JP2011068728A - Production method for hydrocarbon oil and lubricant base oil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for obtaining a hydrocarbon oil suitable for a fuel oil base oil and/or a lubricant base oil, particularly a high-quality lubricant base oil from a raw material hydrocarbon oil containing a normal paraffin stably and with a high yield. <P>SOLUTION: This production method for a hydrocarbon oil is for producing a hydrocarbon oil by contacting a raw material oil containing a 10 or more C normal paraffin with a hydrogenation-isomerization catalyst containing: a carrier which is a molded form containing as a catalyst active ingredient, crystalline aluminosilicate having a mono-dimensional 10-membered ring structure in which the center (L) of the length in a longitudinal direction of a needle crystal is in a range of 100 to 200 nm and the ratio L/D which is a ratio of the crystal length (L) relative to the crystal diameter (D) is in a range of 1.5 to 4.4; a metal supported on the carrier and selected from metals of Groups VIII to X in the Periodical Table, Mo, and W; and a baked inorganic oxide, in the presence of molecular hydrogen to convert a part of or the whole of the normal paraffine to an isoparaffin. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a hydrocarbon 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 the desired isoparaffin fraction from the hydrocarbon oil containing the wax component in the field of production of fuel base oil and lubricating base oil, in order to obtain the desired isoparaffin fraction in a high yield, the cracking activity against hydrocarbons and the enhanced There is a need for hydroisomerization catalysts having 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 bringing a linear or slightly branched hydrocarbon raw material having a carbon number of 10 or more into contact 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 451, “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 451, 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.", 2006, Vol. 239, p. 451

Even in the production process described in Patent Document 1, the isomerization selectivity of the catalyst cannot be said to be sufficient, and the cracking activity is not sufficiently suppressed, so that a desired hydrocarbon oil containing a normal paraffin component is used. It has been difficult to obtain an isoparaffin fraction suitable for fuel base oil or lubricating base oil in high yield. In particular, in the production of a high-quality lubricating oil base oil, it is necessary to increase its conversion rate to a level substantially free of normal paraffin, and in that case, normal paraffin and / or isoparaffin, which is an isomerized product, is required. The decomposition reaction became active, and the desired isoparaffin fraction could not be obtained in an economical yield.
In addition, in order to produce isoparaffin with economic rationality, it is necessary that the hydroisomerization catalyst has not only excellent isomerization selectivity but also mechanical strength that can withstand commercial use. It is.

  The present invention has been made in view of the above circumstances, and is suitable for a fuel base oil and / or a lubricating base oil, particularly a high quality lubricating base oil, from a raw material hydrocarbon oil containing normal paraffins. A hydroisomerization catalyst excellent in isomerization selectivity and mechanical strength, a method for producing the hydroisomerization catalyst, and a hydroisomerization catalyst capable of stably obtaining an oil in a high yield It is an object of the present invention to provide a method for producing a hydrocarbon oil suitable for a fuel base oil from a raw material hydrocarbon oil containing normal paraffin to be used, and a method for producing a lubricating base oil using the hydroisomerization catalyst.

  Examples of fuel base oils include middle distillates such as light oil and jet fuel. Under low temperature use, isomerization can be performed to increase the proportion of isoparaffin, lower the pour point, etc., and improve low temperature performance. It has been demanded.

  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 a high viscosity index base oil using a hydrocracking process to reduce sulfur content and aromatic hydrocarbon components. Recently, it has been demanded to further increase the productivity of such base oil.

The inventors of the present invention have completed the present invention as a result of intensive studies to solve the above problems.
That is, the present invention is a method in which a raw oil containing a normal paraffin having 10 or more carbon atoms is contacted with a hydroisomerization catalyst in the presence of molecular hydrogen to convert part or all of the normal paraffin into isoparaffin. A method for producing hydrogen oil, wherein the hydroisomerization catalyst comprises a crystalline aluminosilicate having a one-dimensional 10-membered ring structure obtained through a step of synthesis, calcination, and then ion exchange, the crystalline aluminosilicate A linear alkyldiamine having an alkyl chain length (Cn) of 7 to 9 is used as a template used for the synthesis of the needle, and the center (L) of the long axis direction length of the needle-like crystal is in the range of 100 nm to 300 nm, and The ratio of length (L) to crystal diameter (D) is a crystalline aluminosilicate having an L / D ratio in the range of 1.5 to 4.4 as a catalytically active component. A carrier that is a molded body, and at least one metal selected from the group consisting of a metal belonging to Groups 8 to 10 of the periodic table, molybdenum and tungsten, which is supported on the carrier, and the carrier includes alumina, A calcined inorganic oxide obtained by calcining at least one inorganic oxide selected from silica, titania, boria, zirconia, magnesia, ceria, zinc oxide, and phosphorous oxide in response to a thermal history including heating at 500 ° C. or higher. The present invention provides a method for producing a hydrocarbon oil.
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 method for producing a hydrocarbon oil of the present invention, a carrier comprising a specific crystalline aluminosilicate (also referred to as a zeolite) and a specific inorganic oxide, and a specific active metal supported on the carrier are contained. Since the hydroisomerization catalyst according to the present invention has sufficient mechanical strength and high isomerization selectivity, the hydrocarbon oil having an increased isomerization rate from the above-mentioned raw material oil can be efficiently used. Can be obtained.

  The present invention is also directed to the above hydrocarbon oil production method, wherein the above-mentioned raw material oil is hydrotreated and / or hydrocracked straight-run middle distillate and vacuum gas oil, slack wax, dewaxed oil, paraffin. Provided is a method for producing a hydrocarbon oil, which is at least one selected from the group consisting of wax, microcrystalline wax, petrolatum, and Fischer-Tropsch synthetic oil.

  The present invention also provides the method for producing a hydrocarbon oil, wherein the crystalline aluminosilicate having a one-dimensional 10-membered ring structure is selected from the group consisting of ZSM-22, ZSM-23, and ZSM-48 type zeolite. Provided is a method for producing a hydrocarbon oil characterized by being a seed.

The present invention also provides a method for producing a hydrocarbon oil, wherein the inorganic oxide is alumina in the method for producing a hydrocarbon oil.

  The present invention also provides a method for producing a hydrocarbon oil, characterized in that, in the method for producing a hydrocarbon oil, the metal supported on the carrier is platinum and / or palladium.

  The present invention also provides the hydrocarbon oil, wherein the molar ratio of silicon atoms to aluminum atoms ([Si] / [Al]) in the crystalline aluminosilicate is 10 to 400. An oil production method is provided.

  The present invention also includes a step of obtaining a dewaxed oil by contacting a feedstock containing normal paraffin having 10 or more carbon atoms with a hydroisomerization catalyst in the presence of molecular hydrogen, and hydrofinishing the dewaxed oil. A process for obtaining a hydrorefined oil, and a process for distilling the hydrorefined oil to obtain a lubricating oil fraction, wherein the hydroisomerization catalyst comprises: It includes a crystalline aluminosilicate having a one-dimensional 10-membered ring structure obtained through synthesis, baking, and then ion exchange, and an alkyl chain length (Cn) of 7 to 9 as a template used for the synthesis of the crystalline aluminosilicate. The ratio L / D ratio of the length (L) to the crystal diameter (D) using a certain linear alkyldiamine, the center (L) of the length in the major axis direction of the needle crystal is in the range of 100 nm to 300 nm 1.5-4 The support is a molded body containing a crystalline aluminosilicate as a catalytically active component in the range of 4 and selected from the group consisting of metals, molybdenum and tungsten supported on the support and belonging to Groups 8 to 10 of the periodic table And at least one inorganic oxide selected from alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide is heated at 500 ° C. or higher. A method for producing a lubricating base oil characterized by comprising a calcined inorganic oxide that is calcined in response to a thermal history including

  According to the method for producing a lubricating base oil of the present invention, the present invention comprises the carrier comprising a specific crystalline aluminosilicate and a specific inorganic oxide, and the specific active metal supported on the carrier. Since the hydroisomerization catalyst according to the present invention has sufficient mechanical strength and high isomerization selectivity, the lubricating oil base has an increased isomerization rate from the above-mentioned raw material oil and has suppressed undesirable decomposition reactions. It becomes possible to obtain oil efficiently.

  The present invention also provides the method for producing a lubricating base oil according to the present invention, wherein the above-mentioned raw material oil is slack wax, deoiled wax, paraffin wax, microcrystalline wax, petrolatum, Fischer-Tropsch synthetic wax, and hydrocracked vacuum gas oil. Provided is a method for producing a lubricating base oil, which is at least one selected from the group consisting of oils.

［式（Ｉ）中、Ｃｎは、接触前の原料油中に含まれる炭素数１０以上のノルマルパラフィンのうちで最小の炭素数を示す。］ In the method for producing a lubricating base oil according to the present invention, a feedstock containing a normal paraffin having 10 or more carbon atoms and a hydroisomerization catalyst in the presence of hydrogen are defined by the following formula (I): A process for producing a lubricating base oil, comprising the step of bringing the normal paraffin into contact at a conversion rate of 95% by mass or more is provided.

[In formula (I), Cn represents the minimum carbon number among normal paraffins having 10 or more carbon atoms contained in the raw material oil before contact. ]

  The present invention also provides the method for producing a lubricating base oil, wherein the crystalline aluminosilicate having a one-dimensional 10-membered ring structure is selected from the group consisting of ZSM-22, ZSM-23, and ZSM-48 type zeolite. Provided is a method for producing a lubricating base oil, which is one type.

The present invention also provides the method for producing a lubricating base oil, wherein the inorganic oxide is alumina.

  The present invention also provides the method for producing a lubricating base oil, wherein the metal supported on the carrier is platinum or / and palladium.

  The present invention also provides the lubricating base oil, wherein the molar ratio ([Si] / [Al]) of silicon atoms to aluminum atoms in the crystalline aluminosilicate is 10 to 400. A method for producing an oil base oil is provided.

  According to the present invention, using a hydroisomerization catalyst having excellent hydroisomerization selectivity and mechanical strength, it is suitable for a fuel base oil and / or a lubricating base oil from a raw hydrocarbon oil containing normal paraffin. A method for producing a hydrocarbon oil suitable for a fuel base oil from a raw material hydrocarbon oil containing normal paraffin, and a raw material hydrocarbon containing normal paraffin, which can stably obtain a high yield of hydrocarbon oil A method for producing a lubricating base oil that makes it possible to obtain a high-performance lubricating base oil from oil in a high yield can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

  The hydroisomerization catalyst according to the present invention is characterized by being produced by a specific method. Hereinafter, the hydroisomerization catalyst of this invention is demonstrated along the aspect of the preferable manufacture.

The crystalline aluminosilicate (zeolite) constituting the hydroisomerization catalyst according to the present invention has a high level of both high isomerization activity and suppressed decomposition activity in the hydroisomerization reaction of normal paraffin, Those having a one-dimensional pore structure consisting of 10-membered rings (crystalline aluminosilicate having a one-dimensional 10-membered ring structure) are preferred. Examples of such zeolite include AEL, EUO, FER, HEU, MEL, MFI, NES, TON, MTT, WEI, and ^* MRE. 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 above-mentioned 10-membered ring one-dimensional pore structure, the zeolite includes TON, zeolite having an MTT structure, and ^* MRE structure in terms of high isomerization activity and low decomposition activity. preferable. More preferably ZSM-22 zeolite is a zeolite having a TON structure, and is preferably ZSM-23 zeolite is a zeolite having a MTT ^structure, * as the zeolites having an MRE structure ZSM-48 type zeolite are preferred.

The crystalline aluminosilicate constituting the hydroisomerization catalyst according to the present invention is hydrothermally synthesized by a known method from a silica source, an alumina source, and a template added to construct the predetermined pore structure.
The template used for the synthesis of the crystalline aluminosilicate is a linear alkyldiamine having an alkyl chain length (Cn) of 7 to 9. Examples of such linear alkyldiamine include 1,7-diaminoheptane, 1,8-diaminooctane, and 1,9-diaminononane.

The crystalline aluminosilicate having a one-dimensional 10-membered ring structure is such that the center (L) of the length in the major axis direction of the acicular crystal is in the range of 100 nm to 300 nm, preferably in the range of 120 nm to 280 nm. Ratio of the center (L) of the length in the major axis direction of the needle crystal to the diameter (D): L / D ratio is in the range of 1.5 to 4.4, preferably in the range of 1.8 to 4.2. It is.
The lower limit of the center (L) of the long axis direction length of the acicular crystal is 100 nm or more in terms of stability of the crystal structure, preferably 120 nm, and the upper limit of L is 300 nm in terms of improvement of isomerization selectivity. It is below, and 280 nm or less is preferable.
The crystal diameter (D) is not particularly limited, but is preferably 50 nm or more from the viewpoint of increasing the active site.

Ratio of the center (L) of the long axis direction length of the needle crystal to the crystal diameter (D): The lower limit value of the L / D ratio is 1.5 or more in terms of stability of the crystal structure, and 1.8 or more The upper limit is 4.4 or less in terms of improving the catalyst activity, and preferably 4.2 or less.
Here, the center (L) of the length in the major axis direction of the acicular crystal means the median value (nm) of the particle size distribution obtained from the SEM (scanning electron microscope) image of the crystal, and the crystal diameter (D ) Means the median value (nm) of crystal diameters determined by the same method as in (L) above.

  The molar ratio ([Si] / [Al]) of silicon atoms and aluminum atoms constituting the crystalline aluminosilicate having a one-dimensional 10-membered ring structure (hereinafter referred to as “Si / Al ratio”) is 10 to 400. It is preferable that it is, 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 synthesized and then calcined crystalline aluminosilicate (calcined zeolite) usually has an alkali metal cation as a counter cation. The firing is performed to remove the template in the hydrothermally synthesized crystalline aluminosilicate, and the firing temperature is preferably 500 to 600 ° C, more preferably 530 to 580 ° C.
The calcined 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 zeolite is exchanged for ammonium ions and / or protons.

  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. The ion-exchanged zeolite obtained by ion-exchange of the calcined zeolite in the presence of ammonium ions (here, ammonium-type zeolite) releases ammonia during subsequent calcining, and the counter cation becomes a proton to produce Bronsted acid. It becomes a 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 amount of counter cation contained in the zeolite used.

The ion exchange treatment may be performed on the powdered calcined zeolite alone, and prior to the ion exchange treatment, the calcined zeolite is blended with an inorganic oxide as a binder, molded, and the resulting molded product is obtained. You may do it for.
The ion exchange treatment is preferably performed by a conventional method, that is, a method in which the calcined zeolite 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.

Further, from the viewpoint of increasing the efficiency of ion exchange, it is preferable to exchange the solution with a new one more than twice, and more preferably to exchange the solution twice with a new one during the ion exchange of the calcined zeolite with the solution. When the solution is exchanged once, for example, the calcined zeolite is immersed in a solution containing ammonium ions and / or protons, and this is heated and refluxed for 24 hours, and then the solution is exchanged for a new one and then heated and refluxed for another 24 hours. As a result, the ion exchange efficiency can be increased.
By the ion exchange treatment, almost all counter cations such as alkali metals in the calcined zeolite can be exchanged for ammonium ions and / or protons.

  Next, it is preferable to mix 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, at least one inorganic oxide selected from alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide is used as the inorganic oxide. Among these, from the viewpoint of further improving the isomerization selectivity of the hydroisomerization catalyst, an inorganic oxide mainly composed of alumina containing 50% by mass or more of an alumina component is preferable.

  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 body obtained as described above is fired at a temperature of 500 to 600 ° C., preferably 500 to 580 ° C., more preferably 500 to 560 ° C. in an atmosphere containing molecular oxygen. And it is preferable to make the support | carrier baked by receiving the heat history containing the heating of 500 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 calcined zeolite, and the inorganic oxide becomes calcined inorganic oxide.

In the present embodiment, it is not preferable that the firing temperature is lower than 500 ° C. because the mechanical strength of the carrier tends not to be sufficiently improved. On the other hand, a calcination temperature exceeding 600 ° C. is not preferable because the isomerization selectivity of the resulting hydroisomerization catalyst tends not to be sufficiently improved.
As described above, the calcination may be performed in the form of a powdery zeolite alone, in addition to the molded product obtained by molding a composition in which an inorganic oxide is blended with ion-exchanged zeolite. However, in that case, a molded body obtained by molding a composition obtained by blending the obtained calcined zeolite with an inorganic oxide is at a temperature of 500 ° C. or higher for the purpose of imparting mechanical strength, for example, in the range of 500 to 600 ° C. It is necessary to perform firing at the inner temperature.

  The hydroisomerization catalyst according to the present invention is obtained by the above, on the support that is a molded body fired by receiving a thermal history including heating at 500 ° C. or higher, a metal belonging to Groups 8 to 10 of the periodic table, It is formed by supporting at least one metal of molybdenum and tungsten (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 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. In addition, when the hydroisomerization catalyst according to the present invention is used for hydroisomerization of a hydrocarbon oil containing a large amount of sulfur-containing compounds and / or nitrogen-containing compounds, from the viewpoint of sustainability of catalyst activity, A combination of nickel-cobalt, nickel-molybdenum, cobalt-molybdenum, nickel-molybdenum-cobalt, nickel-tungsten-cobalt and the like is preferable.

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 zeolite and the calcined inorganic oxide 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 zeolite and the calcined inorganic oxide constituting the support. When the hydroisomerization catalyst of 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 and the zeolite and calcined inorganic oxide.

  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. As the atmosphere containing molecular oxygen, air is preferable. 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, its oxide, or a similar species.

  As described above, in a preferred embodiment of the production of the hydroisomerization catalyst according to the present invention, “zeolite calcination”, “ion exchange”, and “molding of a composition containing an inorganic oxide”, “500 to 600 ° C. The process includes the steps of “firing the molded body by heating”, “supporting the active metal on the support”, and “firing the support carrying the active metal”.

  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, high activity for isomerization / dewaxing of hydrocarbon oil can be more reliably imparted to the catalyst.

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

  Examples of the method for producing the hydroisomerization catalyst of the present invention include those exemplified as the procedure for obtaining a preferred embodiment of the above-described hydroisomerization catalyst of the present invention.

  Below, the manufacturing method of the hydrocarbon oil of this invention and the manufacturing method of lube base oil are demonstrated.

First, the manufacturing method of hydrocarbon oil is demonstrated.
In the method for producing a hydrocarbon oil of the present invention, a feedstock oil containing a normal paraffin having 10 or more carbon atoms is brought into contact with the hydroisomerization catalyst according to the present invention in the presence of molecular hydrogen, and A step of converting a part or all into isoparaffin is provided.

  The raw material oil used in the method for producing a hydrocarbon oil of the present invention is not particularly limited as long as it contains a normal paraffin having 10 or more carbon atoms, and preferably contains a normal paraffin having 15 or more carbon atoms. It is. Specifically, from relatively light distillation fractions such as kerosene and jet fuel, all crude oil, atmospheric distillation residue, vacuum tower residue, vacuum residue, circulating oil, synthetic crude oil (for example, shale oil, Tar oil, etc.), light oil fractions (including hydrorefined gas oil fractions), vacuum gas oils, waxy oils, fuel fractions or waxes derived from FT synthetic oils, and other heavy oils A variety of high boiling point feedstocks can be mentioned. In addition to normal paraffin, these hydrocarbon oils may contain a wax component composed of a naphthenic hydrocarbon having a long-chain linear alkyl group in the side chain, or an aromatic hydrocarbon.

  Particularly preferred as the feedstock oil to be isomerized by the hydrocarbon oil production method of the present invention is a hydrocarbon oil composed of hydrocarbons having a boiling point of about 180 ° C. or more and having 10 or more carbon atoms. Lighter hydrocarbon oils usually contain substantially no wax component that affects fluidity at low temperatures, and therefore there is little need for isomerization treatment, making it difficult to achieve the effects of the present invention. .

  On the other hand, distillate feedstock containing a wax component, that is, middle distillate feedstock including light oil, kerosene and jet fuel, lube oil feedstock, heating oil, and other distillation fractions, and their flow It is particularly effective to apply the production method according to the present invention to the fraction in which the point and the viscosity need to be maintained within a predetermined range. Such hydrocarbon oils include, for example, straight-run middle distillates corresponding to hydrotreated or hydrocracked kerosene / light oil fractions, heavy gas oils and vacuum gas oils, lubricating oil raffinates, and lubricating oil raw materials. , Bright stock, slack wax (crude wax), waxy oil, deoiled wax, paraffin wax, microcrystalline wax, petrolatum, synthetic oil, Fischer-Tropsch synthetic oil, high pour point polyolefin, linear alpha olefin wax, etc. It is done. These can be used individually by 1 type or in combination of 2 or more types.

  The hydroisomerization temperature in the method for producing a hydrocarbon oil of the present invention is generally 200 to 450 ° C, preferably 220 to 400 ° C. When the reaction temperature is lower than 200 ° C., the isomerization of normal paraffin contained in the raw material oil is difficult to proceed, and the wax component tends to be insufficiently reduced and removed. On the other hand, when the reaction temperature exceeds 450 ° C., the decomposition of the raw material oil becomes remarkable, and the yield of the target product oil tends to decrease.

  The hydroisomerization pressure in the method for producing a hydrocarbon oil of the present invention is generally 0.1 to 20 MPa, preferably 0.5 to 18 MPa. When the reaction pressure is less than 0.1 MPa, the deterioration of the catalyst due to coke generation tends to be accelerated. On the other hand, when the reaction pressure exceeds 20 MPa, the cost for constructing the apparatus tends to increase, and it tends to be difficult to realize an economical process.

Liquid hourly space velocity relative to the catalyst of the feedstocks hydroisomerization reaction in the method for manufacturing a hydrocarbon oil of the present invention generally 0.01～100H ^-1, preferably 0.1~50h ^-1. When the liquid space velocity is less than 0.01 h ⁻¹ , the decomposition of the hydrocarbon oil tends to proceed excessively, and the production efficiency of the target base oil tends to decrease. On the other hand, when the liquid space velocity exceeds 100 h ⁻¹ , isomerization of normal paraffin contained in the hydrocarbon oil becomes difficult to proceed, and the reduction and removal of the wax component tend to be insufficient.

Supply ratio of hydrogen to feedstock of the hydroisomerization reaction in the method for manufacturing a hydrocarbon oil of the present invention is generally 100 to 1000 nm ³ / ^{m 3,} preferably 200~800Nm ³ / ^{m 3.} When the supply ratio is less than 100 Nm ³ / m ³ , for example, when the raw material oil contains sulfur and nitrogen compounds, desulfurization that occurs concurrently with the isomerization reaction, hydrogen sulfide generated by the denitrogenation reaction, and ammonia gas are the active metals on the catalyst. Adsorption poisoning tends to make it difficult to obtain a predetermined catalyst performance. On the other hand, when the supply ratio exceeds 1000 Nm ³ / m ³ , a hydrogen supply facility with a large capacity is required, so that it is difficult to realize an economical process.

  The conversion rate of normal paraffin in the hydroisomerization reaction in the method for producing hydrocarbon oil of the present invention is appropriately adjusted according to the intended use of the product oil.

Next, the manufacturing method of the lubricating base oil of the present invention will be described.
In the case of a method for producing a lubricating base oil, a dewaxed oil is obtained by bringing a feedstock containing normal paraffins having 10 or more carbon atoms into contact with the hydroisomerization catalyst according to the present invention in the presence of molecular hydrogen. And a step of hydrofinishing the dewaxed oil to obtain a hydrorefined oil, and a step of distilling the hydrorefined oil to obtain a lubricating oil fraction.

  Furthermore, in the step of contacting the raw oil containing normal paraffin having 10 or more carbon atoms with the hydroisomerization catalyst according to the present invention in the presence of molecular hydrogen to obtain dewaxed oil, the following formula (I): It is preferable to contact on the conditions which the conversion rate of the defined normal paraffin becomes 95 mass% or more, it is more preferable to contact on the conditions which become 98 mass% or more, and it is made to contact on the conditions which become 100 mass% substantially More preferably.

[In formula (I), Cn represents the minimum carbon number among normal paraffins having 10 or more carbon atoms contained in the raw material oil before contact. ]

  Here, “conversion is substantially 100% by mass” means that the content of normal paraffin contained in the product oil after contact is 0.1% by mass or less.

  The raw material oil used in the method for producing a lubricating base oil of the present invention is not particularly limited as long as it contains a normal paraffin having 10 or more carbon atoms, but preferably the initial boiling point of the desired lubricating base oil. It is preferable to include a hydrocarbon oil having a higher initial boiling point. As such a raw material oil, a petroleum fraction, a synthetic oil / wax, etc., whose boiling point in terms of atmospheric pressure exceeds 360 ° C., and a synthetic oil / wax are suitable. Specifically, heavy gas oil, vacuum gas oil, lubricating oil Raffinate, bright stock, slack wax (crude wax), waxy oil, deoiled wax, paraffin wax, microcrystalline wax, petrolatum, synthetic oil, Fischer-Tropsch synthetic wax, high pour point polyolefin, linear alpha olefin wax, etc. Can be mentioned. These can be used individually by 1 type or in combination of 2 or more types. Furthermore, it is preferable that these oils have been subjected to hydrotreatment or mild hydrocracking. By these treatments, substances that reduce the activity of hydroisomerization catalysts such as sulfur-containing compounds and nitrogen-containing compounds, and substances that lower the viscosity index of lubricating base oils such as aromatic hydrocarbons and naphthenic hydrocarbons It can be reduced or eliminated.

The above-mentioned relatively heavy hydrocarbon oil is used as a raw material oil, and in the presence of molecular hydrogen, by contacting with the hydroisomerization catalyst according to the present invention, isomerization of normal paraffin contained in the raw material oil, That is, the dewaxing reaction of hydrocarbon oil can proceed while sufficiently suppressing lightening. Thereby, the base oil whose boiling point of atmospheric pressure conversion exceeds 360 degreeC is 90 volume% or more can be obtained with a high yield. Further, according to the method for producing a lubricating base oil according to the present invention, a lubricating base oil containing a large number of isomers having a branched chain structure can be obtained. In particular, for a high-quality lubricating base oil, the normal paraffin content is required to be 0.1% by mass or less, but according to the method for producing a lubricating base oil according to the present invention, this requirement is required. A lubricating base oil satisfying the level can be obtained in a high yield.
The hydroisomerization reaction temperature, hydroisomerization reaction pressure, liquid space velocity, feed ratio of hydrogen and feedstock, etc. in the method for producing a lubricating base oil according to the present invention are the same as those of the hydrocarbon oil described above. It conforms to the conditions of the manufacturing method.

  In the hydroisomerization of hydrocarbon oils containing normal paraffins, the conversion of normal paraffins can usually be increased by increasing the reaction temperature, for example, and the normal paraffin content in the resulting reaction product is reduced. Therefore, the low temperature fluidity of the hydrocarbon oil can be improved. However, when the reaction temperature is increased, the cracking reaction of the hydrocarbon oil and isomerization product as raw materials is promoted, so that the light fraction increases as the conversion of normal paraffin increases. Since this increase in the light fraction causes a decrease in the viscosity index of the hydrocarbon oil, in order to keep the performance as a lubricating base oil within a predetermined range, the light fraction is separated by distillation, Need to be removed. In particular, when high-performance lubricant base oils such as Group III + according to the classification of lubricating oil grades of the American Petroleum Institute are produced by catalytic dewaxing of hydrocarbon oils, the normal paraffin conversion rate in the hydrocarbon oil that is the raw material Needs to be substantially 100%. In the conventional method for producing a lubricating base oil using a catalyst for catalytic dewaxing, the yield of the above-mentioned high performance lubricating base oil is extremely low under the condition that the normal paraffin conversion is substantially 100%. It becomes. On the other hand, according to the manufacturing method of the lubricating base oil according to the present invention, even when the hydrotreating step is performed under the condition that the normal paraffin conversion is substantially 100%, the high performance The yield of the lubricating base oil can be maintained at a high level.

  The facilities for carrying out the method for producing the hydrocarbon oil and the method for producing the lubricating base oil of the present invention are not particularly limited, and known ones can be used. The reaction equipment may be any of a continuous flow type, a batch type, and a semi-batch type, but a continuous flow type is preferable from the viewpoint of productivity and efficiency. The catalyst layer may be a fixed bed, a fluidized bed, or a stirring bed, but is preferably a fixed bed from the viewpoint of equipment costs. The reaction phase is preferably a gas-liquid mixed phase.

  In the method for producing a hydrocarbon oil and the method for producing a lubricating base oil of the present invention, the hydrocarbon oil as a feedstock is hydrotreated as a pre-stage of the isomerization step (dewaxing step) by the hydroisomerization reaction. Alternatively, hydrogenolysis treatment may be performed. Known equipment, catalysts, and reaction conditions are used. By carrying out these pretreatments, the activity of the hydroisomerization catalyst according to the present invention can be maintained for a longer period of time, and environmental loads such as sulfur-containing and nitrogen-containing compounds in the product can be maintained. Substances can be reduced.

  In the method for producing a lubricating base oil of the present invention, a step of obtaining a hydrorefined oil by hydrofinishing the dewaxed oil obtained in the dewaxing step is necessary. The hydrofinishing treatment can be generally carried out by bringing the finished product into contact with a supported metal hydrogenation catalyst (for example, platinum supported on alumina) in the presence of hydrogen. By performing such hydrofinishing, the hue, oxidation stability, etc. of the reaction product obtained in the dewaxing process are improved, and the quality of the product can be improved. The hydrofinishing may be carried out in a reaction facility different from the dewaxing step, but downstream of the catalyst layer of the hydroisomerization catalyst according to the present invention provided in the reactor for performing the dewaxing step. A catalyst layer for hydrofinishing may be provided on the substrate, followed by the labor removal step.

  In general, isomerization refers to a reaction that changes only the molecular structure without changing the carbon number (molecular weight), and decomposition refers to a reaction that involves a decrease in carbon number (molecular weight). In the catalytic dewaxing reaction using isomerization reaction, the carbon number (molecular weight) of the product should constitute the target base oil even if the hydrocarbon and isomerization product of the raw material are decomposed to some extent. Is within the predetermined allowable range, and the decomposition product may be a constituent of the base oil.

In the method for producing a lubricating base oil of the present invention, a step of distilling the hydrorefined oil obtained in the hydrofinishing step to obtain a lubricating oil fraction is required.
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. Naphtha / kerosene oil fraction, 70 Pale fraction at 343-390 ° C., SAE-10 fraction at 390-440 ° C., SAE-20 fraction at 440-510 ° C., bottom fraction above 510 ° C. -30 fractions and the like.

  According to the manufacturing method of the lubricating base oil according to the present invention described above, a high quality lubricating base oil can be efficiently produced.

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

[Production of hydroisomerization catalyst]
(1) Hydroisomerization catalyst A
A ZSM-22 type zeolite comprising a crystalline aluminosilicate having a Si / Al ratio of 36 was obtained from Chem. According to the method described in Commun, 3303, 2007., it was produced by hydrothermal synthesis according to the following procedure.
Colloidal silica (Ludox AS-30: manufactured by Aldrich), aluminum sulfate 18 hydrate (manufactured by Wako Pure Chemical), potassium hydroxide (manufactured by Wako Pure Chemical), 1,8-diaminooctane (SDA: Aldrich) Each) was mixed at the following mass ratio to obtain a gel-like substance.
SiO ₂ -0.3SDA (Structure Directing Agent: template) _{-0.3KOH-0.022Al-40H} 2 O
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 at a rotational speed of 20 rpm on a tumbling apparatus in an oven at 160 ° C. for 72 hours. The hydrothermal synthesis reaction was allowed to proceed. After completion of the hydrothermal synthesis reaction, the reactor is cooled, the solid content generated from each reactor is collected by filtration, washed with ion-exchanged water, dried overnight in an oven at 80 ° C., and 650 ° C. And a ZSM-22 type zeolite having a Si / Al ratio of 36 (hereinafter sometimes referred to as “ZSM-22”).

The ZSM-22 obtained above was taken in a flask, mixed at a ratio of ZSM-22: NH ₄ NO ₃ : H ₂ O = 1: 2: 50 (mass ratio), and ionized at 80 ° C. for 24 hours. The exchange operation was repeated three times.
Thereafter, the solid content was collected by filtration, washed with ion-exchanged water, and dried overnight in a dryer at 80 ° C. to obtain ion-exchanged NH ₄ type ZSM-22.

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. The molded body was dried in a 120 ° C. drier for 3 hours under air flow, and further fired at 550 ° C. for 3 hours under air flow to obtain molded and calcined carrier particles.

Tetraamminedichloroplatinum (II) (Pt (NH ₃ ) ₄ Cl ₂ ) was dissolved in ion-exchanged water corresponding to the water absorption amount (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 obtained was dried overnight in a dryer at 60 ° C., and then calcined at 550 ° C. for 3 hours under air flow to obtain 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”.

(2) Hydroisomerization catalyst B
Catalyst B was prepared in the same manner as Catalyst A, except that 1,9-diaminononane (manufactured by Aldrich) was used instead of 1,8-diaminooctane.
(3) Hydroisomerization catalyst C
Catalyst C was prepared in the same manner as Catalyst A except that 1,7-diaminoheptane (manufactured by Aldrich) was used in place of 1,8-diaminooctane.
(4) Hydroisomerization catalyst D
Catalyst D was prepared in the same manner as Catalyst A, except that 1,6-diaminohexane (Aldrich) was used instead of 1,8-diaminooctane.

[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 in an air stream to obtain a hydrotreating catalyst.

<Raw oil>
As raw material oil used in Examples and Comparative Examples, desulfurization straight-run gas oil fraction obtained by processing Middle Eastern crude oil, commercially available slack wax, vacuum gas oil hydrocracking obtained by processing Middle Eastern crude oil Table 2 shows the properties of the oil.
The boiling point range is JIS K2254 “Petroleum product-distillation test method”, the density is JIS K2249 “Crude oil and petroleum products—Density test method and density / mass / volume conversion table”, and the pour point is JIS K2269 “Crude oil and petroleum In the “Product Pour Point and Petroleum Product Cloud Point Test Method”, the content of normal paraffin having 10 or more carbon atoms is a value determined by gas chromatography analysis.

Example 1
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, a desulfurization straight-run gas oil fraction having the properties shown in Table 2 as feedstock was passed under the conditions of a reaction temperature of 331 ° C., a hydrogen partial pressure of 4 MPa, LHSV of 3.0 h ⁻¹ , and a hydrogen / oil ratio of 335 Nm ³ / m ³ Hydroisomerized. The normal paraffin conversion rate of the obtained product oil is 90% by mass or more, and the product oil yield (ratio of the 200 to 370 ° C. fraction of the product oil when the 200 to 370 ° C. fraction of the raw oil is defined as 100) is It was 95 mass% or more. The results obtained are listed in Table 3. The pour point in Table 3 was measured based on JIS K2269.

(Example 2)
The same procedure as in Example 1 was conducted except that the hydroisomerization catalyst was changed to catalyst B and the reaction temperature of the hydroisomerization reaction conditions was changed to 328 ° C. The results obtained are listed in Table 3.

(Example 3)
The same procedure as in Example 1 was conducted except that the hydroisomerization catalyst was changed to catalyst C and the reaction temperature of the hydroisomerization reaction conditions was changed to 332 ° C. The results obtained are listed in Table 3.

(Comparative Example 1)
The same procedure as in Example 1 was conducted except that the hydroisomerization catalyst was changed to catalyst C, the reaction temperature of the hydroisomerization reaction conditions was changed to 330 ° C., and the hydrogen / oil ratio was changed to 335 Nm ³ / m ³ . The results obtained are listed in Table 3.

Example 4
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, slack wax having the properties shown in Table 2 was hydroisomerized by passing oil under conditions of a reaction temperature of 328 ° C., a hydrogen partial pressure of 5 MPa, LHSV of 1.0 h ⁻¹ , and a hydrogen / oil ratio of 500 Nm ³ / m ³ . The dewaxed oil obtained had a normal paraffin concentration of less than 0.01% by mass.

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 (18 MPa). Thereafter, the dewaxed oil after the hydroisomerization treatment was passed as a raw material oil under the conditions of a reaction temperature of 220 ° C., a hydrogen partial pressure of 18 MPa, LHSV2h ⁻¹ , and a hydrogen / oil ratio of 3000 scfb for hydrorefining. The yield of the hydrorefined oil with respect to the obtained dewaxed oil was 99 mass% or more, Saybolt color was +30 or more, the sulfur content was 0.1 mass ppm, and the nitrogen content was 0.1 mass ppm.

The hydrorefined oil obtained by hydrofinishing was further distilled under reduced pressure to obtain a 70-pale fraction having a boiling point of 343 to 390 ° C and an SAE-10 fraction having a boiling point of 390 to 440 ° C in terms of atmospheric distillation.
The yields of the obtained lubricant base oil equivalent to 70 pail and lubricant base oil equivalent to SAE-10 were 35% by mass and 43% by mass, respectively. Further, the pour point and viscosity index of a lubricating base oil corresponding to 70 pale are −27.5 ° C. and 121, respectively, and the pour point and viscosity index of a lubricating base oil corresponding to SAE-10 are −25. 0 ° C. and 141.
The results obtained above are shown in Table 3. 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 raw material oil above 343 degreeC is set to 100. FIG.

(Example 5)
A dewaxed oil was obtained by performing hydroisomerization in the same manner as in Example 4 except that the catalyst B was filled in the reaction tube instead of the catalyst A and the reaction temperature of the hydroisomerization reaction conditions was 324 ° C. . The dewaxed oil obtained had a normal paraffin concentration of less than 0.01% by mass.
Thereafter, the same operation as in Example 4 was performed. The results are shown in Table 3.

(Example 6)
A dewaxed oil was obtained by performing hydroisomerization in the same manner as in Example 4 except that the catalyst C was filled in the reaction tube instead of the catalyst A, and the reaction temperature of the hydroisomerization reaction conditions was 330 ° C. . The dewaxed oil obtained had a normal paraffin concentration of less than 0.01% by mass.
Thereafter, the same operation as in Example 4 was performed. The results are shown in Table 3.

(Example 7)
The hydroisomerization treatment was performed in the same manner as in Example 4 except that the raw oil was changed from slack wax to vacuum gas oil hydrocracked oil, and the reaction temperature of the hydroisomerization reaction conditions was 335 ° C. and the hydrogen partial pressure was 18 MPa, A dewaxed oil was obtained. The dewaxed oil obtained had a normal paraffin concentration of less than 0.01% by mass.
Thereafter, the same operation as in Example 4 was performed. The results are shown in Table 3.

(Example 8)
In the same manner as in Example 4 except that the catalyst B was filled in the reaction tube instead of the catalyst A, the reaction temperature of the hydroisomerization reaction conditions was 329 ° C., and the hydrogen partial pressure was 18 MPa. Hydroisomerization was performed to obtain a dewaxed oil. The dewaxed oil obtained had a normal paraffin concentration of less than 0.01% by mass.
Thereafter, the same operation as in Example 4 was performed. The results are shown in Table 3.

Example 9
In the same manner as in Example 4 except that the catalyst C was filled in the reaction tube instead of the catalyst A, the reaction temperature of the hydroisomerization reaction conditions was 336 ° C., and the hydrogen partial pressure was 18 MPa. Hydroisomerization was performed to obtain a dewaxed oil. The dewaxed oil obtained had a normal paraffin concentration of less than 0.01% by mass.
Thereafter, the same operation as in Example 4 was performed. The results are shown in Table 3.

(Comparative Example 2)
A dewaxed oil was obtained by performing hydroisomerization in the same manner as in Example 4 except that the catalyst C was filled in the reaction tube instead of the catalyst A and the reaction temperature of the hydroisomerization reaction conditions was 327 ° C. . The dewaxed oil obtained had a normal paraffin concentration of less than 0.01% by mass.
Thereafter, the same operation as in Example 4 was performed. The results are shown in Table 3.

  When the same feedstock is processed using the hydroisomerization catalysts A, B, and C that satisfy the predetermined conditions according to the present application, the temperature is lower than when the hydroisomerization catalyst D that does not satisfy the predetermined conditions is used. A product oil excellent in performance could be obtained in a high yield.

  According to the present invention, a high-quality hydrocarbon oil suitable for a fuel base oil and / or a lubricant base oil can be stably obtained in a high yield from a raw material hydrocarbon oil containing normal paraffin.

Claims (13)

In a method for producing hydrocarbon oil, a feed oil containing normal paraffin having 10 or more carbon atoms is brought into contact with a hydroisomerization catalyst in the presence of molecular hydrogen to convert part or all of the normal paraffin into isoparaffin. There,
The hydroisomerization catalyst includes a crystalline aluminosilicate having a one-dimensional 10-membered ring structure obtained through steps of synthesis, calcination, and then ion exchange, and an alkyl chain length as a template used for the synthesis of the crystalline aluminosilicate. A linear alkyldiamine having (Cn) of 7 to 9 is used, and the center (L) of the long axis direction length of the needle crystal is in the range of 100 nm to 300 nm, and the length relative to the crystal diameter (D) ( L) The ratio L / D ratio is in the range of 1.5 to 4.4, and the support is a molded body containing crystalline aluminosilicate as a catalytic active component,
Containing at least one metal selected from the group consisting of a metal belonging to Groups 8 to 10 of the periodic table, molybdenum and tungsten, supported on the carrier;
The carrier is baked by receiving at least one inorganic oxide selected from alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide in response to a thermal history including heating at 500 ° C. or higher. The manufacturing method of hydrocarbon oil characterized by including the baked inorganic oxide which becomes.   The feedstock is hydrotreated and / or hydrocracked straight-run middle distillate and vacuum gas oil, slack wax, dewaxed oil, paraffin wax, microcrystalline wax, petrolatum, and Fischer-Tropsch synthetic oil. The method for producing a hydrocarbon oil according to claim 1, wherein the method is at least one selected from the group consisting of:   The crystalline aluminosilicate having a one-dimensional 10-membered ring structure is at least one selected from the group consisting of ZSM-22, ZSM-23 and ZSM-48 type zeolites. 2. A method for producing a hydrocarbon oil according to 2.   The method for producing a hydrocarbon oil according to any one of claims 1 to 3, wherein the inorganic oxide is alumina.   The method for producing a hydrocarbon oil according to any one of claims 1 to 4, wherein the metal supported on the carrier is platinum and / or palladium.   6. The carbonization according to claim 1, wherein the molar ratio ([Si] / [Al]) between silicon atoms and aluminum atoms in the crystalline aluminosilicate is 10 to 400. 6. A method for producing hydrogen oil. A process of obtaining a dewaxed oil by bringing a feedstock containing normal paraffin having 10 or more carbon atoms into contact with a hydroisomerization catalyst in the presence of molecular hydrogen;
Hydrofinishing the dewaxed oil to obtain a hydrorefined oil;
Distilling the hydrorefined oil to obtain a lubricating oil fraction;
A method for producing a lubricating base oil comprising:
The hydroisomerization catalyst includes a crystalline aluminosilicate having a one-dimensional 10-membered ring structure obtained through steps of synthesis, calcination, and then ion exchange, and an alkyl chain length as a template used for the synthesis of the crystalline aluminosilicate. A linear alkyldiamine having (Cn) of 7 to 9 is used, and the center (L) of the long axis direction length of the needle crystal is in the range of 100 nm to 300 nm, and the length relative to the crystal diameter (D) ( L) The ratio L / D ratio is in the range of 1.5 to 4.4, and the support is a molded body containing crystalline aluminosilicate as a catalytic active component,
Containing at least one metal selected from the group consisting of a metal belonging to Groups 8 to 10 of the periodic table, molybdenum and tungsten, supported on the carrier;
The carrier is baked by receiving at least one inorganic oxide selected from alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide and phosphorus oxide under a thermal history including heating at 500 ° C. or more. The manufacturing method of lubricating base oil characterized by including the baked inorganic oxide which becomes.   The raw material oil is at least one selected from the group consisting of slack wax, deoiled wax, paraffin wax, microcrystalline wax, petrolatum, Fischer-Tropsch synthetic wax, and hydrocracked oil of vacuum gas oil. The method for producing a lubricating base oil according to claim 7. Conditions under which the conversion ratio of the normal paraffin defined by the following formula (I) is 95% by mass or more in the presence of hydrogen, the raw oil containing normal paraffin having 10 or more carbon atoms and the hydroisomerization catalyst Contacting with
The manufacturing method of the lubricating base oil of Claim 7 or Claim 8 characterized by the above-mentioned.

[In formula (I), Cn represents the minimum carbon number among normal paraffins having 10 or more carbon atoms contained in the raw material oil before contact. ]   The crystalline aluminosilicate having a one-dimensional 10-membered ring structure is at least one selected from the group consisting of ZSM-22, ZSM-23, and ZSM-48 type zeolites. The manufacturing method of the lubricating base oil as described in any one of Claims.   The method for producing a lubricating base oil according to any one of claims 7 to 10, wherein the inorganic oxide is alumina.   The method for producing a lubricant base oil according to any one of claims 7 to 11, wherein the metal supported on the carrier is platinum and / or palladium.   Lubrication according to any one of claims 7 to 12, wherein the molar ratio ([Si] / [Al]) between silicon atoms and aluminum atoms in the crystalline aluminosilicate is 10 to 400. A method for producing an oil base oil.