CN110589848B - Clinoptilolite synthesis method with columnar morphology - Google Patents
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Abstract
The invention provides a method for synthesizing clinoptilolite with columnar morphology. Firstly, mixing sodium hydroxide or a mixture of sodium hydroxide and potassium hydroxide with a silicon source, an aluminum source, water and ethanol or propanol, stirring, crystallizing and filtering to obtain a solution I; then stirring sodium hydroxide or a mixture of sodium hydroxide and potassium hydroxide with a silicon source, an aluminum source and water for crystallization, and filtering to obtain a solid II and a solution II; or completely dissolving the prepared clinoptilolite in a sodium hydroxide solution or a mixed solution of sodium hydroxide and potassium hydroxide, and filtering to obtain a filtrate, and recording the filtrate as a solution III. And finally adding the obtained solid II or solution III as an inducing species into the solution I, fully stirring, crystallizing at 80-200 ℃ for 10-96 hours, taking the kettle, cooling to room temperature, performing solid-liquid separation, washing and drying. The method can synthesize clinoptilolite with columnar morphology, and the product keeps good crystallinity and purity, and no wastewater is discharged in the whole production process.
Description
The technical field is as follows:
the invention belongs to the technical field of zeolite molecular sieve synthesis, and particularly relates to a method for synthesizing clinoptilolite molecular sieve with columnar morphology.
The background art comprises the following steps:
the clinoptilolite molecular sieve has a ten-membered ring and eight-membered ring cross structure, the framework of the clinoptilolite molecular sieve is composed of elements such as silicon, aluminum and oxygen, and the sizes of the channels are 0.75 multiplied by 0.31nm,0.46 multiplied by 0.36nm and 0.47 multiplied by 0.28nm respectively. The unique pore structure, strong ion exchange performance and high adsorption capacity show wide application prospect in the fields of gas separation, wastewater treatment, soil improvement, industrial catalysis and the like. Because the synthesis conditions are very harsh, and other heterogeneous phases are often associated in the synthesis product, the application and development are greatly limited. Therefore, in recent years, people mainly study how to improve the synthesis conditions, reduce the crystallization temperature and shorten the crystallization time, thereby improving the crystallinity of the product and reducing the impure phase.
Earlier, ames et al (American Minerals,1963,48 2 O·Al 2 O 3 ·8SiO 2 ·8.5H 2 And performing hydrothermal crystallization on the O at the temperature of between 250 and 300 ℃ for 2 to 3 days to obtain the clinoptilolite. Subsequently, goto et al (American Minerals,1977, 62. Itabashi et al (Zeolite, 1986, 6) hydrothermally synthesized by aluminosilicate gel in the presence of both Na and K ions (without seeding) at 150 ℃ for crystallization for 144h gave clinoptilolite as a single phase. Satokawa et al (EP 0681991[ P ]].1995.，EP0681991[P].1995.，DE69511319T[P].2000.，JP3677807B[P].2005.，JPH0826721A[P]1996.) and Williams et al (Chemical Communications,1997,21, 2113-2114) can synthesize Na, K-clinoptilolite with higher purity at higher temperature (100-200 ℃) for longer time (1-15 days). U.S. Pat. No. 4,503,023 discloses the preparation of high-silicon clinoptilolite using ammonium fluorosilicate as additive.
In recent years, there has been much interest in the synthesis of clinoptilolite by the seed crystal method (Nature, 1983,304 255. The present invention of Chinese patent application No. 201610588084.4 proposes that clinoptilolite can be synthesized by a structure-induced species method.
However, the synthesis of clinoptilolite with columnar morphology has been rarely reported.
Disclosure of Invention
The invention provides a solvothermal synthesis method, and clinoptilolite with a columnar morphology is obtained by using the solvothermal synthesis method, namely, the clinoptilolite with the columnar morphology is successfully synthesized by using ethanol or propanol as a main solvent in the presence of a small amount of water through a solvothermal method.
In the clinoptilolite with columnar morphology, the key point of the synthesis method of the clinoptilolite is the addition of ethanol or propanol. Because both ethanol and propanol can form hydrogen bonds with water, the spatial network structure formed by hydrolytic polycondensation of a silicon source or an aluminum source is influenced under alkaline conditions. Alternatively, ethanol or propanol over Na 2 O-K 2 O-SiO 2 -Al 2 O 3 In the synthesis system, a larger steric hindrance effect is provided by coordination with aluminum in the metaaluminate, so that the polymerization rate of the metaaluminate and silicate ions in the crystallization process is effectively controlled, and finally, the lamellar topology of the primary structure (ten-membered ring and eight-membered ring) is induced to be favorable for stacking towards the columnar morphology. Obviously, ethanol or propanol and its use with Na 2 O-K 2 O-SiO 2 -Al 2 O 3 The proportioning relationship is very critical.
In addition, the ethanol or the propanol can be completely removed by washing at room temperature, and the final product does not need to be roasted at high temperature. Meanwhile, the ethanol or propanol contained in the washing liquid has low toxicity and can be completely recycled.
A method for synthesizing clinoptilolite with columnar morphology is characterized by comprising the following steps:
(1) Uniformly mixing sodium hydroxide or a mixture of sodium hydroxide and potassium hydroxide with a silicon source, an aluminum source, water and ethanol (or propanol), and fully stirring at room temperature until the mixture is clear to prepare a solution I; wherein the amount of each raw material is SiO based on silicon source 2 In terms of aluminum source, al is calculated 2 O 3 Calculated as Na, sodium hydroxide 2 Calculated as O, potassium hydroxide expressed as K 2 Calculated as O, their molar ratio is Al 2 O 3 ：SiO 2 ：(Na 2 O+K 2 O)：H 2 O：CH 3 CH 2 OH(CH 3 CH 2 CH 2 OH) = l:5-30:0.5-6:200-900:70-277. And K is 2 O：Na 2 O＝0-2；
(2) According to the following steps: 0.5-4 (Na) 2 O+K 2 O)：Al 2 O 3 ：8-20SiO 2 ：150-350H 2 Mixing and stirring sodium hydroxide or a mixture of sodium hydroxide and potassium hydroxide, a silicon source, an aluminum source and water for 30-50 minutes according to the molar ratio of O, continuing stirring and aging at 60-180 ℃ for 6-96 hours, cooling to room temperature, and filtering to obtain a solid II and a solution II; wherein the molar ratio Na/(Na + K) is =1-0.3.
Or: completely dissolving the prepared clinoptilolite in a sodium hydroxide solution with the concentration of 1-3M or a mixed solution of 1-3M of sodium hydroxide and potassium hydroxide, wherein the molar ratio of the sodium hydroxide to the potassium hydroxide in the mixed solution is Na/(Na + K) =0.5-1; the ratio of the clinoptilolite solid to the sodium hydroxide solution or the mixed solution of the sodium hydroxide and the potassium hydroxide is 1g:50-150mL, stirring at room temperature-100 ℃ for 1-24 hours, cooling to room temperature, and filtering to obtain a filtrate, which is marked as solution III;
(3) Adding the solid II or the solution III obtained in the step (2) into the solution I prepared in the step (1), fully stirring 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 clinoptilolite with a columnar morphology after solid-liquid separation, washing and drying; wherein the solid II is added as an inducing species in an amount of 0.5 to 30wt% based on the solution I. Or the solution II or the solution III is added in an amount of 0.5 to 30wt% based on the solution I.
2. Further, in the steps (1) and (2), the silicon source is selected from one or more of white carbon black, silica sol and water glass.
3. Further, the aluminum source in 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, or potassium metaaluminate.
4. Further, the crystallization mode in the step (3) is static or dynamic.
5. Further, the step (3) is washed by a mixed solution of water and ethanol (or propanol), and then dried for 3-24 hours at 120-250 ℃ to obtain clinoptilolite with a columnar morphology.
Compared with the prior art, the method can synthesize clinoptilolite with columnar morphology, and the product keeps good crystallinity and purity. The whole production process has no wastewater discharge.
Therefore, the synthesis method has the characteristics of high yield, low energy consumption, simple process, easy operation and the like, and is particularly suitable for large-scale industrial production.
Drawings
FIG. 1 is the XRD spectrum of clinoptilolite in example 1;
FIG. 2 is an SEM photograph of clinoptilolite from example 1;
Detailed Description
Example 1
(1) Uniformly mixing 0.2077g of sodium hydroxide, 0.2907g of potassium hydroxide, 0.2945g of aluminum hydroxide and 10ml of deionized water, fully stirring at 150 ℃ until the mixture is clear, and then adding 30ml of ethanol and 3.52ml (30 wt%) of silica sol to prepare a solution I;
(2) 0.5192g of sodium hydroxide, 0.7268g of potassium hydroxide, 0.7362g of aluminum hydroxide, 25ml of deionized water and 8.8ml (30 wt%) of silica sol are mixed, stirred at room temperature for 50 minutes, stirred and aged at 150 ℃ for 6 hours, cooled to room temperature and filtered to obtain a solid II.
(3) And (3) adding the solid II obtained in the step (2) as an inducing species into the solution I prepared in the step (1) according to the weight percent of the solution I, fully stirring until the solid II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing for 96 hours at the temperature of 150 ℃, taking the kettle, cooling to room temperature, carrying out solid-liquid separation, washing with a mixed solution of water and ethanol, and then drying for 12 hours at the temperature of 130 ℃ to obtain the clinoptilolite with the columnar morphology.
The X-ray diffraction pattern (shown in figure 1) and the scanning electron micrograph (shown in figure 2) show that the obtained solid product conforms to the characteristic columnar morphology.
Example 2
(1) Mixing 0.3115g of sodium hydroxide, 0.4361g of potassium hydroxide, 0.4417g of aluminum hydroxide and 15ml of deionized water uniformly, stirring the mixture fully at 150 ℃ until the mixture is clear, and adding 25ml of ethanol and 5.28ml (30 wt%) of silica sol to prepare solution I;
(2) 0.5192g of sodium hydroxide, 0.7268g of potassium hydroxide, 0.7362g of aluminum hydroxide, 25ml of deionized water and 8.8ml (30 wt%) of silica sol are mixed, stirred at room temperature for 50 minutes, stirred and aged at 150 ℃ for 10 hours, cooled to room temperature and filtered to obtain a solid II.
(3) And (3) adding the solid II obtained in the step (2) as an inducing species into the solution I prepared in the step (1) according to 10wt% of the solution I, fully stirring until the solid II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing at 150 ℃ for 96 hours, taking the kettle, cooling to room temperature, performing solid-liquid separation, washing with a mixed solution of water and ethanol, and then drying at 130 ℃ for 12 hours to obtain the clinoptilolite with the columnar morphology.
Example 3
(1) Uniformly mixing 0.4154g of sodium hydroxide, 0.5814g of potassium hydroxide, 0.5890g of aluminum hydroxide and 20ml of deionized water, fully stirring at 150 ℃ until the mixture is clear, and then adding 20ml of ethanol and 7.04ml (30 wt%) of silica sol to prepare a solution I;
(2) 0.5192g of sodium hydroxide, 0.7268g of potassium hydroxide, 0.7362g of aluminum hydroxide, 25ml of deionized water and 8.8ml (30 wt%) of silica sol are mixed, stirred at room temperature for 50 minutes, stirred and aged at 150 ℃ for 60 hours, cooled to room temperature and filtered to obtain a solid II.
(3) And (3) adding the solid II obtained in the step (2) as an inducing species into the solution I prepared in the step (1) according to 10wt% of the solution I, fully stirring until the solid II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing at 150 ℃ for 96 hours, taking the kettle, cooling to room temperature, performing solid-liquid separation, washing with a mixed solution of water and ethanol, and then drying at 130 ℃ for 12 hours to obtain the clinoptilolite with the columnar morphology.
Example 4
(1) Uniformly mixing 0.5222g of sodium hydroxide, 0.6868g of potassium hydroxide, 3.5407g of aluminum nitrate and 30ml of deionized water, fully stirring at 150 ℃ until the mixture is clear, and adding 77ml of ethanol and 9.0ml (30 wt%) of silica sol to prepare a solution I;
(2) 3.5407g of aluminum nitrate, 0.5049g of sodium hydroxide, 0.6756g of potassium hydroxide, 20ml of deionized water and 9.4ml (30 wt%) of silica sol are mixed, stirred at room temperature for 30 minutes, then stirred and aged at 150 ℃ for 60 hours, cooled to room temperature and filtered to obtain liquid II.
(3) And (3) adding the liquid II obtained in the step (2) as an inducing species into the solution I prepared in the step (1) according to 20wt% of the solution I, fully stirring until the liquid II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 160 ℃ for 90 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the product with a mixed solution of water and ethanol, and drying the product at 130 ℃ for 12 hours to obtain the clinoptilolite with the columnar morphology.
Example 5
(1) Uniformly mixing 1.2761g of aluminum hydroxide, 3.4871g of water glass, 1.3742g of potassium hydroxide and 51.5ml of deionized water, fully stirring at 150 ℃ until the mixture is clear, and then adding 72.7ml of ethanol and 13.0ml (30 wt%) of silica sol to prepare a solution I;
(2) 7.362g of aluminum hydroxide, 36.8892g of water glass, 7.268g of potassium hydroxide, 250ml of deionized water and 66.37ml (30 wt%) of silica sol are mixed, stirred at room temperature for 40 minutes, then stirred and aged at 120 ℃ for 55 hours, and after cooling to room temperature, solid II is obtained by filtration.
(3) And (3) adding the solid II obtained in the step (2) as an inducing species into the solution I prepared in the step (1) according to 20wt% of the solution I, fully stirring until the solid II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 150 ℃ for 90 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the product with a mixed solution of water and ethanol, and drying the product at 130 ℃ for 12 hours to obtain the clinoptilolite with the columnar morphology.
Example 6
(1) Uniformly mixing 1.6147g of aluminum sulfate, 0.4933g of sodium hydroxide, 0.7786g of potassium hydroxide and 25ml of deionized water, fully stirring at 150 ℃ until the mixture is clear, and then adding 25.5ml of ethanol and 8.8ml (30 wt%) of silica sol to prepare a solution I;
(2) 1.6147g of aluminum sulfate, 0.4933g of sodium hydroxide, 0.7786g of potassium hydroxide, 28ml of deionized water and 9.0ml (30 wt%) of silica sol are mixed and stirred at room temperature for 50 minutes, then stirred and aged at 150 ℃ for 12 hours, and after cooling to room temperature, solid II is obtained by filtration.
(3) And (3) adding the solid II obtained in the step (2) as an inducing species into the solution I prepared in the step (1) according to 20wt% of the solution I, fully stirring until the solid II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 140 ℃ for 96 hours, taking the kettle, cooling the kettle to room temperature, carrying out solid-liquid separation, washing the product with a mixed solution of water and ethanol, and then drying the product at 120 ℃ for 24 hours to obtain the clinoptilolite with the columnar morphology.
Example 7
(1) Uniformly mixing 0.7362g of aluminum hydroxide, 0.6102g of sodium hydroxide, 0.6153g of potassium hydroxide and 25ml of deionized water, fully stirring at 150 ℃ until the mixture is clear, and then adding 93.4ml of ethanol and 4.9262g of white carbon black to prepare a solution I;
(2) 1g of the prepared clinoptilolite was completely dissolved in 150ml of 1M sodium hydroxide, stirred at 100 ℃ for 1 hour and filtered to give a filtrate which was designated as solution III.
(3) And (3) adding the solution III obtained in the step (2) as an inducing species into the solution I prepared in the step (1) according to 5wt% of the solution I, fully stirring until the solution III is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 130 ℃ for 95 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the mixture with a mixed solution of water and ethanol, and then drying the mixture at 120 ℃ for 24 hours to obtain the clinoptilolite with the columnar morphology.
Example 8
(1) 1.2585g of aluminum chloride, 0.5192g of sodium hydroxide, 0.7268g of potassium hydroxide and 25ml of deionized water are uniformly mixed, fully stirred at 150 ℃ until the mixture is clear, and then 42ml of ethanol and 8.8ml (30 wt%) of silica sol are added to prepare a solution I;
(2) 1g of the prepared clinoptilolite was completely dissolved in 100ml of 2M sodium hydroxide, stirred at 50 ℃ for 12 hours and filtered to give a filtrate which was designated as solution III.
(3) And (3) adding the solution III obtained in the step (2) as an inducing species into the solution I prepared in the step (1) according to 5wt% of the solution I, fully stirring until the solution III is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 130 ℃ for 95 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the mixture with a mixed solution of water and ethanol, and then drying the mixture at 120 ℃ for 24 hours to obtain the clinoptilolite with the columnar morphology.
Example 9
(1) Uniformly mixing 0.7362g of aluminum hydroxide, 0.5563g of sodium hydroxide, 0.6908g of potassium hydroxide and 25ml of deionized water, fully stirring at 150 ℃ until the mixture is clear, and then adding 31.0ml of ethanol and 4.9262g of white carbon black to prepare a solution I;
(2) 1g of the prepared clinoptilolite is completely dissolved in 100ml of a mixed solution of 3M sodium hydroxide and potassium hydroxide (wherein the sodium hydroxide accounts for 56% of the whole mixed solution by mass), and after stirring for 24 hours at room temperature, a filtrate is obtained by filtration and is marked as a solution III.
(3) And (3) adding the solution III obtained in the step (2) as an inducing species into the solution I prepared in the step (1) according to 5wt% of the solution I, fully stirring until the solution III is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 120 ℃ for 96 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the product with a mixed solution of water and ethanol, and drying the product at 120 ℃ for 24 hours to obtain the clinoptilolite with the columnar morphology.
Example 10
(1) Uniformly mixing 0.4814g of alumina, 0.6138g of sodium hydroxide, 0.6749g of potassium hydroxide and 26.3ml of deionized water, fully stirring at 150 ℃ until the mixture is clear, and then adding 31.1ml of ethanol and 5.1595g of white carbon black to prepare a solution I;
(2) Completely dissolving 1g of prepared clinoptilolite in 50ml of a 2M sodium hydroxide and potassium hydroxide mixed solution (wherein the sodium hydroxide accounts for 56% of the whole mixed solution by mass), stirring at room temperature for 24 hours, and filtering to obtain a filtrate marked as solution III
(3) And (3) adding the solution III obtained in the step (2) serving as an inducing species into the solution I prepared in the step (1) according to 25wt% of the solution I, fully stirring until the solution III is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 145 ℃ for 96 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the mixture with a mixed solution of water and ethanol, and drying the mixture at 120 ℃ for 24 hours to obtain the clinoptilolite with the columnar morphology.
Example 11
(1) Uniformly mixing 0.2077g of sodium hydroxide, 0.2907g of potassium hydroxide, 0.2945g of aluminum hydroxide and 10ml of deionized water, fully stirring at 150 ℃ until the mixture is clear, and then adding 30ml of propanol and 3.52ml (30 wt%) of silica sol to prepare a solution I;
(2) 0.7362g of aluminum hydroxide, 0.4198g of sodium hydroxide, 0.8817g of potassium hydroxide, 25ml of deionized water, and 8.9ml (30 wt%) of silica sol were mixed and stirred at room temperature for 40 minutes, followed by aging under stirring at 165 ℃ for 20 hours, cooling to room temperature and filtration to obtain solid II.
(3) And (3) adding the solid II obtained in the step (2) as an inducing species into the solution I prepared in the step (1) according to the weight percent of the solution I, fully stirring until the solid II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 130 ℃ for 96 hours, taking the kettle, cooling the kettle to room temperature, carrying out solid-liquid separation, washing the mixture with a mixed solution of water and ethanol, and then drying the mixture at 250 ℃ for 3 hours to obtain the clinoptilolite with a columnar morphology.
Example 12
(1) Mixing 0.3115g sodium hydroxide, 0.4361g potassium hydroxide, 0.4417g aluminum hydroxide and 15ml deionized water uniformly, stirring thoroughly at 150 ℃ until clear, and adding 25ml propanol and 5.28ml (30 wt%) silica sol to obtain solution I;
(2) 0.5192g of sodium hydroxide, 0.7268g of potassium hydroxide, 0.7362g of aluminum hydroxide, 25ml of deionized water and 8.8ml (30 wt%) of silica sol are mixed, stirred at room temperature for 50 minutes, then stirred and aged at 130 ℃ for 70 hours, cooled to room temperature and filtered to obtain a solid II.
(3) And (3) adding the solid II obtained in the step (2) as an inducing species into the solution I prepared in the step (1) according to the weight percent of the solution I, fully stirring until the solid II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 165 ℃ for 84 hours, taking the kettle, cooling the kettle to room temperature, carrying out solid-liquid separation, washing the product with a mixed solution of water and ethanol, and then drying the product at 250 ℃ for 1 hour to obtain the clinoptilolite with a columnar morphology.
Example 13
(1) Uniformly mixing 0.4154g of sodium hydroxide, 0.5814g of potassium hydroxide, 0.5890g of aluminum hydroxide and 20ml of deionized water, fully stirring at 150 ℃ until the mixture is clear, and adding 20ml of propylene alcohol and 7.04ml (30 wt%) of silica sol to prepare a solution I;
(2) 0.7362g of aluminum hydroxide, 0.4727g of sodium hydroxide, 0.8075g of potassium hydroxide, 21ml of deionized water and 9.6ml (30 wt%) of silica sol were mixed and stirred at room temperature for 40 minutes, then stirred and aged at 140 ℃ for 10 hours, cooled to room temperature and filtered to obtain solid II.
(3) And (3) adding the solid II obtained in the step (2) as an inducing species into the solution I prepared in the step (1) according to 10wt% of the solution I, fully stirring until the solid II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 165 ℃ for 90 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the product with a mixed solution of water and ethanol, and drying the product at 130 ℃ for 12 hours to obtain the clinoptilolite with the columnar morphology.
Example 14
(1) Uniformly mixing 0.7362g of aluminum hydroxide, 0.8811g of sodium hydroxide, 0.6167g of potassium hydroxide and 38.2ml of deionized water, fully stirring at 150 ℃ until the mixture is clear, and then adding 94.1ml of propanol and 11ml of silica sol to prepare a solution I;
(2) 1g of the prepared clinoptilolite was completely dissolved in 100ml of a 1.5M sodium hydroxide and potassium hydroxide mixed solution (wherein sodium hydroxide accounts for 60% by mass of the whole mixed solution), and after stirring at 50 ℃ for 12 hours, the filtrate was filtered to obtain a solution III.
(3) And (3) adding the solution III obtained in the step (2) as an inducing species into the solution I prepared in the step (1) according to 10wt% of the solution I, fully stirring until the solution III is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 175 ℃ for 50 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the product with a mixed solution of water and ethanol, and drying the product at 180 ℃ for 18 hours to obtain the clinoptilolite with the columnar morphology.
Example 15
(1) Adding 0.7561g of aluminum hydroxide, 0.9758g of sodium hydroxide and 0.9155g of potassium hydroxide into 41.5ml of deionized water, uniformly mixing, fully stirring at 150 ℃ until the mixture is clear, and adding 43ml of propanol and 15.8ml of silica sol to prepare a solution I;
(2) 1g of the prepared clinoptilolite was completely dissolved in 120ml of 2M sodium hydroxide solution, stirred at room temperature for 20 hours and then filtered to give a filtrate which was designated as solution III.
(3) And (3) adding the solution III obtained in the step (2) as an inducing species into the solution I prepared in the step (1) according to 10wt% of the solution I, fully stirring until the solution III is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 170 ℃ for 30 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the product with a mixed solution of water and ethanol, and drying the product at 180 ℃ for 18 hours to obtain the clinoptilolite with the columnar morphology.
Example 16
(1) 0.8341g of aluminum hydroxide, 1.4657g of sodium hydroxide, 0.8813g of potassium hydroxide and 48.12ml of deionized water are mixed uniformly and stirred well at 150 ℃ until clear, and then 28.1ml of propanol and 20.1ml (30 wt%) of silica sol are added to prepare solution I;
(2) 0.7362g of aluminum hydroxide, 0.5281g of sodium hydroxide, 0.3179g of potassium hydroxide, 25ml of deionized water and 6.7ml (30 wt%) of silica sol were mixed and stirred at room temperature for 50 minutes, then stirred and aged at 110 ℃ for 80 hours, cooled to room temperature and filtered to obtain solid II.
(3) And (3) adding the solid II obtained in the step (2) serving as an inducing species into the solution I prepared in the step (1) according to 0.5wt% of the solution I, fully stirring until the solid II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 175 ℃ for 30 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the product with a mixed solution of water and ethanol, and drying the product at 180 ℃ for 18 hours to obtain the clinoptilolite in a columnar shape.
Example 17
(1) Uniformly mixing 5.4170g of aluminum hydroxide, 0.6940g of sodium hydroxide and 125ml of deionized water, fully stirring at 150 ℃ until the mixture is clear, and then adding 552.3ml of ethanol and 28.9ml of silica sol to prepare a solution I;
(2) 1.2386g of aluminum hydroxide, 2.5408g of sodium hydroxide, 50ml of deionized water and 26.5ml (30 wt%) of silica sol are mixed and stirred at room temperature for 30 minutes, then stirred and aged at 60 ℃ for 96 hours, and after cooling to room temperature, solid II is obtained by filtration.
(3) And (3) adding the solid II obtained in the step (2) serving as an inducing species into the solution I prepared in the step (1) according to 0.5wt% of the solution I, fully stirring until the solid II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 80 ℃ for 96 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the kettle with a mixed solution of water and ethanol, and drying the kettle at 180 ℃ for 18 hours to obtain the clinoptilolite in a columnar shape.
Example 18
(1) Uniformly mixing 0.4814g of alumina, 0.7552g of sodium hydroxide, 2.1146g of potassium hydroxide and 76.5ml of deionized water, fully stirring at 150 ℃ until the mixture is clear, and adding 19ml of ethanol and 23.6ml of silica sol to prepare a solution I;
(2) Mixing 12.3505g of alumina, 1.4550g of sodium hydroxide, 4.7450g of potassium hydroxide, 161ml of silica sol and 327ml of deionized water, stirring at room temperature for 50 minutes, continuing stirring and aging at 180 ℃ for 6 hours, cooling to room temperature, and filtering to obtain a solid II.
(3) And (3) adding the solid II obtained in the step (2) as an inducing species into the solution I prepared in the step (1) according to 30wt% of the solution I, fully stirring until the solid II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 200 ℃ for 10 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the product with a mixed solution of water and ethanol, and drying the product at 180 ℃ for 18 hours to obtain the clinoptilolite with the columnar morphology.
Example 19
(1) Uniformly mixing 5.4170g of aluminum hydroxide, 0.6940g of sodium hydroxide and 125ml of deionized water, fully stirring at 150 ℃ until the mixture is clear, and then adding 720ml of propanol and 28.9ml of silica sol to prepare a solution I;
(2) 1.2386g of aluminum hydroxide, 2.5408g of sodium hydroxide, 50ml of deionized water and 26.5ml (30 wt%) of silica sol are mixed and stirred at room temperature for 30 minutes, then stirred and aged at 60 ℃ for 96 hours, and after cooling to room temperature, solid II is obtained by filtration.
(3) And (3) adding the solid II obtained in the step (2) as an inducing species into the solution I prepared in the step (1) according to 0.5wt% of the solution I, fully stirring until the solid II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 80 ℃ for 96 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the product with a mixed solution of water and ethanol, and drying the product at 180 ℃ for 18 hours to obtain the clinoptilolite with the columnar morphology.
Example 20
(1) Uniformly mixing 0.4814g of alumina, 0.7552g of sodium hydroxide, 2.1146g of potassium hydroxide and 76.5ml of deionized water, fully stirring at 150 ℃ until the mixture is clear, and then adding 24.8ml of propanol and 23.6ml of silica sol to prepare a solution I;
(2) Mixing 12.3505g of alumina, 1.4550g of sodium hydroxide, 4.7450g of potassium hydroxide, 161ml of silica sol and 327ml of deionized water, stirring at room temperature for 50 minutes, continuing stirring and aging at 180 ℃ for 6 hours, cooling to room temperature, and filtering to obtain a solid II.
(3) And (3) adding the solid II obtained in the step (2) as an inducing species into the solution I prepared in the step (1) according to 30wt% of the solution I, fully stirring until the solid II is uniformly mixed, then putting the mixture into a reaction kettle, crystallizing the mixture at 200 ℃ for 10 hours, taking the kettle, cooling the kettle to room temperature, performing solid-liquid separation, washing the product with a mixed solution of water and ethanol, and drying the product at 180 ℃ for 18 hours to obtain the clinoptilolite with the columnar morphology.
Claims (4)
1. A synthetic method of clinoptilolite with a nano columnar morphology is characterized by comprising the following steps:
(1) Uniformly mixing sodium hydroxide or a mixture of sodium hydroxide and potassium hydroxide with a silicon source, an aluminum source, water and monohydric alcohol, and fully stirring at room temperature until the mixture is clear to prepare a solution I; wherein the amount of each raw material is SiO according to the silicon source 2 In terms of aluminum source, al is calculated 2 O 3 Sodium hydroxide is calculated as Na 2 Calculated as O, potassium hydroxide expressed as K 2 Calculated as O, their molar ratio is Al 2 O 3 ：SiO 2 ：(Na 2 O+K 2 O)：H 2 O：CH 3 CH 2 OH(CH 3 CH 2 CH 2 OH) = l:5-30:0.5-6:200-900:70-277; and K is 2 O：Na 2 O＝0-2；
(2) Comprises the following steps: 0.5-4 (Na) 2 O+K 2 O)：Al 2 O 3 ：8-20SiO 2 ：150-350H 2 Mixing and stirring sodium hydroxide or a mixture of sodium hydroxide and potassium hydroxide, a silicon source, an aluminum source and water for 30-50 minutes according to the molar ratio of O, continuing stirring and aging at 60-180 ℃ for 6-96 hours, cooling to room temperature, and filtering to obtain a solid II and a solution II; wherein the molar ratio Na/(Na + K) is =1-0.3;
or: completely dissolving the prepared clinoptilolite in a sodium hydroxide solution with the concentration of 1-3M or a mixed solution of 1-3M sodium hydroxide and potassium hydroxide, wherein the molar ratio of the sodium hydroxide to the potassium hydroxide in the mixed solution is Na/(Na + K) =0.5-1; the ratio of the clinoptilolite solid to the sodium hydroxide solution or the mixed solution of the sodium hydroxide and the potassium hydroxide is 1g:50-150mL, stirring at room temperature-100 ℃ for 1-24 hours, cooling to room temperature, and filtering to obtain a filtrate, which is marked as solution III;
(3) Adding the solid II or the solution III obtained in the step (2) into the solution I prepared in the step (1), fully stirring 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 clinoptilolite with a columnar morphology after solid-liquid separation, washing and drying; wherein the amount of solid II added as an inducing species is 0.5-30wt% of solution I; or the solution II or the solution III is added in an amount of 0.5 to 30wt% based on the solution I.
2. The method of claim 1, wherein the silicon source in steps (1) and (2) is selected from one or more of silica white, silica sol, and water glass.
3. The method of claim 1 wherein the aluminum source in steps (1) and (2) is selected from one or more of alumina, gibbsite, boehmite, pseudoboehmite, surge boehmite, aluminum chloride, aluminum nitrate, aluminum sulfate, sodium metaaluminate, or potassium metaaluminate.
4. The preparation method according to claim 1, wherein the clinoptilolite having a columnar morphology is obtained by washing in step (3) with water and ethanol or a mixed solution of water and propanol, and then drying at 120-250 ℃ for 3-24 hours.
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| CN109626388A (en) * | 2019-02-02 | 2019-04-16 | 北京工业大学 | A kind of preparation method of nano lamellar clinoptilolite molecular sieve |
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| "低碳链饱和醇对L沸石合成的影响";詹予忠等;《郑州大学学报(工学版)》;20130531;第34卷(第3期);第38-41页 * |
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