WO2018120476A1 - Supramolecular composite nano-filtration membrane and preparation method therefor and use thereof - Google Patents
Supramolecular composite nano-filtration membrane and preparation method therefor and use thereof Download PDFInfo
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- WO2018120476A1 WO2018120476A1 PCT/CN2017/078785 CN2017078785W WO2018120476A1 WO 2018120476 A1 WO2018120476 A1 WO 2018120476A1 CN 2017078785 W CN2017078785 W CN 2017078785W WO 2018120476 A1 WO2018120476 A1 WO 2018120476A1
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- monomer
- phase
- solution
- cucurbituril
- nanofiltration membrane
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- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 54
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/26—Electrical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Definitions
- the invention relates to a supramolecular composite nanofiltration membrane, a preparation method and application thereof, and belongs to the technical field of polymer membranes.
- Nanofiltration is a new membrane separation technology developed between late osmosis and ultrafiltration in the late 1980s. It was called “low pressure reverse osmosis” or “loose reverse osmosis”. Nanofiltration technology is a new type of pressure-driven membrane process developed to meet the needs of industrial softened water and reduce costs.
- the molecular weight cut-off of the nanofiltration membrane is between 200 and 1000.
- the membrane pore size is about 1 nm, and it is suitable to separate a dissolved component having a size of about 1 nm, so it is called “nanofiltration”. Due to the special pore size range of the nanofiltration membrane and the special treatment (composite, charge) during preparation, it has a special separation performance.
- nanofiltration membrane separation has two characteristics, namely the screening effect and the charge effect.
- a substance having a molecular weight greater than the molecular weight cut-off of the membrane will be trapped by the membrane, and vice versa, which is the sieving effect of the membrane;
- the charge effect of the membrane also known as the Donnan effect, refers to the electrostatic interaction of the charge carried by the ions and the membrane.
- the filtration of uncharged molecules mainly relies on the steric hindrance effect, that is, the charge effect, and the sieving effect can be used to separate substances of different molecular weights; while the filtration of charged substances mainly depends on the charge effect, the surface separation of nanofiltration membranes has been Polyelectrolyte consists of a little charge on the surface of the membrane. Most of the nanofiltration membranes have a negative charge on the surface. They interact with each other through electrostatic interactions, which hinders the penetration of multivalent ions. This is the nanofiltration membrane that still has high desalination under low pressure conditions. The main reason for performance.
- the nanofiltration membrane is mainly used in the following aspects:
- nanofiltration membranes The largest application area of nanofiltration membranes is the softening of drinking water and the removal of organic matter. With the addition of water pollution, people are more and more concerned about the quality of drinking water.
- Traditional drinking water treatment mainly removes suspended solids and bacteria in water through flocculation, sedimentation, sand filtration, and chlorination. The removal rate of various dissolved chemicals is very low, and the water resources are increasingly scarce.
- the increase in environmental pollution and the improvement of drinking water standards in various countries, and the "deep drinking water treatment technology" that can remove various organic substances and harmful chemical substances have received increasing attention.
- Membrane separation experiments show that the nanofiltration membrane can remove microtoxic by-products, heavy metals, natural organic matter and sulfate nitrate produced by the disinfection process. At the same time, it has the advantages of good water quality, stability, low chemical dosage, energy saving, easy management and maintenance, and can basically achieve zero emission.
- Nanofiltration membrane has been successfully applied to the treatment of wastewater from papermaking, electroplating, printing and dyeing industries with its special separation performance.
- tissue wastewater has the characteristics of high CODCr concentration and high chroma. Especially the removal of chroma has always been a difficult point in wastewater treatment.
- Nanofiltration membrane technology is a new separation technology developed in recent years. It is mainly based on pore size screening effect and charging effect to achieve separation of materials. It has high rejection rate for organic matter and high-valent ions with relative molecular weight greater than 200. Therefore, the nanofiltration technology is especially suitable for the treatment of printing and dyeing wastewater, and the osmotic pressure of the nanofiltration membrane is much lower than that of reverse osmosis, so that the operating pressure of the nanofiltration process is lower, so that the purpose of lower water treatment cost can be achieved.
- the nanofiltration membrane technology can purify and concentrate biochemical reagents, not only can reduce the consumption of organic solvents and water, but also can remove trace organic pollution and low molecular weight salts, and finally achieve energy saving and product quality improvement.
- Nanofiltration membranes have been successfully applied to the concentration and purification of various antibiotics such as erythromycin, chlortetracycline, vancomycin and penicillin.
- Vitamin B12 is obtained by fermentation, and the traditional production process is complicated and the yield is low.
- the microfiltration is used to replace the traditional filtration, and the microfiltration fermentation supernatant can be concentrated by 10 times or more with the nanofiltration membrane, thereby greatly reducing the amount of the extracting agent and increasing the production capacity of the equipment.
- the extracted aqueous phase also has a small amount of vitamin B12 and a certain solvent, which can be intercepted by nanofiltration to reduce product loss.
- the solvent used in the purification of the crude product can also be recovered by treatment with a nanofiltration membrane.
- the nanofiltration membrane has high anti-pollution ability, the bacteria are not easy to survive on the surface of the nanofiltration membrane. Because the nanofiltration membrane can remove a part of the salt, the corrosion of the evaporator on the evaporator can be reduced.
- the common process of yeast and cheese processing It solves the problem of wastewater discharge and can also improve economic benefits, and the nanofiltration membrane is also beneficial for the recovery and utilization of organic acids in the fermentation solution. When the solution is at a low pH, these acids are not dissociated and easily pass through the nanofiltration membrane; at high pH, most of the acid membrane is trapped due to the mutual repulsion between the dissociated acid and the membrane, while The membrane also retains the saccharide compound, which is beneficial for recycling.
- the pH of the fermentation solution is adjusted to be in an appropriate range, and the organic acid in the fermentation solution is removed by a nanofiltration membrane, and the yeast, unfermented sugar and other useful components are retained, and the retentate is returned to the fermentation.
- Reuse in the container not only can reduce the inhibition of the fermentation process, but also facilitate the recycling of yeast and sugar. Not only does it increase production, it also reduces the cost of high-cost raw materials.
- the nanofiltration membrane can also be used for the treatment of wastewater in the fields of textiles, leather processing, and the separation of chiral substances. Due to its special separation performance, nanofiltration will be more and more widely used in many fields such as improving drinking water quality, demineralized water, dyes, pigments, purification and concentration of pharmaceutical and biochemical products, and deep separation of oil and water, dyes, printing, and textiles. , chemical and pharmaceutical wastewater decolorization and other fields.
- the solvent-resistant, acid-resistant nanofiltration membrane has a wider application prospect.
- the invention aims at the shortcoming of the current composite nanofiltration membrane flux and the low interception rate of the small molecular dye.
- the flux and the rejection rate of the composite nanofiltration membrane are improved, and the aqueous phase is polymerized at the interface.
- a new material is added to the solution to modify the membrane, which is a preparation method of a supramolecular composite nanofiltration membrane.
- the first aspect of the invention is a first aspect of the invention.
- a supramolecular composite nanofiltration membrane comprising a base layer and a surface layer thereof, wherein the modified layer refers to a polymer layer distributed with cucurbituril; and the base layer is an organic nanofiltration membrane.
- the material of the base layer is selected from the group consisting of polyamide, polyimide, cellulose acetate, sulfonated polysulfone, sulfonated polyethersulfone or polyvinyl alcohol.
- the base layer may also be coated on the support layer, and the support layer may be selected from a nonwoven fabric or the like.
- the polymer layer is formed by polymerizing a first monomer and a second monomer; the first monomer is a piperazine monomer or an amine group-containing monomer, The second monomer is an acid chloride monomer.
- a preparation method of a supramolecular composite nanofiltration membrane comprises the following steps:
- the first solution and the second solution are immiscible.
- the first solution is water and the second solution is n-hexane.
- the first monomer is a piperazine-based monomer or an amine-containing monomer
- the second monomer is an acid chloride-based monomer
- the first monomer has a mass concentration in the first phase of from 0.01 to 5%, and the quality of the cucurbituril in the first phase The concentration is 0.01 to 5%; the mass concentration of the second monomer in the second phase is 0.01 to 5%.
- the application refers to the filtration or separation of charged materials, neutral substances or mixtures thereof.
- a method of loading a supramolecule on a surface of an organic separation membrane comprising the steps of:
- the first solution containing cucurbituril and the first monomer is applied to the second solution, and the cucurbituril is supported on the organic separation membrane by interfacial polymerization of the first monomer and the second monomer.
- Fig. 1 is a SEM image showing the morphology of a polyimide composite nanofiltration membrane prepared in Comparative Example 1 of the present invention.
- Example 2 is a SEM image of the morphology of the supramolecular-polyimide composite nanofiltration membrane prepared in Example 5 of the present invention.
- the nanofiltration membrane proposed by the invention is composed of at least two layers, and the first layer is a base layer, which can be a common nanofiltration membrane material layer, for example: polyamide, cellulose acetate, sulfonated polysulfone, sulfonated polyethersulfone and Polyvinyl alcohol or the like is not particularly limited, and it is a substrate as the upper layer.
- the other layer is a surface modification layer, and the modification layer is also a polymer layer in which a super molecule (which may preferably be cucurbituril in the present invention) is distributed, and the modified layer also has a certain selective permeability.
- it can be supported on the base layer by an interfacial polymerization method.
- the method can also support the cucurbituril on other organic polymer membranes, such as a microfiltration membrane, an ultrafiltration membrane, and the like.
- the cucurbituril in the above modified layer is a supramolecular having a large ring cavity and a barrel-like molecular structure having open ends
- the preparation method thereof may be prepared by an interfacial polymerization method, for example, first, a first solution containing cucurbituril and a first monomer is added to a substrate, and then a second solution containing the second monomer is added.
- the first solution used herein may be water
- the second solution may be an organic solution which is immiscible with water, and is not particularly limited as long as the cucurbituril, the first monomer and the second monomer can be preferably dissolved and carried out.
- the interface reaction can be.
- the first monomer and the second monomer are not particularly limited as long as the crosslinking reaction can be carried out at the interface.
- the first monomer may be piperazine or m-phenylenediamine, and the second monomer may be used.
- An acid chloride monomer such as trimesoyl chloride.
- the nanofiltration membrane prepared above can be applied to a usual nanofiltration process, for example, separation and retention of electrolytes, organic Separation and interception of objects.
- a polymer modified layer containing cucurbituril to the surface of the nanofiltration membrane, the water flux and the molecular weight cut off for a neutral substance such as PEG are increased.
- Polyimide (P84) and polyethylene glycol 400 (PEG) are dissolved in a solvent of N-methylpyrrolidone (NMP) at a mass ratio, and the mass ratio of P84, PEG and NMP is 20:12:50. After mechanical stirring at room temperature of 25 ° C for 20 to 24 hours, after it is completely dissolved, it is allowed to stand for 8 to 12 hours for defoaming treatment, and the obtained casting liquid is obtained;
- NMP N-methylpyrrolidone
- the prepared polyimide nanofiltration membrane substrate was used for the preparation of the modified layer in the following examples.
- the prepared polyethersulfone-based film was used in the preparation of the modified layer in the following examples.
- the polyamide-based film is fixed on the interfacial polymerization device, and a certain amount of the first phase solution is immersed on the surface of the film to be in contact with the surface for 150 seconds, taken out, and then the polyimide support film is rolled by a rubber roller to remove excess The solution was poured into an equal amount of the second phase, soaked for 60 seconds. After the reaction was completed, the surface was rinsed with a solution of n-hexane to remove excess reactants and then stored in pure water for use.
- Example 5 The difference from Example 5 is that cucurbituril is not added to the first equivalent, and the surface of the polyimide-based film is coated with an interfacial polymerization layer only by interfacial polymerization.
- the polyimide-based film prepared in Example 1, the polyethersulfone-based film prepared in Example 2, the composite film prepared in Examples 3 to 6, and Comparative Example 1 were prepared to obtain a polymerized layer.
- the polyimide composite membrane was subjected to a characterization test of pure water flux.
- the cucurbituril-modified nanofiltration membrane prepared in the present invention has a large water flux.
- the entrapment performance of the film prepared above was tested with 100 ppm of methylene blue under a pressure of 0.6 MPa, and the rejection was as follows.
- Example 1 Polyimide Film 19.4
- Example 2 Polyethersulfone membrane 22.3
- Example 3 cucurbituril composite polyamide film 98.3
- Example 4 cucurbituril composite polyamide film 96.3
- Example 5 Hululurea Composite Polyamide Film 98.2
- Example 6 cucurbituril composite polyamide film 97.7 Polyamide film with polymerization layer in Comparative Example 1 98.5
- Example 5 it can be seen from Example 5 as compared with Comparative Example 1 that the retention of the dye can be better improved by adding cucurbituril modification to the polyimide film; and the nanoparticles in Examples 1 and 2 The rejection of the filter on the dye is very low.
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Abstract
Provided are a supramolecular composite nano-filtration membrane and a preparation method therefor and the use thereof. The supramolecular composite nano-filtration membrane comprises: a base layer and a modification layer covering a surface thereof. The modification layer is a polymer layer with cucurbituril distributed therein; and the base layer is an organic membrane. The preparation method comprises the following steps: a first monomer and cucurbituril are dissolved into a first solution to obtain a first phase; a second monomer is dissolved into a second solution to obtain a second phase; the first phase is applied onto the base layer; the second phase is then applied onto the first phase; and an interface polymerization reaction is carried out, so as to obtain the composite nano-filtration membrane used for liquid filtration.
Description
本发明涉及一种超分子复合纳滤膜及其制备方法和应用，属于聚合物膜技术领域。The invention relates to a supramolecular composite nanofiltration membrane, a preparation method and application thereof, and belongs to the technical field of polymer membranes.
纳滤(NF)是20世纪80年代末后期发展起来的一种介于反渗透和超滤之间的新型膜分离技术，早期称为“低压反渗透”或“疏松反渗透”。纳滤技术是为了适应工业软化水的需求及降低成本而发展起来的一种新型压力驱动膜过程。纳滤膜的截留分子量在200-1000之间。膜孔径在1nm左右，适宜分离大小约为1nm的溶解组分，故称为“纳滤”。由于纳滤膜特殊的孔径范围和制备时的特殊处理(复合、荷电化)，使其具有较特殊的分离性能。纳滤膜的一个很大特征是膜表面或膜中存在带电基团，因此纳滤膜分离具有两个特征，即筛分效应和电荷效应。分子量大于膜的截留分子量的物质将被膜截留，反之则透过，这就是膜的筛分效应；膜的电荷效应又称Donnan效应，是指离子与膜所带的电荷的静电作用。对不带电荷的分子的过滤主要靠位阻效应即电荷效应，利用筛分效应可以将不同分子量的物质分离；而对带有电荷的物质的过滤主要靠电荷效应，纳滤膜表面分离曾由聚电解质构成，膜表面带有一点的电荷，大多数纳滤膜表面带有负电荷，它们通过静电相互作用，阻碍多价离子的渗透，这是纳滤膜在低压条件下仍具有较高脱盐性能的主要原因。Nanofiltration (NF) is a new membrane separation technology developed between late osmosis and ultrafiltration in the late 1980s. It was called "low pressure reverse osmosis" or "loose reverse osmosis". Nanofiltration technology is a new type of pressure-driven membrane process developed to meet the needs of industrial softened water and reduce costs. The molecular weight cut-off of the nanofiltration membrane is between 200 and 1000. The membrane pore size is about 1 nm, and it is suitable to separate a dissolved component having a size of about 1 nm, so it is called "nanofiltration". Due to the special pore size range of the nanofiltration membrane and the special treatment (composite, charge) during preparation, it has a special separation performance. A very important feature of nanofiltration membranes is the presence of charged groups on the membrane surface or membrane, so nanofiltration membrane separation has two characteristics, namely the screening effect and the charge effect. A substance having a molecular weight greater than the molecular weight cut-off of the membrane will be trapped by the membrane, and vice versa, which is the sieving effect of the membrane; the charge effect of the membrane, also known as the Donnan effect, refers to the electrostatic interaction of the charge carried by the ions and the membrane. The filtration of uncharged molecules mainly relies on the steric hindrance effect, that is, the charge effect, and the sieving effect can be used to separate substances of different molecular weights; while the filtration of charged substances mainly depends on the charge effect, the surface separation of nanofiltration membranes has been Polyelectrolyte consists of a little charge on the surface of the membrane. Most of the nanofiltration membranes have a negative charge on the surface. They interact with each other through electrostatic interactions, which hinders the penetration of multivalent ions. This is the nanofiltration membrane that still has high desalination under low pressure conditions. The main reason for performance.
根据纳滤膜的特点，纳滤膜主要应用于以下几个方面：According to the characteristics of the nanofiltration membrane, the nanofiltration membrane is mainly used in the following aspects:
饮用水的净化：Purification of drinking water:
纳滤膜最大的应用领域是饮用水的软化和有机物的脱除，随着水污染的加具，人们对饮用水水质越来越关心。传统的饮用水处理主要通过絮凝、沉降、砂滤、和加氯消毒来去除水中的悬浮物和细菌，而对各种溶解化学物质的脱除率却很低，随着水资源贫乏的日益严峻、环境污染的加剧和各国饮用水标准的提高，可脱除各种有机物和有害化学物质的“饮用水深度处理技术”日益受到人们的重视。膜分离实验表明，纳滤膜可以去除消毒过程产生的微毒副产物、重金属、天然有机物及硫酸盐硝酸盐等。同时具有处理水质好、稳定、化学药剂用量少、节能、易于管理和维护，基本可以达到零排放等优点。The largest application area of nanofiltration membranes is the softening of drinking water and the removal of organic matter. With the addition of water pollution, people are more and more concerned about the quality of drinking water. Traditional drinking water treatment mainly removes suspended solids and bacteria in water through flocculation, sedimentation, sand filtration, and chlorination. The removal rate of various dissolved chemicals is very low, and the water resources are increasingly scarce. The increase in environmental pollution and the improvement of drinking water standards in various countries, and the "deep drinking water treatment technology" that can remove various organic substances and harmful chemical substances have received increasing attention. Membrane separation experiments show that the nanofiltration membrane can remove microtoxic by-products, heavy metals, natural organic matter and sulfate nitrate produced by the disinfection process. At the same time, it has the advantages of good water quality, stability, low chemical dosage, energy saving, easy management and maintenance, and can basically achieve zero emission.
工业废水处理：Industrial wastewater treatment:
现代工业的发展在为社会创造巨大经济利益的同时，也产生了严重的环境污染问题，越来越多的海洋、湖泊及河流等由于大量工业废水的排入而被污染，给人类及动植物的生存造
成严重威胁，膜分离技术的特点使其在工业废水处理方面发挥着重要作用。纳滤膜以其特殊的分离性能成功的应用于造纸、电镀、印染等行业废水的处理上。在工业印染废水中，组织废水具有高CODCr浓度高和高色度的特点，尤其是色度的去除一直是废水处理的难点，废水中绝大多数染料为复杂芳环结构，不易降解，不易被氧化，废水处理的难度很大；同时废水中所含的盐也进一步降低废水的可生物降解性。从理论上讲，多种物理化学方法可以用于染料废水的脱色处理，如絮凝沉淀、吸附、离子交换、膜处理、化学氧化、光氧化、电解及生物处理方法等，但是单一的处理方法都无法将废水处理到可回收的程度。高浓度的印染废水对环境造成严重的污染，直接影响纺织工业的持续发展，随着国家和社会对环境保护的要求日益严格，开发有效的染料废水处理方法和工艺是十分有必要。纳滤膜技术是近几年发展起来的一种新型分离技术，主要基于孔径筛分效应和荷电效应来实现对物料的分离，对相对分子量大于200的有机物和高价离子具有很高的截留率，所以纳滤技术尤其适用于印染废水的处理，而且纳滤膜的渗透压远低于反渗透，所以使纳滤过程的操作压较低，从而可以达到较低水处理成本的目的。While the development of modern industry has created enormous economic benefits for the society, it has also caused serious environmental pollution problems. More and more oceans, lakes and rivers have been polluted due to the discharge of large amounts of industrial wastewater, giving humans, animals and plants. Survival
A serious threat, the characteristics of membrane separation technology make it play an important role in industrial wastewater treatment. Nanofiltration membrane has been successfully applied to the treatment of wastewater from papermaking, electroplating, printing and dyeing industries with its special separation performance. In industrial printing and dyeing wastewater, tissue wastewater has the characteristics of high CODCr concentration and high chroma. Especially the removal of chroma has always been a difficult point in wastewater treatment. Most of the dyes in wastewater are complex aromatic ring structures, which are not easy to degrade and are not easy to be Oxidation, wastewater treatment is very difficult; at the same time, the salt contained in the wastewater further reduces the biodegradability of the wastewater. In theory, a variety of physical and chemical methods can be used for the decolorization of dye wastewater, such as flocculation, adsorption, ion exchange, membrane treatment, chemical oxidation, photooxidation, electrolysis and biological treatment methods, but a single treatment method It is not possible to treat the wastewater to a level that is recyclable. The high concentration of printing and dyeing wastewater causes serious pollution to the environment and directly affects the sustainable development of the textile industry. With the increasingly strict environmental protection requirements of the state and society, it is very necessary to develop effective dye wastewater treatment methods and processes. Nanofiltration membrane technology is a new separation technology developed in recent years. It is mainly based on pore size screening effect and charging effect to achieve separation of materials. It has high rejection rate for organic matter and high-valent ions with relative molecular weight greater than 200. Therefore, the nanofiltration technology is especially suitable for the treatment of printing and dyeing wastewater, and the osmotic pressure of the nanofiltration membrane is much lower than that of reverse osmosis, so that the operating pressure of the nanofiltration process is lower, so that the purpose of lower water treatment cost can be achieved.
制药：Pharmaceutical:
利用纳滤膜技术可以提纯和浓缩生化试剂，不仅仅可以降低有机溶剂与水的消耗量，而且可以去除微量的有机污染及低分子量盐，最终达到节能、提高产品质量的效果。纳滤膜已成功地应用于红霉素、金霉素、万古霉素和青霉素等多种抗生素的浓缩和纯化过程中。维生素B12由发酵得到，传统的生产工艺复杂，产率低。用微滤替代传统的过滤，经微滤的发酵清液用纳滤膜可浓缩10倍以上，从而大大减少了萃取剂用量，并提高了设备的生产能力。被萃取后的水相还有少量的维生素B12及一定的溶剂，通过纳滤可进行截留，以减少产品的损失。粗产品纯化过程中所使用的溶剂，也可以用纳滤膜处理回收使用。The nanofiltration membrane technology can purify and concentrate biochemical reagents, not only can reduce the consumption of organic solvents and water, but also can remove trace organic pollution and low molecular weight salts, and finally achieve energy saving and product quality improvement. Nanofiltration membranes have been successfully applied to the concentration and purification of various antibiotics such as erythromycin, chlortetracycline, vancomycin and penicillin. Vitamin B12 is obtained by fermentation, and the traditional production process is complicated and the yield is low. The microfiltration is used to replace the traditional filtration, and the microfiltration fermentation supernatant can be concentrated by 10 times or more with the nanofiltration membrane, thereby greatly reducing the amount of the extracting agent and increasing the production capacity of the equipment. The extracted aqueous phase also has a small amount of vitamin B12 and a certain solvent, which can be intercepted by nanofiltration to reduce product loss. The solvent used in the purification of the crude product can also be recovered by treatment with a nanofiltration membrane.
食品加工：food processing:
由于纳滤膜具有较高的抗污染能力，细菌不易在纳滤膜表面生存繁衍，由于纳滤膜能脱除一部分盐，能减少盐对蒸发器的腐蚀。常用语酵母和奶酪的加工过程。它解决废水排放的问题，还可提高经济效益，而且纳滤膜也有利于发酵溶液中有机酸的回收利用。在溶液处于低pH值时，这些酸并未离解，很容易透过纳滤膜；而在高pH值条件下，由于离解的酸与膜之间相互的排斥作用使得大部分酸被膜截留，同时膜也截留了糖类化合物，有利于回收再利用。因此，调节发酵溶液的pH值，使它处于适当的范围，并用纳滤膜脱除发酵溶液中的有机酸，截留酵母菌、未发酵的糖以及其他有用成分，将这些截留物质再返回到发酵容器中重新利用，这样不仅可以减弱产物对发酵过程的抑制作用，同时有利于回收利用酵母菌和糖类。
不仅提高了产量，还减少了高成本原料的费用。Because the nanofiltration membrane has high anti-pollution ability, the bacteria are not easy to survive on the surface of the nanofiltration membrane. Because the nanofiltration membrane can remove a part of the salt, the corrosion of the evaporator on the evaporator can be reduced. The common process of yeast and cheese processing. It solves the problem of wastewater discharge and can also improve economic benefits, and the nanofiltration membrane is also beneficial for the recovery and utilization of organic acids in the fermentation solution. When the solution is at a low pH, these acids are not dissociated and easily pass through the nanofiltration membrane; at high pH, most of the acid membrane is trapped due to the mutual repulsion between the dissociated acid and the membrane, while The membrane also retains the saccharide compound, which is beneficial for recycling. Therefore, the pH of the fermentation solution is adjusted to be in an appropriate range, and the organic acid in the fermentation solution is removed by a nanofiltration membrane, and the yeast, unfermented sugar and other useful components are retained, and the retentate is returned to the fermentation. Reuse in the container, not only can reduce the inhibition of the fermentation process, but also facilitate the recycling of yeast and sugar.
Not only does it increase production, it also reduces the cost of high-cost raw materials.
另外，纳滤膜还可以用于纺织、皮革加工等领域废水的处理以及手性物质的分离。由于其特殊的分离性能，纳滤将越来越广泛地应用于许多领域如提高饮用水质量、软化水、染料、色素、医药与生化产品的提纯与浓缩以及油水深度分离、染料、印刷、纺织、化学与医药废水的脱色等领域。耐溶剂、耐酸碱的纳滤膜应用前景更广。In addition, the nanofiltration membrane can also be used for the treatment of wastewater in the fields of textiles, leather processing, and the separation of chiral substances. Due to its special separation performance, nanofiltration will be more and more widely used in many fields such as improving drinking water quality, demineralized water, dyes, pigments, purification and concentration of pharmaceutical and biochemical products, and deep separation of oil and water, dyes, printing, and textiles. , chemical and pharmaceutical wastewater decolorization and other fields. The solvent-resistant, acid-resistant nanofiltration membrane has a wider application prospect.
但是，纳滤膜在应用于分离过程中，截留率和水通量都需要提高的需求。However, in the application of nanofiltration membranes, the rejection and water flux need to be increased.
发明内容Summary of the invention
本发明针对目前复合纳滤膜通量小，对小分子染料截留率低的不足，为了改善界面聚合层的厚度和电性提高复合纳滤膜的通量和截留率，提出在界面聚合水相溶液中加入一种新型材料对膜进行改性，即一种超分子复合纳滤膜制备方法。本发明通过以下步骤得以实现：The invention aims at the shortcoming of the current composite nanofiltration membrane flux and the low interception rate of the small molecular dye. In order to improve the thickness and electrical property of the interfacial polymeric layer, the flux and the rejection rate of the composite nanofiltration membrane are improved, and the aqueous phase is polymerized at the interface. A new material is added to the solution to modify the membrane, which is a preparation method of a supramolecular composite nanofiltration membrane. The invention is achieved by the following steps:
本发明的第一个方面：The first aspect of the invention:
一种超分子复合纳滤膜，包括有基层及其表面覆盖的修饰层，所述的修饰层是指分布有葫芦脲的聚合物层；所述的基层是有机纳滤膜。A supramolecular composite nanofiltration membrane comprising a base layer and a surface layer thereof, wherein the modified layer refers to a polymer layer distributed with cucurbituril; and the base layer is an organic nanofiltration membrane.
所述的葫芦脲是指葫芦脲[n](n＝5～12中的任意整数)及其衍生物。The cucurbituril refers to cucurbituril [n] (any integer of n = 5 to 12) and derivatives thereof.
所述的基层的材质选自聚酰胺、聚酰亚胺、醋酸纤维素、磺化聚砜、磺化聚醚砜或聚乙烯醇等。The material of the base layer is selected from the group consisting of polyamide, polyimide, cellulose acetate, sulfonated polysulfone, sulfonated polyethersulfone or polyvinyl alcohol.
所述的基层还可以覆盖于支撑层之上，所述的支撑层可以选自无纺布等。The base layer may also be coated on the support layer, and the support layer may be selected from a nonwoven fabric or the like.
在一个实施例中，所述的聚合物层是由第一单体和第二单体相互聚合而成；所述的第一单体是哌嗪类单体或者含胺基单体，所述的第二单体是酰氯类单体。In one embodiment, the polymer layer is formed by polymerizing a first monomer and a second monomer; the first monomer is a piperazine monomer or an amine group-containing monomer, The second monomer is an acid chloride monomer.
本发明的第二个方面：The second aspect of the invention:
一种超分子复合纳滤膜的制备方法，包括如下步骤：A preparation method of a supramolecular composite nanofiltration membrane comprises the following steps:
i).将第一单体、葫芦脲溶解于第一溶液中，得到第一相；i) dissolving the first monomer, cucurbituril in the first solution to obtain a first phase;
ii).将第二单体溶解于第二溶液中，得到第二相；Ii) dissolving the second monomer in the second solution to obtain a second phase;
iii).将第一相施加于基层上，再将第二相施加于第一相上，进行界面聚合反应，得到复合膜。Iii). Applying the first phase to the substrate, and applying the second phase to the first phase, performing interfacial polymerization to obtain a composite film.
所述的第一溶液和第二溶液不互溶。The first solution and the second solution are immiscible.
在一个实施例中，第一溶液是水，第二溶液是正己烷。In one embodiment, the first solution is water and the second solution is n-hexane.
在一个实施例中，第一单体是哌嗪类单体或者含胺基单体，第二单体是酰氯类单体。In one embodiment, the first monomer is a piperazine-based monomer or an amine-containing monomer, and the second monomer is an acid chloride-based monomer.
在一个实施例中，第一单体在第一相中的质量浓度为0.01～5％，葫芦脲在第一相中的质
量浓度为0.01～5％；第二单体在第二相中的质量浓度为0.01～5％。In one embodiment, the first monomer has a mass concentration in the first phase of from 0.01 to 5%, and the quality of the cucurbituril in the first phase
The concentration is 0.01 to 5%; the mass concentration of the second monomer in the second phase is 0.01 to 5%.
本发明的第三个方面：The third aspect of the invention:
超分子复合纳滤膜在液体过滤中的应用。Application of supramolecular composite nanofiltration membrane in liquid filtration.
所述的应用，是指荷电物质、中性物质或者他们的混合物的过滤或分离。The application refers to the filtration or separation of charged materials, neutral substances or mixtures thereof.
本发明的第四个方面：The fourth aspect of the invention:
一种在有机分离膜的表面负载超分子的方法，包括如下步骤：A method of loading a supramolecule on a surface of an organic separation membrane, comprising the steps of:
i).将含有第二单体的第二溶液施加于有机分离膜上；i) applying a second solution containing the second monomer to the organic separation membrane;
ii).再将含有葫芦脲和第一单体的第一溶液施加于第二溶液上，通过第一单体与第二单体的界面聚合反应，将葫芦脲负载于有机分离膜上。Ii). The first solution containing cucurbituril and the first monomer is applied to the second solution, and the cucurbituril is supported on the organic separation membrane by interfacial polymerization of the first monomer and the second monomer.
所述的超分子葫芦脲是一种瓜环状分子，内部具有刚性疏水空腔，子两端各有6个C＝O官能团，可以和很多带正电物质相互作用，外部有很强的亲水性，可以提高膜表面的亲水性，分子平均粒径为1～2nm。The supramolecular cucurbituril is a melon ring-shaped molecule having a rigid hydrophobic cavity inside, and six C=O functional groups at each end of the leg, which can interact with many positively charged substances, and has a strong external Water-based, the hydrophilicity of the surface of the film can be improved, and the average molecular particle diameter is 1 to 2 nm.
在界面聚合水相中加入葫芦脲后通过扫描电镜发现复合纳滤膜表面的界面聚合层变得更为致密，结节状凸起变得均匀，截留分子量变大，这导致复合纳滤膜的水通量显著提升，最高可达到22L/m2·h·bar，对分子量为319g/mol的亚甲基蓝截留率最高达到99.5％。After adding cucurbituril to the interfacial polymerization aqueous phase, it was found by scanning electron microscopy that the interfacial polymerization layer on the surface of the composite nanofiltration membrane became denser, the nodular protrusion became uniform, and the molecular weight cut-off became larger, which led to the composite nanofiltration membrane. The water flux is significantly improved up to 22 L/m 2 ·h·bar, and the methylene blue rejection rate of the molecular weight of 319 g/mol is up to 99.5%.
图1是本发明对照例1中制备的聚酰亚胺复合纳滤膜形貌表面SEM图。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a SEM image showing the morphology of a polyimide composite nanofiltration membrane prepared in Comparative Example 1 of the present invention.
图2是本发明实施例5中制备的超分子-聚酰亚胺复合纳滤膜形貌表面SEM图。2 is a SEM image of the morphology of the supramolecular-polyimide composite nanofiltration membrane prepared in Example 5 of the present invention.
下面通过具体实施方式对本发明作进一步详细说明。但本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限定本发明的范围。实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市场购买获得的常规产品。The invention will now be further described in detail by way of specific embodiments. However, those skilled in the art will understand that the following examples are merely illustrative of the invention and should not be construed as limiting the scope of the invention. Where specific techniques or conditions are not indicated in the examples, they are carried out according to the techniques or conditions described in the literature in the art or in accordance with the product specifications. The reagents or instruments used are not specified by the manufacturer, and are conventional products that can be purchased through the market.
本文使用的近似语在整个说明书和权利要求书中可用于修饰任何数量表述，其可在不导致其相关的基本功能发生变化的条件下准许进行改变。因此，由诸如“约”的术语修饰的值并不局限于所指定的精确值。在至少一些情况下，近似语可与用于测量该值的仪器的精度相对应。除非上下文或语句中另有指出，否则范围界限可以进行组合和/或互换，并且这种范围
被确定为且包括本文中所包括的所有子范围。除了在操作实施例中或其他地方中指明之外，说明书和权利要求书中所使用的所有表示成分的量、反应条件等等的数字或表达在所有情况下都应被理解为受到词语“约”的修饰。The Approximations used herein can be used to modify any number of expressions in the entire specification and claims, which can be modified to change without departing from the basic function. Therefore, a value modified by a term such as "about" is not limited to the precise value specified. In at least some cases, the approximation may correspond to the accuracy of the instrument used to measure the value. Range boundaries can be combined and/or interchanged, unless otherwise stated in the context or statement, and such scope
It is determined to be and including all sub-ranges included herein. Except in the operating examples or elsewhere, all numbers or expressions indicating quantities of ingredients, reaction conditions, and the like, used in the specification and claims, should be understood in all instances as "The modification."
以范围形式表达的值应当以灵活的方式理解为不仅包括明确列举出的作为范围限值的数值，而且还包括涵盖在该范围内的所有单个数值或子区间，犹如每个数值和子区间被明确列举出。例如，“大约0.1％至约5％”的浓度范围应当理解为不仅包括明确列举出的约0.1％至约5％的浓度，还包括有所指范围内的单个浓度(如，1％、2％、3％和4％)和子区间(例如，0.1％至0.5％、1％至2.2％、3.3％至4.4％)。Values expressed in terms of ranges should be understood in a flexible manner to include not only the numerical values that are explicitly recited as the range limits, but also all individual values or sub-ranges that are within the range, as if each value and sub-range are List it. For example, a concentration range of "about 0.1% to about 5%" should be understood to include not only a concentration of about 0.1% to about 5% that is explicitly listed, but also a single concentration within a range of indications (eg, 1%, 2). %, 3%, and 4%) and subintervals (eg, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%).
本发明提出的纳滤膜是由至少两层所构成，一层为基层，可以为常见的纳滤膜材质层，例如：聚酰胺、醋酸纤维素、磺化聚砜、磺化聚醚砜和聚乙烯醇等，没有特别限定，它是作为上一层的基材。另一层为表面修饰层，修饰层也是一层聚合物层，在该聚合物层中还分布有超分子(本发明中可以优选葫芦脲)，该修饰层也具有一定的选择透过性，本发明中可以采用界面聚合法将其负载于基层上，同样地，该方法也能够将葫芦脲负载于其它的有机聚合物膜上，例如微滤膜、超滤膜等。The nanofiltration membrane proposed by the invention is composed of at least two layers, and the first layer is a base layer, which can be a common nanofiltration membrane material layer, for example: polyamide, cellulose acetate, sulfonated polysulfone, sulfonated polyethersulfone and Polyvinyl alcohol or the like is not particularly limited, and it is a substrate as the upper layer. The other layer is a surface modification layer, and the modification layer is also a polymer layer in which a super molecule (which may preferably be cucurbituril in the present invention) is distributed, and the modified layer also has a certain selective permeability. In the present invention, it can be supported on the base layer by an interfacial polymerization method. Similarly, the method can also support the cucurbituril on other organic polymer membranes, such as a microfiltration membrane, an ultrafiltration membrane, and the like.
在上述的修饰层中的葫芦脲是一种超分子，具有大环空腔、两端开口的桶状的分子结构，可以适用于本发明的葫芦脲可以包括有：葫芦脲[n](n＝5～12中的任意整数)，也可以是它的衍生物，其是一种瓜环状分子，内部具有刚性疏水空腔，子两端各有C＝O官能团，外部有很强的亲水性，可以提高膜表面的亲水性，分子平均粒径为1-2nm。The cucurbituril in the above modified layer is a supramolecular having a large ring cavity and a barrel-like molecular structure having open ends, and the cucurbiturine which can be suitably used in the present invention may include: cucurbituril [n] (n Any of the integers from 5 to 12, or a derivative thereof, is a melon ring molecule having a rigid hydrophobic cavity inside, a C=O functional group at each end, and a strong pro externally Water-based, can improve the hydrophilicity of the surface of the film, and the average molecular particle diameter is 1-2 nm.
另外，它的制备方法可以是通过界面聚合法制备得到，例如：首先在基材上添加含有葫芦脲和第一单体的第一溶液，再将其与含有第二单体的第二溶液的接触，且第一溶液与第二溶液相互不互溶，第一单体与第二单体会在界面处发生聚合，形成表面的修饰层，由于葫芦脲是溶解于第一溶液中，并且其具有空腔结构，因此第一单体会被包覆于空腔中，经过界面聚合反应之后，会形成透过葫芦脲而相互交联的聚合修饰层，使得葫芦脲分布于修饰层上，进而实现葫芦脲在基层上的负载。In addition, the preparation method thereof may be prepared by an interfacial polymerization method, for example, first, a first solution containing cucurbituril and a first monomer is added to a substrate, and then a second solution containing the second monomer is added. Contacting, and the first solution and the second solution are mutually insoluble, and the first monomer and the second monomer are polymerized at the interface to form a surface modified layer, since the cucurbituril is dissolved in the first solution, and a cavity structure, so that the first monomer is encapsulated in the cavity, and after the interfacial polymerization reaction, a polymeric modification layer cross-linked by cucurbiturone is formed, so that the cucurbituril is distributed on the modified layer, thereby realizing The load of cucurbituril on the substrate.
这里所用的第一溶液可以为水、第二溶液可以为与水不互溶的有机溶液，没有特别限定，只要能够将葫芦脲、第一单体和第二单体能够较好的溶解、并进行界面反应即可。The first solution used herein may be water, and the second solution may be an organic solution which is immiscible with water, and is not particularly limited as long as the cucurbituril, the first monomer and the second monomer can be preferably dissolved and carried out. The interface reaction can be.
其中，第一单体和第二单体没有特别限定，只要能够进行在界面上进行交联反应即可，例如：第一单体可以采用哌嗪、间苯二胺，第二单体可以采用酰氯类单体，例如均苯三甲酰氯。The first monomer and the second monomer are not particularly limited as long as the crosslinking reaction can be carried out at the interface. For example, the first monomer may be piperazine or m-phenylenediamine, and the second monomer may be used. An acid chloride monomer such as trimesoyl chloride.
上述制备得到的纳滤膜可以应用于通常的纳滤过程，例如：电解质的分离与截留、有机
物的分离与截留等。本发明中，由于通过在纳滤膜的表面增加了含有葫芦脲的聚合物修饰层，使得膜的表面被拉伸，使得水通量和对于中性物质(例如PEG)的截留分子量有增大的趋势，同时，由于其具有的电荷效果，对于负电荷的物质的截留率又有所提高。The nanofiltration membrane prepared above can be applied to a usual nanofiltration process, for example, separation and retention of electrolytes, organic
Separation and interception of objects. In the present invention, since the surface of the film is stretched by adding a polymer modified layer containing cucurbituril to the surface of the nanofiltration membrane, the water flux and the molecular weight cut off for a neutral substance such as PEG are increased. The trend, meanwhile, due to its charge effect, the rejection of negatively charged substances has increased.
实施例1聚酰亚胺基膜的制备Example 1 Preparation of Polyimide Base Film
⑴将聚酰亚胺(P84)与聚乙二醇400(PEG)按一定质量比溶解于N-甲基吡咯烷酮(NMP)溶剂中，P84、PEG和NMP的质量比为20:12:50，在25℃室温下机械搅拌20～24小时，待其完全溶解后，静置8～12h脱泡处理，得到的铸膜液；(1) Polyimide (P84) and polyethylene glycol 400 (PEG) are dissolved in a solvent of N-methylpyrrolidone (NMP) at a mass ratio, and the mass ratio of P84, PEG and NMP is 20:12:50. After mechanical stirring at room temperature of 25 ° C for 20 to 24 hours, after it is completely dissolved, it is allowed to stand for 8 to 12 hours for defoaming treatment, and the obtained casting liquid is obtained;
⑵将聚酯无纺布固定在玻璃板上，控制刮刀厚度为100μm，将铸膜液刮涂在聚酯无纺布上，控制挥发时间5～10秒后，浸入水凝固浴中，发生相分离固化成膜，浸泡5分钟后取出即得湿态聚酰亚胺膜，制备好的基膜保存在去离子水中。(2) Fix the polyester non-woven fabric on the glass plate, control the thickness of the doctor blade to 100 μm, apply the casting solution on the polyester non-woven fabric, control the volatilization time for 5 to 10 seconds, and then immerse in the water coagulation bath to cause phase. The film was separated and solidified, and after being immersed for 5 minutes, the wet polyimide film was taken out, and the prepared base film was stored in deionized water.
制备得到的聚酰亚胺纳滤膜基层用于以下实施例中修饰层的制备。The prepared polyimide nanofiltration membrane substrate was used for the preparation of the modified layer in the following examples.
实施例2聚醚砜基膜的制备Example 2 Preparation of Polyethersulfone Base Film
⑴将聚醚砜与聚乙二醇400(PEG)按一定质量比溶解于N-甲基吡咯烷酮(NMP)溶剂中，P84、PEG和NMP的质量比为20:12:50，在25℃室温下机械搅拌20～24小时，待其完全溶解后，静置8～12h脱泡处理，得到的铸膜液；(1) Dissolving polyethersulfone and polyethylene glycol 400 (PEG) in a solvent of N-methylpyrrolidone (NMP) at a mass ratio of P84, PEG and NMP at a mass ratio of 20:12:50 at room temperature of 25 °C After mechanical stirring for 20 to 24 hours, after it is completely dissolved, it is allowed to stand for 8 to 12 hours for defoaming treatment, and the obtained casting liquid is obtained;
⑵将聚酯无纺布固定在玻璃板上，控制刮刀厚度为100μm，将铸膜液刮涂在聚酯无纺布上，控制挥发时间5～10秒后，浸入水凝固浴中，发生相分离固化成膜，浸泡5分钟后取出即得湿态聚醚砜膜，制备好的基膜保存在去离子水中。(2) Fix the polyester non-woven fabric on the glass plate, control the thickness of the doctor blade to 100 μm, apply the casting solution on the polyester non-woven fabric, control the volatilization time for 5 to 10 seconds, and then immerse in the water coagulation bath to cause phase. The film was separated and solidified, and after immersion for 5 minutes, the wet polyethersulfone film was taken out, and the prepared base film was stored in deionized water.
制备得到的聚醚砜基膜用于以下实施例中修饰层的制备。The prepared polyethersulfone-based film was used in the preparation of the modified layer in the following examples.
实施例3葫芦脲修饰的聚酰亚胺复合膜的制备Example 3 Preparation of a ruthenium-modified polyimide composite membrane
配制2wt％的无水哌嗪(PIP)水相溶液，加入0.1wt％的葫芦脲6(CB6)，搅拌，直至完全溶解，作为第一相；Preparing a 2 wt% anhydrous piperazine (PIP) aqueous phase solution, adding 0.1 wt% of cucurbituril 6 (CB6), stirring until completely dissolved, as the first phase;
配制0.1wt％的均苯三甲酰氯有机相溶液，有机溶剂为正己烷，作为第二相；Preparing a 0.1 wt% solution of a trimesoyl chloride organic phase, the organic solvent being n-hexane as a second phase;
将聚酰亚胺基膜固定在界面聚合装置上，倒入一定量的第一相溶液浸没膜表面，使其与表面接触120秒，取出，然后用橡胶辊滚压聚酰亚胺支撑膜，去除多余的溶液，倒入等量的第二相，浸泡60秒，待反应完成后用正己烷溶液冲洗表面，去除多余的反应物然后保存在纯水中待用。
Fixing the polyimide-based film on the interfacial polymerization device, pour a certain amount of the first phase solution into the surface of the film, contact it with the surface for 120 seconds, take it out, and then roll the polyimide support film with a rubber roller. The excess solution was removed, an equal amount of the second phase was poured, and soaked for 60 seconds. After the reaction was completed, the surface was rinsed with a n-hexane solution to remove excess reactants and then stored in pure water for use.
实施例4葫芦脲修饰的聚酰亚胺复合膜的制备Example 4 Preparation of a ruthenium-modified polyimide composite membrane
配制1wt％的无水哌嗪(PIP)水相溶液，加入0.5wt％的葫芦脲8(CB8)，搅拌，直至完全溶解，作为第一相；Preparing a 1 wt% anhydrous piperazine (PIP) aqueous phase solution, adding 0.5 wt% of cucurbituril 8 (CB8), stirring until completely dissolved, as the first phase;
配制0.3wt％的均苯三甲酰氯有机相溶液，有机溶剂为正己烷，作为第二相；Preparing a 0.3 wt% solution of a trimesoyl chloride organic phase, the organic solvent being n-hexane as a second phase;
将聚酰亚胺基膜固定在界面聚合装置上，倒入一定量的第一相溶液浸没膜表面，使其与表面接触150秒，取出，然后用橡胶辊滚压聚酰亚胺支撑膜，去除多余的溶液，倒入等量的第二相，浸泡80秒，待反应完成后用正己烷溶液冲洗表面，去除多余的反应物然后保存在纯水中待用。Fixing the polyimide-based film on the interfacial polymerization device, pour a certain amount of the first phase solution into the surface of the film, contact it with the surface for 150 seconds, take it out, and then roll the polyimide support film with a rubber roller. The excess solution was removed, an equal amount of the second phase was poured, and immersed for 80 seconds. After the reaction was completed, the surface was rinsed with a n-hexane solution, and the excess reactant was removed and stored in pure water for use.
实施例5葫芦脲修饰的聚酰亚胺复合膜的制备Example 5 Preparation of a ruthenium-modified polyimide composite membrane
配制3wt％的无水哌嗪(PIP)水相溶液，加入0.7wt％的葫芦脲7(CB7)，搅拌，直至完全溶解，作为第一相；Preparing a 3 wt% anhydrous piperazine (PIP) aqueous phase solution, adding 0.7 wt% of cucurbituril 7 (CB7), stirring until completely dissolved, as the first phase;
配制0.2wt％的均苯三甲酰氯有机相溶液，有机溶剂为正己烷，作为第二相；Preparing a 0.2 wt% solution of a trimesoyl chloride organic phase, the organic solvent being n-hexane as a second phase;
将聚酰胺基膜固定在界面聚合装置上，倒入一定量的第一相溶液浸没膜表面，使其与表面接触110秒，取出，然后用橡胶辊滚压聚酰亚胺支撑膜，去除多余的溶液，倒入等量的第二相，浸泡40秒，待反应完成后用正己烷溶液冲洗表面，去除多余的反应物然后保存在纯水中待用。Fix the polyamide base film on the interfacial polymerization device, pour a certain amount of the first phase solution into the surface of the film, contact it with the surface for 110 seconds, take it out, and then roll the polyimide support film with a rubber roller to remove excess The solution was poured into an equal amount of the second phase, soaked for 40 seconds. After the reaction was completed, the surface was rinsed with a solution of n-hexane to remove excess reactants and then stored in pure water for use.
实施例6葫芦脲修饰的聚酰亚胺复合膜的制备Example 6 Preparation of a ruthenium-modified polyimide composite membrane
配制1wt％的无水哌嗪(PIP)水相溶液，加入0.2wt％的葫芦脲7(CB7)，搅拌，直至完全溶解，作为第一相；Preparing a 1 wt% anhydrous piperazine (PIP) aqueous phase solution, adding 0.2 wt% of cucurbituril 7 (CB7), stirring until completely dissolved, as the first phase;
配制0.4wt％的均苯三甲酰氯有机相溶液，有机溶剂为正己烷，作为第二相；Preparing a 0.4 wt% solution of a trimesoyl chloride organic phase, the organic solvent being n-hexane as a second phase;
将聚酰胺基膜固定在界面聚合装置上，倒入一定量的第一相溶液浸没膜表面，使其与表面接触150秒，取出，然后用橡胶辊滚压聚酰亚胺支撑膜，去除多余的溶液，倒入等量的第二相，浸泡60秒，待反应完成后用正己烷溶液冲洗表面，去除多余的反应物然后保存在纯水中待用。The polyamide-based film is fixed on the interfacial polymerization device, and a certain amount of the first phase solution is immersed on the surface of the film to be in contact with the surface for 150 seconds, taken out, and then the polyimide support film is rolled by a rubber roller to remove excess The solution was poured into an equal amount of the second phase, soaked for 60 seconds. After the reaction was completed, the surface was rinsed with a solution of n-hexane to remove excess reactants and then stored in pure water for use.
对照例1覆有聚合层的聚酰亚胺复合膜的制备Comparative Example 1 Preparation of Polyimide Composite Film Covered with Polymer Layer
与实施例5的区别在于：未在第一相当中加入葫芦脲，仅仅通过界面聚合反应在聚酰亚胺基膜表面覆一层界面聚合层。The difference from Example 5 is that cucurbituril is not added to the first equivalent, and the surface of the polyimide-based film is coated with an interfacial polymerization layer only by interfacial polymerization.
对照例1和实施例5制备得到的聚酰亚胺复合膜的SEM照片如图1和图2所示，从图中
可以看出，通过在表面聚合过程中加入了葫芦脲修饰之后，可以使表面膜层更加均匀，有助于提高抗污染性，表面粗糙容易导致膜过滤过程中容易出现膜污染。SEM photographs of the polyimide composite film prepared in Comparative Example 1 and Example 5 are shown in Fig. 1 and Fig. 2, from the figure.
It can be seen that by adding cucurbituril to the surface polymerization process, the surface film layer can be made more uniform, which helps to improve the anti-pollution property, and the surface roughness is likely to cause membrane fouling during the membrane filtration process.
将实施例1中制备得到的聚酰亚胺基膜、实施例2中制备得到的聚醚砜基膜、实施例3～6中制备得到的复合膜和对照例1制备得到覆有聚合层的聚酰亚胺复合膜进行纯水通量的表征试验。The polyimide-based film prepared in Example 1, the polyethersulfone-based film prepared in Example 2, the composite film prepared in Examples 3 to 6, and Comparative Example 1 were prepared to obtain a polymerized layer. The polyimide composite membrane was subjected to a characterization test of pure water flux.
| 纯水通量L/m2·h·barPure water flux L/m 2 ·h·bar | |
| 实施例1聚酰亚胺基膜Example 1 Polyimide base film | 435435 |
| 实施例2聚醚砜基膜Example 2 polyethersulfone base film | 11261126 |
| 实施例3葫芦脲复合聚酰胺膜Example 3 cucurbituril composite polyamide film | 16.416.4 |
| 实施例4葫芦脲复合聚酰胺膜Example 4 cucurbituril composite polyamide film | 15.315.3 |
| 实施例5葫芦脲复合聚酰胺膜Example 5 Hululurea Composite Polyamide Film | 14.814.8 |
| 实施例6葫芦脲复合聚酰胺膜Example 6 cucurbituril composite polyamide film | 17.317.3 |
| 对照例1中的带聚合层的聚酰胺膜Polyamide film with polymerization layer in Comparative Example 1 | 4.84.8 |
从上表中可以看出，本发明中制备得到的葫芦脲修饰的纳滤膜具有较大的水通量。As can be seen from the above table, the cucurbituril-modified nanofiltration membrane prepared in the present invention has a large water flux.
采用上述制备好的膜用100ppm的亚甲基蓝在0.6MPa压力下测试的截留性能，截留率如下。The entrapment performance of the film prepared above was tested with 100 ppm of methylene blue under a pressure of 0.6 MPa, and the rejection was as follows.
| 截留率％Interception rate% | |
| 实施例1聚酰亚胺膜Example 1 Polyimide Film | 19.419.4 |
| 实施例2聚醚砜膜Example 2 Polyethersulfone membrane | 22.322.3 |
| 实施例3葫芦脲复合聚酰胺膜Example 3 cucurbituril composite polyamide film | 98.398.3 |
| 实施例4葫芦脲复合聚酰胺膜Example 4 cucurbituril composite polyamide film | 96.396.3 |
| 实施例5葫芦脲复合聚酰胺膜Example 5 Hululurea Composite Polyamide Film | 98.298.2 |
| 实施例6葫芦脲复合聚酰胺膜Example 6 cucurbituril composite polyamide film | 97.797.7 |
| 对照例1中的带聚合层的聚酰胺膜Polyamide film with polymerization layer in Comparative Example 1 | 98.598.5 |
通过实施例5与对照例1相比可以看出，通过在聚酰亚胺膜上增加葫芦脲修饰之后，可以较好地提高对染料的截留率；而实施例1和实施例2中的纳滤膜对染料的截留率非常低。
It can be seen from Example 5 as compared with Comparative Example 1 that the retention of the dye can be better improved by adding cucurbituril modification to the polyimide film; and the nanoparticles in Examples 1 and 2 The rejection of the filter on the dye is very low.
Claims (10)
- 一种超分子复合纳滤膜，其特征在于，包括有基层及其表面覆盖的修饰层，所述的修饰层是指分布有葫芦脲的聚合物层；所述的基层是有机膜。A supramolecular composite nanofiltration membrane comprising a base layer and a surface layer thereof, wherein the modified layer refers to a polymer layer in which cucurbituril is distributed; and the base layer is an organic film.
- 根据权利要求1所述的超分子复合纳滤膜，其特征在于，所述的葫芦脲是指葫芦脲[n]或其衍生物，其中n＝5～12中的任意整数。The supramolecular composite nanofiltration membrane according to claim 1, wherein the cucurbituril refers to cucurbituril [n] or a derivative thereof, wherein n = any one of 5 to 12.
- 根据权利要求1所述的超分子复合纳滤膜，其特征在于，所述的基层的材质选自聚酰胺、聚酰亚胺、醋酸纤维素、磺化聚砜、磺化聚醚砜或聚乙烯醇等。The supramolecular composite nanofiltration membrane according to claim 1, wherein the material of the base layer is selected from the group consisting of polyamide, polyimide, cellulose acetate, sulfonated polysulfone, sulfonated polyethersulfone or poly. Vinyl alcohol and the like.
- 根据权利要求1所述的超分子复合纳滤膜，其特征在于，所述的基层还可以覆盖于支撑层之上，所述的支撑层可以选自无纺布等。The supramolecular composite nanofiltration membrane according to claim 1, wherein the base layer may further cover the support layer, and the support layer may be selected from a nonwoven fabric or the like.
- 根据权利要求1所述的超分子复合纳滤膜，其特征在于，所述的聚合物层是由第一单体和第二单体相互聚合而成；所述的第一单体是哌嗪类单体或者含胺基单体，所述的第二单体是酰氯类单体。The supramolecular composite nanofiltration membrane according to claim 1, wherein the polymer layer is formed by polymerizing a first monomer and a second monomer; and the first monomer is piperazine. A monomer or an amine group-containing monomer, and the second monomer is an acid chloride monomer.
- 权利要求1～5任一项所述的超分子复合纳滤膜的制备方法，其特征在于，包括如下步骤：The method for preparing a supramolecular composite nanofiltration membrane according to any one of claims 1 to 5, comprising the steps of:i).将第一单体、葫芦脲溶解于第一溶液中，得到第一相；i) dissolving the first monomer, cucurbituril in the first solution to obtain a first phase;ii).将第二单体溶解于第二溶液中，得到第二相；Ii) dissolving the second monomer in the second solution to obtain a second phase;iii).将第一相施加于基层上，再将第二相施加于第一相上，进行界面聚合反应，得到复合膜。Iii). Applying the first phase to the substrate, and applying the second phase to the first phase, performing interfacial polymerization to obtain a composite film.
- 根据权利要求6所述的超分子复合纳滤膜的制备方法，其特征在于，所述的第一溶液和第二溶液不互溶；第一溶液是水，第二溶液是正己烷。The method for preparing a supramolecular composite nanofiltration membrane according to claim 6, wherein the first solution and the second solution are mutually insoluble; the first solution is water and the second solution is n-hexane.
- 根据权利要求6所述的超分子复合纳滤膜的制备方法，其特征在于，第一单体是哌嗪类单体或者含胺基单体，第二单体是酰氯类单体；第一单体在第一相中的质量浓度为0.01～5％；第二单体在第二相中的质量浓度为0.01～5％；葫芦脲在第一相中的质量浓度为为0.01～5％。The method for preparing a supramolecular composite nanofiltration membrane according to claim 6, wherein the first monomer is a piperazine monomer or an amine group-containing monomer, and the second monomer is an acid chloride monomer; The mass concentration of the monomer in the first phase is 0.01 to 5%; the mass concentration of the second monomer in the second phase is 0.01 to 5%; and the mass concentration of the cucurbituril in the first phase is 0.01 to 5%. .
- 权利要求1～5任一项所述的超分子复合纳滤膜在液体过滤中的应用。Use of the supramolecular composite nanofiltration membrane according to any one of claims 1 to 5 for liquid filtration.
- 一种在有机分离膜的表面负载超分子的方法，其特征在于，包括如下步骤：A method for loading a supramolecule on a surface of an organic separation membrane, comprising the steps of:i).将含有第二单体的第二溶液施加于有机分离膜上；i) applying a second solution containing the second monomer to the organic separation membrane;ii).再将含有葫芦脲和第一单体的第一溶液施加于第二溶液上，通过第一单体与第二单体的界面聚合反应，将葫芦脲负载于有机分离膜上。 Ii). The first solution containing cucurbituril and the first monomer is applied to the second solution, and the cucurbituril is supported on the organic separation membrane by interfacial polymerization of the first monomer and the second monomer.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111644081A (en) * | 2020-05-23 | 2020-09-11 | 浙江迪萧环保科技有限公司 | Preparation method of novel high-stability composite nanofiltration membrane |
| CN112755810A (en) * | 2020-12-18 | 2021-05-07 | 中化(宁波)润沃膜科技有限公司 | Positively charged composite nanofiltration membrane and preparation method thereof |
| CN113491955A (en) * | 2021-06-04 | 2021-10-12 | 中国石油大学(华东) | Composite membrane with heterostructure separation layer and preparation method thereof |
| CN114249463A (en) * | 2021-12-30 | 2022-03-29 | 新疆神邦环境工程有限公司 | Method for efficiently recovering inorganic salt in cotton dyeing residual liquid |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101462388A (en) * | 2009-01-13 | 2009-06-24 | 四川大学 | Compound film enhanced by inclusion complex of ring molecule and polymer and preparation method thereof |
| CN100522966C (en) * | 2002-01-03 | 2009-08-05 | 学校法人浦项工科大学校 | Hydroxycucurbituril derivatives, their preparation methods and uses |
| CN101792115A (en) * | 2010-03-16 | 2010-08-04 | 清华大学 | Cucurbituril subject-object based chemical nano structure membrane and preparation method and application thereof |
| CN104324619A (en) * | 2014-03-12 | 2015-02-04 | 唐山曹妃甸海清源科技有限公司 | Compound nanofiltration membrane with high selectivity, and preparation method thereof |
| CN105435658A (en) * | 2014-08-28 | 2016-03-30 | 中国石油化工股份有限公司 | A preparing method of a supermolecule composite separating membrane |
| CN106178993A (en) * | 2016-08-23 | 2016-12-07 | 东华理工大学 | A kind of supermolecule polymer NF membrane and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101112675A (en) * | 2006-07-27 | 2008-01-30 | 中国科学院大连化学物理研究所 | Method for modifying compound film surface |
| CN102327746B (en) * | 2011-08-23 | 2014-04-02 | 复旦大学 | Anti-pollution cyclodextrin-polymer composite nano-filtration membrane and preparation method thereof |
| CN103272486A (en) * | 2013-06-18 | 2013-09-04 | 天津工业大学 | Composite film containing calixarene structure on surface layer |
| CN106178973B (en) * | 2016-08-24 | 2018-10-09 | 杭州易膜环保科技有限公司 | A kind of energy-saving NF membrane and preparation method thereof for water cleaning systems |
-
2016
- 2016-12-29 CN CN201611244794.1A patent/CN106731841B/en active Active
-
2017
- 2017-03-30 WO PCT/CN2017/078785 patent/WO2018120476A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100522966C (en) * | 2002-01-03 | 2009-08-05 | 学校法人浦项工科大学校 | Hydroxycucurbituril derivatives, their preparation methods and uses |
| CN101462388A (en) * | 2009-01-13 | 2009-06-24 | 四川大学 | Compound film enhanced by inclusion complex of ring molecule and polymer and preparation method thereof |
| CN101792115A (en) * | 2010-03-16 | 2010-08-04 | 清华大学 | Cucurbituril subject-object based chemical nano structure membrane and preparation method and application thereof |
| CN104324619A (en) * | 2014-03-12 | 2015-02-04 | 唐山曹妃甸海清源科技有限公司 | Compound nanofiltration membrane with high selectivity, and preparation method thereof |
| CN105435658A (en) * | 2014-08-28 | 2016-03-30 | 中国石油化工股份有限公司 | A preparing method of a supermolecule composite separating membrane |
| CN106178993A (en) * | 2016-08-23 | 2016-12-07 | 东华理工大学 | A kind of supermolecule polymer NF membrane and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111644081A (en) * | 2020-05-23 | 2020-09-11 | 浙江迪萧环保科技有限公司 | Preparation method of novel high-stability composite nanofiltration membrane |
| CN112755810A (en) * | 2020-12-18 | 2021-05-07 | 中化(宁波)润沃膜科技有限公司 | Positively charged composite nanofiltration membrane and preparation method thereof |
| CN112755810B (en) * | 2020-12-18 | 2023-05-12 | 中化(宁波)润沃膜科技有限公司 | Positively charged composite nanofiltration membrane and preparation method thereof |
| CN113491955A (en) * | 2021-06-04 | 2021-10-12 | 中国石油大学(华东) | Composite membrane with heterostructure separation layer and preparation method thereof |
| CN114249463A (en) * | 2021-12-30 | 2022-03-29 | 新疆神邦环境工程有限公司 | Method for efficiently recovering inorganic salt in cotton dyeing residual liquid |
| CN115041026A (en) * | 2022-06-10 | 2022-09-13 | 浙江理工大学 | Preparation method of novel organic solvent nanofiltration membrane with macrocyclic molecules introduced |
| CN116747715A (en) * | 2023-04-14 | 2023-09-15 | 浙江大学 | High-water flux nanofiltration membrane with gradient structure separation layer and preparation method thereof |
| CN116747715B (en) * | 2023-04-14 | 2024-01-23 | 浙江大学 | High-water flux nanofiltration membrane with gradient structure separation layer and preparation method thereof |
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