CN109133088B - Preparation method of molecular sieve membrane with high separation efficiency - Google Patents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- 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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/0039—Inorganic membrane manufacture
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0044—Inorganic membrane manufacture by chemical reaction
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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- B01D71/028—Molecular sieves
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- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
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Abstract
The invention relates to the technical field of molecular sieve membrane preparation, in particular to a preparation method of a molecular sieve membrane with high separation efficiency. The method comprises the steps of firstly, taking fresh black tea leaves as raw materials, obtaining black tea fungus fermentation liquor through fermentation, then obtaining nano silicon dioxide through the action of sodium silicate and acid through heating, adding aluminum nitrate into a mixture of a bacterial cellulose membrane and the nano silicon dioxide to obtain a molecular sieve membrane support body, mixing an alkali source, a silicon source, an aluminum source and deionized water in proportion, stirring and aging to obtain molecular sieve membrane crystallization liquid, finally mixing and heating the molecular sieve membrane support body and the molecular sieve membrane crystallization liquid to obtain a molecular sieve membrane with high separation efficiency, combining the nano silicon dioxide on the surface of the bacterial cellulose membrane, removing a bacterial fiber membrane from a reducing liquid through high-temperature sintering, using the reducing liquid as the molecular sieve membrane support body, and having a network structure of nano fibers, so that the thickness of the molecular sieve membrane is reduced, the separation efficiency of the molecular sieve membrane is improved, and the method has a.
Description
Technical Field
The invention relates to the technical field of molecular sieve membrane preparation, in particular to a preparation method of a molecular sieve membrane with high separation efficiency.
Background
Membrane separation is a separation technique developed in recent years which utilizes a barrier (membrane) in which one or more substances can pass through a semipermeable barrier faster than other substances in order to separate a feed mixture containing two or more substances. The membrane separation technology mainly comprises microfiltration, ultrafiltration, reverse osmosis, nanofiltration, electrodialysis, gas separation and pervaporation.
The molecular sieve is a microporous inorganic crystal material formed by taking a silicon-oxygen tetrahedron and an aluminum-oxygen tetrahedron as basic frameworks, is a novel inorganic membrane material which can realize molecular sieving and has wide application prospect in the fields of organic matter dehydration, micromolecular gas separation and the like due to the unique sieving property, hydrophilic/hydrophobic property, shape-selective catalysis and the like.
The molecular sieve as an inorganic membrane material has the following advantages:
(1) the molecular sieve has regular and regular pore channels and single pore diameter distribution, the size of the pore channels of the molecular sieve is similar to the size of the molecules of a plurality of important industrial raw materials, and the molecules can be separated by molecular sieving or shape selective diffusion.
The molecular sieve has good chemical stability and thermal stability.
The diversity of the molecular sieve structure leads to the diversity of the properties of the molecular sieve, such as different pore sizes and different hydrophilicity and hydrophobicity, so that the proper molecular sieve can be selected as a membrane material according to different separation requirements.
The modifiability of the pore passages and pore outer surfaces of the molecular sieve results in tunable modification of the pore size and adsorption properties of the molecular sieve, thereby allowing precise control of the separation. The molecular sieve membrane has the characteristics of excellent shape-selective separation and catalytic performance, high temperature resistance, strong chemical corrosion resistance and the like, and can be applied to various fields such as gas separation, steam separation, liquid pervaporation separation, membrane catalytic reaction, subject-object reaction, environmental protection, life engineering, electrodes, sensors and the like.
However, since the conventional molecular sieve membrane has a certain mechanical strength, and the membrane thickness obtained in the preparation process is large, the separation efficiency of the membrane is not in an ideal state, and how to have a certain mechanical strength while reducing the thickness of the molecular sieve membrane to improve the separation efficiency becomes one of the hot spots in current research. In addition, most molecular sieve membrane synthesis is directly carried out on the carrier, because of the difference of thermal expansion coefficients, the membrane is easy to fall off, and the crystal membrane basically has no orientation, thus influencing the efficacy and development of the molecular sieve membrane.
Therefore, there is a need to develop a molecular sieve membrane that can solve the above problems.
Disclosure of Invention
The invention mainly solves the technical problem and provides a preparation method of a molecular sieve membrane with high separation efficiency aiming at the defect that the separation effect is not ideal due to the large membrane thickness of the existing molecular sieve.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a molecular sieve membrane with high separation efficiency is characterized by comprising the following specific preparation steps:
(1) uniformly mixing fresh black tea leaves, white sugar and distilled water, then putting the mixture into a disinfected beaker, heating the mixture in water bath at the temperature of 40-50 ℃ for 20-30 min to obtain a water bath heating product, then adding the water bath heating product into a fermentation tank, adding black tea fungus suspension into the fermentation tank, carrying out sealed fermentation for 5-6 days at the temperature of 40-50 ℃, and taking out a gelatinous bacterial cellulose membrane formed on the surface layer of fermentation liquor by using tweezers to obtain a bacterial cellulose membrane;
(2) putting the obtained bacterial cellulose membrane at the bottom of a beaker, adding a sodium silicate solution into the beaker, adding a hydrochloric acid solution into the beaker, adjusting the pH of the solution to 4-5 to obtain a mixed solution, pouring the mixed solution into a heating device, setting the temperature to be 50-60 ℃, heating for reaction for 2-3 hours, and taking out the bacterial cellulose membrane after the reaction at the bottom of the beaker after the reaction is finished;
(3) mixing the reacted bacterial cellulose membrane with an aluminum nitrate solution, carrying out shaking reaction on a shaking table for 10-15 min to obtain a reaction solution, dropwise adding a glucose solution into the reaction solution, carrying out stirring reaction for 30-40 min at the temperature of 40-50 ℃, and collecting the modified bacterial cellulose membrane;
(4) adding the modified bacterial cellulose membrane into a muffle furnace, and reacting at high temperature to obtain a molecular sieve membrane support for later use;
(5) mixing sodium silicate, sodium aluminate, plant ash and deionized water, stirring for reaction to obtain a stirred material, putting the stirred material into an ageing device, and ageing for 20-24 hours at 120-150 ℃ to obtain a molecular sieve membrane crystallization liquid;
(6) mixing a standby molecular sieve membrane support body and the molecular sieve membrane crystallization liquid, then putting the mixture into a reaction kettle, heating and synthesizing the mixture in a water bath for 40-50 min at the temperature of 80-90 ℃ to obtain a hydrothermal synthesis product, washing the hydrothermal synthesis product with deionized water, then putting the hydrothermal synthesis product into an oven, setting the temperature to be 100-110 ℃, drying for 50-60 min, and collecting a dried product to obtain the molecular sieve membrane with high separation efficiency.
The mass ratio of the fresh black tea leaves, the white sugar and the distilled water in the step (1) is 2: 1: 3, the concentration of the black tea fungus suspension is 106cfu/mL, and the mass of the black tea fungus suspension is 7-10% of the mass of the water bath heating product.
The mass fraction of the sodium silicate solution in the step (2) is 40%, and the mass fraction of the hydrochloric acid solution is 30%.
The mass ratio of the bacterial cellulose membrane after the reaction in the step (3) to the aluminum nitrate solution is 1: 1, the mass fraction of the aluminum nitrate solution is 30%, the mass fraction of the glucose solution dripped into the reaction solution is 25%, and the mass of the glucose solution is 10% of the mass of the reaction solution.
And (4) controlling the temperature in the muffle furnace to be 700-800 ℃ and the reaction time to be 3-4 h.
The mass ratio of the sodium silicate to the sodium aluminate to the plant ash to the deionized water in the step (5) is 3: 2: 3, the stirring speed is 40-60 r/min, and the stirring time is 30-40 min.
And (3) the mass ratio of the molecular sieve membrane support body for later use in the step (6) to the molecular sieve membrane crystallization liquid is 2: 1.
The invention has the beneficial effects that:
(1) the invention firstly uses fresh black tea leaves as raw materials, black tea fungus fermentation liquor is obtained through fermentation, acetic acid bacteria in the black tea fungus fermentation liquor can be metabolized to form a bacterial cellulose membrane, then sodium silicate and acid act, nano silicon dioxide is obtained through heating, aluminum nitrate is added into the mixture of the bacterial cellulose membrane and the nano silicon dioxide, the aluminum nitrate is reduced into simple substance aluminum through glucose, the bacterial cellulose membrane is removed through high-temperature sintering, a molecular sieve membrane support body is obtained, an alkali source, a silicon source, an aluminum source and deionized water are mixed according to a proportion, stirring and aging are carried out, a molecular sieve membrane crystallization liquid is obtained, finally the molecular sieve membrane support body and the molecular sieve membrane crystallization liquid are mixed for water bath heating reaction and then are dried, and the molecular sieve membrane with high separation efficiency is obtained, the invention uses the fresh black tea leaves as the raw materials, the black tea fungus fermentation liquor is obtained through fermentation, the acetic acid bacteria in, the bacterial cellulose membrane is a natural biopolymer, and has a hyperfine nano fiber network, the bacterial cellulose membrane disappears in high-temperature sintering, sodium silicate reacts under an acidic condition to prepare orthosilicic acid precipitate, the prepared orthosilicic acid solution is heated to react to generate nano silicon dioxide, so that the nano silicon dioxide is combined on the surface of the bacterial cellulose membrane, the silicon dioxide is in a flocculent and reticular quasi-particle structure, the bacterial cellulose membrane combined with the nano silicon dioxide can be used as a template of a molecular sieve membrane, a glucose solution has reducibility, aluminum nitrate is reduced into an aluminum simple substance under the action of a reducibility substance, the collected modified bacterial cellulose membrane contains the bacterial cellulose membrane combined with the nano silicon dioxide and the simple substance aluminum, the bacterial cellulose membrane is removed after high-temperature sintering, a pore structure is generated, as the molecular sieve membrane support body, the nano-fiber structure is provided, so that the thickness of the molecular sieve membrane is reduced, the separation efficiency of the molecular sieve membrane is improved, and the molecular sieve membrane support body has a wide application prospect.
Detailed Description
Uniformly mixing fresh black tea leaves, white sugar and distilled water in a mass ratio of 2: 1: 3, putting the mixture into a disinfected beaker, heating the mixture in water bath at the temperature of 40-50 ℃ for 20-30 min to obtain a water bath heating product, adding the water bath heating product into a fermentation tank, and adding the water bath heating product into the fermentation tank, wherein the concentration of the water bath heating product is 10% and the mass of the water bath heating product is 7-10%6Sealing and fermenting cfu/mL black tea fungus suspension for 5-6 days at the temperature of 40-50 ℃, and taking out the gel-like bacterial cellulose membrane formed on the surface layer of the fermentation liquid by using a pair of tweezers to obtain the bacterial cellulose membrane; putting the obtained bacterial cellulose membrane at the bottom of a beaker, adding a sodium silicate solution with the mass fraction of 40% into the beaker, adding a hydrochloric acid solution with the mass fraction of 30% into the beaker, adjusting the pH of the solution to be 4-5 to obtain a mixed solution, pouring the mixed solution into a heating device, setting the temperature to be 50-60 ℃, carrying out heating reaction for 2-3 h, and taking out the bacterial cellulose membrane after the reaction at the bottom of the beaker after the reaction is finished; mixing the components in a mass ratio of 1: 1, mixing the reacted bacterial cellulose membrane with 30 mass percent of aluminum nitrate solution, shaking the mixture in a shaking table to perform oscillation reaction for 10-15 min to obtain reaction liquid, then dropwise adding 10 mass percent of 25 mass percent of glucose solution into the reaction liquid, stirring and reacting for 30-40 min at the temperature of 40-50 ℃, and collectingCollecting to obtain a modified bacterial cellulose membrane; adding the modified bacterial cellulose membrane into a muffle furnace, and reacting for 3-4 hours at the temperature of 700-800 ℃ to obtain a molecular sieve membrane support for later use; mixing sodium silicate, sodium aluminate, plant ash and deionized water in a mass ratio of 3: 2: 3, stirring at a stirring speed of 40-60 r/min for 30-40 min to obtain a stirred material, putting the stirred material into a ageing device, and ageing at 120-150 ℃ for 20-24 h to obtain a molecular sieve membrane crystallization liquid; putting a standby molecular sieve membrane support and the molecular sieve membrane crystallization liquid into a reaction kettle according to the mass ratio of 2: 1, heating and synthesizing in a water bath for 40-50 min at the temperature of 80-90 ℃ to obtain a hydrothermal synthesis product, washing the hydrothermal synthesis product with deionized water, putting the hydrothermal synthesis product into an oven, setting the temperature at 100-110 ℃, drying for 50-60 min, and collecting a dried product to obtain the molecular sieve membrane with high separation efficiency.
Uniformly mixing fresh black tea leaves, white sugar and distilled water in a mass ratio of 2: 1: 3, putting the mixture into a sterilized beaker, heating the mixture in water bath at 40 ℃ for 20min to obtain a water bath heating product, adding the water bath heating product into a fermentation tank, adding black tea fungus suspension with the concentration of 106cfu/mL and the mass of 7% of the water bath heating product into the fermentation tank, fermenting the mixture in a sealed manner for 5 days at the temperature of 40 ℃, and taking out a gelatinous bacterial cellulose membrane formed on the surface layer of fermentation liquor by using tweezers to obtain a bacterial cellulose membrane; putting the obtained bacterial cellulose membrane at the bottom of a beaker, adding a sodium silicate solution with the mass fraction of 40% into the beaker, adding a hydrochloric acid solution with the mass fraction of 30% into the beaker, adjusting the pH of the solution to be 4 to obtain a mixed solution, pouring the mixed solution into a heating device, setting the temperature to be 50 ℃, heating and reacting for 2 hours, and taking out the bacterial cellulose membrane after reaction at the bottom of the beaker after the reaction is finished; mixing the components in a mass ratio of 1: 1, mixing the reacted bacterial cellulose membrane with an aluminum nitrate solution with the mass fraction of 30%, oscillating the mixture in a shaking table for 10min to obtain a reaction solution, dripping a glucose solution with the mass fraction of 25% and the mass fraction of 10% of the reaction solution into the reaction solution, stirring the mixture for reaction for 30min at the temperature of 40 ℃, and collecting the mixture to obtain a modified bacterial cellulose membrane; adding the modified bacterial cellulose membrane into a muffle furnace, and reacting for 3 hours at the temperature of 700 ℃ to obtain a molecular sieve membrane support for later use; mixing sodium silicate, sodium aluminate, plant ash and deionized water at a mass ratio of 3: 2: 3, stirring at a stirring speed of 40r/min for 30min to obtain a stirred matter, and aging the stirred matter in an aging device at 120 ℃ for 20h to obtain a molecular sieve membrane crystallization liquid; placing the prepared molecular sieve membrane support and the molecular sieve membrane crystallization liquid into a reaction kettle according to the mass ratio of 2: 1, heating and synthesizing in a water bath for 40min at the temperature of 80 ℃ to obtain a hydrothermal synthesis product, washing the hydrothermal synthesis product with deionized water, placing the hydrothermal synthesis product into an oven, setting the temperature at 100 ℃, drying for 50min, and collecting the dried product to obtain the molecular sieve membrane with high separation efficiency.
Uniformly mixing fresh black tea leaves, white sugar and distilled water in a mass ratio of 2: 1: 3, putting the mixture into a sterilized beaker, heating the mixture in water bath at 45 ℃ for 25min to obtain a water bath heating product, adding the water bath heating product into a fermentation tank, adding black tea fungus suspension with the concentration of 106cfu/mL and the mass of 8% of the water bath heating product into the fermentation tank, fermenting the mixture in a sealed manner for 5 days at 45 ℃, and taking out a gelatinous bacterial cellulose membrane formed on the surface layer of fermentation liquor by using tweezers to obtain a bacterial cellulose membrane; putting the obtained bacterial cellulose membrane at the bottom of a beaker, adding a sodium silicate solution with the mass fraction of 40% into the beaker, adding a hydrochloric acid solution with the mass fraction of 30% into the beaker, adjusting the pH of the solution to be 4 to obtain a mixed solution, pouring the mixed solution into a heating device, setting the temperature to be 55 ℃, heating and reacting for 2 hours, and taking out the bacterial cellulose membrane after reaction at the bottom of the beaker after the reaction is finished; mixing the components in a mass ratio of 1: 1, mixing the reacted bacterial cellulose membrane with an aluminum nitrate solution with the mass fraction of 30%, oscillating the mixture in a shaking table for reaction for 13min to obtain a reaction solution, dripping a glucose solution with the mass fraction of 25% and the mass fraction of 10% of the reaction solution into the reaction solution, stirring the mixture for reaction for 35min at the temperature of 45 ℃, and collecting the mixture to obtain a modified bacterial cellulose membrane; adding the modified bacterial cellulose membrane into a muffle furnace, and reacting for 3 hours at the temperature of 750 ℃ to obtain a molecular sieve membrane support for later use; mixing sodium silicate, sodium aluminate, plant ash and deionized water at a mass ratio of 3: 2: 3, stirring at a stirring speed of 50r/min for 35min to obtain a stirred substance, and aging the stirred substance in an aging device at 135 ℃ for 22h to obtain a molecular sieve membrane crystallization liquid; putting the prepared molecular sieve membrane support and the molecular sieve membrane crystallization liquid into a reaction kettle according to the mass ratio of 2: 1, heating and synthesizing in a water bath for 45min at the temperature of 85 ℃ to obtain a hydrothermal synthesis product, washing the hydrothermal synthesis product with deionized water, putting the hydrothermal synthesis product into an oven, setting the temperature at 105 ℃, drying for 55min, and collecting the dried product to obtain the molecular sieve membrane with high separation efficiency.
Uniformly mixing fresh black tea leaves, white sugar and distilled water in a mass ratio of 2: 1: 3, putting the mixture into a sterilized beaker, heating the mixture in water bath at 50 ℃ for 30min to obtain a water bath heating product, adding the water bath heating product into a fermentation tank, adding black tea fungus suspension with the concentration of 106cfu/mL and the mass of 10% of the water bath heating product into the fermentation tank, carrying out sealed fermentation at 50 ℃ for 6 days, and taking out a gelatinous bacterial cellulose membrane formed on the surface layer of fermentation liquor by using tweezers to obtain a bacterial cellulose membrane; putting the obtained bacterial cellulose membrane at the bottom of a beaker, adding a sodium silicate solution with the mass fraction of 40% into the beaker, adding a hydrochloric acid solution with the mass fraction of 30% into the beaker, adjusting the pH of the solution to be 5 to obtain a mixed solution, pouring the mixed solution into a heating device, setting the temperature to be 60 ℃, heating and reacting for 3 hours, and taking out the bacterial cellulose membrane after reaction at the bottom of the beaker after the reaction is finished; mixing the components in a mass ratio of 1: 1, mixing the reacted bacterial cellulose membrane with an aluminum nitrate solution with the mass fraction of 30%, oscillating and reacting for 15min by a shaking table to obtain a reaction solution, dripping a glucose solution with the mass fraction of 25% and the mass fraction of 10% of the reaction solution into the reaction solution, stirring and reacting for 40min at the temperature of 50 ℃, and collecting to obtain a modified bacterial cellulose membrane; adding the modified bacterial cellulose membrane into a muffle furnace, and reacting for 4 hours at the temperature of 800 ℃ to obtain a molecular sieve membrane support for later use; mixing sodium silicate, sodium aluminate, plant ash and deionized water at a mass ratio of 3: 2: 3, stirring at a stirring speed of 60r/min for 40min to obtain a stirred substance, and aging the stirred substance in an aging device at 150 ℃ for 24h to obtain a molecular sieve membrane crystallization liquid; placing the prepared molecular sieve membrane support and the molecular sieve membrane crystallization liquid into a reaction kettle according to the mass ratio of 2: 1, heating and synthesizing in a water bath for 50min at the temperature of 90 ℃ to obtain a hydrothermal synthesis product, washing the hydrothermal synthesis product with deionized water, placing the hydrothermal synthesis product into an oven, setting the temperature at 110 ℃, drying for 60min, and collecting the dried product to obtain the molecular sieve membrane with high separation efficiency.
Comparative example A molecular sieve membrane produced by a certain company of the sea city was used as a comparative example
The molecular sieve membrane with high separation efficiency prepared by the invention and the molecular sieve membrane in the comparative example are detected, and the detection results are shown in table 1:
toughness testing
And testing by using an electronic universal testing machine. The test was repeated 5 times and the average was taken.
The pure water flux is the amount of pure water permeating per unit area of the membrane per unit time at a certain temperature and working pressure. Pure water flux is directly proportional to filtration efficiency.
Before testing, two ends of the molecular sieve membranes of preparation examples 1 to 3 of the invention and the comparative example are respectively sealed to prepare a molecular sieve membrane assembly, then pure water is respectively introduced into one end (a water inlet) of the membrane assembly under the condition that the surface pressure is 0.1MPa, the volume V (L) of the pure water penetrating through the other end (a water outlet) of the membrane assembly within 30min is measured, and the Pure Water Flux (PWF) of the molecular sieve membrane is calculated.
Pure water flux = volume of pure water permeated/(external surface area of molecular sieve membrane tube × time required for permeation through molecular sieve membrane × operating pressure)
CO2/CH4Gas separation test conditions: the temperature was 20 ℃, the atmospheric pressure was 102.4kPa, the feed gas flow was 4000mL/min, and the molar composition was 50/50vol% (i.e., CO)2︰CH4At a molar ratio of 1: 1). Measuring the gas flow at the permeation side by using a soap film flowmeter; the gas composition on the permeate side was analyzed by gas chromatography.
Calculation formula of gas permeability: p = V/(sxp). Wherein V is a permeate gas (CO)2Or CH4) The flow rate of (2) is in mol/S, and S is the membrane area inm2(ii) a P is the pressure difference between the feed side and the permeate side of the membrane tube, in Pa.
Separation selectivity calculation formula: f ═ pCO2/pCH4I.e. CO2And CH4The permeability of (c).
TABLE 1 measurement results of Properties
As can be seen from the data in Table 1, the molecular sieve membrane with high separation efficiency prepared by the method has the characteristics of compactness, continuity, good separation performance and the like, and has excellent mechanical properties, good filtration efficiency, good economic benefits and social benefits.
Claims (6)
1. A preparation method of a molecular sieve membrane with high separation efficiency is characterized by comprising the following specific preparation steps:
(1) uniformly mixing fresh black tea leaves, white sugar and distilled water, then putting the mixture into a disinfected beaker, heating the mixture in water bath at the temperature of 40-50 ℃ for 20-30 min to obtain a water bath heating product, then adding the water bath heating product into a fermentation tank, adding black tea fungus suspension into the fermentation tank, carrying out sealed fermentation for 5-6 days at the temperature of 40-50 ℃, and taking out a gelatinous bacterial cellulose membrane formed on the surface layer of fermentation liquor by using tweezers to obtain a bacterial cellulose membrane;
(2) putting the obtained bacterial cellulose membrane at the bottom of a beaker, adding a sodium silicate solution into the beaker, adding a hydrochloric acid solution into the beaker, adjusting the pH of the solution to 4-5 to obtain a mixed solution, pouring the mixed solution into a heating device, setting the temperature to be 50-60 ℃, heating for reaction for 2-3 hours, and taking out the bacterial cellulose membrane after the reaction at the bottom of the beaker after the reaction is finished;
(3) mixing the reacted bacterial cellulose membrane with an aluminum nitrate solution, carrying out shaking reaction on a shaking table for 10-15 min to obtain a reaction solution, dropwise adding a glucose solution into the reaction solution, carrying out stirring reaction for 30-40 min at the temperature of 40-50 ℃, and collecting the modified bacterial cellulose membrane; the mass ratio of the reacted bacterial cellulose membrane to the aluminum nitrate solution is 1: 1, the mass fraction of an aluminum nitrate solution is 30%, the mass fraction of a glucose solution dripped into a reaction solution is 25%, and the mass of the glucose solution is 10% of the mass of the reaction solution;
(4) adding the modified bacterial cellulose membrane into a muffle furnace, and reacting at high temperature to obtain a molecular sieve membrane support for later use;
(5) mixing sodium silicate, sodium aluminate, plant ash and deionized water, stirring for reaction to obtain a stirred material, putting the stirred material into an ageing device, and ageing for 20-24 hours at 120-150 ℃ to obtain a molecular sieve membrane crystallization liquid;
(6) mixing a standby molecular sieve membrane support body and the molecular sieve membrane crystallization liquid, then putting the mixture into a reaction kettle, heating and synthesizing the mixture in a water bath for 40-50 min at the temperature of 80-90 ℃ to obtain a hydrothermal synthesis product, washing the hydrothermal synthesis product with deionized water, then putting the hydrothermal synthesis product into an oven, setting the temperature to be 100-110 ℃, drying for 50-60 min, and collecting a dried product to obtain the molecular sieve membrane with high separation efficiency.
2. The method for preparing a molecular sieve membrane with high separation efficiency according to claim 1, wherein the method comprises the following steps: the mass ratio of the fresh black tea leaves, the white sugar and the distilled water in the step (1) is 2: 1: 3, and the concentration of the black tea fungus suspension is 106cfu/mL, wherein the mass of the black tea fungus suspension is 7-10% of that of the water bath heating product.
3. The method for preparing a molecular sieve membrane with high separation efficiency according to claim 1, wherein the method comprises the following steps: the mass fraction of the sodium silicate solution in the step (2) is 40%, and the mass fraction of the hydrochloric acid solution is 30%.
4. The method for preparing a molecular sieve membrane with high separation efficiency according to claim 1, wherein the method comprises the following steps: and (4) controlling the temperature in the muffle furnace to be 700-800 ℃ and the reaction time to be 3-4 h.
5. The method for preparing a molecular sieve membrane with high separation efficiency according to claim 1, wherein the method comprises the following steps: the mass ratio of the sodium silicate to the sodium aluminate to the plant ash to the deionized water in the step (5) is 3: 2: 3, the stirring speed is 40-60 r/min, and the stirring time is 30-40 min.
6. The method for preparing a molecular sieve membrane with high separation efficiency according to claim 1, wherein the method comprises the following steps: and (3) the mass ratio of the molecular sieve membrane support body for later use in the step (6) to the molecular sieve membrane crystallization liquid is 2: 1.
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| US6447856B1 (en) * | 2000-11-22 | 2002-09-10 | The Board Of Regents Of The University Of Nebraska | Hydrothermal gel process for preparation of silicalite particles and process for preparation of composite membrane |
| JP2002335911A (en) * | 2001-05-21 | 2002-11-26 | Japan Organo Co Ltd | Method for concentrating and refining polyphenol |
| CN105032359A (en) * | 2010-03-30 | 2015-11-11 | 索尼公司 | Fungicide, photo catalytic composite material, adsorbent, and depurative |
| CN104874300A (en) * | 2015-04-30 | 2015-09-02 | 天津大学 | Chitosan-sulfonated carbon molecular sieve hybrid composite membrane and preparation and application |
| CN108479417A (en) * | 2018-04-28 | 2018-09-04 | 邹峰 | It is a kind of using glass hollow fiber as the preparation method of carrier molecule sieve membrane |
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