JP5312013B2 - Hydroisomerization catalyst, method for producing the same, method for dewaxing hydrocarbon oil, and method for producing lubricating base oil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogenation isomerization catalyst which enables obtaining a base oil for lubricating oils and/or fuels, especially a hydrocarbon oil suitable for high-quality base oils for lubricating oils, from a hydrocarbon oil containing normal paraffins and has excellent isomerization selectivity and mechanical strength. <P>SOLUTION: The hydrogenation isomerization catalyst comprises a support including a formed material formed by baking through a heat history including heating at 350&deg;C or higher and at least one metal selected from metals of groups 8-10 in the periodic table, molybdenum and tungsten and supported by the support. The support contains (a) a baked zeolite formed by ion-exchanging an organic template-containing zeolite containing an organic template and having a ten-membered-ring mono-dimensional porous structure in a solution containing ammonium ion and/or proton to obtain an ion-exchanged zeolite and baking the ion-exchanged zeolite through heat histories including heating at 350&deg;C or higher and (b) a baked inorganic oxide formed by baking at least one inorganic oxide selected from alumina, silica, titania, boria, zirconia, magnesia, ceria, zinc oxide, phosphorus oxide and composite oxides consisting of two or more of the oxides through heat histories including heating at 350&deg;C or higher. The heat histories include baking the ion-exchanged zeolite not yet heated at 350&deg;C or higher by heating in a temperature range of 350-450&deg;C. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a hydroisomerization catalyst, a method for producing the same, a method for dewaxing hydrocarbon oil using the hydroisomerization catalyst, and a method for producing 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. In recent years, when hydrocarbons obtained by Fischer-Tropsch synthesis (hereinafter sometimes referred to as “FT synthesis”) do not contain environmentally hazardous substances such as sulfur compounds, lubricants and fuels are produced. However, these hydrocarbons also contain many wax components.

  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. For this reason, many synthetic base oils such as polyalphaolefins have been used in such fields.

  From 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.

On the other hand, a catalyst used for commercial use is generally used in the form of a molded body for the purpose of improving ease of handling and reducing the pressure loss of the reaction fluid in the catalyst bed. is there. 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

  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 lubricating base oil or fuel 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 hydrocarbon oils suitable for lubricating base oils and / or fuel base oils, particularly high-quality lubricating base oils, from hydrocarbon oils containing normal paraffins. A hydroisomerization catalyst excellent in isomerization selectivity and mechanical strength that can be stably obtained in a high yield, a method for producing the hydroisomerization catalyst, and carbonization using the hydroisomerization catalyst It is an object of the present invention to provide a method for dewaxing hydrogen oil and a method for producing a lubricating base oil using the hydroisomerization catalyst.

  The present inventor has studied the improvement of the isomerization selectivity of a hydroisomerization catalyst, an ion exchange zeolite obtained by ion exchange of a zeolite containing an organic template in a solution containing a cationic species, or The calcined product, and at least one metal selected from the group consisting of a metal belonging to Groups 8 to 10 of the periodic table of elements, molybdenum and tungsten supported on the ion-exchanged zeolite or the calcined product. The hydroisomerization catalyst obtained by calcining the catalyst composition has been found to have excellent isomerization selectivity at a high normal paraffin conversion, and a patent application has been filed.

  And, as a result of intensive studies by the present inventors in order to solve the above-mentioned problems, hydrogen containing a specific zeolite and a specific inorganic oxide support, and a specific active metal supported on the support. The hydroisomerization catalyst has sufficient mechanical strength and exhibits excellent isomerization selectivity at high normal paraffin conversion in the hydroisomerization reaction of hydrocarbon oils containing normal paraffins. The headline and the present invention were completed.

That is, the present invention comprises a carrier which is a molded body fired by receiving a thermal history including heating at 350 ° C. or higher, and a metal supported on the carrier and belonging to Groups 8 to 10 of the periodic table, molybdenum and tungsten. And at least one metal selected from the group,
The carrier is
(1) 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
(2) 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 complex 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 provides a hydroisomerization catalyst including 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. To do.

  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 hydroisomerization catalyst of the present invention, by having the above-described configuration, both mechanical strength and isomerization selectivity can be satisfied at a high level. Hydrocarbon oils suitable for oil and / or fuel base oils, particularly high-quality lubricating base oils, can be obtained stably and in high yield.

  The organic template-containing zeolite is at least one selected from the group consisting of ZSM-22, ZSM-23 and ZSM-48 type zeolites in that it has a crystal structure suitable for selective hydrogenation of normal paraffins. Preferably there is.

  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 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.

The present invention also provides a first 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. Process,
At least one inorganic oxide selected from the group consisting of the above 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 obtaining the carrier by calcining the molded body by heating at least within a range of 350 ° C. to 450 ° C .;
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;
The manufacturing method of a hydroisomerization catalyst provided with this is provided.

  According to the method for producing a hydroisomerization catalyst of the present invention, by providing the above steps, both the isomerization selectivity and the mechanical strength are excellent, and the hydrocarbon base oil containing normal paraffin and the lubricating base oil and / or It is possible to obtain a hydroisomerization catalyst that makes it possible to stably obtain a hydrocarbon oil suitable for a fuel base oil, particularly a high-quality lubricating base oil, in a high yield.

  In the method for producing a hydroisomerization catalyst of the present invention, from the viewpoint of further improving the mechanical strength of the catalyst, the third step is to heat the molded body within a range of 350 ° C. to 450 ° C. and then to 450 ° C. It is preferably a step of obtaining the above-mentioned carrier by baking by heating within a range of more than 650 ° C.

  In the present invention, a hydrocarbon oil containing a normal paraffin having 10 or more carbon atoms is brought into contact with the hydroisomerization catalyst of the present invention in the presence of hydrogen, so that a part or all of the normal paraffin is partly brought into contact. A process for dewaxing hydrocarbon oils that are converted to isoparaffins is provided.

  The hydrocarbon oil is preferably at least one selected from the group consisting of slack wax, deoiled wax, paraffin wax, microcrystalline wax, petratum, and Fischer-Tropsch synthetic wax.

［式（Ｉ）中、Ｃｎは、接触前の炭化水素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。］ The present invention also provides a hydrocarbon oil containing a normal paraffin having 10 or more carbon atoms in the presence of hydrogen and the hydroisomerization catalyst of the present invention, wherein the normal paraffin defined by the following formula (I) is used. Provided is a method for producing a lubricating base oil comprising a step of contacting under a condition that the conversion rate is substantially 100 mass%.

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

  ADVANTAGE OF THE INVENTION According to this invention, the hydroisomerization catalyst excellent in hydroisomerization selectivity and mechanical strength, and its manufacturing method can be provided. In addition, according to the present invention, a hydrocarbon oil suitable for a lubricating base oil and / or a fuel base oil is stably obtained in a high yield from a hydrocarbon oil containing normal paraffin using a hydroisomerization catalyst. Provided are a method for dewaxing a hydrocarbon oil, and a method for producing a lubricant base oil that enables a high-performance lubricant base oil to be obtained in a high yield from a hydrocarbon oil containing normal paraffins. can do.

<Hydroisomerization catalyst>
The hydroisomerization catalyst of 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 organic template-containing zeolite used as a starting material for the calcined zeolite (a) constituting the hydroisomerization catalyst of the present invention has a high level of high isomerization activity and suppressed cracking activity in the hydroisomerization reaction of normal paraffin. From the viewpoint of achieving both, 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 as a starting material of the calcined zeolite (a) constituting the hydroisomerization catalyst of the present invention and having a 10-membered ring one-dimensional pore structure includes a silica source, an alumina source, and the above-mentioned Hydrothermal synthesis is performed by a known method from an organic template added to construct a 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 exchange zeolite that is not heated at 350 ° C. or higher and has an organic template remaining at a relatively low temperature as described above is extremely effective in improving the isomerization selectivity of the hydroisomerization catalyst of the present invention. is 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. 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 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 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 calcined zeolite (a) and 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 of 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 molded body by heating at 450 ° C. ”or“ Baking of molded body by heating at 350 to 450 ° C. and then higher than 450 ° C. and below 650 ° C. ”,“ Supporting of active metal on carrier ”, and Each step of “calcination of a support on which an active metal is supported” is included.

  What is important in the hydroisomerization catalyst of the present invention is that in addition to the use of the above-mentioned specific zeolite, specific inorganic oxide, and specific active metal, in the process of its production, “an organic template-containing zeolite containing an organic template” "Part of the organic template included in the material is removed by ion exchange instead of calcination", "Compared to 350-450 ° C for ion-exchanged zeolite that is not heated at 350 ° C or higher and remains partially organic template To remove at least a part of the organic template remaining in the zeolite by firing at a low temperature ”and“ the support is a molded body fired by receiving a heat history including heating at 350 ° C. or higher. ”In three points. In the production of the hydroisomerization catalyst of the present invention, the embodiment in which the above-mentioned steps are carried out and the order thereof, as long as the above three points are ensured, the occurrence of problems in each step of the catalyst production, and 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 high activity with respect to dewaxing of hydrocarbon oil can be more reliably imparted to the catalyst.

  In the hydroisomerization catalyst of 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. A metal may be further supported.

<Method for producing hydroisomerization catalyst>
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.

<Dewaxing method of hydrocarbon oil>
Next, the hydrocarbon oil dewaxing method of the present invention will be described. In the hydrocarbon dewaxing method of the present invention, in the presence of hydrogen, a hydrocarbon oil containing a normal paraffin having 10 or more carbon atoms and the hydroisomerization catalyst of the present invention are brought into contact with each other to obtain one of the normal paraffins. A step of converting part or all into isoparaffin.

  The hydrocarbon oil to be used in the hydrocarbon oil dewaxing method 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. To do. 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, vacuum gas oil, waxy oil, fuel fraction or wax content derived from FT synthetic oil, and various high-oil feedstocks such as other heavy oils. 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 hydrocarbon oil to be dewaxed by the hydrocarbon oil dewaxing 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 do not substantially contain a wax component that affects fluidity at low temperatures, so that the need for dewaxing is low and the effects of the present invention are difficult to obtain.

  On the other hand, distillate feedstock containing a wax component, that is, intermediate oil fraction feedstock including light oil, kerosene and jet fuel, lube oil feedstock, heating oil, and other distillation cuts, It is particularly effective to apply the dewaxing method according to the present invention to the fraction in which the pour point and the viscosity need to be maintained within a predetermined range. Examples of such hydrocarbon oils include hydrotreated or hydrocracked diesel oil, heavy diesel oil, vacuum diesel oil, lubricating oil raffinate, lubricating oil raw material, bright stock, slack wax (crude wax), and waxy oil. , Deoiled wax, paraffin wax, microcrystalline wax, petrolatum, synthetic oil, FT synthetic oil, high pour point polyolefin, linear α-olefin wax and the like. These can be used individually by 1 type or in combination of 2 or more types.

  In the hydrocarbon oil dewaxing method of the present invention, the reaction conditions for converting at least a part of normal paraffin to isoparaffin are preferably set according to the above-described method for producing a base oil according to the present invention. .

  The temperature of the hydroisomerization reaction in the hydrocarbon dewaxing method of the present invention is generally 200 to 450 ° C, preferably 220 to 400 ° C. When the reaction temperature is less than 200 ° C., isomerization of normal paraffin contained in the hydrocarbon oil as a raw material becomes difficult to proceed, and the reduction and removal of the wax component tend to be insufficient. On the other hand, when the reaction temperature exceeds 450 ° C., the hydrocarbon oil is significantly decomposed and the yield of the target base oil tends to decrease.

  The pressure of the hydroisomerization reaction in the dewaxing of the hydrocarbon of the present invention is generally 0.1 to 20 MPa, preferably 0.5 to 15 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 be high, and it tends to be difficult to realize an economical process.

Liquid hourly space velocity relative to the catalyst of the hydrocarbon oil hydroisomerization reaction in the dewaxing method of hydrocarbon present invention generally 0.01～100Hr ^-1, preferably 0.1~50hr ^-1. When the liquid space velocity is less than 0.01 hr ⁻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 hr ⁻¹ , the 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 hydroisomerization reaction with hydrocarbon oil in the dewaxing method of hydrocarbon present invention 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 ratio of normal paraffin in the hydroisomerization reaction in the hydrocarbon dewaxing method of the present invention is appropriately adjusted according to the intended use of the base oil.

［式（Ｉ）中、Ｃｎは、接触前の炭化水素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。］
ここで、「転化率が実質的に１００質量％」とは、接触後の炭化水素油中に含まれるノルマルパラフィンの含有量が０．１質量％以下であることを意味する。 <Method for producing lubricating base oil>
Next, the manufacturing method of the lubricating base oil of the present invention will be described. In the method for producing a lubricating base oil of the present invention, a hydrocarbon oil containing a normal paraffin having 10 or more carbon atoms in the presence of hydrogen and the hydroisomerization catalyst of the present invention are represented by the following formula (I): The normal paraffin conversion defined is brought into contact under the condition that the conversion is substantially 100% by mass.

[In formula (I), Cn shows the minimum carbon number among the normal paraffins having 10 or more carbon atoms contained in the hydrocarbon oil before contact. ]
Here, “conversion is substantially 100% by mass” means that the content of normal paraffin contained in the hydrocarbon oil after contact is 0.1% by mass or less.

  The hydrocarbon oil to be 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. It is preferred to include a hydrocarbon oil having an initial boiling point higher than the 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 Examples include raffinate, bright stock, slack wax (crude wax), waxy oil, deoiled wax, paraffin wax, microcrystalline wax, petrolatum, synthetic oil, FT synthetic oil, high pour point polyolefin, and linear α-olefin wax. . 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 feedstock, and this is brought into contact with the hydroisomerization catalyst according to the present invention in the presence of hydrogen, thereby isomerizing the normal paraffin contained in the hydrocarbon 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. Moreover, according to the manufacturing method of the base oil which concerns on this invention, the base oil which contains many isomers which have a branched chain structure can be obtained. In particular, a high-quality lubricating base oil is required to have a normal paraffin content of 0.1% by mass or less. According to the base oil manufacturing method of the present invention, this required level is satisfied. A lubricating base oil can be obtained in high yield.

  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 lube base oils such as Group III + according to the classification of lubricant 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 a 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 equipment for carrying out the method for dewaxing a hydrocarbon oil and the method for producing a lubricating base oil of the present invention is 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 hydrocarbon oil dewaxing method and the lubricating base oil production method of the present invention, as a pre-stage of the dewaxing step by the hydroisomerization reaction, the feed hydrocarbon oil is hydrotreated or hydrocracked. May be. 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, the reaction product obtained in the dewaxing step can be further processed, for example, by hydrofinishing. The hydrofinishing can be generally carried out by bringing the work to be finished 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 separate 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 hydrogenation finishing may be provided on the substrate to carry out the above-mentioned 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.

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

Example 1
(Production of hydroisomerization catalyst)
<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”.

(Dewaxing wax)
A stainless steel reaction tube having an inner diameter of 15 mm and a length of 380 mm is filled with 100 ml of the hydroisomerization catalyst A obtained above, and reduction treatment is performed for 12 hours under an average catalyst layer temperature of 350 ° C. under hydrogen flow (hydrogen partial pressure of 3 MPa). Went. Thereafter, petroleum wax as a raw material (carbon number distribution C20 to C43, composition is shown in FIG. 1), reaction temperature 200 ° C., hydrogen partial pressure 3 MPa, LHSV 2.0 h ⁻¹ , hydrogen / oil ratio 500 NL / L. The dewaxing process by the hydroisomerization reaction was started. After reacting for 72 hours, the reaction product was collected and analyzed. In FIG. 1, a indicates the amount of isoparaffin, and b indicates the amount of normal paraffin.

  Thereafter, while maintaining the hydrogen partial pressure, LHSV, and hydrogen / oil ratio, the reaction temperature was increased stepwise to 350 ° C. to increase the normal paraffin conversion in the feedstock. Each reaction product was collected and analyzed when the reaction was stabilized at the reaction temperature of each stage for 72 hours.

(Separation and recovery of lube base oil fraction)
Based on the analysis results of each product oil, the product oil obtained at each reaction temperature at which the normal paraffin conversion rate defined by the formula (I) was 100% was fractionated by the following operation. The following lubricating base oil fraction was collected.

  The product oils at each reaction temperature at which the normal paraffin conversion was 100% were first fractionated into naphtha, kerosene fraction and heavy fraction, respectively. Further, by fractionating this heavy fraction, a lubricating base oil fraction (hereinafter referred to as “lubricating base oil”) having a boiling range of 330 to 410 ° C. and a kinematic viscosity at 100 ° C. of 2.7 ± 0.1 cSt. And a lube base oil fraction (hereinafter referred to as “lubricant base oil fraction 2”) having a boiling range of 410 to 450 ° C. and a kinematic viscosity at 100 ° C. of 4.0 ± 0.1 cSt. "). The lowest reaction temperature at which the pour point of the lubricating base oil fraction 2 was −22.5 ° C. or lower and the viscosity index was 140 or higher was defined as Tc. Tc in this example was 320 ° C. The yield of the lubricating base oil fractions 1 and 2 obtained at a reaction temperature of 320 ° C. and the properties of the lubricating base oil fraction 2 are shown together with the production conditions and crushing strength of the hydroisomerization catalyst A. It is shown in 1. The composition of the product oil at a reaction temperature of 320 ° C. is shown in FIG. In FIG. 2, a indicates the amount of isoparaffin, and b indicates the amount of normal paraffin.

(Example 2)
(Production of hydroisomerization catalyst)
An ion-exchanged NH ₄ type ZSM-22 is obtained by the same operation as in Example 1, and further, a molded body similar to that of Example 1 is obtained by extrusion molding using alumina as a binder by the same operation as in Example 1. It was.

  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 carrier particles thus molded and calcined were loaded with platinum, dried and calcined in the same manner as in Example 1 to obtain a hydroisomerization catalyst B. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Dewaxing of wax and separation / recovery of lube base oil fraction)
Except for using the hydroisomerization catalyst B instead of the hydroisomerization catalyst A, the wax was dewaxed and analyzed for each product oil, and the lubricating base oil was separated and recovered in the same manner as in Example 1. It was. As a result, Tc was 320 ° C. The yield of the lubricating base oil fractions 1 and 2 and the properties of the lubricating base oil fraction 2 obtained from the product oil obtained at the reaction temperature of 320 ° C. in the same section as in Example 1 were determined according to the hydroisomerization catalyst B. Table 1 shows the manufacturing conditions and crushing strength.

(Example 3)
(Production of hydroisomerization catalyst)
Molded and fired carrier particles were obtained by the same operation as in Example 2 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 Example 1 to obtain hydroisomerization catalyst C. The crushing strength of the obtained catalyst particles was 9.0 N / mm.

(Dewaxing of wax and separation / recovery of lube base oil fraction)
Except for using the hydroisomerization catalyst C instead of the hydroisomerization catalyst A, the wax was dewaxed and analyzed for each product oil, and the lubricating base oil was separated and recovered in the same manner as in Example 1. It was. As a result, Tc was 340 ° C. The yield of the lubricating base oil fractions 1 and 2 and the properties of the lubricating base oil fraction 2 obtained from the product oil obtained at the reaction temperature of 340 ° C. in the same section as in Example 1 were determined according to the hydroisomerization catalyst C. Table 1 shows the manufacturing conditions and crushing strength.

Example 4
(Production of hydroisomerization catalyst)
By the same operation as Example 1, the same molded body as Example 1 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 Example 1 to obtain a hydroisomerization catalyst D. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Dewaxing of wax and separation / recovery of lube base oil fraction)
Except for using the hydroisomerization catalyst D instead of the hydroisomerization catalyst A, the wax was dewaxed and analyzed for each produced oil, and the lubricating base oil was separated and recovered in the same manner as in Example 1. It was. As a result, Tc was 320 ° C. The yield of the lubricating base oil fractions 1 and 2 and the properties of the lubricating base oil fraction 2 obtained from the product oil obtained at the reaction temperature of 320 ° C. in the same section as in Example 1 were determined according to the hydroisomerization catalyst D. Table 1 shows the manufacturing conditions and crushing strength.

(Example 5)
(Production of hydroisomerization catalyst)
<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 instead of ZSM-22 containing the organic template, ion exchange was performed by the same operation as the ion exchange of ZSM-22 of Example 1. 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 body was obtained by the same operation as in Example 2, and thereafter, at 400 ° C. and 550 ° C. by the same operation as in Example 2. Firing was performed to obtain molded and fired carrier particles.

<Platinum support, firing>
In the same manner as in Example 2, except that the molded and fired carrier particles containing ZSM-23 obtained as described above were used instead of the molded and fired carrier particles containing ZSM-22, platinum was supported and dried. And calcination was performed to obtain a hydroisomerization catalyst E. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Dewaxing of wax and separation / recovery of lube base oil fraction)
Except for using the hydroisomerization catalyst E instead of the hydroisomerization catalyst A, the wax was dewaxed and analyzed for each produced oil, and the lubricating base oil was separated and recovered in the same manner as in Example 1. It was. As a result, Tc was 330 ° C. The yield of the lubricating base oil fractions 1 and 2 and the properties of the lubricating base oil fraction 2 obtained from the product oil at the reaction temperature of 330 ° C. in the same section as in Example 1 were determined by the hydroisomerization catalyst E. Table 1 shows the manufacturing conditions and crushing strength.

(Example 6)
(Production of hydroisomerization catalyst)
<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.

<Manufacture of ion exchange ZSM-48>
Except for using ZSM-48 containing the organic template obtained above in place of ZSM-22 containing the organic template, ion exchange was performed in the same manner as the ion exchange of ZSM-22 in Example 1. 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 body was obtained by the same operation as in Example 2, and thereafter, at 400 ° C. and 550 ° C. by the same operation as in Example 2. Firing was performed to obtain molded and fired carrier particles.

<Platinum support, firing>
In the same manner as in Example 2, except that the molded and baked carrier particles containing ZSM-48 obtained above were used instead of the molded and baked carrier particles containing ZSM-22, platinum loading and drying were performed. And the hydroisomerization catalyst F was obtained by calcination. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Dewaxing of wax and separation / recovery of lube base oil fraction)
Except for using the hydroisomerization catalyst F instead of the hydroisomerization catalyst A, the wax was dewaxed and analyzed for each produced oil, and the lubricating base oil was separated and recovered in the same manner as in Example 1. It was. As a result, Tc was 318 ° C. The yield of the lubricating base oil fractions 1 and 2 and the properties of the lubricating base oil fraction 2 obtained from the product oil at the reaction temperature of 318 ° C. in the same section as in Example 1 were determined according to the hydroisomerization catalyst F. Table 1 shows the manufacturing conditions and crushing strength.

(Comparative Example 1)
(Production of hydroisomerization catalyst)
Except having changed the calcination temperature of a molded object from 400 degreeC to 470 degreeC, the carrier particle shape | molded and baked was obtained by the same operation as Example 1.

  The obtained carrier particles were loaded with platinum, dried and calcined in the same manner as in Example 1 to obtain a hydroisomerization catalyst G. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Dewaxing of wax and separation / recovery of lube base oil fraction)
Except for using the hydroisomerization catalyst G in place of the hydroisomerization catalyst A, the wax was dewaxed and analyzed for each product oil, and the lubricating base oil was separated and recovered in the same manner as in Example 1. It was. As a result, Tc was 316 ° C. The yield of the lube base oil fractions 1 and 2 and the properties of the lube base oil fraction 2 obtained from the product oil at the reaction temperature of 316 ° C. in the same section as in Example 1 were determined according to the hydroisomerization catalyst G. Table 1 shows the manufacturing conditions and crushing strength.

(Comparative Example 2)
(Production of hydroisomerization catalyst)
Powdered ZSM-22 containing an organic template synthesized by the same method as in Example 1 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 Example 1 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 in Example 1. Then, the hydroisomerization catalyst H was obtained by performing the same operations as in Example 1, followed by drying, calcination, platinum support, and calcination. The crushing strength of the obtained catalyst particles was 12.0 N / mm.

(Dewaxing of wax and separation / recovery of lube base oil fraction)
Except for using the hydroisomerization catalyst H instead of the hydroisomerization catalyst A, the wax was dewaxed and analyzed for each product oil, and the lubricating base oil was separated and recovered in the same manner as in Example 1. It was. As a result, Tc was 314 ° C. The yield of the lube base oil fractions 1 and 2 and the properties of the lube base oil fraction 2 obtained from the product oil at the reaction temperature of 314 ° C. in the same section as in Example 1 were determined according to the hydroisomerization catalyst H. Table 1 shows the manufacturing conditions and crushing strength.

(Comparative Example 3)
(Production of hydroisomerization catalyst)
Powdered ZSM-22 containing an organic template synthesized by the same method as in Example 1 was baked and ion exchanged by the same operation as in Comparative Example 2.

A molded body was obtained from the NH ₄ type ZSM-22 obtained above and alumina as a binder by the same operation as in Example 1. Then, the obtained molded body was calcined 3 times at 470 ° C. under air flow, and then supported with platinum and calcined by the same operation as in Example 1 to obtain a hydroisomerization catalyst I. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Dewaxing of wax and separation / recovery of lube base oil fraction)
Except for using the hydroisomerization catalyst I instead of the hydroisomerization catalyst A, the wax was dewaxed and analyzed for each product oil, and the lubricating base oil was separated and recovered in the same manner as in Example 1. It was. As a result, Tc was 312 ° C. The yield of the lube base oil fractions 1 and 2 and the properties of the lube base oil fraction 2 obtained from the product oil at the reaction temperature of 312 ° C. in the same section as in Example 1 were determined according to the hydroisomerization catalyst I. Table 1 shows the manufacturing conditions and crushing strength.

(Comparative Example 4)
(Production of hydroisomerization catalyst)
The hydroisomerization catalyst J was prepared in the same manner as in Example 5 except that the temperature of the first stage for calcining the molded body obtained from ion-exchanged ZSM-23 and alumina was changed to 400 ° C and 470 ° C. Got. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Dewaxing of wax and separation / recovery of lube base oil fraction)
Except for using the hydroisomerization catalyst J instead of the hydroisomerization catalyst A, the wax was dewaxed and analyzed for each product oil, and the lubricating base oil was separated and recovered in the same manner as in Example 1. It was. As a result, Tc was 325 ° C. The yield of the lubricating base oil fractions 1 and 2 and the properties of the lubricating base oil fraction 2 obtained from the product oil at the reaction temperature of 325 ° C. in the same section as in Example 1 and the properties of the lubricating base oil fraction 2 were determined. Table 1 shows the manufacturing conditions and crushing strength.

(Comparative Example 5)
(Production of hydroisomerization catalyst)
The hydroisomerization catalyst K was obtained in the same manner as in Example 6 except that the temperature of the first stage of firing the molded body obtained from ion-exchanged ZSM-48 and alumina was changed to 400 ° C and 470 ° C. Got. The crushing strength of the obtained catalyst particles was 13.0 N / mm.

(Dewaxing of wax and separation / recovery of lube base oil fraction)
Except for using the hydroisomerization catalyst K instead of the hydroisomerization catalyst A, the wax was dewaxed and analyzed for each produced oil, and the lubricating base oil was separated and recovered in the same manner as in Example 1. It was. As a result, Tc was 316 ° C. The yield of the lube base oil fractions 1 and 2 and the properties of the lube base oil fraction 2 obtained from the product oil at the reaction temperature of 316 ° C. in the same section as in Example 1 and the properties of the lube base oil fraction 2 were determined. Table 1 shows the manufacturing conditions and crushing strength.

It is a graph which shows the composition of the petroleum-type wax used for the dewaxing process by a hydroisomerization reaction. 2 is a graph showing the composition of a product oil obtained by dewaxing treatment by hydroisomerization reaction in Example 1 at a reaction temperature of 320 ° C. FIG.

Claims (11)

A carrier that is a molded body fired by receiving a thermal history including heating of 350 ° C. or higher, and at least selected from the group consisting of metals, molybdenum, and tungsten that are supported on the carrier and belong to Groups 8 to 10 of the periodic table A kind of metal, and
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 hydroisomerization catalyst, wherein 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.   The hydroisomerization catalyst according to claim 1, wherein the organic template-containing zeolite is at least one selected from the group consisting of ZSM-22, ZSM-23, and ZSM-48 type zeolites.   The hydroisomerization catalyst according to claim 1 or 2, wherein the inorganic oxide is alumina.   The hydroisomerization catalyst according to any one of claims 1 to 3, wherein the support is a molded body that is calcined by receiving a thermal history including heating in a range of more than 450 ° C and not more than 650 ° C. .   The hydroisomerization catalyst according to any one of claims 1 to 4, wherein the metal supported on the carrier is platinum or palladium.   The hydroisomerization according to any one of claims 1 to 5, wherein a molar ratio ([Si] / [Al]) of silicon atoms to aluminum atoms in the organic template-containing zeolite is 10 to 400. 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 obtaining the carrier by calcining the molded body by heating in the range of at least 350 ° C. to 450 ° C .;
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;
A process for producing a hydroisomerization catalyst.   The third step is a step of heating the molded body within a range of 350 ° C. to 450 ° C. and then baking it by heating within a range of 450 ° C. to 650 ° C. to obtain the carrier. The manufacturing method of the hydroisomerization catalyst of Claim 7.   In the presence of hydrogen, a hydrocarbon oil containing a normal paraffin having 10 or more carbon atoms and the hydroisomerization catalyst according to any one of claims 1 to 6 are brought into contact with each other to obtain one of the normal paraffins. A method for dewaxing hydrocarbon oil, wherein a part or all of it is converted to isoparaffin.   The hydrocarbon oil according to claim 9, wherein the hydrocarbon oil is at least one selected from the group consisting of slack wax, deoiled wax, paraffin wax, microcrystalline wax, petratum, and Fischer-Tropsch synthetic wax. Wax method. The hydrocarbon oil containing a normal paraffin having 10 or more carbon atoms in the presence of hydrogen and the hydroisomerization catalyst according to any one of claims 1 to 6 are defined by the following formula (I): A step of contacting under a condition that the conversion of the normal paraffin is substantially 100% by mass;
A method for producing a lubricating base oil.

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

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