JPH0254809B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing pseudokyumene or duurene, and more specifically, a method for efficiently producing pseudokyumene or duurene from benzene, toluene, or xylene by using a specific crystalline silicate containing fluorine as a catalyst. Regarding the method. Conventionally, methods using a Lewis acid catalyst and methods using an acid type catalyst such as sulfuric acid are known as methods for producing pseudokyumene and duurene.
However, in the former method, it is necessary to use a corrosion-resistant device, and the selectivity of the product is not sufficient. Furthermore, the latter method has the disadvantage that the conversion rate of the raw material compound is low. As a result of extensive research to overcome the drawbacks of the conventional methods as described above, the present inventors have discovered that when methylating benzene, toluene or xylene, fluorine-containing crystalline aluminosilicate, fluorine-containing crystalline borosilicate, or fluorine-containing crystalline borosilicate, By using crystalline boroaluminosilicate as a catalyst,
It was discovered that pseudokyumene and duurene can be produced efficiently. The present invention was completed based on this knowledge. That is, the present invention provides benzene in the presence of a catalyst,
Production of pseudokyumene or duurene, which is characterized in that a fluorine-containing crystalline aluminosilicate, a fluorine-containing crystalline borosilicate, or a fluorine-containing crystalline boroaluminosilicate is used as a catalyst in producing pseudokyumene or duurene by methylating toluene or xylene. The present invention provides a method. The catalyst used in the method of the present invention is a fluorine-containing crystalline aluminosilicate, crystalline borosilicate, or crystalline boroaluminosilicate as described above. These are generally obtained by subjecting crystalline aluminosilicate, borosilicate, or boroaluminosilicate to a fluorination treatment. Various types of crystalline aluminosilicate can be used here, but specifically,
ZSM-5, ZSM-11, ZSM-12, ZSM-23,
Representative examples include ZSM-35, ZSM-38, and ZSM-48. There are various methods for preparing such crystalline aluminosilicate, but generally it can be prepared by adding various silica sources, alumina sources, and crystallizing agents to an aqueous medium and carrying out a hydrothermal reaction. For example, ammonium type crystalline aluminosilicate is prepared as follows. That is, first, an aqueous solution containing aluminum sulfate, concentrated sulfuric acid, and tetrapropylammonium bromide (solution A), an aqueous solution of water glass consisting of silicon oxide, sodium oxide, and water (solution B), and an aqueous sodium chloride solution (solution C) were prepared, respectively. , this solution A
and B are added dropwise to solution C, the pH of the mixture is adjusted as necessary, and this is heated in an autoclave. Thereafter, a sodium type crystalline aluminosilicate is obtained through a process of cooling, washing, drying and calcination. Further, the obtained sodium type crystalline aluminosilicate is treated with an aqueous ammonium nitrate solution to obtain an ammonium type crystalline aluminosilicate. The crystalline silicate thus obtained is in powder form, but it can also be molded by adding a binder such as alumina sol. On the other hand, various types of crystalline borosilicate can be used, such as JP-A-53-
55500, JP 55-7598, JP 56
Examples thereof include crystalline borosilicates described in Japanese Patent Application Laid-open No. 84313, Japanese Patent Application Laid-open No. 57-123817, and Japanese Patent Application Laid-open No. 129820-1984. Although there are various methods for preparing such a crystalline borosilicate, it is usually carried out in accordance with the method for preparing the crystalline aluminosilicate described above. In this case, a boron source such as boric acid may be used instead of an alumina source such as aluminum sulfate. Furthermore, various crystalline boroaluminosilicates can be used, such as those described in JP-A-55-6752. There are various methods for preparing such crystalline boroaluminosilicate, but it is generally carried out in accordance with the method for preparing crystalline aluminosilicate described above, in which boric acid is added together with a silica source and an alumina source. A boron source such as the following may be used. Even if the crystalline aluminosilicate, crystalline borosilicate, or crystalline boroaluminosilicate obtained by the above method is used as a catalyst as it is, it is not possible to produce pseudokyumene or durene with high selectivity, and the reaction During,
It is not possible to maintain high catalytic activity over a long period of time. Therefore, in the method of the present invention, such a crystalline silicate (crystalline aluminosilicate, crystalline borosilicate, crystalline boroaluminosilicate) is subjected to a fluorination treatment to contain fluorine and used as a catalyst. This fluorination treatment can be carried out by various methods, and in short, fluorine is introduced into a crystalline silicate (aluminosilicate, borosilicate, boroaluminosilicate) to form a crystalline silicate containing fluorine (aluminosilicate, borosilicate, borosilicate). Any treatment that results in a boroaluminosilicate (boroaluminosilicate) may be used. Specifically, one of the three types of crystalline silicates mentioned above is mixed with an organic fluorine compound such as chlorofluorocarbon gas at a concentration of 400 to 600%.
Possible methods include contact treatment at ℃ or contact treatment with hydrogen fluoride, sodium fluoride, boron trifluoride, monofluoroacetic acid, etc. in a liquid phase. There are various types of chlorofluorocarbon gases mentioned above, including chlorofluorocarbon-11.
(CFCl ₃ ), Freon-12 (CF ₂ Cl ₂ ), Freon-13
(CF ₃ Cl), Freon-21 (CHFCl ₂ ), Freon-22
(CHF ₂ Cl), Freon-23 (CHF ₃ ), Freon 113
(CF ₂ ClCFCl ₂ ), Freon-114 (CF ₂ ClCF ₂ Cl), etc. Alternatively, when preparing crystalline silicates (crystalline aluminosilicate, crystalline borosilicate, crystalline boroaluminosilicate), fluorine is added in the hydrothermal reaction stage along with the silica source, alumina source, or boron source. These crystalline silicates can also contain fluorine by adding a source. In this case, the fluorine source is preferably a water-soluble compound such as hydrofluoric acid or sodium fluoride. The fluorine-containing crystalline silicate obtained by the above treatment is molded as it is or with the addition of a suitable binder such as alumina, and further
The product calcined at 1000°C is used as a catalyst for the methylation reaction in the method of the present invention. In the method of the present invention, benzene, toluene, xylene (p-xylene, o-xylene, m-xylene or a mixture thereof) is used as a raw material compound.
of which xylene is particularly preferred;
This is methylated with a methylating agent in the presence of the above catalyst to produce pseudokyumene and duurene.
The methylating agent used here includes various agents such as methanol, dimethyl ether, methyl chloride, and methyl bromide, but methanol and dimethyl ether are particularly preferred. The amount of this methylating agent to be used may be determined as appropriate depending on the reaction conditions, the type of desired reaction product, etc., but usually the ratio of the raw material compound benzene, toluene, or xylene to the raw material compound/methylation The agent should be between 4/1 and 11/20 (molar ratio), preferably between 1/1 and 1/10 (molar ratio). In the method of the present invention, there are no particular restrictions on conditions other than those described above, but general conditions are as follows:
Reaction temperature: 250-400°C, preferably 280-350°C, reaction pressure: normal pressure - 100Kg/ ^cm2G , preferably normal pressure - 10
Kg/cm ² G, liquid hourly space velocity (LHSV) 0.05~
100 hr ⁻¹ , preferably 0.1 to 10 hr ⁻¹ . According to the method of the present invention, there are few side reactions such as suppressing the transmethylation reaction of raw materials and products and the decomposition of the methylating agent, and as a result, the conversion rate of benzene, toluene or xylene, and the selectivity of pseudokyumene and duurene are reduced. will improve. Furthermore, since the catalyst has a very long life, continuous operation can be performed while maintaining high catalytic activity for a long period of time. Furthermore, in the method of the present invention, by appropriately selecting reaction conditions and reaction time,
Either or both of pseudokyumene and duurene can be produced in desired proportions. For example, when using xylene as a raw material, if the reaction conditions are relatively mild and the reaction is carried out for a short time, methylation will not proceed much and a large amount of pseudokyumene will be obtained; If the reaction time is increased, the production rate of duurene will increase. Furthermore, pseudokyumene can be methylated to obtain duurene. Therefore, the method of the present invention is extremely advantageous and has high utility value as an industrial method for producing pseudokyumene and durene. Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Reference Example 1 (Preparation of crystalline borosilicate) Solution A in which 0.67 g of boric acid, 17.68 g of concentrated sulfuric acid, and 26.32 g of tetrapropylammonium bromide were added to 250 ml of water, and water glass (composition: silicon oxide)
28.95% by weight, sodium oxide 9.40% by weight, water
Solution B in which 211.1g (61.65% by weight) was added to 250ml of water
were prepared respectively. Then solutions A and B were added with 79.0 g of sodium chloride.
were simultaneously added dropwise to a solution of 122 ml of water at room temperature over 60 minutes. The resulting mixed solution was adjusted to pH 9.5 using sulfuric acid, and the solution was placed in an autoclave and heat-treated at a reaction temperature of 170° C. for 20 hours.
While cooling, the contents of the autoclave were filtered, and the resulting solid was washed with water. After adding 300 ml of a 1N ammonium nitrate aqueous solution, the mixture was incubated at 90°C for 8 hours.
Ammonium type crystalline borosilicate was obtained by performing ion exchange twice. Thereafter, the contents were filtered, washed with water, dried at 120°C for 24 hours, and calcined at 550°C for 6 hours to obtain 58 g of H-type crystalline borosilicate. The composition of this crystalline borosilicate is SiO ₂ /
B ₂ O ₃ =100 (molar ratio). Alumina sol was added to the powdered H-type crystalline borosilicate thus obtained so that the binder content was 20% by weight, and after drying at 120°C for 3 hours,
C. for 6 hours in air to obtain H-type crystalline borosilicate shaped into pellets. Example 1 The pellet-like crystalline borosilicate obtained in Reference Example 1 was charged into a catalyst preparation tube, and Flon-114 (1,1,2,2-tetrafluoro-1,2-dichloroethane) was heated at 500°C. was supplied at a rate of 70 ml/min for 1 hour to carry out the fluorination treatment to obtain a fluorine-containing crystalline borosilicate. This borosilicate was packed into a flow-type reactor, and the raw materials p-xylene and methyl alcohol were mixed at a molar ratio of 1:4 and fed, and the reaction temperature was 300°C and the mixture was heated under normal pressure.
The reaction was carried out as LHSV1hr ^-1 . Reaction progress 4
The results after hours are shown in Table 1. Comparative Example 1 In Example 1, the reaction was carried out in the same manner as in Example 1, except that the crystalline borosilicate obtained in Reference Example 1 was directly charged into a reactor and the reaction temperature was set at 330°C. Table 1 shows the results after 4 hours of reaction. Reference example 2 (Preparation of crystalline aluminosilicate (ZSM-5)) 6.2 g of aluminum sulfate (18 hydrate), concentrated sulfuric acid
Solution A in which 17.68 g and 26.32 g of tetrapropylammonium bromide were added to 250 ml of water and 211.1 g of water glass (composition: silicon oxide 28.95 wt%, sodium oxide 9.40 wt%, water 61.65 wt%) in 250 ml of water
A solution B was prepared in which each solution was added to the following. Next, add solutions A and B to 79.0 g of sodium chloride and 122 ml of water.
were simultaneously added dropwise over 60 minutes at room temperature. The resulting mixture was PHed using sulfuric acid.
Adjusted to 9.5. This solution was placed in an autoclave and heated at a reaction temperature of 170°C for 20 hours. While cooling, the contents of the autoclave were filtered, and the resulting solid was washed with water. After adding 300 ml of a 1N ammonium nitrate aqueous solution, the mixture was incubated at 90°C for 8 hours.
After performing ion exchange twice, ammonium type crystalline aluminosilicate was obtained. Thereafter, the contents were filtered, washed with water, dried at 120°C for 24 hours, and then calcined at 550°C for 6 hours to obtain H-type crystalline aluminosilicate. The composition of the obtained H-type crystalline aluminosilicate zeolite was SiO ₂ /Al ₂ O ₃ =100 (molar ratio). Alumina sol was added to this H-type crystalline aluminosilicate so that the binder content was 20% by weight, molded, dried at 120°C for 3 hours, and further
A catalyst was obtained by calcining in air at 550°C for 6 hours. Example 2 In Example 1, the fluorination treatment of the catalyst and the methylation reaction of p-xylene were carried out in the same manner as in Example 1, except that the catalyst obtained in Reference Example 2 was used. The results after 4 hours of reaction are shown in Table 1. Comparative Example 2 The reaction was carried out in the same manner as in Example 1, except that the catalyst obtained in Reference Example 2 was used as it was. Table 1 shows the results after 4 hours of reaction. Reference example 3 (Preparation of crystalline boroaluminosilicate) Boron oxygen 3.35g, aluminum sulfate (18 hydrate)
6.2 g of concentrated sulfuric acid, 17.68 g of tetrapropylammonium bromide, and 26.32 g of tetrapropylammonium bromide in 250 ml of water, and water glass (composition: 28.95% by weight of silicon oxide).
Sodium oxide 9.40% by weight, water 61.65% by weight)
Solution B was prepared by adding 211.1 g to 250 ml of water. Then solutions A and B were added with 79.0 g of sodium chloride.
were simultaneously added dropwise to a solution of 122 ml of water at room temperature over 60 minutes. The resulting mixed solution was adjusted to pH 9.5 using sulfuric acid, and the solution was placed in an autoclave and heat-treated at a reaction temperature of 170° C. for 20 hours.
While cooling, the contents of the autoclave were filtered, and the resulting solid was washed with water. After adding 300 ml of a 1N ammonium nitrate aqueous solution, the mixture was incubated at 90°C for 8 hours.
Ammonium type crystalline boroaluminosilicate was obtained by performing ion exchange twice. The contents were then filtered, washed with water, dried at 120°C for 24 hours, and heated to 550°C.
C. for 6 hours to obtain 58 g of H-type crystalline boroaluminosilicate. The composition of the obtained H-type crystalline boroaluminosilicate is SiO ₂ /Al ₂ O ₃ /B ₂ O ₃
=100/1/5 (molar ratio). The powdered H-type crystalline boroaluminosilicate thus obtained has a binder content of 20% by weight.
Add alumina sol and mold to give 120
After drying at ℃ for 3 hours, it was calcined in air at 550 ℃ for 6 hours to obtain a catalyst. Example 3 In Example 1, the fluorination treatment of the catalyst and the methylation reaction of p-xylene were carried out in the same manner as in Example 1, except that the catalyst obtained in Reference Example 3 was used. Table 1 shows the results after 4 hours of reaction. Comparative Example 3 In Example 1, a reaction was carried out in the same manner as in Example 1, except that the catalyst obtained in Reference Example 3 was used as it was. Table 1 shows the results after 4 hours of reaction. Reference example 4 Sodium aluminate (Al ₂ O ₃ 35wt% and
Contains 30wt% Na ₂ O) 0.12g, sodium hydroxide
Solution A in which 1.5 g of ammonium fluoride and 0.80 g of ammonium fluoride were dissolved in 185 ml of water, and 14.2 g of tetrapropylammonium bromide was further dissolved therein, and 38.0 g of an aqueous silica sol solution with a solid content of silica of 30 wt%.
Solution B was prepared. These solutions A and B were simultaneously dropped over 30 minutes into a container containing 20 ml of water at room temperature. The resulting mixture was PHed using sulfuric acid.
9.5, and this solution was placed in an autoclave and heat-treated at a reaction temperature of 170°C for 20 hours. Under cooling,
After filtering the contents of the autoclave and washing the obtained solid with water, 300 ml of 1N ammonium nitrate aqueous solution was added and ion exchange was performed three times at 90°C for 8 hours to obtain ammonium-type fluorine-containing crystalline aluminium. Obtained silicate. The contents were then filtered, washed with water, dried at 120°C for 24 hours, and calcined at 550°C for 6 hours to obtain H-type fluorine-containing crystalline aluminosilicate. Next, alumina sol was added to this fluorine-containing crystalline aluminosilicate so that the binder content was 20 wt%, and the mixture was molded, dried at 120°C for 3 hours, and further calcined in air at 550°C for 6 hours to obtain a catalyst. . Example 4 In Example 1, the methylation reaction of p-xylene was carried out in the same manner as in Example 1 except that the catalyst obtained in Reference Example 4 was used. Table 1 shows the results after 4 hours of reaction. Example 5 A reaction was carried out in the same manner as in Example 1, except that toluene was used in place of p-xylene as the reaction raw material in Example 1, and the reaction temperature was 330°C. Table 1 shows the results after 4 hours of reaction. 【table】

Claims (1)

[Claims] 1. In producing pseudokyumene or duurene by methylating benzene, toluene, or xylene in the presence of a catalyst, a fluorine-containing crystalline aluminosilicate, a fluorine-containing crystalline borosilicate, or a fluorine-containing crystalline borosilicate is used as a catalyst. A method for producing pseudokyumene or durene, characterized by using aluminosilicate. 2. The method according to claim 1, wherein methyl alcohol or dimethyl ether is used as the methylating agent.