JP2002241322A - Method for producing adamantane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an adamantane in a good efficiency by using a solid catalyst without using hydrogen chloride. SOLUTION: This method for producing a hydrocarbon having an adamantane structure by isomerizing a >=10C tricyclic saturated hydrocarbon is characterized by using a zeolite containing 1 kind or >=2 kinds of metals selected from metals of the VIII group of the periodic table (in 8th to 10th group in the new Periodic table) and fluorine, as a catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a hydrocarbon having an adamantane structure by isomerizing a tricyclic saturated hydrocarbon having 10 or more carbon atoms.

[0002]

2. Description of the Related Art Adamantane isomerizes trimethylenenorbornane (hereinafter sometimes abbreviated as TMN) obtained by hydrogenating dicyclopentadiene (hereinafter sometimes abbreviated as DCPD) with a catalyst. Is a compound obtained by the Industrially, aluminum chloride has been conventionally used as a catalyst. However, when producing adamantane using aluminum chloride as a catalyst, it is necessary to use a large amount of the catalyst. Moreover, this catalyst cannot be reused because it forms a complex with heavy components during 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. Also, since aluminum chloride is highly corrosive, it is necessary to use an expensive apparatus made of a corrosion-resistant material. Furthermore, when aluminum chloride is used, the produced adamantane is colored, so that a recrystallization step and a decolorization step using activated carbon or the like are required, and the post-treatment is complicated. On the other hand, as a solid catalyst, a catalyst in which an active metal such as platinum, rhenium, nickel, cobalt or the like is supported on a zeolite which has been subjected to cation exchange using a rare earth metal or an alkaline earth metal by an impregnation method is known (Japanese Patent Publication No. 52-1982). No. 2909). However, even in the case of using such a solid catalyst, the yield of adamantane is low (TMN conversion: 79.5%, adamantane selectivity: 10.1%, adamantane yield: 8.0%, unless hydrogen chloride is present). ). Therefore, hydrogen chloride is indispensable, and due to the strong corrosiveness of hydrogen chloride, it is necessary to use an expensive apparatus made of a corrosion-resistant material (see Japanese Patent Publication No. 52-2909).

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method capable of efficiently producing adamantane using a solid catalyst without using hydrogen chloride.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that, as a solid catalyst, at least one of metals belonging to Group VIII of the periodic table (metals belonging to Groups 8 to 10 in the new periodic table). It has been found that the above object can be achieved by using a zeolite containing one kind of metal and fluorine. The present invention has been completed based on such findings. That is, the present invention relates to a process for producing a hydrocarbon having an adamantane structure by isomerizing a tricyclic saturated hydrocarbon having 10 or more carbon atoms, as a catalyst, a group VIII of the periodic table (8th in the new periodic table). It is intended to provide a process for producing adamantane, characterized by using a zeolite containing one or more metals selected from metals of Group 10 to 10) and fluorine.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The catalyst used in the process of the present invention is
As described above, the zeolite contains one or more metals selected from the metals of Group VIII of the periodic table (Groups 8 to 10 in the new periodic table) and fluorine. Here, the metal of Group VIII of the periodic table (Groups 8 to 10 in the new periodic table) is not particularly limited, and iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium,
There are iridium and platinum, of which platinum is particularly preferred.

[0006] The catalyst used in the present invention can be produced as follows. Examples of the method for containing a metal include an ion exchange method and an impregnation method. In the case of the ion exchange method, one or more metals selected from Group VIII of the periodic table are brought into contact with zeolite, for example, as an aqueous solution of a metal salt or a metal complex salt, and the cation site of the Y-type or X-type zeolite is contacted. (For example, H ⁺ , NH ₄ ⁺ ) is obtained by ion exchange, drying and firing. Also,
In the case of the impregnation method, after mixing with an aqueous solution of a metal salt or a metal complex salt, the mixture may be evaporated to dryness using a rotary evaporator or the like to carry out impregnation. As a method for containing fluorine, there are a method of supporting a fluorine-containing compound on zeolite and a method of contact-treating zeolite with a fluorine-containing compound. Examples of the fluorine-containing compound include fluorine-containing inorganic compounds such as ammonium fluoride, hydrogen fluoride, and boron trifluoride, and fluorine-containing organic compounds such as 1,2-dichloro-1,1,2,2-tetrafluoroethane. it can. In the case of the loading method, for example, an aqueous solution of ammonium fluoride is mixed with zeolite, and then evaporated to dryness using a rotary evaporator to carry out impregnation. In the case of the contact treatment method, for example, 1,2-dichloro-1,1,2,2-tetrafluoroethane may be brought into contact with zeolite in a gas phase at 200 to 600 ° C. The order in which the zeolite contains metal and fluorine is not limited.

[0007] In the catalyst of the present invention, VIII of the periodic table
The content of one or more metals and fluorine selected from the group (groups 8 to 10 in the new periodic table) and fluorine is not particularly limited. 0.1% by weight or more, and in the case of fluorine, 0.01% by weight
It is preferable that this is the case. The shape of the catalyst may be arbitrary such as powder or granule.

The starting material used in the method of the present invention is a tricyclic saturated hydrocarbon having 10 or more carbon atoms. Specifically, for example, trimethylene norbornane, dimethyl trimethylene norbornane, perhydroacenaphthene, perhydrogen Fluorene, perhydrophenalene, 1,2-cyclopentanoperhydronaphthalene, perhydroanthracene, perhydrophenanthrene, 9-methylperhydroanthracene, and the like. These tricyclic saturated hydrocarbons can be produced by known methods, for example, by hydrogenation of the corresponding unsaturated hydrocarbon.

In the method of the present invention, the isomerization reaction is carried out in the presence of the above-mentioned catalyst at a reaction temperature of about 150 to 300 ° C. and a reaction pressure of normal pressure or pressure. The reaction format may be continuous or batchwise. It is preferable to carry out this reaction in the coexistence of hydrogen from the viewpoint of improving the yield of adamantane. The amount of the catalyst used is 0.01 to 2 (catalyst weight / raw material weight), preferably 0.05 to 1 (catalyst weight / raw material weight) in the case of a batch system. The regeneration of the catalyst can be performed by a method such as firing in air.

[0010]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 2000 g of 235 g of Na type Y zeolite (hereinafter referred to as NaY) having a SiO ₂ / Al ₂ O ₃ molar ratio of 5.0
In pure water with stirring, and 114 g of ammonium sulfate
Was added and dissolved, and the mixture was heated to 60 ° C. and stirred for 30 minutes. This slurry was filtered and washed with 2500 g of pure water. This is dried at 110 ° C overnight, and then dried in air at 600 ° C.
For 3 hours to obtain a primary ion exchange product. This primary ion exchange product was suspended in 2000 g of pure water, and 228 g
After adding ammonium sulfate, the mixture was heated to 95 ° C. and stirred for 30 minutes. Then, it was washed with 2000 g of pure water. This operation was repeated three times, and the obtained secondary ion-exchanged product was
Type ₄ Y type zeolite (hereinafter referred to as NH ₄ Y) was used.
The obtained NH ₄ Y180g stirred suspension of pure water 2000 g, a 1.71% tetraammineplatinum chloride solution 18
0 g was added and the mixture was stirred at 60 ° C. for 30 minutes. This was filtered and washed, and dried at 110 ° C. overnight to obtain 0.6% Pt / N.
H ₄ Y was obtained. An aqueous solution was prepared by dissolving 0.1950 g of NH ₄ F in 4 ml of pure water. While kneading 10 g of the catalyst obtained by the above operation, an aqueous NH ₄ F solution was gradually added.
After all the aqueous solutions were added, the mixture was dried at 130 ° C. for 12 hours (F addition amount: 1% by weight). 4 g of the obtained catalyst was filled in a stainless steel (SUS) reaction tube, and calcined at 500 ° C. for 3 hours under normal pressure and air flow. After replacing with nitrogen, normal pressure,
Hydrogen reduction was performed at 500 ° C. for 3 hours under a stream of water. Then, T
Starting supply of MN and hydrogen, 200 ° C., 2 MPa, weight hourly space velocity (WHSV) = 2.4 h ⁻¹ (based on TMN),
The reaction was continuously performed under the condition of hydrogen / TMN molar ratio = 2. Table 1 shows the results 50 hours after the start of TMN supply.
The TMN conversion, adamantane selectivity, and adamantane yield were calculated according to the following equations. TMN conversion rate = (1-weight of TMN after reaction / T before reaction)
MN weight) × 100 Adamantane selectivity = [weight of adamantane formed / (weight of TMN before reaction−weight of TMN after reaction)] × 100 Adamantane yield = TMN conversion rate × adamantane selectivity / 100

Comparative Example 1 Preparation of a catalyst, pretreatment of the catalyst and reaction were carried out in the same manner as in Example 1 except that no NH ₄ F was added. TMN
Table 1 shows the results 50 hours after the start of the supply.

[0013]

[Table 1]

[0014]

According to the present invention, the solid catalyst contains one or more metals selected from the metals of Group VIII of the periodic table (Groups 8 to 10 in the new periodic table) and fluorine. By using a zeolite, the yield of adamantanes can be remarkably improved, and since a highly corrosive substance such as hydrogen chloride is not used in the production, it is necessary to use a corrosion-resistant material in the production equipment. Therefore, adamantane can be produced efficiently at low cost.

Continued on the front page (72) Inventor Shunji Tsuruta 13-2 Kitaminato-cho, Wakamatsu-ku, Kitakyushu-shi, Fukuoka (72) Inventor Masamitsu Ogata 580 Horikawa-cho, Saiwai-ku, Kawasaki-shi, Kanagawa F-term (reference) 4G069 AA03 AA08 BA07A BA07B BC64A BC69A BC75A BC75B BD15A BD15B CB41 DA06 FA01 FB44 ZA04A ZA04B ZD01 4H006 AA02 AC27 AC28 BA22 BA26 BA71 DA15 4H039 CA40 CH30 CJ10

Claims (3)

[Claims] In producing a hydrocarbon having an adamantane structure by isomerizing a tricyclic saturated hydrocarbon having 10 or more carbon atoms, a group VIII of the periodic table (8 to 10 in the new periodic table) is used as a catalyst. One or two selected from metals of group 10)
A process for producing adamantanes, comprising using a zeolite containing at least one kind of metal and fluorine. 2. The method for producing adamantane according to claim 1, wherein the metal of Group VIII (Groups 8 to 10 in the new periodic table) of the periodic table is platinum. 3. The method for producing adamantane according to claim 1, wherein the zeolite is a Y-type zeolite.