CN109626392B - Preparation method of nano clinoptilolite molecular sieve - Google Patents
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Abstract
The invention provides a preparation method of a nano clinoptilolite molecular sieve. Firstly, mixing and stirring sodium hydroxide or a mixture of sodium hydroxide and potassium hydroxide with silica sol, an aluminum source and water to obtain a solution I; or the nano clinoptilolite molecular sieve prepared by the method is completely dissolved in sodium hydroxide or a mixed solution of the sodium hydroxide and potassium hydroxide to obtain a solution II. And then adding the solution I or the solution II into a synthesis system formed by a silane coupling agent and silica sol serving as a silicon source, sodium hydroxide or a mixture of the sodium hydroxide and the potassium hydroxide, an aluminum source and water, crystallizing at 80-200 ℃ for 10-96 hours, cooling to room temperature, carrying out solid-liquid separation, washing and drying. The silane coupling agent is favorable for preventing the condensation polymerization reaction of silicate ions and aluminate ions, thereby changing the reaction mechanism of forming the primary structural unit or the secondary structural unit of the clinoptilolite molecular sieve by the aluminosilicate ions. The obtained nano clinoptilolite molecular sieve has the characteristics of high relative crystallinity, small grain size and the like.
Description
Technical Field
The invention belongs to the field of inorganic synthetic microporous materials, and particularly relates to a preparation method of a nano clinoptilolite molecular sieve.
Background
Clinoptilolite molecular sieves have been widely used in the fields of gas separation, wastewater treatment and soil improvement, and industrial catalysis. At present, the average particle size of artificially synthesized or natural minerals is generally more than 1 μm, so that guest molecules have larger mass transfer and diffusion resistance in longer pore passages and the final service performance of the guest molecules is directly influenced. Research shows that the problems can be effectively solved by reducing the grain size of the molecular sieve, and the molecular sieve has excellent performance particularly in the aspects of improving catalytic activity or adsorption separation and the like. Therefore, many researchers have focused on methods and techniques for synthesizing small-grained zeolite molecular sieves with controlled particle size. However, recently, there are few reports on the synthesis method of nano clinoptilolite molecular sieves, mainly because the synthesis conditions are very harsh (American Minerals,1963,48:1374), and other heterogeneous phases are often associated with the synthesized product (American Minerals,1977,62:330), which greatly limits the application and development.
Disclosure of Invention
Aiming at the problem that the nano clinoptilolite molecular sieve is difficult to synthesize, the nano clinoptilolite molecular sieve with the grain size of 50-300nm can be obtained by adding the silane coupling agent into a synthesis system. The silane coupling agent is organosilicon containing different hydrophobic functional groups (methyl, dimethyl and trimethyl), and can be hydrolyzed to different degrees when meeting water under the alkaline condition. Therefore, the hydrolyzed silane coupling agent and the silica sol in the synthesis system are easy to generate hydroxyl condensation reaction to form silicate ions with hydrophobic functional groups and further prevent the silicate ions from being condensed with aluminate ions, thereby changing the reaction mechanism of the aluminosilicate ions to form a primary structural unit or a secondary structural unit of the clinoptilolite molecular sieve.
A preparation method of a nanometer clinoptilolite molecular sieve is characterized by comprising the following steps:
step 1, mixing and stirring sodium hydroxide or a mixture of sodium hydroxide and potassium hydroxide, silica sol, an aluminum source and water for 0.5 to 1 hour at room temperature, continuing stirring and aging for 6 to 96 hours at 60 to 180 ℃, and cooling to room temperature to obtain a solution I; wherein the amount of each raw material is SiO based on the silica sol2Calculated by Al as the aluminum source2O3Calculated as Na, sodium hydroxide2Calculated as O, potassium hydroxide is calculated as K2The O is measured by a meter,
the molar composition of the solution I is 0.5-4 (Na)2O+K2O)：Al2O3：8-20SiO2：150-350H2O (where Na/(Na + K) ═ 1-0.3);
the molar composition of the solution III is Al2O3：SiO2：(Na2O+K2O)：H2O ═ l: 10-30: 0.5-6: 200-2O：Na2O＝0-2；
The addition amount of the silane coupling agent accounts for the total silicon Source (SiO)2) The molar ratio of (A) is 5-45%;
step 3, adding the solution I obtained in the step 1 into the solution III prepared in the step 2, fully stirring the mixture until the mixture is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at the temperature of 80-200 ℃ for 10-96 hours, taking the kettle, cooling the kettle to room temperature, and obtaining the nano clinoptilolite molecular sieve after solid-liquid separation, washing and drying;
the amount of solution I added is 0.5-30wt% of solution III.
Or completely dissolving the prepared nano clinoptilolite molecular sieve in 1-3M sodium hydroxide solution or 1-3M mixed solution of sodium hydroxide and potassium hydroxide, wherein the sodium hydroxide in the mixed solution accounts for 30-80% of the total mixed solution by mass percent; the ratio of the nano clinoptilolite molecular sieve solid to the sodium hydroxide solution or the mixed solution of the sodium hydroxide and the potassium hydroxide is 1 g: 50-150mL, stirred at room temperature-100 ℃ for 1-24 hours, and then cooled to room temperature to obtain solution II.
Adding the obtained solution II into the solution III prepared in the step (2), fully stirring until the solution II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing at the temperature of 80-200 ℃ for 10-96 hours, taking the kettle, cooling to room temperature, carrying out solid-liquid separation, washing and drying to obtain the nano clinoptilolite molecular sieve; the amount of solution II added is 0.5-30wt% of solution III.
Further, the silane coupling agent is one or more of methyl triethoxysilane, dimethyl diethoxy silane, trimethyl ethoxy silane and methacryloxypropyl trimethoxysilane.
Further, the density of the silica sol in the steps (1) and (2) is 1100-1300g/L, SiO2The mass fraction of (A) is 29-31%.
Further, the aluminum source in the steps (1) and (2) is selected from one or more of aluminum oxide, gibbsite, boehmite, pseudo-boehmite, surge boehmite, aluminum chloride, aluminum nitrate, aluminum sulfate, sodium metaaluminate and/or potassium metaaluminate.
The further crystallization is static or dynamic.
Further, the step (3) is washed by a mixed solution of water and ethanol, and then dried at the temperature of 120-250 ℃ for 6-24 hours to obtain the nano clinoptilolite molecular sieve.
Drawings
FIG. 1 is an X-ray diffraction pattern of the nano clinoptilolite molecular sieve obtained in example 1.
FIG. 2 is a scanning electron micrograph of the nano clinoptilolite molecular sieve obtained in example 1.
Detailed Description
In the example, the density of the silica sol was 1100-1300g/L, SiO2The mass fraction of (A) is 29-31%. The percentage of the ethanol water solution is the mass percentage of the ethanol.
Example 1
1) Preparation of solution I: 0.5192g of sodium hydroxide, 0.7268g of potassium hydroxide, 25ml of deionized water, 0.7362g of aluminum hydroxide and 8.8ml (30 wt%) of silica sol are weighed at room temperature and placed in a 50ml polytetrafluoroethylene lining, the mixture is stirred at room temperature for 1h, then stirred and aged at 150 ℃ for 48 h, and after the mixture is cooled to room temperature, the mixture is stored for later use.
2) Preparation of solution III: 0.5192g of sodium hydroxide, 0.7268g of potassium hydroxide, 0.7362g of aluminum hydroxide, 25ml of deionized water, 0.4ml of dimethyldiethoxysilane and 8.4ml (30% by weight) of silica sol were mixed at room temperature with stirring to give solution III.
And (3) adding the obtained solution I into the solution III prepared in the step (2) according to the amount of the substance in the solution III, fully stirring until the solution I is uniformly mixed, putting the mixture into a reaction kettle, crystallizing at 150 ℃ for 72 hours, taking the kettle, cooling to room temperature, carrying out solid-liquid separation, washing with 35% ethanol solution, and drying at 140 ℃ for 20 hours to obtain the nano clinoptilolite molecular sieve.
The X-ray diffraction spectrum (shown in figure 1) and the scanning electron micrograph (shown in figure 2) show that the obtained solid product conforms to the characteristic nanometer oblique crystal morphology, and the grain size is about 50-300 nm.
Example 2
1) Preparation of solution II: 1g of clinoptilolite molecular sieve synthesized by the patent, 100ml of deionized water, 4g of sodium hydroxide and 5.6g of potassium hydroxide are mixed, stirred at room temperature for 24 hours and then cooled to room temperature to obtain solution II.
2) Preparation of solution III: 0.5192g of sodium hydroxide, 0.7268g of potassium hydroxide, 0.7362g of aluminum hydroxide, 25ml of deionized water, 0.5ml of methyltriethoxysilane and 8.4ml (30% by weight) of silica sol were mixed at room temperature and stirred continuously to prepare a solution III.
Adding the obtained solution I into the solution III prepared in the step (2) according to 0.5 wt% of the amount of the substance in the solution III, fully stirring until the solution I is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 150 ℃ for 72 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the product with 40% ethanol solution, and drying the product at 130 ℃ for 22 hours to obtain the nano clinoptilolite molecular sieve.
Example 3
1) Preparation of solution I: 0.5192g of sodium hydroxide, 0.6686g of potassium hydroxide, 25ml of deionized water, 0.7168g of aluminum hydroxide and 8.8ml (30 wt%) of silica sol are weighed at room temperature and placed in a 50ml polytetrafluoroethylene lining, the mixture is stirred at room temperature for 1h, then stirred and aged at 150 ℃ for 72 h, and after the mixture is cooled to room temperature, the mixture is stored for later use.
2) Preparation of solution III: 0.4776g of sodium hydroxide, 0.6686g of potassium hydroxide, 0.7362g of aluminum hydroxide, 25ml of deionized water, 1ml of dimethyldiethoxysilane and 8.1ml (30% by weight) of silica sol were mixed at room temperature with stirring to give solution III.
Adding the obtained solution I into the solution III prepared in the step (2) according to the amount of 5 wt% of the substance in the solution III, fully stirring until the solution I is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing at 150 ℃ for 48 hours, taking the kettle, cooling to room temperature, performing solid-liquid separation, washing with 30% ethanol solution, and drying at 130 ℃ for 24 hours to obtain the nano clinoptilolite molecular sieve.
Example 4
1) Preparation of solution I: 0.1880g of sodium hydroxide and 12.7ml of deionized water are weighed at room temperature and placed in a 50ml polytetrafluoroethylene lining, 1.6074g of aluminum sulfate and 6.5ml (29 wt%) of silica sol are added under magnetic stirring, the mixture is stirred at room temperature for 0.5h, then stirring and aging are continued at 60 ℃ for 96 h, and after cooling to room temperature, the mixture is stored for standby.
2) Preparation of solution III: 0.7885g of potassium hydroxide, 0.2816g of sodium hydroxide and 57ml of deionized water were weighed into a 100ml polytetrafluoroethylene liner at room temperature, 0.6019g of aluminum sulfate, 3.7ml of trimethylethoxysilane and 4.84ml of silica sol were added under magnetic stirring, and the mixture was mixed with continuous stirring to prepare solution III.
Adding the obtained solution I into the solution III prepared in the step (2) according to the amount of 30wt% of the substance in the solution III, fully stirring until the solution I is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 200 ℃ for 10 hours in a dynamic mode, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the product with 30% ethanol solution, and drying the product at 120 ℃ for 24 hours to obtain the nano clinoptilolite molecular sieve.
Example 5
1) Preparation of solution I: 0.3617g of sodium hydroxide, 0.2118g of potassium hydroxide and 15ml of deionized water are weighed at room temperature and placed in a 50ml polytetrafluoroethylene lining, 0.5602g of aluminum hydroxide and 8ml (29 wt%) of silica sol are added under magnetic stirring, the mixture is stirred at room temperature for 0.8h, then stirred and aged at 100 ℃ for 80 h, and after the mixture is cooled to room temperature, the mixture is stored for later use.
2) Preparation of solution III: weighing 0.1625g of potassium hydroxide, 0.1166g of sodium hydroxide and 24ml of deionized water at room temperature, placing the weighed materials in a 100ml polytetrafluoroethylene lining, adding 0.3870g of sodium metaaluminate, 0.4626g of potassium metaaluminate, 0.8ml of methacryloxypropyl trimethoxysilane and 8.1ml of silica sol under magnetic stirring, and mixing the mixture with continuous stirring to prepare a solution III.
Adding the obtained solution I into the solution III prepared in the step (2) according to the amount of 3 wt% of the substance in the solution III, fully stirring until the solution I is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 180 ℃ in a dynamic mode for 24 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the product with 30% ethanol solution, and drying the product at 150 ℃ for 10 hours to obtain the nano clinoptilolite molecular sieve.
Example 6
1) Preparation of solution I: 0.5272g of sodium hydroxide, 0.7212g of potassium hydroxide, 25ml of deionized water, 0.7358g of aluminum hydroxide and 8.2ml (30 wt%) of silica sol are weighed at room temperature into a 50ml polytetrafluoroethylene lining, the mixture is stirred at room temperature for 0.7h, then stirred and aged at 160 ℃ for 65 h, and after the mixture is cooled to room temperature, the mixture is stored for later use.
2) Preparation of solution III: 0.5192g of sodium hydroxide, 0.7268g of potassium hydroxide, 1.2553g of aluminum chloride, 25ml of deionized water, 1.3ml of methyltriethoxysilane and 3.602g of white carbon black are mixed at room temperature, and solution III is prepared by continuous stirring.
Adding the obtained solution I into the solution III prepared in the step (2) according to the amount of 5 wt% of the substance in the solution III, fully stirring until the solution I is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing at 175 ℃ for 36 hours, taking the kettle, cooling to room temperature, performing solid-liquid separation, washing with 75% ethanol solution, and drying at 200 ℃ for 10 hours to obtain the nano clinoptilolite molecular sieve.
Example 7
1) Preparation of solution I: 0.2254g of sodium hydroxide, 0.7362g of potassium hydroxide and 59.15ml of deionized water are weighed at room temperature and placed in a 100ml polytetrafluoroethylene lining, 1g of aluminum nitrate and 7.57ml (31 wt%) of silica sol are added under magnetic stirring, the mixture is stirred at room temperature for 1h, then stirring and aging are carried out at 180 ℃ for 6h, and after the mixture is cooled to room temperature, the mixture is stored for later use.
2) Preparation of solution III: 0.1880g of sodium hydroxide was mixed with 2.01g of aluminum nitrate and 17ml of deionized water in a 50ml polytetrafluoroethylene liner at room temperature and thoroughly stirred at room temperature until clear, and then 2.4ml of methyltriethoxysilane and 6ml of silica sol (30 wt%) were mixed and stirred continuously to obtain solution III.
Adding the obtained solution I into the solution III prepared in the step (2) according to the amount of 30wt% of the substance in the solution III, fully stirring until the solution I is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture in a static mode at 80 ℃ for 96 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the product with 80% ethanol solution, and drying the product at 250 ℃ for 6 hours to obtain the nano clinoptilolite molecular sieve.
Example 8
1) Preparation of solution I: 0.5622g of sodium hydroxide, 0.6480g of potassium hydroxide, 25ml of deionized water, 0.7278g of aluminum hydroxide and 8.4ml (30 wt%) of silica sol are weighed at room temperature and placed in a 50ml polytetrafluoroethylene lining, the mixture is stirred at room temperature for 1h, then stirred and aged at 120 ℃ for 60 h, and after the mixture is cooled to room temperature, the mixture is stored for later use.
2) Preparation of solution III: 0.5088g of sodium hydroxide, 0.7123g of potassium hydroxide, 7360g of aluminum hydroxide, 25ml of deionized water, 0.8ml of methyltriethoxysilane and 8.1ml of silica sol were mixed at room temperature and stirred continuously to prepare a solution III.
Adding the obtained solution I into the solution III prepared in the step (2) according to the amount of 5 wt% of the substance in the solution III, fully stirring until the solution I is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing at 160 ℃ for 40 hours, taking the kettle, cooling to room temperature, performing solid-liquid separation, washing with 40% ethanol solution, and drying at 120 ℃ for 24 hours to obtain the nano clinoptilolite molecular sieve.
Example 9
1) Preparation of solution II: 1g of clinoptilolite molecular sieve, 150ml of deionized water, 2.52g of sodium hydroxide and 5.88g of potassium hydroxide are mixed, stirred at room temperature for 24 hours and then cooled to room temperature to obtain solution II.
2) Preparation of solution III: 0.5088g of sodium hydroxide, 0.7062g of potassium hydroxide were mixed at room temperature with 1.2553g of aluminum chloride and 30ml of deionized water, 1ml of methacryloxypropyltrimethoxysilane and 8ml (30% by weight) of silica sol, and stirring was continued to prepare solution III.
Adding the obtained solution II into the solution III prepared in the step (2) according to 1 wt% of the amount of the substance in the solution III, fully stirring until the solution II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing at 170 ℃ for 40 hours, taking the kettle, cooling to room temperature, performing solid-liquid separation, washing with 65% ethanol solution, and drying at 130 ℃ for 20 hours to obtain the nano clinoptilolite molecular sieve.
Example 10
1) Preparation of solution II: mixing 1g of clinoptilolite molecular sieve, 120ml of deionized water, 3.36g of sodium hydroxide and 3.36g of potassium hydroxide, stirring at 80 ℃ for 3 hours, and cooling to room temperature to obtain a solution II.
2) Preparation of solution III: 0.5340g of sodium hydroxide, 0.7559g of potassium hydroxide, 0.7362g of aluminum hydroxide, 25ml of deionized water, 2.2ml of methyltriethoxysilane and 7ml (30% by weight) of silica sol were mixed at room temperature and stirred continuously to prepare a solution III.
Adding the obtained solution I into the solution III prepared in the step (2) according to 0.5 wt% of the amount of the substance in the solution III, fully stirring until the solution I is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 150 ℃ for 60 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the product with 30% ethanol solution, and drying the product at 140 ℃ for 20 hours to obtain the nano clinoptilolite molecular sieve.
Example 11
1) Preparation of solution II: 3g of clinoptilolite molecular sieve synthesized by the patent, 300ml of deionized water, 6.72g of sodium hydroxide and 1.68g of potassium hydroxide are stirred for 1 hour at 100 ℃ and then cooled to room temperature to obtain solution II.
2) Preparation of solution III: 0.4295g of sodium hydroxide, 0.6871g of potassium hydroxide were mixed at room temperature with 0.4814g of aluminum oxide and 40ml of deionized water, 0.6ml of trimethoxyethoxysilane and 8.4ml (30% by weight) of silica sol, and stirring was continued to prepare solution III.
Adding the obtained solution II into the solution III prepared in the step (2) according to 1.5 wt% of the amount of the substance in the solution III, fully stirring until the solution II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 150 ℃ for 48 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the product with 75% ethanol solution, and drying the product at 140 ℃ for 15 hours to obtain the nano clinoptilolite molecular sieve.
Example 12
1) Preparation of solution II: 2g of clinoptilolite molecular sieve synthesized by the patent is completely dissolved in 300ml of 1M sodium hydroxide solution, stirred for 3 hours at 50 ℃ and then cooled to room temperature to obtain solution II.
2) Preparation of solution III: 0.4295g of sodium hydroxide, 0.6871g of potassium hydroxide were mixed at room temperature with 0.4814g of aluminum oxide and 40ml of deionized water, 2.5ml of trimethylethoxysilane and 6.2ml (30% by weight) of silica sol, and stirring was continued to prepare solution III.
And (3) adding the obtained solution II into the solution III prepared in the step (2) according to the amount of 1 wt% of the substance in the solution III, fully stirring until the solution II is uniformly mixed, putting the mixture into a reaction kettle, crystallizing at 150 ℃ for 48 hours, taking the kettle, cooling to room temperature, carrying out solid-liquid separation, washing with 35% ethanol solution, and drying at 140 ℃ for 20 hours to obtain the nano clinoptilolite molecular sieve.
Example 13
1) Preparation of solution I: 15ml of deionized water, 0.7180g of potassium metaaluminate, 1.5g of water glass (modulus n is 3) and 8ml of silica sol are weighed at room temperature, the mixture is stirred for 0.6h at room temperature, then stirred and aged for 75 h at 147 ℃, and after cooling to room temperature, the mixture is stored for standby.
2) Preparation of solution III: 0.5192g of sodium hydroxide, 0.7268g of potassium hydroxide, 0.7362g of aluminum hydroxide, 25ml of deionized water, 1.1ml of methyltriethoxysilane and 8.0ml (30% by weight) of silica sol were mixed at room temperature and stirred continuously to prepare a solution III.
Adding the obtained solution I into the solution III prepared in the step (2) according to 10 wt% of the amount of the substance in the solution III, fully stirring until the solution I is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing at 150 ℃ for 50 hours, taking the kettle, cooling to room temperature, performing solid-liquid separation, washing with 55% ethanol solution, and drying at 140 ℃ for 20 hours to obtain the nano clinoptilolite molecular sieve.
Example 14
1) Preparation of solution I: 0.1440g of sodium hydroxide, 0.6428g of potassium hydroxide, 30ml of deionized water and 0.7417g of sodium metaaluminate are weighed at room temperature, the mixture is stirred for 0.8h at room temperature in 50ml of polytetrafluoroethylene lining and 8.8ml (30 wt%) of silica sol, then stirring and aging are carried out for 68 h at 145 ℃, and the mixture is stored for standby after being cooled to room temperature.
2) Preparation of solution III: 0.5192g of sodium hydroxide, 0.7268g of potassium hydroxide, 0.7362g of gibbsite, 25ml of deionized water, 1.4ml of dimethyldiethoxysilane and 7.8ml (30% by weight) of silica sol were mixed at room temperature with stirring to prepare solution III.
Adding the obtained solution I into the solution III prepared in the step (2) according to 10 wt% of the amount of the substance in the solution III, fully stirring until the solution I is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing at 150 ℃ for 48 hours, taking the kettle, cooling to room temperature, performing solid-liquid separation, washing with 35% ethanol solution, and drying at 140 ℃ for 20 hours to obtain the nano clinoptilolite molecular sieve.
Example 15
1) Preparation of solution I: 0.5192g of sodium hydroxide, 0.7268g of potassium hydroxide, 10ml of deionized water, 0.5663g of pseudo-boehmite and 8.8ml (30 wt%) of silica sol are weighed at room temperature, the mixture is stirred for 1 hour at room temperature in a 50ml polytetrafluoroethylene lining, then stirred and aged for 72 hours at 150 ℃, and after the mixture is cooled to room temperature, the mixture is stored for later use.
2) Preparation of solution III: 0.5192g of sodium hydroxide, 0.7268g of potassium hydroxide, 0.7362g of aluminum hydroxide, 25ml of deionized water, 0.4ml of dimethyldiethoxysilane and 3.9g of white carbon black are mixed at room temperature, and solution III is prepared by continuous stirring.
Adding the obtained solution I into the solution III prepared in the step (2) according to 3 wt% of the amount of the substance in the solution III, fully stirring until the solution I is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing at 150 ℃ for 48 hours, taking the kettle, cooling to room temperature, performing solid-liquid separation, washing with 32% ethanol solution, and drying at 135 ℃ for 22 hours to obtain the nano clinoptilolite molecular sieve.
Example 16
1) Preparation of solution II: 2g of clinoptilolite molecular sieve synthesized by the patent is completely dissolved in 250ml of 2M sodium hydroxide solution, stirred for 4 hours at 60 ℃ and then cooled to room temperature to obtain solution II.
2) Preparation of solution III: 0.4395g of sodium hydroxide, 0.7871g of potassium hydroxide and 0.7362g of aluminum hydroxide and 20ml of deionized water, 3.3ml of trimethylethoxysilane and 6.2ml (30% by weight) of silica sol are added in succession at room temperature, with continuous stirring, to prepare a solution III.
Adding the obtained solution II into the solution III prepared in the step (2) according to 0.5 wt% of the amount of the substance in the solution III, fully stirring until the solution II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 150 ℃ for 48 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the product with 35% ethanol solution, and drying the product at 140 ℃ for 20 hours to obtain the nano clinoptilolite molecular sieve.
Example 17
1) Preparation of solution II: 1g of clinoptilolite molecular sieve synthesized by the patent is completely dissolved in 100ml of 3M sodium hydroxide solution, stirred for 3 hours at 50 ℃ and then cooled to room temperature to obtain solution II.
2) Preparation of solution III: 0.4018g of sodium hydroxide, 0.7268g of potassium hydroxide and 0.7362g of aluminum hydroxide and 25ml of deionized water, 1.1ml of trimethylethoxysilane and 7.9ml (30% by weight) of silica sol are added in succession at room temperature, with continuous stirring, to prepare solution III.
Adding the obtained solution II into the solution III prepared in the step (2) according to 1 wt% of the amount of the substance in the solution III, fully stirring until the solution II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing at 170 ℃ for 40 hours, taking the kettle, cooling to room temperature, performing solid-liquid separation, washing with 40% ethanol solution, and drying at 130 ℃ for 20 hours to obtain the nano clinoptilolite molecular sieve.
Claims (6)
1. A preparation method of a nanometer clinoptilolite molecular sieve is characterized by comprising the following steps:
step 1, mixing and stirring sodium hydroxide or a mixture of sodium hydroxide and potassium hydroxide, silica sol, an aluminum source and water at room temperature for 0.5 to 1 hour, continuing stirring and aging at 60 to 180 ℃ for 6 to 96 hours, and cooling to room temperature to obtain a solution I; wherein the amount of each raw material is SiO based on the silica sol2Calculated by Al as the aluminum source2O3Calculated as Na, sodium hydroxide2Calculated as O, potassium hydroxide is calculated as K2Calculated by O, the molar composition of the solution I is 0.5-4 (Na)2O +K2O) ：Al2O3 ：8-20 SiO2 ：150-350 H2O; wherein Na/(Na + K) = 1-0.3;
step 2, adding sodium hydroxide or sodium hydroxide at room temperatureMixing the mixture with potassium hydroxide, an aluminum source and water uniformly, fully stirring at room temperature until the mixture is clear, then mixing a silane coupling agent and silica sol, and continuously stirring to prepare a solution III; wherein the amount of each raw material is SiO based on the silica sol2Calculated by Al as the aluminum source2O3Calculated as Na, sodium hydroxide2Calculated as O, potassium hydroxide expressed as K2Calculated by O, the molar composition of the solution III is Al2O3 ：SiO2 ： (Na2O +K2O) ：H2O = l: 10-30: 0.5-6: 200-2O ：Na2O = 0-2; the adding amount of the silane coupling agent accounts for 5-45% of the molar ratio of the total silicon source; total silicon source is SiO2Counting;
step 3, adding the solution I obtained in the step 1 into the solution III prepared in the step 2, fully stirring the mixture until the mixture is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at the temperature of 80-200 ℃ for 10-96 hours, taking the kettle, cooling the kettle to room temperature, and obtaining the nano clinoptilolite molecular sieve after solid-liquid separation, washing and drying; the addition amount of the solution I is 0.5-30wt% of the solution III;
the silane coupling agent is one or more of methyl triethoxysilane, dimethyl diethoxy silane, trimethyl ethoxy silane and methacryloxypropyl trimethoxysilane.
2. The method for preparing the nano clinoptilolite molecular sieve of claim 1, wherein the prepared nano clinoptilolite molecular sieve is completely dissolved in 1-3M sodium hydroxide solution or 1-3M mixed solution of sodium hydroxide and potassium hydroxide, wherein the sodium hydroxide in the mixed solution accounts for 30-80% of the total mixed solution of sodium hydroxide and potassium hydroxide by mass percent; the ratio of the nano clinoptilolite molecular sieve solid to the sodium hydroxide solution or the mixed solution of the sodium hydroxide and the potassium hydroxide is 1 g: 50-150mL, stirring at room temperature-100 ℃ for 1-24 hours, and cooling to room temperature to obtain a solution II;
adding the obtained solution II into the solution III prepared in the step 2, fully stirring until the solution II is uniformly mixed, then putting the solution II into a reaction kettle, crystallizing at the temperature of 80-200 ℃ for 10-96 hours, taking the kettle, cooling to room temperature, and carrying out solid-liquid separation, washing and drying to obtain the nano clinoptilolite molecular sieve;
the amount of solution II added is 0.5-30wt% of solution III.
3. The method for preparing a nano clinoptilolite molecular sieve as claimed in claim 1, wherein the silica sol in steps 1 and 2 has a density of 1100-1300g/L and SiO2The mass fraction of (A) is 29-31%.
4. The method for preparing a nano clinoptilolite molecular sieve as claimed in claim 1, wherein said aluminium source in steps 1 and 2 is selected from one or more of alumina, gibbsite, boehmite, pseudo-boehmite, surge boehmite, aluminium chloride, aluminium nitrate, aluminium sulphate, sodium metaaluminate and/or potassium metaaluminate.
5. The method for preparing a nano clinoptilolite molecular sieve of claim 1, wherein: the crystallization mode is static or dynamic.
6. The method for preparing a nano clinoptilolite molecular sieve as claimed in claim 1, wherein the nano clinoptilolite molecular sieve is obtained by washing with a mixed solution of water and ethanol, and then drying at 120-250 ℃ for 6-24 hours.
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