CN114797490A - Preparation method of high-selectivity separation membrane for separating anionic salt - Google Patents
Preparation method of high-selectivity separation membrane for separating anionic salt Download PDFInfo
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- CN114797490A CN114797490A CN202210776053.7A CN202210776053A CN114797490A CN 114797490 A CN114797490 A CN 114797490A CN 202210776053 A CN202210776053 A CN 202210776053A CN 114797490 A CN114797490 A CN 114797490A
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- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- 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
- B01D69/10—Supported membranes; Membrane supports
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
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Abstract
The invention discloses a preparation method of a high-selectivity separation membrane for separating anionic salts, which comprises the following steps of (1) dissolving a surfactant and a porous organic molecular cage in water to prepare a host-guest solution, stirring for 2-10 hours at the stirring temperature of 30-50 ℃, centrifuging, and washing to obtain a supramolecular complex of the surfactant and the porous organic molecular cage; (2) mixing the supermolecule complex, the acid absorbent and the balance of water to prepare an aqueous solution; (3) contacting the support membrane with an aqueous solution to obtain the support membrane adsorbed with the supramolecular complex; (4) the support film absorbed with supermolecular complex contacts with organic phase solution containing binary or above acyl chloride molecules to generate interfacial polymerization reaction. The invention adopts the preparation method of the high-selectivity separation membrane for separating the anion salt with the structure, so as to solve the problem that the monovalent/divalent anion salt of the traditional nanofiltration membrane material has low selectivity and is difficult to meet the requirement of industrial salt purity.
Description
Technical Field
The invention relates to the technical field of nanofiltration membrane separation, in particular to a preparation method of a high-selectivity separation membrane for separating anionic salts.
Background
NaCl/Na 2 SO 4 The separation of the inorganic salt mixture solution has great application requirements in the fields of strong brine recycling, chlor-alkali brine denitration, water softening, harmful ion removal and the like. The concentrated water of the seawater desalination plant, the outlet water of the sewage treatment plant, the salt-containing wastewater of the mineral exploitation and processing industry and the like have NaCl, NaCl/Na as main components 2 SO 4 And the salt is low in industrial application value, and monovalent/divalent salt separation is needed to improve the salt purity of the product. The wastewater of the chlor-alkali production industry contains high-concentration Na + 、Cl - And SO 4 2- Ions, adopting reasonable treatment technology to recover Na 2 SO 4 And water, the resource recycling can be realized.
The nanofiltration membrane separation technology is a new monovalent/divalent inorganic salt solution separation method, and has wide application potential in economy and operability. The preparation of the high-performance nanofiltration membrane is the key for improving the separation efficiency of the monovalent/divalent inorganic salts. The preparation process of the nanofiltration membrane mainly comprises an interface polymerization method, a layer-by-layer self-assembly method and a phase inversion method. The commercial nanofiltration membrane is a polyamide membrane prepared by interfacial polymerization of piperazine and trimesoyl chloride, has high rejection rate on divalent salt, but the selectivity of monovalent/divalent inorganic salt of the nanofiltration membrane cannot meet the requirement of industrial salt separation. Therefore, to be able to realize NaCl/Na 2 SO 4 The efficient and precise separation of the monovalent salt requires the development of a high-selectivity nanofiltration membrane with monovalent salt channels.
Disclosure of Invention
The invention aims to provide a preparation method of a high-selectivity separation membrane for separating anion salts, so as to solve the problems that the monovalent/divalent anion salts of the traditional nanofiltration membrane material have low selectivity and are difficult to meet the requirement of industrial salt purity.
In order to achieve the above objects, the present invention provides a method for preparing a high selectivity separation membrane for separating an anion salt, comprising the steps of:
(1) dissolving a surfactant and a porous organic molecular cage in water to prepare a host-guest solution, stirring for 2-10 hours at a stirring temperature of 30-50 ℃, centrifuging, and washing to obtain a supramolecular complex of the surfactant and the porous organic molecular cage; the mass fraction of the porous organic molecular cages in the host-guest solution is 0.1-2%, and the molar ratio of the porous organic molecular cages to the surfactant is 1: 1-1: 10;
(2) mixing 0.1-2% of the supramolecular complex, 0.1-2% of an acid absorbent and the balance of water according to mass fraction to prepare an aqueous solution;
(3) contacting the support membrane with an aqueous solution to obtain the support membrane adsorbed with the supramolecular complex;
(4) contacting the support membrane adsorbed with the supermolecule complex with an organic phase solution containing binary and above acyl chloride molecules to generate interfacial polymerization reaction; the organic phase solution comprises 0.1-2% of organic phase monomer and the balance of organic solvent by mass;
(5) and (3) placing the membrane obtained in the step into a drying oven for heat treatment to obtain the monovalent/divalent inorganic salt separation membrane.
Preferably, the surfactant is selected from one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, tween 20, dodecyl trimethyl ammonium bromide and hexadecyl trimethyl ammonium bromide.
More preferably, the surfactant is one or more of sodium dodecyl sulfate and dodecyl trimethyl ammonium bromide.
Preferably, the porous organic molecular cage is prepared from 1,3, 5-benzenetricarboxylic aldehyde and 1, 2-cyclohexanediamine through a dehydration condensation and unsaturated bond addition reaction method, is one or more of RCC1, RCC2, RCC3 and RCC4, and has a window pore diameter of 2-10A.
Preferably, the support membrane is selected from polymer porous membranes with the molecular weight cutoff of 10 kDa to 50 kDa.
Preferably, the material of the polymer porous membrane is one or more of polyethylene, polypropylene, polyvinylidene fluoride, polyamide, polyacrylonitrile, polysulfone, polyethersulfone, polyimide and polytetrafluoroethylene.
Preferably, the acid absorbent is selected from one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate.
More preferably, the acid absorbent is one or more of sodium carbonate and sodium bicarbonate.
Preferably, the di-and above-mentioned acyl chloride molecules are selected from one or more of 1,3, 5-benzene tri-formyl chloride, suberoyl malonyl chloride, glutaryl chloride, terephthaloyl chloride, 1, 7-pimeloyl chloride, sebacoyl dichloride, adipoyl chloride, sebacoyl chloride, azelaioyl chloride, 1, 3-benzene disulfonyl chloride, 4 '-biphenyl disulfonyl chloride, 4' -oxybis (benzoyl chloride) isophthaloyl chloride.
More preferably, the di-and poly-acyl chloride molecules are selected from one or more of 1, 3-benzene disulfonyl chloride and terephthaloyl chloride.
Preferably, the organic solvent is selected from one or more of n-hexane, n-heptane, isohexane, cyclohexane, cycloheptane and isoheptane.
More preferably, the organic solvent is selected from one or more of n-hexane and n-heptane.
Preferably, in the step (3), the contact operation of the support membrane and the aqueous solution is soaking or dipping, the contact time is 1-10 min, and the temperature of the aqueous solution is 15-40 ℃.
Preferably, in the step (4), the contact operation is soaking or dipping, the contact time is 1-10 min, and the temperature of the organic phase mixed solution is 15-40 ℃.
The mechanism of the invention is as follows: the surfactant in the host-guest solution can replace high-energy water molecules in the inner cavity of the porous organic molecular cage through hydrophobic interaction to form a supramolecular complex with host-guest interaction, so that the water solubility and the dispersibility of RCC3 are improved, and the diffusion of a water phase monomer RCC3@ DTAB to a phase interface is promoted. Furthermore, amino groups of a porous organic molecular cage in the supramolecular complex and acyl chloride groups of binary and above acyl chloride molecules form a supramolecular separation membrane with an ordered, porous and topological structure through interfacial polymerization reaction. Wherein, is porousThe window diameter of the organic molecular cage can exert the transmission channel of monovalent ions and water molecules and exert NaCl/Na 2 SO 4 The function of selective separation. The surface of the supermolecular separation membrane can reject hydrated ions with larger radius and higher hydration energy and Na through the pore diameter of the separation membrane + And Cl - Equivalent ratio of monovalent hydrated ions to SO 4 2- And Mg 2+ The isodivalent hydrated ions have larger hydrated ion radius and more stable hydrated layer structure, the hydrated layer is not easy to fall off during transmembrane transmission, the steric hindrance is relatively large, and the membrane channel only allows water molecules and monovalent ions (Na) + And Cl - ) And (4) permeating. Therefore, the supramolecular separation membrane of the present invention has supramolecular channels for efficient separation of monovalent/divalent salts, thereby having high permeation flux and monovalent/divalent salt selectivity.
The type and concentration of the porous organic molecular cage, the type and concentration of the surfactant, and the type and concentration of the binary and higher acyl chloride molecules are related to the structure of the supramolecular membrane formed. The pH value of the aqueous phase solution can be adjusted by adding the acid acceptor, and the polymerization reaction of the porous organic molecular cage and binary and above acyl chloride molecules is promoted. The prepared separation membrane has negative charge on the surface and is used for anion (Cl) - 、SO 4 2- ) Has strong repulsive effect, and can promote the separation of monovalent/divalent anion salt (NaCl/Na) 2 SO 4 Etc.). The electrostatic repulsion strength depends mainly on the total amount of charge carried by the ions. With Cl - Equivalent monovalent hydrated ion phase ratio, SO 4 2- The plasma carries more charge and therefore has greater electrostatic repulsion. Thus, Na of the separation membrane 2 SO 4 The retention rate is higher than NaCl.
Therefore, the invention adopts the NaCl/Na with the structure 2 SO 4 The preparation method of the high-selectivity separation membrane has at least one or part of the following beneficial effects:
（1）NaCl/Na 2 SO 4 the separation layer of the high-selectivity separation membrane is stable and firm, has large permeation flux and good long-term operation stability;
（2）NaCl/Na 2 SO 4 the selectivity is high, and the method can be applied to the reuse of strong brine, the denitration of chlor-alkali brine, the softening of water and the removal of harmful ions;
（3）NaCl/Na 2 SO 4 the preparation method with high selectivity has the advantages of simple process, mild preparation conditions, wide application range, easy amplification and popularization and easy realization of industrial production.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a scanning electron microscope image of the surface of a support film in example 1 of the present invention;
FIG. 2 shows NaCl/Na in example 1 of the present invention 2 SO 4 Scanning electron microscope images of the surface of the high selectivity separation membrane;
FIG. 3 shows NaCl/Na in example 1 of the present invention 2 SO 4 Scanning electron microscope image of the cross section of the high selectivity separation membrane.
Detailed Description
The present invention will be further described below, and it should be noted that the present embodiment is based on the technical solution, and a detailed implementation manner and a specific operation process are provided, but the present invention is not limited to the present embodiment.
The materials used in the present invention: in the present invention and the following examples, all the raw materials may be commercially available without any particular limitation.
The separation and selectivity parameters of the membrane are mainly determined by the permeation flux: (P) Retention rate: (R) And optionally (α) And (4) forming. Permeate flux: (P) The volume of solution permeated in unit time, unit pressure and unit membrane area is calculated according to the following formula:
wherein the content of the first and second substances,P(unit: L.m) -2 ·h -1 ·bar -1 ) Is the permeation flux of the solution and is,V'(unit: L) is the volume of permeate collected over a period of time,A(unit: m) 2 ) Is the effective filtration area of the membrane,Δt(unit: h) is the permeation time,ΔP(unit: bar) is the transmembrane pressure.
Retention rate: (R) The degree of interception of inorganic salt in solution by a separation membrane is obtained by the salt concentration of feed liquid and penetrating fluid, and the calculation formula is as follows:
wherein the content of the first and second substances,C p (unit: g. L) -1 ) Is the concentration of the permeate liquid,C f (unit: g. L) -1 ) Is the concentration of the raw material liquid.
Selectivity (α) The selective capability of the separation membrane to the monovalent and divalent mixed salt is obtained by the rejection rate of the monovalent and divalent ions, and the calculation formula is as follows:
wherein the content of the first and second substances,R m (unit:%) is the rejection of monovalent salts;R d (unit:%) is the retention of the divalent salt.
The salt concentration in the rejection test was 1000 mg.L -1 NaCl or 1000 mg. L -1 Na 2 SO 4 . NaCl/Na in the selectivity test 2 SO 4 The concentration of the mixed salt is 2000 mg.L -1 And the monovalent/divalent ion concentration ratio is 1: 1. The monovalent or divalent ion concentration was measured by inductively coupled plasma emission spectroscopy (ICP-OES, VISTA-MPX, Varian).
Preparation of porous organic molecular cage RCC 3:
(1) 0.5 g of 1,3, 5-benzenetricarboxylic acid was weighed out and dissolved in 10 mL of dichloromethane, and labeled as solution A. 0.5 g of 1, 2-cyclohexanediamine was weighed out and dissolved in 10 mL of dichloromethane and labeled as solution B. The solution B was added to the solution A, and 10. mu.L of trifluoroacetic acid was added to promote the formation of imine bonds. After stirring for 7 days, the white precipitate was collected, washed and dried to obtain a white powder.
(2) The white powder was dissolved in 25 mL dichloromethane and methanol solution (V: V =1: 1), 0.5 g sodium borohydride was added, stirred at room temperature for 15 h, 1 mL deionized water was added, and stirred for another 9 h. Collecting a sample, and performing rotary evaporation, washing and drying to obtain the porous organic molecular cage powder.
(3) Weighing 100 g of molecular cage powder, dissolving in 10 mL of acetone, standing for 24 h, centrifuging to collect the sample, placing into 10 mL of a mixed solution of dichloromethane and ethanol (vol: vol =1: 1), adding 0.1 mL of deionized water, stirring for 48 h, and removing the solvent to obtain purified RCC3 particles for later use.
Example 1
Preparing a sodium dodecyl trimethyl benzene sulfonate aqueous solution containing 0.1% of porous organic molecular cage RCC3 and 0.1% of RCC3 in a molar ratio of 1:1 (mol: mol), and stirring for 2 hours at 30 ℃; 0.4% sodium carbonate was added as an aqueous mixture. An n-heptane solution containing 0.5% of terephthaloyl chloride was prepared as an organic phase mixture. Firstly, placing the water phase mixed solution on the surface of a polysulfone support membrane, adsorbing for 10 min at 30 ℃, removing the redundant solution, then placing the organic phase mixed solution on the surface of the membrane, reacting for 1 min, removing the redundant solution, washing away unreacted monomers by using normal hexane, then placing the membrane in a forced air drying oven at 80 ℃ for drying for 10 min, and storing the prepared separation membrane in deionized water to be further tested for the separation performance.
Tests show that the separation membrane has NaCl rejection rate of 20% and Na rejection rate 2 SO 4 The rejection rate of the sodium chloride is 98 percent, and the NaCl/Na content is 2 SO 4 Selectivity is 42, water permeation flux is 14 L.m -2 ·h -1 ·bar -1 。
Example 2
Preparing an aqueous solution containing 1% of porous organic molecular cage RCC4, sodium dodecyl sulfate and 0.4% of sodium bicarbonate, wherein the molar ratio of the sodium dodecyl sulfate to the 1% RCC4 is 1:4 (mol: mol), and stirring the aqueous solution at 50 ℃ for 8 hours; then adding the mixture to obtain a water phase mixed solution. An n-hexane solution containing 1.2% of 1, 3-benzenedisulfonyl chloride was prepared as an organic phase mixed solution. Firstly, placing the water phase mixed solution on the surface of a polyamide support membrane, adsorbing for 5 min at 50 ℃, removing the redundant solution, then placing the organic phase mixed solution on the surface of the membrane, reacting for 9 min, removing the redundant solution, washing away unreacted monomers by using normal hexane, then placing the membrane in a forced air drying oven at 80 ℃ for drying for 10 min, and storing the prepared separation membrane in deionized water to be further tested for the separation performance.
Tests show that the rejection rate of the separation membrane to NaCl is 15%, and the rejection rate to Na 2 SO 4 The rejection rate of (A) is 95%, NaCl/Na 2 SO 4 Selectivity is 20, water permeation flux is 25 L.m -2 ·h -1 ·bar -1 。
Example 3
Preparing sodium dodecyl sulfate containing 1.4% of porous organic molecular cage RCC2 and 1.4% of RCC2 in a molar ratio of 1:6 (mol: mol), and stirring for 4 hours at 40 ℃; then, 0.4% aqueous sodium hydroxide solution was added as an aqueous mixture. An n-heptane solution containing 0.5% of 1, 3-benzenedisulfonyl chloride was prepared as an organic phase mixture. Firstly, placing the water phase mixed solution on the surface of a polyimide support membrane, adsorbing for 3 min at 40 ℃, removing the redundant solution, then placing the organic phase mixed solution on the surface of the membrane, reacting for 7 min, removing the redundant solution, washing away unreacted monomers by using normal hexane, then placing the membrane in a forced air drying oven at 80 ℃ for drying for 10 min, and storing the prepared separation membrane in deionized water to be further tested for separation performance.
Tests show that the separation membrane has NaCl rejection rate of 30% and Na rejection rate 2 SO 4 The rejection rate of (A) is-99%, NaCl/Na 2 SO 4 Selectivity is 47, water permeation flux is 15 L.m -2 ·h -1 ·bar -1 。
Comparative example
The aqueous mixture of this comparative example contained no porous molecular cages, as in example 1.
Tests show that the separation membrane has a NaCl rejection rate of 10% and a Na rejection rate 2 SO 4 The rejection rate of (A) is 65%, NaCl/Na 2 SO 4 Selectivity is 17, water permeation flux is 4 L.m -2 ·h -1 ·bar -1 。
As can be seen from the results of comparing example 1 with the comparative example, example 1 was conducted for NaCl and Na 2 SO 4 The retention rate of NaCl/Na is greatly different 2 SO 4 The selectivity is high, the water permeation flux of example 1 is far greater than that of the comparative example, which shows that the comparative example does not add an organic porous molecular cage in the reaction process of an organic monomer and an aqueous phase monomer, the organic monomer and the aqueous phase monomer directly undergo a polymerization reaction, and water molecules and monovalent ion channels with ordered, porous and topological structures cannot be formed, so that the high water permeation flux and NaCl/Na are difficult to obtain 2 SO 4 High selectivity separation membranes.
The separation membrane obtained in example 1 was subjected to a long-term stability test, and the water permeation flux and NaCl/Na of the membrane were measured by a continuous separation test for 72 hours 2 SO 4 The selectivity was essentially unchanged, indicating that NaCl/Na was produced 2 SO 4 The separation membrane has good long-term stability. Scanning Electron microscope was used to obtain highly selective NaCl/Na solution in example 1 2 SO 4 The separation membrane is characterized, fig. 1 shows the surface morphology of the support membrane, and as shown in fig. 2 and fig. 3 shows the surface morphology and the cross-sectional morphology of the obtained membrane, it can be known through analysis that the surface of the separation membrane is smooth, and the attached particles are also small, which shows that the RCC3 supramolecules complexed by the surfactant exhibit better dispersibility in the aqueous solution, and the cross-sectional diagram shows that the separation membrane exhibits a selective layer thickness of about 100 nm. The appearance change of the surface and the section is mainly caused by that the introduction of DTAB improves the dispersity of RCC3 molecules in aqueous solution and promotes the interfacial polymerization reaction between water/organic phase monomers.
Therefore, the invention adopts the NaCl/Na with high selectivity of the structure 2 SO 4 The preparation method of the separation membrane has the advantages of simple preparation method, mild conditions, wide application range, easy amplification and realization of industrial production, and the prepared high-selectivity NaCl/Na 2 SO 4 The separation layer of the separation membrane has strong firmness, large permeation flux and good long-term operation stability.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.
Claims (10)
1. A method for preparing a high-selectivity separation membrane for separating anionic salts is characterized by comprising the following steps:
(1) dissolving a surfactant and a porous organic molecular cage in water to prepare a host-guest solution, stirring for 2-10 hours at a stirring temperature of 30-50 ℃, centrifuging, and washing to obtain a supramolecular complex of the surfactant and the porous organic molecular cage; the mass fraction of the porous organic molecular cages in the host-guest solution is 0.1-2%, and the molar ratio of the porous organic molecular cages to the surfactant is 1: 1-1: 10;
(2) mixing 0.1-2% of the supramolecular complex, 0.1-2% of an acid absorbent and the balance of water according to mass fraction to prepare an aqueous solution;
(3) contacting the support membrane with an aqueous solution to obtain the support membrane adsorbed with the supramolecular complex;
(4) contacting the support membrane adsorbed with the supermolecule complex with an organic phase solution containing binary and above acyl chloride molecules to generate interfacial polymerization reaction; the organic phase solution comprises 0.1-2% of organic phase monomer and the balance of organic solvent according to mass fraction;
(5) and (3) placing the membrane obtained in the step into a drying oven for heat treatment to obtain the monovalent/divalent inorganic salt separation membrane.
2. The method for preparing a high selectivity separation membrane for separating anionic salts according to claim 1, wherein: the surfactant is selected from one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, tween 20, dodecyl trimethyl ammonium bromide and hexadecyl trimethyl ammonium bromide.
3. The method for preparing a high selectivity separation membrane for separating anionic salts according to claim 1, wherein: the porous organic molecular cage is prepared from 1,3, 5-benzenetricarboxylic aldehyde and 1, 2-cyclohexanediamine by a dehydration condensation and unsaturated bond addition reaction method.
4. The method for preparing a high selectivity separation membrane for separating anionic salts according to claim 1, wherein: the support membrane is selected from a polymer porous membrane with the molecular weight cutoff of 10-50 kDa.
5. The method for preparing a high selectivity separation membrane for separating anionic salts according to claim 4, wherein: the material of the polymer porous membrane is one of polyethylene, polypropylene, polyvinylidene fluoride, polyamide, polyacrylonitrile, polysulfone, polyethersulfone, polyimide and polytetrafluoroethylene.
6. The method for preparing a high selectivity separation membrane for separating anionic salts according to claim 1, wherein: the acid absorbent is one or more selected from sodium hydroxide, sodium carbonate and sodium bicarbonate.
7. The method for preparing a high selectivity separation membrane for separating anionic salts according to claim 1, wherein: the binary and above acyl chloride molecules are selected from one or more of 1,3, 5-benzene trimethyl acyl chloride, suberoyl malonyl chloride, glutaryl chloride, terephthaloyl chloride, 1, 7-pimeloyl chloride, sebacoyl dichloride, adipoyl chloride, sebacoyl chloride, azelaioyl chloride, 1, 3-benzene disulfonyl chloride, 4 '-biphenyl disulfonyl chloride and 4,4' -oxydi (benzoyl chloride) isophthaloyl chloride.
8. The method for preparing a high selectivity separation membrane for separating anionic salts according to claim 1, wherein: the organic solvent is selected from one or more of n-hexane, n-heptane, isohexane, cyclohexane, cycloheptane and isoheptane.
9. The method for preparing a high selectivity separation membrane for separating anionic salts according to claim 1, wherein: in the step (3), the contact operation of the support membrane and the aqueous phase solution is soaking or dipping, the contact time is 1-10 min, and the temperature of the aqueous phase solution is 15-40 ℃.
10. The method for preparing a high selectivity separation membrane for separating anionic salts according to claim 1, wherein: in the step (4), the contact operation is soaking or dipping, the contact time is 1-10 min, and the temperature of the organic phase mixed solution is 15-40 ℃.
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| CN115400613A (en) * | 2022-10-24 | 2022-11-29 | 天津大学 | Gas separation membrane with high carbon dioxide permeation rate and preparation method thereof |
| CN115400613B (en) * | 2022-10-24 | 2023-01-17 | 天津大学 | Gas separation membrane with high carbon dioxide permeation rate and preparation method thereof |
| CN115738742A (en) * | 2022-12-05 | 2023-03-07 | 蓝星（杭州）膜工业有限公司 | Salt lake lithium-extracting charged positive membrane and preparation method thereof |
| CN115738742B (en) * | 2022-12-05 | 2023-06-13 | 蓝星（杭州）膜工业有限公司 | Positive charged membrane for extracting lithium from salt lake and preparation method thereof |
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