WO2022032730A1 - 一种耐溶剂反渗透复合膜的制备方法 - Google Patents

一种耐溶剂反渗透复合膜的制备方法 Download PDF

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WO2022032730A1
WO2022032730A1 PCT/CN2020/111593 CN2020111593W WO2022032730A1 WO 2022032730 A1 WO2022032730 A1 WO 2022032730A1 CN 2020111593 W CN2020111593 W CN 2020111593W WO 2022032730 A1 WO2022032730 A1 WO 2022032730A1
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polysulfone
solvent
reverse osmosis
composite membrane
osmosis composite
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PCT/CN2020/111593
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English (en)
French (fr)
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武少禹
张建峰
徐媛媛
刘星
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南京水联天下海水淡化技术研究院有限公司
南京水杯子科技股份有限公司
南京水联天下新材料开发有限公司
南京帝膜净水材料开发有限公司
安徽昂可特膜科技有限公司
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Publication of WO2022032730A1 publication Critical patent/WO2022032730A1/zh

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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
    • B01D71/56—Polyamides, e.g. polyester-amides
    • 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
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • 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
    • 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
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • 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
    • B01D71/02—Inorganic material
    • 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
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
    • 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

Definitions

  • the invention belongs to the technical field of preparation of separation membrane materials, relates to a preparation method of a reverse osmosis composite membrane, and in particular relates to a preparation method of a polyamide (PA) reverse osmosis composite membrane with solvent resistance and high temperature resistance.
  • PA polyamide
  • Membrane separation has become one of the most important technologies by addressing some of the above pressing issues. Membrane separation technology is becoming more and more important in the separation industry, and can be applied to the separation of various molecular weight components in the gas phase or liquid phase. Basic Principles of Membrane Technology, 2nd edition, M. Mulder, Kluwer Academic Press, Dordrecht, p. 564). Membrane separation includes microfiltration, ultrafiltration, nanofiltration and reverse osmosis. Reverse osmosis (RO) is currently the most widely used seawater desalination technology in the world. Compared with other technologies, it has higher efficiency and lower cost. 65% of the total desalination plant.
  • RO Reverse osmosis
  • RO membranes strongly depends on the membrane material and structure, and most commercial RO membranes are thin-film composites (TFCs) made of polymers with high mechanical, thermal, and chemical stability.
  • TFCs thin-film composites
  • the composite membrane widely used in the water treatment industry mainly adopts the method of interfacial polymerization, and the polyamide film is composited on the surface of the microporous supporting bottom membrane. The general process is described in detail in technological US Patent 4,277,344.
  • the microporous bottom membrane formed by coating polysulfone on polyester non-woven fabric is immersed in diamine or polyamine aqueous solution, and then the excess amine solution on the membrane surface is removed by air shower, rolling and other methods, and then immersed in In the organic non-polar solution of polybasic acid chloride, interfacial polymerization reaction occurs with acid chloride, thereby forming a dense ultra-thin polyamide active layer with separation function on the surface. After film formation, sufficient washing and appropriate thermal curing treatment can increase the film performance.
  • the polysulfone in the polyamide composite membrane structure is a non-crosslinked linear structure, so in the process of treating wastewater containing organic solvents, especially solvents such as polysulfone materials such as amides, alkanones, sulfoxides, etc., the solvent
  • the swelling effect on polysulfone greatly shrinks the membrane pores, thereby causing a rapid attenuation of the water flux.
  • the same problem also exists in the treatment of high-temperature wastewater, which greatly limits the application range of polyamide composite membranes.
  • the present invention aims to propose a preparation method of a solvent-resistant and high-temperature-resistant reverse osmosis composite membrane;
  • the material is introduced into a membrane layer, which generates free radical groups through light to carry out redox reaction, which makes it show better structural stability than pure polymer reverse osmosis membrane, and at the same time improves the hydrophilicity and pollution resistance of the membrane.
  • the present invention provides a preparation method of a solvent-resistant polyamide reverse osmosis composite membrane, comprising the following steps:
  • step (2) contacting the porous polysulfone supported membrane prepared in step (1) with an aqueous solution (aqueous phase) containing inorganic photocatalytic nanomaterials and monomer m-phenylenediamine; removing excess isophthalic diamine on the surface of the porous polysulfone supported membrane
  • amine solution react with n-hexane solution (organic phase) containing inorganic photocatalytic nanomaterials and monomer trimesoyl chloride to form a film containing polyamide layer; use excess n-hexane to make the surface of the film containing polyamide layer undisturbed.
  • the fully reacted trimesoyl chloride solution is removed and heat treated to obtain a solvent-resistant polyamide (PA) reverse osmosis composite membrane.
  • PA solvent-resistant polyamide
  • the inorganic photocatalytic nanomaterials are independently TiO2, La2O3, CeO2, MnO2, ZrO2, ZnO, SnO2, ZnS, CuS, FeS, Ag2S, CdS, C3N4 and their modifications.
  • One or more of the chemical compounds; preferably, the modified compound is graphene oxide modified TiO2 nanoparticles, and its chemical formula is TiO2GO- TiO2 NPs.
  • step (1) in a dimethylformamide (DMF) solution containing inorganic photocatalytic nanomaterials and polysulfone: polysulfone (PSF) is a membrane material, dimethylformamide (DMF) is a solvent, and polysulfone ( PSF) weight percentage is 13-19wt%; the amount of inorganic photocatalytic nanomaterials is 0-5wt% of the total amount of polysulfone and dimethylformamide, preferably 0.1-5.0wt%, more preferably 0.3-2.0 wt%.
  • DMF dimethylformamide
  • PSF polysulfone
  • step (1) when the wet polysulfone film stays in the air, and/or after the polysulfone film leaves the coagulation tank of the pure water coagulation bath, it is irradiated with an ultraviolet lamp or an electron accelerator; the time of staying in the air is 2- 30s (please add).
  • the wavelength of the ultraviolet lamp is 157-436nm
  • the irradiation is 5s-600s
  • the distance from the light source to the film surface is 0.5-1000mm
  • the electron accelerator energy is 1KeV-5MeV
  • the irradiation is 1-300s
  • the distance from the light source to the film surface is 0.5-1000mm.
  • step (2) in the aqueous solution containing inorganic photocatalytic nanomaterials and monomer m-phenylenediamine, the m-phenylenediamine concentration is 1.5-3.0 wt%, and the inorganic photocatalytic nanomaterial content is 0-0.2 wt%, preferably: 0.005-0.1 wt %, more preferably 0.01-0.1 wt %; react in this solution for 10-120 s.
  • step (2) in the n-hexane solution containing inorganic photocatalytic nanomaterials and monomer trimesoyl chloride, the concentration of trimesoyl chloride is 0.05-0.20wt%, and the content of inorganic photocatalytic nanomaterials is 0-0.2wt%, preferably It is 0.005-0.1 wt %, more preferably 0.01-0.1 wt %; the reaction is carried out in this solution for 5-30 s.
  • step (2) the temperature of the heat treatment is 50-120° C., and the time of the heat treatment is 1-10 min.
  • step (2) after the excess m-phenylenediamine solution on the surface of the porous polysulfone supporting membrane, reacts with the n-hexane solution (organic phase) containing inorganic photocatalytic nanomaterials and monomer trimesoyl chloride, and/or heat treatment Then, irradiate with ultraviolet lamp or electron accelerator.
  • the wavelength of the ultraviolet lamp is 248-365nm
  • the irradiation is 5-600s
  • the distance from the light source to the film surface is 0.5-1000mm
  • the electron accelerator energy is 1KeV-5MeV
  • the irradiation is 1-300s
  • the distance from the light source to the film surface is 0.5-1000mm.
  • the present invention also provides a solvent-resistant reverse osmosis composite membrane, comprising a polyamide layer and a polysulfone layer abutting against each other, wherein photoactive nanoparticles are dispersed in the polyamide layer and the polysulfone layer respectively.
  • the present invention proposes a preparation method of a solvent-resistant reverse osmosis composite membrane.
  • the polyamide (PA) thin layer is synthesized by the interfacial polymerization of m-phenylenediamine and trimesoyl chloride.
  • Inorganic photocatalytic nanomaterials are introduced into the membrane layer prepared by this method, and free radicals are generated by light to form a cross-linked structure between polysulfone molecules or polysulfone molecules and polyamide molecules, which makes it perform better than general reverse osmosis membranes.
  • the structural stability of the composite film is improved, and the solvent resistance and high temperature resistance of the composite film are improved.
  • the surface modification improves the dispersibility of metal oxide nanoparticles in related solutions.
  • GO modified TiO2 nanoparticles are monomers in polysulfone casting solution and composite process. Better dispersibility can be obtained in all solutions.
  • Fig. 1 is the structural representation of solvent-resistant polyamide reverse osmosis composite membrane
  • Fig. 2 is a film forming process diagram of a porous polysulfone supported membrane
  • Figure 3 is a process diagram of the film forming process of the solvent-resistant polyamide (PA) reverse osmosis composite membrane
  • Fig. 4 is the synthetic route diagram of graphene oxide modified TiO2 nanoparticles
  • Example 5 is an electron microscope photograph of the cross-section of the composite film obtained in Comparative Example (top) and Example 8 (bottom).
  • FIG. 6 AFM photographs of the surfaces of the composite films obtained in Comparative Example (top) and Example 8 (bottom).
  • the preparation method of graphene oxide modified TiO2 nanoparticles comprising the following steps:
  • a certain amount of graphene oxide was poured into a beaker containing 50 mL of deionized water, and after rapid stirring, the beaker was sealed with parafilm and placed in an ultrasonic instrument, and ultrasonicated for 2 h. Then, a certain amount of hydrochloric acid (HCL), sulfuric acid (H 2 SO 4 ), and titanium tetrachloride (TiCl 4 ) solution was added to the above aqueous solution with a pipette, and then sonicated for 30 min after magnetic stirring for 1 h. The sonicated solution was transferred to the inner tank of a polytetrafluoroethylene hydrothermal kettle, and hydrothermally heated at 180 °C for 24 h. After the hot water is over, wash it several times until neutral. Freeze dry for 24h. Store in a dry environment for experimental use.
  • HCL hydrochloric acid
  • sulfuric acid H 2 SO 4
  • TiCl 4 titanium tetrachloride
  • a certain amount of polysulfone resin (PSF) and the GO-TiO 2 NPs synthesized above were dissolved and dispersed in a certain mass of dimethylformamide (DMF), stirred at 60°C until the PSF was completely dissolved, and vacuumed at room temperature. Deaeration for 8h.
  • the defoamed casting liquid is evenly coated on a non-woven fabric with a thickness of 100um to make a thin layer of casting liquid of a certain thickness. After staying at room temperature for a period of time, it is immersed in a constant temperature gel bath (pure water). After washing in another pure water for a certain period of time, roll it up for use.
  • a certain amount of nanoparticles, m-phenylenediamine, and water are prepared into a transparent aqueous solution; a certain amount of nanoparticles, trimesoyl chloride, and anhydrous n-hexane water are prepared into a transparent organic solution; the above-mentioned bottom film is soaked In the m-phenylenediamine solution for a certain period of time, then take it out to remove the excess m-phenylenediamine solution on the surface of the bottom film, and then contact and react with the trimesoyl chloride solution for a certain period of time to form a film containing a polyamide layer; alkane to remove the unreacted trimesoyl chloride solution on the surface of the membrane containing the polyamide layer, then heat treatment to solidify, wash, and wind up to obtain a polyamide reverse osmosis composite membrane.
  • Example 1 Disperse 2wt% GO-TiO 2 NPs in a casting solution containing 18wt% polysulfone and 80% dimethylformamide, other base membrane fabrication and composite processes are the same as in the comparative example, and the test conditions are the same as those in the comparative example The same results are listed in Table 1.
  • the retention rate of NaCl after DMF treatment was 95.1%, and the water flux was 0.70M 3 /M 2 .d.
  • the detailed results and the determination of DMF insoluble solids content are shown in Table 1.
  • Example 2 Other film-forming conditions were the same as those in Example 1.
  • the polysulfone wet film was irradiated with a deuterium ultraviolet lamp (254 nm) for 20 seconds before entering the pure water coagulation bath.
  • the test conditions were the same as those of the comparative example, the rejection rate of NaCl after DMF treatment was 97.9%, and the water flux was 0.87M 3 /M 2 .d.
  • the detailed results and the determination of DMF insoluble solids content are shown in Table 1.
  • Example 3 Other membrane preparation conditions were the same as those in Example 1, and the polysulfone membrane was irradiated with a deuterium ultraviolet lamp for 120 seconds during the process of entering the pure water coagulation bath.
  • the test conditions were the same as those of the comparative example, the rejection rate of NaCl after DMF treatment was 98.2%, and the water flux was 0.92M 3 /M 2 .d.
  • the detailed results and the determination of DMF insoluble solids content are shown in Table 1.
  • Example 4 Other film-forming conditions were the same as those of Example 3. After composite film-forming, the film surface was irradiated with a deuterium ultraviolet lamp for 120 seconds before heating and curing. The test conditions were the same as those of the comparative example, the rejection rate of NaCl after DMF treatment was 98.4%, and the water flux was 0.98M 3 /M 2 .d. The detailed results and the determination of DMF insoluble solids content are shown in Table 1.
  • Example 5 Other film-forming conditions were the same as those of Example 3. During the film-forming process of the composite film, a deuterium ultraviolet lamp (254 nm) was used to irradiate the film surface for 60 seconds. The test conditions were the same as those of the comparative example, the retention rate of NaCl after DMF treatment was 98.2%, and the water flux was 1.23M 3 /M 2 .d. The detailed results and the determination of DMF insoluble solids content are shown in Table 1.
  • Example 6 Other film-forming conditions were the same as those in Example 1. During the process of entering the polysulfone membrane into the pure water coagulation bath, the membrane surface was irradiated with a 10KeV electron accelerator for 120 seconds. The test conditions were the same as those of the comparative example, the rejection rate of NaCl after DMF treatment was 97.5%, and the water flux was 1.02M 3 /M 2 .d. The detailed results and the determination of DMF insoluble solids content are shown in Table 1.
  • Example 7 Other film-forming conditions were the same as those in Example 6. During the composite film-forming and washing process, the surface of the film was irradiated with a 10KeV electron accelerator for 200 seconds. The test conditions were the same as those of the comparative example, the rejection rate of NaCl after DMF treatment was 95.2%, and the water flux was 1.45M 3 /M 2 .d. The detailed results and the determination of DMF insoluble solids content are shown in Table 1.
  • Example 8 The polysulfone base film was prepared under the same conditions as in Example 3.
  • the aqueous phase monomer of the composite membrane contained 0.02% GO-TiO 2 NPs and 2% m-phenylenediamine, and the organic phase monomer contained 0.01% TiO 2 nanoparticles and 0.1% trimesoyl chloride, and the surface of the film was irradiated with a deuterium ultraviolet lamp for 600 seconds during the cleaning process of the composite film.
  • the test conditions were the same as those of the comparative example, the retention rate of NaCl after DMF treatment was 97.3%, and the water flux was 1.45M 3 /M 2 .d.
  • Table 1 The detailed results and the determination of DMF insoluble solids content are shown in Table 1.
  • Embodiment 9-17 is the solvent resistance of the photoactive material additives of different types and contents and the obtained composite films of different irradiation conditions, see Table 1 in detail.
  • Comparative example 18wt% polysulfone was dissolved in 82wt% N,N-dimethylformamide solvent with heating and stirring until it was completely dissolved, and after vacuum defoaming, it was brought to room temperature. A wet film with a thickness of about 150 microns was scraped on the surface of a polyester non-woven fabric with a thickness of 100 microns by a film casting machine. After staying in the air for a certain period of time, it was immersed in a pure water coagulation bath to form a polysulfone supporting bottom film with a thickness of about 60 microns. .
  • the polysulfone base film was immersed in an aqueous solution containing 2.0% m-phenylenediamine for 2 minutes, the surface of the film was pressed with a rubber roller to semi-dry, and then immersed in a 0.1% n-hexane solution of trimesoyl chloride for 20 seconds. After taking it out, put it into an oven at 110°C for 10 minutes, and then wash it thoroughly with alkaline solution, acid solution, alcohol solution and pure water in turn to test the membrane properties.
  • the composite membrane obtained by this comparative example has a rejection rate of 99.0% for NaCl and a water flux of 1.1M under the test conditions of 25° C., 1000ppm NaCl aqueous solution, 1.5MPa pressure, and 15% recovery rate (the above are referred to as standard test conditions). /M2.d .
  • the tested membrane was circulated for 24 hours in an aqueous solution containing 10000 ppm DMF with a pressure of 1.0 MPa above and a recovery rate of 15%, washed with pure water for 1 hour, and tested with standard test conditions, the rejection rate of NaCl dropped to 94.0% , the water flux is 0.63M 3 /M 2 .d.
  • Table 1 The detailed results and the determination of DMF insoluble solids content are shown in Table 1.
  • the reverse osmosis membrane sheets prepared in Examples 1 to 3 and the comparative example were made into 4040 standard roll-type membrane elements, and the reverse osmosis operation experiment was carried out to test the corresponding rejection rate and water flux.
  • Test starting conditions 1000 ppm NaCl in water, operating pressure 150 psi, recovery 15%.
  • the pure water flux is the water flux at standard temperature (25°C) after temperature coefficient correction.
  • the 4040 membrane element was cleaned with pure water under the pressure of 60Psi for 30min, and then used to contain 1% DMF and 1000ppm NaCl, the operating pressure was 150psi, and the recovery rate was 15%.
  • the pure water flux was measured continuously for 24 hours at standard temperature (25°C) after temperature coefficient correction, and the water flux and desalination rate were recorded and calculated.
  • the composite film was carefully peeled off from the non-woven fabric layer, dried in a vacuum oven at 100C for 4 hours, accurately weighed (W1 g), and wrapped with a clean and dry nickel mesh of known weight (W0 g).
  • the samples were placed in a Soxhlet extractor with 6 samples per set of extraction devices. Add 200ml of DMF, heat under reflux for more than 48 hours, and after the solvent is cooled to room temperature, take out the sample and place it in a beaker, and wash with an appropriate amount of anhydrous ethanol. Dry in an oven at 100°C for more than 4 hours, take out the sample, put it in a desiccator to cool for more than 30min, and accurately weigh the total weight W2 of the nickel mesh and gel.
  • the DMF-insoluble components in the composite film include the polyamide layer, inorganic nanoparticles and the gel produced after irradiation.

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Abstract

一种耐溶剂反渗透复合膜的制备方法，利用光催化改性技术，将无机光催化纳米材料引入了复合膜中的聚砜底膜及聚酰胺超薄复合层，通过紫外光照或电子束辐照产生自由基团提高复合膜各层内及界面层间的交联度，使其表现出比纯聚酰胺复合膜更优良的耐溶剂性能，同时耐氧化及耐高温性能也得到改善。

Description

一种耐溶剂反渗透复合膜的制备方法 技术领域
本发明属于分离膜材料的制备技术领域，涉及一种反渗透复合膜的制备方法，具体涉及一种耐溶剂耐高温的聚酰胺(PA)反渗透复合膜的制备方法。
背景技术
能源和环境问题，包括安全水危机、全球变暖和能源供应萎缩，近年来一直引起人们的极大关注。到目前为止，各种技术已经被初步探索，以获得清洁水，捕获“温室”气体，并找到替代能源。通过解决上述一些紧迫问题，膜分离已成为最重要的技术之一。膜分离技术在分离工业中越来越重要，可应用于气相或液相中各种分子量组分的分离，膜分离的特殊优点是不需要加热，因此能量的使用大大低于传统的热分离过程(Basic Principles of Membrane Technology，第二版，M.Mulder，Kluwer学术出版社，Dordrecht，564页)。膜分离包括微滤、超滤、纳滤和反渗透，反渗透(RO)是目前世界上应用最广泛的海水淡化技术，与其他技术相比，效率更高，成本更低，它占世界所有海水淡化装置总量的65％。
RO膜的性能在很大程度上取决于膜材料和结构，大多数商用RO膜是由具有高机械、热稳定性和化学稳定性的聚合物制成的薄膜复合材料(TFCs)。当前广泛用于水处理行业中的复合膜主要采取界面聚合的方式，将聚酰胺薄膜复合到微孔支撑底膜表面。通常的工艺过程，在开创性的美国专利4277344有详细介绍。首先将聚砜涂敷到聚酯无纺布上而形成的微孔底膜，浸入到二胺或多胺水溶液中，然后通过风淋，辊压等方法去除膜表面多余胺溶液，再浸入到多元酰氯的有机非极性溶液中与酰氯发生界面聚合反应，从而在表面形成致密的具有分离功能的聚酰胺超薄活性层，成膜后，充分洗涤及适当的热固化处理可增加膜性能。聚酰胺类复合膜结构中的聚砜为非交联的线型结构，因此在处理含有机溶剂尤其是聚砜材料的溶剂如酰胺类，烷酮类，亚砜类等的废水过程中，溶剂对聚砜的溶胀作用，使膜孔大幅收缩，从而使水通量急速衰减。在处理高温废水中也存在同样问题，这大大限制了聚酰胺类复合膜的使用范围。
因此，迫切需要节能和环保的耐溶剂及耐高温分离膜技术。
发明内容
发明目的：针对反渗透膜耐溶剂性能及耐高温性能差限制了其应用范围的问题，本发明旨在提出一种耐溶剂耐高温反渗透复合膜的制备方法；通过该方法将 无机光催化纳米材料引入了膜层，通过光照产生自由基团进行氧化还原反应，使其表现出比纯聚合物反渗透膜更优良的结构稳定性，同时改善了膜的亲水性与耐污染的能力。
技术方案：本发明提供了一种耐溶剂聚酰胺反渗透复合膜的制备方法，包括如下步骤：
(1)配制含无机光催化纳米材料和聚砜的二甲基甲酰胺(DMF)溶液，将该溶液用刮刀或挤出法在无纺布表面涂布，形成湿的聚砜薄膜，停留在空气中一段时间后进入纯水凝固浴的凝固槽中，形成多孔聚砜支撑膜；
(2)将步骤(1)制成的多孔聚砜支撑膜与含无机光催化纳米材料及单体间苯二胺的水溶液(水相)接触；除去多孔聚砜支撑膜表面过量的间苯二胺溶液后，与含无机光催化纳米材料及单体均苯三甲酰氯的正己烷溶液(有机相)反应，形成含有聚酰胺层的膜；用过量的正己烷将含有聚酰胺层的膜表面未反应完全的均苯三甲酰氯溶液除去，热处理，得到耐溶剂聚酰胺(PA)反渗透复合膜。
步骤(1)和步骤(2)中，所述无机光催化纳米材料分别独立地为TiO2、La2O3、CeO2、MnO2、ZrO2、ZnO、SnO2、ZnS、CuS、FeS、Ag2S、CdS、C3N4及其改性化合物中的一种或几种；优选地，改性化合物为氧化石墨烯改性TiO2纳米颗粒，其化学式为TiO2GO-TiO 2NPs。
步骤(1)中，含无机光催化纳米材料和聚砜的二甲基甲酰胺(DMF)溶液中：聚砜(PSF)为膜材料，二甲基甲酰胺(DMF)为溶剂，聚砜(PSF)重量百分比为13-19wt％；无机光催化纳米材料用量为聚砜和二甲基甲酰胺总用量的0-5wt％，优选地为0.1-5.0wt％，更有选地为0.3-2.0wt％。
步骤(1)中，在湿的聚砜薄膜停留在空气中时，和/或聚砜薄膜离开纯水凝固浴的凝固槽后，用紫外灯或电子加速器照射；停留空气中的时间为2-30s(请补充)。
优选地，紫外灯波长为157-436nm，照射5s-600s，光源到膜表面距离为0.5-1000mm；电子加速器能量1KeV-5MeV，照射1-300s，光源到膜表面距离为0.5-1000mm。
步骤(2)中，含无机光催化纳米材料及单体间苯二胺的水溶液中，间苯二胺浓度为1.5-3.0wt％，无机光催化纳米材料含量0-0.2wt％，优选地为0.005-0.1wt％，更有选地为0.01-0.1wt％；在该溶液中反应10-120s。
步骤(2)中，含无机光催化纳米材料及单体均苯三甲酰氯的正己烷溶液中，均苯三甲酰氯浓度为0.05-0.20wt％，无机光催化纳米材料含量0-0.2wt％，优选地为0.005-0.1wt％，更有选地为0.01-0.1wt％；在该溶液中反应5-30s。
步骤(2)中，热处理的温度为50-120℃，热处理的时间为1-10min。
步骤(2)中，多孔聚砜支撑膜表面过量的间苯二胺溶液后，与含无机光催化纳米材料及单体均苯三甲酰氯的正己烷溶液(有机相)反应后，和/或热处理后，用紫外灯或电子加速器照射。
优选地，紫外灯波长为248-365nm，照射5-600s，光源到膜表面距离为0.5-1000mm；电子加速器能量1KeV-5MeV，照射1-300s，光源到膜表面距离为0.5-1000mm。
本发明还提供了一种耐溶剂反渗透复合膜，包括互相靠接的聚酰胺层和聚砜层，所述聚酰胺层和聚砜层内分别分散光活性纳米颗粒。
有益效果：
第一，本发明提出一种耐溶剂反渗透复合膜的制备方法，聚酰胺(PA)薄层是由间苯二胺和均苯三甲酰氯的界面聚合合成的。通过该方法制备将无机光催化纳米材料引入了膜层，通过光照产生自由基团使聚砜分子或聚砜分子与聚酰胺分子间形成交联结构，使其表现出比通用反渗透膜更优良的结构稳定性，提高复合膜的耐溶剂及耐高温性能。
第二，表面改性使得金属氧化物纳米颗粒在相关溶液中的分散性得到提高，比如相比普通TO2纳米颗粒，GO改性TiO 2纳米颗粒在聚砜铸膜液及复合过程中的单体溶液中均可以得到更好的分散性。
附图说明
图1为耐溶剂聚酰胺反渗透复合膜的结构示意图；
图2为多孔聚砜支撑膜的成膜工艺过程图；
图3为耐溶剂聚酰胺(PA)反渗透复合膜的成膜工艺过程图；
图4为氧化石墨烯改性TiO2纳米颗粒的合成路线图；
图5为对比例(上)及实施例8(下)所得复合膜断面的电镜照片图。
图6对比例(上)及实施例8(下)所得复合膜表面AFM照片。
具体实施方式
以下为本发明的优选实施方式，仅用于解释本发明，而非用于限制本发明， 且由该说明所作出的相关改进都属于本发明所附权利要求所保护的范围：
氧化石墨烯改性TiO2纳米颗粒的制备方法，包括以下步骤：
取一定量的氧化石墨烯倒入装有50mL去离子水烧杯中，快速搅拌后用封口膜将烧杯封口放入超声仪器中，超声2h。之后用移液管移取一定量的盐酸(HCL)、硫酸(H 2SO 4)、四氯化钛(TiCl 4)溶液加入在上述水溶液中，磁力搅拌1h后再超声30min。将超声好的溶液转移至聚四氟乙烯水热釜内胆中，180℃下水热24h。水热结束后，多次水洗至中性。冷冻干燥24h。放置在干燥的环境下实验备用。
氧化石墨烯改性TiO2纳米颗粒掺杂的支撑底膜的制备：
将一定量的聚砜树脂(PSF)及上述合成的GO-TiO 2NPs，溶解分散于称取一定质量的二甲基甲酰胺(DMF)，在60C下，搅拌至PSF完全溶解，室温下真空脱泡8h。将脱泡的铸膜液均匀涂覆到100um厚的无纺布上，制成一定厚度的铸膜液薄层，在室温下滞留一段时间后，浸入恒温的凝胶浴槽中(纯水)，在另外纯水中清洗一定时间后，收卷待用。
氧化石墨烯改性TiO2纳米颗粒掺杂聚酰胺复合膜的制备：
将一定量的纳米颗粒，间苯二胺，及水配制成透明的水溶液；将一定量的纳米颗粒，均苯三甲酰氯，及无水正己烷水配制成透明的有机溶液；将上述底膜浸泡在间苯二胺溶液中一定时间，然后取出，除去该底膜表面过量的间苯二胺溶液，之后与均苯三甲酰氯溶液接触反应一定时间，形成含有聚酰胺层的膜；用过量的正己烷将含有聚酰胺层的膜表面未反应完全的均苯三甲酰氯溶液除去，然后进行热处理固化，洗涤，收卷得到聚酰胺反渗透复合膜。
实施例1：把2wt％GO-TiO 2NPs分散到含18wt％聚砜和80％二甲基甲酰胺的铸膜液中，其它底膜制造及复合工艺与对比例相同,测试条件同对比例相同,结果列入表1。经DMF处理后的NaCl的截留率95.1％，水通量0.70M 3/M 2.d。详细结果及DMF不溶解固体含量测定见表1。
实施例2：其它制膜条件与实施例1相同，聚砜湿膜在进入纯水凝固浴前用氘紫外灯(254nm)照射膜表面20秒。测试条件同对比例相同,经DMF处理后的NaCl的截留率97.9％，水通量0.87M 3/M 2.d。详细结果及DMF不溶解固体含量测定见表1。
实施例3：其它制膜条件与实施例1相同，聚砜膜进入纯水凝固浴过程中用 氘紫外灯照射膜表面120秒。测试条件同对比例相同,经DMF处理后的NaCl的截留率98.2％，水通量0.92M 3/M 2.d。详细结果及DMF不溶解固体含量测定见表1。
实施例4：其它制膜条件与实施例3相同，复合成膜后，加热固化前用氘紫外灯照射膜表面120秒。测试条件同对比例相同,经DMF处理后的NaCl的截留率98.4％，水通量0.98M 3/M 2.d。详细结果及DMF不溶解固体含量测定见表1。
实施例5：其它制膜条件与实施例3相同，复合膜成膜过程中用氘紫外灯(254nm)照射膜表面60秒。测试条件同对比例相同,经DMF处理后的NaCl的截留率98.2％，水通量1.23M 3/M 2.d。详细结果及DMF不溶解固体含量测定见表1。
实施例6：其它制膜条件与实施例1相同，聚砜膜进入纯水凝固浴过程中用10KeV的电子加速器辐照膜表面120秒。测试条件同对比例相同,经DMF处理后的NaCl的截留率97.5％，水通量1.02M 3/M 2.d。详细结果及DMF不溶解固体含量测定见表1。
实施例7：其它制膜条件与实施例6相同，复合成膜洗涤过程中用10KeV的电子加速器辐照膜表面200秒。测试条件同对比例相同,经DMF处理后的NaCl的截留率95.2％，水通量1.45M 3/M 2.d。详细结果及DMF不溶解固体含量测定见表1。
实施例8：聚砜底膜制膜条件与实施例3相同，复合膜水相单体含0.02％GO-TiO 2NPs及2％间苯二胺，有机相单体含0.01％TiO 2纳米颗粒及0.1％均苯三甲酰氯，复合膜清洗过程中用氘紫外灯照射膜表面600秒。测试条件同对比例相同,经DMF处理后的NaCl的截留率97.3％，水通量1.45M 3/M 2.d。详细结果及DMF不溶解固体含量测定见表1。
实施例9-17为不同种类及含量的光活性材料添加物及不同辐照条件所得复合膜的耐溶剂性能，详细见表1.
对比例:将18wt％的聚砜溶解82wt％的N,N-二甲基甲酰胺溶剂中加热搅拌至完全溶解，真空脱泡后将至室温。通过铸膜机在100微米厚的聚酯无纺布表面刮制约150微米厚的湿膜，空气中停留一定时间后，浸入到纯水凝固浴中，形成约60微米厚的聚砜支撑底膜。将该聚砜底膜浸入含2.0％的间苯二胺水溶液中2分钟，用橡皮辊压膜表面至半干后浸入0.1％的均苯三甲酰氯的正己烷溶液20秒。取出后放入110℃的烘箱处理10分钟，然后依次用碱溶液,酸溶液,醇溶液及纯水彻底清洗后测试膜性能。此对比例所得的复合膜在25℃，1000ppm NaCl水溶 液，1.5MPa压力，15％回收率的测试条件下(以上称标准测试条件)，对NaCl的截留率99.0％,水通量为1.1M 3/M 2.d。将测试过的该膜在含10000ppm DMF水溶液中用以上1.0MPa的压力及15％回收率下循环24小时，纯水冲洗1小时后，用标准测试条件测试，对NaCl的截留率下降到94.0％,水通量为0.63M 3/M 2.d。详细结果及DMF不溶解固体含量测定见表1。
膜性能测试
将实施例1～3和对比例制得的反渗透膜片制成4040标准卷式膜元件，进行反渗透操作实验，测试相应的脱盐率和水通量。
测试出始条件：1000ppmNaCl的水溶液，操作压力150psi，回收率15％。纯水通量为经过温度系数校正后的标准温度下(25℃)的水通量。
耐溶剂性能测试
4040膜元件用纯水在60Psi压力下清洗30min，后用含1％DMF及1000ppmNaCl,操作压力150psi，回收率15％。纯水通量为经过温度系数校正后的标准温度下(25℃)的水通量连续测试24h，记录及计算水通量及脱盐率。
复合膜内DMF不溶解固体含量检测
将复合膜小心从无纺布层剥离，100C真空烘箱干燥4小时，准确称重(W1克)，用已知重量(W0克)的洁净干燥的镍网包好。将样品放入索氏抽提器，每套抽提装置放6个样品。加入200ml DMF,加热回流48小时以上,待溶剂冷却至室温后，取出样品置于烧杯中，用适量无水乙醇清洗。在100℃的烘箱中干燥4小时以上，取出样品,放入干燥器中冷却30min以上，准确称量镍网和凝胶总重W2。
DMF不溶固体含量＝(W 2–W0)/W1×100％
复合膜内不溶于DMF的成分包括聚酰胺层，无机纳米颗粒及辐照后产生的凝胶。
表1
Figure PCTCN2020111593-appb-000001

Claims (11)

  1. 一种耐溶剂聚酰胺反渗透复合膜的制备方法，其特征在于：包括如下步骤：
    (1)配制含无机光催化纳米材料和聚砜的二甲基甲酰胺(DMF)溶液，将该溶液用刮刀或挤出法在无纺布表面涂布，形成湿的聚砜薄膜，停留在空气中一段时间后进入纯水凝固浴的凝固槽中，形成多孔聚砜支撑膜；
    (2)将步骤(1)制成的多孔聚砜支撑膜与含无机光催化纳米材料及单体间苯二胺的水溶液(水相)接触；除去多孔聚砜支撑膜表面过量的间苯二胺溶液后，与含无机光催化纳米材料及单体均苯三甲酰氯的正己烷溶液(有机相)反应，形成含有聚酰胺层的膜；用过量的正己烷将含有聚酰胺层的膜表面未反应完全的均苯三甲酰氯溶液除去，热处理，得到耐溶剂聚酰胺(PA)反渗透复合膜。
  2. 根据权利要求1所述的一种耐溶剂聚酰胺反渗透复合膜的制备方法，其特征在于：步骤(1)和步骤(2)中，所述无机光催化纳米材料分别独立地为TiO2、La2O3、CeO2、MnO2、ZrO2、ZnO、SnO2、ZnS、CuS、FeS、Ag2S、CdS、C3N4及其改性化合物中的一种或几种；优选地，改性化合物为氧化石墨烯改性TiO2纳米颗粒，其表达式为GO-TiO 2NPs。
  3. 根据权利要求1所述的一种耐溶剂聚酰胺反渗透复合膜的制备方法，其特征在于：步骤(1)中，含无机光催化纳米材料和聚砜的二甲基甲酰胺(DMF)溶液中：聚砜(PSF)为膜材料，二甲基甲酰胺(DMF)为溶剂，聚砜(PSF)含量占聚砜和二甲基甲酰胺总量的13-19wt％；无机光催化纳米材料用量为聚砜和二甲基甲酰胺总用量的0-5wt％，优选地为0.1-5.0wt％，更有选地为0.3-2.0wt％。
  4. 根据权利要求1所述的一种耐溶剂聚酰胺反渗透复合膜的制备方法，其特征在于：步骤(1)中，在湿的聚砜薄膜停留在空气中时，和/或聚砜薄膜离开纯水凝固浴的凝固槽后，用紫外灯或电子加速器照射；停留空气中的时间为1-30s。
  5. 根据权利要求4所述的一种耐溶剂聚酰胺反渗透复合膜的制备方法，其特征在于：紫外灯波长为157-436nm，照射5s-600s，光源到膜表面距离为0.5-1000mm；电子加速器能量1KeV-5MeV，照射1-300s，光源到膜表面距离为0.5-1000mm。
  6. 根据权利要求1所述的一种耐溶剂聚酰胺反渗透复合膜的制备方法，其 特征在于：步骤(2)中，含无机光催化纳米材料及单体间苯二胺的水溶液中，间苯二胺浓度为1.5-3.0wt％，无机光催化纳米材料含量0-0.2wt％，优选地为0.005-0.1wt％，更有选地为0.01-0.1wt％；在该溶液中反应10-120s。
  7. 根据权利要求1所述的一种耐溶剂聚酰胺反渗透复合膜的制备方法，其特征在于：步骤(2)中，含无机光催化纳米材料及单体均苯三甲酰氯的正己烷溶液中，均苯三甲酰氯浓度为0.05-0.20wt％，无机光催化纳米材料含量0-0.2wt％，优选地为0.005-0.1wt％，更有选地为0.01-0.1wt％；在该溶液中反应5-30s。
  8. 根据权利要求1所述的一种耐溶剂聚酰胺反渗透复合膜的制备方法，其特征在于：步骤(2)中，热处理的温度为50-120℃，热处理的时间为1-10min。
  9. 根据权利要求1所述的一种耐溶剂聚酰胺反渗透复合膜的制备方法，其特征在于：步骤(2)中，多孔聚砜支撑膜表面过量的间苯二胺溶液后，与含无机光催化纳米材料及单体均苯三甲酰氯的正己烷溶液(有机相)反应后，和/或热处理后，用紫外灯或电子加速器照射。
  10. 根据权利要求9所述的一种耐溶剂聚酰胺反渗透复合膜的制备方法，其特征在于：紫外灯波长为157-436nm，照射5-600s，光源到膜表面距离为0.5-1000mm；电子加速器能量1KeV-5MeV，照射1-300s，光源到膜表面距离为0.5-1000mm。
  11. 一种耐溶剂反渗透复合膜，其特征在于：包括互相靠接的聚酰胺层和聚砜层，所述聚酰胺层和聚砜层内分别分散光活性纳米颗粒。
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