JP2011005446A - Zeolite catalyst and method for producing compound having adamantane structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst by which adamantanes are produced at high selectivity and at high yield in the isomerization of a tricyclic saturated hydrocarbon compound having at least ten carbon atoms; and to provide a method for producing adamantanes by using the catalyst concerned.SOLUTION: The catalyst contains zeolite having MWW-type topology. In this case, the ratio of the external surface area of the catalyst to the whole surface area is 0.3 or larger, and the external surface area is 145-600 m/g.

Description

  The present invention relates to a zeolite catalyst and a method for producing a compound having an adamantane structure (hereinafter sometimes referred to as adamantanes). More specifically, the present invention relates to a catalyst containing a specific zeolite and capable of producing adamantanes with high selectivity and high yield, and a method for producing adamantanes using the catalyst.

  Adamantane has a structure in which four cyclohexane rings are bonded in a cage shape, and is a highly symmetrical and stable compound. Since a compound having such an adamantane structure exhibits a unique function, It is known to be useful as an electronic material such as a resist, a raw material for agricultural pharmaceuticals, and a raw material for high-functional industrial materials. As a method for producing this adamantane, a method for isomerizing a tricyclic saturated hydrocarbon compound having 10 or more carbon atoms is generally employed. For example, adamantane is obtained by isomerizing trimethylene norbornane (TMN) obtained by hydrogenating dicyclopentadiene (DCPD) with a catalyst, and aluminum chloride is usually used industrially as the catalyst ( For example, see Patent Document 1). Also known is a method for producing adamantanes using a cation-exchanged zeolite carrying an active metal such as platinum, rhenium, nickel or cobalt (for example, see Patent Document 2).

  As described above, various catalysts are known as catalysts for the production of adamantanes, but each has a problem and further technical development is required. For example, when adamantanes are produced using aluminum chloride, it is necessary to increase the amount of catalyst used relative to the raw material. In addition, since this catalyst forms a complex with heavy components produced as a by-product during the reaction, it cannot be reused as a catalyst after completion of the reaction. Therefore, when this method is used, a large amount of waste aluminum is generated, and the disposal process causes a problem of environmental pollution. In addition, since aluminum chloride is highly corrosive, it is necessary to use an apparatus made of an expensive corrosion-resistant material. Further, when aluminum chloride is used, the produced adamantane is colored, so that a decoloring step using recrystallization or activated carbon is necessary, and the post-treatment is complicated.

  In addition, when a catalyst in which a metal such as platinum, rhenium, nickel, cobalt, etc., is supported on an ultrastable Y-type zeolite or Y-type zeolite that has been cation-exchanged in a batch reaction by an impregnation method, relatively adamantanes are collected. Although the rate is high, the coexistence of hydrogen chloride is essential, and otherwise the yield of adamantanes is low (Non-Patent Documents 1 and 2). In this case, since hydrogen chloride is highly corrosive, there is a problem that it is necessary to use an apparatus of an expensive corrosion-resistant material.

  Further, when adamantanes are produced by flow reaction using a catalyst in which platinum of 1% by mass or less is supported on a cation-exchanged Y-type zeolite without coexisting hydrogen chloride (for example, Patent Document 3), Since there are many hydrocracking products by reaction, the selectivity of adamantane is low and the yield is also low (TMN conversion 91.5%, adamantane selectivity 16.1%, adamantane yield 15.5%). Furthermore, the conditions under high-pressure hydrogen are essential for suppressing catalyst deterioration, and it is difficult to suppress by-product hydrocracking products and it is difficult to improve adamantane selectivity.

JP-A-2-235826 Japanese Patent Publication No.52-2909 JP 2005-118718 A

Guo Jianwei et al. PETROCEMICHAL INDUSTRY, 1998, vol.27, No.1 GAO Zi et al. CHINESE Journal of chemistry, 1994, vol.12, No.1

  The present invention has been made in view of the above circumstances, and a catalyst capable of producing adamantanes with high selectivity and high yield in an isomerization reaction of a tricyclic saturated hydrocarbon compound having 10 or more carbon atoms, and the catalyst. It aims at providing the method of manufacturing adamantane using it.

As a result of intensive studies, the present inventors have found that the above problems can be solved by a specific zeolite catalyst. The present invention has been completed based on such findings.
That is, the present invention
1. A catalyst containing a zeolite having an MWW type topology, a ratio of an outer surface area to a total surface area of 0.3 or more, and an outer surface area of 145 to 600 m ² / g;
2. The catalyst according to 1, wherein the zeolite has a crystal size of 0.1 to 40 nm,
3. The catalyst according to 1 or 2, wherein Si / Al (mol / mol) is 5 to 17,
4). The catalyst according to any one of 1 to 3, wherein the catalyst is an active metal-supported catalyst, and the active metal is a metal selected from Group 8 to Group 10 of the periodic table and rhenium,
5. The catalyst according to 4 above, wherein the active metal is platinum,
6). The catalyst according to 4 or 5, wherein the amount of the active metal supported is 1% by mass or less based on the total amount of the catalyst,
7). The following steps 1-4
Step 1: Step of preparing a zeolite precursor by hydrothermal synthesis method Step 2: Step of firing after Step 1 Step 3: Step of performing ammonium ion exchange treatment or acid treatment after Step 2 Step 4: Firing after Step 3 A method for producing a catalyst according to any one of the above 1 to 6, comprising a step of adding a zeolite having a MWW topology and / or a zeolite precursor separately produced in step 1 to a raw material. A method for producing a catalyst, characterized by hydrothermal synthesis;
8). 8. a method for producing a compound having an adamantane structure by isomerizing a tricyclic saturated hydrocarbon compound having 10 or more carbon atoms using the catalyst according to any one of 1 to 6; 9. The production method according to 8 above, wherein the tricyclic saturated hydrocarbon compound is a compound selected from trimethylene norbornane, dimethyltrimethylene norbornane, perhydroacenaphthene and perhydrofluorene.

  According to the present invention, a catalyst capable of producing adamantanes with high selectivity and high yield in an isomerization reaction of a tricyclic saturated hydrocarbon compound having 10 or more carbon atoms, and producing adamantanes using the catalyst A method is provided.

2 is an X-ray diffraction pattern of the catalyst (catalyst A) obtained in Example 1. FIG. 2 is an X-ray diffraction pattern of the catalyst (catalyst B) obtained in Example 2. 3 is an X-ray diffraction pattern of the catalyst (catalyst C) obtained in Example 3. 4 is an X-ray diffraction pattern of the catalyst (catalyst D) obtained in Example 4. 3 is an X-ray diffraction pattern of the catalyst (catalyst E) obtained in Comparative Example 1. 3 is an X-ray diffraction pattern of a catalyst (catalyst F) obtained in Comparative Example 2. 3 is an X-ray diffraction pattern of a catalyst (catalyst G) obtained in Comparative Example 3. 4 is an X-ray diffraction pattern of the catalyst (catalyst H) obtained in Comparative Example 4.

  The zeolite catalyst of the present invention is a catalyst containing a zeolite having an MWW type topology. Specific examples of zeolite having an MWW type topology include MCM-22 zeolite, SSZ-25 zeolite, ITQ-1 zeolite, PSH-3 zeolite and ERB-1 zeolite.

  The nomenclature of the zeolitic material is determined by the International Zeolite Associates Structure Commission (IZA-SC). The commission is given the authority by the IUPAC to assign structural codes to zeolites with all identified unique frame structure topologies. At present, the final term is recorded in the zeolite structure type atlas (4th edition, authors: WM Meyer, DH Olson, Ch. Bellocher), and at the following website: You can access regularly revised records: www.iza-sc.ethz.ch/IZA-SC/Atlas/AtlasHome.html. This handbook records the topology of each zeolite type that is believed to have a new independent structure, and currently lists about 125 independent zeolite structures. The zeolitic material assigned as an MWW type topology by IZA-SC is a multilayer material and has two pores due to the presence of a 10-membered ring and a 12-membered ring. In the Atlas of the zeolite structure type, there are five different materials having the same topology (ie, MCM-22 zeolite, ERB-1 zeolite, ITQ-1 zeolite, PSH-3 zeolite and SSZ-25 zeolite). It is classified into. MWW-type zeolite is described as having various uses. In U.S. Pat. No. 4,826,667, SSZ-25 zeolite is mainly used for catalytic hydrocarbon conversion reactions such as catalytic cracking, hydrocracking, hydrodewaxing, olefin and aromatic compound forming reactions (eg xylene isomerization). Are useful as adsorbents, fillers and water softeners. U.S. Pat. No. 4,954,325 describes 16 different uses of the material known as MCM-22 zeolite.

In the zeolite catalyst of the present invention, the ratio of the outer surface area to the total surface area (sometimes referred to as the outer surface ratio) is 0.3 or more. In a catalyst having an outer surface ratio of 0.3 or more, the yield of adamantane tends to increase as the outer surface ratio increases. Although there is no restriction | limiting in particular about the upper limit, Usually, it is 0.6 or less. Moreover, the zeolite catalyst of the present invention has an outer surface area of 145 to 600 m ² / g. If the outer surface area is less than 145 m ² / g, the yield of adamantanes is lowered, and zeolites exceeding 600 m ² / g are usually difficult to synthesize.
In the present invention, in order to obtain the outer surface ratio and the outer surface area, a nitrogen adsorption method generally used as a method for measuring the specific surface area of the porous substance was used.
The nitrogen adsorption method is a method in which a dried sample is placed in a glass cell, vacuum degassed, nitrogen gas is introduced in small portions at a temperature of 77K, and the equilibrium pressure and adsorption amount are measured. Is a common method of measuring. Using the adsorption isotherm obtained by this measurement method, a t-plot analysis is performed on a sample having pores. The “t-plot analysis” analyzes data obtained by the nitrogen adsorption method. This uses a t-curve, that is, a standard isotherm in which the thickness t of the adsorbed film is plotted against the relative pressure p / p ₀ (Lippens, t-plot method by de Boer). Specifically, it is represented by the following formula (1).
t = (V / V _m ) σ (1)
(In the above formula, t denotes the thickness of the adsorbed film, v / v _m represents the average number of adsorption layers in the adsorption film, sigma is representative of the thickness of the monomolecular layer)
A plot of the adsorption amount v on t is t-plot, and a straight line broken at the t value corresponding to the pore diameter is obtained. The outer surface area of the sample having pores can be obtained from the high-pressure side, that is, the slope of the straight line having the larger t value. The measurement of the nitrogen adsorption method and the analysis of the BET surface area and the outer surface area by t-plot can be performed using a commercially available adsorption measurement device such as Nippon Bell Co., Ltd. or Yuasa Ionics.

The crystal size of the zeolite in the catalyst of the present invention is usually 0.1 to 40 nm, preferably 1 to 40 nm. According to a usual synthesis method, the crystal size is 0.1 nm or more, and the yield of adamantanes is improved by being 40 nm or less. The crystal size is a calculated value obtained from the following equation (2) using the half width of the peak appearing in the vicinity of 2θ = 26 ° ± 1 of the X-ray diffraction pattern obtained from the XRD measurement.
D = Kλ / Bcos θ (2)
(In the above formula, D represents the crystal size, K represents the Scherrer constant, λ represents the X-ray wavelength, B represents the broadening of the diffraction line width due to the finite crystal size, and θ represents XRD. (It represents the diffraction angle (RAD) of the peak obtained from the measurement)
In the present invention, the Scherrer constant is 0.9, and the X-ray wavelength is CuKα1 line (1.5406 mm). The measurement of the line width peculiar to the apparatus was performed by measuring the half width of the Si (111) diffraction peak appearing in the vicinity of 2θ = 28.4 ° using NBS standard silicon SRM640a (average particle diameter 6 μm).
The X-ray diffraction pattern can be measured with, for example, a powder X-ray diffraction apparatus Ultimate III manufactured by Rigaku Corporation.

  In the catalyst of the present invention, Si / Al (mol / mol) is usually 5 to 17, preferably 5.5 to 16. Within this range, the crystal size of the zeolite is reduced, and the yield of adamantanes is improved.

  The method for producing a zeolite having an MWW type topology used in the present invention is not particularly limited. For example, a zeolite precursor is prepared by a hydrothermal synthesis method as described below, followed by treatment such as calcination, ammonium ion exchange, and calcination again. Thus, the zeolite used in the present invention can be produced.

Examples of the zeolite precursor include silica sources such as fumed silica, aluminum sources such as sodium aluminate, bases such as alkali metal hydroxides and mineralizers such as fluorides, organic amines or salts thereof serving as templates, And a hydrothermal synthesis method in which the solvent is heat-treated. Examples of the organic amine used as a template or a salt thereof include adamantane quaternary ammonium ions, hexamethyleneimine, and piperidine, and hexamethyleneimine is particularly preferable. The reaction conditions for the hydrothermal synthesis method are not particularly limited, but are usually 80 to 225 ° C. and 1 to 60 days.
A zeolite having an MWW topology is obtained by firing the zeolite precursor obtained by the hydrothermal synthesis. The baking treatment can be performed by a normal method, for example, heating in an atmosphere of 200 to 700 ° C. in an atmosphere such as air or nitrogen, under atmospheric pressure, reduced pressure or increased pressure for 0.5 to 48 hours. This can be done.

The ammonium ion exchange treatment can be performed using an aqueous solution of an ammonium salt such as ammonium chloride, ammonium nitrate, or ammonium sulfate. Further, instead of ammonium ion exchange treatment, acid treatment may be performed using an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, or an organic acid such as formic acid or acetic acid.
By calcination after the above treatment, a zeolite having a proton type MWW topology can be obtained. The baking treatment can be performed by a normal method, for example, heating in an atmosphere of 200 to 700 ° C. in an atmosphere such as air or nitrogen, under atmospheric pressure, reduced pressure or increased pressure for 0.5 to 48 hours. This can be done.
Although the zeolite used in the present invention can be produced by the above method, in particular, the outer surface area and the crystal size can be adjusted by the Si / Al ratio.

  Furthermore, when preparing the zeolite precursor, a zeolite or zeolite precursor having an MWW type topology manufactured separately may be added to the raw material, and hydrothermal synthesis may be performed using this. According to this method, the hydrothermal synthesis time can be greatly shortened, and the zeolite catalyst of the present invention can be efficiently prepared. The amount of zeolite or zeolite precursor having an MWW topology to be added is usually 0.001 to 60% by mass, preferably 1 to 40% by mass, based on the charged amount of silica.

  The catalyst of the present invention may be an active metal supported catalyst. By supporting the active metal, catalyst deterioration is suppressed. Examples of the active metal include metals belonging to Groups 8 to 10 of the periodic table and rhenium, preferably a metal selected from ruthenium, rhodium, palladium, iridium, platinum and rhenium, and platinum is particularly preferable. It is. These active metals may be supported alone or in combination of two or more. The amount of the active metal supported is not particularly limited, but is usually 1% by mass or less, preferably 0.0001 to 1% by mass based on the total amount of the catalyst from the viewpoint of catalyst activity. Within this range, catalyst deterioration is suppressed, and adamantanes are obtained in high yield.

Examples of the active metal loading method include an ion exchange method and an impregnation method.
In the case of an ion exchange method, an aqueous salt or complex salt solution of the active metal is brought into contact with a predetermined zeolite, and cation sites in the zeolite, such as alkali metal ions, H ⁺ , NH ₄ ^{+ and the} like, are ion-exchanged and then dried. The desired catalyst can be obtained by firing treatment.
In the case of the impregnation method, a desired catalyst can be obtained by mixing a predetermined zeolite and a salt or complex salt of an active metal, distilling off water according to a conventional method, and then calcining the dried solid.
The temperature of the firing treatment is appropriately selected according to the type of metal used in the ion exchange method, the type of metal used in the impregnation method, and the like. There is no restriction | limiting in particular about the shape of the catalyst of this invention obtained in this way, Powder form, a granular form, cylindrical form, etc. may be arbitrary.

  The catalyst of the present invention is suitably used as a catalyst for the isomerization reaction of a tricyclic saturated hydrocarbon compound, and particularly a compound having an adamantane structure by using a tricyclic saturated hydrocarbon compound having 10 or more carbon atoms as a raw material. Can be produced with high selectivity and high yield. Hereinafter, a method for producing a compound having an adamantane structure will be described.

In the method for producing adamantanes using the zeolite catalyst of the present invention, examples of the raw material include tricyclic saturated hydrocarbon compounds having 10 or more carbon atoms. Among these, tricyclic saturated hydrocarbon compounds having 10 to 15 carbon atoms and those having a relatively large strain between carbon-carbon bonds are preferable. For example, trimethylene norbornane [tetrahydrodicyclopentadiene], dimethyltrimethylene Examples thereof include norbornane, perhydroacenaphthene, perhydrofluorene, perhydrophenalene, 1,2-cyclopentanoperhydronaphthalene, perhydroanthracene, perhydrophenanthrene. Furthermore, the alkyl substituted body of these compounds, for example, 9-methyl perhydroanthracene, etc. are mentioned as a suitable thing. Of these, trimethylene norbornane, dimethyltrimethylene norbornane, perhydroacenaphthene and perhydrofluorene are particularly preferred.
These tricyclic saturated hydrocarbon compounds having 10 or more carbon atoms can be easily obtained by hydrogenating raw material compounds such as dicyclopentadiene and acenaphthene in the presence of a known hydrogenation catalyst such as Raney nickel or platinum. Can get to.

When isomerizing the tricyclic saturated hydrocarbon compound having 10 or more carbon atoms, the reaction can be carried out in the presence of a monocyclic saturated hydrocarbon compound, an aromatic compound, water, alcohols, and the like. When the reaction is carried out in the presence of these compounds, the selectivity of adamantanes is improved.
Here, examples of the monocyclic saturated hydrocarbon compound to coexist include cyclopentane, cyclohexane, ethylcyclohexane, methylcyclohexane, and the like. In particular, cyclohexane or ethylcyclohexane or a mixture thereof is suitable. Examples of aromatic compounds include aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and anthracene; oxygen-containing aromatic compounds such as phenol, benzaldehyde, benzoic acid, benzyl alcohol, and anisole; Nitrogen aromatic compounds; halogen-containing aromatic compounds such as chlorobenzene and bromobenzene. Among these aromatic compounds, aromatic hydrocarbon compounds such as benzene, toluene, xylene, naphthalene and anthracene are particularly preferable. On the other hand, examples of alcohols include monohydric alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, tert-butyl alcohol, and benzyl alcohol, and polyhydric alcohols such as ethylene glycol and glycerin.
There is no restriction | limiting in particular in the addition amount of these compounds to coexist, It can select suitably according to various situations.

If the reaction temperature of the isomerization reaction is too high, by-products due to the decomposition reaction increase, the selectivity of the adamantane tends to decrease, and the yield of the adamantane tends to decrease. On the other hand, if the reaction temperature is too low, the conversion rate of the raw materials tends to decrease and the yield of adamantanes tends to decrease. Therefore, the reaction temperature is usually 150 to 450 ° C., preferably 200 to 400 ° C., and more preferably 250 to 350 ° C. Within this range, the higher the reaction temperature, the higher the yield of adamantanes.
The reaction pressure of the isomerization reaction is usually normal pressure or increased pressure. It is desirable to carry out under pressure so that it may become a liquid phase reaction.
The isomerization reaction may be performed in the presence of hydrogen. By coexisting hydrogen, catalyst deterioration is suppressed.

The reaction format may be either a flow type or a batch type. In the case of the flow type, the weight hourly space velocity (WHSV) is usually selected in the range of 0.01 to 50 h ⁻¹ , preferably 0.1 to 30 h ^−1. The lower the WHSV, the higher the yield of adamantanes. Become. The molar ratio of hydrogen / tricyclic saturated hydrocarbon compound having 10 or more carbon atoms is usually in the range of 0 to 10, preferably 0 to 5. Within the range, the yield of adamantanes increases. On the other hand, in the case of a batch type, the catalyst / raw material mass ratio is usually selected within the range of 0.01 to 2, preferably 0.05 to 1. The reaction time is usually about 1 to 50 hours.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples. The catalyst performance was evaluated by the following calculation.
(1) Conversion rate: (1-raw material mass after reaction / raw material mass before reaction) × 100 (mass%)
(2) Adamantane (ADM) class selectivity: [mass of generated ADMs / (mass of raw material before reaction-mass of raw material after reaction)] × 100 (mass%)
(3) Yield of adamantane (ADM): (mass of produced ADMs / mass of raw material before reaction) × 100 (mass%)

[Example 1] Preparation of catalyst A 131 g of pure water, 2.33 g of sodium aluminate, 0.008 g of sodium hydroxide, 8.25 g of hexamethyleneimine and 10.0 g of fumed silica were added to a Teflon container. The gel was prepared by stirring at room temperature for 0.5 hour. The obtained gel was charged into a Teflon (registered trademark) autoclave and heated at 150 ° C. for 168 hours while stirring at 20 rpm in a hydrothermal synthesizer. The obtained crystal product was filtered, washed with water, and dried at 120 ° C. overnight. The dried crystal product was baked at 540 ° C. for 12 hours in an air atmosphere to obtain a white powder.
400 g of a 1 mol / L ammonium nitrate aqueous solution was added to 4 g of the obtained white powder, and the mixture was heated and stirred at 80 ° C. for 1 hour, and then filtered and washed with water. By repeating this operation four times, ammonium ion exchange was performed. The white powder after the ion exchange was dried at 120 ° C. and then calcined at 540 ° C. for 12 hours to obtain a zeolite having a proton type MWW topology as a white powder.
An aqueous solution in which 0.0072 g of Pt (NH ₃ ) ₄ Cl ₂ .H ₂ O was dissolved in 2.8 ml of pure water was prepared. A few drops of Pt (NH ₃ ) ₄ Cl ₂ .H ₂ O aqueous solution was dropped into 4 g of the above white powder and kneaded well. After all the Pt (NH ₃ ) ₄ Cl ₂ · H ₂ O aqueous solution was added, it was calcined in air at 300 ° C. for 3 hours to obtain a 0.1 mass% Pt-supported catalyst. The physical properties of the obtained catalyst A are shown in Table 1, and the results of measuring the X-ray diffraction pattern using an X-ray diffractometer using Cu-Kα radiation are shown in FIG.

[Example 2] Preparation of catalyst B A catalyst was prepared in the same manner as in Example 1 except that 3.88 g of sodium aluminate was added and sodium hydroxide was not added. The physical properties of the obtained catalyst B are shown in Table 1, and the X-ray diffraction pattern is shown in FIG.

[Example 3] Preparation of catalyst C A catalyst was prepared in the same manner as in Example 1 except that sodium aluminate (1.55 g) and sodium hydroxide (0.34 g) were used. The physical properties of the obtained catalyst C are shown in Table 1, and the X-ray diffraction pattern is shown in FIG.

[Example 4] Preparation of catalyst D A catalyst was prepared in the same manner as in Example 1 except that 10% by mass of the white powder obtained in Example 1 was added to the mass of silica and the heating time was 96 hours. Was prepared. The physical properties of the catalyst D obtained are shown in Table 1, and the X-ray diffraction pattern is shown in FIG.

[Comparative Example 1] Preparation of catalyst E A catalyst was prepared in the same manner as in Example 1 except that sodium aluminate was 5.81 g and sodium hydroxide was not added. The physical properties of the obtained catalyst E are shown in Table 1, and the X-ray diffraction pattern is shown in FIG.

[Comparative Example 2] Preparation of catalyst F A catalyst was prepared in the same manner as in Example 1 except that 1.30 g of sodium aluminate and 0.44 g of sodium hydroxide were used. The physical properties of the catalyst F obtained are shown in Table 1, and the X-ray diffraction pattern is shown in FIG.

[Comparative Example 3] Preparation of Catalyst G A catalyst was prepared in the same manner as in Example 1 except that 0.93 g of sodium aluminate and 0.60 g of sodium hydroxide were used. The physical properties of the catalyst G obtained are shown in Table 1, and the X-ray diffraction pattern is shown in FIG.

Comparative Example 4 Preparation of Catalyst H A catalyst was prepared in the same manner as in Example 1 except that the heating time was 96 hours. The physical properties of the catalyst H obtained are shown in Table 1, and the X-ray diffraction pattern is shown in FIG.

Example 5
2 g of the catalyst obtained in Example 1 was filled in a SUS reaction tube and calcined at 300 ° C. for 3 hours in a normal pressure and air stream. Thereafter, supply of an ethylcyclohexane solution of 77% by mass trimethylenenorbornane (TMN) was started, and continuous under the conditions of 300 ° C., reaction pressure 6 MPa, H ₂ /TMN=2.5, WHSV = 7 h ⁻¹ (TMN standard). Reaction was carried out. Table 2 shows the results after 50 hours from the start of raw material supply.

Example 6
The reaction was conducted in the same manner as in Example 5 except that the reaction temperature was 325 ° C. Table 2 shows the results after 50 hours from the start of raw material supply.

Example 7
The reaction was performed in the same manner as in Example 5 except that WHSV was changed to 1.75 h ⁻¹ (TMN standard). Table 2 shows the results after 50 hours from the start of raw material supply.

Example 8
The reaction was performed in the same manner as in Example 5 except that the catalyst prepared in Example 2 was used. Table 2 shows the results after 50 hours from the start of raw material supply.

Example 9
The reaction was performed in the same manner as in Example 5 except that the catalyst prepared in Example 2 and WHSV were changed to 1.75 h ⁻¹ (TMN standard). Table 2 shows the results after 50 hours from the start of raw material supply.

Example 10
The reaction was performed in the same manner as in Example 5 except that the catalyst prepared in Example 3 was used. Table 2 shows the results after 50 hours from the start of raw material supply.

Example 11
The reaction was carried out in the same manner as in Example 5 except that the catalyst prepared in Example 3 and WHSV were changed to 1.75 h ⁻¹ (TMN standard). Table 2 shows the results after 50 hours from the start of raw material supply.

Example 12
The reaction was performed in the same manner as in Example 5 except that the catalyst prepared in Example 4 was used. Table 2 shows the results after 50 hours from the start of raw material supply.

Example 13
The reaction was performed in the same manner as in Example 5 except that the raw material was an ethylcyclohexane solution of 80% by mass perhydroacenaphthene. Table 2 shows the results after 50 hours from the start of raw material supply.

Example 14
The reaction was conducted in the same manner as in Example 5 except that the raw material was an ethylcyclohexane solution of 80% by mass perhydrofluorene. Table 2 shows the results after 50 hours from the start of raw material supply.

[Comparative Example 5]
2 g of the catalyst obtained in Comparative Example 1 was filled in a SUS reaction tube and calcined at 300 ° C. for 3 hours in a normal pressure and air stream. Thereafter, supply of an ethylcyclohexane solution of 77% by mass trimethylenenorbornane (TMN) was started, and continuous under the conditions of 300 ° C., reaction pressure 6 MPa, H ₂ /TMN=2.5, WHSV = 7 h ⁻¹ (TMN standard). Reaction was carried out. Table 2 shows the results after 50 hours from the start of raw material supply.

[Comparative Example 6]
The reaction was performed in the same manner as in Comparative Example 5 except that the catalyst prepared in Comparative Example 2 was used. Table 2 shows the results after 50 hours from the start of raw material supply.

[Comparative Example 7]
The reaction was performed in the same manner as in Comparative Example 5 except that the catalyst prepared in Comparative Example 3 was used. Table 2 shows the results after 50 hours from the start of raw material supply.

[Comparative Example 8]
The reaction was carried out in the same manner as in Comparative Example 5 except that the catalyst prepared in Comparative Example 2 and WHSV were changed to 1.75 h ⁻¹ (TMN standard). Table 2 shows the results after 50 hours from the start of raw material supply.

[Comparative Example 9]
The reaction was carried out in the same manner as in Comparative Example 5 except that the catalyst prepared in Comparative Example 3 and WHSV were changed to 1.75 h ⁻¹ (TMN standard). Table 2 shows the results after 50 hours from the start of raw material supply.

[Comparative Example 10]
The reaction was performed in the same manner as in Comparative Example 5 except that the catalyst prepared in Comparative Example 4 was used. Table 2 shows the results after 50 hours from the start of raw material supply.

  According to the present invention, a catalyst used for the isomerization reaction of a tricyclic saturated hydrocarbon compound having 10 or more carbon atoms is obtained, and adamantanes are produced with high selectivity and high yield by using the catalyst. Can do.

Claims (9)

A catalyst containing a zeolite having an MWW type topology, a ratio of an outer surface area to a total surface area of 0.3 or more, and an outer surface area of 145 to 600 m ² / g.   The catalyst according to claim 1, wherein the zeolite has a crystal size of 0.1 to 40 nm.   The catalyst according to claim 1 or 2, wherein Si / Al (mol / mol) is 5 to 17.   The catalyst according to any one of claims 1 to 3, wherein the catalyst is an active metal-supported catalyst, and the active metal is a metal selected from Group 8 to Group 10 of the periodic table and rhenium.   The catalyst according to claim 4, wherein the active metal is platinum.   The catalyst according to claim 4 or 5, wherein the amount of the active metal supported is 1% by mass or less based on the total amount of the catalyst. The following steps 1-4
Step 1: Step of preparing a zeolite precursor by hydrothermal synthesis method Step 2: Step of firing after Step 1 Step 3: Step of performing ammonium ion exchange treatment or acid treatment after Step 2 Step 4: Firing after Step 3 A method for producing a catalyst according to any one of the above 1 to 6, comprising a step of adding a zeolite having a MWW topology and / or a zeolite precursor separately produced in step 1 to a raw material. A method for producing a catalyst, comprising performing hydrothermal synthesis.   A method for producing a compound having an adamantane structure by isomerizing a tricyclic saturated hydrocarbon compound having 10 or more carbon atoms using the catalyst according to any one of claims 1 to 6.   The production method according to claim 8, wherein the tricyclic saturated hydrocarbon compound is a compound selected from trimethylene norbornane, dimethyltrimethylene norbornane, perhydroacenaphthene and perhydrofluorene.

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