CN109173746A - The compound membrane preparation method of micropollutants in a kind of high efficiency filter water - Google Patents
The compound membrane preparation method of micropollutants in a kind of high efficiency filter water Download PDFInfo
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- CN109173746A CN109173746A CN201811038688.7A CN201811038688A CN109173746A CN 109173746 A CN109173746 A CN 109173746A CN 201811038688 A CN201811038688 A CN 201811038688A CN 109173746 A CN109173746 A CN 109173746A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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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
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Abstract
The invention discloses a kind of compound membrane preparation methods of micropollutants in high efficiency filter water.Include the following steps: to dissolve in a solvent using functionalization beta-cyclodextrin as film additive and film forming polymer, pore-foaming agent, crosslinking agent by setting proportion, it is made into casting solution, be cross-linked in situ by appropriateness of the functionalization beta-cyclodextrin in casting solution, using immersion precipitation phase inversion process preparation can high efficiency filter organic micro-pollutants composite membrane.While the composite membrane is kept compared with high water-permeability, there is very high removal rate to the micropollutants in water.The composite membrane can not only filter the pollutants such as removal planktonic organism, algae, bacterium, albumen, colloid, virus, moreover it is possible to the small organic molecules micropollutants such as Adsorption antibiotic, hormone, plasticiser.The preparation process of the composite membrane is simple, controllable, at low cost, can be widely applied to the separation fields such as Domestic water purifying, sewage treatment, purification of water quality, is a kind of efficient, stable material for water treatment, is with a wide range of applications.
Description
Technical field
The present invention relates to the compound membrane preparation methods for proposing micropollutants in a kind of high efficiency filter water, are related to absorption and film point
From technology, belong to functional form field of membrane material.
Background technique
Mankind's water quality makes moderate progress in recent years, with the development of economy and modernization acceleration, human material, educational level
Flat to be significantly improved, the fineness of life is also promoted therewith, and requirement of the people for water quality is also higher and higher, including drinking water
And domestic water.Therefore, the requirement of water process also significantly improves, and water treatment technology is badly in need of improving therewith.Currently, water treatment technology
Mainly there are flocculent precipitation, membrane separation process, centrifugal separation etc..Separation realizes that water body is net after flocculent precipitation needs staticly settle
Change, and be only applicable to the biggish water body of pollutant concentration, is the water treating method that a kind of efficiency is relatively low, separation fineness is low；From
Centrifugal separation is then to need a large amount of energy consumptions during the separation process, and separation accuracy is not high, is the separation that a kind of energy consumption is high, precision is low
Method.Membrane separation technique mainly realizes separation by the sieve effect in film itself aperture, does not need additional energy consumption, separation accuracy
It controllably, is a kind of isolation technics efficient, easy to operate being widely used at present.
With the aggravation of environmental pollution, cause in water body containing a large amount of organic micro-pollutants for example polycyclic aromatic hydrocarbon, remains of pesticide,
Plasticizer, antibiotic, hormone etc..These organic micro-pollutants can generate greatly harm to human body, including cause human body
Endocrine disorder destroys body immune mechanism, and carcinogenic, teratogenesis, causing a disease becomes, and generates reproductive disease, influences child development, causing property
Precocious, feeblemindedness damages liver and causes cardiovascular disease etc..For the removal of organic micro-pollutants such in water body, pass
The membrane separation technique of system can not successfully manage, although reverse osmosis membrane can be sieving through elimination except these are organic micro- by aperture
Pollutant, but minimum water flux and the efficiency for needing additional high pressure to seriously affect practical application.Compared to for egg
The conventional film chromatographic technique of separation and the purification of white matter, water purification membrane chromatography technology are the height of a kind of combination UF membrane and adsorbing separation
Water purification technology is imitated, larger size pollutant is filtered using the aperture sieve effect of conventional film and membrane chromatography adsorbs organic micro- dirt
The double action for contaminating object, realizes purification of water quality rapidly and efficiently.The core of water purification membrane chromatography technology is that film chromatography medium separates
Membrane material, the absorption aglucon being largely dependent upon in seperation film, can efficient absorption go water removal in organic micro-pollution
Object is decided by adsorption group therein.Therefore, seek a kind of to can be used as adsorption group for the adsorbent material in seperation film very
Key, at the same adsorption group can be effectively fixed in seperation film play the role of efficient absorption be researcher need solve
Problem.
Adsorbing separation film combines aperture screening and the big characteristic of specific adsorption two, is used for the existing correlation of purification of water body
Patent report.In patent 200910230074.3, using phase inversion be prepared for it is a kind of based on the heavy metal of sulfonate resin from
Sub- polymer material for selective adsorption, for the removing of heavy metal ion in water or enrichment, the recycling of noble metal, and can be in acid
Regeneration is realized after washing and is recycled.In the patent No. 201510907970.4, it is prepared for a kind of resin compounded adsorbed film, it can be with
Regulate and control adsorption capacity and film-strength by the content of resin, the high efficiency extraction applied to bromine in seawater.In the patent No.
In 201410689361.1, a kind of porous adsorption membrane is prepared for using sol-gal process, can be used for handling containing heavy metal, organic
The waste water of object, and excellent adsorption effect is shown, saturated extent of adsorption is higher.Although these materials have heavy metal ion etc.
There is higher saturated extent of adsorption, not only need to consider saturated extent of adsorption in practical application while being contemplated that the rate of adsorption, i.e.,
Static Adsorption and dynamic adsorption are intended to higher, can just accomplish efficient adsorbing separation organic micro-pollutants in this way.Therefore, lead to
The selection for crossing adsorbent constructs a kind of Novel composite membrane, and the research for efficient absorption removal organic micro-pollutants has important meaning
Justice.
Currently, having sorbent material of many document reports for water body purification, including clay mineral matter, Industry Waste
The types such as slag, biology, active carbon, resin, wherein most commonly seen is clay mineral matter class, biological species and active carbon class.
Kaolin particle is doped in the bulk material of polyether sulfone by Marino etc. using phase inversion, by regulating and controlling kaolinic content
Be prepared for a series of composite membranes for arsenic ion adsorbing and removing, and show excellent absorption property [Tiziana Marino,
Francesca Russo,Lina Rezzouk,et al.PES-Kaolin Mixed Matrix Membranes for
Arsenic Removal from Water.Membranes.2017.7.57]；Habiba etc. is prepared for mixing by electrostatic spinning
The polyvinyl alcohol nano of miscellaneous chitosan and zeolite, for the absorption of chromium, iron and nickel ion, under the concentration of 10-20mg/L
Eliminating rate of absorption has excellent stability [Habiba, Umma, etal.Chitosan/ (polyvinyl up to 100%
alcohol)/zeolite electrospun composite nanofibrous membrane for adsorption of
Cr6+,Fe3+and Ni2+.Journal of hazardous materials 322(2017):182-194.]；Bolisetty
Hybridized film is prepared Deng active carbon to be doped in protein starch sample fiber, is used for Heavy Metals in Waters ion and radioactive waste
Adsorbing and removing, processing still keeps efficient level while for different kinds of ions, and can be used for the recycling of valuable noble metal
[Bolisetty S,Mezzenga R.Amyloid-carbon hybrid membranes for universal water
purification[J].Nature nanotechnology,2016,11(4):365.].But these adsorbents are to organic micro-
The eliminating rate of absorption of pollutant is not high enough or Adsorption rate is slow, and it is de- to be rarely used for organic micro-pollutants absorption in water
It removes, finding material of a kind of pair of organic micro-pollutants with excellent adsorption effect is that researcher is continually striving to direction.Beta-cyclodextrin
With excellent absorption property, fabulous adsorption capacity is all shown to heavy metal ion and organic micro-pollutants, this makes it
It receives significant attention.
Beta-cyclodextrin is the ring dress oligosaccharide compound obtained by Starch Hydrolysis, cheap, has excellent adsorptivity
Can, it is a kind of industrial scale applications material, molecular structural formula and three-D space structure as shown in Figure 1, it is a kind of rotary table space
Configuration, the characteristic with internal drainage external hydrophilicity, can pass through the Subjective and Objectives such as Van der Waals force, hydrophobic interaction power, hydrogen bond simultaneously
Interaction carries out specific adsorption to target molecule.He etc. is using beta-cyclodextrin and aromatic monomer copolymerization mesoporous beta-
Cyclodextrin high molecular material has high-specific surface area, outstanding absorption property is shown to lead, copper, cadmium ion, especially to lead
Most strong [Junyong He, Yulian Li, Chengming Wang, the et al.Rapid adsorption of the adsorption capacity of ion
of Pb,Cu and Cd from aqueous solutions byβ-cyclodextrin polymers.Applied
surface science.2017.426.29-39].In addition to there is excellent absorption property, beta-cyclodextrin pair to heavy metal ion
Organic micro-pollutants adsorption capacity equally with super strength.The mesoporous beta-cyclodextrin high molecular material of the synthesis such as Alsbaiee is used
In the removal of organic micro-pollutants, compared to non-porous beta-cyclodextrin material and activated carbon, the material is to ethinyloestradiol, isopropyl poisonous weeds
The adsorption rate of the Some Organic Pollutants such as amine, bisphenol-A improves 15-200 times, and has the very high rate of adsorption [Alaaeddin
Alsbaiee,Brian J.Smith,Leilei Xiao,et al.Rapid Removal of Organic
Micropollutants from Water by a Porousβ-cyclodextrin Polymer,
Nature.2016.529.190-194].Although beta-cyclodextrin has excellent absorption property, it is rarely reported beta-cyclodextrin
Applied to polymer body material, the seperation film with excellent absorption property is prepared.This is because beta-cyclodextrin is a kind of hydrophilic
The small-molecule substance of property, is easily lost during being film-made as additive, substantially reduces adsorption effect.
The present invention provides a kind of Constructed wetlands of new sorbent material, by the functionalization β-with excellent absorption property
Cyclodextrin is blended with other additives, crosslinking agent and membrane body material prepares a kind of high efficiency composition film based on beta-cyclodextrin,
And the efficient removal of micropollutants in water can be used for.The composite membrane is while possessing traditional seperation film good separation performance, no
Only there is good hydrophily and stability, while having excellent absorption property includes saturated extent of adsorption and the rate of adsorption.It should
The preparation method of composite membrane is simple, and operating procedure is easy, is suitable for industrialization large-scale production, has in terms of the following purification of water quality
Have broad application prospects.
Summary of the invention
The purpose of the present invention is to provide a kind of compound membrane preparation methods of micropollutants in high efficiency filter water, poly- to form a film
Conjunction object is skeleton, and using functionalization beta-cyclodextrin as additive, and introducing crosslinked agent and pore-foaming agent are adopted by way of blending
The composite membrane is prepared with phase inversion.The composite membrane has high Adsorption energy to the organic micro-pollutants in water body
Power, its absorption property can also maintain higher level while keeping higher permeability, lead in Domestic water purifying, sewage treatment etc.
Domain all has important application value.
The compound membrane preparation method of micropollutants is by following technical side in a kind of high efficiency filter water provided by the invention
What case was realized, comprising the following steps:
(1) film forming polymer, functionalization beta-cyclodextrin, pore-foaming agent, crosslinking agent are mixed with solvent by certain mass ratio, in
It is dissolved at 40~100 DEG C through mechanical stirring, reacts 5~10 hours, casting solution is obtained after vacuumizing and defoaming；The mass ratio of each component
As follows: film forming polymer is 10~30%；Functionalization beta-cyclodextrin is 1~10%；Pore-foaming agent is 10~20%；Crosslinking agent is
0.5~5%；Solvent is 35~78.5%；
(2) casting solution is coated with by knifing machine or hollow fibre spinneret squeezes out, be immersed in curing molding in coagulating bath,
Form polymer primary membrane；
(3) polymer primary membrane is thoroughly cleaned in deionized water, obtains composite membrane, be used for the mistake of micropollutants
Elimination removes.
Above-mentioned each component can specifically use following preferred embodiment: the film forming polymer is Kynoar, polychlorostyrene second
Alkene, polyhexamethylene adipamide, polyethylene terephthalate, polyacrylonitrile, polyetherimide, polysulfones, gathers polycaprolactam
Any one in ether sulfone.The functionalization beta-cyclodextrin includes amino beta-cyclodextrin, carboxyl beta-cyclodextrin, carboxymethyl β-ring
One or both of dextrin, allyl beta-cyclodextrin, hydroxyl butyl beta-cyclodextrin.The pore-foaming agent is polyethylene glycol, poly- second
One or more of alkene pyrrolidone, polyvinyl alcohol, glucan.The crosslinking agent is polyethyleneimine, glutaraldehyde, epoxy
One or more of chloropropane, diisocyanate, citric acid.The solvent is DMAC N,N' dimethyl acetamide, N, N- diformazan
Base formamide, N-Methyl pyrrolidone, any one in dimethyl sulfoxide.The coagulating bath is pure water or pure water and solvent
Mixed solution, the weight percent of pure water is 10~100%, and the weight percent of solvent is 0~90%.
The composite membrane shape of above method preparation is tabular or hollow fiber；The compound membrane aperture is in 0.01-5
Between micron.
The compound membrane preparation method of micropollutants in a kind of high efficiency filter water of the present invention, using functionalization beta-cyclodextrin as one
Kind self assembly adsorbent, is effectively fixed in film forming polymer, obtains the composite membrane for efficiently removing organic micro-pollutants.This is compound
Film has good hydrophily and stability, and have to micropollutants while possessing tradition separation membrane separating property
Excellent strainability can not only filter the large scales micropollutants such as removal planktonic organism, algae, suspended particulate substance, bacterium,
The smaller sizes micropollutants such as macromolecular, colloid, virus can be removed, moreover it is possible to specific efficient Adsorption antibiotic, hormone, modeling
The small organic molecules micropollutants such as agent.The preparation process of the composite membrane is simple, has low cost, high application value, Neng Gouyou
Effect is used for the fields such as Domestic water purifying, sewage treatment.
Detailed description of the invention
It is related to the statement of molecular structure in the present invention, and micropollutants composite membrane in the high efficiency filter water prepared
Product, attached drawing are merely to illustrate, in attached drawing:
Fig. 1 is the diagram of the molecular structural formula and three-D space structure of beta-cyclodextrin；
Fig. 2 is the profile scanning electron microscope of micropollutants composite membrane in high efficiency filter water under different formulations.
Specific embodiment
Specific embodiments of the present invention are described below, but the present invention should not be limited by the examples.From disclosed by the invention interior
Appearance is associated or derived all deformations, is considered protection scope of the present invention.
The compound membrane preparation method of micropollutants, includes the following steps: in a kind of high efficiency filter water
(1) film forming polymer, functionalization beta-cyclodextrin, pore-foaming agent, crosslinking agent are mixed with solvent by certain mass ratio, in
At 40~100 DEG C casting solution is obtained after vacuumizing and defoaming within 5~10 hours through mechanical stirring dissolution, reaction.The mass ratio of each component
As follows: film forming polymer is 10~30%；Functionalization beta-cyclodextrin is 1~10%；Pore-foaming agent is 10~20%；Crosslinking agent is
0.5~5%；Solvent is 35~78.5%；
(2) casting solution is coated with by knifing machine or hollow fibre spinneret squeezes out, be immersed in curing molding in coagulating bath,
Form polymer primary membrane；
(3) polymer primary membrane is thoroughly cleaned in deionized water, obtains composite membrane, be used for micropollutants in water
Adsorption.
Above-mentioned each component can specifically use following preferred embodiment: the film forming polymer is Kynoar, polychlorostyrene second
Alkene, polyhexamethylene adipamide, polyethylene terephthalate, polyacrylonitrile, polyetherimide, polysulfones, gathers polycaprolactam
Any one in ether sulfone.The functionalization beta-cyclodextrin includes amino beta-cyclodextrin, carboxyl beta-cyclodextrin, carboxymethyl β-ring
One or both of dextrin, allyl beta-cyclodextrin, hydroxyl butyl beta-cyclodextrin.The pore-foaming agent is polyethylene glycol, poly- second
One or more of alkene pyrrolidone, polyvinyl alcohol, glucan.The crosslinking agent is polyethyleneimine, glutaraldehyde, epoxy
One or more of chloropropane, diisocyanate, citric acid.The solvent is DMAC N,N' dimethyl acetamide, N, N- diformazan
Base formamide, N-Methyl pyrrolidone, any one in dimethyl sulfoxide.The coagulating bath is pure water or pure water and solvent
Mixed solution, the weight percent of pure water is 10~100%, and the weight percent of solvent is 0~90%.The composite membrane
Shape is tabular or hollow fiber；The compound membrane aperture is between 0.01-5 microns.
The structure of the composite membrane of micropollutants and performance characterization side in a kind of high efficiency filter water in subsequent embodiment of the present invention
Method:
Surface topography and structure: clip appropriate amount of sample, such as with the section structure of the field emission microscopy observation composite membrane
Fig. 2, and record.
Flux test: cutting normal size diaphragm, be fixed in ultrafiltration cup, and deionized water precompressed is used at 0.1MPa
Then 30min measures pure water flux (L/m at the same pressure2h)。
Micropollutants rejection: at 0.1MPa with concentration be 1.0g/L micropollutants solution precompressed 30min after, collect
20mL filtrate measures its absorbance with ultraviolet specrophotometer, reference standard curve meter measure micropollutants that pH is 7.4 (Gu
Determine molecular weight) rejection of solution.
Micropollutants absorption test: the different micro- dirts of scanning respectively in 200-800nm using uv-visible absorption spectra instrument
The UV-visible absorption spectrum for contaminating object solution, determines its characteristic peak positions.Certain density micropollutants solution is configured, and
Measure the absorbance value A of the solution0.It filters the pollutant solution respectively at 0.1MPa, measures corresponding absorbance in filtrate
At。
(1) Dynamic Adsorption: Dynamic Adsorption test is carried out to perforated membrane with flux measuring device, calculates real-time absorption
Rate records total treating capacity Q (mL) of micropollutants solution until adsorption rate is lower than 90%.
(2) Static Adsorption: clip appropriate amount of sample is put into micropollutants solution and stirs.It is sampled by same time, use is ultraviolet
The absorbance value of spectrophotometer detection solution.After solution absorbance value is constant, drying and heavy m are taken the film out, according to public affairs
The equilibrium adsorption capacity q of sample can be obtained in formulae(mg/g)。
In formula: A∞The ultraviolet absorptivity of solution when to balance；m0For solution B PA initial quality (mg).
Embodiment 1:
The concentration requirement of 1.1 reference numeral of according to the form below, by Kynoar, amino beta-cyclodextrin, polyethylene glycol, polyethylene
Imines is mixed with n,N-dimethylacetamide, through mechanical stirring 5h, after completely dissolution, casting solution is obtained after deaeration, filtering, is stood
30min.Casting solution is coated with by knifing machine, and is immersed in pure water and is mixed in coagulating bath with n,N-dimethylacetamide and is solidified into
Type, 25 DEG C of washings obtain sheet composite membrane, are further sufficiently cleaned with deionized water, then stand dry in air, obtain hole
Diameter is the composite membrane of 10nm.Test its water flux, BSA rejection.Test is to organic micro-pollutants bisphenol-A (BPA) and bisnaphthol
The absorption property of (2-NO).
Table 1.1: Kynoar/amino beta-cyclodextrin efficient absorption organic micro-pollutants composite membrane preparation condition
Table 1.2: Kynoar/amino beta-cyclodextrin efficient absorption organic micro-pollutants composite membrane performance data
Embodiment 2:
The concentration requirement of 2.1 reference numeral of according to the form below, by polyvinyl chloride, carboxyl beta-cyclodextrin, polyvinylpyrrolidone, penta
Dialdehyde is mixed with n,N-Dimethylformamide, through mechanical stirring 6h, after completely dissolution, casting solution is obtained after deaeration, filtering, is stood
30min.Casting solution is squeezed out by hollow fibre spinneret, and is immersed in pure water and mixes coagulating bath with n,N-Dimethylformamide
Middle curing molding, 25 DEG C of washings obtain the composite membrane of hollow fiber, are further sufficiently cleaned with deionized water, then in air
Standing is dried, and the composite membrane that aperture is 1 μm is obtained.Test its water flux, Escherichia coli rejection.It is tested to organic micro-pollution
The absorption property of object chlorophenesic acid (2,4-DCP) and plasticiser 4,4' dihydroxydiphenyl sulfone (BPS).
Table 2.1: polyvinyl chloride/carboxyl beta-cyclodextrin efficient absorption organic micro-pollutants composite membrane preparation condition
Table 2.2: polyvinyl chloride/carboxyl beta-cyclodextrin efficient absorption organic micro-pollutants composite membrane performance data
Embodiment 3:
The concentration requirement of 3.1 reference numeral of according to the form below, by polycaprolactam, carboxymethyl-β-cyclodextrin, polyvinyl alcohol, epoxy
Chloropropane is mixed with N-Methyl pyrrolidone, through mechanical stirring 8h, after completely dissolution, casting solution is obtained after deaeration, filtering, is stood
30min.Casting solution is coated with by knifing machine, and is immersed in pure water and N-Methyl pyrrolidone mixing coagulating bath and is solidified into
Type, 25 DEG C of washings obtain sheet composite membrane, are further sufficiently cleaned with deionized water, then stand dry in air, obtain hole
The composite membrane that diameter is 5 μm, it is as shown in Figure 2 a that 3-2 is formulated section structure.Test its water flux, dinoflagellate rejection.It is right to test its
Organic micro-pollutants chlorophenesic acid (2,4-DCP) and absorption property to dioctyl phthalate (DEHP).
Table 3.1: polycaprolactam/carboxymethyl-β-cyclodextrin efficient absorption organic micro-pollutants composite membrane preparation condition
Table 3.2: polycaprolactam/carboxymethyl-β-cyclodextrin efficient absorption organic micro-pollutants composite membrane performance data
Embodiment 4:
The concentration requirement of 4.1 reference numeral of according to the form below, by polyhexamethylene adipamide, allyl beta-cyclodextrin, glucan, two
Isocyanates is mixed with n,N-dimethylacetamide, through mechanical stirring 10h, after completely dissolution, obtains casting film after deaeration, filtering
Liquid stands 30min.Casting solution is squeezed out by hollow fibre spinneret, and it is mixed with n,N-dimethylacetamide to be immersed in pure water
Curing molding in coagulating bath is closed, 25 DEG C of washings obtain the composite membrane of hollow fiber, are further sufficiently cleaned with deionized water, then
It stands and dries in air, obtain the composite membrane that pore size is 2 μm.Test its water flux, chrysophyceae rejection.It is tested to having
The absorption property of machine micropollutants 4,4' dihydroxydiphenyl sulfone (BPS) and erythromycin.
Table 4.1: the compound film preparation item of polyhexamethylene adipamide/allyl beta-cyclodextrin efficient absorption organic micro-pollutants
Part
Table 4.2: polyhexamethylene adipamide/allyl beta-cyclodextrin efficient absorption organic micro-pollutants composite membrane performance number
According to
Embodiment 5:
The concentration requirement of 5.1 reference numeral of according to the form below, by polyethylene terephthalate, hydroxyl butyl beta-cyclodextrin, Portugal
Glycan, citric acid are mixed with N-Methyl pyrrolidone, through mechanical stirring 6h, after completely dissolution, obtain casting film after deaeration, filtering
Liquid stands 30min.By casting solution by knifing machine be coated with, and be immersed in pure water in N-Methyl pyrrolidone mixing coagulating bath
Curing molding, 25 DEG C of washings obtain the composite membrane of sheet, are further sufficiently cleaned with deionized water, then stand dry in the air in air
It is dry, the composite membrane that pore size is 2 μm is obtained, 5-2 section structure is as shown in Figure 2 b.Test its water flux, BSA rejection.
Test its adsorptivity to organic micro-pollutants chlorophenesic acid (2,4-DCP) and the double rubigan trichloroethanes (DDT) of plasticiser
Energy.
Table 5.1: polyethylene terephthalate/hydroxyl butyl beta-cyclodextrin efficient absorption organic micro-pollutants composite membrane
Preparation condition
Table 5.2: polyethylene terephthalate/hydroxyl butyl beta-cyclodextrin efficient absorption organic micro-pollutants composite membrane
Performance data
Embodiment 6:
The concentration requirement of 6.1 reference numeral of according to the form below, by polyacrylonitrile, amino beta-cyclodextrin and carboxyl beta-cyclodextrin (etc.
Mass ratio), polyvinyl alcohol, citric acid mixed with dimethyl sulfoxide, through mechanical stirring 8h, after completely dissolution, after deaeration, filtering
To casting solution, 30min is stood.Casting solution is squeezed out by hollow fibre spinneret, and it is mixed with dimethyl sulfoxide to be immersed in pure water
Curing molding in coagulating bath is closed, 30 DEG C of washings obtain the composite membrane of hollow fiber, are further sufficiently cleaned with deionized water, then
It stands and dries in air, obtain the composite membrane that pore size is 2 μm, 6-2 section structure is as shown in Figure 2 c.It is logical to test its water
Amount, colloid rejection.Test its absorption property to organic micro-pollutants chlorophenesic acid (2,4-DCP) and erythromycin.
Table 6.1: polyacrylonitrile/more groups beta-cyclodextrin efficient absorption organic micro-pollutants composite membrane preparation condition
Table 6.2:: polyacrylonitrile/more groups beta-cyclodextrin efficient absorption organic micro-pollutants composite membrane performance data
Embodiment 7:
The concentration requirement of 7.1 reference numeral of according to the form below, by polyetherimide, carboxymethyl-β-cyclodextrin, polyvinyl alcohol and Portugal
Glycan (waiting mass ratioes), epoxychloropropane are mixed with n,N-dimethylacetamide, through mechanical stirring 8h, after completely dissolution, deaeration,
Casting solution is obtained after filtering, stands 30min.Casting solution is squeezed out by hollow fibre spinneret, and is immersed in pure water and N, N-
Dimethyl acetamide mixes curing molding in coagulating bath, and 25 DEG C of washings obtain the composite membrane of hollow fiber, further spend from
Sub- water sufficiently cleans, then stands dry in air, obtains the composite membrane that pore size is 2 μm.Its water flux is tested, BSA is cut
Stay rate.Test the absorption property of its rubigan trichloroethanes (DDT) and erythromycin double to organic micro-pollutants plasticiser.
Table 7.1: polyetherimide/carboxymethyl-β-cyclodextrin efficient absorption organic micro-pollutants composite membrane preparation condition
Table 7.2: polyetherimide/carboxymethyl-β-cyclodextrin efficient absorption organic micro-pollutants composite membrane performance data
Embodiment 8:
The concentration requirement of 8.1 reference numeral of according to the form below, by polysulfones, allyl beta-cyclodextrin, polyvinylpyrrolidone, poly- second
Alkene imines and citric acid (waiting mass ratioes) are mixed with n,N-Dimethylformamide, through mechanical stirring 8h, after completely dissolution, deaeration,
Casting solution is obtained after filtering, stands 30min.Casting solution is coated with by knifing machine, and is immersed in pure water and N, N- dimethyl methyl
Curing molding in amide mixing coagulating bath, 30 DEG C of washings obtain the composite membrane of sheet, are further sufficiently cleaned with deionized water, then
It stands and dries in air, obtain the composite membrane that pore size is 1 μm.Test its water flux, Escherichia coli rejection.Test it
To organic micro-pollutants bisnaphthol (2-NO) and to the absorption property of dioctyl phthalate (DEHP).
Table 8.1: polysulfones/allyl beta-cyclodextrin efficient absorption organic micro-pollutants composite membrane preparation condition
Table 8.2:: polysulfones/allyl beta-cyclodextrin efficient absorption organic micro-pollutants composite membrane performance data
Embodiment 9:
9.1 reference numeral of according to the form below concentration requirement, by polyether sulfone, hydroxyl butyl beta-cyclodextrin, polyvinyl alcohol, citric acid with
Dimethyl sulfoxide mixing after completely dissolution, obtains casting solution, stands 30min through mechanical stirring 8h after deaeration, filtering.By casting film
Liquid is squeezed out by hollow fibre spinneret, and is immersed in pure water and curing molding in dimethyl sulfoxide mixing coagulating bath, 25 DEG C of water
It washes to obtain the composite membrane of hollow fiber, further sufficiently be cleaned with deionized water, then stand dry in air, obtain aperture
The composite membrane that size is 2 μm, 9-2 section structure are as shown in Figure 2 d.Test its water flux, dinoflagellate rejection.It is tested to having
The absorption property of machine micropollutants plasticiser double rubigan trichloroethanes (DDT) and bisnaphthol (2-NO).
Table 9.1: polyether sulfone/hydroxyl butyl beta-cyclodextrin efficient absorption organic micro-pollutants composite membrane preparation condition
Table 9.2: polyether sulfone/hydroxyl butyl beta-cyclodextrin efficient absorption organic micro-pollutants composite membrane performance data
Above-described embodiment show removal organic micro-pollutants composite membrane of the invention while with higher flux, it is right
Organic micro-pollutants such as remains of pesticide, antibiotic, hormone, polycyclic aromatic hydrocarbon, plasticiser in water body etc. all have very superior
Adsorption effect all has very excellent performance either in the rate of adsorption or on saturated adsorption capacity.Therefore, described
Composite membrane can be used for the efficient removal of organic micro-pollutants in water body, and be that one kind is efficient, stable is worth with major application
Seperation film.The preparation method of the composite membrane is easy, easy to industrialized production, has low cost, high application value, can be effective
For fields such as Domestic water purifying, sewage treatments.
Claims (9)
1. the compound membrane preparation method of micropollutants in a kind of high efficiency filter water, which comprises the steps of:
(1) film forming polymer, functionalization beta-cyclodextrin, pore-foaming agent, crosslinking agent are mixed with solvent by certain mass ratio, in 40~
Mechanical stirring dissolves at 100 DEG C, reacts 5~10 hours, casting solution is obtained after vacuumizing and defoaming；The mass ratio of each component is as follows:
Film forming polymer is 10~30%；Functionalization beta-cyclodextrin is 1~10%；Pore-foaming agent is 10~20%；Crosslinking agent be 0.5~
5%；Solvent is 35~78.5%；
(2) casting solution is coated with by knifing machine or hollow fibre spinneret squeezes out, be immersed in curing molding in coagulating bath, formed
Polymer primary membrane；
(3) polymer primary membrane is placed in deionized water and is thoroughly cleaned, obtain composite membrane, the mistake applied to micropollutants in water
Elimination removes.
2. the compound membrane preparation method of micropollutants in a kind of high efficiency filter water according to claim 1, which is characterized in that
The film forming polymer is Kynoar, polyvinyl chloride, polycaprolactam, polyhexamethylene adipamide, poly terephthalic acid
Glycol ester, polyacrylonitrile, polyetherimide, polysulfones, any one in polyether sulfone.
3. the compound membrane preparation method of micropollutants in a kind of high efficiency filter water according to claim 1, which is characterized in that
The functionalization beta-cyclodextrin includes amino beta-cyclodextrin, carboxyl beta-cyclodextrin, carboxymethyl-β-cyclodextrin, allyl β-ring paste
One or both of essence, hydroxyl butyl beta-cyclodextrin.
4. the compound membrane preparation method of micropollutants in a kind of high efficiency filter water according to claim 1, which is characterized in that
The pore-foaming agent is one or more of polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, glucan.
5. the compound membrane preparation method of micropollutants in a kind of high efficiency filter water according to claim 1, which is characterized in that
The crosslinking agent is one or more of polyethyleneimine, glutaraldehyde, epoxychloropropane, diisocyanate, citric acid.
6. the compound membrane preparation method of micropollutants in a kind of high efficiency filter water according to claim 1, which is characterized in that
The coagulating bath is the mixed solution of pure water or pure water and solvent, and the weight percent of pure water is 10~100%, the weight of solvent
Measuring percentage is 0~90%.
7. the compound membrane preparation method of micropollutants in a kind of high efficiency filter water according to claim 1, which is characterized in that
The solvent is DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, N-Methyl pyrrolidone, appointing in dimethyl sulfoxide
It anticipates one kind.
8. the composite membrane of micropollutants, feature exist in a kind of high efficiency filter water of method according to claim 11 preparation
In the composite membrane shape is tabular or hollow fiber.
9. the composite membrane of micropollutants in high efficiency filter water according to claim 1, which is characterized in that the composite membrane
Aperture is between 0.01~5 micron.
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