WO2023092781A1 - 反渗透膜的制备方法和由其制备的反渗透膜 - Google Patents

反渗透膜的制备方法和由其制备的反渗透膜 Download PDF

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WO2023092781A1
WO2023092781A1 PCT/CN2021/140512 CN2021140512W WO2023092781A1 WO 2023092781 A1 WO2023092781 A1 WO 2023092781A1 CN 2021140512 W CN2021140512 W CN 2021140512W WO 2023092781 A1 WO2023092781 A1 WO 2023092781A1
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reverse osmosis
osmosis membrane
phase
compounds
solution
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French (fr)
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胡利杰
梁松苗
张佳佳
王兵辉
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沃顿科技股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • 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
    • 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
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/36—Polytetrafluoroethene
    • 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
    • B01D71/52—Polyethers
    • 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
    • B01D71/56—Polyamides, e.g. polyester-amides
    • 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
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/60—Polyamines
    • 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
    • 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
    • B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
    • 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
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • 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
    • 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
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • 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

Definitions

  • the present disclosure relates to the technical field of water treatment membranes, more specifically to the technical field of reverse osmosis membranes, in particular to a method for preparing an anti-pollution reverse osmosis membrane that can be used for seawater desalination and has high flux and high desalination rate and A reverse osmosis membrane prepared therefrom.
  • the total amount of water bodies owned by the earth is about 1.386 billion cubic kilometers, and the total amount of seawater accounts for 97.5% of the total amount of water bodies, while the total amount of fresh water accounts for only 2.5% of the total amount of water bodies. Therefore, seawater desalination has gradually become an effective way to solve the global water shortage problem.
  • the traditional seawater desalination process mainly includes distillation, multi-stage flash evaporation, freezing method, etc. The process is complicated, the efficiency is low, the energy consumption of the system is high, and the scope of application in the industrial field is limited.
  • reverse osmosis technology As a new technology for seawater desalination, reverse osmosis technology has the characteristics of good treatment effect, high recovery rate, low energy consumption and low cost, and has gradually become the best choice for new seawater desalination plants.
  • the reverse osmosis membrane used for seawater desalination is usually faced with the problems of easy contamination of the membrane surface and poor permeability of the membrane (usually manifested in low water flux) due to the constraints of the membrane material and the use environment in the actual application process. question.
  • Membrane fouling and poor permeability will lead to high operating pressure, high operating energy consumption, and low desalination efficiency in the seawater desalination process, which will limit the use of seawater desalination reverse osmosis technology. Therefore, it is very important to solve the problems of easy fouling of membrane and low permeability of membrane to promote the development of reverse osmosis technology for industrial seawater desalination.
  • Hydrophilic modification of the membrane surface is an effective means to enhance the anti-fouling ability of the membrane.
  • the simplest and easiest method is to coat a layer of hydrophilic layer on the surface of the functional layer of the membrane to enhance its antifouling performance.
  • Patent Document 1 discloses coating a dense hydrophilic cross-linked polyvinyl alcohol (PVA) layer on the surface of a membrane to enhance the anti-fouling ability of the membrane.
  • PVA polyvinyl alcohol
  • Patent Document 2 discloses that by introducing PVA molecules into the polyamide desalting layer, some of the hydroxyl groups of PVA are reacted with acid chloride groups, while the unreacted hydroxyl groups participate in the PVA exchange together with the hydroxyl groups on the subsequently coated PVA molecules.
  • the formation reaction of the joint layer makes the polyamide desalination layer and the PVA cross-linked layer connected by chemical bonding, which improves the adhesion of the hydrophilic PVA coating layer, thereby further improving the anti-pollution durability of the reverse osmosis membrane used for seawater desalination. promote.
  • the disadvantage of this method is that the hydrophilic PVA coating layer is easy to block the pores of the membrane separation layer, resulting in a serious decrease in the permeability of the membrane, that is, the water flux.
  • the existing reverse osmosis membranes used for seawater desalination have the problems of easy contamination of membrane materials and low permeability during practical application and operation, which have become bottlenecks restricting the development of current seawater desalination reverse osmosis technology. Improving the selective separation and permeability of reverse osmosis membranes for seawater desalination, and ensuring their anti-fouling durability are the biggest challenges in the field of seawater desalination applications.
  • the purpose of the present disclosure is to provide a method for preparing a reverse osmosis membrane and a reverse osmosis membrane prepared therefrom, which not only have high flux and high desalination rate, but also have excellent anti-pollution and durability properties for effective use in seawater desalination.
  • the functional layer also known as the separation layer, desalination layer
  • the separation layer desalination layer
  • the reverse osmosis membrane used for seawater desalination must have high selective separation, Excellent permeability and stability of permeability and anti-pollution performance during long-term use.
  • the active functional groups with a high content of hyperbranched polymers can be used as crosslinking sites to chemically react with the acid chloride monomers that participate in the interfacial polymerization to form the functional layer and be combined into the functional layer formed by the interfacial polymerization.
  • the present disclosure uses a hyperbranched polymer as the first phase additive contained in the first phase solution and contains The acid chloride monomer in the second phase solution reacts chemically to increase the cross-linking degree of the functional layer, thereby ensuring a high desalination rate of the reverse osmosis membrane used for seawater desalination.
  • the halogen atom in the halogenated heterocyclic compound has high reactivity and is easy to controllably adjust.
  • the temperature during the interfacial polymerization reaction within an appropriate range, the halogen atom and the halogen atom contained in the The reaction between the amine monomers in the first phase solution can adjust the structure and crosslinking degree of the functional layer formed by the interfacial polymerization reaction, realize the adjustment of the porosity of the functional layer, and improve the water flux of the membrane.
  • the porosity of the functional layer can be adjusted, thereby improving the flux of the reverse osmosis membrane.
  • the introduction of the heterocyclic structure also endows the functional layer with good acid and alkali resistance cleaning performance, which improves the performance attenuation problem faced by the reverse osmosis membrane in the process of pickling or alkali cleaning in order to restore the performance of the membrane after being polluted.
  • the service life of the reverse osmosis membrane in the seawater desalination process is prolonged, and the durability of the membrane is improved.
  • the reverse osmosis membrane can achieve high salt rejection rate, high flux, acid washing and alkali washing resistance, and service durability.
  • the inventors of the present disclosure have also found that in the post-treatment, by adding an activator to the post-treatment solution and adjusting the temperature of the post-treatment in an appropriate range, the unreacted halogen atoms in the halogenated heterocyclic compounds can be Sufficient hydrolysis occurs to generate hydrophilic hydroxyl groups on the surface of the membrane, improving the anti-fouling durability of the reverse osmosis membrane.
  • the present disclosure provides a method for preparing a reverse osmosis membrane, the method comprising the following steps:
  • the polymer porous base membrane is sequentially contacted with a first phase solution and a second phase solution to form a functional layer, wherein the first phase solution includes an amine compound, a first phase additive and water, and the second phase solution Contains acid chloride compounds, a second phase additive and a solvent, the first phase additive is a hyperbranched polymer, the second phase additive is a halogenated heterocyclic compound, and the step of forming a functional layer is performed at a temperature of 5 to 60°C under the conditions;
  • the reverse osmosis membrane is obtained after post-treatment, wherein the post-treatment includes contacting with an aqueous solution containing an activator at a temperature of 60°C to 90°C, and the activator is selected from sodium carbonate, potassium carbonate, sodium sulfite, propane At least one of sodium succinate, sodium succinate, potassium succinate, sodium hydrogen oxalate, sodium dihydrogen phosphate, sodium citrate, potassium citrate, sodium lactate, sodium bicarbonate, tert-butylamine, triethylamine, and sodium oxalate.
  • the post-treatment includes contacting with an aqueous solution containing an activator at a temperature of 60°C to 90°C, and the activator is selected from sodium carbonate, potassium carbonate, sodium sulfite, propane At least one of sodium succinate, sodium succinate, potassium succinate, sodium hydrogen oxalate, sodium dihydrogen phosphate, sodium citrate, potassium citrate, sodium lactate, sodium bicarbonate, tert
  • the polymer solution comprises a polymer and a solvent
  • the polymer is selected from polysulfone, polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene, polyether ether ketone, At least one of polynaphthalene polyether nitrile ketone and polynaphthalene polyether ketone.
  • the hyperbranched polymer is at least one selected from dendritic polyamines, dendritic polyols, star polyols, star polyamines, and star heteroarm polyamines .
  • the content of the first phase additive is 0.01wt%-2wt%.
  • the halogenated heterocyclic compound is a halide of at least one heterocyclic compound selected from the following heterocyclic compounds: pyrazine compounds, pyridazine compounds, Thiazole compounds, quinoline compounds, triazine compounds, indole compounds, purine compounds, pyrimidine compounds, imidazole compounds.
  • the content of the second phase additive is 0.02wt%-0.5wt%.
  • the content of the activator is 0.01wt%-0.2wt%.
  • the present disclosure also provides a reverse osmosis membrane prepared according to the preparation method described in the present disclosure.
  • the reverse osmosis membrane prepared according to the preparation method described in the present disclosure can be effectively used for seawater desalination.
  • the cross-linking degree of the functional layer can be improved and the porosity of the functional layer can be adjusted through the method of the present disclosure.
  • the method is simple in operation, does not require modification of existing equipment, and has economical and effective production costs.
  • the reverse osmosis membrane prepared by the disclosed method not only has high water flux and extremely high salt rejection rate, but also has excellent pickling and alkali washing resistance, service durability and anti-pollution durability.
  • Figure 1 shows the comparison results of the anti-pollution performance of the reverse osmosis membranes of Comparative Example 1 and Example 8.
  • the present disclosure relates to a preparation method of a composite reverse osmosis membrane, which comprises the following steps:
  • the polymer porous base membrane is sequentially contacted with a first phase solution and a second phase solution to form a functional layer, wherein the first phase solution includes an amine compound, a first phase additive and water, and the second phase solution Contains acid chloride compounds, a second phase additive and a solvent, the first phase additive is a hyperbranched polymer, the second phase additive is a halogenated heterocyclic compound, and the step of forming a functional layer is performed at a temperature of 5 to 60°C under the conditions;
  • the reverse osmosis membrane is obtained after post-treatment, wherein the post-treatment includes contacting with an aqueous solution containing an activator at a temperature of 60°C to 90°C, and the activator is selected from sodium carbonate, potassium carbonate, sodium sulfite, propane At least one of sodium succinate, sodium succinate, potassium succinate, sodium hydrogen oxalate, sodium dihydrogen phosphate, sodium citrate, potassium citrate, sodium lactate, sodium bicarbonate, tert-butylamine, triethylamine, and sodium oxalate.
  • the post-treatment includes contacting with an aqueous solution containing an activator at a temperature of 60°C to 90°C, and the activator is selected from sodium carbonate, potassium carbonate, sodium sulfite, propane At least one of sodium succinate, sodium succinate, potassium succinate, sodium hydrogen oxalate, sodium dihydrogen phosphate, sodium citrate, potassium citrate, sodium lactate, sodium bicarbonate, tert
  • the hyperbranched polymer By using the hyperbranched polymer as the first phase additive contained in the first phase solution, the hyperbranched polymer has a high content of active functional groups as crosslinking sites to participate in interfacial polymerization contained in the second phase solution
  • the acid chloride monomer that reacts to form the functional layer reacts chemically and is bound to the polymer skeleton of the functional layer formed by the interfacial polymerization reaction, thereby improving the crosslinking degree and stability of the functional layer formed by the interfacial polymerization reaction, thereby ensuring High desalination rate of reverse osmosis membranes for seawater desalination.
  • halogenated heterocyclic compound as a second phase additive contained in the second phase solution and adjusting the temperature of the interfacial polymerization reaction in an appropriate range, the halogen atom and the amine contained in the first phase solution are adjusted
  • the chemical reaction between similar monomers can adjust the structure and crosslinking degree of the functional layer formed by the interfacial polymerization reaction, and realize the adjustment of the porosity of the functional layer, thereby improving the flux of the reverse osmosis membrane.
  • the introduction of the heterocyclic structure also endows the functional layer with good acid and alkali cleaning performance, which improves the performance attenuation problem faced by the reverse osmosis membrane in the process of pickling or alkali cleaning in order to restore the performance of the membrane after being polluted. , prolong the service life of the reverse osmosis membrane in the seawater desalination process, and improve the durability of the membrane.
  • the unreacted halogen atoms in the halogenated heterocyclic compounds are fully hydrolyzed, and hydrophilic hydroxyl groups are generated on the membrane surface to improve reverse osmosis Membrane antifouling durability.
  • the polymer solution is prepared as the casting solution, and the casting solution is coated on the reinforcement material to form a polymer porous base membrane (also known as a polymer porous support membrane), preferably, the reinforcement
  • the material is non-woven fabric, such as polypropylene (PP, also known as polypropylene) non-woven fabric, polyester (PET) non-woven fabric, acrylic (PAN) non-woven fabric and polyvinyl chloride (PVC) non-woven fabric.
  • the coating method is not particularly limited, and a casting method, a dip coating method, a blade coating method, and the like can be used.
  • the casting solution is coated on the reinforcing material and then immersed in a coagulation bath, so that the casting solution is solidified to form a polymer porous base membrane.
  • the coagulation bath is a water bath, and the temperature of the coagulation bath is not particularly limited, and is usually in the range of 10°C-30°C.
  • the polymer solution includes a polymer and a solvent
  • the polymer is selected from polysulfone, polyethersulfone, polyvinylidene fluoride, polytetrafluoroethylene, polyetheretherketone, and xaphthalene At least one of biphenyl polyether nitrile ketone and polynaphthalene polyether ketone.
  • the concentration of the polymer is 10-30 wt%.
  • the solvent contained in the polymer solution is not particularly limited as long as it can dissolve the polymer, such as N,N-dimethylformamide (DMF), N,N-di Methylacetamide (DMAC), N-methyl-2-pyrrolidone, etc.
  • the polymer porous base membrane is sequentially contacted with a first phase solution and a second phase solution to form a functional layer, wherein the first phase solution contains an amine compound, a first phase additive and water, the second-phase solution includes acid chloride compounds, a second-phase additive and a solvent, the first-phase additive is a hyperbranched polymer, and the second-phase additive is a halogenated heterocyclic compound.
  • the contact time is not particularly limited, but is usually 0.5 min to 5 min.
  • the amine compound in the preparation method of the present disclosure, there is no limitation on the amine compound, and the amine compound commonly used in the art for interfacial polymerization can be used, for example, such as o-phenylenediamine, m-phenylenediamine, tere-phenylenediamine, etc.
  • the concentration of the amine compound is 0.5-5 wt%.
  • the hyperbranched polymer is at least one selected from dendritic polyamines, dendritic polyols, star polyols, star polyamines, and star heteroarm polyamines. .
  • the dendritic polyamine examples include polyethyleneimine, polyamide-amine, polydopamine, polyethyleneamine, polyetherimide, polymethacrylimide, polybismaleimide, etc. ;
  • the dendritic polyol can enumerate such as ⁇ -cyclodextrin, ⁇ -cyclodextrin, ⁇ -cyclodextrin, cyclodextrin sodium sulfate, tannic acid, xylan, sorbitol, chitosan Sugar etc.
  • As said star polyol can enumerate such as four-arm polyethylene glycol-alcohol, six-arm polyethylene glycol-alcohol, eight-arm polyethylene glycol-alcohol, twelve-arm polyethylene glycol-alcohol etc.
  • the star-shaped polyamine such as four-arm polyvinyl alcohol-amine, six-arm polyvinyl alcohol-amine, eight-arm polyvinyl alcohol-amine, four-arm polyimide-
  • the content of the first phase additive is 0.01wt%-2wt%.
  • the degree of cross-linking of the functional layer is not enough, and the effect of improving the desalination rate of the prepared reverse osmosis membrane is not good; when the content is higher than 2wt%, the first phase additive will cause a large amount of consumption
  • the second phase monomer affects the main skeleton structure of the prepared reverse osmosis membrane, resulting in defects in the functional layer.
  • the acyl chloride compound in the preparation method of the present disclosure, there is no limitation on the acyl chloride compound, and the acyl chloride compound commonly used in the art for interfacial polymerization can be used, for example, such as trimesoyl chloride, terephthaloyl chloride, o-chloride Benzoyl chloride and isophthaloyl chloride, etc.
  • the concentration of the acid chloride compound is 0.1-1 wt%.
  • the halogenated heterocyclic compound is a halide of at least one heterocyclic compound selected from the following heterocyclic compounds: pyrazine compounds, pyridazine compounds, thiazole compounds , quinoline compounds, triazine compounds, indole compounds, purine compounds, pyrimidine compounds, imidazole compounds.
  • halopyrazine compounds include 2,3-dichloropyrazine, 2,5-dichloropyrazine, 2-chloro-3-methyl-5-bromopyrazine, 2-amino-3- Chloro-6-bromopyrazine, 2,3,5-trichloropyrazine, 2,3,5,6-tetrachloropyrazine, 2-chloro-3-bromopyrazine, 2,3-dichloro-5 -Bromopyrazine, 2,3-dichloro-5,6-dibromopyrazine, 2-chloro-3,5,6-tribromopyrazine, 2,3,5,6-tetrabromopyrazine, etc.;
  • halogenated pyridazine compounds include 3,4-dichloropyridazine, 5,6-dichloropyridazine, 3,4,5-trichloropyridazine, 3,5,6-trichloropyri
  • the content of the second phase additive is 0.02wt% ⁇ 0.5wt%.
  • the content is lower than 0.02wt%, the control of the porosity of the functional layer is insufficient, which will lead to poor flux enhancement effect of the prepared reverse osmosis membrane, and poor antifouling performance improvement effect in the post-treatment process.
  • the content is higher than 0.5wt%, it will affect the main skeleton structure of the functional layer, and the reduction of the content of the acyl chloride monomer will cause the crosslinking degree of the functional layer to be low, resulting in obvious hair performance of the prepared reverse osmosis membrane. reduce.
  • the post-treatment includes contacting with an aqueous solution containing an activator, preferably, the activator is selected from sodium carbonate, potassium carbonate, sodium sulfite, sodium malonate, sodium succinate, butyrate At least one of potassium diacid, sodium hydrogen oxalate, sodium dihydrogen phosphate, sodium citrate, potassium citrate, sodium lactate, sodium bicarbonate, t-butylamine, triethylamine, and sodium oxalate.
  • an activator is selected from sodium carbonate, potassium carbonate, sodium sulfite, sodium malonate, sodium succinate, butyrate At least one of potassium diacid, sodium hydrogen oxalate, sodium dihydrogen phosphate, sodium citrate, potassium citrate, sodium lactate, sodium bicarbonate, t-butylamine, triethylamine, and sodium oxalate.
  • the above contact temperature with the aqueous solution containing the activator is carried out under the condition of 60°C to 90°C.
  • the temperature is lower than 60°C, the unreacted halogen atoms in the halogenated heterocyclic compounds are difficult to be hydrolyzed to form hydrophilic hydroxyl groups, which is not conducive to the improvement of the anti-pollution performance of the prepared reverse osmosis membrane; when the temperature is higher than 90
  • the activator solution is close to the boiling state, which affects the control of the activation process.
  • the contact time is not particularly limited, but is usually 30 minutes to 180 minutes.
  • the content of the activator is 0.01wt%-0.2wt%.
  • the concentration of the activator is low, the activation ability is insufficient, and the unreacted halogen atoms in the halogenated heterocyclic compounds cannot be fully hydrolyzed and converted into hydrophilic hydroxyl groups, resulting in the prepared reverse osmosis
  • the improvement of the anti-fouling performance of the membrane is limited; when the content is higher than 0.2wt%, the concentration of the activator is too high, and the stability of the desalination layer structure on the surface of the prepared reverse osmosis membrane is reduced, resulting in serious degradation of membrane performance.
  • the step of forming the functional layer is carried out at a temperature of 5 to 60°C.
  • the temperature is lower than 5°C, the diffusion ability of halogenated heterocyclic compounds is limited, and the reactivity is low, so it is difficult to regulate the porosity of the desalination layer of the reverse osmosis membrane, resulting in poor flux enhancement effect of the membrane.
  • Good when the temperature is higher than 60 ° C, the halogen atoms in the halogenated heterocyclic compound structure will be completely reacted, which is not conducive to the formation of hydrophilic hydroxyl groups on the surface of the reverse osmosis membrane during post-treatment activation and the anti-fouling performance of the membrane improvement.
  • the preparation method of the reverse osmosis membrane of the present disclosure includes the following steps:
  • the polymer solution is scraped and coated on the non-woven fabric with a scraper, and immersed in a water bath to form a polymer porous base film;
  • the first phase solution containing hyperbranched polymer evenly on the surface of the polymer porous base membrane, fully contact with it for 0.5-5 minutes, remove the excess residual solution on the surface of the polymer porous base membrane by an air knife, and then apply the halogen-containing solution evenly.
  • the second phase solution of heterocyclic compounds the first phase solution and the second phase solution are fully contacted for 0.5 to 5 minutes at a temperature of 5 to 60 ° C, so that interfacial polymerization can occur to form a crosslinked structure and form a functional layer;
  • the present disclosure also relates to a reverse osmosis membrane prepared by the preparation method according to the present disclosure.
  • the reverse osmosis membrane comprises, from bottom to top: a non-woven fabric layer, a polymer porous support layer, and a functional layer (also called the desalination layer).
  • the reverse osmosis membrane not only has high water flux and high desalination rate, but also has excellent pickling and alkali washing resistance, service durability and anti-pollution durability, and can be effectively applied to seawater desalination.
  • the polysulfone solution is directly scraped and coated on the non-woven fabric with a scraper, and immersed in a water bath to form a polysulfone porous base membrane;
  • the first phase solution is evenly applied to the surface of the polysulfone porous base membrane, fully contacted for 3min, wherein the first phase solution consists of 3wt% m-phenylenediamine, 0.05wt% sodium lauryl sulfate, 0.02wt% sodium hydroxide and the remaining amount of water composition.
  • the second phase solution is composed of 0.3wt% trimesoyl chloride and the remainder of n-hexane, at a temperature of 20 ° C, Make the first-phase and second-phase solutions fully contact for 1 min to obtain a reverse osmosis membrane; soak it in deionized water for use.
  • the polysulfone solution is directly scraped and coated on the non-woven fabric with a scraper, and immersed in a water bath to form a polysulfone porous base membrane;
  • the first phase solution containing polydopamine is evenly applied to the surface of the polysulfone porous base membrane, fully contacted for 3min, wherein the first phase solution consists of 0.15wt% polydopamine, 3wt% m-phenylenediamine, 0.05wt% dodecylsulfuric acid Sodium, 0.02wt% sodium hydroxide and the balance of water, by using an air knife to remove excess residual solution on the surface of the polysulfone porous base membrane, and then uniformly apply the second phase containing 2,3,5-trichloropyrazine Solution, wherein the second phase solution is composed of 0.02wt% 2,3,5-trichloropyrazine, 0.3wt% trimesoyl chloride and the rest of n-hexane, and the first phase solution and the second phase solution are made at a temperature of 20°C
  • the two-phase solution is fully contacted for 1 min to form a functional layer;
  • Example 2 In addition to changing 0.15wt% polydopamine to 0.15wt% octaarm polyvinyl alcohol-amine, changing 0.02wt% 2,3,5-trichloropyrazine to 0.02wt% 2-bromo-4,5-dichloroimidazole Example 2 was carried out in the same manner as in Example 1 except that 0.05 wt% of sodium carbonate was changed to 0.05 wt% of sodium sulfite.
  • Example 3 In addition to changing 0.15wt% polydopamine to 0.30wt% ⁇ -cyclodextrin, changing 0.02wt% 2,3,5-trichloropyrazine to 0.02wt% 2-chloro-6,8-dibromopurine and changing Example 3 was carried out in the same manner as in Example 1 except that 0.05 wt% of sodium carbonate was changed to 0.05 wt% of potassium oxalate.
  • Example 4 In addition to changing 0.15wt% polydopamine to 0.30wt% hexaarmethylenediamine core polydopamine-polyethyleneimine, changing 0.02wt% 2,3,5-trichloropyrazine to 0.02wt% 3,5, Example 4 was carried out in the same manner as Example 1 except for 6-trichloropyridazine and changing 0.05 wt% sodium carbonate to 0.05 wt% sodium dihydrogenphosphate.
  • Example 5 Except changing 0.15wt% polydopamine to 0.45wt% polyamidoamine, changing 0.02wt% 2,3,5-trichloropyrazine to 0.02wt% 2,5,6-trichloro-1,3,4 Example 5 was carried out in the same manner as Example 1 except for triazine and changing 0.05 wt% sodium carbonate to 0.05 wt% t-butylamine.
  • Example 6 Except changing 0.15wt% polydopamine to 0.45wt% polyamidoamine, changing 0.02wt% 2,3,5-trichloropyrazine to 0.04wt% 2,4,6-tribromo-5-methylpyrimidine
  • Example 6 was carried out in the same manner as Example 1, except that 0.05 wt% sodium carbonate was changed to 0.1 wt% triethylamine, and the post-activation treatment was performed at a temperature of 80° C. for 90 min.
  • the operating pressure is 800 psi
  • the influent water is an aqueous solution with a sodium chloride concentration of 32000 ppm
  • the operating time is 30 minutes.
  • the reverse osmosis membrane prepared by the disclosed method has a water flux as high as 50 L/m 2 h or more, and has a very high desalination rate, and can effectively realize efficient desalination treatment of seawater.
  • BSA bovine serum albumin
  • Fig. 1 Result is shown in Fig. 1, as seen from Fig. 1, before carrying out pollution treatment, the water flux of the reverse osmosis membrane prepared in embodiment 8 is significantly higher than the reverse osmosis membrane prepared in comparative example 1, and in the pollution process, contrast
  • the water flux of the reverse osmosis membrane prepared in Example 1 and the reverse osmosis membrane prepared in Example 8 all decreased, and after being polluted and cleaned, the recovery rate of the water flux of the reverse osmosis membrane prepared in Example 8 was higher than 98%, basically recovered to the level of water flux before being polluted, however, after the reverse osmosis membrane of Comparative Example 1 was polluted and cleaned, the water flux was significantly lower than the level of water flux before being polluted. Therefore, it can be seen from the results in FIG. 1 that the reverse osmosis membrane prepared according to the disclosed method has excellent anti-fouling properties.
  • Test the water flux and desalination rate before cleaning, 1 cleaning, 2 cleanings, 3 cleanings and 4 cleanings.
  • the water flux and desalination rate are tested under the following operating conditions: the operating pressure is 800psi, the influent water is an aqueous solution with a sodium chloride concentration of 32000ppm, and the running time is 30min. The results are listed in Table 3 below.
  • the reverse osmosis membrane prepared by the method of the present disclosure has a water flux of up to 50 L/m 2 h and a very high desalination rate before acid and alkali washing. After pickling and alkali washing, the salt rejection rate basically maintained the initial level, and the flux not only did not decrease, but also slightly increased.
  • the cross-linking degree of the functional layer can be improved and the porosity of the functional layer can be adjusted through the method disclosed in the present disclosure.
  • the method is simple in operation, does not require modification of existing equipment, and has economical and effective production costs.
  • the reverse osmosis membrane prepared by the disclosed method not only has high water flux and extremely high salt rejection rate, but also has excellent pickling and alkali washing resistance, service durability and anti-pollution durability, and can be effectively applied to seawater fade.

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Abstract

一种反渗透膜的制备方法和由其制备的反渗透膜。所述方法包括以下步骤：配制聚合物溶液作为铸膜液，使所述铸膜液在增强材料上形成聚合物多孔基膜，将所述聚合物多孔基膜依次与第一相溶液、第二相溶液接触以形成功能层，其中所述第一相溶液包含胺类化合物、第一相添加剂和水，所述第二相溶液包含酰氯类化合物、第二相添加剂和溶剂，所述第一相添加剂是超支化聚合物，所述第二相添加剂是卤代杂环类化合物；经后处理得到反渗透膜。通过所述方法制备的反渗透膜兼具高通量和高脱盐率，并且具有优异的抗污染耐久性、耐酸洗、耐碱洗。制备的反渗透膜可有效地应用于海水淡化。

Description

反渗透膜的制备方法和由其制备的反渗透膜 技术领域
本公开涉及水处理膜的技术领域，更具体地涉及反渗透膜的技术领域，特别涉及一种可用于海水淡化的兼具高通量和高脱盐率的抗污染的反渗透膜的制备方法和由其制备的反渗透膜。
背景技术
根据相关调查资料显示，地球所拥有的水体总量在13.86亿立方千米左右，海水总量占水体总量的97.5％，而淡水总量仅占水体总量的2.5％。因此，海水淡化已逐渐成为解决全球水资源短缺问题的有效途径。传统的海水淡化工艺主要包括蒸馏、多级闪蒸、冷冻法等，工艺过程复杂、效率低，系统能耗高，在工业领域的使用范围有限。
反渗透技术作为用于海水淡化的新技术具有处理效果好、回收率高、能耗与成本低等特点，已经逐渐成为新建的海水淡化装置的不二之选。然而，用于海水淡化的反渗透膜在实际应用过程中由于受到膜材料和使用环境的制约，通常面临膜表面容易被污染、膜的渗透性能差(通常具体表现在水通量偏低)的问题。
膜被污染和较差的渗透性能将导致在海水淡化过程中运行压力大、运行能耗高、淡化效率低，从而导致海水淡化反渗透技术的使用受限。因此，解决膜容易被污染和膜的渗透性能低的问题对于促进工业海水淡化反渗透技术的发展至关重要。
针对用于海水淡化的反渗透膜的污染问题，工业领域通常采用的方法是对被污染后的膜元件进行酸洗或碱洗，以达到恢复膜性能的目的。然而，长时间或者多次的酸碱清洗后，膜材料的稳定性会明显降低，进而导致膜性能严重衰减。因此，需要开发具有优良的抗污染性能的膜材料以从根本上解决在海水淡化过程中膜容易被污染的问题。
对膜表面进行亲水改性是增强膜的抗污染能力的一种有效手段。最简单易行的方法是在膜的功能层表面涂覆一层亲水层以增强其抗污染性能。
专利文献1(CN101130444A)公开了在膜片表面涂覆致密的亲水交联聚乙烯醇(PVA)层，以增强膜的抗污染能力。然而，由于PVA层与膜表面的脱盐层之间仅通过物理作用 粘结，粘合力差，因此在实际运行过程中PVA层容易脱落，从而导致抗污染耐久性不足。
专利文献2(CN102921315A)公开了通过在聚酰胺脱盐层中引入PVA分子，使PVA的部分羟基与酰氯基团反应，而未反应的羟基则与随后涂覆的PVA分子上的羟基共同参与PVA交联层的生成反应，使聚酰胺脱盐层与PVA交联层通过化学键合作用连接，提高了亲水PVA涂覆层的附着力，从而使用于海水淡化的反渗透膜的抗污染耐久性得到进一步提升。但是该方法的不足之处在于，亲水PVA涂覆层易堵塞膜分离层孔道，造成膜的渗透性能即水通量严重下降。
因此，现有的用于海水淡化的反渗透膜在实际应用运行过程中存在膜材料容易被污染以及渗透性能较低的问题已经成为制约当前海水淡化反渗透技术发展的瓶颈。提升用于海水淡化的反渗透膜的选择分离性和渗透性能，并且确保其抗污染耐久性是目前海水淡化应用领域面临的最大挑战。
发明内容
发明要解决的问题
针对现有技术中存在的上述问题，本公开的目的在于提供一种反渗透膜的制备方法和由其制备的反渗透膜，不仅具备高通量和高脱盐率，而且具有优异的抗污染耐久性，以有效地用于海水淡化。
用于解决问题的方案
本公开的发明人通过深入研究认为，考虑到海水主体溶液的成分和海水淡化效率，用于海水淡化的反渗透膜的功能层(又称分离层，脱盐层)必须具备高的选择分离性、优异的渗透性能以及长期使用时渗透性能和抗污染性能的稳定性。
本公开的发明人发现，超支化聚合物所具有的高含量的活性官能团可以作为交联位点与参与界面聚合反应形成功能层的酰氯类单体发生化学反应而被结合至通过界面聚合反应形成的功能层的聚合物骨架上，从而提高通过界面聚合反应形成的功能层的交联度和稳定性，本公开通过使用超支化聚合物作为包含在第一相溶液中的第一相添加剂与包含在第二相溶液中的酰氯类单体发生化学反应，提高功能层的交联度，从而确保了用于海水淡化的反渗透膜的高脱盐率。
本公开的发明人还发现，卤代杂环类化合物中的卤素原子反应活性高、易于可控地调节，通过将界面聚合反应时的温度调节在合适的范围内，可以调节卤素原子与包含在第一相溶液中的胺类单体之间的反应，从而调节通过界面聚合反应而形成的功能层的结构和交联度，实现对功能层的疏松度的调节，提高膜的水通量。本公开通过使用卤代杂环类化合物作为包含在第二相溶液中的第二相添加剂与包含在第一相溶液中的胺类单体发生化学反应，可以调节功能层的疏松度，从而提高了反渗透膜的通量。此外，杂环结构的引入也赋予功能层以良好的耐酸碱清洗性能，改善了反渗透膜在被污染后为了恢复膜的性能而进行的酸洗或碱洗过程中面临的性能衰减问题，延长了反渗透膜在海水淡化过程中的使用寿命，提高了膜的使用耐久性。
在本公开中，通过使用第一相添加剂和第二相添加剂可以同时实现反渗透膜的高脱盐率、高通量、耐酸洗碱洗性能、使用耐久性。
此外，本公开的发明人还发现，在后处理中，通过在后处理溶液中添加活化剂并且调节后处理的温度在合适的范围内，可以使卤代杂环类化合物中未反应的卤素原子发生充分水解，在膜表面生成亲水性羟基，改善反渗透膜的抗污染耐久性。
本公开提供了一种反渗透膜的制备方法，所述方法包括以下步骤：
配制聚合物溶液作为铸膜液，使所述铸膜液在增强材料上形成聚合物多孔基膜；
将所述聚合物多孔基膜依次与第一相溶液、第二相溶液接触以形成功能层，其中所述第一相溶液包含胺类化合物、第一相添加剂和水，所述第二相溶液包含酰氯类化合物、第二相添加剂和溶剂，所述第一相添加剂是超支化聚合物，所述第二相添加剂是卤代杂环类化合物，形成功能层的步骤在温度为5至60℃的条件下进行；
经后处理得到反渗透膜，其中所述后处理包括与包含活化剂的水溶液在温度为60℃至90℃的条件下接触，所述活化剂为选自碳酸钠、碳酸钾、亚硫酸钠、丙二酸钠、丁二酸钠、丁二酸钾、草酸氢钠、磷酸二氢钠、柠檬酸钠、柠檬酸钾、乳酸钠、碳酸氢钠、叔丁胺、三乙胺、草酸钠的至少一种。
根据本公开所述的制备方法，其中所述聚合物溶液包含聚合物和溶剂，所述聚合物为选自聚砜、聚醚砜、聚偏氟乙烯、聚四氟乙烯、聚醚醚酮、杂萘联苯聚醚腈酮、杂萘联苯聚醚酮的至少一种。
根据本公开所述的制备方法，其中，所述超支化聚合物为选自树枝形聚胺、树枝状多元醇、星形多元醇、星形多元胺、星形杂臂聚胺的至少一种。
根据本公开所述的制备方法，其中，以所述第一相溶液的重量计，所述第一相添加剂的含量为0.01wt％～2wt％。
根据本公开所述的制备方法，其中，所述卤代杂环类化合物为选自以下杂环类化合物中的至少一种杂环类化合物的卤代物：吡嗪类化合物、哒嗪类化合物、噻唑类化合物、喹啉类化合物、三嗪类化合物、吲哚类化合物、嘌呤类化合物、嘧啶类化合物、咪唑类化合物。
根据本公开所述的制备方法，其中，以所述第二相溶液的重量计，所述第二相添加剂的含量为0.02wt％～0.5wt％。
根据本公开所述的制备方法，其中，以所述包含活化剂的水溶液的重量计，所述活化剂的含量为0.01wt％～0.2wt％。
本公开还提供一种根据本公开所述的制备方法制得的反渗透膜。
根据本公开所述的制备方法制得的反渗透膜可有效地用于海水淡化。
发明的效果
通过本公开的方法可以提高功能层的交联度和调节功能层的疏松度，该方法操作过程简单，无需对现有设备进行改造，生产成本经济有效。通过本公开的方法制备的反渗透膜不仅具有较高的水通量和极高的脱盐率，而且具有优异的耐酸洗碱洗性能、使用耐久性和抗污染耐久性。
附图说明
图1示出对照例1和实施例8的反渗透膜的抗污染性能对比结果。
具体实施方式
本公开涉及一种复合反渗透膜的制备方法，其包括以下步骤：
配制聚合物溶液作为铸膜液，使所述铸膜液在增强材料上形成聚合物多孔基膜；
将所述聚合物多孔基膜依次与第一相溶液、第二相溶液接触以形成功能层，其中所 述第一相溶液包含胺类化合物、第一相添加剂和水，所述第二相溶液包含酰氯类化合物、第二相添加剂和溶剂，所述第一相添加剂是超支化聚合物，所述第二相添加剂是卤代杂环类化合物，形成功能层的步骤在温度为5至60℃的条件下进行；
经后处理得到反渗透膜，其中所述后处理包括与包含活化剂的水溶液在温度为60℃至90℃的条件下接触，所述活化剂为选自碳酸钠、碳酸钾、亚硫酸钠、丙二酸钠、丁二酸钠、丁二酸钾、草酸氢钠、磷酸二氢钠、柠檬酸钠、柠檬酸钾、乳酸钠、碳酸氢钠、叔丁胺、三乙胺、草酸钠的至少一种。
本公开的制备方法的技术构思在于以下几点：
通过使用超支化聚合物作为包含在第一相溶液中的第一相添加剂，使超支化聚合物所具有的高含量的活性官能团作为交联位点与包含在第二相溶液中的参与界面聚合反应形成功能层的酰氯类单体发生化学反应而被结合至通过界面聚合反应形成的功能层的聚合物骨架上，从而提高通过界面聚合反应形成的功能层的交联度和稳定性，从而确保了用于海水淡化的反渗透膜的高脱盐率。
通过使用卤代杂环类化合物作为包含在第二相溶液中的第二相添加剂并且将界面聚合反应时的温度调节在合适的范围内，来调节卤素原子与包含在第一相溶液中的胺类单体之间的化学反应，从而调节通过界面聚合反应而形成的功能层的结构和交联度，实现对功能层的疏松度的调节，从而提高了反渗透膜的通量。
此外，杂环结构的引入也赋予功能层以良好的耐酸碱清洗性能，改善了反渗透膜在被污染后，为了恢复膜的性能而进行的酸洗或碱洗过程中面临的性能衰减问题，延长了反渗透膜在海水淡化过程中的使用寿命，提高了膜的使用耐久性。
通过在后处理溶液中添加活化剂并且调节后处理的温度在合适的范围内，使卤代杂环类化合物中未反应的卤素原子发生充分水解，在膜表面生成亲水性羟基，改善反渗透膜的抗污染耐久性。
在本公开的制备方法中，配制聚合物溶液作为铸膜液，并且使铸膜液涂布在增强材料上形成聚合物多孔基膜(又称聚合物多孔支撑膜)，优选地，所述增强材料为无纺布，例如聚丙烯(PP，又称丙纶)无纺布、涤纶(PET)无纺布、腈纶(PAN)无纺布和氯纶(PVC)无纺布。对于涂布方法没有特别限定，可以使用流延法、浸涂法、刮涂法等。
将铸膜液涂布在增强材料上之后接着浸在凝固浴中，使得铸膜液凝固形成聚合物多孔基膜。在本公开的制备方法中，优选地，凝固浴为水浴，对于凝固浴的温度没有特别限定，通常在10℃-30℃的范围内。
在本公开的制备方法中，所述聚合物溶液包含聚合物和溶剂，所述聚合物为选自聚砜、聚醚砜、聚偏氟乙烯、聚四氟乙烯、聚醚醚酮、杂萘联苯聚醚腈酮、杂萘联苯聚醚酮的至少一种。优选地，以所述聚合物溶液的重量计，所述聚合物的浓度为10-30wt％。
在本公开的制备方法中，对于包含在聚合物溶液中的溶剂没有特别限定，只要能够溶解聚合物即可，可以列举如N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAC)、N-甲基-2-吡咯烷酮等。
在本公开的制备方法中，将所述聚合物多孔基膜依次与第一相溶液、第二相溶液接触以形成功能层，其中所述第一相溶液包含胺类化合物、第一相添加剂和水，所述第二相溶液包含酰氯类化合物、第二相添加剂和溶剂，所述第一相添加剂是超支化聚合物，所述第二相添加剂是卤代杂环类化合物。
对于接触时间，没有特别限定，通常为0.5min至5min。
在本公开的制备方法中，对于胺类化合物没有限定，可以采用本领域通常使用的用于界面聚合反应的胺类化合物，例如，可以列举诸如邻苯二胺、间苯二胺、对苯二胺、N,N-二甲基间苯二胺、均苯三胺、哌嗪、3-胺基哌嗪、1,4-环己二胺、N,N-二甲基环己二胺、三乙醇胺、二异丁胺、正己胺、癸胺、十二烷胺、聚醚胺等。优选地，以所述第一相溶液的重量计，所述胺类化合物的浓度为0.5-5wt％。
在本公开的制备方法中，优选地，所述超支化聚合物为选自树枝形聚胺、树枝状多元醇、星形多元醇、星形多元胺、星形杂臂聚胺的至少一种。
作为所述树枝形聚胺，可以列举诸如聚乙烯亚胺、聚酰胺-胺、聚多巴胺、聚乙烯胺、聚醚酰亚胺、聚甲基丙烯酰亚胺、聚双马来酰亚胺等；作为所述树枝状多元醇，可以列举诸如α-环糊精、β-环糊精、γ-环糊精、环糊精硫酸钠、单宁酸、木聚糖、山梨糖醇、壳聚糖等；作为所述星形多元醇，可以列举诸如四臂聚乙二醇-醇、六臂聚乙二醇-醇、八臂聚乙二醇-醇、十二臂聚乙二醇-醇等；作为所述星形多元胺，可以列举诸如四臂聚乙烯醇-胺、六臂聚乙烯醇-胺、八臂聚乙烯醇-胺、四臂聚酰亚胺-胺、六臂聚酰亚胺-胺等；作为 所述星形杂臂聚胺，可以列举诸如四杂臂偶氮聚乙二胺三嗪-聚酰胺-胺、四杂臂偶氮聚乙二胺三嗪-缩水甘油醚、六杂臂乙二胺核聚多巴胺-聚乙烯亚胺、八杂臂乙二胺核聚甲基丙烯酰亚胺-聚乙烯胺等。
在本公开的制备方法中，优选地，以所述第一相溶液的重量计，所述第一相添加剂的含量为0.01wt％～2wt％。当含量低于0.01wt％时，则功能层的交联度不足，所制备的反渗透膜发脱盐率提升效果不佳；当含量高于2wt％时，则第一相添加剂将导致消耗大量的第二相单体，影响所制备的反渗透膜的主体骨架结构，导致功能层出现缺陷。
在本公开的制备方法中，对于酰氯类化合物没有限定，可以采用本领域通常使用的用于界面聚合反应的酰氯类化合物，例如，可以列举诸如均苯三甲酰氯、对苯二甲酰氯、邻氯苯甲酰氯和间苯二甲酰氯等。优选地，以所述第二相溶液的重量计，所述酰氯类化合物的浓度为0.1-1wt％。
在本公开的制备方法中，所述卤代杂环类化合物为选自以下杂环类化合物中的至少一种杂环类化合物的卤代物：吡嗪类化合物、哒嗪类化合物、噻唑类化合物、喹啉类化合物、三嗪类化合物、吲哚类化合物、嘌呤类化合物、嘧啶类化合物、咪唑类化合物。
作为卤代吡嗪类化合物，可以列举诸如2,3-二氯吡嗪、2,5-二氯吡嗪、2-氯-3-甲基-5-溴吡嗪、2-氨基-3-氯-6-溴吡嗪、2,3,5-三氯吡嗪、2,3,5,6-四氯吡嗪、2-氯-3-溴吡嗪、2,3-二氯-5-溴吡嗪、2,3-二氯-5,6-二溴吡嗪、2-氯-3,5,6-三溴吡嗪、2,3,5,6-四溴吡嗪等；作为卤代哒嗪类化合物，可以列举诸如3,4-二氯哒嗪、5,6-二氯哒嗪、3,4,5-三氯哒嗪、3,5,6-三氯哒嗪、3-氯-5-溴哒嗪、3-氯-6-溴哒嗪、3-氯-5,6-二溴哒嗪、3-甲基-4-氯-5-溴哒嗪、3,4,5-三溴哒嗪、3-氯-4-甲基-5,6-二溴哒嗪等；作为卤代噻唑类化合物，可以列举诸如2,4,5-三氯噻唑、2,4-二氯噻唑、2,5-二氯噻唑、4,5-二氯噻唑、2-氯-4,5-二溴噻唑、2,4-二溴-5-氯噻唑、2,4,5-三溴噻唑、2-甲基-4,5-二氯噻唑、2,5-二溴-4-氯噻唑、4-甲基-2,5-二氯噻唑等；作为卤代喹啉类化合物，可以列举诸如2,3-二氯-4-溴喹啉、3,4-二氯-6-溴喹啉、2,3,5-三氯-4,5-二溴喹啉、2-氯-5,6-二溴喹啉、3,5-二氯-6,7,8-三溴喹啉、2,4,6-三氯-3,5,7-三溴喹啉、2,3-二甲基-4-溴-5-氯喹啉、3,5,6-三甲基-4-溴-8氯喹啉等；作为卤代三嗪类化合物，可以列举诸如2,4-二氯-1,3,5-三嗪、3,5-二氯-1,2,4-三嗪、2,5,6-三氯-1,3,4-三嗪、3,5,6-三氯-1,2,4-三嗪等；作为卤代吲哚类化合物，可以列举诸如2,3,5-三氯吲哚、4,5,6-三氯吲哚、 2-氯-4-溴吲哚、2-甲基-4,6-二溴吲哚、2,5,6-三氯-4-甲基吲哚、2,4-二甲基-3,5-二氯-7-溴吲哚、3-氯-5,6-二溴吲哚等；作为卤代嘌呤类化合物，可以列举诸如2,6-二氯嘌呤、2,8-二氯嘌呤、2-氯-6溴嘌呤、2,6,8-三氯嘌呤、2-氯-6,8-二溴嘌呤等；作为卤代嘧啶类化合物，可以列举诸如2,5-二氯嘧啶、5,6-二氯嘧啶、2,5,6-三氯嘧啶、2-氯-5,6-二溴嘧啶、2,4,6-三溴-5-甲基嘧啶、2,4-二甲基-5氯-6-溴嘧啶等；作为卤代咪唑类化合物，可以列举诸如2,4-二氯咪唑、2,5-二氯咪唑、2-氯-4-溴咪唑、2,4,5-三氯咪唑、2-溴-4,5-二氯咪唑、2,4-二溴-5-溴咪唑、2-甲基-4,5-二氯咪唑等。
在本公开的制备方法中，优选地，以所述第二相溶液的重量计，所述第二相添加剂的含量为0.02wt％～0.5wt％。当含量低于0.02wt％时，则对功能层的疏松程度的调控不足，将导致所制备的反渗透膜的通量提升效果不佳，且会导致后处理过程中对抗污性能的提升效果不明显；当含量高于0.5wt％时，则会影响功能层的主体骨架结构，且酰氯类单体的含量降低会造成功能层的交联度偏低，导致所制备的反渗透膜发性能明显降低。
在本公开的制备方法中，所述后处理包括与包含活化剂的水溶液接触，优选地，所述活化剂为选自碳酸钠、碳酸钾、亚硫酸钠、丙二酸钠、丁二酸钠、丁二酸钾、草酸氢钠、磷酸二氢钠、柠檬酸钠、柠檬酸钾、乳酸钠、碳酸氢钠、叔丁胺、三乙胺、草酸钠的至少一种。
在本公开的制备方法中，以上与包含活化剂的水溶液的接触温度为60℃至90℃的条件下进行。当温度低于60℃时，则卤代杂环类化合物中未反应的卤素原子难以发生水解形成亲水性羟基，不利于所制备的反渗透膜的抗污染性能的提升；当温度高于90℃时，则活化剂溶液接近沸腾状态，影响对于活化过程的控制。对于接触时间，没有特别限定，通常为30min至180min。
在本公开的制备方法中，优选地，以所述包含活化剂的水溶液的重量计，所述活化剂的含量为0.01wt％～0.2wt％。当含量低于0.01wt％时，则活化剂的浓度偏低，活化能力不足，不能使卤代杂环类化合物中未反应的卤素原子充分发生水解转化成亲水性的羟基，致使所制备的反渗透膜的抗污染性能提升受限；当含量高于0.2wt％时，则活化剂的浓度偏高，所制备的反渗透膜表面的脱盐层结构的稳定性下降，导致膜的性能严重衰减。
在本公开的制备方法中，所述形成功能层的步骤在温度为5至60℃的条件下进行。 当温度低于5℃时，则卤代杂环类化合物的扩散能力受限，且反应活性低，难以起到调控反渗透膜的脱盐层的疏松程度的作用，造成膜的通量提升效果不佳；当温度高于60℃时，则卤代杂环类化合物结构中的卤素原子会被反应完全，不利于后处理活化过程中反渗透膜表面亲水性羟基的生成及膜的抗污染性能的提升。
作为一个非限制性实例，本公开的反渗透膜的制备方法包括以下步骤：
将聚合物溶液用刮刀刮涂在无纺布上，浸入水浴中形成聚合物多孔基膜；
将含有超支化聚合物的第一相溶液均匀施加于聚合物多孔基膜的表面，充分接触0.5～5min，通过风刀除去聚合物多孔基膜表面上多余的残留溶液，然后再均匀施加含有卤代杂环类化合物的第二相溶液，在温度为5至60℃的条件下，使第一相溶液和第二相溶液充分接触0.5～5min，以发生界面聚合反应生成交联结构从而形成功能层；
在温度为60℃至90℃的条件下，浸入包含活化剂的水溶液中进行后处理，以在膜表面生成亲水性羟基，制备得到反渗透膜。
本公开还涉及一种通过根据本公开的制备方法制备得到的反渗透膜，优选地，所述反渗透膜从下至上依次包括：无纺布层、聚合物多孔支撑层、以及功能层(又称脱盐层)。所述反渗透膜不仅具有较高的水通量和极高的脱盐率，而且具有优异的耐酸洗碱洗性能、使用耐久性和抗污染耐久性，可以有效地应用于海水淡化。
实施例
下面结合具体的实施例进一步详细说明本公开，但本公开的技术方案绝不限于以下实施例。需要说明的是，实施例中采用的试剂、原料和设备等除非特别说明，皆为商购可得的常规产品。
对照例1
将聚砜溶液用刮刀直接刮涂在无纺布上，浸入水浴中以形成聚砜多孔基膜；
将第一相溶液均匀施加于聚砜多孔基膜表面，充分接触3min，其中第一相溶液由3wt％间苯二胺、0.05wt％十二烷基硫酸钠、0.02wt％氢氧化钠和余量的水组成。通过使用风刀除去多孔基膜表面多余的残留溶液，然后再均匀施加第二相溶液，其中第二相溶液由0.3wt％均苯三甲酰氯和余量的正己烷组成，在温度20℃下，使第一相和第二相溶液充分接触1min，得到反渗透膜；将其浸泡于去离子水中待用。
实施例1
将聚砜溶液用刮刀直接刮涂在无纺布上，浸入水浴中以形成聚砜多孔基膜；
将含有聚多巴胺的第一相溶液均匀施加于聚砜多孔基膜表面，充分接触3min，其中第一相溶液由0.15wt％聚多巴胺、3wt％间苯二胺、0.05wt％十二烷基硫酸钠、0.02wt％氢氧化钠和余量的水组成，通过使用风刀除去聚砜多孔基膜表面多余的残留溶液，然后再均匀施加含2,3,5-三氯吡嗪的第二相溶液，其中第二相溶液由0.02wt％2,3,5-三氯吡嗪、0.3wt％均苯三甲酰氯和余量的正己烷组成，在温度20℃下，使第一相溶液和第二相溶液充分接触1min，以形成功能层；
在温度80℃下，浸入包含0.05wt％碳酸钠的水溶液中进行活化后处理60min，得到反渗透膜。
实施例2
除了将0.15wt％聚多巴胺改变为0.15wt％八臂聚乙烯醇-胺、将0.02wt％2,3,5-三氯吡嗪改变为0.02wt％2-溴-4,5-二氯咪唑和将0.05wt％碳酸钠改变为0.05wt％亚硫酸钠以外，以与实施例1相同的方式进行实施例2。
实施例3
除了将0.15wt％聚多巴胺改变为0.30wt％α-环糊精、将0.02wt％2,3,5-三氯吡嗪改变为0.02wt％2-氯-6,8-二溴嘌呤和将0.05wt％碳酸钠改变为0.05wt％草酸钾以外，以与实施例1相同的方式进行实施例3。
实施例4
除了将0.15wt％聚多巴胺改变为0.30wt％六杂臂乙二胺核聚多巴胺-聚乙烯亚胺、将0.02wt％2,3,5-三氯吡嗪改变为0.02wt％3,5,6-三氯哒嗪和将0.05wt％碳酸钠改变为0.05wt％磷酸二氢钠以外，以与实施例1相同的方式进行实施例4。
实施例5
除了将0.15wt％聚多巴胺改变为0.45wt％聚酰胺-胺、将0.02wt％2,3,5-三氯吡嗪改 变为0.02wt％2,5,6-三氯-1,3,4-三嗪和将0.05wt％碳酸钠改变为0.05wt％叔丁胺以外，以与实施例1相同的方式进行实施例5。
实施例6
除了将0.15wt％聚多巴胺改变为0.45wt％聚酰胺-胺、将0.02wt％2,3,5-三氯吡嗪改变为0.04wt％2,4,6-三溴-5-甲基嘧啶和将0.05wt％碳酸钠改变为0.1wt％三乙胺、在温度80℃下进行活化后处理90min以外，以与实施例1相同的方式进行实施例6。
实施例7
除了将0.15wt％聚多巴胺改变为0.45wt％聚酰胺-胺、将0.02wt％2,3,5-三氯吡嗪改变为0.04wt％2-氯-4,5-二溴噻唑和将0.05wt％碳酸钠改变为0.2wt％丁二酸钾、在温度40℃下，使第一相溶液和第二相溶液充分接触2min、在温度90℃下进行活化后处理120min以外，以与实施例1相同的方式进行实施例7。
实施例8
除了将0.15wt％聚多巴胺改变为0.45wt％聚酰胺-胺、将0.02wt％2,3,5-三氯吡嗪改变为0.06wt％2,3-二氯-4-溴喹啉和将0.05wt％碳酸钠改变为0.2wt％柠檬酸钠、在温度40℃下，使第一相溶液和第二相溶液充分接触2min、在温度90℃下进行活化后处理150min以外，以与实施例1相同的方式进行实施例8。
反渗透膜的水通量、脱盐率(NaCl截留率)的测试
取实施例1至8中制备的反渗透膜，在如下的操作条件下测试水通量和脱盐率：运行压力为800psi，进水为氯化钠浓度为32000ppm的水溶液，运行时间为30min。
膜片的水通量、脱盐率如下表1所示：
表1
编号 水通量(L/m 2h) NaCl截留率(％)
对照例1 45.6 99.20
实施例1 53.8 99.46
实施例2 51.4 99.58
实施例3 49.6 99.63
实施例4 45.3 99.70
实施例5 40.3 99.86
实施例6 43.1 99.77
实施例7 46.8 99.72
实施例8 52.4 99.69
由上表1的结果可知，通过本公开的方法制备的反渗透膜具有高达50L/m 2h以上的水通量，并且具有极高的脱盐率，可以有效地实现对于海水的高效淡化处理。
反渗透膜的亲水性的测试
取实施例5至8中制备的反渗透膜，测试其表面的水滴接触角，结果列于下表2中。
表2
编号 水滴接触角(°)
实施例5 48.7
实施例6 44.2
实施例7 39.4
实施例8 36.2
由表2的结果可见，通过本公开的方法制备的反渗透膜具有优异的亲水性。
反渗透膜的抗污染性能的测试
取对照例1和实施例8制备的反渗透膜，采用牛血清白蛋白(BSA)浓度为50ppm的水溶液对膜进行连续污染8h，对被污染前、污染过程中和清洗后的通量进行测试，在如下的操作条件下测试水通量：运行压力为800psi，进水为氯化钠浓度为32000ppm的水溶液，运行时间为30min。在如下操作条件下进行清洗：进水为纯水，设置运行压力为40psi，调控进水流量为8m 3/h，水温设置为25℃，运行15min后停止，完成清洗过程。
将结果示于图1中，由图1可见，在进行污染处理前，实施例8中制备的反渗透膜的水通量显著高于对照例1制备的反渗透膜，在污染过程中，对照例1制备的反渗透膜和实施例8中制备的反渗透膜的水通量均有所降低，在经污染且清洗后，实施例8制备的反渗透膜的水通量的恢复率高于98％，基本上恢复到被污染之前的水通量的水平，然而，对 照例1的反渗透膜在经污染且清洗后，水通量明显低于被污染之前的水通量的水平。因此，由图1的结果可以看出，根据本公开的方法制备的反渗透膜具有优异的抗污染性。
反渗透膜的耐酸洗碱洗性能的测试
取实施例8制备的反渗透膜，经过4次盐酸浓度为0.3wt％的酸洗和4次氢氧化钠浓度为0.3wt％的碱洗，酸洗和碱洗交替进行，每次清洗时间为4h，每完成1次4h酸洗和1次4h碱洗视为完成1次清洗。
测试：清洗前、完成1次清洗、完成2次清洗、完成3次清洗和完成4次清洗时的水通量和脱盐率，在如下的操作条件下测试水通量和脱盐率：运行压力为800psi，进水为氯化钠浓度为32000ppm的水溶液，运行时间为30min。将结果列于下表3。
表3
  通量(L/m 2h) 脱盐率(％)
初始值 51.4 99.60
1次清洗 53.4 99.48
2次清洗 52.8 99.60
3次清洗 53.0 99.54
4次清洗 53.6 99.56
由表3的结果可见，通过本公开的方法制备的反渗透膜在进行酸洗碱洗前，具有高达50L/m 2h以上的水通量，并且具有极高的脱盐率，在进行多次酸洗碱洗之后，脱盐率仍然基本保持了初始时的水平，通量不仅没有降低，而且略有提高。
由表3的结果可见，通过本公开的方法制备的反渗透膜具有优异的耐酸洗碱洗性能。
以上所述的具体实施例，对本公开的目的、技术方案和有益效果进行了进一步的详细说明，应理解的是，以上所述仅为本公开的实施例而已，并不用于限制本公开，凡在本公开的原则和精神之内，所做的任何修改、等同替换、改进等，均应包含在本公开的保护范围之内。
产业上的可利用性
通过本公开的方法可以提高功能层的交联度和调节功能层的疏松度，该方法操作过程简单，无需对现有设备进行改造，生产成本经济有效。通过本公开的方法制备的反渗透膜不仅具有较高的水通量和极高的脱盐率，而且具有优异的耐酸洗碱洗性能、使用耐久性和抗污染耐久性，可以有效地应用于海水淡化。

Claims (9)

  1. 一种反渗透膜的制备方法，其特征在于，包括以下步骤：
    配制聚合物溶液作为铸膜液，使所述铸膜液在增强材料上形成聚合物多孔基膜；
    将所述聚合物多孔基膜依次与第一相溶液、第二相溶液接触以形成功能层，其中所述第一相溶液包含胺类化合物、第一相添加剂和水，所述第二相溶液包含酰氯类化合物、第二相添加剂和溶剂，所述第一相添加剂是超支化聚合物，所述第二相添加剂是卤代杂环类化合物，形成功能层的步骤在温度为5至60℃的条件下进行；
    经后处理得到反渗透膜，其中所述后处理包括与包含活化剂的水溶液在温度为60℃至90℃的条件下接触，所述活化剂为选自碳酸钠、碳酸钾、亚硫酸钠、丙二酸钠、丁二酸钠、丁二酸钾、草酸氢钠、磷酸二氢钠、柠檬酸钠、柠檬酸钾、乳酸钠、碳酸氢钠、叔丁胺、三乙胺、草酸钠的至少一种。
  2. 根据权利要求1所述的制备方法，其中，所述聚合物溶液包含聚合物和溶剂，所述聚合物为选自聚砜、聚醚砜、聚偏氟乙烯、聚四氟乙烯、聚醚醚酮、杂萘联苯聚醚腈酮、杂萘联苯聚醚酮的至少一种。
  3. 根据权利要求1或2所述的制备方法，其中，所述超支化聚合物为选自树枝形聚胺、树枝状多元醇、星形多元醇、星形多元胺、星形杂臂聚胺的至少一种。
  4. 根据权利要求1或2所述的制备方法，其中，以所述第一相溶液的重量计，所述第一相添加剂的含量为0.01wt％～2wt％。
  5. 根据权利要求1或2所述的制备方法，其中，所述卤代杂环类化合物为选自以下杂环类化合物中的至少一种杂环类化合物的卤代物：吡嗪类化合物、哒嗪类化合物、噻唑类化合物、喹啉类化合物、三嗪类化合物、吲哚类化合物、嘌呤类化合物、嘧啶类化合物、咪唑类化合物。
  6. 根据权利要求1或2所述的制备方法，其中，以所述第二相溶液的重量计，所述第二相添加剂的含量为0.02wt％～0.5wt％。
  7. 根据权利要求1或2所述的制备方法，其中，以所述包含活化剂的水溶液的重量计，所述活化剂的含量为0.01wt％～0.2wt％。
  8. 一种根据权利要求1～7任一项所述的制备方法制得的反渗透膜。
  9. 一种根据权利要求8所述的反渗透膜在海水淡化中的应用。
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