CN114984608B - Method for preparing spherical reverse osmosis membrane storage crystal particles - Google Patents
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- 239000012528 membrane Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 43
- 238000003860 storage Methods 0.000 title claims abstract description 24
- 239000002245 particle Substances 0.000 title claims abstract description 18
- 239000004005 microsphere Substances 0.000 claims abstract description 58
- 239000000243 solution Substances 0.000 claims abstract description 43
- 238000005266 casting Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002425 crystallisation Methods 0.000 claims abstract description 23
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- 239000000017 hydrogel Substances 0.000 claims abstract description 19
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- 238000002791 soaking Methods 0.000 claims abstract description 11
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- 150000002500 ions Chemical class 0.000 claims abstract description 7
- 239000012047 saturated solution Substances 0.000 claims abstract description 5
- 229920002301 cellulose acetate Polymers 0.000 claims description 23
- 239000004760 aramid Substances 0.000 claims description 7
- 229920003235 aromatic polyamide Polymers 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000010924 continuous production Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 239000011780 sodium chloride Substances 0.000 description 17
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 15
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 9
- 229910052939 potassium sulfate Inorganic materials 0.000 description 9
- 235000011151 potassium sulphates Nutrition 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229920001747 Cellulose diacetate Polymers 0.000 description 3
- 229920001661 Chitosan Polymers 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 238000000879 optical micrograph Methods 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
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- 239000011734 sodium Substances 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
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- 230000008020 evaporation Effects 0.000 description 2
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- 239000012071 phase Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 241001052560 Thallis Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011868 grain product Nutrition 0.000 description 1
- 239000003721 gunpowder Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002035 hexane extract Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/02—Crystallisation from solutions
-
- 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
- B01D67/0002—Organic membrane manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Medicinal Preparation (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method for preparing spherical reverse osmosis film storage crystal particles, which comprises the steps of soaking hydrogel microspheres in a saturated solution of required crystals to enable the microspheres to absorb water and swell; preparing a casting solution or a liquid reverse osmosis membrane of the film meeting the conditions; the membrane is a reverse osmosis membrane with selectivity to solute, and the pore diameter of the surface micropores is smaller than the diameter of solute molecules or ions; uniformly wrapping the casting solution on the soaked hydrogel microspheres; and selecting proper temperature and time according to the prepared crystal, and drying in an incubator to solidify the film so as to realize the crystallization process in the film. The preparation method of the green nontoxic reverse osmosis membrane has the characteristics of short process flow, simple and convenient operation, capability of preparing different types of reverse osmosis membranes suitable for different crystals, and the like, and provides a one-step continuous process for preparing spherical reverse osmosis membrane storage crystal particles.
Description
Technical Field
The invention belongs to the field of crystallization and reverse osmosis membrane combination, and particularly relates to a method for preparing spherical reverse osmosis membrane storage crystal particles.
Background
Chemical crystallization is a chemical process with high efficiency, low energy consumption and low pollution, and is very popular in the modern industry. At present, the catalyst is not only applied to the traditional fields of food industry, chemical fertilizer and pesticide, inorganic salt production, medicine industry and the like, but also successfully extends to the industries of emerging biochemical industry, aerospace material, catalyst manufacture, electrochemistry, electronic material production and the like. The importance of developing high-end functional crystal grain products is fully recognized in all countries of the world, and therefore, the system engineering research of the modern industrial crystallization technology, which is a key core common technology, is rapidly developed to strive to preempt and monopoly the high-end functional product market.
Crystallization is the process whereby a substance precipitates in a crystalline state from a vapor, solution or melt. At present, research on crystallization is mainly focused on research on the process mechanism, such as factors influencing crystal growth, and the like, while less attention is paid to problems such as storage after crystal generation.
After the crystals are generated and separated out, the crystals have special physicochemical properties and can be changed under the action of external environment, if the storage mode is improper, the problems of moisture absorption, hardening, heating and melting and the like of the crystals can be caused, even some crystals are active in chemical properties, and can rub against each other in the storage process to burn or explode, for example, medicinal material particles and gunpowder crystals have the characteristics. Research into the storage of crystals is therefore of great importance in promoting the development of the crystallization industry. Meanwhile, the spherical space has better fluidity and compactness, and is an optimal storage form. The main storage mode at present is to package and store crystals after the crystals are separated from the solution and dried.
The present invention provides a one-step continuous process for preparing spherical reverse osmosis membrane storage crystal particles in a non-dry state.
Disclosure of Invention
The invention aims to provide a method for preparing spherical reverse osmosis membrane storage crystal particles, by which a spherical reverse osmosis membrane with selectivity can be manufactured. The crystallization process is completed in the film, so that the stable and closed growth environment of the crystal is ensured, and the crystal can be well protected due to the coating of the film, thereby providing convenience for the storage of crystal particles.
In order to achieve the above purpose, the present invention is implemented by adopting the following technical scheme (as shown in fig. 1):
a method for preparing spherical reverse osmosis membrane storage crystal particles comprising the steps of:
(1) Soaking the hydrogel microspheres in a saturated solution of the required crystals to enable the microspheres to absorb water and swell;
(2) Preparing a casting solution or a liquid reverse osmosis membrane of the film meeting the conditions; the membrane is a reverse osmosis membrane with selectivity to solute, and the pore diameter of the surface micropores is smaller than the diameter of solute molecules or ions;
(3) Uniformly wrapping the casting solution on the soaked hydrogel microspheres;
(4) And selecting proper temperature and time according to the prepared crystal, and drying in an incubator to solidify the film so as to realize the crystallization process in the film.
The crystal in the step (1) comprises the particle diameter of 10 nm-100 nm.
The crystal comprises Na-containing + 、Cu 2+ 、Ni 2+ Ion crystals and small organic molecule crystals.
The small organic molecule crystal comprises dodecanedioic acid.
The film in the step (2) comprises a cellulose acetate film, an aromatic polyamide film and a mixed film made of the two materials.
And (4) enabling the microspheres to rotate at a constant speed in the drying process so as to ensure that the film is uniformly formed on the microspheres.
The invention utilizes hydrogel microspheres to absorb solution containing crystals, and controls the solution in a latticed solid space. The crystallization in the microsphere is limited by the internal latticed space, so that the microsphere has the characteristics of relatively stable internal flow field and small influence of external conditions on the crystallization process, and the generated crystal can keep a specific form. And then coating the membrane casting solution of the reverse osmosis membrane on the microspheres, and rapidly solidifying the reverse osmosis membrane into a solid state by utilizing the characteristic of smooth surfaces of the microspheres. The reverse osmosis membrane is a film with water-based groups, has the function of screening and preferential adsorption on water molecules, namely, can effectively intercept all dissolved salts and organic matters with molecular weight larger than 100 by utilizing substances which can intercept the water molecules, and simultaneously allows the water molecules to pass through, so that the water exuded by the hydrogel microspheres in the drying process can pass through the reverse osmosis membrane, solute crystals can be remained in the membrane (in practical application, can refer to the sea water desalination process.) because the casting solution is liquid fluid, and the surface of the microspheres is smooth, the microspheres need to rotate at a constant speed in the drying process, and the casting solution can be uniformly wrapped on the microspheres to generate the reverse osmosis membrane with a certain thickness. Therefore, the film wraps the crystal in the liquid state, so that the internal crystal is effectively protected, and the influence of external conditions on the crystal is reduced (as shown in fig. 2).
The preparation method of the green nontoxic reverse osmosis membrane has the characteristics of short process flow, simple and convenient operation, capability of preparing different types of reverse osmosis membranes suitable for different crystals, and the like, and provides a one-step continuous process for preparing spherical reverse osmosis membrane storage crystal particles.
Drawings
FIG. 1 is a flow chart of the preparation of the present invention.
Wherein: (1) the method comprises the following steps Hydrogel microspheres; (2) the method comprises the following steps A saturated solution of the desired crystal; (3) the method comprises the following steps A culture dish; (4) the method comprises the following steps Casting film liquid; (5) the method comprises the following steps A magnetic stirrer; (6) the method comprises the following steps Microspheres wrapped by casting solution; (7) the method comprises the following steps Constant temperature box
Fig. 2 is a schematic diagram of the internal structure of the present invention.
(a) The hydrogel microspheres are coated with the casting solution, and the microspheres are dried at constant temperature.
Wherein, (1): hydrogel microspheres filled with a saturated solution; (8) the method comprises the following steps A reverse osmosis membrane; (9) the method comprises the following steps A network structure inside the microsphere; and (3) a step of: a cavity in which the crystal is stored;dried microspheres;
FIG. 3 is an optical microscope image of the internal structure of microspheres after drying by the spherical cellulose acetate membrane storage sodium chloride crystal method prepared in example 1.
FIG. 4 is an external morphology of the spherical cellulose acetate membrane prepared in example 1 obtained by the method of storing sodium chloride crystals.
Fig. 5 is an optical microscope image of the internal structure of a slice obtained by the method of storing sodium chloride crystals in a spherical cellulose acetate film prepared in example 1.
Fig. 6 is an SEM image of a film obtained by the spherical cellulose acetate film storage sodium chloride crystal method prepared in example 1.
Fig. 7 is an SEM image of sodium chloride crystals obtained by the method of storing sodium chloride crystals in a spherical cellulose acetate film prepared in example 1 and sodium chloride crystals under natural crystallization (a is sodium chloride crystals under natural crystallization; b is sodium chloride crystals obtained by evaporation crystallization under film encapsulation).
FIG. 8 is an optical microscopic image of the internal structure of a slice obtained by the method of storing dodecanedioic acid crystals in a spherical cellulose acetate film prepared in example 2.
FIG. 9 is an optical microscope image of the internal structure of a cut piece obtained by the method of storing sodium chloride crystals in a spherical aromatic polyamide membrane prepared in example 3.
FIG. 10 is an SEM image of a film obtained by storing potassium sulfate crystals in a spherical cellulose acetate film prepared in example 4
FIG. 11 is an SEM image of potassium sulfate crystals obtained by the method for storing potassium sulfate crystals in a spherical cellulose acetate film prepared in example 4 and potassium sulfate crystals under natural crystallization (a is a naturally crystallized potassium sulfate crystal; b is a potassium sulfate crystal obtained by evaporation crystallization under film encapsulation).
Detailed Description
The invention will be described in further detail with reference to the accompanying drawings and specific embodiments
(1) Soaking hydrogel microsphere in desired crystal (particle diameter between 10 nm-100 nm such as Na-containing + 、Cu 2+ 、Ni 2+ Plasma crystal, and organic small molecular crystal such as dodecanedioic acid, etc.), and taking out the microspheres after the microspheres are swelled by absorbing water;
(2) Preparing a casting solution or a liquid reverse osmosis membrane of a reverse osmosis membrane which meets the conditions and has selectivity to solute, wherein the pore diameter of the surface micropores of the casting solution or the liquid reverse osmosis membrane is smaller than the diameter of solute molecules or ions; the membrane is a reverse osmosis membrane with a certain selectivity to solute, and has a surface microporous pore diameter smaller than that of solute molecule or ion, wherein cellulose acetate membrane, aromatic polyamide membrane and mixed membrane containing the above two materials can be suitable for most crystals, especially with particle diameter between 10nm and 100nm such as Na-containing + 、Cu 2+ 、Ni 2+ Plasma crystals, and small organic molecule crystals such as dodecanedioic acid.
(3) Uniformly wrapping the casting solution on the soaked hydrogel microspheres;
(4) The film is solidified by drying in an oven at a proper temperature and time according to the prepared crystals, and crystallization process in the film is realized. The microspheres should be rotated at a constant speed during the drying process to ensure that the film is uniformly formed on the microspheres.
Example 1
The method for preparing spherical cellulose acetate membrane storage sodium chloride crystal in the embodiment comprises the following steps:
(1) Soaking hydrogel microspheres in saturated sodium chloride solution, and taking out the microspheres for later use after the microspheres absorb water and swell;
(2) Preparing sodium chloride crystal with pore size smaller than Na + Ion diameter cellulose acetate film casting solution: slowly adding cellulose diacetate into an acetone solvent in batches under the experimental conditions of the experimental temperature of 10-20 ℃ and the relative humidity of 50-75% (the dosage ratio of the acetone solvent to the cellulose acetate is 100ml: 5-10 g) while stirring for 12-14 hours, then adding distilled water (the dosage ratio of the acetone solvent to the distilled water is 4-25:1), continuing stirring for 2-6 hours, and finally standing for deaeration for 12-20 hours to obtain transparent and uniform casting film liquid;
(3) Scraping the casting film liquid on a clean glass plate or a non-woven fabric; uniformly dripping a small amount of distilled water on the scraped casting film liquid to accelerate wet film forming, and ensuring good plasticity; after the wet film is preliminarily molded, the wet film is gently taken out by forceps and is wrapped on the microspheres after absorbing the solution, and the wet film is wrapped for multiple times to ensure compactness.
(4) And drying for 24-48 hours at the temperature of 40 ℃ in a constant temperature box until the reverse osmosis membrane and the microspheres are completely dried, so as to realize the crystallization process in the membrane. As shown in fig. 3, 4, 5. The network structure in the hydrogel microspheres, and the crystals generated inside the microspheres, are evident in fig. 3; figures 4 and 6 show that the spherical film prepared after drying has smooth surface and certain thickness, and can reduce the interference of external environment; fig. 5 and 7 show crystal structures, smooth and transparent surfaces, complete morphology, no deliquescence, and comparison with sodium chloride crystal habit under natural crystallization, which proves that the sodium chloride crystal forms are stable after the reverse osmosis membrane is wrapped, namely, the cellulose acetate membrane plays a role in protecting the crystals.
Example 2
The method for preparing the spherical cellulose acetate membrane for storing dodecanedioic acid crystals comprises the following steps of:
(1) Soaking hydrogel microspheres in a saturated dodecanedioic acid solution, and taking out the microspheres for later use after the microspheres absorb water and swell;
(2) Preparing a cellulose acetate membrane casting solution with the micropore aperture smaller than the molecular diameter of the dodecanedioic acid crystal, which meets the screening condition of the dodecanedioic acid crystal: slowly adding cellulose diacetate into an acetone solvent in batches under the experimental conditions of the experimental temperature of 10-20 ℃ and the relative humidity of 50-75% (the dosage ratio of the acetone solvent to the cellulose acetate is 100ml: 10-15 g) while stirring for 16-24 hours, then adding distilled water (the dosage ratio of the acetone solvent to the distilled water is 4-25:1), continuing stirring for 4-8 hours, and finally standing and defoaming for 24 hours to obtain transparent and uniform casting film liquid;
(3) Scraping the casting film liquid on a clean glass plate or a non-woven fabric; uniformly dripping a small amount of distilled water on the scraped casting film liquid to accelerate wet film forming, and ensuring good plasticity; after the wet film is preliminarily molded, the wet film is gently taken out by forceps and is wrapped on the microspheres after absorbing the solution, and the wet film is wrapped for multiple times to ensure compactness.
(4) Drying for 32-48 h at 60 ℃ in a constant temperature box to realize the crystallization process in the film. As shown in fig. 6. Fig. 6 shows a crystal structure with a smooth and transparent surface and a complete morphology without deliquescence. After the reverse osmosis membrane is wrapped, the dodecanedioic acid crystal is stable in crystal form, namely the cellulose acetate membrane plays a role in protecting the crystal.
Example 3
The method for preparing spherical aromatic polyamide membrane storage sodium chloride crystal comprises the following steps:
(1) Soaking hydrogel microspheres in saturated sodium chloride solution, and taking out the microspheres for later use after the microspheres absorb water and swell;
(2) Preparing sodium chloride crystal with pore size smaller than Na + Ion diameter aromatic polyamide film casting solution: 5g of m-phenylenediamine, 0.1g of sodium dodecyl benzene sulfonate, 10g of thionyl chloride, 6ml of glycerol and 210ml of deionized water are mixed to form a mixed solution, and 0.8wt% of camphorsulfonic acid solution and 0.5wt% of sodium hydroxide solution are used for regulating pH=7.8, so that an aqueous phase solution is obtained; the trimesoyl chloride solution was dissolved in Isopa-G solution to give an oil having a concentration of 24wt%A phase solution; adding the coated thalli into normal hexane, uniformly mixing, adding 2v/v% linoleic acid, setting the temperature to be 30 ℃ and reacting for 4 hours; and (5) centrifuging to obtain n-hexane extract. Immersing the polysulfone support membrane in the aqueous phase solution for 1.5 minutes, and removing the redundant aqueous phase solution; transferring to an oil phase solution for interfacial polymerization for 2 minutes; activating in n-hexane extractive solution for 2 min; setting the temperature to 80 ℃ and drying for 5 minutes to obtain a polyamide reverse osmosis membrane; adding 1wt% of potassium persulfate into 0.8g/L chitosan solution to obtain a chitosan mixed solution; placing the polyamide reverse osmosis membrane into the chitosan mixed solution for soaking for 35 minutes; transferring to sodium chlorate solution of 1g/L for soaking for 30 minutes, and placing into sodium bisulfate solution of 2g/L for soaking for 25 minutes; washing with hot water at 75 ℃ to obtain a composite reverse osmosis membrane;
(3) After the wet film is preliminarily formed, the wet film is wrapped on the microspheres after absorbing the solution, and the wet film is wrapped for multiple times to ensure tightness.
(4) Drying for 24-48 h at 40 ℃ in a constant temperature box to realize the crystallization process in the film. As shown in fig. 7. Fig. 7 shows a crystal structure with a smooth and transparent surface and a complete morphology without deliquescence. After the reverse osmosis membrane is wrapped, the crystal form of the sodium chloride crystal is stable, namely the aromatic polyamide membrane plays a role in protecting the crystal.
Example 4
The method for preparing the spherical cellulose acetate film storage potassium sulfate crystal comprises the following steps:
(1) Soaking hydrogel microspheres in saturated potassium sulfate solution, and taking out the microspheres for later use after the microspheres absorb water and swell;
(2) Preparing microporous pore diameter smaller than K meeting potassium sulfate crystal screening condition + Ion diameter cellulose acetate film casting solution: slowly adding cellulose diacetate into an acetone solvent in batches under the experimental conditions of the experimental temperature of 10-20 ℃ and the relative humidity of 50-75% (the dosage ratio of the acetone solvent to the cellulose acetate is 100ml: 5-10 g) while stirring for 12-14 hours, then adding distilled water (the dosage ratio of the acetone solvent to the distilled water is 4-25:1), continuously stirring for 2-6 hours, finally standing for deaeration for 12-20 hours to obtain transparent and uniform casting film liquid；
(3) Scraping the casting film liquid on a clean glass plate or a non-woven fabric; uniformly dripping a small amount of distilled water on the scraped casting film liquid to accelerate wet film forming, and ensuring good plasticity; after the wet film is preliminarily molded, the wet film is gently taken out by forceps and is wrapped on the microspheres after absorbing the solution, and the wet film is wrapped for multiple times to ensure compactness.
(4) And drying for 24-48 hours at the temperature of 40 ℃ in a constant temperature box until the reverse osmosis membrane and the microspheres are completely dried, so as to realize the crystallization process in the membrane. As shown in fig. 10 and 11. The network structure in the hydrogel microspheres, and the crystals generated inside the microspheres, are evident in fig. 3; FIG. 10 shows that the spherical film prepared after drying has smooth surface and certain thickness, and can reduce the interference of external environment; fig. 11 shows a crystal structure, a smooth and transparent surface, a complete morphology, and no deliquescence. After the reverse osmosis membrane is wrapped, the potassium sulfate crystal is stable in crystal form, namely the cellulose acetate membrane plays a role in protecting the crystal.
The technical scheme disclosed and proposed by the invention can be realized by a person skilled in the art by appropriately changing the condition route and other links in consideration of the content of the present invention, although the method and the preparation technology of the invention have been described by the preferred embodiment examples, the related person can obviously modify or recombine the method and the technical route described herein to realize the final preparation technology without departing from the content, spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be included within the spirit, scope and content of the invention. The invention belongs to the known technology.
Claims (3)
1. A method for preparing spherical reverse osmosis membrane storage crystal particles, comprising the steps of:
(1) Soaking the hydrogel microspheres in a saturated solution of the required crystals to enable the microspheres to absorb water and swell;
(2) Preparing a casting solution or a liquid reverse osmosis membrane of the film meeting the conditions; the membrane is a reverse osmosis membrane with selectivity to solute, and the pore diameter of the surface micropores is smaller than the diameter of solute molecules or ions;
(3) Uniformly wrapping the casting solution on the soaked hydrogel microspheres;
(4) According to the prepared crystal, selecting proper temperature and time, drying in an incubator to solidify the film and realize the crystallization process in the film;
the diameter of the crystal particles in the step (1) is 10 nm-100 nm; the crystal contains Na + 、Cu 2+ 、Ni 2+ An ionic crystal or a small organic molecule crystal of one of the above.
2. The method of preparing spherical reverse osmosis membrane storage crystal particles of claim 1, wherein the membrane of step (2) is one of a cellulose acetate membrane, an aromatic polyamide membrane, and a mixed membrane comprising the two materials.
3. The method of preparing spherical reverse osmosis membrane storage crystal particles according to claim 1, wherein step (4) is performed by rotating the microspheres at a constant speed during the drying process to ensure uniform formation of the membrane on the microspheres.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4793980A (en) * | 1978-09-21 | 1988-12-27 | Torobin Leonard B | Hollow porous microspheres as substrates and containers for catalyst |
| WO2017174016A1 (en) * | 2016-04-08 | 2017-10-12 | 华南理工大学 | Medical macromolecular microsphere adsorbent for blood perfusion apparatus and manufacturing method thereof |
| CN107519767A (en) * | 2017-09-25 | 2017-12-29 | 天津工业大学 | The method that the phase separation of inorganic salt solution coordinated regulation prepares Super-hydrophobic micropore film |
| CN108636307A (en) * | 2018-04-18 | 2018-10-12 | 天津大学 | The method that film coats crystal is prepared by crystallization in microcapsules |
| CN111844827A (en) * | 2020-07-23 | 2020-10-30 | 天津工业大学 | Preparation method of microfiber leather facing layer film with microporous channel |
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| US6387399B1 (en) * | 1994-12-02 | 2002-05-14 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Microencapsulated bioactive agents and method of making |
| US11278847B2 (en) * | 2019-07-30 | 2022-03-22 | NL Chemical Technology, Inc | Reverse osmosis membrane with hydrogel coating |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4793980A (en) * | 1978-09-21 | 1988-12-27 | Torobin Leonard B | Hollow porous microspheres as substrates and containers for catalyst |
| WO2017174016A1 (en) * | 2016-04-08 | 2017-10-12 | 华南理工大学 | Medical macromolecular microsphere adsorbent for blood perfusion apparatus and manufacturing method thereof |
| CN107519767A (en) * | 2017-09-25 | 2017-12-29 | 天津工业大学 | The method that the phase separation of inorganic salt solution coordinated regulation prepares Super-hydrophobic micropore film |
| CN108636307A (en) * | 2018-04-18 | 2018-10-12 | 天津大学 | The method that film coats crystal is prepared by crystallization in microcapsules |
| CN111844827A (en) * | 2020-07-23 | 2020-10-30 | 天津工业大学 | Preparation method of microfiber leather facing layer film with microporous channel |
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