CN113716576A - Method for preparing hollow spherical zeolite by using natural zeolite - Google Patents
Method for preparing hollow spherical zeolite by using natural zeolite Download PDFInfo
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- CN113716576A CN113716576A CN202110867216.8A CN202110867216A CN113716576A CN 113716576 A CN113716576 A CN 113716576A CN 202110867216 A CN202110867216 A CN 202110867216A CN 113716576 A CN113716576 A CN 113716576A
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
- C01B33/28—Base exchange silicates, e.g. zeolites
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
Abstract
The invention discloses a method for preparing hollow spherical zeolite by utilizing natural zeolite, which comprises the following steps: (1) preparing an ammonia water solution; (2) adding natural zeolite powder into the ammonia water solution prepared in the step (1), and stirring and reacting for 3-24 hours in a constant-temperature water bath at 40-100 ℃ to prepare zeolite suspension; (3) spray drying the zeolite suspension obtained in the step (2) to obtain zeolite hollow spheres; (4) and (4) transferring the zeolite hollow sphere obtained in the step (3) into a muffle furnace, and roasting at the temperature of 150-400 ℃ in the nitrogen atmosphere to obtain the hollow spherical zeolite. The method does not need to add a template agent, a surfactant and a seed crystal to prepare the zeolite hollow sphere, does not need to remove the template agent and the surfactant through aftertreatment, and has the advantages of less related chemical reagents, simple preparation process, large size of the hollow spherical zeolite, high yield and easy industrial application.
Description
Technical Field
The invention belongs to the field of zeolite molding, and relates to a method for preparing hollow spherical zeolite by using natural zeolite.
Background
The zeolite has unique aluminosilicate frame structure, uniform pore channel structure and rich pore cavities (micropores are less than 2nm, and mesopores are 2-5 nm) formed in the crystal, the specific surface area of the zeolite is fully increased, and the zeolite has strong unique performances of ion exchange, adsorption, sieving, catalysis and the like. On the other hand, the zeolite has a permanent negative electricity structure, and cations in crystal lattices are widely distributed, so that positive charge groups are easy to be adsorbed on the surface of the zeolite through ion exchange. However, the zeolite material has some disadvantages in practical application, mainly manifested by low adsorption efficiency for anionic pollutants, poor separation effect from water phase, weak anti-impurity interference ability, and poor adsorption specificity, and the above disadvantages limit the engineering application of zeolite, so it is necessary to modify it.
At present, the modification application of zeolite mainly focuses on introducing adsorption active groups to the surface and pore cavities of the zeolite so as to improve the adsorption efficiency and selective adsorption performance of the zeolite. The modification method of the zeolite material mainly comprises physical modification, acid-base modification, rare earth modification, surfactant modification and the like, and the adsorption performance of the zeolite material is changed by changing the surface charge, the cation type and the active group of the zeolite adsorbent. However, no relevant literature report on the preparation of hollow spherical zeolite by modifying natural zeolite exists at present.
Disclosure of Invention
Aiming at the problems of complex preparation process and high difficulty caused by adding an organic template agent and seed crystals in the conventional zeolite hollow microsphere preparation technology, the invention provides a method for preparing hollow spherical zeolite by modifying natural zeolite, which does not need to add the template agent, a surfactant and the seed crystals, and has simple process and mild conditions.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing hollow spherical zeolite by using natural zeolite comprises the following steps:
(1) preparing an ammonia water solution;
(2) adding natural zeolite powder into the ammonia water solution prepared in the step (1), and stirring and reacting for 3-24 hours in a constant-temperature water bath at 40-100 ℃ to prepare zeolite suspension;
(3) spray drying the zeolite suspension obtained in the step (2) to obtain zeolite hollow spheres;
(4) and (4) transferring the zeolite hollow sphere obtained in the step (3) into a muffle furnace, and roasting at the temperature of 150-400 ℃ in the nitrogen atmosphere to obtain the hollow spherical zeolite.
Preferably, in the step (1), the mass fraction of the ammonia water solution is 1.4 wt% to 66.6 wt%.
Preferably, in the step (2), the reaction temperature is 40-90 ℃.
Preferably, in the step (2), the reaction time is 6-12 h.
Preferably, in step (3), the spray drying conditions are as follows: the feeding flow is 200-1000 ml/h, and the inlet temperature is 160-200 ℃. Further preferred spray drying conditions are: the feed flow was 800ml/h and the inlet temperature was 180 ℃.
Preferably, in the step (4), the calcination time is 1 to 8 hours. Further preferred calcination conditions are: the mixture was calcined at 200 ℃ for 2 hours in a nitrogen atmosphere.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) according to the invention, under mild conditions (40-100 ℃ under normal pressure), the mesoporous hollow spherical zeolite adsorption material is prepared by modifying natural zeolite powder with ammonia water, and by means of spray drying, roasting and other process means. The method does not need to add a template agent, a surfactant and a seed crystal to prepare the zeolite hollow sphere, does not need to remove the template agent and the surfactant through aftertreatment, and has the advantages of less related chemical reagents, simple preparation process, large size of the hollow spherical zeolite, high yield and easy industrial application.
(2) The hollow spherical zeolite prepared by the method can be used as a microcapsule and a catalyst carrier, and has wide application prospects in the fields of environment, chemical industry and the like.
Drawings
FIG. 1 is a scanning electron microscope chromatogram of a natural zeolite powder;
FIG. 2 is a scanning electron microscopy atlas of example 1;
FIG. 3 is a graph showing the adsorption and desorption curves of example 1;
FIG. 4 is a scanning electron microscopy atlas of example 2;
FIG. 5 is a scanning electron microscopy atlas of example 3;
FIG. 6 is a scanning electron microscopy atlas of example 4;
FIG. 7 is a scanning electron microscopy atlas of example 5.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited thereto: example 1
A method for preparing hollow spherical zeolite by using natural zeolite comprises the following steps: measuring ammonia water and deionized water to prepare an ammonia water solution with the mass fraction of 12.55 wt%, adding 1.0g of natural zeolite powder into the solution, and stirring and reacting for 9 hours under the condition of 80 ℃ constant-temperature water bath. And drying the suspension obtained by the reaction by spray drying equipment, wherein the feeding flow is 800ml/h, the inlet temperature is 180 ℃, transferring a powder sample obtained by spray drying into a muffle furnace, and drying for 2h at 200 ℃ in a nitrogen atmosphere to obtain the hollow spherical zeolite.
Example 2
A method for preparing hollow spherical zeolite by using natural zeolite comprises the following steps: measuring ammonia water and deionized water to prepare an ammonia water solution with the mass fraction of 6.94 wt%, adding 1.0g of natural zeolite powder into the solution, and stirring and reacting for 6 hours under the condition of a constant-temperature water bath at 60 ℃. And drying the suspension obtained by the reaction by spray drying equipment, wherein the feeding flow is 800ml/h, the inlet temperature is 180 ℃, transferring a powder sample obtained by spray drying into a muffle furnace, and drying for 2h at 200 ℃ in a nitrogen atmosphere to obtain the hollow spherical zeolite with the particle size range of 3-5 mu m. The sample thus obtained was subjected to BET characterization test under a nitrogen atmosphere and had a specific surface area of 14.9015m2The pore volume is 11.1387 nm.
Example 3
A method for preparing hollow spherical zeolite by using natural zeolite comprises the following steps: measuring ammonia water and deionized water to prepare an ammonia water solution with the mass fraction of 15.38 wt%, adding 1.0g of natural zeolite powder into the solution, and stirring and reacting for 12 hours under the condition of 100 ℃ constant-temperature water bath. And drying the suspension obtained by the reaction by spray drying equipment, wherein the feeding flow is 800ml/h, the inlet temperature is 180 ℃, transferring a powder sample obtained by spray drying into a muffle furnace, and drying for 2h at 200 ℃ in a nitrogen atmosphere to obtain the hollow spherical zeolite.
Example 4
A method for preparing hollow spherical zeolite by using natural zeolite comprises the following steps: measuring ammonia water and deionized water to prepare an ammonia water solution with the mass fraction of 15.38 wt%, adding 1.0g of natural zeolite powder into the solution, and stirring and reacting for 3 hours under the condition of a constant-temperature water bath at 40 ℃. And drying the suspension obtained by the reaction by spray drying equipment, wherein the feeding flow is 800ml/h, the inlet temperature is 180 ℃, transferring a powder sample obtained by spray drying into a muffle furnace, and drying for 2h at 200 ℃ in a nitrogen atmosphere to obtain the hollow spherical zeolite.
Example 5
A method for preparing hollow spherical zeolite by using natural zeolite comprises the following steps: measuring ammonia water and deionized water to prepare an ammonia water solution with the mass fraction of 9.74 wt%, adding 1.0g of natural zeolite powder into the solution, and stirring and reacting for 9 hours under the condition of 80 ℃ constant-temperature water bath. And drying the suspension obtained by the reaction by spray drying equipment, wherein the feeding flow is 800ml/h, the inlet temperature is 180 ℃, transferring a powder sample obtained by spray drying into a muffle furnace, and drying for 2h at 200 ℃ in a nitrogen atmosphere to obtain the hollow spherical zeolite.
Claims (8)
1. A method for preparing hollow spherical zeolite by using natural zeolite comprises the following steps:
(1) preparing an ammonia water solution;
(2) adding natural zeolite powder into the ammonia water solution prepared in the step (1), and stirring and reacting for 3-24 hours in a constant-temperature water bath at 40-100 ℃ to prepare zeolite suspension;
(3) spray drying the zeolite suspension obtained in the step (2) to obtain zeolite hollow spheres;
(4) and (4) transferring the zeolite hollow sphere obtained in the step (3) into a muffle furnace, and roasting at the temperature of 150-400 ℃ in the nitrogen atmosphere to obtain the hollow spherical zeolite.
2. The method of claim 1, wherein: in the step (1), the mass fraction of the ammonia water solution is 1.4 wt% -66.6 wt%.
3. The method of claim 1, wherein: in the step (2), the reaction temperature is 40-90 ℃.
4. The method of claim 1, wherein: in the step (2), the reaction time is 6-12 h.
5. The method of claim 1, wherein: in the step (3), the spray drying conditions are as follows: the feeding flow is 200-1000 ml/h, and the inlet temperature is 160-200 ℃.
6. The method of claim 1, wherein: in the step (3), the spray drying conditions are as follows: the feed flow was 800ml/h and the inlet temperature was 180 ℃.
7. The method of claim 1, wherein: in the step (4), the roasting time is 1-8 hours.
8. The method of claim 1, wherein: in the step (4), the roasting conditions are as follows: the mixture was calcined at 200 ℃ for 2 hours in a nitrogen atmosphere.
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Citations (6)
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| CN109179446A (en) * | 2018-09-28 | 2019-01-11 | 青岛大学 | A kind of hollow nano H-type ZSM-5 molecular sieve and preparation method thereof |
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2021
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Patent Citations (6)
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| CN1834021A (en) * | 2006-04-07 | 2006-09-20 | 浙江工业大学 | Prepn. process of mesic hole hollow ball-shape titania powder |
| CN101920970A (en) * | 2010-02-10 | 2010-12-22 | 清华大学 | Preparation method of silicate nano hollow structure material |
| CN102616792A (en) * | 2012-03-26 | 2012-08-01 | 辽宁工业大学 | Method for preparing hollow spherical silicon dioxide with mesoporous shell |
| CN106185981A (en) * | 2016-07-16 | 2016-12-07 | 太原理工大学 | A kind of preparation method of hollow ZSM 5 microsphere of zeolite |
| CN108714412A (en) * | 2018-05-28 | 2018-10-30 | 苏州佑君环境科技有限公司 | A kind of preparation method of fluorine ion absorber |
| CN109179446A (en) * | 2018-09-28 | 2019-01-11 | 青岛大学 | A kind of hollow nano H-type ZSM-5 molecular sieve and preparation method thereof |
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