′, N′-hexamethyl-1,7-diaminoheptane dibromide), which is an organic template, was prepared from the aforementioned US Pat. No. 4,490,342, Synthesis was carried out by using a part of the method described in Example A. That is, in an eggplant-shaped flask, 50 g of 1,7-dibromoheptane and 100 ml of ethanol were mixed, and 70 g of triethylamine (33% by mass ethanol solution) was added thereto with stirring, followed by heating and refluxing 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 intended Diquat-7 (dibromide salt).

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

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

  Next, Solution F was poured into Solution E with stirring. The obtained gel was transferred to a stainless steel autoclave reactor having an internal volume of 120 ml, and the reaction was allowed to proceed in an oven at 160 ° C. for 72 hours while rotating the autoclave reactor itself at a rotational speed of about 60 rpm. After completion of the reaction, the reactor is cooled, and the generated solid content is 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 is obtained. The containing ZSM-23 was obtained.

<Production of ion exchange ZSM-23>
Except for using ZSM-23 containing the organic template obtained above in place of ZSM-22 containing the organic template, the same operation as the ion exchange of ZSM-22 of the hydroisomerization catalyst A was performed, Ion exchanged NH ₄ type ZSM-23 was obtained.

<Binder formulation, molding, firing>
From the ion-exchanged ZSM-23 obtained above and alumina as a binder, a molded product is obtained by the same operation as the hydroisomerization catalyst B, and thereafter 400 by the same operation as the hydroisomerization catalyst B. Firing was performed at 550 ° C. and 550 ° C. to obtain molded and fired carrier particles.

<Platinum support, firing>
In the same manner as in the hydroisomerization catalyst B except that the molded and calcined carrier particles containing ZSM-23 obtained above were used instead of the molded and calcined carrier particles containing ZSM-22, The hydroisomerization catalyst E was obtained by carrying, drying and firing. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Hydroisomerization catalyst F)
<Synthesis of ZSM-48 type zeolite>
ZSM-48 type zeolite containing an organic template and having a Si / Al ratio of 30 (hereinafter sometimes referred to as “ZSM-48”) is described in Applied Catalysis A: General vol. 299 (2006) 167-174. 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%) had been previously dissolved. To the mixture, 26.2 g of hexanediamine was added and stirred at room temperature. 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 material gel. The obtained gel was introduced into a stainless steel autoclave and kept at 160 ° C. with stirring for 3 days. Thereafter, after the autoclave contents were cooled to room temperature, ZSM-48 type zeolite crystals were obtained by suction filtration and washing solid matter on the filter paper with ion exchange water.

<Manufacture of ion exchange ZSM-48>
Except for using ZSM-48 containing the organic template obtained above instead of ZSM-22 containing the organic template, the same operation as the ion exchange of ZSM-22 of the hydroisomerization catalyst A was performed, Ion exchanged NH ₄ type ZSM-48 was obtained.

<Binder formulation, molding, firing>
From the ion-exchanged ZSM-48 obtained above and alumina as a binder, a molded product is obtained by the same operation as the hydroisomerization catalyst B, and thereafter 400 by the same operation as the hydroisomerization catalyst B. Firing was performed at 550 ° C. and 550 ° C. to obtain molded and fired carrier particles.

<Platinum support, firing>
In the same manner as in the hydroisomerization catalyst B, except that the molded and calcined carrier particles containing ZSM-48 obtained above were used instead of the molded and calcined carrier particles containing ZSM-22, platinum was obtained. The hydroisomerization catalyst F was obtained by carrying, drying and calcining. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Hydroisomerization catalyst G)
Except having changed the calcination temperature of a molded object from 400 degreeC to 470 degreeC, the support | carrier particle | grains shape | molded and baked were obtained by operation similar to the hydroisomerization catalyst A.

  The obtained carrier particles were loaded with platinum, dried and calcined in the same manner as in the hydroisomerization catalyst A to obtain a hydroisomerization catalyst G. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Hydroisomerization catalyst H)
Powdered ZSM-22 containing an organic template obtained by synthesis in the same manner as hydroisomerization catalyst A was calcined at 550 ° C. for 6 hours under air flow.

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

A molded body was obtained from the NH ₄ type ZSM-22 obtained above and alumina as a binder by the same operation as the hydroisomerization catalyst A. Then, the hydroisomerization catalyst H was obtained by drying, firing, platinum support, and firing by the same operation as the hydroisomerization catalyst A. The crushing strength of the obtained catalyst particles was 12.0 N / mm.

(Hydroisomerization catalyst I)
Powdered ZSM-22 containing an organic template obtained by synthesis in the same manner as in the hydroisomerization catalyst A was calcined and ion exchanged in the same manner as in the hydroisomerization catalyst H.

A molded body was obtained from the NH ₄ type ZSM-22 obtained above and alumina as a binder by the same operation as the hydroisomerization catalyst A. The obtained molded body was calcined at 470 ° C. for 3 times under air flow, and then supported with platinum and calcined in the same manner as in the hydroisomerization catalyst A to obtain a hydroisomerization catalyst I. . The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Hydroisomerization catalyst J)
The hydroisomerization is carried out in the same manner as in the hydroisomerization catalyst E except that the temperature of the first stage for firing the molded body obtained from the ion exchange ZSM-23 and alumina is changed to 400 ° C. and 470 ° C. Catalyst J was obtained. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Hydroisomerization catalyst K)
The hydroisomerization is carried out in the same manner as in the hydroisomerization catalyst F except that the temperature of the first stage for firing the molded body obtained from the ion exchange ZSM-48 and alumina is changed to 400 ° C. and 470 ° C. The catalyst K was obtained. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

[Production of hydrotreating catalyst]
A commercially available amorphous silica / alumina support was extruded into a 1/16 cylinder, and this was calcined at 550 ° C. for 3 hours under air flow to obtain a catalyst support. The resulting support was impregnated with 0.2% by mass and 0.3% by mass of platinum and palladium as active metals, respectively, and calcined at 550 ° C. for 3 hours under air flow to obtain a hydrotreating catalyst. .

<Manufacture of lubricating base oil>
Example 1
<Preparation of raw oil>
As the feedstock, general vacuum gas oil obtained from Middle Eastern crude oil was used. The boiling point range of the vacuum gas oil was 343 ° C. to 550 ° C., and the sulfur content and the nitrogen content were 2.41% by mass and 0.2% by mass, respectively.

<Hydrolysis of feedstock>
The hydrocracking reaction of the raw material oil was performed under the following conditions. A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm is filled with 200 ml of the hydrocracking catalyst prepared above, and the catalyst layer is catalyzed by the raw material oil for 24 hours under an average catalyst layer temperature of 300 ° C. under hydrogen flow (hydrogen partial pressure of 10 MPa). Sulfurization was performed. Thereafter, the reaction temperature was raised to 385 ° C. and maintained at LHSV 0.3 h ⁻¹ and a hydrogen / oil ratio of 5000 scfb to carry out hydrocracking reaction of vacuum gas oil. When the obtained hydrocracked oil was distilled, the yield (cracking rate) of the fraction below 343 ° C. was 57% by mass, and the yield of the lubricating oil fraction at 343 ° C. or higher was 43% by mass. .

<Hydroisomerization of hydrocracked oil>
A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was filled with 200 ml of the catalyst A obtained above, and reduction treatment was performed for 12 hours under an average catalyst layer temperature of 350 ° C. and hydrogen flow (5 MPa). Thereafter, hydrocracked oil having a boiling point of 343 ° C. or higher obtained as a raw material oil was passed through under the conditions of a reaction temperature of 320 ° C., a hydrogen partial pressure of 3 MPa, LHSV2h ⁻¹ , and a hydrogen / oil ratio of 3000 scfb for hydroisomerization. . The resulting dewaxed oil A had a normal paraffin concentration of less than 0.01% by mass.

<Hydrofinishing of dewaxed oil>
A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was filled with 200 ml of the hydrorefined catalyst obtained above, and subjected to a reduction treatment for 12 hours under an average catalyst layer temperature of 350 ° C. and flowing hydrogen (5 MPa). Thereafter, the dewaxed oil A after the hydroisomerization treatment as a raw material oil was passed through under the conditions of a reaction temperature of 320 ° C., a hydrogen partial pressure of 5 MPa, LHSV2h ⁻¹ , and a hydrogen / oil ratio of 3000 scfb for hydrorefining. The yield of the hydrorefined oil A with respect to the obtained dewaxed oil A was 99% by mass or more, the Saybolt color was +30 or more, the sulfur content was 0.1 mass ppm, and the nitrogen content was 0.1 mass ppm. It was.

<Distillation of hydrorefined oil>
The hydrorefined oil A obtained by hydrofinishing is further distilled under reduced pressure, in a 70-pale fraction having a boiling point of 343 to 390 ° C., an SAE-10 fraction having a boiling point of 390 to 440 ° C., and a boiling point of 440 to 400 equivalent in terms of atmospheric distillation. By subjecting a SAE-20 fraction at 510 ° C. and a SAE-30 fraction having a boiling point of 510 ° C. or higher to a fraction, a lubricant base oil equivalent to 70 pail, a lubricant base oil equivalent to SAE-10, and a SAE-20 equivalent The lubricating base oil (SAE-30) and the lubricating base oil (bottom oil) corresponding to SAE-30 were obtained.

  The yields of the obtained lubricant base oil equivalent to 70 Pale, lubricant base oil equivalent to SAE-10, lubricant base oil equivalent to SAE-20 and lubricant base oil equivalent to SAE-30 were 14.4 respectively. They were mass%, 38.2 mass%, 33.0 mass%, and 8.5 mass%. Further, the viscosity index, pour point, sulfur content, and nitrogen content of a lubricating base oil equivalent to 70 pail are equivalent to 108, -27.5 ° C, 0.1 mass ppm, 0.1 mass ppm, and SAE-10, respectively. The viscosity index, pour point, sulfur content, and nitrogen content of the lubricating base oil are 122, -17.5 ° C, 0.2 mass ppm, 0.2 mass ppm, and the viscosity of the lubricating base oil corresponding to SAE-20, respectively. Index, pour point, sulfur content, nitrogen content are 130, -12.5 ° C, 0.2 mass ppm, 0.2 mass ppm, viscosity index of lubricating base oil corresponding to SAE-30, pour point, sulfur, respectively. The minute and nitrogen contents were 129, -12.5 ° C, 0.3 mass ppm, and 0.5 mass ppm, respectively.

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

(Example 2)
A dewaxed oil B was obtained by hydroisomerizing the hydrocracked oil at 343 ° C. or higher in the same manner as in Example 1 except that the reaction tube was filled with the catalyst B instead of the catalyst A. The resulting dewaxed oil B had a normal paraffin concentration of less than 0.01% by 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 hydroisomerizing a hydrocracked oil at 343 ° C. or higher in the same manner as in Example 1 except that the reaction tube was filled with the catalyst C instead of the catalyst A. The resulting dewaxed oil C had a normal paraffin concentration of less than 0.01% by 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 hydroisomerizing the hydrocracked oil at 343 ° C. or higher in the same manner as in Example 1 except that the reaction tube was filled with the catalyst D instead of the catalyst A. The resulting dewaxed oil D had a normal paraffin concentration of less than 0.01% by 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 hydroisomerizing the hydrocracked oil at 343 ° C. or higher in the same manner as in Example 1 except that the reaction tube was filled with the catalyst E instead of the catalyst A. The dewaxed oil E obtained had a normal paraffin concentration of less than 0.01% by mass.

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

(Example 6)
The dewaxed oil F was obtained by hydroisomerizing the hydrocracked oil at 343 ° C. or higher in the same manner as in Example 1 except that the reaction tube was filled with the catalyst F instead of the catalyst A. The resulting dewaxed oil F had a normal paraffin concentration of less than 0.01% by 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 hydroisomerizing the hydrocracked oil at 343 ° C. or higher in the same manner as in Example 1 except that the reaction tube was filled with the catalyst G instead of the catalyst A. The resulting dewaxed oil G had a normal paraffin concentration of less than 0.01% by mass.

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

(Comparative Example 2)
The dewaxed oil H was obtained by hydroisomerizing the hydrocracked oil at 343 ° C. or higher in the same manner as in Example 1 except that the reaction tube was filled with the catalyst H instead of the catalyst A. The obtained dewaxed oil H had a normal paraffin concentration of less than 0.01% by mass.

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

(Comparative Example 3)
The dewaxed oil I was obtained by hydroisomerizing the hydrocracked oil at 343 ° C. or higher in the same manner as in Example 1 except that the catalyst I was charged in the reaction tube instead of the catalyst A. The resulting dewaxed oil I had a normal paraffin concentration of less than 0.01% by mass.

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

(Comparative Example 4)
The dewaxed oil J was obtained by hydroisomerizing the hydrocracked oil at 343 ° C. or higher in the same manner as in Example 1 except that the catalyst J was filled in the reaction tube instead of the catalyst A. The resulting dewaxed oil J had a normal paraffin concentration of less than 0.01% by 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 hydroisomerizing the hydrocracked oil at 343 ° C. or higher in the same manner as in Example 1 except that the reaction tube was filled with the catalyst K instead of the catalyst A. The obtained dewaxed oil K had a normal paraffin concentration of less than 0.01% by mass.

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

  When the hydroisomerization catalysts A to F satisfying the predetermined conditions according to the present application are used, the lubricating oil satisfying the Group III standard as compared with the case of using the hydroisomerization catalysts G to K not satisfying the predetermined conditions It can be seen that a base oil (lubricating base oil equivalent to 70 pail, lubricating base oil equivalent to SAE-10, lubricating base oil equivalent to SAE-20, lubricating base oil equivalent to SAE-30) can be obtained efficiently. It was.

(Example 7)
<Preparation of raw oil>
As the feedstock, general vacuum gas oil obtained from Middle Eastern crude oil was used. The boiling point range of the vacuum gas oil was 343 ° C. to 550 ° C., and the sulfur content and the nitrogen content were 2.41% by mass and 0.2% by mass, respectively.

<Hydrolysis of feedstock>
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 is filled with 200 ml of the hydrocracking catalyst prepared above, and the catalyst layer is catalyzed by the raw material oil for 24 hours under an average catalyst layer temperature of 300 ° C. under hydrogen flow (hydrogen partial pressure of 10 MPa). Sulfurization was performed. Thereafter, the reaction temperature was raised to 385 ° C. and maintained at LHSV 0.3 h ⁻¹ and a hydrogen / oil ratio of 5000 scfb to carry out hydrocracking reaction of vacuum gas oil. When the obtained hydrocracked oil was distilled, the yield (cracking rate) of the fraction below 343 ° C. was 57% by mass, and the yield of the lubricating oil fraction at 343 ° C. or higher was 43% by mass. . Furthermore, when a lubricating oil fraction at 343 ° C. or higher was distilled under reduced pressure, a 70-pale fraction (boiling point 343 to 390 ° C. in terms of atmospheric distillation), an SAE-10 fraction (boiling point 390 to 440 ° C. in terms of atmospheric distillation), The yields of the SAE-20 fraction (boiling point 440 to 510 ° C. in terms of atmospheric distillation) and the SAE-30 fraction (boiling point 510 ° C. or more in terms of atmospheric distillation) are 15% by mass, 40% by mass, and 35%, respectively. The mass was 10% by mass.

<Hydroisomerization of hydrocracked oil>
A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was filled with 200 ml of the catalyst A obtained above, and reduction treatment was performed for 12 hours under an average catalyst layer temperature of 350 ° C. and hydrogen flow (5 MPa). Thereafter, each of the 70 pale, SAE-10, SAE-20, and SAE-30 fractions obtained above as raw material oils was reacted at a reaction temperature of 320 ° C., a hydrogen partial pressure of 3 MPa, LHSV2h ⁻¹ , and a hydrogen / oil ratio of 3000 scfb. Under conditions, the oil was passed through and hydroisomerized. The yields of dewaxed oil obtained for each fraction were 96.1% by mass, 95.5% by mass, 94.2% by mass, 90% for 70 Pale, SAE-10, SAE-20, and SAE-30, respectively. It was 0.0 mass%. Moreover, each viscosity index, pour point, sulfur content, and nitrogen content are 108, −27.5 ° C., 0.1 mass ppm, 0.1 mass ppm at 70 pail, 122, −17.5 at SAE-10. C, 0.2 mass ppm, 0.2 mass ppm, 130 for SAE-20, -12.5 ° C, 0.2 mass ppm, 0.2 mass ppm, 128 for SAE-30, -12.5 ° C, They were 0.3 mass ppm and 0.3 mass ppm.

<Hydrofinishing of dewaxed oil>
A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was filled with 200 ml of the hydrorefined catalyst obtained above, and subjected to a reduction treatment for 12 hours under an average catalyst layer temperature of 350 ° C. and flowing hydrogen (5 MPa). Thereafter, each of the 70 pail, SAE-10, SAE-20, and SAE-30 fractions after the hydroisomerization treatment as a raw oil was reacted at a reaction temperature of 320 ° C., a hydrogen partial pressure of 5 MPa, LHSV2h ⁻¹ , and a hydrogen / oil ratio. The oil was passed through under conditions of 3000 scfb for hydrorefining. The yield of the hydrorefined oil obtained for each fraction was 99% by volume or more, and the Saybolt color was +30 or more.

(Example 8)
<Preparation of raw oil>
As the feedstock, general vacuum gas oil obtained from Middle Eastern crude oil was used. The boiling point range of the vacuum gas oil was 343 ° C. to 550 ° C., and the sulfur content and the nitrogen content were 2.41% by mass and 0.2% by mass, respectively.

<Hydrolysis of feedstock>
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 is filled with 200 ml of the hydrocracking catalyst prepared above, and the catalyst layer is catalyzed by the raw material oil for 24 hours under an average catalyst layer temperature of 300 ° C. under hydrogen flow (hydrogen partial pressure of 10 MPa). Sulfurization was performed. Thereafter, the reaction temperature was raised to 385 ° C. and maintained at LHSV 0.3 h ⁻¹ and a hydrogen / oil ratio of 5000 scfb to carry out hydrocracking reaction of vacuum gas oil. When the obtained hydrocracked oil was distilled, the yield (cracking rate) of the fraction below 343 ° C. was 57% by mass, and the yield of the lubricating oil fraction at 343 ° C. or higher was 43% by mass. .

<Hydroisomerization of hydrocracked oil>
A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was filled with 200 ml of the catalyst A obtained above, and reduction treatment was performed for 12 hours under an average catalyst layer temperature of 350 ° C. and hydrogen flow (5 MPa). Thereafter, the hydrocracked oil of 343 ° C. or higher obtained as a raw material oil was passed through under the 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 scfb for hydroisomerization. The resulting dewaxed oil A had a normal paraffin concentration of less than 0.01% by mass.

<Distillation of dewaxed oil>
The dewaxed oil A thus obtained was distilled under reduced pressure, in a 70-pale fraction having a boiling point of 343 to 390 ° C., an SAE-10 fraction having a boiling point of 390 to 440 ° C., and an SAE-20 fraction having a boiling point of 440 to 510 ° C. in terms of atmospheric distillation. And a SAE-30 fraction having a boiling point of 510 ° C. or higher are each fractionated to obtain a lubricating base oil equivalent to 70 Pale, a lubricating base oil equivalent to SAE-10, a lubricating base oil equivalent to SAE-20, SAE, A lubricating base oil (bottom oil) corresponding to −30 was obtained.

  The yields of the obtained lubricant base oil equivalent to 70 pail, lubricant base oil equivalent to SAE-10, lubricant base oil equivalent to SAE-20 and lubricant base oil equivalent to SAE-30 were 15% by mass, respectively. , 40% by mass, 35% by mass, and 10% by mass. Further, the viscosity index, pour point, sulfur content, and nitrogen content of a lubricating base oil equivalent to 70 pail are equivalent to 108, -27.5 ° C, 0.1 mass ppm, 0.1 mass ppm, and SAE-10, respectively. The viscosity index, pour point, sulfur content, and nitrogen content of the lubricating base oil are 122, -17.5 ° C, 0.2 mass ppm, 0.2 mass ppm, and the viscosity of the lubricating base oil corresponding to SAE-20, respectively. Index, pour point, sulfur content, nitrogen content are 130, -12.5 ° C, 0.2 mass ppm, 0.2 mass ppm, viscosity index of lubricating base oil corresponding to SAE-30, pour point, sulfur, respectively. And nitrogen content were 128, -12.5 ° C, 0.3 mass ppm, and 0.3 mass ppm, respectively.

<Hydrofinishing of dewaxed oil>
A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm was filled with 200 ml of the hydrorefined catalyst obtained above, and subjected to a reduction treatment for 12 hours under an average catalyst layer temperature of 350 ° C. and flowing hydrogen (5 MPa). Thereafter, a lubricating base oil equivalent to 70 pail, a lubricating base oil equivalent to SAE-10, a lubricating base oil equivalent to SAE-20, a SAE- Each of the 30 base oils was subjected to hydrorefining under conditions of a reaction temperature of 320 ° C., a hydrogen partial pressure of 5 MPa, LHSV2h ⁻¹ , and a hydrogen / oil ratio of 3000 scfb. The yield of hydrorefined oil of each obtained lubricating base oil was 99% by volume or more, and the Saybolt color was +30 or more.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the lubricating base oil which can obtain efficiently the lubricating base oil which satisfy | fills API group III specification from petroleum-type raw material oil, and the lubricating base oil obtained by it are provided. be able to.

DESCRIPTION OF SYMBOLS 10 ... Reaction tower, 20 ... Distillation tower, 30 ... Reaction tower, 40 ... Reaction tower, 50 ... Distillation tower, 100, 110, 120 ... Lubricating oil base oil manufacturing apparatus.

Claims (11)

Hydrocracked oil obtained by hydrocracking a feedstock containing at least one selected from the group consisting of vacuum gas oil, atmospheric residue and vacuum residue, hydroisomerization catalyst in the presence of molecular hydrogen Obtaining a dewaxed oil by contacting with
Hydrofinishing the dewaxed oil to obtain a hydrorefined oil;
Distilling the hydrorefined oil to obtain a lubricating oil fraction;
With
The hydroisomerization catalyst,
The support is a molded body fired by receiving a thermal history including heating at 350 ° C. or higher, and is selected from the group consisting of a metal belonging to Groups 8 to 10 of the periodic table, molybdenum and tungsten supported on the support. Containing at least one metal,
The carrier is
(A) An ion exchange zeolite obtained by ion exchange of 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 is 350 ° C. A calcined zeolite that is calcined by receiving a heat history including the above heating, and
(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 a combination of two or more thereof, A calcined inorganic oxide that is calcined by receiving a thermal history including heating at 350 ° C. or higher,
Including
The thermal history received by the calcined zeolite includes that the ion-exchanged zeolite not heated at 350 ° C. or higher is calcined by heating within a range of 350 ° C. to 450 ° C. A method for producing a lubricating base oil. A step of distilling a hydrocracked oil obtained by hydrocracking a feedstock containing at least one selected from the group consisting of a vacuum gas oil, an atmospheric residue and a 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 a dewaxed oil;
Hydrofinishing the dewaxed oil;
With
The hydroisomerization catalyst,
The support is a molded body fired by receiving a thermal history including heating at 350 ° C. or higher, and is selected from the group consisting of a metal belonging to Groups 8 to 10 of the periodic table, molybdenum and tungsten supported on the support. Containing at least one metal,
The carrier is
(A) An ion exchange zeolite obtained by ion exchange of 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 is 350 ° C. A calcined zeolite that is calcined by receiving a heat history including the above heating, and
(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 a combination of two or more thereof, A calcined inorganic oxide that is calcined by receiving a thermal history including heating at 350 ° C. or higher,
Including
The thermal history received by the calcined zeolite includes that the ion-exchanged zeolite not heated at 350 ° C. or higher is calcined by heating within a range of 350 ° C. to 450 ° C. A method for producing a lubricating base oil. Hydrocracked oil obtained by hydrocracking a feedstock containing at least one selected from the group consisting of vacuum gas oil, atmospheric residue and vacuum residue, hydroisomerization catalyst in the presence of molecular hydrogen Obtaining a dewaxed oil by contacting with
Distilling the dewaxed oil to obtain a lubricating oil fraction;
Hydrofinishing the lubricating oil fraction;
With
The hydroisomerization catalyst,
The support is a molded body fired by receiving a thermal history including heating at 350 ° C. or higher, and is selected from the group consisting of a metal belonging to Groups 8 to 10 of the periodic table, molybdenum and tungsten supported on the support. Containing at least one metal,
The carrier is
(A) An ion exchange zeolite obtained by ion exchange of 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 is 350 ° C. A calcined zeolite that is calcined by receiving a heat history including the above heating, and
(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 a combination of two or more thereof, A calcined inorganic oxide that is calcined by receiving a thermal history including heating at 350 ° C. or higher,
Including
The thermal history received by the calcined zeolite includes that the ion-exchanged zeolite not heated at 350 ° C. or higher is calcined by heating within a range of 350 ° C. to 450 ° C. A method for producing a lubricating base oil.   4. The organic template-containing zeolite is at least one selected from the group consisting of ZSM-22, ZSM-23, and ZSM-48 type zeolites. 5. A method for producing a lubricating base oil.   The method for producing a lubricating base oil according to any one of claims 1 to 4, wherein the inorganic oxide is alumina.   The lubrication according to any one of claims 1 to 5, wherein the carrier is a molded body fired by receiving a thermal history including heating in a range of more than 450 ° C and not more than 650 ° C. A method for producing an oil base oil.   The method for producing a lubricating base oil according to any one of claims 1 to 6, wherein the metal supported on the carrier is platinum and / or palladium.   The molar ratio ([Si] / [Al]) between silicon atoms and aluminum atoms in the organic template-containing zeolite is 10 to 400, according to any one of claims 1 to 7, A method for producing a lubricating base oil. The hydroisomerization catalyst,
A first step of obtaining an ion exchange zeolite by ion exchange of 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-exchanged zeolite and a composite oxide consisting of alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide, and combinations of two or more thereof. A second step of obtaining a molded body by molding a composition comprising
A third step of calcining the molded body by heating at least within a range of 350 ° C. 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 belonging to Groups 8 to 10 of the periodic table, molybdenum and tungsten;
It is obtained by the manufacturing method of a hydroisomerization catalyst provided with this. The manufacturing method of the lubricating base oil as described in any one of Claims 1-3 characterized by the above-mentioned.   The third step is a step of obtaining the carrier by firing the molded body within a range of 350 ° C. to 450 ° C. and then heating it within a range of 450 ° C. to 650 ° C. The method for producing a lubricating base oil according to claim 9.   The sulfur content obtained by the method for producing a lubricating base oil according to any one of claims 1 to 10 is 0.03% by mass or less, and the viscosity index is 120 or more. Lubricating base oil.

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