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CN118751086B - Preparation method of silver-loaded SSZ-13 molecular sieve nanocrystalline mixed matrix membrane - Google Patents

Preparation method of silver-loaded SSZ-13 molecular sieve nanocrystalline mixed matrix membrane Download PDF

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CN118751086B
CN118751086B CN202411060923.6A CN202411060923A CN118751086B CN 118751086 B CN118751086 B CN 118751086B CN 202411060923 A CN202411060923 A CN 202411060923A CN 118751086 B CN118751086 B CN 118751086B
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silver
molecular sieve
ssz
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CN118751086A (en
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代岩
付佳辉
郭明钢
周永哲
郗元
皇振海
李冰璇
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Dalian University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/028—Molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B01D67/00791—Different components in separate layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/06—Flat membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/36—Polytetrafluoroethene

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Abstract

The invention provides a preparation method of a silver-loaded SSZ-13 molecular sieve nanocrystalline mixed matrix membrane. The preparation method of the silver-loaded SSZ-13 molecular sieve nanocrystalline mixed matrix membrane comprises the steps of mixing a template agent, a silicon source and water in proportion, uniformly mixing, drying to obtain a mixture, and uniformly mixing the template agent, an aluminum source, ammonium salt, silver salt, ammonia water and water in sequence and proportion to obtain a mixed solution. And uniformly stirring the mixture and the mixed solution. And (3) under the steam-assisted condition, sequentially performing ageing and crystallization treatment on the secondary mixture to obtain a crystallization product. Uniformly dispersing silver-loaded SSZ-13 molecular sieve nanocrystals serving as a filler into a polymer matrix solution, and carrying out ultrasonic stirring to obtain the silver-loaded SSZ-13 molecular sieve nanocrystal mixed matrix membrane. The SSZ-13 molecular sieve nanocrystalline loaded with silver prepared by the one-step method is of a monocrystalline structure, has high dispersibility and low agglomeration, can obviously improve the number of active centers, and avoids the problems of pore channel blockage and structural collapse which are possibly caused by the conventional synthetic treatment stage, so that the SSZ-13 molecular sieve nanocrystalline can fully exert the pore channel characteristics. The method has obvious advantages in the aspects of specific surface area, particle size, pore opening number, adsorption performance and the like. The mixed matrix membrane prepared by taking the inorganic/organic interface particles as the filler can effectively reduce the defects of the inorganic/organic interface and the particle agglomeration phenomenon, thereby remarkably improving the overall performance.

Description

Preparation method of silver-loaded SSZ-13 molecular sieve nanocrystalline mixed matrix membrane
Technical Field
The invention relates to the field of preparation of SSZ-13 molecular sieve films, in particular to a preparation method of a silver-loaded SSZ-13 molecular sieve nanocrystalline mixed matrix film.
Background
The traditional separation technology generally comprises absorption, adsorption, low-temperature distillation and the like, but the methods have the defects of complex operation, high cost, large volume, high energy consumption and the like. In contrast, membrane separation technology is considered as an effective means to solve global problems of environment and energy. The membrane separation technology has the remarkable advantages of high selectivity, easiness in modularized design, simplicity in operation, low energy consumption, low cost and the like, is widely applied to industries such as energy, electric power, petroleum, chemical industry and the like, and particularly has outstanding performance in the field of CO 2 separation. Compared with the traditional CO 2 separation technology, the membrane separation technology has unique superiority.
The Mixed Matrix Membrane (MMMs) is a generic term for membranes prepared by uniformly distributing filler particles in a polymer matrix. The advantages of the polymer in the aspects of processability, mechanical property, low cost and the like and the advantages of the filler in the aspects of gas permeability and selectivity are combined, and the restriction of Trade-off effect between the permeability and the selectivity of the polymer film is hopeful to be broken through. Meanwhile, the preparation of the mixed matrix film can utilize the mature process of the existing polymer film preparation, so that the problems of high difficulty, high cost, difficult amplification and the like in the preparation of the crystal material film are avoided. Mixed matrix membranes have attracted attention and research by many researchers in the field of membrane separation.
The addition of the inorganic filler, especially the porous filler, effectively improves the free volume fraction of the polymer, reduces entanglement among polymer molecule chain segments, and reduces mass transfer resistance of gas molecules in the membrane, thereby greatly improving the gas permeability of the mixed matrix membrane. However, because of the existence of the interfacial phase, the gas will permeate the side of the filler channel and the interfacial phase channel with the smaller diffusion resistance, and thus the state of the interfacial phase directly affects the working efficiency of the filler. When the interface is small, the gas will diffuse within the continuous filler cells, however, the gas transport path may be prolonged due to the limited cell openings of the porous material. When the interface is relatively sharp, the interface defects may be connected into a pinhole-like structure by the aggregation of the filler, so that gas has a chance to directly complete permeation through the connected interface, resulting in complete loss of selectivity of the mixed matrix membrane.
In order to improve the gas separation performance of the mixed matrix membrane, the filler should provide a low resistance pore structure within the matrix that combines high gas permeability and sieving properties and can interact strongly with the polymer matrix to reduce interfacial phase size.
However, inorganic/organic interface defects and agglomeration of inorganic particles can lead to a decrease in membrane separation performance by affecting the gas diffusion path. To meet this need, a novel preparation technique can be used to prepare inorganic materials with high dispersibility and low agglomeration. The material has larger external specific surface area, smaller particle size and more pore openings, and can better exert the pore characteristics, thereby improving the membrane separation performance.
The molecular sieve has the excellent characteristics. SSZ-13 is based on SiO 4 and A10 4 tetrahedrons, and is orderly arranged into a crystal structure with eight-membered ring pore channels and three-dimensional cross pore channels through oxygen atom connection. The SSZ-13 molecular sieve has uniform pore canal with the size ofThe specific surface area can reach 700m 2/g, and belongs to small-pore molecular sieves. And SSZ-13 has higher CO 2 adsorption capacity. These properties make SSZ-13 a promising candidate for filling polymer matrices. However, the products obtained by the current preparation technology are mostly porous materials with granularity of more than 1 μm, which limits the effective exertion of the pore characteristics of the porous materials, and the porous materials are particularly applied to the fields of catalysis and adsorption. In order to improve adsorption and catalytic performance, the molecular sieve is ideal in that (1) the molecular sieve has larger external specific surface area to increase the number of active centers, (2) the reduction of particle size is beneficial to the diffusion of reactants and products, thereby improving the catalyst efficiency and enabling ion exchange to occur more easily, and (3) the molecular sieve has more pore openings to reduce the possibility of blocking pore channels by reactants, prolong the operation period of the catalyst and enable the ion exchange to be carried out more fully in the pore channels.
Although the prior art for synthesizing SSZ-13 molecular sieve nanocrystals exists, the synthesis method has the technical defects of complex process, low synthesis efficiency, difficult separation and collection of the nano molecular sieve from mother liquor, large amount of structure directing agent and mineralizer, high synthesis cost, large amount of discharged waste liquid pollution and the like to different degrees. And SSZ-13 is not easy to synthesize a product with high crystallinity, and the introduction of metal elements into the SSZ-13 for further improving the adsorption and catalytic performances of the SSZ-13 is extremely easy to cause pore canal blockage and even structural collapse. This greatly limits the commercial production and use of SSZ-13 molecular sieve nanocrystals. Therefore, it is significant and valuable to develop a synthetic route for high crystallinity and metal loaded SSZ-13 molecular sieve nanocrystals, which is used to synthesize mixed matrix membranes to solve the inorganic/organic interface defects and the problem of agglomeration of inorganic particles.
Disclosure of Invention
The present invention aims to solve several key problems in the prior art, firstly, the defects of inorganic/organic interfaces and the phenomenon of inorganic particle agglomeration, which reduce the separation performance of the membrane by affecting the gas diffusion path. Secondly, SSZ-13 molecular sieve nanocrystals have defects in terms of crystallinity, complexity of synthesis process and synthesis efficiency, and can easily cause pore channel blockage and even structural collapse when metal elements are introduced. In order to solve the problems, a novel preparation method is provided for preparing silver-loaded SSZ-13 molecular sieve nanocrystals. By the method, SSZ-13 nanocrystalline with high crystallinity and stable structure can be prepared, silver-loaded SSZ-13 molecular sieve nanocrystalline can be synthesized in one step by introducing silver ammonia complex in the synthesis process, the number of active centers is remarkably increased, and the problems of pore channel blockage and structural collapse possibly caused by the conventional synthesis treatment stage are avoided. In addition, the prepared nanocrystals are single-crystal structures with high dispersibility and low aggregation, which enables them to more effectively exert pore characteristics. And the method has obvious advantages in the aspects of specific surface area, particle size, pore opening number, adsorption performance and the like. The mixed matrix membrane prepared by taking the inorganic/organic interface defect and the particle agglomeration can be effectively reduced by taking the inorganic/organic interface defect and the particle agglomeration as the filler, so that the overall performance is improved.
In order to achieve the aim, the technical scheme adopted by the invention is that the preparation method of the silver-loaded SSZ-13 molecular sieve nanocrystalline mixed matrix film comprises the following steps:
Step 1, fully mixing a template agent, namely a silicon source and water according to a molar ratio of 1:0.5-5:30-50, and drying at 40-60 ℃ after uniformly mixing to prepare a mixture;
step 2, preparing a mixed solution by using a template agent, an aluminum source, an ammonium salt, a silver salt, ammonia water and water according to a molar ratio of 1:0.02-0.3:0.05-3.2:0.02-4:0-5.2:30-50;
And 3, adding the mixture in the step 1 into the mixed solution in the step 2, and uniformly stirring, wherein the mixed experimental proportioning template comprises a silicon source, an aluminum source, an ammonium salt, an ammonia water and water=1:0.2-3.8:0.01-0.05:0.03-2.3:0.01-3.2:0-4.5:8-35.
Step 4, placing the mixture in the step 3 into an open glass vessel, placing the glass vessel into a reaction kettle, and sequentially aging and crystallizing the sample under the steam-assisted condition to obtain a crystallized product;
And step 5, washing and drying the crystallization product in sequence, and calcining in an air atmosphere to obtain the Ag-loaded SSZ-13 molecular sieve nanocrystalline, wherein the temperature is raised stepwise in the calcining process.
And 6, uniformly dispersing silver-loaded SSZ-13 molecular sieve nanocrystals serving as a filler into the polymer matrix solution, and stirring and dispersing by ultrasonic and magnetic force to obtain a film casting solution containing the filler.
And 7, carrying out ultrasonic defoaming treatment on the casting solution obtained in the step 6 for 30-240 min, standing for 5-15 min, pouring the casting solution onto a clean polytetrafluoroethylene flat plate, drying the casting solution in a constant-temperature oven at 40-80 ℃ for 12-24 h, and then placing the casting solution in a vacuum oven to be vacuumized for continuously removing the solvent for 12-24 h to obtain the Ag-loaded SSZ-13 molecular sieve nanocrystalline mixed matrix film.
Further, the silicon source is one or more of white carbon black, porous silicon and silica sol;
further, the template agent in the step 1 is N, N, N-trimethyl-adamantane ammonium hydroxide.
Further, the aluminum source in the step 2 is one or more of aluminum isopropoxide, aluminum oxide, aluminum hydroxide and aluminum trichloride;
further, the ammonium salt in the step 2 is one or more of ammonium chloride, ammonium nitrate and ammonium bicarbonate.
Further, the silver salt in the step 2 is one or more of silver nitrate, silver chloride, silver iodide, silver fluoride and silver bromide.
Further, the drying process described in step 1 should ensure that the final mass of the mixture does not exceed the initial total mass of the templating agent and the silicon source. In particular, the weight of the mixture after drying should be at least 90% of the initial total mass of template and silicon source, but should not exceed this total mass. Ensuring that the weight loss of the template agent in the mixture during drying is controlled within a reasonable range.
Further, the raw materials in the step 2 are added in sequence, namely, firstly, an aluminum source is added into the template agent, and after the aluminum source is completely dissolved into a clear solution, ammonium salt is added in sequence. After the ammonium salt is completely dissolved, a silver-ammonia complex generated by the reaction of silver salt and ammonia water is added, which is favorable for uniformly synthesizing silver ions into the skeleton structure of the nanocrystalline, so that aggregation of metal particles is avoided, and the blocking of pore channels is prevented.
Further, the step 4 of sequentially carrying out ageing and crystallization treatment on the mixture under the condition of steam assistance comprises the steps of transferring the mixture into an open glass vessel, transferring the glass vessel into a kettle liner of a hydrothermal reaction kettle, adding deionized water into the kettle liner, wherein the volume of the deionized water accounts for 1/6-1/5 of that of the kettle liner and water outside the glass vessel is prevented from entering the glass vessel, and carrying out ageing treatment on the mixture under the condition of 60-100 ℃ and steam assistance, wherein the ageing time is 0-12 days, the crystallization treatment temperature is 20-120 ℃, and the crystallization time is 0-8 days.
Further, the calcination in the step 5 is calcination under an air atmosphere, the calcination temperature is raised stepwise, the calcination is performed for 3-6 hours at 120-150 ℃, the calcination is performed for 3-6 hours at 220-260 ℃, the calcination temperature is 500-580 ℃, and the calcination time is 3-12 hours.
Further, the preparation method of the polymer matrix solution in the step 6 comprises the steps of uniformly mixing absolute ethyl alcohol and deionized water, heating the mixture to 60-120 ℃ under the stirring condition in an oil bath, and then adding the polymer matrix into the mixture, and stirring the mixture for 4-5 hours at 60-120 ℃ to completely dissolve the polymer matrix to obtain the polymer matrix solution;
the volume ratio of the ethanol to the water is 5-12:1-6;
The solid-liquid mass ratio of the polymer matrix solution is 1-10:90-150.
Further, the polymer matrix in the step 7 is one or more of polyamide copolyether (PEBA) and Polyimide (PI).
Further, the nano-crystalline fraction of the SSZ-13 molecular sieve loaded with silver in the film casting solution in the step 6 is 1-40wt%.
The invention discloses a preparation method of a silver-loaded SSZ-13 molecular sieve nanocrystalline mixed matrix membrane, by which SSZ-13 nanocrystalline with high crystallinity and stable structure can be prepared, and silver-loaded SSZ-13 molecular sieve nanocrystalline can be synthesized in one step by introducing silver ammonia complex in the synthesis process, so that the number of active centers is obviously increased, and the problems of pore channel blockage and structural collapse possibly caused by the conventional synthesis treatment stage are avoided. In addition, the prepared nanocrystals are single-crystal structures with high dispersibility and low aggregation, which enables them to more effectively exert pore characteristics. And the method has obvious advantages in the aspects of specific surface area, particle size, pore opening number, adsorption performance and the like. The mixed matrix membrane prepared by taking the inorganic/organic interface defect and the particle agglomeration can be effectively reduced by taking the inorganic/organic interface defect and the particle agglomeration as the filler, so that the overall performance is improved.
The silver-loaded SSZ-13 molecular sieve nanocrystalline mixed matrix membrane prepared by the invention can be applied to multiple fields of petroleum, chemical industry, environmental protection and the like, and has wide market prospect. For example, the silver-loaded SSZ-13 molecular sieve nanocrystalline mixed matrix membrane prepared by the method is applied to separation and purification of CO 2, wherein CO 2 permeation evaluation is carried out on the silver-loaded SSZ-13 molecular sieve nanocrystalline mixed matrix membrane, so that the selectivity of CO 2/N2 can be greatly improved.
Drawings
FIG. 1 is an XRD pattern of silver-loaded SSZ-13 molecular sieve nanocrystals prepared in example 1 of the present invention.
FIG. 2 is an SEM image of silver-loaded SSZ-13 molecular sieve nanocrystals prepared in example 1 of the present invention.
FIG. 3 is an SEM image of SSZ-13 prepared according to comparative example 1 of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. It will be apparent that the embodiments described are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation method of the silver-loaded SSZ-13 molecular sieve nanocrystalline mixed matrix membrane provided by the embodiment of the invention comprises the following steps:
step 1) fully mixing a template agent and silicon source water according to a molar ratio of 1:0.5-5:30-50, and drying at 40-60 ℃ after uniformly mixing to obtain a mixture, wherein the final mass of the mixture is ensured not to exceed the initial total mass of the template agent and the silicon source and is more than 90% of the initial total mass of the template agent and the silicon source in the drying process;
step 2) preparing a mixed solution by adding an aluminum source, an ammonium salt, a silver salt, ammonia water and water into the template according to the molar ratio of 1:0.02-0.3:0.05-3.2:0.02-4:0-5.2:30-50, wherein the adding sequence of the raw materials is that the aluminum source is firstly added into the template, and the ammonium salt is sequentially added after the aluminum source is completely dissolved into a clear solution. After the ammonium salt is completely dissolved, adding a silver ammonia complex generated by the reaction of silver salt and ammonia water;
step 3) adding the mixture in the step 1 into the mixed solution in the step 2 and uniformly stirring, wherein the mixed experimental proportioning template comprises a silicon source, an aluminum source, an ammonium salt, an ammonia water and water=1:0.2-3.8:0.01-0.05:0.03-2.3:0.01-3.2:0-4.5:8-35;
Step 4) transferring the mixture in the step 3 into an open glass vessel, transferring the glass vessel into a hydrothermal reaction kettle liner, adding deionized water into the kettle liner, wherein the volume of the deionized water is 1/6-1/5 of that of the kettle liner, and water outside the glass vessel is prevented from entering the glass vessel;
Step 5) washing and drying the crystallization product in sequence, and calcining in an air atmosphere to obtain silver-loaded SSZ-13 molecular sieve nanocrystals, wherein the temperature is raised stepwise in the calcining process, the calcination is carried out for 3-6 hours at 120-150 ℃, the calcination is carried out for 3-6 hours at 220-260 ℃ at the first, the calcination temperature is 500-580 ℃ at the last, and the calcination time is 3-12 hours;
Step 6) uniformly mixing absolute ethyl alcohol and deionized water, heating the mixture to 60-120 ℃ under stirring conditions in an oil bath, then adding a polymer matrix into the mixture, keeping the temperature of 60-120 ℃ and stirring the mixture for 4-5 hours to completely dissolve the mixture to obtain a polymer matrix solution, wherein the volume ratio of the ethyl alcohol to the water is 5-12:1-6, the solid-liquid mass ratio of the polymer matrix solution is 1-10:90-150, uniformly dispersing silver-loaded SSZ-13 molecular sieve nanocrystals serving as a filler into the polymer matrix solution, and performing ultrasonic and magnetic stirring dispersion to obtain a casting film solution containing the filler, wherein the crystal fraction of the silver-loaded SSZ-13 molecular sieve nanocrystals in the casting film solution is 1-40 wt%;
And 7) carrying out ultrasonic defoaming treatment on the casting solution obtained in the step 6 for 30-240 min, standing for 5-15 min, pouring the casting solution on a clean polytetrafluoroethylene flat plate, drying the casting solution in a constant-temperature oven at 40-80 ℃ for 12-24 h, and then placing the casting solution in a vacuum oven to be vacuumized for continuously removing the solvent for 12-24 h to obtain the silver-loaded SSZ-13 molecular sieve nanocrystalline mixed matrix film.
Further, the silicon source is one or more of white carbon black, porous silicon and silica sol;
further, the template agent in the step 1 is N, N, N-trimethyl-adamantane ammonium hydroxide.
Further, the aluminum source in the step 2 is one or more of aluminum isopropoxide, aluminum oxide, aluminum hydroxide and aluminum trichloride;
further, the ammonium salt in the step 2 is one or more of ammonium chloride, ammonium nitrate and ammonium bicarbonate.
Further, the silver salt in the step 2 is one or more of silver nitrate, silver chloride, silver iodide, silver fluoride and silver bromide.
Further, the polymer matrix in the step 7 is one or more of polyamide copolyether (PEBA) and Polyimide (PI).
The preparation method of the silver-loaded SSZ-13 molecular sieve nanocrystalline has the advantages of simple synthesis steps and high synthesis efficiency, can prepare the SSZ-13 nanocrystalline with high crystallinity and stable structure, and can synthesize the silver-loaded SSZ-13 molecular sieve nanocrystalline in one step by introducing a silver ammonia complex in the synthesis process, thereby remarkably improving the number of active centers and avoiding the problems of pore channel blockage and structural collapse possibly caused by the conventional synthesis treatment stage. In addition, the prepared nanocrystals are single-crystal structures with high dispersibility and low aggregation, which enables them to more effectively exert pore characteristics. And the method has obvious advantages in the aspects of specific surface area, particle size, pore opening number, adsorption performance and the like. The mixed matrix membrane prepared by taking the inorganic/organic interface defect and the particle agglomeration can be effectively reduced by taking the inorganic/organic interface defect and the particle agglomeration as the filler, so that the overall performance is improved.
Example 1
Step 1, fully mixing 4g of N, N-trimethyl-adamantane ammonium hydroxide with the mass fraction of 25% and 1.0g of white carbon black, uniformly mixing to be liquid gel, and drying in a 40 ℃ forced air drying box for 10 hours to prepare a mixture;
Step 2, dissolving 0.12g of aluminum isopropoxide in 5.4g of N, N-trimethyl-adamantane ammonium hydroxide with mass fraction of 25%, adding 0.05g of ammonium nitrate, adding 0.1g of silver nitrate after dissolving, and uniformly stirring to prepare a mixed solution;
And 3, adding the mixture in the step 1 into the mixed solution in the step 2, and uniformly stirring.
Step 4, placing the mixture in the step 3 into an open glass vessel, placing the glass vessel into a 100mL hydrothermal reaction kettle, adding 5mL deionized water outside the glass vessel, aging the sample for 3 days at 90 ℃ and crystallizing for 3 days at 160 ℃ under the steam-assisted condition to obtain a crystallized product;
And 5, washing and drying the crystallization product in sequence, and calcining in an air atmosphere to obtain silver-loaded SSZ-13 molecular sieve nanocrystals, wherein the temperature is raised stepwise in the calcining process, the temperature is calcined at 120 ℃ for 3 hours, the temperature is calcined at 240 ℃ for 3 hours, and the temperature is calcined at 550 ℃ for 12 hours to obtain silver-loaded SSZ-13 molecular sieve nanocrystals.
And 6, weighing 18mL of ethanol and 9mL of distilled water, mixing, heating to 80 ℃ under stirring, and adding 1.05g of Pebax-1657 into the mixture, and stirring at 80 ℃ for 5 hours to completely dissolve the mixture to obtain the polymer matrix solution. Uniformly dispersing 0.05g of silver-loaded SSZ-13 molecular sieve nanocrystalline serving as a filler into 6.53g of polymer matrix solution at 1000rpm/min, stirring at a rotating speed for 30min for dispersion, and stirring and dispersing by ultrasonic for 30min to obtain a casting film liquid containing the filler.
And 7, carrying out ultrasonic defoaming treatment on the casting solution obtained in the step 6 for 30min, standing for 15min, pouring the casting solution onto a clean polytetrafluoroethylene flat plate, putting the casting solution into a constant-temperature oven at 80 ℃ for drying for 24h, and then putting the casting solution into a vacuum oven for vacuumizing and continuously removing the solvent for 24h to obtain the silver-loaded SSZ-13 molecular sieve nanocrystalline mixed matrix film.
As shown in figure 1, the silver-loaded SSZ-13 molecular sieve nanocrystalline has good crystallization, no amorphous phase, one-to-one correspondence between peak positions and a standard CHA topological structure spectrogram, no impurity peaks except SSZ-13 exist, no impurity phases of other zeolite and no peak positions of silver appear, and the silver ions are proved to directly participate in the synthesis of an internal framework of the molecular sieve, so that the silver-ammonia complex synthesis system has good dispersibility and no agglomeration phenomenon. As shown in FIG. 2, the silver-loaded SSZ-13 molecular sieve has uniform nano grain size, about 200nm and good dispersibility, and proves that the nano crystal is successfully synthesized.
The separation performance of the mixed matrix membrane was tested to be PCO 2＝128.98Barrer,CO2/N2 selectivity 78.73.
Example 2
Step 1, fully mixing 5g of N, N-trimethyl-adamantane ammonium hydroxide with the mass fraction of 25% and 0.8g of white carbon black, uniformly mixing to be liquid gel, and drying in a 50 ℃ blast drying box for 8 hours to prepare a mixture;
Step 2, dissolving 0.08g of aluminum isopropoxide in 6g of N, N-trimethyl-adamantane ammonium hydroxide with mass fraction of 25%, adding 0.05g of ammonium chloride, adding 0.1g of silver chloride and 3mL of silver ammonia complex prepared by ammonia water after dissolving, and uniformly mixing;
And 3, adding the mixture in the step 1 into the mixed solution in the step 2, and uniformly stirring.
Step 4, placing the mixture in the step 3 into an open glass vessel, placing the glass vessel into a 100mL hydrothermal reaction kettle, adding 5mL deionized water outside the glass vessel, aging the sample for 3 days at 90 ℃ and crystallizing for 3 days at 160 ℃ under the steam-assisted condition to obtain a crystallized product;
And 5, washing and drying the crystallization product in sequence, and calcining in an air atmosphere to obtain silver-loaded SSZ-13 molecular sieve nanocrystals, wherein the temperature is raised stepwise in the calcining process, the temperature is calcined at 120 ℃ for 3 hours, the temperature is calcined at 240 ℃ for 3 hours, and the temperature is calcined at 550 ℃ for 12 hours to obtain silver-loaded SSZ-13 molecular sieve nanocrystals.
And 6, weighing 18mL of ethanol and 9mL of distilled water, mixing, heating to 80 ℃ under stirring, and adding 2.1g of Pebax-1657 into the mixture, and stirring at 80 ℃ for 5 hours to completely dissolve the mixture to obtain the polymer matrix solution. Uniformly dispersing 0.1g of molecular sieve nanocrystalline serving as a filler into 6.83g of polymer matrix solution at 1000rpm/min, stirring at a rotating speed for 30min for dispersion, and stirring and dispersing by ultrasonic for 30min to obtain a casting film liquid containing the filler.
And 7, carrying out ultrasonic defoaming treatment on the casting solution obtained in the step 6 for 30min, standing for 15min, pouring the casting solution onto a clean polytetrafluoroethylene flat plate, putting the casting solution into a constant-temperature oven at 80 ℃ for drying for 24h, and then putting the casting solution into a vacuum oven for vacuumizing and continuously removing the solvent for 24h to obtain the silver-loaded SSZ-13 molecular sieve nanocrystalline mixed matrix film.
The separation performance of the mixed matrix membrane was tested as PCO 2＝180.98Barrer,CO2/N2 selectivity 89.65.
Example 3
Step 1, fully mixing 10g of N, N-trimethyl-adamantane ammonium hydroxide with the mass fraction of 25% and 1.2g of 4 white carbon black, and placing the mixture in a vacuum oven at a temperature of 40 ℃ for 8 hours to prepare a mixture;
Step 2, dissolving 0.05g of aluminum oxide in 7.2g of N, N-trimethyl-adamantane ammonium hydroxide with mass fraction of 25%, adding 0.10g of ammonium nitrate, adding 0.24g of silver chloride and 3mL of silver ammonia complex prepared by ammonia water after dissolving, and uniformly mixing;
And 3, adding the mixture in the step 1 into the mixed solution in the step 2, and uniformly stirring.
Step 4, placing the mixture in the step 3 into an open glass vessel, placing the glass vessel into a 100mL hydrothermal reaction kettle, adding 5mL deionized water outside the glass vessel, aging the sample for 3 days at 90 ℃ and crystallizing for 2 days at 160 ℃ under the steam-assisted condition to obtain a crystallized product;
And 5, washing and drying the crystallization product in sequence, and calcining in an air atmosphere to obtain silver-loaded SSZ-13 molecular sieve nanocrystals, wherein the temperature is raised stepwise in the calcining process, the temperature is calcined at 120 ℃ for 3 hours, the temperature is calcined at 240 ℃ for 3 hours, and the temperature is calcined at 550 ℃ for 12 hours to obtain silver-loaded SSZ-13 molecular sieve nanocrystals.
And 6, weighing 18mL of ethanol and 9mL of distilled water, mixing, heating to 80 ℃ under stirring, and adding 2.08g of Pebax-1657 into the mixture, and stirring at 80 ℃ for 5 hours to completely dissolve the mixture to obtain the polymer matrix solution. Uniformly dispersing 0.05g of molecular sieve nanocrystalline serving as a filler into 6.83g of polymer matrix solution at 1000rpm/min, stirring at a rotating speed for 30min for dispersion, and stirring and dispersing by ultrasonic for 30min to obtain a casting film liquid containing the filler.
And 7, carrying out ultrasonic defoaming treatment on the casting solution obtained in the step 6 for 30min, standing for 15min, pouring the casting solution onto a clean polytetrafluoroethylene flat plate, putting the casting solution into a constant-temperature oven at 80 ℃ for drying for 24h, and then putting the casting solution into a vacuum oven for vacuumizing and continuously removing the solvent for 24h to obtain the silver-loaded SSZ-13 molecular sieve nanocrystalline mixed matrix film.
The separation performance of the mixed matrix membrane was tested as PCO 2＝160.98Barrer,CO2/N2 selectivity 82.95.
Example 4
Step 1, fully mixing 12g of N, N-trimethyl-adamantane ammonium hydroxide with the mass fraction of 25% and 3.75g of 40% silica sol, uniformly mixing, and placing the mixture in a vacuum oven at 40 ℃ for 8 hours to prepare a mixture;
Step 2, dissolving 0.05g of aluminum oxide in 6g of N, N-trimethyl-adamantane ammonium hydroxide with mass fraction of 25%, adding 0.10g of ammonium nitrate, adding 0.4g of silver nitrate after dissolving, and uniformly mixing;
And 3, adding the mixture in the step 1 into the mixed solution in the step 2, and uniformly stirring.
Step 4, placing the mixture in the step 3 into an open glass vessel, placing the glass vessel into a 100mL hydrothermal reaction kettle, adding 5mL deionized water outside the glass vessel, aging the sample for 4 days at 70 ℃ and crystallizing for 5 days at 160 ℃ under the steam-assisted condition to obtain a crystallized product;
And 5, washing and drying the crystallization product in sequence, and calcining in an air atmosphere to obtain silver-loaded SSZ-13 molecular sieve nanocrystals, wherein the temperature is raised stepwise in the calcining process, the temperature is calcined at 120 ℃ for 3 hours, the temperature is calcined at 240 ℃ for 3 hours, and the temperature is calcined at 550 ℃ for 12 hours to obtain silver-loaded SSZ-13 molecular sieve nanocrystals.
And 6, weighing 18mL of ethanol and 9mL of distilled water, mixing, heating to 80 ℃ under stirring, and adding 0.2g of Pebax-1657 into the mixture, and stirring at 80 ℃ for 5 hours to completely dissolve the mixture to obtain the polymer matrix solution. Uniformly dispersing 0.15g of molecular sieve nanocrystalline serving as a filler into 6.68g of polymer matrix solution at 1000rpm/min, stirring at a rotating speed for 30min for dispersion, and stirring and dispersing by ultrasonic for 30min to obtain a casting film liquid containing the filler.
And 7, carrying out ultrasonic defoaming treatment on the casting solution obtained in the step 6 for 30min, standing for 15min, pouring the casting solution onto a clean polytetrafluoroethylene flat plate, putting the casting solution into a constant-temperature oven at 80 ℃ for drying for 24h, and then putting the casting solution into a vacuum oven for vacuumizing and continuously removing the solvent for 24h to obtain the silver-loaded SSZ-13 molecular sieve nanocrystalline mixed matrix film.
The separation performance of the mixed matrix membrane was tested to be PCO 2＝145.98Barrer,CO2/N2 selectivity 80.95.
Comparative example 1
Step 1, stirring 5.4816 g of N, N-trimethyl-adamantane ammonium hydroxide, 0.01g of sodium metaaluminate and 0.06g of ammonium chloride uniformly, adding 0.8g of white carbon black, and stirring uniformly to obtain a mixture.
Transferring the mixture into a hydrothermal reaction kettle liner, adding 5ml of deionized water into the kettle liner, ageing the mixture at 25 ℃ for 3 days, heating the hydrothermal reaction kettle to 160 ℃, and crystallizing the mixture for 24 hours to obtain a crystallized product.
And step 3, centrifugally washing the crystallized product for 3 times, drying at 50 ℃ for 8 hours, and calcining at 550 ℃ for 4 hours in a muffle furnace to obtain the SSZ-13 molecular sieve.
Step 4. 18mL of ethanol and 9mL of distilled water were weighed and mixed, heated to 80℃under stirring, and then 2.12g of Pebax-1657 (polyamide copolymer) was added thereto and stirred for 8 hours at 80℃to be completely dissolved to prepare a polymer matrix solution. Dispersing 0.05g of SSZ-13 molecular sieve as a filler into 6.5g of polymer matrix solution at 1000rpm/min, stirring at a rotating speed for 60min for dispersion, and stirring and dispersing by ultrasonic for 30min to obtain a casting film liquid containing the filler.
And 5, carrying out ultrasonic defoaming treatment on the casting solution obtained in the step 4 for 60min, standing for 10min, pouring the casting solution onto a clean polytetrafluoroethylene flat plate, drying the casting solution in a constant-temperature oven at 80 ℃ for 24h, and then placing the casting solution in a vacuum oven to carry out vacuumizing and continuously removing the solvent for 24h to obtain the SSZ-13 molecular sieve mixed matrix membrane.
The separation performance of the mixed matrix membrane was tested as PCO 2＝90.98Barrer,CO2/N2 selectivity 55.73.
FIG. 3 shows SSZ-13 molecular sieves (obtained after the treatment of step 3) prepared by conventional methods, which are micron-sized crystals, large in size and irregular. The mixed matrix film prepared by the crystal is easy to agglomerate, and the prepared film material is uneven and has more defects.

Claims (10)

1.一种负载银的SSZ-13分子筛纳米晶混合基质膜的制备方法，其特征在于，包括以下步骤：1. A method for preparing a silver-loaded SSZ-13 molecular sieve nanocrystal mixed matrix membrane, comprising the following steps: 步骤1、将模板剂：硅源：水按照摩尔比为1：0.5~5：30~50充分混合，混合均匀后，在40-60℃干燥，制得混合物；Step 1, fully mix the template: silicon source: water in a molar ratio of 1:0.5-5:30-50, mix evenly, and then dry at 40-60° C. to obtain a mixture; 步骤2、将模板剂：铝源：铵盐：银盐：氨水：水按照摩尔比为1：0.02~0.3：0.05~3.2：0.02~4：0~5.2：30~50，制得混合溶液；Step 2, preparing a mixed solution by mixing template agent: aluminum source: ammonium salt: silver salt: ammonia water: water in a molar ratio of 1: 0.02-0.3: 0.05-3.2: 0.02-4: 0-5.2: 30-50; 步骤3、将步骤1中的混合物加入步骤2中的混合溶液中并搅拌均匀，混合后的实验配比模板剂：硅源：铝源：铵盐：银盐：氨水：水=1：0.2~3.8：0.01~0.05：0.03~2.3：0.01~3.2：0~4.5：8~35；Step 3, adding the mixture in step 1 to the mixed solution in step 2 and stirring evenly, the experimental ratio after mixing is template agent: silicon source: aluminum source: ammonium salt: silver salt: ammonia water: water = 1: 0.2~3.8: 0.01~0.05: 0.03~2.3: 0.01~3.2: 0~4.5: 8~35; 步骤4、将步骤3中的混合物置入开口玻璃器皿中，将玻璃器皿放入反应釜中，在蒸汽辅助的条件下，对样品依次进行陈化和晶化处理，获得结晶产物；Step 4, placing the mixture in step 3 into an open glass container, placing the glass container into a reactor, and sequentially performing aging and crystallization treatments on the sample under steam-assisted conditions to obtain a crystalline product; 步骤5、对所述结晶产物依次经过洗涤、干燥，并在空气氛围煅烧后，获得负载银的SSZ-13分子筛纳米晶，其中煅烧过程阶梯升温；Step 5, washing and drying the crystal product in sequence, and calcining in an air atmosphere to obtain silver-loaded SSZ-13 molecular sieve nanocrystals, wherein the calcination process is stepwise heated; 步骤6、将负载银的SSZ-13分子筛纳米晶作为填料均匀地分散到聚合物基质溶液中，超声及磁力搅拌分散，得到含有填料的铸膜液；Step 6, uniformly dispersing the silver-loaded SSZ-13 molecular sieve nanocrystals as fillers into the polymer matrix solution, and dispersing by ultrasonic and magnetic stirring to obtain a casting solution containing fillers; 步骤7、将步骤6得到的铸膜液超声脱泡处理30～240min，并静置5～15min，之后将其倒入洁净的聚四氟乙烯平板上，将其放入40～80℃恒温烘箱中干燥12～24小时，随后将其放入真空烘箱中抽真空继续除溶剂12～24小时，得到负载银的SSZ-13分子筛纳米晶混合基质膜。Step 7, subject the casting solution obtained in step 6 to ultrasonic degassing for 30 to 240 minutes, and let it stand for 5 to 15 minutes, then pour it onto a clean polytetrafluoroethylene plate, place it in a constant temperature oven at 40 to 80°C and dry it for 12 to 24 hours, then place it in a vacuum oven and continue to remove the solvent for 12 to 24 hours to obtain a silver-loaded SSZ-13 molecular sieve nanocrystal mixed matrix membrane. 2.根据权利要求1所述一种负载银的SSZ-13分子筛纳米晶混合基质膜的制备方法，其特征在于，步骤1所述硅源为白炭黑、多孔硅和硅溶胶中的一种或几种；2. The method for preparing a silver-loaded SSZ-13 molecular sieve nanocrystal mixed matrix membrane according to claim 1, characterized in that the silicon source in step 1 is one or more of white carbon black, porous silicon and silica sol; 和/或，步骤1所述模板剂为N,N,N-三甲基-金刚烷氢氧化铵；And/or, the template agent in step 1 is N,N,N-trimethyl-adamantane ammonium hydroxide; 和/或，步骤2所述铝源为异丙醇铝、三氧化二铝、氢氧化铝和三氯化铝中的一种或几种；And/or, the aluminum source in step 2 is one or more of aluminum isopropoxide, aluminum oxide, aluminum hydroxide and aluminum chloride; 和/或，步骤2所述铵盐为氯化铵、硝酸铵、碳酸氢铵中的一种或几种；And/or, the ammonium salt in step 2 is one or more of ammonium chloride, ammonium nitrate, and ammonium bicarbonate; 和/或，步骤2所述银盐为硝酸银、氯化银、碘化银、氟化银、溴化银中的一种或几种。And/or, the silver salt in step 2 is one or more of silver nitrate, silver chloride, silver iodide, silver fluoride, and silver bromide. 3.根据权利要求1所述一种负载银的SSZ-13分子筛纳米晶混合基质膜的制备方法，其特征在于，步骤1干燥过程应确保混合物的最终质量不超过模板剂与硅源的初始总质量。3. The method for preparing a silver-loaded SSZ-13 molecular sieve nanocrystal mixed matrix membrane according to claim 1, characterized in that the drying process in step 1 should ensure that the final mass of the mixture does not exceed the initial total mass of the template and the silicon source. 4.根据权利要求1所述一种负载银的SSZ-13分子筛纳米晶混合基质膜的制备方法，其特征在于，步骤1混合物干燥后的质量应至少达到模板剂与硅源初始总质量的90%，但不得超过该总质量，以确保混合物在干燥过程中模板剂的质量损失控制在一个合理的范围内。4. The method for preparing a silver-loaded SSZ-13 molecular sieve nanocrystal mixed matrix membrane according to claim 1, characterized in that the mass of the mixture after drying in step 1 should be at least 90% of the initial total mass of the template and the silicon source, but should not exceed the total mass to ensure that the mass loss of the template during the drying process of the mixture is controlled within a reasonable range. 5.根据权利要求1或2所述一种负载银的SSZ-13分子筛纳米晶混合基质膜的制备方法，其特征在于，步骤2中原料的加入顺序：首先向模板剂中加入铝源，待其完全溶解至澄清溶液后，再依次加入铵盐，铵盐溶解完全后，加入由银盐与氨水反应生成的银氨络合物，这有助于银离子均匀地合成到纳米晶的骨架结构中，避免金属颗粒的聚集，防止其堵塞孔道。5. A method for preparing a silver-loaded SSZ-13 molecular sieve nanocrystal mixed matrix membrane according to claim 1 or 2, characterized in that the raw materials are added in the following order in step 2: first, an aluminum source is added to the template, and after the template is completely dissolved into a clear solution, ammonium salt is added in sequence, and after the ammonium salt is completely dissolved, a silver-ammine complex generated by the reaction of a silver salt and ammonia water is added, which helps silver ions to be uniformly synthesized into the nanocrystal's skeleton structure, avoids the aggregation of metal particles, and prevents them from clogging the pores. 6.根据权利要求1所述一种负载银的SSZ-13分子筛纳米晶混合基质膜的制备方法，其特征在于，步骤4在蒸汽辅助的条件下，对所述混合物依次进行陈化和晶化处理具体包括以下步骤：将混合物移入到开口玻璃器皿中，再将玻璃器皿转入水热反应釜釜衬中，釜衬中加入去离子水，去离子水体积占釜衬体积的1/6~1/5并要防止玻璃器皿外的水进入玻璃器皿中；在60～100℃的温度，蒸汽辅助的条件下，对混合物进行陈化处理，其陈化时间为0～12天；晶化处理温度为20～120℃，晶化时间为0～8天。6. The method for preparing a silver-loaded SSZ-13 molecular sieve nanocrystal mixed matrix membrane according to claim 1, characterized in that step 4, under steam-assisted conditions, sequentially performs aging and crystallization treatments on the mixture, specifically comprising the following steps: transferring the mixture into an open glass container, then transferring the glass container into a hydrothermal reactor lining, adding deionized water into the reactor lining, wherein the volume of the deionized water accounts for 1/6 to 1/5 of the volume of the reactor lining and preventing water outside the glass container from entering the glass container; performing aging treatment on the mixture at a temperature of 60 to 100° C. under steam-assisted conditions, and the aging time is 0 to 12 days; the crystallization treatment temperature is 20 to 120° C., and the crystallization time is 0 to 8 days. 7.根据权利要求1一种负载银的SSZ-13分子筛纳米晶混合基质膜的制备方法，其特征在于，步骤5所述煅烧为空气氛围下煅烧，煅烧温度阶梯升温，首先120-150℃煅烧3-6小时，其次220-260℃煅烧3-6小时，最后煅烧温度为500-580℃，煅烧时间为3-12小时。7. A method for preparing a silver-loaded SSZ-13 molecular sieve nanocrystal mixed matrix membrane according to claim 1, characterized in that the calcination in step 5 is performed in an air atmosphere, and the calcination temperature is increased stepwise, first calcining at 120-150° C. for 3-6 hours, then calcining at 220-260° C. for 3-6 hours, and finally calcining at a temperature of 500-580° C. for 3-12 hours. 8.根据权利要求1所述一种负载银的SSZ-13分子筛纳米晶混合基质膜的制备方法，其特征在于，步骤6所述聚合物基质溶液的制备方法为，将无水乙醇与去离子水混合均匀，在油浴锅中搅拌条件下将其加热至60～120℃，8. The method for preparing a silver-loaded SSZ-13 molecular sieve nanocrystal mixed matrix membrane according to claim 1, characterized in that the polymer matrix solution in step 6 is prepared by uniformly mixing anhydrous ethanol and deionized water, heating the mixture to 60-120° C. under stirring in an oil bath, 之后向其中加入聚合物基质保持60～120℃搅拌4～5小时使其完全溶解，得到聚合物基质溶液；Then, a polymer matrix is added thereto and stirred at 60 to 120° C. for 4 to 5 hours to completely dissolve the polymer matrix solution; 所述乙醇与水的体积比为5～12：1～6；The volume ratio of ethanol to water is 5-12:1-6; 所述聚合物基质溶液固液质量比为1~10：90~150。The solid-liquid mass ratio of the polymer matrix solution is 1-10:90-150. 9.根据权利要求1或8所述一种负载银的SSZ-13分子筛纳米晶混合基质膜的制备方法，其特征在于，步骤6所述聚合物基质为聚酰胺共聚醚PEBA、聚酰亚胺PI的一种或几种。9. The method for preparing a silver-loaded SSZ-13 molecular sieve nanocrystal mixed matrix membrane according to claim 1 or 8, characterized in that the polymer matrix in step 6 is one or more of polyamide copolyether PEBA and polyimide PI. 10.根据权利要求1所述一种负载银的SSZ-13分子筛纳米晶混合基质膜的制备方法，其特征在于，步骤6所述铸膜液中负载银的SSZ-13分子筛纳米晶质量分数为1～40wt％。10. The method for preparing a silver-loaded SSZ-13 molecular sieve nanocrystal mixed matrix membrane according to claim 1, characterized in that the mass fraction of the silver-loaded SSZ-13 molecular sieve nanocrystals in the casting solution in step 6 is 1 to 40 wt%.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114560475A (en) * 2022-03-09 2022-05-31 南京工业大学 A kind of preparation method of metal-modified M-SSZ-13 molecular sieve membrane
CN117732255A (en) * 2023-12-21 2024-03-22 大连理工大学盘锦产业技术研究院 A method for preparing LTA molecular sieve nanocrystal mixed matrix membrane

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070209505A1 (en) * 2006-03-10 2007-09-13 Chunqing Liu High Flux Mixed Matrix Membranes for Separations
US8048198B2 (en) * 2007-11-08 2011-11-01 Uop Llc High performance mixed matrix membranes incorporating at least two kinds of molecular sieves
CN102512985A (en) * 2011-12-30 2012-06-27 中国科学院宁波材料技术与工程研究所 Preparation method for antibacterial fluorine-containing polymer hollow fiber micro-porous membrane
CN103361885B (en) * 2013-06-28 2015-11-11 上海纳米技术及应用国家工程研究中心有限公司 A kind of preparation method of antibacterial fibroin fiber film
CN108607600B (en) * 2016-12-10 2020-09-08 中国科学院大连化学物理研究所 Catalyst with high-dispersion noble metal loaded on molecular sieve, and preparation and application thereof
TWI831784B (en) * 2018-05-28 2024-02-11 大陸商中國石油化工科技開發有限公司 NaY molecular sieve with aluminum-rich surface and preparation method thereof
CN111056561B (en) * 2019-12-30 2021-09-07 卓悦环保新材料（上海）有限公司 Small-grain SSZ-13 molecular sieve containing hierarchical pores and synthesis method thereof
CN111704145A (en) * 2020-06-05 2020-09-25 浙江天地环保科技股份有限公司 Method for in-situ synthesis of nano hydrogen type Cu-SSZ-13 molecular sieve
CN114950167B (en) * 2022-06-08 2023-03-03 大连理工大学 Preparation method of ultrahigh-load MOFs-based mixed matrix membrane
CN116002709B (en) * 2023-01-31 2023-12-22 南京工业大学 Preparation method of SSZ-13 molecular sieve membrane
CN118105853A (en) * 2024-04-15 2024-05-31 大连理工大学盘锦产业技术研究院 A method for improving CO separation by using topological molecular sieve (ZSM-5) to improve mixed matrix membrane2Method of performance

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114560475A (en) * 2022-03-09 2022-05-31 南京工业大学 A kind of preparation method of metal-modified M-SSZ-13 molecular sieve membrane
CN117732255A (en) * 2023-12-21 2024-03-22 大连理工大学盘锦产业技术研究院 A method for preparing LTA molecular sieve nanocrystal mixed matrix membrane

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
付佳辉.《蒸汽辅助浓缩凝胶晶化法合成可分散的沸石纳米晶》.中国优秀硕士学位论文全文数据库,工程科技Ⅰ辑,2024, 第59-60页. *

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