CN111392743B - Preparation method of low-silica-alumina-ratio faujasite molecular sieve - Google Patents
Preparation method of low-silica-alumina-ratio faujasite molecular sieve Download PDFInfo
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- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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Abstract
The invention discloses a preparation method of a low silicon-aluminum ratio faujasite molecular sieve, which uses a two-step hydrothermal method, takes sodium metaaluminate as an aluminum source and water glass as a silicon source; adding water glass into a mixed solution of sodium hydroxide, potassium hydroxide and sodium metaaluminate to prepare precursor gel, and synthesizing the low-silica-alumina-ratio faujasite molecular sieve by hydrothermal reaction by controlling proper aging temperature, aging time, crystallization temperature and crystallization time; the method does not need seed crystal, and has the advantages of simple preparation process, low cost and good reproducibility. The BET specific surface area of the X-type faujasite with the low silicon-aluminum ratio prepared by the invention is 690-760 m2And the structure is stable under the high-temperature and high-humidity conditions, and the adsorbent can be used for adsorbing gaseous radioactive iodine in the post-treatment process of the spent fuel in the nuclear power plant.
Description
Technical Field
The invention relates to a preparation method of an faujasite molecular sieve, in particular to a preparation method of an faujasite molecular sieve with a low silica-alumina ratio, which is prepared by a two-step hydrothermal method, can be used in the field of gaseous iodine adsorption, and provides a material for trapping gaseous radioactive iodine in the post-treatment process of spent fuel in a nuclear power plant.
Background
Faujasite, as a porous zeolite molecular sieve material with stable structure, chemical properties and high specific surface area, is widely applied in the fields of chemical catalysis, gas adsorption and the like. Among them, low-silicon aluminum can be classified according to the number ratio of silicon atoms to aluminum atoms in the zeolite frameworkSpecific X type faujasite (SiO)2/Al2O3Generally between 2.2 and 3.0) and a high silica to alumina ratio2/Al2O3Above 3.0). The molecular sieve with lower silicon-aluminum ratio has more negative skeleton charge, thus having stronger gas adsorption and ion exchange capacities. In order to fully exert the potential of the X-type molecular sieve in the aspect of adsorption, researchers have conducted extensive research on the synthesis method of the molecular sieve. Among them, the two-step hydrothermal method has received extensive attention from researchers because of its simple steps, low raw material cost and high product quality. Ogura Masaru et al indicate that the synthesis of low silica-alumina ratio faujasite by the two-step hydrothermal method has greater feasibility, and the low-temperature and long-time aging is more favorable for the formation of crystal nucleus; the Wangcheng et al uses potassium hydroxide, sodium aluminate and silicic acid as raw materials according to (3-5) Na2O:(1～1.5)K2O:(1.5～2.5)SiO2:(1.5～2.5)Al2O3:(80～100)H2Aging for 24h at 25 ℃ and crystallizing for 4h at 100 ℃ to obtain the molecular sieve with the BET specific surface area of 503 square meters per gram.
However, the existing research aiming at the artificial synthesis of faujasite mainly relates to the chemical catalysis field, the given charge ratio, temperature, time and the like are different, and the field of gaseous iodine adsorption has only proper literature reports. In the field of spent fuel reprocessing in nuclear power plants, the capture of gaseous radioactive iodine is an important research topic.
Disclosure of Invention
The invention aims to provide a preparation method of a low-silica-alumina-ratio faujasite molecular sieve, which is used for preparing the low-silica-alumina-ratio faujasite molecular sieve by a two-step hydrothermal method and is suitable for adsorption of gaseous radioactive iodine.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of the low silicon-aluminum ratio faujasite molecular sieve does not contain an organic template agent, and the specific surface area of the prepared low silicon-aluminum ratio faujasite molecular sieve is 690-760 m2The preparation method is used for trapping gaseous radioactive iodine in the post-treatment process of the spent fuel of the nuclear power plant, and comprises the following steps:
(1) dissolving sodium metaaluminate in deionized water to obtain sodium metaaluminate solution, mixing sodium hydroxide and potassium hydroxide according to n (Na)2O):n(K2Adding sodium metaaluminate solution with the molar ratio of O) to 0.77 to prepare mixed solution; then pressing n (Na) under the reaction condition that the temperature is 20-35 ℃ and the stirring speed is 300-500 rpm2O+K2O):n(SiO2):n(Al2O3):n(H2Adding water glass and deionized water into the mixed solution according to the molar ratio of O) to 7.1:2.2:1:122 to prepare a white gel precursor;
(2) and (2) transferring the white gel precursor into a reaction kettle with a polytetrafluoroethylene lining by using a two-step hydrothermal method, firstly keeping the white gel precursor at 50 ℃ for 36 hours, then heating to 100 ℃ for 3-5 hours, taking out after quenching, centrifugally washing until the pH value of clear liquid is less than or equal to 8, and drying at 100 ℃ for 24 hours to obtain the low-silica-alumina-ratio faujasite molecular sieve.
The invention effectively inhibits the generation of sodalite impurity phase by aging for a long time at the low temperature of 50 ℃, promotes the dissolution of precursor solid phase by crystallization for a short time at the high temperature of 100 ℃, and accelerates the generation of crystal nucleus; the addition of water glass at 20 ℃ to 35 ℃ helps to make full use of the induction time of the gel reaction to mix the reactants uniformly.
Compared with the prior art, the low-silicon-aluminum ratio faujasite and the preparation method thereof provided by the invention have the following advantages:
(1) the preparation method provided by the invention does not contain an organic template, so that the production cost is reduced, and the unstable performance of the solid adsorbent caused by the deterioration of the organic template under the conditions of high temperature (about 150 ℃) and irradiation in the actual service environment is avoided.
(2) The prepared low-silica-alumina-ratio faujasite molecular sieve has larger specific surface area of 690-760 m2And/g, is more favorable for adsorbing the gaseous radioactive iodine.
Drawings
Fig. 1 shows the XRD test results of example 1.
FIG. 2 shows the BET test results of example 1.
Figure 3 is the XRD test result of example 2.
FIG. 4 shows the BET test results of example 2.
Detailed Description
The invention is further illustrated in detail by the following examples and combinations:
example 1:
(1) dissolving sodium metaaluminate in deionized water to obtain sodium metaaluminate solution, mixing sodium hydroxide and potassium hydroxide according to n (Na)2O):n(K2O) 0.77, sodium metaaluminate solution is added to prepare mixed solution. Then, n (Na) was added under reaction conditions of 30 ℃ and a stirring speed of 500rpm2O+K2O):n(SiO2):n(Al2O3):n(H2Adding water glass and deionized water into the mixed solution according to the molar ratio of O) to 7.1:2.2:1:122 to prepare a white gel precursor.
(2) And (2) transferring the white gel precursor into a reaction kettle with a polytetrafluoroethylene lining by using a two-step hydrothermal method, firstly keeping the white gel precursor at 50 ℃ for 36 hours, then heating to 100 ℃ for 3 hours, quenching the reaction kettle with cold water, taking out the reaction kettle, centrifugally washing until the pH of clear liquid is less than or equal to 8, and drying at 100 ℃ for 24 hours to obtain the low-silica-alumina-ratio faujasite molecular sieve.
By comparison with the crystal structure card database # pdf 26-0895, it was confirmed that the synthesized faujasite type X molecular sieve was as shown in fig. 1. The BET test data is shown in figure 2, and the multipoint BET analysis indicated that the sample had a total specific surface area of 696.071 square meters per gram.
Example 2:
(1) dissolving sodium metaaluminate in deionized water to obtain sodium metaaluminate solution, mixing sodium hydroxide and potassium hydroxide according to n (Na)2O):n(K2O) 0.77, sodium metaaluminate solution is added to prepare mixed solution. Then, n (Na) was added under reaction conditions of 20 ℃ and a stirring speed of 300rpm2O+K2O):n(SiO2):n(Al2O3):n(H2Adding water glass and deionized water into the mixed solution according to the molar ratio of O) to 7.1:2.2:1:122 to prepare a white gel precursor.
(2) And (2) transferring the white gel precursor into a reaction kettle with a polytetrafluoroethylene lining by using a two-step hydrothermal method, firstly keeping the white gel precursor at 50 ℃ for 36 hours, then heating to 100 ℃ for 5 hours, quenching the reaction kettle with cold water, then taking out the reaction kettle, centrifugally washing until the pH of clear liquid is less than or equal to 8, and drying at 100 ℃ for 24 hours to obtain the low-silica-alumina-ratio faujasite molecular sieve.
Upon comparison with the crystal structure card database # pdf 26-0895, it was confirmed that the synthesized ion-exchanged type X faujasite molecular sieve was as shown in fig. 3. The BET test data is shown in figure 4, and the multipoint BET analysis indicated that the sample had a total specific surface area of 751.123 square meters per gram.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations. The foregoing examples or embodiments are merely illustrative of the present invention, which may be embodied in other specific forms or in other specific forms without departing from the spirit or essential characteristics thereof. The described embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. The scope of the invention should be indicated by the appended claims, and any changes that are equivalent to the intent and scope of the claims should be construed to be included therein.
Claims (2)
1. A preparation method of faujasite molecular sieve with low silica-alumina ratio is characterized in that: the preparation method does not contain an organic template agent, and the specific surface area of the prepared low-silicon-aluminum-ratio faujasite molecular sieve is 690-760 m2The preparation method is used for trapping gaseous radioactive iodine in the post-treatment process of the spent fuel of the nuclear power plant, and comprises the following steps:
(1) dissolving sodium metaaluminate in deionized water to obtain sodium metaaluminate solution, mixing sodium hydroxide and potassium hydroxide according to n (Na)2O):n(K2Adding sodium metaaluminate solution with the molar ratio of O) to 0.77 to prepare mixed solution; then pressing n (Na) under the reaction condition that the temperature is 20-35 ℃ and the stirring speed is 300-500 rpm2O+K2O):n(SiO2):n(Al2O3):n(H2Adding water glass and deionized water into the mixed solution according to the molar ratio of O) to 7.1:2.2:1:122 to prepare a white gel precursor;
(2) and (2) transferring the white gel precursor into a reaction kettle with a polytetrafluoroethylene lining by using a two-step hydrothermal method, firstly keeping the white gel precursor at 50 ℃ for 36 hours, then heating to 100 ℃ for 3-5 hours, taking out after quenching, centrifugally washing until the pH value of clear liquid is less than or equal to 8, and drying at 100 ℃ for 24 hours to obtain the low-silica-alumina-ratio faujasite molecular sieve.
2. The method for preparing the faujasite molecular sieve with low silica-alumina ratio as claimed in claim 1, wherein the method comprises the following steps: the generation of sodalite impurity phase is effectively inhibited by the long-time aging retention at the low temperature of 50 ℃, the dissolution of precursor solid phase is promoted by the short-time crystallization retention at the high temperature of 100 ℃, and the generation of crystal nucleus is accelerated; the addition of water glass at 20 ℃ to 35 ℃ helps to make full use of the induction time of the gel reaction to mix the reactants uniformly.
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| CN113845127A (en) * | 2021-09-26 | 2021-12-28 | 武汉工程大学 | Metal ion modified Y-type molecular sieve and preparation method and application thereof |
| CN114105165A (en) * | 2021-12-21 | 2022-03-01 | 中科催化新技术(大连)股份有限公司 | Method for recycling synthetic mother liquor of low-silica-alumina-ratio X-type molecular sieve |
Citations (2)
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| CN101524638A (en) * | 2009-04-23 | 2009-09-09 | 中国海洋石油总公司 | Preparation method of submicron molecular sieve carbon dioxide absorbent |
| CN102874837A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Preparation method of low silica aluminium molecular sieve LSX directly synthesized from kaolin |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101524638A (en) * | 2009-04-23 | 2009-09-09 | 中国海洋石油总公司 | Preparation method of submicron molecular sieve carbon dioxide absorbent |
| CN102874837A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Preparation method of low silica aluminium molecular sieve LSX directly synthesized from kaolin |
Non-Patent Citations (2)
| Title |
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| LSX分子筛的合成及吸附性能研究;王洪亮;《硅酸盐通报》;20130131;第32卷(第1期);第121-125页 * |
| 两步水热法合成低硅X分子筛 (LSX);王有和等;《硅酸盐通报》;20091031;第28卷(第5期);第900-904页 * |
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