JPH0480855B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel borosilicate, and more particularly to a crystalline borosilicate that exhibits an X-ray diffraction pattern different from conventionally known borosilicate and has unique properties. Crystalline borosilicate is an inorganic crystalline body having a rigid three-dimensional structure similar to that of crystalline aluminosilicate, which is generally referred to as zeolite. In zeolite, the ratio of the sum of amminium atoms and silicon atoms to oxygen atoms is 1:2, and the electron valence of the aluminum-containing tetrahedron is balanced by containing various cations within the crystal. is maintained. This zeolite is known to have effective catalytic activity for various reactions due to its crystal structure, silica/alumina molar ratio, cations contained, etc. In addition, in recent years, boron (USP 4, 269, 813), iron (JP 56-22623),
Vanadium (German Patent Application No. 2,831,631
Attempts have been made to incorporate chromium (Japanese Unexamined Patent Publication No. 57-7817) into the framework of zeolite to achieve unique catalytic performance. As one such attempt, the present inventors also
As a result of intensive research on zeolites containing boron instead of aluminum and/or silicon, we found that a specific organic amine, namely 1,8-diamino-4-aminomethyloctane, was allowed to coexist during crystallization, resulting in a specific production process. It was discovered that a new crystalline borosilicate exhibiting an X-ray diffraction pattern clearly different from conventionally known crystalline borosilicate can be obtained by producing it under the following conditions, and based on this knowledge, the present invention was developed. It was completed. That is, the present invention has (a) the following composition expressed by the molar ratio of oxides, M _2/o O・xSiO ₂・yAl ₂ O ₃・zB ₂ O ₃ (where M is n y+z=1, y≧0, z≧0.3, x
≧5. ) (b) This relates to a borosilicate (hereinafter referred to as AZ-2) characterized by having a characteristic diffraction image shown in Table 1 below in an X-ray diffraction diagram.

[Table] However, X-ray diffraction analysis uses CuKα rays. This includes silica feed material, alumina feed material, boron oxide feed material, sodium feed material,
A composition containing water and 1,8-diamine-4-aminomethyloctane and having a molar ratio of each component in the following range is heated to a temperature of 100 to 250°C, which is sufficient to form crystals. It is produced by reacting for a certain period of time. Na/ _SiO2 =0.01~0.5 _H2O / _SiO2 =2~100 1,8-diamino-4-aminomethyloctane/
_SiO2 = 0.1 _{~ 10 Al2O3} / _SiO2 = 0~0.05 _B2O3 / _SiO2 = 0.005~0.5 Crystalline borosilicate thus obtained
AZ-2 is a conventionally known borosilicate,
For example, it has an X-ray diffraction pattern that is clearly different from that of borosilicate (see JP-A-53-55500), which is similar to zeolite ZSM-5. Table 2 shows the X-ray diffraction data of crystalline borosilicate AZ-2 produced by the above method and crystalline borosilicate similar to zeolite ZSM-5 produced based on JP-A-53-55500. An example is shown.

[Table] As is clear from Table 2, AZ-2 of the present invention is
It can be seen that the relative intensity of each peak is significantly different compared to ZSM-5 similar crystalline borosilicate. In particular, the strongest peak of AZ-2 is 2θ = 8.9°, while that of ZSM-5 similar borosilicate is 23.2°, and the intensity of 2θ = 8.9° and 23.2° in each X-ray diffraction pattern of both. When calculating the ratio, AZ
-2 is about 5 times that of ZSM-5 similar borosilicate. Furthermore, the intensity ratio between the two diffraction angles (2θ) of 7.9° and 8.9° is significantly different. That is, ZSM−
The intensity ratio of 2θ=8.9° to 2θ=7.9° for 5-similar borosilicate is about 0.8, whereas that of AZ-2 is about 5, and the difference in intensity ratio between the two is about 6 times. Thus, the fact that AZ-2 exhibits a unique X-ray diffraction pattern indicates that it has a unique and novel crystal structure different from ZSM-5-like borosilicate. The crystalline borosilicate produced by the above method contains sodium ions, hydrogen ions, and ammonium cations of 1,8-diamino-4-aminomethyloctane as cations at the stage of synthesis by hydrothermal synthesis. I am, but
By calcining in air at high temperatures of 300° C. or higher, the ammonium cations of this amine can be converted to hydrogen ions. Furthermore, regarding cations other than those mentioned above, cations of all metals on the periodic table can be introduced by the same method as ion exchange in ordinary crystalline aluminosilicate. Especially when used as a catalyst, a, b, a on the periodic table (short period type),
Cations of the b, a, b, b, and rare earth groups are preferred. Moreover, even if ion exchange is performed, the X-ray diffraction pattern hardly changes. AZ-2 of the present invention is synthesized starting from a silica feed material, an alumina feed material, a boron oxide feed material, a sodium feed material, water, and 1,8-diamino-4-aminomethyloctane. The silica feed material used in the above method is:
Silica powder, silicic acid, silica sol, sodium silicate aqueous solution, etc. are used, but silica sol is preferred. As the sodium supply substance used in the above method, sodium hydroxide, sodium chloride, sodium silicate, etc. are used, but sodium hydroxide is preferred. Further, the amount of the sodium supplying substance used is in the range of 0.01 to 0.5, preferably 0.05 to 0.3 in Na/SiO ₂ molar ratio. The alumina feed material in the above method may or may not be actively added. There are no particular restrictions on the alumina supply substance used when actively adding it, as long as it is commonly used in the production of conventional crystalline aluminosilicate.
For example, alumina powder, aluminum sulfate, sodium aluminate, etc. are used. Furthermore, even if it is not actively added, unless the silica source and sodium source of the raw material are purified using a particularly special refining method, approximately several hundred ppm of aluminum will be mixed into the raw material as an impurity. As the boron oxide supplying substance in the above method, boron powder, boric acid, sodium borate, etc. are used, but boric acid is preferred. The ratio of these silica feed materials, alumina feed materials, and boron oxide feed materials is Al ₂ O ₃ /
The _SiO2 molar ratio is in the range of 0 _to 0.05, preferably 0 to 0.02, and the _B2O3 / _SiO2 molar ratio is in the range of 0.005 to 0.5, preferably 0.01 to 0.1. In the present invention, it is necessary to coexist 1,8-diamino-4-aminomethyloctane during crystallization, and the amount of amine used in this case is 0.1 to 1 mol per 1 mol of silica, preferably 0.5 ~5 moles. In addition, the production of crystalline borosilicate in the above method is carried out in the presence of water, and the amount of water at this time is H ₂ O / SiO ₂ molar ratio of 2 to 100, preferably 5 to 50. range. In the present invention, the silica supply material, alumina supply material, boron oxide supply material, sodium supply material, 1,8-diamino-4-aminomethyloctane, and water are mixed into a raw material composition having the composition ratio as described above. In order to obtain a crystalline borosilicate which is required to be used as a crystalline borosilicate and which exhibits the unique X-ray diffraction pattern of the present invention, it is important to produce the crystalline borosilicate under the following conditions. First, it is preferable to thoroughly mix the raw material composition described above using a rotary mixer, homogenizer, etc. before crystallization. Furthermore, this raw material composition
Preferably, the pH is adjusted to a range of 11 to 13, for example by adding an acid. Next, the raw material composition thus prepared is heated to a temperature of 100 to 250°C, preferably 120 to 200°C under normal pressure or self-generated pressure to crystallize the crystalline borosilicate. The reaction time at this time depends on the temperature and pressure, but is usually 5 to 50 minutes.
200 hours. The crystalline borosilicate thus obtained can be used as a catalyst, for example, in hydrocarbon cracking reactions, alkylation reactions, disproportionation reactions, hydrocarbon synthesis reactions from methanol, and the like. In particular, the crystalline borosilicate of the present invention is suitable as a catalyst for the production of 1,4-disubstituted benzene by alkylation reaction and the production of lower olefin from methanol. For example, when producing para-diethylbenzene from ethylbenzene and ethylene, conventional methods using aluminum chloride etc. produce ortho, meta, and para isomers in a ratio of about 10:60:30, whereas AZ-2 It has been found that when diethylbenzene is used as a catalyst, the proportion of para isomers in diethylbenzene is as high as 60% or more. In addition, regarding the production of lower olefins from methanol, conventional crystalline aluminosilicate such as ZSM-5 has high aromatization activity, so C ₄
The selectivity of the following lower olefins was about 40%, but when AZ-2 is used as a catalyst, lower olefins can be obtained at a very high rate of 60% or more. For the X-ray diffraction data of the crystalline borosilicate in the present invention, Geigerflex (manufactured by Rigaku Denki) was used as an X-ray diffractometer and CuKα rays were used as the X-rays. In this measurement, a relative error of several percent may occur due to variations in the crystalline borosilicate itself and measurement errors, but the relative positions and relative intensities of the diffraction angles hardly change. Next, the present invention will be explained in more detail with reference to Examples. Example 1 1,8-diamino-4-aminomethyloctane
Dissolve 20 g of boric acid (H ₃ BO ₃ ), 0.5 g of boric acid (H 3 BO 3 ), and 1 g of sodium hydroxide in 34 g of water, and then add silica sol (30
40 g of wt% SiO ₂ ) were added to obtain a homogeneous solution.
8 g of 20% sulfuric acid was added dropwise to this solution while stirring to obtain a homogeneous gel. Furthermore, this gel was stirred at high speed at 10,000 rpm in a homogenizer, and then left standing at 180° C. for 70 hours in a Teflon-lined pressure container to perform crystallization. After overwashing the obtained product, it was incubated at 120°C for 5
The X-ray diffraction pattern after drying for an hour and further baking in air at 500° C. for 6 hours is shown in FIG. 1, and the electron micrograph is shown in FIG. In addition, SiO ₂ /B ₂ O ₃ obtained from chemical analysis,
The SiO ₂ /Al ₂ O ₃ molar ratio was 30 and 500, respectively. Example 2 1,8-diamino-4-aminomethyloctane
640g, boric acid 16g, sodium hydroxide 32g with water
A homogeneous solution was obtained in addition to 1100 g. To this solution, 1300 g of silica sol (30% by weight SiO ₂ ) was added with stirring to obtain a homogeneous solution. Furthermore, this solution
260 g of 20% sulfuric acid was added and stirred at high speed at 5000 rpm in a mixer to obtain a homogeneous gel. The resulting gel was placed in a Teflon-lined autoclave and heated to 170°C.
It was crystallized for 90 hours. After overwashing the obtained product, it was incubated at 120°C for 5
The X-ray diffraction pattern after drying for an hour and calcining in air at 500° C. for 8 hours is shown in FIG. In addition, this product was determined by chemical analysis.
SiO ₂ /B ₂ O ₃ molar ratio is 30, SiO ₂ /Al ₂ O ₃ molar ratio is
It was 300. Example 3 1,8-diamino-4-aminomethyloctane
20g, boric acid 0.5g, aluminum sulfate [Al ₂
(SO ₄ ) ₃・18H ₂ O〕0.3g, sodium hydroxide 1.0g
was added to 45 g of water to obtain a homogeneous solution. 40 g of silica sol (30% by weight SiO ₂ ) was added dropwise to this solution with stirring, and 20% sulfuric acid was added to adjust the pH to 11.5 to obtain a homogeneous gel. After putting this gel into a homogenizer and stirring at high speed for 10 minutes at 15000 rpm,
Crystallization was performed at 180°C for 50 hours in a Teflon-lined pressure vessel. After overwashing the obtained product, it was incubated at 120°C for 5
FIG. 4 shows the X-ray diffraction pattern after drying for an hour and baking in air at 500° C. for 8 hours. Further, the SiO ₂ /B ₂ O ₃ molar ratio determined by chemical analysis was 60, and the SiO ₂ /Al ₂ O ₃ molar ratio was 90. Comparative Example According to the example of JP-A No. 53-55500,
A crystalline borosilicate similar to ZSM-5 was synthesized. 0.25g boric acid and 1.6g sodium hydroxide
It was dissolved in 60 g of water and 9.4 g of tetrapropylammonium bromide and 12.7 g of silica sol (30% by weight SiO ₂ ) were added to obtain a homogeneous solution. Pour this solution into a Teflon-lined pressure-resistant container and heat it to 165°C.
It was crystallized for 7 days. The X-ray diffraction pattern of the obtained product after over-washing, drying at 120° C. for 5 hours, and calcining in air at 500° C. for 8 hours is shown in FIG. Example 4 AZ-2 obtained in Example 1 was ion-exchanged in a 1N ammonium chloride aqueous solution for 24 hours, washed and dried, and calcined in air at 500°C for 5 hours to remove diethylbenzene from ethylbenzene and ethylene. Used as a catalyst for synthesis reactions. The reaction conditions were: ethylenebenzene/ethylene molar ratio 3.0, AZ-2 2 g, WHSV 4.0 hr ^-1 , reaction temperature 350° C., and normal pressure. The results obtained 2 to 3 hours after the start of the reaction were that the ethylbenzene reduction rate was 23%, the diethylbenzene selectivity was 94%, and the proportion of para-isomer in diethylbenzene was 72%. Example 5 Using AZ-2 obtained in Example 3, a synthesis reaction of ethyltoluene from toluene and ethylene was carried out. The reaction conditions are toluene/ethylene/H ₂
Molar ratio 8/1/6, SV1200hr ^-1 , pressure 3.0Kg/cm ²
(Gauge pressure) The reaction temperature was 400°C. Table 3 shows the results 2 to 3 hours and 18 to 19 hours after the start of the reaction.

[Table] Example 6 AZ-2 synthesized in Example 2 was ion-exchanged in a 1N ammonium chloride aqueous solution for 24 hours, washed, dried, and calcined in air at 500°C for 5 hours.
A synthesis reaction of hydrocarbons from methanol was carried out.
The reaction conditions were methanol/N ₂ molar ratio 1/3, reaction temperature 350°C, SV 3000hr ^-1 and normal pressure. The results 5 to 6 hours after the start of the reaction were that the methanol conversion rate was 100%, the hydrocarbon selectivity was 90%, and the product distribution in the obtained hydrocarbons was as follows.

[Table] Total carbon number of generated hydrocarbons Example 7 AZ-2 obtained in Example 1 was treated with 1N La
After ion exchange with (NO ₃ ) ₃ ·6H ₂ O aqueous solution for 24 hours, excessive washing, and drying at 120° C. for 5 hours, the X-ray diffraction pattern was the same as that in FIG. 1 of Example 1. Example 8 AZ-2 obtained in Example 1 was treated with 1N CuCl ₂ .
After ion exchange with 2H ₂ O aqueous solution for 24 hours, excessive washing, and drying at 120° C. for 5 hours, the X-ray diffraction pattern was the same as that in FIG. 1 of Example 1.

[Brief explanation of the drawing]

Figure 1 shows the product X obtained in Example 1.
Line diffraction pattern, Figure 2 is an electron micrograph showing the crystal structure of the product obtained in Example 1,
Figure 3 shows the X-ray diffraction pattern of the product obtained in Example 2, Figure 4 shows the X-ray diffraction pattern of the product obtained in Example 3, and Figure 5 shows the X-ray diffraction pattern of the product obtained in Example 3. This is an X-ray diffraction pattern of the product.

Claims (1)

[Claims] 1 (a) It has the following composition expressed in molar ratio of oxides, M _2/o O・xSiO ₂ .yAl ₂ O ₃・zB ₂ O ₃ (wherein M is Indicates at least one n-valent cation, y+z=1, y≧0, z≧0.3, x
≧5. ) (b) A borosilicate characterized by having a characteristic diffraction image shown in the table below in an X-ray diffraction diagram. [Table] However, X-ray diffraction analysis uses CuKα rays.