JPH0247403B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new method for producing ferrierite-type zeolite, which belongs to zeolites having five-membered oxygen rings, and more specifically, to a method for producing ferrierite-type zeolite, which is highly pure and SiO ₂ /Al ₂ O without using any organic mineralizing agent. ₃
The present invention provides a method for easily producing ferrierite-type zeolite having a high molar ratio with extremely high reproducibility. Zeolite is a crystalline aluminosilicate containing zeolite water, and its composition is generally expressed by the following empirical formula. M _2/o O・Al ₂ O ₃・xSiO ₂・yH ₂ O (Here, n is the valence of the cation M, x is a number of 2 or more, and y is a number of 0 or more.) Also, its basics The structure consists of a SiO ₄ tetrahedron with silicon as the center and four oxygen atoms coordinated at its vertices, and an AlO ₄ tetrahedron with aluminum as the center instead of silicon, with an atomic ratio of O/(Al+Si) of 2. They are regularly bonded three-dimensionally by sharing oxygen with each other. As a result, a three-dimensional network structure having pores of different sizes and shapes is formed due to the different bonding methods of the tetrahedra. or,
The negative charge of the AlO ₄ tetrahedron is electrically neutralized by bonding with cations such as alkali metals or alkaline earth metals. Generally, the number of pores formed in this way is 2 to 3.
The size of the pores ranges from angstroms to tens of angstroms, but the size of the pores can be changed by replacing the metal cations bonded to the AlO ₄ tetrahedra with other metal cations of different sizes. Zeolite uses these pores to act as an industrial gas/liquid dehydrating agent or as a molecular sieve that adsorbs and separates only specific molecules, and when metal cations are exchanged with hydrogen ions, it acts as a solid acid. It is also used in many industrial catalysts that take advantage of its properties. Ferrierite type zeolite also exists in nature, and its typical composition is (Na ₂ , Mg)O.Al ₂ O ₃ .11.1SiO ₂ .6.5H ₂ O. Its crystal structure consists of a skeletal unit of 5-membered oxygen rings, and is characterized by having 4.3 x 5.5 Å pores consisting of 10-membered oxygen rings and 3.4 x 4.8 Å pores consisting of 8-membered oxygen rings. Can be attached. Various methods for synthesizing ferrierite-type zeolite have been proposed so far, as described below.
However, these methods have advantages and disadvantages, and the reality is that no industrially satisfactory method has yet been developed. For example, (1) the method proposed by CLKibby et al. requires a high temperature of approximately 300°C or higher for crystallization;
This necessitates the use of a high-temperature, high-pressure reaction vessel. [Journal of Catalysis Vol.35, 256
~272 pages (1974)] (2) Furthermore, although the method disclosed in JP-A-51-106700 can be carried out at a relatively low temperature, the raw material silica-alumina is Furthermore, the presence of potassium ions in the reaction system is essential. It is also an essential condition to add mineralizing agents such as sodium and/or potassium salts of organic or inorganic polybasic acids. As described above, this method requires complicated selection of raw materials, setting of reaction conditions, etc., and cannot be used as an industrial production method. (3) JP-A-50-127898 and JP-A-55-
The method disclosed in Japanese Patent No. 85415 requires the use of N-methylpyridine hydroxide and piperidine and/or alkyl-substituted piperidine as organic mineralizing agents. These organic amines are not only expensive, but also incorporated into the zeolite produced, so when using the ferrierite-type zeolite obtained by this method as an adsorbent or catalyst, it is necessary to synthesize the The zeolite is calcined in the presence of oxygen at a high temperature of over 500℃,
These amines must be removed before use. In order to direct the zeolite to such specific uses, it is necessary to pre-treat the zeolite itself. (4) The method disclosed in JP-A-53-144500 uses so-called butanediamine or an organic nitrogen-containing cation derived therefrom.
This is a method for synthesizing ferrierite-type zeolite called ZSM-35, but this method also has the disadvantage that the synthesized zeolite must be pretreated in the same way as method (3) above before it can be used for various purposes. have Until now, zeolites such as ferrierite, mordenite, and ZSM-5, in which the zeolite skeleton unit is composed of a 5-membered oxygen ring, have a relatively high SiO ₂ /Al ₂ O ₃ molar ratio. Although known, the synthesis method generally employs a method that requires the addition of an organic nitrogen-containing compound or other organic compound to the reaction system, as described above. Furthermore, in these known methods, particularly expensive aqueous colloidal silica has usually been used as a silica source in order to increase the activity of the reaction mixture. The present inventors have investigated the conditions for producing crystalline aluminosilicate zeolite from the M2 _/o O- _Al2O3 - _SiO2 - _H2O system (n is the valence of the cation M), especially _the silica As a result of many years of intensive research into the selection of raw materials including the alumina source, the preparation conditions of the reaction mixture, and the crystallization mechanism of zeolite, we have developed a method that is fundamentally different from the known methods described above. It is something. That is, the present invention is capable of producing granular amorphous alumina having a specific composition without using any organic or inorganic mineralizers that have been added to the reaction system and without using expensive aqueous colloidal silica as a silica source. High purity and
They completed a method to easily obtain ferrierite-type zeolite with a high SiO ₂ /Al ₂ O ₃ molar ratio with good reproducibility. The present invention uses inexpensive raw materials without using expensive organic mineralizers, and with high purity and SiO ₂ /
The purpose is to provide a method for easily producing ferrierite-type zeolite with a high Al ₂ O ₃ molar ratio, and although the conventional method is possible in the laboratory, it is difficult to produce industrially in terms of economy, quality, operation, etc. Considering that there are many difficulties, the industrial significance of the present invention is extremely large. The present invention will be explained in more detail. In the present invention, aluminum is 6 to 10 wt% as Al ₂ O ₃ and alkali metal is A ₂ O (A is By crystallizing a homogeneous compound containing 1.5 to 10 wt% of alkali metal (indicating an alkali metal) in water or an aqueous alkali metal hydroxide solution with a concentration of 4 wt% or less at 100 to 300°C, it is possible to create a mineral without using an organic mineralizer. The present invention provides a method for producing ferrierite zeolite with high purity and a high SiO ₂ /Al ₂ O ₃ molar ratio. In this specification, simultaneous and continuous reaction means an embodiment in which the alkali metal silicate aqueous solution and the aluminum-containing aqueous solution are supplied to the reaction zone simultaneously and while maintaining a substantially constant ratio. As an alkali metal silicate aqueous solution,
It is an aqueous solution of lithium silicate, sodium silicate, potassium silicate, etc. Examples of the aluminum-containing aqueous solution include aqueous solutions of aluminum sulfate, aluminum nitrate, aluminum chloride, sodium aluminate, potassium aluminate, and the like. Further, a caustic alkali or a mineral acid may be added to these as necessary to adjust the amount of the alkali or acid. Both aqueous solutions may be commercially available alkali metal silicate aqueous solutions, aluminum mineral salt aqueous solutions, or alkali aluminate aqueous solutions, or silica sources such as silica sand and hydrated solid silicic acid may be used with caustic alkali, or aluminum hydroxide, active It is also possible to dissolve an aluminum source such as alumina with a mineral acid or with a caustic alkali to prepare an aqueous solution of each.
The concentrations of both aqueous solutions are not particularly limited and can be used at any concentration. The most preferred embodiment for preparing a homogeneous compound by this method is a method in which both aqueous solutions are simultaneously and continuously fed into an overflow type reaction tank equipped with a stirrer and reacted under stirring. This method is effective because the produced homogeneous compound is approximately spherical or in the form of fine particle agglomerates, and most of the particle diameters are distributed in the range of 1 to 500 μm, with only a trace amount of fine particles of 1 μm or less. In the practice of this invention, it is preferred to use homogeneous compounds of 10 to 100 microns. The supply ratio of both aqueous solutions is set depending on the SiO ₂ /Al ₂ O ₃ molar ratio of the target ferrierite zeolite, and can be arbitrarily determined. At this time, the reaction solution suspends the granular homogeneous compound produced by the reaction and becomes a slurry, but the pH of the slurry is controlled by the amount of alkali or acid added to both aqueous solutions, and usually the pH is 5. The pH is adjusted to a range of 6 to 9, more preferably a range of 6 to 8. Further, the time the slurry stays in the reaction tank is preferably 3 minutes or more. The term "residence time" as used herein means the time from when both aqueous solutions are simultaneously and continuously supplied to the reaction tank until the reaction slurry containing the homogeneous compound produced by the reaction is discharged from the reaction tank. When the residence time is shorter than 3 minutes, the generation rate of fine particles increases. Furthermore, as the proportion of fine particles of 1 μm or less increases, there is an undesirable tendency to increase the load in the separation process of the generated compounds, as will be described later. On the other hand, when the residence time is 3 minutes or more, most of the product becomes spherical and the presence of fine particles becomes very small. Further, as the residence time becomes longer, the particle size increases and at the same time the bond between the particles becomes stronger, and the hardness of the spherical particles increases. Therefore, by controlling the residence time, it is possible to change the size and hardness of the spherical particles produced, making it possible to adjust the reactivity of the homogeneous compound itself depending on the purpose. As another example of the embodiment of the present invention, a so-called continuous batch preparation method may of course be applied, in which both aqueous solutions are simultaneously and continuously supplied at a fixed ratio to a reaction tank under stirring conditions without discharging the reaction slurry. However, in this case, it is necessary to feed one batch of raw materials over at least 5 minutes, preferably 30 minutes or more, without rapidly adding both aqueous solutions. The reaction temperature during the production of the homogeneous compound is not particularly limited, and the resulting compound becomes spherical regardless of whether it is at low or high temperatures, and there is no significant difference in the reactivity of the resulting compound. A unique fact in the present invention is that when the granular homogeneous compound obtained by simultaneously and continuously reacting the alkali metal silicate aqueous solution and aluminum-containing aqueous solution is used as a raw material, a highly pure ferrierite type zeolite can be obtained. However, if the raw material is a paste-like amorphous aluminosilicate compound obtained by a so-called batch reaction method in which one aqueous solution is added to the other,
Even if crystallization is carried out under exactly the same conditions as in the present invention, the desired ferrierite-type zeolite cannot be obtained at all. In addition to this fact, what is even more unique is that the composition of the spherical homogeneous compound that is produced by simultaneously and continuously reacting both aqueous solutions with adjusted concentrations at a fixed ratio is the same, regardless of the size of the spherical particles. First, since they are all microscopically uniform, it is possible to completely prevent coexistence of impurities caused by non-uniform composition. Furthermore, if one aqueous solution is added to the other aqueous solution in the so-called normal batch method, the viscosity of the reaction slurry will increase abnormally, and no matter how strong the stirring is, the resulting slurry will be It is impossible to achieve uniformity. Even if the mixture is sufficiently mixed and appears to be homogeneous at first glance, microscopic non-uniformity in composition cannot be avoided. The fact that it was completely impossible to obtain the desired zeolite when an amorphous aluminosilicate compound obtained by batch reaction was used as a raw material was precisely due to the heterogeneity of this composition. It is something. This is precisely why the granular amorphous aluminosilicate compound of the present invention was referred to as a homogeneous phase compound earlier, and the technical framework of the present invention truly resides here. Furthermore, in the case of a batch method, the above-mentioned pasty reaction product has an extremely high viscosity, and the concentration of the active ingredient is inevitably limited to a fairly low range. On the other hand, since the homogeneous compound in the present invention is a spherical particle with a size of 1 to 500μ, the viscosity of the reaction slurry is very low, and strong stirring unlike the above-mentioned batch method is not required. The concentration can be increased significantly. Since the homogeneous compound obtained by the method of one representative example of the present invention is obtained in the form of spherical objects of appropriate size, solid-liquid separation and washing are extremely easy, and this point is also one of the characteristics of the present invention. be. Therefore, an ordinary centrifuge or vacuum filtration machine can be used for solid-liquid separation, and since it has excellent dehydration properties and can be obtained in the form of a wet cake with a low water content, it is necessary to crystallize it into ferrierite-type zeolite. A wide range of water balance settings is possible when preparing reaction mixtures. It is advantageous to use the homogeneous compound after washing in the form of a wet cake, but it is of course also possible to use it in dry form. In general, in order to produce pure zeolite free of impurities, the mixing ratio of each raw material component is very important. In the case of the above example of the present invention, the composition of the homogeneous compound obtained is determined by the conditions for reacting both the alkali metal silicate aqueous solution and the aluminum-containing aqueous solution and the conditions for washing, filtering, drying, etc. As the above homogeneous compound for producing ferrierite type zeolite, 6 to 10 wt% of Al ₂ O ₃ and
If A ₂ O of 1.5 to 10 wt% is outside this range, high purity ferrierite type zeolite cannot be produced. The homogeneous compound thus obtained is then heated in water or an aqueous alkali metal solution to crystallize it into a ferrierite-type zeolite. In preparing a starting slurry for crystallization by adding a certain amount of a homogeneous compound of known composition to water or an aqueous alkali metal hydroxide solution depending on the composition, the homogeneous compound is converted into a high-purity ferrierite-type zeolite. It is necessary to adjust the concentration and amount of the alkali metal hydroxide aqueous solution to achieve crystallization. The aqueous alkali metal hydroxide solution used for crystallizing the homogeneous compound in the present invention is an aqueous solution of sodium hydroxide, potassium hydroxide, lithium hydroxide, etc., or may be a mixed aqueous solution of two or more of these.

[Table] However, in the table, A represents an alkali metal and AOH represents an alkali metal hydroxide. In the present invention, the most preferable conditions for obtaining a ferrierite zeolite with high purity and high crystallinity are the starting slurry system for crystallization with respect to the aluminum component Al ₂ O ₃ in the homogeneous compound while satisfying the above range. The purpose is to adjust the molar ratio of the total alkali metal hydroxide component expressed as AOH in the range of 2 to 4, and the molar ratio expressed as AOH to the silicon component SiO ₂ in the homogeneous compound to be in the range of 0.2 or less.
Further, the amount of the aqueous alkali metal hydroxide solution is set so that the ratio of the weight of the solid content to the total weight of the starting slurry for crystallization is in the range of 0.04 to 0.4. As described above, the particle size of the homogeneous compound obtained by the representative example of the present invention is relatively large and the hardness is also large, so that it does not become fine even under stirring.
Therefore, without significantly increasing slurry viscosity,
Since the amount of water in the starting slurry can be reduced to the extent that no impurities are produced, it has become possible to significantly increase the yield in batch reactions.
This is also one of the major features of the present invention. Crystallization in the present invention is carried out by placing a starting slurry for crystallization containing a homogeneous compound in an autoclave at a temperature of 100 to 300°C, preferably at a temperature of 150°C or higher. During crystallization, it is desirable to stir the autoclave in order to equalize the temperature within the autoclave.
After crystallization is completed, the formed crystals are separated from the mother liquor, washed with water, and dried to obtain crystal powder. The crystal particles obtained here are granular ferrierite-type zeolite crystal aggregates of about 1 to 500 μm in size, which maintain the substantially spherical uniform particle shape of the compound. The ferrierite-type zeolite obtained according to the present invention may be ion-exchanged with appropriate cations as necessary, and then may be used as an adsorbent and as a crystal aggregate, after pulverization, or as a molded body with a binder added. Can be used as a catalyst. The present invention will be explained in more detail in Examples. Example 1 A sulfuric acid acidic aluminum sulfate aqueous solution (Al ₂ O ₃ = 4.44w/v%, H ₂ SO ₄ = 25.69w/
v%) and sodium silicate aqueous solution (Na ₂ O=
6.56w/v%, SiO ₂ =20.00w/v%, Al ₂ O ₃ =
0.22w/v%), 0.25/hr and 0.75 respectively
The reaction was carried out under stirring by simultaneously and continuously feeding at a feeding rate of /hr. In addition, the overflow port of the reaction tank was installed so that 0.5 of the amount of post-reaction (slurry) was always present in the reaction tank, and any more than that would overflow, and the residence time of the reaction slurry was set to 30 minutes. PH of the slurry
was 6.2, and the reaction temperature was 32°C. The slurry product that overflowed from the reaction tank is separated into solid and liquid using a centrifuge, and is then added to the washing solution.
It was washed with water until SO ₄ =ions were no longer detected to obtain a homogeneous compound having the composition shown in Table 1. Furthermore, an electron micrograph of this homogeneous compound is shown in Figure 1. Sodium hydroxide aqueous solution 505 with a concentration of 0.89wt%
355.6 g of the above homogeneous compound was added to the mixture and stirred to prepare a starting slurry. Pour this slurry into an autoclave and
Crystallization was carried out by holding at ℃ and its autogenous pressure for 72 hours. After the reaction was completed, the produced solid was separated from the mother liquor by filtration, washed with water, and then dried at 110°C. Electron micrograph of this product (1000x)
and powder X-ray diffraction patterns are shown in Figures 2 and 3.
In Figure 3, the vertical axis represents the diffraction intensity, and the horizontal axis represents 2θ (°).
represents. As a result of chemical analysis of this sample,
Its composition is on an anhydrous basis, 1.0Na ₂ O・Al ₂ O ₃・
It was _19.3SiO2 . A portion of this sample was activated in a Macbein-Baker type adsorption apparatus under vacuum at 350°C for 2 hours, and then the amount of n-hexane adsorbed was measured at 25°C and 95°C.
It was 7.9wt% in mmHg. Example 2 Sodium hydroxide aqueous solution 297 with a concentration of 0.71 wt%
209.2 g of the homogeneous compound prepared in Example 1 was added to the mixture and stirred to prepare a starting slurry. This slurry was charged into an autoclave and held at 180° C. and its autogenous pressure for 72 hours to effect crystallization. After the reaction was completed, the produced solid was separated from the mother liquor by filtration, washed with water, and then dried at 110°C. The powder X-ray diffraction pattern of this product was essentially the same as in Figure 3. As a result of chemical analysis of this sample,
Its _composition was _{1.0Na2O.Al2O3.19.5SiO2} on _{an anhydrous} basis. After activating a portion of this sample in a Macbein-Baker adsorption apparatus under vacuum at 350°C for 2 hours, the amount of n-hexane adsorbed was measured at 25°C and 95°C.
It was 6.6wt% in mmHg. Example 3 A homogeneous compound having the composition shown in Table 1 was prepared by substantially the same method as in Example 1. A starting slurry was prepared by adding 895 g of this homogeneous compound to 1247 ml of water and stirring. This slurry was held at 190° C. and its autogenous pressure for 75 hours to effect crystallization. After the reaction was completed, the produced solid was separated from the mother liquor by filtration, washed with water, and then dried at 110°C. The powder X-ray diffraction pattern of this product was essentially the same as in Figure 3. Comparative Example 1 Aluminum sulfate (Al ₂ O ₃ = 16.80wt) in 536g of water
%, H ₂ SO ₄ = 48.45wt%), and further
24.7 g of 97% concentrated sulfuric acid was added. Add No. 3 water glass (SiO ₂ = 28.46wt%, Na ₂ O = 9.34wt%,
527.8 g of Al ₂ O ₃ =0.117wt%) was added with stirring. After adding the entire amount, stirring was continued for 30 minutes to prepare a reaction mixture. This reaction mixture was charged into an autoclave and held at 180° C. and its autogenous pressure for 72 hours to effect crystallization. After the reaction was completed, the produced solid was separated from the mother liquor by filtration, washed with water, and then dried at 110°C. As a result of confirming this product by powder X-ray diffraction, α
-It was mordenite containing quartz. Comparative Example 2 Sulfuric acid acidic aluminum sulfate aqueous solution of 1 (Al ₂ O ₃ = 4.85 w/v%, H ₂ SO ₄ = 25.65 w/v%)
3 sodium silicate aqueous solution (SiO ₂ = 20.0w/
v%, _Na2O =6.56w/v%, _Al2O3 = _0.082w /v
%) was added and reacted with stirring. After the entire amount was added, stirring was continued for an additional hour. The resulting slurry product was subjected to solid-liquid separation using a centrifuge, and the solid phase portion was washed with water until no SO ₄ ⁼ ions were detected in the washing solution. The product was amorphous sodium aluminosilicate having the composition shown in Table 1. Sodium hydroxide aqueous solution 484 with a concentration of 0.93wt%
590 g of the above amorphous sodium aluminosilicate was added to the slurry and stirred to prepare a starting slurry. Pour this slurry into an autoclave,
Crystallization was carried out by holding at 180°C and its autogenous pressure for 72 hours. After the reaction is complete, the produced solid is separated from the mother liquor, washed with water, and then
Dry at °C. This product was confirmed to be an amorphous solid by powder X-ray diffraction.

[Table] Example 4 A sulfuric acid acidic aluminum sulfate aqueous solution (Al ₂ O ₃ = 5.23w/v%, H ₂ SO ₄ =
25.52w/v%) and sodium silicate aqueous solution (Na ₂ O = 4.87w/v%, SiO ₂ = 15w/v%,
Al ₂ O ₃ =0.07 w/v%) were simultaneously and continuously fed at feed rates of 21.1 L/Hr and 5.3 L/Hr, respectively, and the reaction was carried out under stirring. In addition, 5.5 L of reaction liquid (slurry) was always present in the reaction tank, and an outlet of the reaction tank was installed so that anything beyond that amount would overflow, and the residence time of the reaction slurry was set to 12.5 minutes. The pH of this slurry was 6.4, and the reaction temperature was 31 degrees Celsius. The slurry product overflowing from the reaction tank is separated into solid and liquid using a centrifuge, and the washing filtrate is washed with water until no SO ₄ ⁼ ions are detected.
A homogeneous compound having the composition shown in Table 2 was obtained. Sodium hydroxide aqueous solution 4348 with a concentration of 1.76w%
3,658 g of the above homogeneous compound was added to the mixture and stirred to prepare a starting slurry. This slurry was placed in an autoclave and held at 170 degrees Celsius under its own pressure for 48 hours with stirring to crystallize. After the reaction was completed, the produced solid was separated by filtration, washed with water, and dried at 110 degrees Celsius.
The powder X-ray diffraction pattern of this product is shown in Figure 4. In the figure, the vertical axis represents the diffraction intensity, and the horizontal axis represents 2θ (°). Further, as a result of chemical analysis, the composition was 0.7K ₂ O・0.31Na ₂ O・Al ₂ O ₃・17.1SiO ₂ on an anhydrous basis. Example 5 To 785 g of an alkaline aqueous solution with a concentration of sodium hydroxide of 0.5 w% and a concentration of potassium hydroxide of 2.12 w%,
Homogeneous compound 615 prepared under the same conditions as Example 4
g was added and stirred to prepare a starting slurry. The composition of the homogeneous compound used is shown in Table-2. Pour this slurry into an autoclave,
It was held at 170 degrees Celsius under its autogenous pressure for 72 hours with stirring to crystallize. After the reaction was completed, the solid produced was separated by filtration, washed with water, and then dried at 110°C. The X-ray diffraction diagram of this substance is essentially a figure-
It was the same as 4. Further, as a result of chemical analysis of this product, its composition was 0.72K ₂ O・0.24Na ₂ O・Al ₂ O ₃・15.8SiO ₂ on an anhydrous basis. Example 6 A sulfuric acid acidic aluminum sulfate aqueous solution (Al ₂ O ₃ = 4.12 w/v%, H ₂ SO ₄ =
26.24w/v%) and a sodium silicate aqueous solution ( _Na2O =4.83w/v%, _SiO2 =15w/v%,
Al ₂ O ₃ =0.08w/v%), respectively 17.6L/Hr,
The reaction was carried out by simultaneously and continuously feeding at a feeding rate of 4.4 L/Hr and stirring. In addition, 5.5 L of the reaction liquid (slurry) was always present in the reaction tank, and an outlet of the reaction tank was installed so that anything beyond that amount would overflow, and the residence time of the reaction slurry was set to 15 minutes. The pH of this slurry was 6.5, and the reaction temperature was 32 degrees Celsius. The slurry that overflowed from the reaction tank was centrifuged and washed with water until no SO ₄ ⁼ ions were detected in the washed filtrate, resulting in a homogeneous compound having the composition shown in Table 2. A starting slurry was prepared by adding 3884 g of the homogeneous compound described above to 4222 g of an alkaline aqueous solution containing a sodium hydroxide concentration of 0.75 w% and a potassium hydroxide concentration of 2.19 w% and stirring. This slurry was placed in an autoclave at 170 degrees Celsius, under its own pressure, and stirred.
It was kept for 72 hours and crystallized. The powder X-ray diffraction pattern of the powder treated in the same manner as in the example below is essentially Figure-4.
It was the same. Moreover, its composition was 0.8K ₂ O・0.18Na ₂ O・Al ₂ O ₃・19.4SiO ₂ on an anhydrous basis.

【table】 [Brief explanation of drawings]

Figure 1: Electron micrograph of the granular homogeneous compound obtained in Example 1. Figure 2: Electron micrograph of the product obtained in Example 1. Figure 3: Powder X-ray diffraction diagram of the product obtained in Example 1 measured using a copper Ka double line. Figure 4 shows the powder X-ray diffraction pattern of the product obtained in Example 4.

Claims (1)

[Claims] 1. Aluminum obtained by simultaneously and continuously reacting an alkali metal silicate aqueous solution and an aluminum-containing aqueous solution, with aluminum as Al ₂ O ₃ in anhydrous terms 6 ~
A granular amorphous aluminosilicate homogeneous phase compound containing 10 wt% of alkali metal and 1.5 to 10 wt% of alkali metal as A ₂ O (A ₂ O indicates an alkali metal) is mixed with water or concentration.
100 in an alkali metal hydroxide aqueous solution of up to 4wt%
A method for producing ferrierite-type zeolite, which is characterized by crystallizing at ~300°C.