JPH0331182B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing adamantanes, and more specifically to a method for producing adamantanes, and more specifically, a lanthanum-exchanged Y containing a specific active metal.
This invention relates to a method for producing adamantanes with high selectivity from tricyclic saturated hydrocarbons having 10 or more carbon atoms by using zeolite obtained by sulfurizing zeolite with ammonium sulfate as a catalyst. Conventionally, cation exchange has been used to produce adamantanes by isomerizing tricyclic saturated hydrocarbons having 10 or more carbon atoms, such as trisic[5,2,1,0 ^2,6 ]decane (TCD). platinum on zeolite,
It is known to use catalysts supporting active metals such as rhenium, nickel, and cobalt. However, these conventional catalysts have the problem that side reactions such as ring-opening reactions of tricyclic saturated hydrocarbons, which are raw materials, tend to occur, and the selectivity of adamantanes, which are target products, is low. Therefore, the present inventors have conducted extensive research in order to solve the problems of the above-mentioned conventional techniques and develop a method for producing adamantanes with high selectivity. As a result, they discovered that the object could be achieved by using as a catalyst a lanthanum-exchanged Y-type zeolite that supported a specific active metal and was treated with ammonium sulfate, leading to the completion of the present invention. That is, the present invention uses platinum,
The present invention provides a method for producing adamantanes, which uses a lanthanum-exchanged Y-type zeolite carrying rhenium and cobalt treated with ammonium sulfate. The catalyst used in the method of the present invention is a lanthanum-exchanged Y-type zeolite carrying platinum, rhenium, and cobalt, which is sulfurized with ammonium sulfate, as described above. An active metal may be supported on this lanthanum-exchanged Y-type zeolite by any suitable means such as immersing the zeolite in an aqueous solution containing platinum, rhenium, and cobalt. The catalyst in the present invention is obtained by sulfurizing such an active metal-supported cation exchange zeolite with ammonium sulfate. This treatment can be carried out by various methods, but usually the above-mentioned zeolite may be placed in an aqueous solution of ammonium sulfate and stirred at an appropriate temperature and time. By performing this treatment, sulfate ions are introduced into the zeolite, but the amount introduced varies depending on the type of zeolite, the type of active metal to be supported, etc., and cannot be uniquely determined. Generally, the proportion of sulfate ions to the lanthanum-exchanged Y-type zeolite supporting a specific active metal may be set at 0.1 to 10% by weight. In the present invention, the zeolite thus obtained may be dried and calcined and used as it is, but after treatment with ammonium sulfate, it may be further heated to 350 to 600°C in a hydrogen stream. Reduction processing is also effective. Here, even if the lanthanum-exchanged Y-type zeolite carrying a specific active metal without ammonium sulfate treatment is directly used as a catalyst for the isomerization reaction, there will be many side reactions and the selectivity of adamantanes will not be high. Moreover, zeolite obtained even when other sulfur-containing compounds are used in the sulfurization treatment without using ammonium sulfate does not serve as a catalyst for producing adamantanes with high selectivity through an isomerization reaction. The raw material compound that can be used in the method of the present invention has a carbon number of
It is a tricyclic saturated hydrocarbon of 10 or more, and is selected depending on the type of adamantane to be produced. Specifically, tricyclo[5,2,1,0 ^2,6 ]decane; perhydroacenaphthene; perhydrofluorene;
Examples include perhydrophenanthrene; 1,2-cyclopentanoperhydronaphthalene; perhydroanthracene; perhydrophenanthrene; 9-methylperhydroanthracene. The conditions for the isomerization reaction in the method of the present invention are not particularly limited and may be determined as appropriate depending on various situations, but generally they are carried out under a gas atmosphere containing hydrogen gas or hydrogen chloride gas at a temperature of 150°C. The temperature may be set within the range of ~300°C and normal pressure ~50 atm. Further, this reaction may be carried out either batchwise or in a flow manner. For batch type, catalyst/raw material ratio is 0.05~
2.0 (wt/wt), and the contact time is preferably in the range of 1 to 50 hours. In the case of a flow type, the weight hourly space velocity (WHSV) is preferably about 0.05 to 5.0 hr ^-1 . According to the method of the present invention, there are few side reactions during the reaction, the intended isomerization reaction proceeds efficiently, and adamantanes are produced with high selectivity. Therefore, the method of the present invention is extremely valuable as an efficient method for producing adamantanes, which are useful as intermediates for various chemical products including pharmaceuticals. Next, the present invention will be explained in more detail with reference to Examples. Experimental example 1 (1) Preparation of catalyst Platinum, rhenium, and cobalt were supported on lanthanum-exchanged Y-type zeolite (manufactured by Union Carbide Co., Ltd., SK500) with aqueous solutions of chloroplatinic acid, ammonium perrhenate, and cobalt nitrate, respectively. Platinum 0.75wt%, rhenium 0.25wt%, cobalt 3wt%
A metal-supported zeolite was prepared. Next, add 100g of this metal-supported zeolite to a concentration of 0.1
The mixture was placed in 500 ml of an aqueous ammonium sulfate solution of 4.5% by weight as sulfate ions on the metal-supported zeolite by evaporation to dryness on a water bath. Furthermore, the obtained zeolite was dried at 120°C for 2 hours, and reduced in a hydrogen stream at 450°C for 1 hour to obtain a zeolite catalyst. (2) Isomerization reaction In a 100 ml autoclave, add 2 g of the catalyst obtained in (1) above and tricyclo[5,2,1,0 ^2,6 ]
Add 4 g of decane (TCD), hydrogen partial pressure 15 atm,
The isomerization reaction was carried out for 2 hours at a hydrogen chloride partial pressure of 1 atm and a temperature of 250°C. The results are shown in Table 1. Experimental Example 2 (1) Preparation of Catalyst A zeolite catalyst was obtained by carrying out the same operations as in Experimental Example 1(1), except that the metal-supported zeolite was not treated with the ammonium sulfate aqueous solution in Experimental Example 1(1). Ta. (2) Isomerization reaction An isomerization reaction was carried out under the same conditions as in Experimental Example 1(2), except that the zeolite obtained in Experimental Example 2(1) above was used as a catalyst. The results are shown in Table 1. 【table】

Claims (1)

[Scope of Claims] 1. A lanthanum-exchanged Y-type zeolite supporting platinum, rhenium, and cobalt as an isomerization catalyst for isomerizing a tricyclic saturated hydrocarbon having 10 or more carbon atoms to produce a hydrocarbon having an adamantane structure. 1. A method for producing adamantanes, the method comprising using adamantane treated with ammonium sulfate. 2. The method according to claim 1, wherein the tricyclic saturated hydrocarbon having 10 or more carbon atoms is tricyclo[5,2,1,0 ^2,6 ]decane.