JPH04317743A - Catalyst for use in production of alkyladamantanes and method for production thereof using said catalyst - Google Patents

Abstract

PURPOSE:To obtain a highly active catalyst for use in the industrial production of alkyladamantanes by a method wherein, after treatment with sulfone acid, gamma-alumina and/or zirconia are baked to support sulfonic acid ions thereon. CONSTITUTION:After treatment with 0.1-3N sulfonic acid, gamma-alumina and/or zieconia are baked at a temp. of 400-750 deg.C to obtain a catalyst for use in the production of alkyladamantanes. The gamma-alumina or zirconia is treated with sulfuric acid usually at room temp. by immersing or spraying method. By conducting the isomerization of perhydroacenaphthene at 5-30atm and 200-270 deg.C in the presence of the aforesaid catalyst, the alkyladamantanes having 12 carbon atoms are produced. The catalyst for use in this isomerization may be in an amt. of at least 1/5 time the perhydroacenaphthene, preferably 1/4 to 4/1. The isomerization may be performed by using a batch type complete mixing tank such as autoclave, pressure distribution method or any other means.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for producing alkyladamantanes useful as raw materials for high-grade functional polymer compounds and pharmaceuticals, and a method for producing alkyladamantanes using the same.

0002

BACKGROUND OF THE INVENTION Several methods for producing alkyladamantanes have already been disclosed. No. 12706, etc.), as well as a method of production using an aluminum halide catalyst in a halogenated hydrocarbon solvent (Japanese Unexamined Patent Publication No. 159330/1989)
It can be roughly divided into two types: JP-A-2-138135, etc.). The method using a zeolite catalyst is an excellent method in that it does not generate a large amount of waste acid unlike the aluminum halide catalyst method and it is easy to separate the catalyst and product, but the method does not have sufficient catalytic activity. In addition, there were other problems, such as low selectivity to adamantanes because decomposition products are produced by ring-opening reactions, etc., and the catalyst composition is complex, increasing catalyst cost. Japanese Patent Application Publication 1986-
According to Publication No. 246333, it is stated that the selectivity of the adamantane production reaction is improved by treating the above-mentioned zeolite catalyst with an ammonium sulfate aqueous solution and calcining it to use a catalyst supporting sulfate ions.
The improvement in yield due to the support of sulfate ions is only 1.6 times, and the selectivity for the decomposition reaction is not described. Also,
Similarly, the catalyst composition is complex.

On the other hand, as an example of research using a solid catalyst other than zeolite, a chlorinated Pt/Al2 O3 catalyst (J. Chem. Soc., 93, 2798 (197
1)), but both catalyst activity and catalyst life are extremely low and cannot be used as industrial catalysts. As mentioned above, catalysts that are highly active, have low selectivity for decomposition reactions, have a simple composition, and are easy to manufacture, enable the industrial production of alkyladamantanes at low cost. It has not been found yet.

0004

[Problems to be Solved by the Invention] As stated above, in applying solid catalysts such as zeolites as catalysts for producing alkyl adamantanes, not only do they currently not have sufficient catalytic activity, but they also suffer from decomposition and formation due to ring-opening reactions, etc. There were other problems, such as low selectivity to adamantanes due to the formation of adamantane compounds, and furthermore, the catalyst composition was complex and the cost of the catalyst was high. Therefore, an object of the present invention is to industrially produce alkyladamantanes at low cost, with high activity and high selectivity, with almost no generation of decomposition products, and with a simple catalyst composition and low catalyst cost. The object of the present invention is to provide a catalyst that is inexpensive and durable for industrial use, and a method for producing alkyladamantanes using this catalyst.

[0005]

[Means for Solving the Problems] The present invention provides a method for isomerizing perhydroacenaphthene to produce alkyl adamantanes having 12 carbon atoms, by treating γ-alumina and/or zirconia with sulfuric acid, and then calcination. The present invention relates to a method for producing alkyl adamantanes, which is characterized by using a catalyst carrying sulfate ions.

[0006] In order to achieve high activity and high selectivity, as well as to ensure that the decomposition reaction hardly progresses, as well as for the catalyst to have a simple composition and be easy to manufacture, the present inventors have developed various solid catalysts with different activities. We carefully considered selectivity. As a result, (1)
A catalyst in which sulfate ions are supported by treating γ-alumina and/or zirconia with sulfuric acid and then calcination has sufficient activity and selectivity for the industrial production of alkyladamantanes, and the preparation of this catalyst is (2) The concentration of sulfuric acid to be treated is 0.1 to 3N, and the firing temperature after sulfuric acid treatment is 400 to 750°C, particularly preferably 450 to 700°C. and (3) that by setting the supported ratio of sulfate ions to 0.5 to 5% by weight, a catalyst with high activity and high selectivity can be obtained with almost no progress of decomposition reaction. Using the catalyst obtained by
The present invention was completed by discovering that the desired alkyl adamantane can be produced in high yield by carrying out the reaction under atmospheric pressure and at a temperature of 200 to 270°C.

That is, the present invention provides γ-alumina and/or
Alternatively, the present invention provides a catalyst for producing alkyladamantanes by isomerizing perhydroacenaphthene obtained by treating zirconia with sulfuric acid and then calcining the same.

The concentration of sulfuric acid used to treat γ-alumina and/or zirconia is 0.1 to 3N, and the firing temperature is 4
00~750℃, and the supporting rate of sulfate ions is 0.5~
Preferably it is 5% by weight.

The present invention also provides a method for producing a C12 alkyl adamantane by isomerizing perhydroacenaphthene using the above catalyst.

The present invention will be explained in more detail below. It is generally known that solid superacidity is developed by supporting sulfate ions on zirconia, and that by using this catalyst, isomerization of butane proceeds at room temperature (for example, G. A. Olah et al. ”Superac
ids”, John Wiley & Sons (19
85) p. 53). The sulfate ion-supported γ-alumina and/or zirconia catalyst used in the present invention is an attempt to repurpose such a super strong acid catalyst.

Incidentally, although it is well known that the adamantane rearrangement reaction generally requires a large amount of a strong acid catalyst, nothing is known about the optimum acid strength range. The present inventors found that when supporting sulfate ions on γ-alumina and/or zirconia, there is a preferable range for the concentration of sulfuric acid to be treated, the firing temperature, and the supporting rate of sulfate ions. It was discovered that the selectivity also decreases, leading to the present invention. The reason for this is not clear, but it is expected that the acid strength will change as the supported state and amount of sulfate ions change, so these are the processing conditions to obtain a catalyst with the optimal acid strength for this reaction. it is conceivable that.

[0012] As mentioned above, Japanese Unexamined Patent Publication No. 1986-24
According to Publication No. 6333, H-Y carrying metal ions
It is stated that the yield of adamantane is improved by treating zeolite type zeolite with an aqueous ammonium sulfate solution and using a catalyst supporting sulfate ions, but in this case, metal ions are present, so after supporting sulfate ions, the metal sulfate is It is thought that the catalyst is generated, and is clearly different from the catalyst used in the present invention.

[0013] The catalyst raw materials used in the present invention, such as γ-alumina and zirconia, are not limited in any way, but in order to increase the number of active points per unit weight of the catalyst supporting sulfate ions, it is preferable to use ones with a large surface area. is preferred.

The conditions for the sulfuric acid treatment are such that the concentration of sulfuric acid used is 0.
．． This is carried out by treating at 1 to 3 N for 1 to 10 hours. When the sulfuric acid concentration is less than 0.1N, there are many decomposition products, and when it exceeds 3N, the activity decreases and a high conversion rate cannot be obtained. Although the treatment temperature and the method of contacting with sulfuric acid are arbitrary, it is usually carried out at room temperature by a dipping method or a spray method. Although the temperature of the sulfuric acid and the method of contacting with the sulfuric acid are arbitrary, it is usually carried out at room temperature by a dipping method or a spraying method.

As mentioned above, the firing temperature after the sulfuric acid treatment is 400 to 750°C, preferably 450 to 700°C. If the firing temperature is less than 400° C., the acid strength will be lowered and the activity will be lowered if it is outside the above range, which is not preferable. The firing time is usually 1 to 10 hours, and the firing may be carried out in a stream of air or an inert stream of nitrogen or the like.

[0016] The supporting rate of sulfate ions is 0.5 to 5% by weight.
It is best to This is because if the supported ratio of sulfate ions is less than 0.5% by weight, the amount of decomposition products increases, and if it exceeds 5% by weight, the conversion rate decreases.

By these treatments, it is possible to produce a sulfate ion-supported γ-alumina and/or zirconia catalyst that exhibits high activity and high selectivity in the production of alkyladamantanes. The shape of the catalyst may be arbitrary, such as powder, granules, or a suitable molded body, depending on the type of reactor.

The raw material perhydroacenaphthene used in the present invention is usually obtained by total hydrogenation of acenaphthene contained in coal tar, but perhydroacenaphthene produced by other methods can also be used.

[0019] In the production of alkyl adamantane,
The weight ratio of the catalyst to perhydroacenaphthene is 1/5.
It is sufficient to use more than double the amount, but from the viewpoint of productivity and economy,
/4 to 4/1 times the amount is preferred. The reaction is carried out at a pressure of 5 to 30 atm to prevent perhydroacenaphthene from vaporizing; however, if the pressure exceeds 30 atm, the reaction rate will decrease, which is not preferable. The reaction temperature is preferably 200 to 270°C. Below 200°C, the reaction rate is extremely slow, and above 270°C, the production of decomposition products increases, making it uneconomical. Although the reaction time depends on the amount of catalyst and the reaction temperature, 1 to 10 hours is appropriate. For example, when the reaction temperature is 250° C. and the catalyst is used at a weight ratio of 1/3 to the raw material, it is sufficient to carry out the reaction for 2 to 4 hours. The method of contacting the perhydroacenaphthene with the catalyst may be arbitrary, such as a batch-type complete mixing tank using an autoclave or the like, or a pressurized flow type.

According to the method of the present invention, a mixture of alkyl adamantane having 12 carbon atoms can be produced from barhydroacenaphthene with high selectivity, so that when used as a mixture, the product can be obtained by very simple distillation. Alkyladamantane mixtures can be obtained. Also,
In order to obtain particularly useful 1,3-dimethyladamantane from the reaction product, the product is rectified because 1,3-dimethyladamantane is the most thermodynamically stable of these alkyladamantane mixtures. After isolating the target 1,3-dimethyladamantane, the distillation residue can be recycled to the reactor and reacted again, thereby producing the target 1,3-dimethyladamantane in a high yield.

[0021]

EXAMPLES The present invention will be specifically explained below based on Examples, but the present invention is not limited thereto.

(Example 1) After molding γ-alumina prepared from aluminum isopropoxide according to a conventional method,
50 g of pulverized granules of about 1 to 2 mm were immersed in 5 L of 1N sulfuric acid at room temperature for 2 hours. Next, after drying this product, it was placed in an evaporating dish and calcined at 600° C. for 4 hours in an air stream to prepare a sulfate ion-supported γ-alumina catalyst. The amount of sulfur supported on this catalyst was measured by a fluorescent X-ray method, and it was found to be 1.8% by weight based on γ-alumina in terms of sulfate ion support.

[0023] 5 g of the above-calcined catalyst and 15 g of perhydroacenaphthene were placed in a stainless steel autoclave having a volume of 50 mL, and after the autoclave was purged with nitrogen, the autoclave was pressurized to 15 atmospheres with nitrogen. Next, the autoclave was heated in an electric furnace and the reaction solution was stirred. The reaction takes place when the internal temperature of the autoclave is 250℃.
It was carried out for 2.5 hours after reaching the temperature. After the reaction was completed, the reaction vessel was cooled, residual gas was purged, and the pressure was returned to normal pressure. After removing the catalyst from the reaction product by filtration, the product was analyzed by gas chromatography. As a result, the conversion rate of perhydroacenaphthene was 73.8%, and the total selectivity to alkyladamantane having 12 carbon atoms (the sum of dimethyladamantane and ethyladamantane) was 76.2%, and the ring-opening reaction etc. The selectivity to the decomposition products produced was only 0.6%.

(Example 2) Zirconia was treated with sulfuric acid in the same manner as in Example 1 except that commercially available zirconia was used and the concentration of sulfuric acid used was 1.5N. This product was calcined in nitrogen at a temperature of 650° C. for 5 hours to obtain a sulfate ion-supported zirconia catalyst. The supporting rate of sulfate ions was 2.5% by weight. Using this catalyst, the isomerization reaction of perhydroxyacenaphthene was carried out in the same manner as in Example 1. As a result of analyzing the product, the conversion rate of pahydroacenaphthene was 8.
4.3%, total selectivity to alkyl adamantane is 98
．． The selectivity for 1% decomposition products was 1.5%.

(Example 3) The concentration of sulfuric acid used to treat zirconia was 0.5N, and the firing temperature after the sulfuric acid treatment was 500°C.
Catalyst preparation and isomerization reaction were carried out in the same manner as in Example 2 except for the following. The conversion rate of perhydroacenaphthene is 91.
9%, total selectivity to alkyl adamantane is 97.8
%, and the selectivity of decomposition products was 1.6%. Also, among the products, the selectivity of 1,3-dimethyladamantane is 1
It was 6.9%. In addition, the sulfate ion support rate of the catalyst is 1
．． It was 2% by weight.

(Example 4) Using the catalyst obtained in Example 3,
The isomerization reaction was performed on a scale five times that of Example 3. The reaction results were similar to Example 3. When 1,3-dimethyladamantane was purified from the reaction product using a distillation column with 20 theoretical plates, 9.8g (corresponding to 13.1% of the charged perhydroacenaphthene) of 1,3-dimethyladamantane was obtained. was gotten. Next, 10 g of perhydroacenaphthene was added to this distillation residue, and the isomerization reaction was performed again using the same catalyst. As a result, the conversion rate of perhydroacenaphthene was 90.2%, the total selectivity to alkyladamantane was 98.5%, and the selectivity of decomposition products was 0.8%.
, the selectivity of 1,3-dimethyladamantane is 27.6%
The same results as the first reaction were obtained.

(Comparative Example 1) An isomerization reaction was carried out using γ-alumina as a catalyst in the same manner as in Example 1 except that the sulfuric acid treatment was not performed. As a result, the conversion rate of perhydroacenaphthene was 3.3%, the total selectivity to alkyladamantane was 15.3%, and the selectivity of decomposition products was 2.0%, indicating that almost no reaction occurred.

[0028]

[Effects of the Invention] By using the catalyst of the present invention, alkyladamantanes, which are attracting attention as raw materials for high-grade functional polymer compounds and pharmaceuticals, can be produced industrially at low cost. In addition, the raw materials for the catalyst used in the present invention are inexpensive;
Moreover, since it has a simple composition and a simple preparation method, it has great industrial significance especially as a method for producing alkyl adamantanes. Furthermore, according to the present invention, 1,3-dimethyladamantane, which is particularly useful among alkyl adamantanes having 12 carbon atoms, can also be produced in high yield, which is a great significance of the present invention.

Claims (6)

[Claims] 1. A catalyst for producing alkyladamantanes, characterized in that γ-alumina and/or zirconia is treated with sulfuric acid and calcined to support sulfate ions. [Claim 2] Claim 1, wherein the concentration of sulfuric acid used to treat γ-alumina and/or zirconia is 0.1 to 3N.
A catalyst for producing an alkyl adamantane as described in . 3. The catalyst for producing alkyl adamantanes according to claim 1 or 2, wherein the temperature at which the γ-alumina and/or zirconia is calcined after the sulfuric acid treatment is 400 to 750°C. 4. The catalyst for producing alkyladamantanes according to claim 1, wherein the supporting ratio of sulfate ions supported on γ-alumina and/or zirconia is 0.5 to 5% by weight. 5. A method for producing an alkyl adamantane, which comprises using the catalyst according to any one of claims 1 to 4 in producing an alkyl adamantane having 12 carbon atoms by isomerizing perhydroacenaphthene. . 6. The method for producing alkyl adamantanes according to claim 5, wherein the isomerization reaction of claim 5 is carried out at 5 to 30 atm and 200 to 270°C.