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WO2018000361A1 - Preparation method for polysulfonamide nanofiltration or reverse osmosis composite membrane by molecular layer assembly - Google Patents

Preparation method for polysulfonamide nanofiltration or reverse osmosis composite membrane by molecular layer assembly Download PDF

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Publication number
WO2018000361A1
WO2018000361A1 PCT/CN2016/087981 CN2016087981W WO2018000361A1 WO 2018000361 A1 WO2018000361 A1 WO 2018000361A1 CN 2016087981 W CN2016087981 W CN 2016087981W WO 2018000361 A1 WO2018000361 A1 WO 2018000361A1
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WIPO (PCT)
Prior art keywords
preparation
polysulfonamide
solution
nanofiltration
reverse osmosis
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French (fr)
Chinese (zh)
Inventor
牛青山
袁涛
胡月芳
郭鑫
李鹏
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China University of Petroleum East China
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China University of Petroleum East China
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Priority to CN201680003641.XA priority Critical patent/CN106999870A/en
Priority to PCT/CN2016/087981 priority patent/WO2018000361A1/en
Publication of WO2018000361A1 publication Critical patent/WO2018000361A1/en
Anticipated expiration legal-status Critical
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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
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • 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
    • 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
    • B01D61/027—Nanofiltration
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/105—Support pretreatment
    • 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
    • B01D69/1214—Chemically bonded layers, e.g. cross-linking
    • 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
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • 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

Definitions

  • the invention relates to a preparation technology of a polymer composite membrane, in particular to a preparation method of a polysulfonamide nanofiltration or reverse osmosis composite membrane which is resistant to acid, alkali, oxidation and surface roughness.
  • Aramid interfacial polymerization technology has been widely used in the field of water treatment such as seawater desalination, reclaimed water, sewage treatment, drinking water preparation, etc. Applications.
  • the performance of membrane materials is also constantly being optimized.
  • membrane surface modification and doping of nanoparticles have become hot research directions to further improve the comprehensive performance of reverse osmosis or nanofiltration composite membrane materials (CN104028126, CN102294178 and literature). Reports Journal of Membrane Science, 320, (2008), Polymer, 48, (2007), Journal of Membrane Science, 367, (2011), Desalination 219, (2008), etc.).
  • the surface functional cortex of the mainstream roll-type nanofiltration or reverse osmosis composite membrane on the market is still based on polyamide formed by polyacid chloride (such as 1,3,5-benzenetricarboxylic acid chloride) and polyamine (such as m-phenylenediamine or piperazine).
  • a crosslinked network structure is prepared (US Pat. No. 5,693,227, US Pat. No. 4,769,148, US Pat. No. 5,152,901).
  • the above monomers are also considered to be the most effective for the preparation of nanofiltration or reverse osmosis membranes by interfacial polymerization.
  • the amide bond in the polyamide structure is hydrolyzed under low and high pH conditions, which restricts the application of the above composite film in harsh environments. Therefore, it is of great practical significance to develop new nanofiltration or reverse osmosis membrane materials and their key preparation techniques that are widely applicable to complex fluids, especially various acid-base industrial fluids.
  • the polysulfonamide structure has excellent acid and alkali resistance, thermal stability and oxidation resistance, and is used for interfacial polymerization preparation of novel nanofiltration or reverse osmosis composite membranes.
  • Patent US6783711 US6873996, US20120152839, CN102120149, etc. and literature Journal of Membrane Science, 143, 181 (1998), Journal of Applied Polymer Science, 48, 187 (1993), Journal of Applied Polymer Science, 54, 1233, (1994), Journal of Applied Polymer Science, 64 , 2381 (1997), etc. have reported the study of interfacial polymerization to prepare polysulfonamide nanofiltration or reverse osmosis membranes.
  • the commercial products of nanofiltration or reverse osmosis membranes based on polysulfonamide structure are still few, mainly due to the poor desalination performance of the composite membrane and low flux.
  • the polysulfonamide has a lower interfacial polymerization activity than the polyamide monomer.
  • the traditional interfacial polymerization technique for preparing polysulfonamide composite membranes is difficult to obtain stable and high membrane separation performance.
  • the performance improvement of polysulfonamide nanofiltration or reverse osmosis membrane materials is still by exploring the best catalyst or acid absorber, increasing the monomer concentration or increasing the heat treatment temperature.
  • the molecular layer assembly technique can effectively compensate for the problem of poor salt rejection of the selective functional layer prepared by crosslinking of the lower reactive monomer.
  • the molecular layer layer assembly preparation composite membrane technology of the invention can effectively compensate for the defects existing in the preparation of the polysulfonamide nanofiltration or reverse osmosis composite membrane by the interfacial polymerization process, so as to achieve higher desalination performance.
  • the present technology is applicable to the layered assembly preparation of composite functional layers between a plurality of low reactivity monomers. Both the reported sulfonyl chloride and polyamine monomers can be used in the preparation of polysulfonamide nanofiltration or reverse osmosis composite membranes using the techniques of the present invention.
  • the invention is directed to the deficiencies of the prior art, and proposes a new method for preparing a polysulfonamide nanofiltration or reverse osmosis composite membrane, and uses the technology to prepare a polysulfonamide having high desalination performance, a smoother membrane surface and lower roughness. Nanofiltration or reverse osmosis membrane.
  • the technical problem to be solved by the present invention is to provide a method for preparing a polysulfonamide nanofiltration or reverse osmosis composite membrane having a simple operation process, high desalination property and low surface roughness.
  • the invention relates to a method for preparing a polysulfonamide nanofiltration or reverse osmosis composite membrane, which is characterized in that the polyamine and the polysulfonyl chloride layer are assembled on the surface of the porous support membrane to form a multilayer crosslinked polysulfonamide according to the principle of molecular layer assembly.
  • the covalent structure gives a polysulfonamide selective functional layer.
  • the method for preparing a polysulfonamide nanofiltration or reverse osmosis composite membrane layer assembly comprises the steps of: molecularly layering a porous support membrane in a solution of a sulfonyl chloride and a polyamine monomer, wherein the concentration of the sulfonyl chloride solution is 0.001%- 5%, the concentration of the sulfonyl chloride in the present invention is preferentially controlled in the range of 0.001% to 1%, the concentration of the polyamine monomer is 0.001% to 15%, and the concentration preferential control range of the present invention is 0.001% to 5%; heat treatment at 40-110 ° C, Wash thoroughly after washing.
  • the molecular layer layer assembly is performed by alternately immersing the porous support film in a solution of a sulfonyl chloride and a polyamine monomer, or uniformly spraying a solution of a sulfonyl chloride and a polyamine monomer on the surface of the porous support film, or by spin coating with a uniform rubber.
  • the method is carried out by spin-coating a solution of a sulfonyl chloride and a polyamine monomer on the surface of the porous support layer.
  • the heat treatment process for preparing the polysulfonamide nanofiltration or reverse osmosis membrane may be performed by immersing, spraying or spin-coating the polysulfonamide structure, or by immersing, spraying or spin coating to assemble a plurality of polysulfonamide structures. .
  • the technical solution includes a porous support membrane pretreatment step.
  • the pretreatment is to wash the porous support membrane with 30-50% aqueous solution of isopropanol or 30-50% aqueous solution of ethanol, and finally rinsed with pure water for use.
  • the technical solution layer is assembled to prepare a polysulfonamide nanofiltration or reverse osmosis composite membrane, and the number of assembled layers ranges from 1 to 50 layers.
  • the technical solution includes adding 0.0%-5% of the nanoparticles to form a polysulfonamide nanofiltration or reverse osmosis composite membrane in a polyamine monomer solution or a sulfonyl chloride monomer solution, and the nanoparticle addition range of the invention The preference is 0.0%-1%.
  • the range of nanoparticles in the technical solution includes known pores or nonporous, cyclic or acyclic Morphological inorganic or organic nanoscale particles.
  • the technical solution comprises introducing a polymer coating during the layer assembly preparation process of the polysulfonamide nanofiltration or reverse osmosis composite membrane to improve the performance of the composite membrane.
  • the polymer may be polyvinyl alcohol (PVA), polyethyleneimine (PEI), polylactic acid (PLA), polyacrylic acid (PAA), poly(2-alkyl-2-oxazoline) (POX), and Other coating materials that are not specified but can serve the same purpose.
  • PVA polyvinyl alcohol
  • PEI polyethyleneimine
  • PLA polylactic acid
  • PAA polyacrylic acid
  • POX poly(2-alkyl-2-oxazoline)
  • the introduction of the polymer coating can be carried out before the layer assembly preparation process, after the layer assembly preparation process, and during the layer assembly preparation process.
  • polysulfonamide nanofiltration or reverse osmosis composite membrane preparation method characterized in that the polysulfonamide structure is formed by a molecular layer assembly process, and the following three layer assembly methods are merely illustrative and not limiting:
  • the porous support membrane is alternately immersed in a solution of a sulfonyl chloride and a polyamine monomer, the concentration of the sulfonyl chloride is 0.001% to 1%, and the concentration of the polyamine monomer is 0.001% to 5%.
  • the alternating soak assembly step is repeated a plurality of times.
  • the sulfonyl chloride and polyamine monomer solution are uniformly sprayed on the surface of the porous support film, the concentration of the sulfonyl chloride is 0.001% to 1%, and the concentration of the polyamine monomer is 0.001% to 5%.
  • the spray assembly step is cycled multiple times. Heat treatment at 40-110 ° C for 1-20 min, the heat treatment process can be carried out in the spray assembly polysulfonamide structure, or after assembling a multi-layer polysulfonamide structure. Finally, it was washed thoroughly with an aqueous ethanol solution for 30-60 min.
  • the sulfonyl chloride and the polyamine monomer solution are respectively spin-coated on the surface of the porous support layer by a spin coating method, the concentration of the sulfonyl chloride is 0.001% to 1%, and the concentration of the polyamine monomer is 0.001% to 5%.
  • the spin coating assembly step Heat treatment at 40-110 °C for 1-20 min, the heat treatment process can be carried out in the spin-coating polysulfonamide structure or after assembling a multi-layer polysulfonamide structure. Finally, it was washed thoroughly with an aqueous ethanol solution for 30-60 min.
  • the spin-coating layer for the preparation of polysulfonamide nanofiltration or reverse osmosis membranes is suitable for the production or modification of equipment according to the principles mentioned in the patent CN 204247481 U.
  • the porous support membrane of the polysulfonamide nanofiltration or reverse osmosis composite membrane of the present invention may be characterized by an organic polymer porous membrane such as polysulfone, polyethersulfone, polyacrylonitrile or the like, or an inorganic porous membrane such as ceramic. Membrane and the like.
  • the polysulfone porous membrane is preferably used in the present invention.
  • the invention relates to a method for preparing a polysulfonamide nanofiltration or reverse osmosis composite membrane, wherein the polysulfonyl chloride is a structure containing two or more "SO2" groups and linking a fat group, a phenyl group, a biphenyl group, a naphthyl group or the like.
  • the monomer is preferably 1,3,6-naphthalenetrisulfonyl chloride in the present invention.
  • the method for preparing a polysulfonamide nanofiltration or reverse osmosis composite membrane wherein the polyamine can be ethylenediamine, triethylenetetraamine (NH2CH2CH2NHCH2CH2NHCH2CH2NH2), meta-xylylenediamine or other multifunctional group of primary amines, a secondary amine; piperazine, or 2,5-dimethylpiperazine, or N,N'-diaminopiperazine, or other reactive piperazine-containing derivative, or a mixture thereof, preferably piperazine of the invention .
  • the polyamine can be ethylenediamine, triethylenetetraamine (NH2CH2CH2NHCH2CH2NHCH2CH2NH2), meta-xylylenediamine or other multifunctional group of primary amines, a secondary amine; piperazine, or 2,5-dimethylpiperazine, or N,N'-diaminopiperazine, or other reactive piperazine-containing derivative, or a mixture
  • the solvent of the polyamine solution may be water or an organic solvent or a mixed solvent thereof, and an organic solvent such as acetone, methanol, ethanol, isopropanol or the like, the present invention Water is preferred as the polyamine solvent.
  • the solvent of the sulfonyl chloride solution may be ethyl acetate, chloroform, toluene, xylene, Isopar series, n-hexane, heptane or n-dodecane or a mixed solvent of the above.
  • the polyamine solution contains 0.0% to 5% of a catalyst or an acid absorbent.
  • the catalyst or acid absorbent of the present invention is triethylamine, or sodium hydroxide, or sodium carbonate, and the like, and triethylamine is preferred in the present invention.
  • the polyamine solution contains 0.0%-10% of a porogen, such as camphorsulfonic acid and its triethylamine salt or the like. The same effect of the substance and so on.
  • nanoparticles are added to the polyamine monomer solution or the sulfonyl chloride monomer solution, and the nanoparticles are characterized by pores or nonporous, cyclic or acyclic. Inorganic or organic nanoscale particles.
  • a surfactant is added to the polyamine monomer solution or the sulfonyl chloride monomer solution, and the surfactant concentration range of the present invention is preferentially selected. It is from 0.0% to 2%.
  • the invention provides a polysulfonamide nanofiltration or reverse osmosis composite membrane method, wherein the surfactant comprises an anionic surfactant such as sodium dodecyl sulfate; a cationic surfactant such as a quaternary ammonium compound; zwitterionic surface active Agents such as lecithin, amino acid type and betaine type; nonionic surfactants such as fatty acid glycerides, polysorbates, etc.; polyoxyethylene type surfactants such as long chain fatty acid esters, fatty alcohol esters, phosphate esters Wait.
  • anionic surfactant such as sodium dodecyl sulfate
  • a cationic surfactant such as a quaternary ammonium compound
  • zwitterionic surface active Agents such as lecithin, amino acid type and betaine type
  • nonionic surfactants such as fatty acid glycerides, polysorbates, etc.
  • polyoxyethylene type surfactants such as long
  • the present invention also requires a polysulfonamide nanofiltration or reverse osmosis composite membrane prepared by the molecular layer assembly method.
  • the polysulfonamide nanofiltration or reverse osmosis composite membrane prepared by the invention is characterized in that the removal rate of the salt such as magnesium sulfate, calcium chloride and sodium chloride or the organic matter having a molecular weight of less than 1000 g/moL can be up to 99% or above.
  • the salt such as magnesium sulfate, calcium chloride and sodium chloride or the organic matter having a molecular weight of less than 1000 g/moL can be up to 99% or above.
  • the invention discloses a method for assembling a polysulfonamide composite membrane molecular layer layer, which is characterized in that a polysulfonamide composite membrane having different removal rates and different water flux properties can be prepared by adjusting the number of assembled layers.
  • the method for preparing a polysulfonamide composite membrane molecular layer layer according to the invention is characterized in that the surface roughness of the prepared polysulfonamide nanofiltration or reverse osmosis membrane is much lower than the surface of the polysulfonamide nanofiltration or reverse osmosis membrane prepared by the interfacial polymerization technique. Roughness.
  • the polysulfonamide structure to which the present invention relates is applicable to the polysulfonamide or modified polysulfonamide structures mentioned in the patents US Pat. No. 6,837,996 and US Pat.
  • the molecular layer assembly technique to which the present invention relates is a reference in Science 2003, 301, 818-821, J. Mater. Chem. 2007, 17, 664-669, Macromolecules, 2010, 43, 9056-9062 and the like. It is intended that two different monomers have mutual reactive groups. When the two monomers are in contact, the layers are assembled under certain conditions to form a crosslinked structure by covalent bonding.
  • the porogen mentioned in the present invention refers to a small molecule substance which is added during the film forming process, does not chemically react with the monomer, and is easily eluted to promote pore formation on the surface of the film.
  • the molecular layer assembly involved in the present invention means that two or more reactive monomers are adsorbed on the surface of the porous support film by alternate soaking, spraying, and spin coating, and the same layer of monomers, layers and layers are generated. The process of assembly cross-linking between the reactions.
  • the spray film formation of the present invention refers to a process in which a monomer compression solution can be atomized and sprayed on a surface of a film by a gas compression machine or a vessel and subjected to a certain condition to form a crosslinked film.
  • the spin coating film of the present invention refers to the principle of centrifugal rotation of a tray, placing the porous supporting film in the center of the tray of the homogenizer, dropping the monomer solution, and immersing for a certain time to set a certain rotation speed to screw out most of the liquid.
  • a thin layer of monomer liquid layer is uniformly spread on the surface of the film.
  • a process of forming a multi-layered monomer liquid layer on the surface of the film by alternately adding a monomer, and crosslinking the film formation after a certain condition.
  • the monolayer molecular layer assembly polysulfonamide composite membrane of the invention is defined as: the surface of the porous support membrane is treated by polyamine and sulfonyl chloride respectively to form a selective polysulfonamide functional layer, which is a single layer polysulfonamide nanofiltration. Or reverse osmosis composite membrane.
  • the addition concentration of the monomer, the acid absorbent, the catalyst and the nano particle of the invention is a mass percentage concentration, and the concentration of each substance added according to the invention can be used to prepare a polysulfonamide nanofiltration or reverse osmosis composite membrane by the technique of the invention. .
  • test conditions for the desalting performance of the polysulfonamide nanofiltration or reverse osmosis composite membrane prepared by the invention are the salt solution concentration of 2000 mg/L, the test pressure is 1.5 MPa, the system control temperature is 25 ° C, the cross flow operation mode test, the raw water flow control At 6-7 LPM.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

Provided is a method for preparing a polysulfonamide nanofiltration or reverse osmosis composite membrane, comprising the following steps: a porous support membrane is subjected to molecular layer assembly in a sulfonyl chloride and polyamine monomer solution, followed by a heat treatment at 40ºC to 110ºC, and finally, thorough washing with an aqueous ethanol solution. The polysulfonamide composite membrane thus prepared is especially suitable for the treatment of acidic or alkaline fluids.

Description

聚磺酰胺纳滤或反渗透复合膜的分子层层组装制备方法Molecular layer assembly preparation method of polysulfonamide nanofiltration or reverse osmosis composite membrane 技术领域Technical field

本发明涉及一种聚合物复合膜的制备技术，具体是指耐酸、耐碱、耐氧化、表面粗糙度低的聚磺酰胺纳滤或反渗透复合膜的制备方法。The invention relates to a preparation technology of a polymer composite membrane, in particular to a preparation method of a polysulfonamide nanofiltration or reverse osmosis composite membrane which is resistant to acid, alkali, oxidation and surface roughness.

背景技术Background technique

芳香聚酰胺界面聚合技术制备反渗透和纳滤膜材料工业应用以来，纳滤和反渗透膜分离技术在海水淡化、中水回用、污水处理、饮用水制备等水处理领域得到越来越广泛的应用。膜材料的性能也在不断地优化提高。经过近40年的快速发展，通过新型界面聚合单体的开发，膜表面改性以及掺杂纳米颗粒等成为进一步改善反渗透或纳滤复合膜材料综合性能的热点研究方向(CN104028126、CN102294178以及文献报道Journal of Membrane Science,320,(2008),Polymer,48,(2007),Journal of Membrane Science,367,(2011),Desalination 219,(2008)等)。Aramid interfacial polymerization technology has been widely used in the field of water treatment such as seawater desalination, reclaimed water, sewage treatment, drinking water preparation, etc. Applications. The performance of membrane materials is also constantly being optimized. After nearly 40 years of rapid development, through the development of new interfacial polymerization monomers, membrane surface modification and doping of nanoparticles have become hot research directions to further improve the comprehensive performance of reverse osmosis or nanofiltration composite membrane materials (CN104028126, CN102294178 and literature). Reports Journal of Membrane Science, 320, (2008), Polymer, 48, (2007), Journal of Membrane Science, 367, (2011), Desalination 219, (2008), etc.).

目前市场上主流卷式纳滤或反渗透复合膜表面功能皮层仍然是基于多元酰氯(如1,3,5-苯三甲酰氯)与多元胺(如间苯二胺或者哌嗪)形成的聚酰胺交联网络结构制备的(US 5693227,US 4769148,US 5152901)。上述单体也被认为是目前界面聚合制备纳滤或反渗透膜最有效的。然而聚酰胺结构中的酰胺键在低和高pH值条件下发生水解，制约了上述复合膜在苛刻环境中的应用。因此开发广泛适用于复杂流体尤其是各种酸碱工业流体的新型纳滤或反渗透膜材料及其关键制备技术具有十分重要现实意义。The surface functional cortex of the mainstream roll-type nanofiltration or reverse osmosis composite membrane on the market is still based on polyamide formed by polyacid chloride (such as 1,3,5-benzenetricarboxylic acid chloride) and polyamine (such as m-phenylenediamine or piperazine). A crosslinked network structure is prepared (US Pat. No. 5,693,227, US Pat. No. 4,769,148, US Pat. No. 5,152,901). The above monomers are also considered to be the most effective for the preparation of nanofiltration or reverse osmosis membranes by interfacial polymerization. However, the amide bond in the polyamide structure is hydrolyzed under low and high pH conditions, which restricts the application of the above composite film in harsh environments. Therefore, it is of great practical significance to develop new nanofiltration or reverse osmosis membrane materials and their key preparation techniques that are widely applicable to complex fluids, especially various acid-base industrial fluids.

近年来，聚磺酰胺结构具有优良的耐酸碱性质、热稳定性以及耐氧化性质，被用于新型纳滤或反渗透复合膜的界面聚合制备研究。专利US6783711、 US6873996、US20120152839、CN102120149等和文献Journal of Membrane Science,143,181(1998),Journal of Applied Polymer Science,48,187(1993),Journal of Applied Polymer Science,54,1233,(1994),Journal of Applied Polymer Science,64,2381(1997)等，都报道了界面聚合制备聚磺酰胺纳滤或反渗透膜的研究。然而基于聚磺酰胺结构的纳滤或反渗透膜商业化产品仍然较少，主要原因是复合膜脱盐性能差，通量低。In recent years, the polysulfonamide structure has excellent acid and alkali resistance, thermal stability and oxidation resistance, and is used for interfacial polymerization preparation of novel nanofiltration or reverse osmosis composite membranes. Patent US6783711 US6873996, US20120152839, CN102120149, etc. and literature Journal of Membrane Science, 143, 181 (1998), Journal of Applied Polymer Science, 48, 187 (1993), Journal of Applied Polymer Science, 54, 1233, (1994), Journal of Applied Polymer Science, 64 , 2381 (1997), etc., have reported the study of interfacial polymerization to prepare polysulfonamide nanofiltration or reverse osmosis membranes. However, the commercial products of nanofiltration or reverse osmosis membranes based on polysulfonamide structure are still few, mainly due to the poor desalination performance of the composite membrane and low flux.

聚磺酰胺相比聚酰胺单体的界面聚合反应活性较低。传统的界面聚合技术制备聚磺酰胺复合膜很难得到稳定且较高的膜分离性能。目前聚磺酰胺纳滤或反渗透膜材料性能的提高仍然是通过探索最佳的催化剂或酸吸收剂，提高单体浓度或者提高热处理温度等方法。然而，就我们所知目前尚没有稳定的高性能聚磺酰胺复合膜材料的制备报道。The polysulfonamide has a lower interfacial polymerization activity than the polyamide monomer. The traditional interfacial polymerization technique for preparing polysulfonamide composite membranes is difficult to obtain stable and high membrane separation performance. At present, the performance improvement of polysulfonamide nanofiltration or reverse osmosis membrane materials is still by exploring the best catalyst or acid absorber, increasing the monomer concentration or increasing the heat treatment temperature. However, as far as we know, there are no reports on the preparation of stable high performance polysulfonamide composite membrane materials.

在复合膜的制备过程中，分子层层组装技术可有效弥补较低活性单体交联制备选择性功能层脱盐率差的问题。本发明的分子层层组装制备复合膜技术可有效地弥补界面聚合过程制备聚磺酰胺纳滤或反渗透复合膜中存在的缺陷，以实现较高的脱盐性能。本发明技术可适用于多种低反应活性单体之间的复合功能层的层层组装制备。已知报道的磺酰氯和多胺单体均可利用本发明技术进行聚磺酰胺纳滤或反渗透复合膜的制备研究。In the preparation process of the composite membrane, the molecular layer assembly technique can effectively compensate for the problem of poor salt rejection of the selective functional layer prepared by crosslinking of the lower reactive monomer. The molecular layer layer assembly preparation composite membrane technology of the invention can effectively compensate for the defects existing in the preparation of the polysulfonamide nanofiltration or reverse osmosis composite membrane by the interfacial polymerization process, so as to achieve higher desalination performance. The present technology is applicable to the layered assembly preparation of composite functional layers between a plurality of low reactivity monomers. Both the reported sulfonyl chloride and polyamine monomers can be used in the preparation of polysulfonamide nanofiltration or reverse osmosis composite membranes using the techniques of the present invention.

发明内容Summary of the invention

本发明是针对现有技术的不足，提出制备聚磺酰胺纳滤或反渗透复合膜的新方法，并利用该技术制备出具有高脱盐性能，膜表面更光滑、粗糙度更低的聚磺酰胺纳滤或反渗透膜。The invention is directed to the deficiencies of the prior art, and proposes a new method for preparing a polysulfonamide nanofiltration or reverse osmosis composite membrane, and uses the technology to prepare a polysulfonamide having high desalination performance, a smoother membrane surface and lower roughness. Nanofiltration or reverse osmosis membrane.

本发明需要解决的技术问题是，提供操作过程简单，具有高脱盐性质及低表面粗糙度的聚磺酰胺纳滤或反渗透复合膜的制备方法。 The technical problem to be solved by the present invention is to provide a method for preparing a polysulfonamide nanofiltration or reverse osmosis composite membrane having a simple operation process, high desalination property and low surface roughness.

本发明制备聚磺酰胺纳滤或反渗透复合膜的方法，其特征是依据分子层层组装的原理，在多孔支撑膜表面催化多元胺与多元磺酰氯层层组装形成多层交联聚磺酰胺共价结构得到聚磺酰胺选择性功能层。The invention relates to a method for preparing a polysulfonamide nanofiltration or reverse osmosis composite membrane, which is characterized in that the polyamine and the polysulfonyl chloride layer are assembled on the surface of the porous support membrane to form a multilayer crosslinked polysulfonamide according to the principle of molecular layer assembly. The covalent structure gives a polysulfonamide selective functional layer.

本发明采用如下技术方案：The invention adopts the following technical solutions:

聚磺酰胺纳滤或反渗透复合膜层层组装制备方法，包括如下步骤：将多孔支撑膜在磺酰氯和多元胺单体溶液中进行分子层层组装，其中磺酰氯溶液的浓度为0.001％-5％，本发明磺酰氯浓度优先控制范围为0.001％-1％，多元胺单体浓度为0.001％-15％，本发明浓度优先控制范围为0.001％-5％；40-110℃下热处理，充分洗涤后保存。The method for preparing a polysulfonamide nanofiltration or reverse osmosis composite membrane layer assembly comprises the steps of: molecularly layering a porous support membrane in a solution of a sulfonyl chloride and a polyamine monomer, wherein the concentration of the sulfonyl chloride solution is 0.001%- 5%, the concentration of the sulfonyl chloride in the present invention is preferentially controlled in the range of 0.001% to 1%, the concentration of the polyamine monomer is 0.001% to 15%, and the concentration preferential control range of the present invention is 0.001% to 5%; heat treatment at 40-110 ° C, Wash thoroughly after washing.

所述的分子层层组装是通过将多孔支撑膜交替浸泡在磺酰氯和多元胺单体溶液中，或在多孔支撑膜表面均匀交替喷涂磺酰氯和多元胺单体溶液，或利用匀胶旋涂法在多孔支撑层表面分别旋涂磺酰氯和多元胺单体溶液实现的。The molecular layer layer assembly is performed by alternately immersing the porous support film in a solution of a sulfonyl chloride and a polyamine monomer, or uniformly spraying a solution of a sulfonyl chloride and a polyamine monomer on the surface of the porous support film, or by spin coating with a uniform rubber. The method is carried out by spin-coating a solution of a sulfonyl chloride and a polyamine monomer on the surface of the porous support layer.

所述制备聚磺酰胺纳滤或反渗透膜热处理过程可以是浸泡、喷涂或者匀胶旋涂组装聚磺酰胺结构过程中，或者浸泡、喷涂或者匀胶旋涂组装多层聚磺酰胺结构后进行。The heat treatment process for preparing the polysulfonamide nanofiltration or reverse osmosis membrane may be performed by immersing, spraying or spin-coating the polysulfonamide structure, or by immersing, spraying or spin coating to assemble a plurality of polysulfonamide structures. .

所述技术方案包括多孔支撑膜预处理步骤。所述预处理为用30-50％异丙醇水溶液或者30-50％的乙醇水溶液洗涤多孔支撑膜，最后用纯水冲洗干净待用。The technical solution includes a porous support membrane pretreatment step. The pretreatment is to wash the porous support membrane with 30-50% aqueous solution of isopropanol or 30-50% aqueous solution of ethanol, and finally rinsed with pure water for use.

所述技术方案层层组装制备聚磺酰胺纳滤或反渗透复合膜，所述组装层数范围为1-50层。The technical solution layer is assembled to prepare a polysulfonamide nanofiltration or reverse osmosis composite membrane, and the number of assembled layers ranges from 1 to 50 layers.

所述技术方案中包括添加0.0％-5％的纳米粒子在多元胺单体溶液或者磺酰氯单体溶液中进行层层组装制备聚磺酰胺纳滤或反渗透复合膜，本发明纳米粒子添加范围优先选择为0.0％-1％。The technical solution includes adding 0.0%-5% of the nanoparticles to form a polysulfonamide nanofiltration or reverse osmosis composite membrane in a polyamine monomer solution or a sulfonyl chloride monomer solution, and the nanoparticle addition range of the invention The preference is 0.0%-1%.

所述技术方案中纳米粒子范围包含现有已知的有孔或无孔、环状或非环状 形貌的无机或有机纳米级粒子。The range of nanoparticles in the technical solution includes known pores or nonporous, cyclic or acyclic Morphological inorganic or organic nanoscale particles.

所述技术方案包在聚磺酰胺纳滤或反渗透复合膜层层组装制备过程中引入聚合物涂层以提高复合膜性能。所述聚合物可以为聚乙烯醇(PVA)、聚乙烯亚胺(PEI)、聚乳酸(PLA)、聚丙烯酸(PAA)、聚(2-烷基-2-噁唑啉)(POX)以及其他未注明但可以起到同样作用的涂层材料。所述聚合物涂层引入可以在层层组装制备过程前、层层组装制备过程后以及层层组装制备过程中进行。The technical solution comprises introducing a polymer coating during the layer assembly preparation process of the polysulfonamide nanofiltration or reverse osmosis composite membrane to improve the performance of the composite membrane. The polymer may be polyvinyl alcohol (PVA), polyethyleneimine (PEI), polylactic acid (PLA), polyacrylic acid (PAA), poly(2-alkyl-2-oxazoline) (POX), and Other coating materials that are not specified but can serve the same purpose. The introduction of the polymer coating can be carried out before the layer assembly preparation process, after the layer assembly preparation process, and during the layer assembly preparation process.

上述的聚磺酰胺纳滤或反渗透复合膜制备方法，其特征聚磺酰胺结构是通过分子层层组装过程形成的，下列三种层层组装方法仅为提供说明而不是限定本发明：The above-mentioned polysulfonamide nanofiltration or reverse osmosis composite membrane preparation method, characterized in that the polysulfonamide structure is formed by a molecular layer assembly process, and the following three layer assembly methods are merely illustrative and not limiting:

将多孔支撑膜交替浸泡在磺酰氯和多元胺单体溶液中，磺酰氯的浓度为0.001％-1％，多元胺单体浓度为0.001％-5％。多次循环该交替浸泡组装步骤。40-110℃热处理1-20min，热处理过程可以在浸泡组装聚磺酰胺结构中，或组装多层聚磺酰胺结构后进行。最后用乙醇水溶液充分洗涤30-60min。The porous support membrane is alternately immersed in a solution of a sulfonyl chloride and a polyamine monomer, the concentration of the sulfonyl chloride is 0.001% to 1%, and the concentration of the polyamine monomer is 0.001% to 5%. The alternating soak assembly step is repeated a plurality of times. Heat treatment at 40-110 ° C for 1-20 min, the heat treatment process can be carried out in the immersion assembly polysulfonamide structure, or after assembling a multi-layer polysulfonamide structure. Finally, it was washed thoroughly with an aqueous ethanol solution for 30-60 min.

在多孔支撑膜表面均匀交替喷涂磺酰氯和多元胺单体溶液，磺酰氯的浓度为0.001％-1％，多元胺单体浓度为0.001％-5％。多次循环该喷涂组装步骤。40-110℃热处理1-20min，热处理过程可以在喷涂组装聚磺酰胺结构中，或组装多层聚磺酰胺结构后进行。最后用乙醇水溶液充分洗涤30-60min。The sulfonyl chloride and polyamine monomer solution are uniformly sprayed on the surface of the porous support film, the concentration of the sulfonyl chloride is 0.001% to 1%, and the concentration of the polyamine monomer is 0.001% to 5%. The spray assembly step is cycled multiple times. Heat treatment at 40-110 ° C for 1-20 min, the heat treatment process can be carried out in the spray assembly polysulfonamide structure, or after assembling a multi-layer polysulfonamide structure. Finally, it was washed thoroughly with an aqueous ethanol solution for 30-60 min.

利用匀胶旋涂法在多孔支撑层表面分别旋涂磺酰氯和多元胺单体溶液，磺酰氯的浓度为0.001％-1％，多元胺单体浓度为0.001％-5％，多次循环该匀胶旋涂组装步骤。40-110℃热处理1-20min，热处理过程可以在匀胶旋涂组装聚磺酰胺结构中，或组装多层聚磺酰胺结构后进行。最后用乙醇水溶液充分洗涤30-60min。匀胶旋涂层层组装制备聚磺酰胺纳滤或反渗透膜所用到的匀胶旋涂设备适合依据专利CN 204247481 U提到的原理生产或改装设备。 The sulfonyl chloride and the polyamine monomer solution are respectively spin-coated on the surface of the porous support layer by a spin coating method, the concentration of the sulfonyl chloride is 0.001% to 1%, and the concentration of the polyamine monomer is 0.001% to 5%. The spin coating assembly step. Heat treatment at 40-110 °C for 1-20 min, the heat treatment process can be carried out in the spin-coating polysulfonamide structure or after assembling a multi-layer polysulfonamide structure. Finally, it was washed thoroughly with an aqueous ethanol solution for 30-60 min. The spin-coating layer for the preparation of polysulfonamide nanofiltration or reverse osmosis membranes is suitable for the production or modification of equipment according to the principles mentioned in the patent CN 204247481 U.

本发明聚磺酰胺纳滤或反渗透复合膜所涉及的多孔支撑膜，其特征是可以为有机聚合物多孔膜如聚砜、聚醚砜、聚丙烯腈等，也可以为无机多孔膜如陶瓷膜等。本发明优选使用聚砜多孔膜。The porous support membrane of the polysulfonamide nanofiltration or reverse osmosis composite membrane of the present invention may be characterized by an organic polymer porous membrane such as polysulfone, polyethersulfone, polyacrylonitrile or the like, or an inorganic porous membrane such as ceramic. Membrane and the like. The polysulfone porous membrane is preferably used in the present invention.

本发明制备聚磺酰胺纳滤或反渗透复合膜方法，所述的多元磺酰氯是含有两个及两个以上“SO2”基团并连接脂肪基、苯基、联苯基、萘基等结构的单体，本发明优选1,3,6-萘三磺酰氯。The invention relates to a method for preparing a polysulfonamide nanofiltration or reverse osmosis composite membrane, wherein the polysulfonyl chloride is a structure containing two or more "SO2" groups and linking a fat group, a phenyl group, a biphenyl group, a naphthyl group or the like. The monomer is preferably 1,3,6-naphthalenetrisulfonyl chloride in the present invention.

本发明制备聚磺酰胺纳滤或反渗透复合膜方法，所述的多元胺可以为乙二胺，三乙烯四胺(triethylenetetraamine,NH2CH2CH2NHCH2CH2NHCH2CH2NH2)，间苯二甲胺或其它多功能团的伯胺、仲胺；哌嗪，或2,5-二甲基哌嗪,或N,N`-二氨基哌嗪,或其他可反应的含有哌嗪结构的衍生物,或上述混合物，本发明优选哌嗪。The method for preparing a polysulfonamide nanofiltration or reverse osmosis composite membrane, wherein the polyamine can be ethylenediamine, triethylenetetraamine (NH2CH2CH2NHCH2CH2NHCH2CH2NH2), meta-xylylenediamine or other multifunctional group of primary amines, a secondary amine; piperazine, or 2,5-dimethylpiperazine, or N,N'-diaminopiperazine, or other reactive piperazine-containing derivative, or a mixture thereof, preferably piperazine of the invention .

本发明聚磺酰胺纳滤或反渗透复合膜制备过程中，所述多元胺溶液的溶剂可以为水或有机溶剂或其混合溶剂，有机溶剂如丙酮、甲醇、乙醇、异丙醇等，本发明优选水作多元胺溶剂。所述磺酰氯溶液的溶剂可以为乙酸乙酯、氯仿、甲苯、二甲苯、Isopar系列、正己烷、庚烷或正十二烷或者上述混合溶剂。In the preparation process of the polysulfonamide nanofiltration or reverse osmosis composite membrane of the present invention, the solvent of the polyamine solution may be water or an organic solvent or a mixed solvent thereof, and an organic solvent such as acetone, methanol, ethanol, isopropanol or the like, the present invention Water is preferred as the polyamine solvent. The solvent of the sulfonyl chloride solution may be ethyl acetate, chloroform, toluene, xylene, Isopar series, n-hexane, heptane or n-dodecane or a mixed solvent of the above.

本发明聚磺酰胺纳滤或反渗透复合膜制备过程中，所述的多元胺溶液中，含有0.0％-5％的催化剂或酸吸收剂。本发明催化剂或酸吸收剂为三乙胺，或氢氧化钠，或碳酸钠等，本发明优选三乙胺。In the preparation process of the polysulfonamide nanofiltration or reverse osmosis composite membrane of the present invention, the polyamine solution contains 0.0% to 5% of a catalyst or an acid absorbent. The catalyst or acid absorbent of the present invention is triethylamine, or sodium hydroxide, or sodium carbonate, and the like, and triethylamine is preferred in the present invention.

本发明聚磺酰胺纳滤或反渗透复合膜制备过程中，所述的多元胺溶液中，含有0.0％-10％的致孔剂，如樟脑磺酸及它的三乙胺盐或其他起到同样作用的物质等。In the preparation process of the polysulfonamide nanofiltration or reverse osmosis composite membrane of the present invention, the polyamine solution contains 0.0%-10% of a porogen, such as camphorsulfonic acid and its triethylamine salt or the like. The same effect of the substance and so on.

本发明聚磺酰胺纳滤或反渗透复合膜制备过程中，在多元胺单体溶液或者磺酰氯单体溶液中添加纳米粒子，其纳米粒子特征为有孔或无孔、环状或非环 状形貌的无机或有机纳米级粒子。In the preparation process of the polysulfonamide nanofiltration or reverse osmosis composite membrane of the present invention, nanoparticles are added to the polyamine monomer solution or the sulfonyl chloride monomer solution, and the nanoparticles are characterized by pores or nonporous, cyclic or acyclic. Inorganic or organic nanoscale particles.

本发明聚磺酰胺纳滤或反渗透复合膜制备过程中，在多元胺单体溶液或者磺酰氯单体溶液中添加0.0％-5％的表面活性剂，本发明表面活性剂浓度添加范围优先选择为0.0％-2％。In the preparation process of the polysulfonamide nanofiltration or reverse osmosis composite membrane of the present invention, 0.0% to 5% of a surfactant is added to the polyamine monomer solution or the sulfonyl chloride monomer solution, and the surfactant concentration range of the present invention is preferentially selected. It is from 0.0% to 2%.

本发明制备聚磺酰胺纳滤或反渗透复合膜方法，所述的表面活性剂包括阴离子表面活性剂，如十二烷基磺酸钠；阳离子表面活性剂，如季铵化物；两性离子表面活性剂，如卵磷脂、氨基酸型和甜菜碱型；非离子表面活性剂，如脂肪酸甘油酯、聚山梨酯等；聚氧乙烯型表面活性剂，如长链脂肪酸酯、脂肪醇酯、磷酸脂等。The invention provides a polysulfonamide nanofiltration or reverse osmosis composite membrane method, wherein the surfactant comprises an anionic surfactant such as sodium dodecyl sulfate; a cationic surfactant such as a quaternary ammonium compound; zwitterionic surface active Agents such as lecithin, amino acid type and betaine type; nonionic surfactants such as fatty acid glycerides, polysorbates, etc.; polyoxyethylene type surfactants such as long chain fatty acid esters, fatty alcohol esters, phosphate esters Wait.

本发明还要求所述的分子层层组装方法制备的聚磺酰胺纳滤或反渗透复合膜。The present invention also requires a polysulfonamide nanofiltration or reverse osmosis composite membrane prepared by the molecular layer assembly method.

本发明制备的聚磺酰胺纳滤或反渗透复合膜，其特征是对盐，如硫酸镁、氯化钙以及氯化钠或者分子量低于1000g/moL的有机物的脱除率最高可以达到99％或以上。The polysulfonamide nanofiltration or reverse osmosis composite membrane prepared by the invention is characterized in that the removal rate of the salt such as magnesium sulfate, calcium chloride and sodium chloride or the organic matter having a molecular weight of less than 1000 g/moL can be up to 99% or above.

本发明制备聚磺酰胺复合膜分子层层组装方法，其特征是可通过调控组装层数，制备具有不同脱除率和不同水通量性能的聚磺酰胺复合膜。The invention discloses a method for assembling a polysulfonamide composite membrane molecular layer layer, which is characterized in that a polysulfonamide composite membrane having different removal rates and different water flux properties can be prepared by adjusting the number of assembled layers.

本发明制备聚磺酰胺复合膜分子层层组装方法，其特征是制备的聚磺酰胺纳滤或反渗透膜表面粗糙度远低于界面聚合技术制备的聚磺酰胺纳滤或反渗透膜的表面粗糙度。The method for preparing a polysulfonamide composite membrane molecular layer layer according to the invention is characterized in that the surface roughness of the prepared polysulfonamide nanofiltration or reverse osmosis membrane is much lower than the surface of the polysulfonamide nanofiltration or reverse osmosis membrane prepared by the interfacial polymerization technique. Roughness.

发明中名词定义Definition of noun in invention

本发明涉及到的聚磺酰胺结构适用于专利US6837996和US20120152839提到的聚磺酰胺或改性聚磺酰胺结构。 The polysulfonamide structure to which the present invention relates is applicable to the polysulfonamide or modified polysulfonamide structures mentioned in the patents US Pat. No. 6,837,996 and US Pat.

本发明涉及到的分子层层组装技术是参考文献Science 2003,301,818-821，J.Mater.Chem.2007,17,664-669，Macromolecules,2010,43,9056-9062等的报道。旨在两种不同单体存在相互反应基团，当两种单体接触以后，通过共价键的方式，在一定条件下层层组装形成交联结构。The molecular layer assembly technique to which the present invention relates is a reference in Science 2003, 301, 818-821, J. Mater. Chem. 2007, 17, 664-669, Macromolecules, 2010, 43, 9056-9062 and the like. It is intended that two different monomers have mutual reactive groups. When the two monomers are in contact, the layers are assembled under certain conditions to form a crosslinked structure by covalent bonding.

本发明提到的致孔剂是指在制膜过程中添加的，不与单体发生化学反应，且容易溶出促进膜表面成孔的小分子物质。The porogen mentioned in the present invention refers to a small molecule substance which is added during the film forming process, does not chemically react with the monomer, and is easily eluted to promote pore formation on the surface of the film.

本发明涉及到的分子层层组装是指两种或多种可反应单体通过交替浸泡、喷涂以及匀胶旋涂等手段吸附在多孔支撑膜表面，发生同一层单体，层与层单体之间的组装交联反应过程。The molecular layer assembly involved in the present invention means that two or more reactive monomers are adsorbed on the surface of the porous support film by alternate soaking, spraying, and spin coating, and the same layer of monomers, layers and layers are generated. The process of assembly cross-linking between the reactions.

本发明喷涂制膜：是指利用气体压缩机械或者器皿能够将单体溶液雾化喷制在膜表面并经过一定条件处理形成交联薄膜的过程。The spray film formation of the present invention refers to a process in which a monomer compression solution can be atomized and sprayed on a surface of a film by a gas compression machine or a vessel and subjected to a certain condition to form a crosslinked film.

本发明匀胶旋涂制膜：是指利用托盘离心旋转的原理，将多孔支撑膜放置在匀胶机托盘中央，滴入单体溶液后，浸泡一定时间设置一定的转速将大部分液体旋出，在膜表面均匀铺展薄层单体液层。通过交替加入单体在膜表面形成多层单体液层，经过一定条件的处理交联成膜的过程。The spin coating film of the present invention refers to the principle of centrifugal rotation of a tray, placing the porous supporting film in the center of the tray of the homogenizer, dropping the monomer solution, and immersing for a certain time to set a certain rotation speed to screw out most of the liquid. A thin layer of monomer liquid layer is uniformly spread on the surface of the film. A process of forming a multi-layered monomer liquid layer on the surface of the film by alternately adding a monomer, and crosslinking the film formation after a certain condition.

本发明单层分子层层组装聚磺酰胺复合膜定义为：多孔支撑膜表面分别经过多元胺和磺酰氯后处理后，形成一层选择性聚磺酰胺功能层，为单层聚磺酰胺纳滤或反渗透复合膜。The monolayer molecular layer assembly polysulfonamide composite membrane of the invention is defined as: the surface of the porous support membrane is treated by polyamine and sulfonyl chloride respectively to form a selective polysulfonamide functional layer, which is a single layer polysulfonamide nanofiltration. Or reverse osmosis composite membrane.

本发明单体、酸吸收剂、催化剂、纳米粒子的添加浓度均为质量百分比浓度，按照本发明所给出各物质添加浓度利用本发明技术均可以制备出聚磺酰胺纳滤或反渗透复合膜。The addition concentration of the monomer, the acid absorbent, the catalyst and the nano particle of the invention is a mass percentage concentration, and the concentration of each substance added according to the invention can be used to prepare a polysulfonamide nanofiltration or reverse osmosis composite membrane by the technique of the invention. .

本发明脱除率(R)定义为：在一定条件下，进料液浓度(Cf)与渗透液中浓度差(Cp)，再除以进料液浓度R＝(Cf-Cp)/Cf。 The removal rate (R) of the present invention is defined as the concentration difference (Cp) between the feed liquid concentration (Cf) and the permeate under certain conditions, and divided by the feed solution concentration R = (Cf - Cp) / Cf.

本发明制备的聚磺酰胺纳滤或反渗透复合膜脱盐性能的测试条件为盐溶液浓度为2000mg/L，测试压力为1.5MPa，系统控制温度为25℃，错流运行方式测试，原水流量控制在6-7LPM。The test conditions for the desalting performance of the polysulfonamide nanofiltration or reverse osmosis composite membrane prepared by the invention are the salt solution concentration of 2000 mg/L, the test pressure is 1.5 MPa, the system control temperature is 25 ° C, the cross flow operation mode test, the raw water flow control At 6-7 LPM.

以上所述的实施例仅仅是对本发明的优选实施方式进行描述，并非对本发明的范围进行限定，在不脱离本发明设计精神的前提下，本领域普通技术人员对本发明的技术方案作出的各种变形和改进，均应落入本发明权利要求书确定的保护范围内。The embodiments described above are only intended to describe the preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and various embodiments of the present invention may be made by those skilled in the art without departing from the spirit of the invention. Modifications and improvements are intended to fall within the scope of the invention as defined by the appended claims.

具体实施方式detailed description

以下实施例给出聚磺酰胺纳滤或反渗透复合膜的层层组装制备过程及工艺条件。然而，以下给出的实施例仅是提供作为说明而不限定本发明。The following examples give the layer assembly process and process conditions of the polysulfonamide nanofiltration or reverse osmosis composite membrane. However, the examples given below are provided by way of illustration only and not limitation of the invention.

Figure PCTCN2016087981-appb-000001
Figure PCTCN2016087981-appb-000001

Figure PCTCN2016087981-appb-000002
Figure PCTCN2016087981-appb-000002

Claims (18)

一种聚磺酰胺纳滤或反渗透复合膜制备方法，包括如下步骤：将多孔支撑膜在磺酰氯和多元胺单体溶液中进行分子层层组装，其中磺酰氯溶液的浓度为0.001％-5％，多元胺单体浓度为0.001％-15％；40-110℃下进行热处理；最后用乙醇水溶液充分洗涤。A method for preparing a polysulfonamide nanofiltration or reverse osmosis composite membrane comprises the steps of: molecularly layering a porous support membrane in a solution of a sulfonyl chloride and a polyamine monomer, wherein the concentration of the sulfonyl chloride solution is 0.001%-5 %, the concentration of the polyamine monomer is 0.001% to 15%; heat treatment is carried out at 40-110 ° C; and finally washed thoroughly with an aqueous ethanol solution. 根据权利要求1所述的制备方法，其特征在于：多孔支撑膜可以为高分子多孔支撑层如聚砜、聚醚砜、或聚丙烯腈，也可以为无机多孔膜如氧化硅、氧化钛、氧化锆陶瓷膜。The preparation method according to claim 1, wherein the porous supporting film may be a porous polymeric support layer such as polysulfone, polyethersulfone, or polyacrylonitrile, or may be an inorganic porous film such as silicon oxide or titanium oxide. Zirconia ceramic membrane. 根据权利要求1所述的制备方法，其特征在于：所述的分子层层组装是通过将多孔支撑膜交替浸泡在磺酰氯和多元胺单体溶液中，或在多孔支撑膜表面均匀交替喷涂磺酰氯和多元胺单体溶液，或利用匀胶旋涂法在多孔支撑膜表面交替旋涂磺酰氯和多元胺单体溶液，并进行热处理后实现的。The preparation method according to claim 1, wherein the molecular layer layer assembly is performed by alternately immersing the porous support film in a solution of a sulfonyl chloride and a polyamine monomer, or uniformly spraying a sulfonate on the surface of the porous support film. The solution of the acid chloride and the polyamine monomer or the solution of the sulfonyl chloride and the polyamine monomer solution is alternately spin-coated on the surface of the porous support film by a spin coating method and heat-treated. 根据权利要求1所述的制备方法，其特征在于：聚磺酰胺纳滤或反渗透复合膜的层层组装制备层数为1-50层。The preparation method according to claim 1, characterized in that the number of layers of the polysulfonamide nanofiltration or reverse osmosis composite membrane is 1 to 50 layers. 根据权利要求1所述制备方法，其特征在于：聚磺酰胺纳滤或反渗透复合膜层层组装制备过程中引入聚合物涂层以提高复合膜性能。The preparation method according to claim 1, characterized in that a polymer coating is introduced during the assembly process of the polysulfonamide nanofiltration or reverse osmosis composite membrane layer to improve the performance of the composite membrane. 根据权利要求5所述制备方法，其特征在于：聚合物涂层可以为聚乙烯醇(PVA)、聚乙烯亚胺(PEI)、聚乳酸(PLA)、聚(2-烷基-2-噁唑啉)(POX)聚丙烯酸(PAA)或其他水溶性、可交联的高分子的单一或混合涂层材料。The preparation method according to claim 5, wherein the polymer coating layer is polyvinyl alcohol (PVA), polyethyleneimine (PEI), polylactic acid (PLA), poly(2-alkyl-2-oxo). A single or mixed coating material of oxazoline) (POX) polyacrylic acid (PAA) or other water soluble, crosslinkable polymer. 根据权利要求5所述制备方法，其特征在于：所述聚合物涂层引入可以在层层组装制备过程前、层层组装制备过程后以及层层组装制备过程中进行。The preparation method according to claim 5, characterized in that the introduction of the polymer coating can be carried out before the layer assembly preparation process, after the layer assembly preparation process, and during the layer assembly preparation process. 根据权利要求1所述的制备方法，其特征在于：层层组装制备聚磺酰胺纳滤 或反渗透膜热处理过程，可以在浸泡或喷涂或匀胶旋涂组装聚磺酰胺结构过程中，或组装多层聚磺酰胺结构后进行。The preparation method according to claim 1, wherein the layer is assembled to prepare a polysulfonamide nanofiltration. Or the reverse osmosis membrane heat treatment process can be carried out in the process of immersing or spraying or spin coating to assemble the polysulfonamide structure, or assembling a plurality of polysulfonamide structures. 根据权利要求1所述的制备方法，其特征在于：所述的多元磺酰氯是含有两个及两个以上“SO2”基团并连接含脂肪基、苯基、联苯基、萘基结构的单体。The preparation method according to claim 1, wherein the polysulfonyl chloride is a structure containing two or more "SO2" groups and linking a fatty group, a phenyl group, a biphenyl group or a naphthyl group. monomer. 根据权利要求1所述的制备方法，其特征在于：溶液溶剂可以为乙酸乙酯、氯仿、甲苯、二甲苯、Isopar系列、正己烷、庚烷、或正十二烷或上述溶剂的混合物。The process according to claim 1, wherein the solution solvent is ethyl acetate, chloroform, toluene, xylene, Isopar series, n-hexane, heptane, or n-dodecane or a mixture of the above solvents. 根据权利要求1所述的制备方法，其特征在于：所述的多元胺单体溶液的溶剂为水或有机溶剂或其混合溶剂，有机溶剂可以为：丙酮、甲醇、乙醇、异丙醇。The preparation method according to claim 1, wherein the solvent of the polyamine monomer solution is water or an organic solvent or a mixed solvent thereof, and the organic solvent may be acetone, methanol, ethanol or isopropanol. 根据权利要求1所述的制备方法，其特征在于：所述的多元胺为乙二胺，三乙烯四胺，间苯二甲胺或其它多功能团的伯胺,仲胺；哌嗪，或2,5-二甲基哌嗪,或N,N`-二氨基哌嗪,或其他可反应的含有哌嗪结构的衍生物,或上述混合物。The preparation method according to claim 1, wherein the polyamine is ethylenediamine, triethylenetetramine, m-xylylenediamine or other multifunctional primary amine, secondary amine; piperazine, or 2,5-Dimethylpiperazine, or N,N'-diaminopiperazine, or other reactive piperazine-containing derivative, or a mixture thereof. 根据权利要求1所述的制备方法，其特征在于：所述的多元胺溶液中，含有0.0％-5％的催化剂或酸吸收剂和0.0％-10％致孔剂。The process according to claim 1, wherein the polyamine solution contains 0.0% to 5% of a catalyst or acid absorbent and 0.0% to 10% of a porogen. 根据权利要求1所述的制备方法，其特征在于：在多元胺单体溶液或者磺酰氯单体溶液中添加0.0％-5％的纳米粒子。The method according to claim 1, wherein 0.0% to 5% of the nanoparticles are added to the polyamine monomer solution or the sulfonyl chloride monomer solution. 根据权利要求14所述的制备方法，其特征在于：所述纳米粒子为有孔或无孔、环状或非环状形貌的无机或有机纳米级粒子。The preparation method according to claim 14, wherein the nanoparticles are inorganic or organic nano-sized particles having a pore or a non-porous, cyclic or acyclic morphology. 根据权利要求1所述的制备方法，其特征在于：在多元胺单体溶液或者磺酰 氯单体溶液中添加0.0％-5％的表面活性剂。The process according to claim 1, wherein the polyamine monomer solution or the sulfonyl group 0.0% to 5% of a surfactant is added to the chlorine monomer solution. 根据权利要求16所述的制备方法，其特征在于：所述的表面活性剂包括阴离子表面活性剂，如十二烷基磺酸钠；阳离子表面活性剂，如季铵化物；两性离子表面活性剂，如卵磷脂、氨基酸型和甜菜碱型；非离子表面活性剂，如脂肪酸甘油酯、聚山梨酯；聚氧乙烯型表面活性剂，如长链脂肪酸酯、脂肪醇酯，磷酸脂。The preparation method according to claim 16, wherein the surfactant comprises an anionic surfactant such as sodium lauryl sulfonate; a cationic surfactant such as a quaternary ammonium compound; a zwitterionic surfactant; Such as lecithin, amino acid type and betaine type; nonionic surfactants, such as fatty acid glycerides, polysorbates; polyoxyethylene type surfactants, such as long chain fatty acid esters, fatty alcohol esters, phosphate esters. 权利要求1-17任一项所述的制备方法制备的聚磺酰胺纳滤或反渗透复合膜。 A polysulfonamide nanofiltration or reverse osmosis composite membrane prepared by the preparation method according to any one of claims 1-17.
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