CN112717712A - Acid-resistant nanofiltration membrane and preparation method and application thereof - Google Patents
Acid-resistant nanofiltration membrane and preparation method and application thereof Download PDFInfo
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- CN112717712A CN112717712A CN202011482126.9A CN202011482126A CN112717712A CN 112717712 A CN112717712 A CN 112717712A CN 202011482126 A CN202011482126 A CN 202011482126A CN 112717712 A CN112717712 A CN 112717712A
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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
- B01D69/02—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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
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- 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
Abstract
The invention provides an acid-resistant nanofiltration membrane and a preparation method and application thereof. The preparation method comprises the following steps: (1) impregnating the support membrane with an aqueous phase reactant solution, taking out the support membrane and removing the surface solution; (2) dipping the support membrane by using the oil phase reactant solution to carry out interfacial polymerization reaction, taking out the support membrane and removing the surface oil phase solution; (3) and (3) repeatedly carrying out the treatment of the step (1) and the treatment of the step (2) on the support membrane obtained in the step (2) to obtain the acid-resistant nanofiltration membrane. The acid-resistant nanofiltration membrane has better inorganic salt ion separation capacity, structural stability under an acidic condition and adjustable separation capacity.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and relates to an acid-resistant nanofiltration membrane as well as a preparation method and application thereof.
Background
Nanofiltration membrane separation is used as a novel green and efficient separation technology, and is widely applied to the fields of drinking water treatment, wastewater reclamation, micromolecule desalination, biological product decoloration and the like in recent years by means of better removal rate of multivalent inorganic salt ions and most organic matters. The interfacial polymerization polyamide nanofiltration membrane has become the most successful nanofiltration membrane for industrial application at present due to the advantages of simple preparation process, high permeation flux, stable structure, good pollution resistance and the like. However, with the continuous development of industry, the diversification and complication of the system to be separated require that the separation membrane not only has good separation selectivity, but also has certain structural stability, so as to maintain a long-term stable separation effect and good membrane life.
In the actual chemical process, the mixed strong acid type feed liquid to be treated is common, most of the current commercial polyamide nanofiltration membranes are prepared by interfacial polymerization reaction between polyamine and polyacyl chloride, and the polyamide structure of the polyamide nanofiltration membranes is easy to hydrolyze under the acidic condition, so that the structure is finally damaged. The preparation of the acid-resistant nanofiltration membrane is the most effective method for solving the problem, and most of the existing acid-resistant preparation technologies focus on the design of interfacial polymerization monomers to improve the stability under an acidic condition.
CN102120149A discloses a preparation method of an acid-resistant nanofiltration membrane, wherein an oil-phase reactant of the acid-resistant nanofiltration membrane is 1,3, 6-naphthalene trisulfonyl chloride, and the oil-phase reactant and polyamine form a polysulfonamide structure through interfacial polymerization reaction, so that a separation layer is improved. However, due to the lower reactivity of sulfonyl chloride monomer, the rejection rate of the prepared acid-resistant nanofiltration membrane on inorganic salt ions needs to be further improved.
CN107930412A discloses a preparation method of an acid-resistant poly (amide-triazine-amine) nanofiltration composite membrane, wherein the acid-resistant membrane takes cyanuric chloride and polyamine as raw materials, a poly (triazine) amine precursor is prepared through nucleophilic substitution reaction, and then the poly (triazine) amine precursor and polyacyl chloride undergo interfacial polymerization reaction to form the acid-resistant poly (amide-triazine-amine) nanofiltration composite membrane, and the membrane is suitable for a salt-water separation system, has good separation performance and good acid resistance. But the preparation method is complicated.
CN109999665A discloses a preparation method of a positively charged acid-resistant nanofiltration membrane, wherein the acid-resistant nanofiltration membrane forms a polyamide separation layer with a highly stable and strongly conjugated triazine structure through interfacial polymerization of polyethyleneimine and cyanuric chloride, has good acid resistance, and has a high rejection rate for magnesium chloride. However, the acid-resistant nanofiltration membrane organic phase reactant, namely the cyanuric chloride, has low reaction activity, requires that the concentration of an aqueous phase reactant is up to 15g/L, and has high polyethyleneimine price and high difficulty in industrial large-scale preparation.
Therefore, the development of the interfacial polymerization acid-resistant nanofiltration membrane with high conjugation stability, high crosslinking degree and adjustable separation capacity for improving the stability under acidic conditions and the separation effect of inorganic salts has important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an acid-resistant nanofiltration membrane and a preparation method and application thereof. The acid-resistant nanofiltration membrane has better inorganic salt ion separation capacity, structural stability under an acidic condition and adjustable separation capacity.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides an acid-resistant nanofiltration membrane comprising a support membrane and an active separation layer supported on the support membrane, the active separation layer comprising an interfacial polymerization product of an aqueous phase reactant and an oil phase reactant, the aqueous phase reactant comprising a sulfonamide monomer, an acid acceptor, and a surfactant.
The sulfonamide monomer contained in the acid-resistant nanofiltration membrane can beThe polysulfonamide structure is formed by the reactants participating in the interfacial polymerization reaction and the oil phase reactant, so that the separation layer prepared by the interfacial polymerization reaction has stronger conjugate stability; meanwhile, compared with the traditional polypiperazine amide structure, the S-O bond in the polysulfonamide structure has relatively weaker polarity, so that H in an acidic environment can be relieved+Attack of oxygen atoms in the separation layer.
In the present invention, the sulfonamide monomer includes an organic substance having at least one sulfonamide group.
Preferably, the sulfonamide monomer is sulfapyridine and/or 3-aminobenzenesulfonamide.
In the present invention, the acid acceptor includes any one of triethylamine, camphorsulfonic acid, ammonia water, pyridine, hydroxylamine, sodium hydroxide or potassium hydroxide or a combination of at least two thereof. Combinations of the at least two, such as triethylamine and camphorsulfonic acid, ammonia and pyridine, hydroxylamine and sodium hydroxide, potassium hydroxide, and the like.
In the present invention, the surfactant includes any one of or a combination of at least two of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, cetyltrimethyl ammonium bromide or tween 80. Combinations of the at least two, for example, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate, cetyltrimethyl ammonium bromide, tween 80, and the like.
In the present invention, the oil phase reactant comprises an acid chloride functional group-containing monomer.
Preferably, the monomer containing an acid chloride functional group is trimesoyl chloride.
In the invention, the support membrane is a porous ultrafiltration support membrane.
Preferably, the porous ultrafiltration support membrane has a molecular weight cut-off of 10000 to 100000Da, such as 10000Da, 30000Da, 50000Da, 80000Da or 100000 Da.
Preferably, the material of the porous ultrafiltration support membrane comprises any one or a combination of at least two of polyethylene, polyamide, polyimide, polyetherimide, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, polysulfone or polyethersulfone. Combinations of at least two of the foregoing, such as polyethylene and polyamide, polyimide and polyetherimide, polytetrafluoroethylene and polyvinylidene fluoride, and polysulfone, and the like.
In another aspect, the present invention provides a method for preparing an acid-resistant nanofiltration membrane as described above, comprising the steps of:
(1) impregnating the support membrane with an aqueous phase reactant solution, taking out the support membrane and removing the surface solution;
(2) dipping the support membrane by using the oil phase reactant solution to carry out interfacial polymerization reaction, taking out the support membrane and removing the surface oil phase solution;
(3) and (3) repeatedly carrying out the treatment of the step (1) and the treatment of the step (2) on the support membrane obtained in the step (2), repeating the treatment for at least 1 time, then heating the support membrane, and soaking the support membrane in deionized water to obtain the acid-resistant nanofiltration membrane.
In the invention, the sulfonamide monomer has good reaction activity, contains sulfur atoms with strong electron-withdrawing ability, and a polysulfonamide structure formed by participating in interfacial polymerization can effectively improve the conjugation stability of the active separation layer, thereby improving the hydrolysis resistance of the active separation layer under an acidic condition; meanwhile, through subsequent multiple interfacial polymerization reactions, the cross-linking degree of the active separation layer is increased, the service life of the membrane under an acidic condition can be greatly prolonged while the interception of high inorganic salt ions is ensured, and the acid-resistant nanofiltration membrane can realize effective interception of the salt ions under a strong acidic condition.
In the invention, the acid-resistant nanofiltration membrane is prepared by adopting a mode of preparing a composite membrane by multiple interfacial polymerization, and the interfacial polymerization reaction times, a support membrane, an active separation layer and sulfonamide monomers, acid receptors, surfactants and acyl chloride functional group monomers in the active separation layer are respectively designed and then coupled. The preparation method is easy to repeat and is beneficial to industrial large-scale preparation.
In order to stabilize the interfacial polymerization layer, it is necessary to remove the support film and the surface solution after the support film is impregnated with the aqueous phase and the interfacial polymerization reaction is performed by impregnating the support film with the oil phase. The heat treatment is to complete the interfacial polymerization reaction, thereby further improving the crosslinking degree of the active separation layer, and the soaking in deionized water is to hydrolyze the unreacted acyl chloride on the support membrane.
In the invention, the preparation method of the aqueous phase reactant solution in the step (1) is a physical blending method.
Preferably, the aqueous phase reactant solution of step (1) contains 0.1-1 g (0.1g, 0.3g, 0.5g, 0.8g or 1g, etc.) of sulfonamide monomer per 100 g.
Preferably, the aqueous reactant solution of step (1) contains 0.01 to 0.2g (e.g., 0.01g, 0.03g, 0.05g, 0.1g, 0.15g, 0.18g, or 0.2 g) of the acid acceptor per 100g of the aqueous reactant solution.
Preferably, the surfactant is contained in an amount of 0.01 to 0.2g (e.g., 0.01g, 0.03g, 0.05g, 0.1g, 0.15g, 0.18g, or 0.2 g) per 100g of the aqueous reactant solution in step (1).
Preferably, the pH of the aqueous phase reactant solution in the step (1) is 10-12, such as 10, 10.5, 11, 11.5 or 12.
Preferably, the time for immersing the support film in the aqueous reactant solution in step (1) is 1-60 min, such as 1min, 5min, 10min, 20min, 30min, 40min, 50min or 60min, preferably 1-20 min.
Preferably, the solvent of the oil phase reactant solution in the step (2) is n-hexane.
Preferably, the oil phase reactant solution of step (2) contains 0.1-2 g (e.g. 0.1g, 0.5g, 0.8g, 1g, 1.3g, 1.5g or 2g, etc.) trimesoyl chloride per 100 g.
Preferably, the time for performing the interfacial polymerization reaction in the step (2) is 10 to 300s, for example, 10s, 20s, 50s, 100s, 150s, 180s, 200s, 250s or 300s, etc., preferably 10 to 180 s.
Preferably, the repeating of step (3) for at least 1 time is repeated for 1-20 times, such as 1 time, 3 times, 5 times, 10 times, 15 times or 20 times, etc., preferably 1-10 times.
Preferably, the heat treatment in step (3) is performed by oven heating or hot plate heating.
Preferably, the temperature of the heat treatment in step (3) is 25 to 70 ℃, for example, 25 ℃, 30 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃.
Preferably, the time of the heat treatment in the step (3) is 5-120 min, such as 5min, 20min, 40min, 60min, 80min, 100min or 120 min.
Preferably, the deionized water soaking time in the step (3) is 2-24 h, such as 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h or 24 h.
As a preferred technical scheme of the invention, the preparation method specifically comprises the following steps:
(1) preparing an aqueous phase reactant solution containing a sulfonamide monomer, an acid receptor and a surfactant by adopting a physical blending method, wherein each 100g of the aqueous phase reactant solution contains 0.1-1 g of the sulfonamide monomer, 0.01-0.2 g of the acid receptor and 0.01-0.2 g of the surfactant, and the pH value of the solution is adjusted to 10-12;
(2) preparing an oil-phase reactant solution containing trimesoyl chloride by using normal hexane as a solvent, wherein each 100g of the oil-phase reactant solution contains 0.1-2 g of solute;
(3) cleaning the surface of the support film;
(4) soaking the support membrane with the aqueous phase reactant solution for 1-20 min, taking out the support membrane to remove the surface solution, soaking the support membrane with the oil phase reactant solution for 10-180 s to perform interfacial polymerization, taking out the support membrane and removing the surface oil phase solution;
(5) and (3) repeating the step (4) for 1-10 times, then carrying out heat treatment on the membrane at 25-70 ℃ in an oven or a heating plate mode for 5-120 min, and soaking the membrane in deionized water for 2-24 h to obtain the acid-resistant nanofiltration membrane.
By using the sulfonamide monomer to participate in multiple interfacial polymerization reactions, the service life of the membrane under acidic conditions is greatly prolonged while high inorganic salt ion interception is ensured, the acid-resistant nanofiltration membrane can effectively intercept salt ions under strong acidic conditions, and industrial application is met.
In another aspect, the invention provides an application of the acid-resistant nanofiltration membrane in acid wastewater reclamation, small molecule desalination or biological product decolorization.
Compared with the prior art, the invention has at least the following beneficial effects:
the sulfonamide monomer of the invention: on one hand, the method has good reaction activity, and can perform sufficient interfacial polymerization reaction with monomers containing acid chloride functional groups, so that the prepared active separation layer has better inorganic salt ion separation capacity (the retention rate of sodium sulfate is 86-99 percent, and the retention rate of sodium chloride is 47-85 percent); on the other hand, the polysulfonamide structure generated by the reaction of the sulfonamide monomer and the monomer containing the acyl chloride functional group can effectively improve the conjugated stability of the active separation layer and enhance the structural stability of the nanofiltration membrane under the extreme acidic condition (the retention rate of sodium sulfate after acid soaking is changed from-1.5% to-0.4%).
Meanwhile, the acid acceptor can effectively neutralize the by-product acid of the interfacial polymerization and promote the forward progress of the interfacial polymerization reaction, the surfactant can enhance the wettability of the interface, and the addition of the acid acceptor and the surfactant is beneficial to improving the crosslinking degree of the separation layer and the uniformity of the surface appearance.
Meanwhile, the subsequent multiple interfacial polymerization reaction steps can directly and orderly regulate and control the crosslinking degree of the active separation layer, and the separation selectivity of inorganic salt ions is improved.
In addition, the acid-resistant nanofiltration membrane adopts a mode of preparing a composite membrane by multiple interfacial polymerization, and the interfacial polymerization reaction times, the support membrane, the active separation layer and the sulfonamide monomer, the acid acceptor, the surfactant and the acyl chloride functional group monomer in the active separation layer are respectively designed and then coupled. The preparation method is easy to repeat and is beneficial to industrial large-scale production.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
In this embodiment, an acid-resistant nanofiltration membrane is provided, which includes a support membrane and an active separation layer supported on the support membrane, where the active separation layer includes an interfacial polymerization product of an aqueous phase reactant and an oil phase reactant, the aqueous phase reactant includes 3-aminobenzenesulfonamide, triethylamine, and sodium dodecyl sulfate, and the oil phase reactant includes trimesoyl chloride.
The preparation method comprises the following steps:
(1) preparing an aqueous phase reactant solution containing 3-aminobenzenesulfonamide, triethylamine and sodium dodecyl sulfate by adopting a physical blending method, so that every 100g of the aqueous phase reactant solution contains 0.2g of 3-aminobenzenesulfonamide, 0.2g of triethylamine and 0.2g of sodium dodecyl sulfate, and adjusting the pH value of the solution to be 11.5;
(2) preparing an oil-phase reactant solution containing trimesoyl chloride by using normal hexane as a solvent, so that 0.5g of solute is contained in every 100g of the oil-phase reactant solution;
(3) cleaning the surface of the polyether sulfone ultrafiltration membrane;
(4) impregnating the polyethersulfone ultrafiltration membrane with the aqueous phase reactant solution for 2min, taking out the ultrafiltration membrane to remove the surface solution, impregnating the ultrafiltration membrane with the oil phase reactant solution for 20s to perform interfacial polymerization reaction, taking out the ultrafiltration membrane and removing the surface oil phase solution;
(5) and (5) repeating the step (4), then carrying out heat treatment on the membrane at 70 ℃ for 10min in an oven or a heating plate mode, and soaking the membrane in deionized water for 24h to obtain the acid-resistant nanofiltration membrane.
Wherein the cut-off molecular weight of the polyethersulfone ultrafiltration membrane is 50000 Da.
Example 2
The acid-resistant nanofiltration membrane comprises a support membrane and an active separation layer loaded on the support membrane, wherein the active separation layer comprises an interfacial polymerization product of an aqueous phase reactant and an oil phase reactant, the aqueous phase reactant comprises sulfapyridine, triethylamine and sodium dodecyl sulfate, and the oil phase reactant comprises trimesoyl chloride.
The preparation method comprises the following steps:
(1) preparing an aqueous phase reactant solution containing sulfapyridine, triethylamine and sodium dodecyl sulfate by adopting a physical blending method, so that every 100g of the aqueous phase reactant solution contains 0.1g of sulfapyridine, 0.1g of triethylamine and 0.1g of sodium dodecyl sulfate, and adjusting the pH value of the solution to be 11;
(2) preparing an oil-phase reactant solution containing trimesoyl chloride by using normal hexane as a solvent, so that 0.25g of solute is contained in every 100g of the oil-phase reactant solution;
(3) cleaning the surface of the polyacrylonitrile ultrafiltration membrane;
(4) impregnating a polyacrylonitrile ultrafiltration membrane with the aqueous phase reactant solution for 1min, taking out the ultrafiltration membrane to remove the surface solution, impregnating the ultrafiltration membrane with the oil phase reactant solution for 60s to perform interfacial polymerization reaction, taking out the ultrafiltration membrane and removing the surface oil phase solution;
(5) and (5) repeating the step (4), then carrying out heat treatment on the membrane at 60 ℃ for 10min in an oven or a heating plate mode, and soaking the membrane in deionized water for 2h to obtain the acid-resistant nanofiltration membrane.
Wherein the molecular weight cut-off of the polyacrylonitrile ultrafiltration membrane is 20000 Da.
Example 3
In this embodiment, an acid-resistant nanofiltration membrane is provided, which includes a support membrane and an active separation layer supported on the support membrane, wherein the active separation layer includes an interfacial polymerization product of an aqueous phase reactant and an oil phase reactant, the aqueous phase reactant includes 3-aminobenzenesulfonamide, sodium hydroxide and sodium dodecylbenzenesulfonate, and the oil phase reactant includes trimesoyl chloride.
The preparation method comprises the following steps:
(1) preparing an aqueous phase reactant solution containing 3-aminobenzenesulfonamide, sodium hydroxide and sodium dodecyl benzene sulfonate by adopting a physical blending method, so that every 100g of the aqueous phase reactant solution contains 1g of 3-aminobenzenesulfonamide, 0.01g of sodium hydroxide and 0.05g of sodium dodecyl benzene sulfonate, and the pH value of the solution is adjusted to be 12;
(2) preparing an oil-phase reactant solution containing trimesoyl chloride by using normal hexane as a solvent, so that 0.1g of solute is contained in every 100g of the oil-phase reactant solution;
(3) cleaning the surface of the polyether sulfone ultrafiltration membrane;
(4) soaking the polyethersulfone ultrafiltration membrane in the aqueous phase reactant solution for 10min, taking out the ultrafiltration membrane to remove the surface solution, soaking the ultrafiltration membrane in the oil phase reactant solution for 10s to perform interfacial polymerization reaction, taking out the ultrafiltration membrane and removing the surface oil phase solution;
(5) and (5) repeating the step (4) for 7 times, then carrying out heat treatment on the membrane at 25 ℃ in an oven or a heating plate mode for 5min, and soaking the membrane in deionized water for 12h to obtain the acid-resistant nanofiltration membrane.
Wherein the molecular weight cut-off of the polyethersulfone ultrafiltration membrane is 10000 Da.
Example 4
In this embodiment, an acid-resistant nanofiltration membrane is provided, which comprises a support membrane and an active separation layer supported on the support membrane, wherein the active separation layer comprises an interfacial polymerization product of an aqueous phase reactant and an oil phase reactant, the aqueous phase reactant comprises sulfapyridine, sodium hydroxide and tween 80, and the oil phase reactant comprises trimesoyl chloride.
The preparation method comprises the following steps:
(1) preparing an aqueous phase reactant solution containing sulfapyridine, sodium hydroxide and tween 80 by adopting a physical blending method, so that every 100g of the aqueous phase reactant solution contains 0.5g of sulfapyridine, 0.1g of sodium hydroxide and 0.1g of tween 80, and adjusting the pH value of the solution to 10;
(2) preparing an oil-phase reactant solution containing trimesoyl chloride by using normal hexane as a solvent, so that each 100g of the oil-phase reactant solution contains 2g of solute;
(3) cleaning the surface of the polyacrylonitrile ultrafiltration membrane;
(4) impregnating a polyacrylonitrile ultrafiltration membrane with the aqueous phase reactant solution for 30min, taking out the ultrafiltration membrane to remove the surface solution, impregnating the ultrafiltration membrane with the oil phase reactant solution for 120s to perform interfacial polymerization reaction, taking out the ultrafiltration membrane and removing the surface oil phase solution;
(5) and (5) repeating the step (4) for 10 times, then carrying out heat treatment on the membrane at 50 ℃ for 60min in an oven or a heating plate mode, and soaking the membrane in deionized water for 10h to obtain the acid-resistant nanofiltration membrane.
Wherein the molecular weight cut-off of the polyacrylonitrile ultrafiltration membrane is 20000 Da.
Example 5
In this embodiment, an acid-resistant nanofiltration membrane is provided, which includes a support membrane and an active separation layer supported on the support membrane, where the active separation layer includes an interfacial polymerization product of an aqueous phase reactant and an oil phase reactant, the aqueous phase reactant includes 3-aminobenzenesulfonamide, ammonia water, and sodium dodecylbenzenesulfonate, and the oil phase reactant includes trimesoyl chloride.
The preparation method comprises the following steps:
(1) preparing an aqueous phase reactant solution containing 3-aminobenzenesulfonamide, ammonia water and sodium dodecyl benzene sulfonate by adopting a physical blending method, so that every 100g of the aqueous phase reactant solution contains 0.8g of 3-aminobenzenesulfonamide, 0.15g of ammonia water and 0.2g of sodium dodecyl benzene sulfonate, and the pH value of the solution is adjusted to be 11.5;
(2) preparing an oil-phase reactant solution containing trimesoyl chloride by using normal hexane as a solvent, so that 1g of solute is contained in every 100g of the oil-phase reactant solution;
(3) cleaning the surface of the polysulfone ultrafiltration membrane;
(4) soaking the polysulfone ultrafiltration membrane in the aqueous phase reactant solution for 60min, taking out the ultrafiltration membrane to remove the surface solution, soaking the ultrafiltration membrane in the oil phase reactant solution for 60s to perform interfacial polymerization reaction, taking out the ultrafiltration membrane and removing the surface oil phase solution;
(5) and (5) repeating the step (4) for 20 times, then carrying out heat treatment on the membrane at the temperature of 30 ℃ for 120min in an oven or a heating plate mode, and soaking the membrane in deionized water for 24h to obtain the acid-resistant nanofiltration membrane.
Wherein the cut-off molecular weight of the polysulfone ultrafiltration membrane is 100000 Da.
Example 6
The acid-resistant nanofiltration membrane comprises a support membrane and an active separation layer loaded on the support membrane, wherein the active separation layer comprises an interfacial polymerization product of an aqueous phase reactant and an oil phase reactant, the aqueous phase reactant comprises sulfapyridine, pyridine and sodium dodecyl benzene sulfonate, and the oil phase reactant comprises trimesoyl chloride.
The preparation method comprises the following steps:
(1) preparing an aqueous phase reactant solution containing sulfapyridine, pyridine and sodium dodecyl benzene sulfonate by adopting a physical blending method, so that every 100g of the aqueous phase reactant solution contains 0.2g of sulfapyridine, 0.2g of pyridine and 0.15g of sodium dodecyl benzene sulfonate, and adjusting the pH value of the solution to 10;
(2) preparing an oil-phase reactant solution containing trimesoyl chloride by using normal hexane as a solvent, so that 1.5g of solute is contained in every 100g of the oil-phase reactant solution;
(3) cleaning the surface of the polysulfone ultrafiltration membrane;
(4) impregnating the polysulfone ultrafiltration membrane with the aqueous phase reactant solution for 3min, taking out the ultrafiltration membrane to remove the surface solution, impregnating the ultrafiltration membrane with the oil phase reactant solution for 180s to perform interfacial polymerization reaction, taking out the ultrafiltration membrane and removing the surface oil phase solution;
(5) and (5) repeating the step (4) for 1 time, then carrying out heat treatment on the membrane at 40 ℃ for 60min in an oven or a heating plate mode, and soaking the membrane in deionized water for 24h to obtain the acid-resistant nanofiltration membrane.
Wherein the cut-off molecular weight of the polysulfone ultrafiltration membrane is 50000 Da.
Comparative example 1
The comparison example provides an acid-resistant nanofiltration membrane, and an NF 10 polyamide membrane with the molecular weight cutoff of less than 500Da is directly used as the acid-resistant nanofiltration membrane.
Comparative example 2
This comparative example differs from example 1 only in that 3-aminobenzenesulfonamide in the starting material was replaced with the same amount of p-aminobenzenesulfonamide.
Comparative example 3
This comparative example differs from example 1 only in that triethylamine in the starting materials was replaced by the same amount of 3-aminobenzenesulfonamide.
Comparative example 4
This comparative example differs from example 1 only in that step (5) is not included in the production process.
The acid-resistant nanofiltration membranes of examples 1 to 6 and comparative examples 1 to 4 were tested for water flux, sodium sulfate and sodium chloride rejection at 25 ℃, and for the change in sodium sulfate rejection after static immersion of each acid-resistant nanofiltration membrane in a sulfuric acid solution with a mass fraction of 20% at 25 ℃ for 7 days. The test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the acid-resistant nanofiltration membranes prepared in examples 1 to 6 have high inorganic salt ion separation capacity (sodium sulfate rejection rate: 86% to 99%, sodium chloride rejection rate: 47% to 85%), and structural stability under acidic conditions (sodium sulfate rejection rate change after acid soaking: 1.5% to 0.4%).
Compared with the polyamide membrane NF 10 membrane in the comparative example 1, the acid-resistant nanofiltration membrane prepared in the examples 1 to 6 has more stable separation performance under an acidic condition, namely, the acid-resistant nanofiltration membrane can still have higher flux and stable sodium sulfate rejection rate under long-time operation in a strong acid environment.
Compared with the comparative example 2, the acid-resistant nanofiltration membrane prepared in the example 1 has a higher rejection rate of inorganic salts, and the change of the rejection rate of sodium sulfate after acid soaking is smaller, so that the selected sulfonamide monomer has higher reactivity compared with other sulfonamide monomers, and the formation of an active separation layer with a more complete structure is facilitated.
Compared with a comparative example 3, the acid-resistant nanofiltration membrane prepared in the example 1 has higher flux and inorganic salt rejection rate, and the acid acceptor added in the water-phase reactant is proved to be helpful for neutralizing the by-product acid in the interfacial reaction process, so that the reaction rate of the interfacial polymerization reaction is improved, and an active separation layer with a more ordered structure is further formed.
Compared with the comparative example 4, the acid-resistant nanofiltration membrane prepared in example 1 has a high rejection rate of inorganic salts, and the change of the rejection rate of sodium sulfate after acid soaking is small, so that multiple times of interfacial polymerization can effectively improve the rejection performance and acid resistance of the acid-resistant nanofiltration membrane on inorganic salt ions.
The applicant states that the acid-resistant nanofiltration membrane and the preparation method thereof according to the present invention are described in the above examples, but the present invention is not limited to the above examples, which means that the present invention is not necessarily dependent on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (10)
1. An acid-resistant nanofiltration membrane, which comprises a support membrane and an active separation layer loaded on the support membrane, wherein the active separation layer comprises an interfacial polymerization product of an aqueous phase reactant and an oil phase reactant, and the aqueous phase reactant comprises a sulfonamide monomer, an acid acceptor and a surfactant.
2. Acid-resistant nanofiltration membrane according to claim 1, wherein the sulfonamide monomers comprise organic materials comprising at least one sulfonamide group;
preferably, the sulfonamide monomer is sulfapyridine and/or 3-aminobenzenesulfonamide.
3. An acid-resistant nanofiltration membrane according to claim 1 or 2, wherein the acid acceptor comprises any one or a combination of at least two of triethylamine, camphorsulfonic acid, ammonia water, pyridine, hydroxylamine, sodium hydroxide or potassium hydroxide.
4. An acid-resistant nanofiltration membrane according to any one of claims 1 to 3, wherein the surfactant comprises any one or a combination of at least two of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, cetyltrimethyl ammonium bromide or tween 80.
5. The acid-resistant nanofiltration membrane according to any one of claims 1 to 4, wherein the oil-phase reactant comprises an acid chloride functional group-containing monomer;
preferably, the monomer containing an acid chloride functional group is trimesoyl chloride.
6. Acid-resistant nanofiltration membrane according to any one of claims 1 to 5, wherein the support membrane is a porous ultrafiltration support membrane;
preferably, the molecular weight cut-off of the porous ultrafiltration support membrane is 10000-100000 Da;
preferably, the material of the porous ultrafiltration support membrane comprises any one or a combination of at least two of polyethylene, polyamide, polyimide, polyetherimide, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, polysulfone or polyethersulfone.
7. The method for preparing an acid-resistant nanofiltration membrane according to any one of claims 1 to 6, wherein the method comprises the following steps:
(1) impregnating the support membrane with an aqueous phase reactant solution, taking out the support membrane and removing the surface solution;
(2) dipping the support membrane by using the oil phase reactant solution to carry out interfacial polymerization reaction, taking out the support membrane and removing the surface oil phase solution;
(3) and (3) repeatedly carrying out the treatment of the step (1) and the treatment of the step (2) on the support membrane obtained in the step (2), repeating the treatment for at least 1 time, then heating the support membrane, and soaking the support membrane in deionized water to obtain the acid-resistant nanofiltration membrane.
8. The method for preparing an acid-resistant nanofiltration membrane according to claim 7, wherein the aqueous-phase reactant solution prepared in step (1) is prepared by a physical blending method;
preferably, every 100g of the aqueous phase reactant solution in the step (1) contains 0.1-1 g of sulfonamide monomer;
preferably, the aqueous phase reactant solution in step (1) contains 0.01-0.2 g of acid acceptor per 100 g;
preferably, every 100g of the aqueous phase reactant solution in the step (1) contains 0.01-0.2 g of surfactant;
preferably, the pH value of the aqueous phase reactant solution in the step (1) is 10-12;
preferably, the time for soaking the support film in the aqueous phase reactant solution in the step (1) is 1-60 min, preferably 1-20 min;
preferably, the solvent of the oil-phase reactant solution in the step (2) is n-hexane;
preferably, the oil phase reactant solution in the step (2) contains 0.1-2 g of trimesoyl chloride per 100g of the oil phase reactant solution;
preferably, the time for carrying out the interfacial polymerization reaction in the step (2) is 10-300 s, preferably 10-180 s;
preferably, the repeating of the step (3) for at least 1 time is repeated for 1 to 20 times, preferably 1 to 10 times;
preferably, the heat treatment in step (3) is performed by oven heating or hot plate heating;
preferably, the temperature of the heat treatment in the step (3) is 25-70 ℃;
preferably, the time of the heat treatment in the step (3) is 5-120 min.
Preferably, the deionized water soaking time in the step (3) is 2-24 h.
9. The method for preparing an acid-resistant nanofiltration membrane according to claim 7 or 8, wherein the method comprises the following steps:
(1) preparing an aqueous phase reactant solution containing a sulfonamide monomer, an acid receptor and a surfactant by adopting a physical blending method, wherein each 100g of the aqueous phase reactant solution contains 0.1-1 g of the sulfonamide monomer, 0.01-0.2 g of the acid receptor and 0.01-0.2 g of the surfactant, and the pH value of the solution is adjusted to 10-12;
(2) preparing an oil-phase reactant solution containing trimesoyl chloride by using normal hexane as a solvent, wherein each 100g of the oil-phase reactant solution contains 0.1-2 g of solute;
(3) cleaning the surface of the support film;
(4) soaking the support membrane with the aqueous phase reactant solution for 1-20 min, taking out the support membrane to remove the surface solution, soaking the support membrane with the oil phase reactant solution for 10-180 s to perform interfacial polymerization, taking out the support membrane and removing the surface oil phase solution;
(5) and (3) repeating the step (4) for 1-10 times, then carrying out heat treatment on the membrane at 25-70 ℃ in an oven or a heating plate mode for 5-120 min, and soaking the membrane in deionized water for 2-24 h to obtain the acid-resistant nanofiltration membrane.
10. The application of the acid-resistant nanofiltration membrane of any one of claims 1 to 6 in recycling of acidic wastewater, small molecule desalination or decolorization of biological products.
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