JPS6024049B2 - Method for producing crystalline aluminosilicate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing crystalline aluminosilicate.

Crystalline aluminosilicates have been found in nature as zeolites since ancient times, and are widely used as water treatment agents, molecular fibers, adsorbents, etc. by applying their ion exchange and adsorption functions.

Crystalline aluminosilicate is generally MSiXNyOZ.
It has a composition expressed as aH20 (M is a cation, x, y.z and a are real numbers), and although M and a change depending on the processing conditions, the powder X-ray diffraction pattern is similar or almost They are identical and have extremely high steric structural stability.

In recent years, there has been a strong demand for synthetic zeolites synthesized by hydrothermal methods because naturally produced zeolites have uneven quality and are unsuitable for industrial applications that require high quality. There is.

Synthetic zeolites are used, for example, as detergent builders and catalyst carriers. In particular, it has recently attracted attention as a catalyst for gasoline synthesis from methanol. Conventionally, various methods for synthesizing synthetic zeolites have been proposed, but all of them have drawbacks such as problems in reproducibility, high cost, and poor purity of the product.

In addition, when synthetic zeolite is produced by a hydrothermal reaction method, in order to avoid the production of amorphous zeolite and selectively obtain crystalline zeolite, generally, after the reaction of the silica component and the alumina component, It is necessary to heat and ripen the reaction product for a long time to crystallize it, which significantly deteriorates the process efficiency. The present invention provides a method for efficiently producing crystalline aluminum/silicate having a desired crystal structure.

That is, according to the present invention, the silica component and the alumina component are subjected to a hydrothermal reaction in an aqueous solution under a flywheel, and then the obtained reaction product is cooled without being heated and aged. A method for producing a crystalline aluminosilicate is provided, characterized in that a surfactant is present.

As the silica component used in the present invention, various types of silicates are used, but usually water glass is used. Furthermore, as the alumina component, any material that can generate aluminum ions or aluminate ions may be used, such as aluminum salts of inorganic acids such as aluminum sulfate, aluminum chloride, and aluminum nitrate, and aluminum salts such as sodium aluminate. Acid salts are applied. Also,
The following surfactants can be used in the present invention.

m Anionic surfactants include, for example, sodium alkyl sulfate, aluminum alkylbenzenesulfonate, sodium long-chain Q-olefin sulfonate, sodium alkyl polyoxyalkylene ether sulfate, sodium long mirror saturated fatty acid, chain unsaturated and/or commonly used such as sodium oxyfatty acids.

Examples of the '2' nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene long-head fatty acid ester, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene nonyl phenyl able, and long-chain fatty acid alkyl ester. Rollamide etc.

Examples of the '31 ionic surfactant include tetraalkyl ammonium salts such as dodecyltrimethylammonium chloride, tetradecyljethyrol benzyl ammonium nitrate, dioctyldimethylammonium chloride, N-dodecyl-2-propylpyridinium chloride, N- N-alkylpyridinium halides such as cetylpyridinium bromide, dodecylamine acetate,
Alkylamine salts such as octadecylamine salts.

■ Examples of amphoteric surfactants include alkylimidazolinium betaines such as 2-alkyl-N-hydroxymethyl-N-hydroxyethylimidazolinium betaine, and alkylglycine betaines such as N-dodecyl-N,N-dimethylglycine betaine. , alkyl diethylene triamino acetates such as dodecyl diethylene triamino acetic acid hydrochloride, alkylaminoalkyl sulfates such as N-lauryl-N,N-dimethylaminopropyl sulfate, N
-decyl-N,N-dimethylaminopropylsulfonic acid and other alkylaminoalkylsulfonic acids, N-dodecylaminomethylphosphoric acid, etc.

These surfactants can be used alone or as a mixture.

According to the present invention, a crystalline aluminosilicate having a composition or structure suitable for the intended use can be easily produced.

Next, the manufacturing conditions of a typical example will be shown. A: Analcym Due to its structure, Analcym has a pore size of 4 and a small porosity, so it does not function as a molecular piece, but because it has a cation exchange chamber, it can be used as a water treatment agent. It is valid.

This product is also used as a builder for detergents. When manufacturing Analsym, the silica component is Si0
Water glass having a 2/Na20 weight ratio of 1 to 2.3 is used.

In addition, the molar ratio of the silica component to the alumina component used is Si
The 02/AI203 molar ratio may be from 0.1 to 100, preferably from 1 to 10. The synthesis temperature is 120
~22pi○ is fine, but more preferably 160~180q
o, and the synthesis time is about 10 minutes to 1 glue hour,
Preferably it is 1 to 1 field time. In the present invention, the amount of surfactant added to the reaction system is determined by the added silica component (Si
The amount is in the range of 2×10-4 to 20% by weight based on 0.02. B: Mordenite Mordenite is used as a water treatment agent and detergent additive due to its cation exchange ability, and it also has a three-dimensional tunnel structure and high porosity, so it is also used as a molecular fiber and adsorbent. It is also used as a political catalyst for petroleum by applying its strong acidic point function.

When manufacturing with mordenite, the silica component is Si.
Water glass having a 02/Na20 weight ratio of 2.2 to 3.2 is used.

The molar ratio of silica component and alumina component used is Si02/
The molar ratio of AI202 may be in the range of 1 to 2000,
Preferably it is 2-100. Synthesis temperature is 120-22
It may be 00○, but preferably 160 to 180 o'clock. The synthesis time is about 1 minute to 1 hour, but usually 1 minute to 1 hour.
~1 feeding time. The amount of surfactant added is based on the silica component (S
i02 equivalent), the range is from 2 x 10-4 to 2% by weight. C: Zeolite as a catalyst for synthesizing gasoline from methanol With the depletion of petroleum, much research has been focused on developing technology to synthesize gasoline from methanol, and it has been found that certain types of zeolite are effective as catalysts for this reaction system. It's being served.

The present invention is also extremely effective for the synthesis of such zeolites. When synthesizing this type of zeolite, water glass having a Si02/Na20 weight ratio of 2.7 or more is used as the silica component.

In addition, the molar ratio of the silica component and the alumina component used is Si
02/AI203 molar ratio in the range of 5 to 3000,
Preferably it is in the range of 10 to 1000. The synthesis temperature is 1
It is 20 to 220 qo, preferably 160 to 18 qo. The synthesis time is 1 minute to 1 hour, usually 1 to 1 field hour. Although the hydrothermal reaction conditions for the synthesis of several representative types of zeolites have been described above, the method of the present invention is effective for the synthesis of any zeolite. By adding the agent, the desired zeolite can be obtained in high yield and high selectivity.

Additionally, the addition of a surfactant avoids the formation of amorphous aluminosilicate, enables the formation of zeolite (crystalline aluminosilicate), and improves the reproducibility of zeolite synthesis, making it possible to avoid the formation of amorphous aluminosilicate and to improve the reproducibility of zeolite synthesis. , which allows for the easy synthesis of the desired zeolite. In the present invention, in order to increase the zeolite yield (the rate of zeolite conversion of the added silica component), it is preferable to add an acid such as hydrochloric acid, sulfuric acid, or nitric acid to the reaction system to adjust the pH of the reaction system.

In addition, in connection with the addition of this acid, in order to suppress excessive gelation of the reaction system caused by the addition of the acid, gelation inhibitors, such as alcohols such as methanol and ethanol, and organic solvents such as maples and ketones, are also used. It is advantageous to add a suitable amount of. In the present invention, in order to increase the zeolite yield, the molar ratio of SiO2 (amount of acid) is 8.2 x 10-2.
~4.1×10-1, preferably 1.6×10-1-3
．． 2×10-1 and gelation inhibitor/Si02 molar ratio is 0
．． Conditions in the range of 1 to 7.5, preferably 0.5 to 5.5 are preferably employed. The crystalline aluminosilicate (zeolite) obtained by the present invention can be used as it is or after being calcined at an appropriate temperature for various purposes.

Furthermore, in the crystalline aluminosilicate MSixA1y○z·a mountain 0 obtained by the present invention, at least a portion of M can be exchanged with other metals such as Fe, Co, and Ni by a normal exchange method. Next, the present invention will be explained in more detail with reference to Examples.

Example 1 In order to synthesize Analcym, No. 1 water glass (Si0
237%, Na2017.5%) 39.6 evening and Wednesday 63.
4' was added to make solution A, and aluminum sulfate hydrate 1.
No. 62 was dissolved in water of No. 86.4 to obtain liquid B.

Add 5 drops of a 10% solution of linear sodium dodecylbenzenesulfonate to both solutions A and B and make a prayer. Mix both solutions and place in an autoclave with an internal volume of 300 cm. The temperature was raised to 180°C, maintained for 4 hours, and then cooled to room temperature. Table 1 shows the X-ray diffraction pattern of the product obtained by washing with water and drying. This pattern is consistent with the X-ray diffraction pattern of Analcyme. For powder X-ray diffraction, Geigerflex manufactured by Rigaku Denki Co., Ltd. was used.
Q-ray was used.

Table 1 Example 2 In order to synthesize mordenite, No. 2 water glass (Si0
228.4%, Na2011.6%) 41.9 evening to Wednesday 6
The above solution from 3.4 was added to obtain solution A, and 1.62 hours of aluminum sulfate hydrate was dissolved in 86.4 inches of water to obtain solution B.

Add 5 drops of 10% solution of linear sodium dodecylbenzenesulfonate to both solutions A and B, mix thoroughly, mix both solutions, charge into an autoclave with an internal volume of 300 pm, and prepare at 50 pm. The temperature was raised to 180℃ while worshiping the lanterns.
After holding for an hour, it was cooled to room temperature. Table 2 shows the X-ray diffraction pattern of the product obtained by washing with water and drying. This X-ray diffraction pattern matched that of mordenite. Table 2 Examples 3-4 In order to obtain zeolite as a catalyst for gasoline synthesis from methanol, No. 3 water glass (Si0229.0%,
Na209.5%) 50.6 days (Example 3), or 4
No. water glass (SiQ 23.3%, Na20 6.4%
)61.1 evening (Example 4) and add 63.4' of water to A
As a liquid, aluminum sulfate hydrate 1.622 to 86.4
It was dissolved in table water to make liquid B.

Add 5 drops of 10% aqueous solution of linear sodium dodecylbenzenesulfonate to both solutions A and B, mix thoroughly, mix both solutions, and place in an autoclave with an internal volume of 300. The temperature was raised to 180° C., maintained for 4 hours, and then cooled to room temperature. Table 3 shows the X-ray diffraction pattern of the product obtained by washing with water and drying. This pattern almost coincided with the X-ray diffraction pattern of zeolite ZSM-5 shown by Wu et al. of Mobil Corporation. The zeolite yield is approximately 6
They were 0% and 70%. Table 3 Example 5 Add 61.1 parts of No. 4 water glass to 63.4 parts of water to make solution A, and dissolve 1.62 parts of aluminum sulfate hydrate in 86.4 parts of water to make solution B. It was made into a liquid.

Add 5 drops of a 10% aqueous solution of linear sodium dodecylbenzenesulfonate to both solutions A and B, mix well, and mix solutions A and B. 2. 24 hours of sulfuric acid solution was added and stirred well, then 20 hours of methanol was added and stirred again. This mixture has a gel-like appearance in part. Add this mixture to 30
Prepared in an autoclave with an internal volume of 0 secretion, 50 bip
The temperature was raised to 1800C while shaking at m, maintained for 4 hours, and then cooled to room temperature. The X-ray diffraction pattern of the product obtained by washing with water and drying almost coincided with the X-ray diffraction pattern of zeolite ZSM-5 shown by Wu et al. of Moble. The zeolite yield was almost 100%. Example 6 61.1 mm of No. 4 water glass and 63.4 mm of water were added to prepare liquid A, and 1.62 mm of aluminum sulfate hydrate was dissolved in 86.4 mm of water to prepare liquid B. .

Add 5 drops of a 10% aqueous solution of sodium dodecylbenzenesulfonate to both solutions A and B and mix thoroughly. B
After mixing both liquids 2. Add 24 ml of aqueous sulfuric acid solution and evaporate well, then add 70 ml of methanol and evaporate again. This mixture has a gel-like appearance in part. Pour this mixture into an autoclave with an internal volume of 300 m
The temperature was raised to 180 o 0 while shaking at 100 pm and 100 pm, maintained for 4 hours, and then cooled to room temperature. Table 4 shows the X-ray diffraction pattern of the product obtained by washing with water and drying. X like this
Zeolite exhibiting a line diffraction pattern has not been known to date. This zeolite is considered to have a novel structure. Fourth
Table Comparative Examples As a result of conducting the same experiment as in Examples 1 to 5 except that no surfactant was added, the obtained solid products were as follows:
According to X-ray diffraction, none of them showed clear peaks and was amorphous (gel).

Claims (1)

[Claims] 1. The method consists of hydrothermally reacting a silica component and an alumina component under stirring in an aqueous solution, and then cooling the obtained reaction product without heating and aging it. A method for producing crystalline aluminosilicate, characterized by the presence of an agent. 2 To obtain anal symmetry, SiO_2/Na_2
2. The method according to claim 1, wherein water glass has an O weight ratio of 1 to 2.3. 3 To obtain mordenite, SiO_2/Na_2
The method according to claim 1, using water glass having an O weight ratio of 2.2 to 3.2. 4. Claim 1 in which water glass having a SiO_2/Na_2O weight ratio of 2.7 or more is used to obtain zeolite as a catalyst for gasoline synthesis from methanol.
Section method. 5. The method according to any one of claims 1 to 4, wherein an acid is added to an aqueous solution. 6. The method according to any one of claims 1 to 5, wherein a gelation inhibitor is added to the aqueous solution. 7. The method of claim 6, wherein the gelation inhibitor is alcohol.