CN110433667A - Antipollution ant-scaling seperation film and preparation method thereof - Google Patents

Antipollution ant-scaling seperation film and preparation method thereof Download PDF

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CN110433667A
CN110433667A CN201910829769.7A CN201910829769A CN110433667A CN 110433667 A CN110433667 A CN 110433667A CN 201910829769 A CN201910829769 A CN 201910829769A CN 110433667 A CN110433667 A CN 110433667A
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acid
scaling
antipollution
ant
film
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CN110433667B (en
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赵颂
齐云龙
魏新渝
王志
王纪孝
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Tianjin University
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Tianjin University
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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
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/14—Membrane materials having negatively charged functional groups
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

A kind of antipollution ant-scaling seperation film and preparation method thereof, the preparation method includes the following steps: that step (1) contacts the active layer of basement membrane with metal salt solution, and adsorption of metal ions is made to form metal adsorption layer on active layer；Step (2) contacts metal adsorption layer with multicomponent organic acid solution, is self-assembly of the organic polyacid complexed layer of metal-by complexing；Step (3) is to repeat step (1) and step (2), is self-assembly of the N layers of organic polyacid complexed layer of metal-, the antipollution ant-scaling seperation film is made；Wherein N is the integer more than or equal to 1.The comprehensive anti-organic pollution of antipollution ant-scaling seperation film of the invention and inorganic salts fouling double effects, and anti-inorganic salts and organic matter pollution resistance performance are excellent.

Description

Antipollution ant-scaling seperation film and preparation method thereof
Technical field
The present invention relates to separation field of membrane preparation more particularly to a kind of antipollution ant-scaling seperation film and preparation method thereof.
Background technique
Reverse osmosis/nanofiltration membrane technology is widely used to seawater and brackish water desalination, drink water purifying and wastewater treatment etc.. Commodity reverse osmosis/nanofiltration membrane is mostly aromatic polyamides composite membrane, and hydrophily is poor, film surface is rougher.With the system rate of recovery It is gradually increased, pollutant (organic matter, microorganism, calcium ions and magnesium ions, silicate ion) concentration greatly improves in water quality, aggravates film Organic pollution and scaling degree cause the decline of film water yield or producing water water quality to be deteriorated.
For the reverse osmosis/nanofiltration membrane for obtaining the excellent combination properties such as antipollution, antibacterial, resistance to oxidation, ant-scaling, researchers By a series of surface modifying method (such as aggregation deposition, graft modification, LBL self-assembly), to weaken pollutant-film table The interaction in face.Wherein, hydrophilic polymer, amphoteric ion polymer, titanium dioxide, Nano silver grain, antibacterial modified Anti-biotic materials such as carbon nanotube and the selenium-containing compound that can generate peroxide radical etc., which all be used to prepare, resists organic dirt The reverse osmosis/nanofiltration membrane of dye and stable against biological contamination.Although there are many study on the modification of reverse osmosis/nanofiltration membrane, few documents Report preparation is provided simultaneously with the reverse osmosis/nanofiltration membrane of antipollution and ant-scaling (especially anti-silicon dirt) performance.For this demand, The present invention provides a kind of preparation method of antipollution ant-scaling seperation film.
Summary of the invention
In view of this, the main purpose of the present invention is to provide a kind of antipollution ant-scaling seperation film and preparation method thereof, To at least be partially solved at least one of above-mentioned the technical issues of referring to.
In order to achieve the above objectives, as one aspect of the present invention, a kind of system of antipollution ant-scaling seperation film is provided Preparation Method, comprising the following steps:
Step (1) contacts the active layer of basement membrane with metal salt solution, and adsorption of metal ions is made to form gold on active layer Belong to adsorption layer；
Step (2) contacts metal adsorption layer with multicomponent organic acid solution, and it is more to be self-assembly of metal-by complexing Layer is complexed in first organic acid；
Step (3) is to repeat step (1) and step (2), is self-assembly of the N layers of organic polyacid complexed layer of metal-, is made The antipollution ant-scaling seperation film；Wherein N is the integer more than or equal to 1；
Preferably, the N is the integer between 1 to 20.
As another aspect of the present invention, a kind of antipollution ant-scaling seperation film is additionally provided, using above-mentioned antipollution The preparation method of ant-scaling seperation film is prepared.
It can be seen from the above technical proposal that antipollution ant-scaling seperation film of the present invention and preparation method thereof at least have with One of lower beneficial effect or in which a part:
(2) polynary organic in the active layer surface self-organization formation multiple layer metal-of basement membrane by metal and multicomponent organic acid Acid complexing layer, is made antipollution ant-scaling seperation film, on the one hand, the hydrophilic radical of its polyacid improves the hydrophilic of its film surface Property, improve the antifouling property of film surface；On the other hand, the sulfonate groups of polyacid improve the bear electrical property of its film surface, from And improve the scaling property energy of film surface；The anti-organic pollution of comprehensive enhancing antipollution ant-scaling seperation film and inorganic salts fouling Double effects, and anti-inorganic salts and organic matter pollution resistance performance are excellent；
(3) formation of the organic polyacid complexed layer of metal-passes through the complexing between metal ion and multicomponent organic acid, Binding force is provided for the self assembly of multilayer, it is good in conjunction with effect；
(4) performance of the antipollution ant-scaling of antipollution ant-scaling seperation film and membrane flux can be polynary organic by metal- The number of plies of acid complexing layer reaches balance；
(5) number of plies of the organic polyacid complexed layer of metal-is regulated and controled by the number of self assembly, and regulation method is simple, is held It is easy to operate；
(6) basement membrane is used from being film-made, by adding water phase additive respectively in aqueous phase solution and organic phase solution and having Machine phase additive makes have the characteristics that hydrophily and bear are electrical from the active layer of film, it is anti-that antipollution is improved on the basis of The antipollution and scaling property energy of fouling seperation film；And basement membrane is used from being film-made, and can prepare a variety of differences by raw material proportioning The basement membrane of specification, optional range is wide, and applicability is wide；
(7) this method preparation process is simple, preparation condition is mild, is suitable for a variety of separation membrane modifyings, reverse osmosis membrane or Nanofiltration membrane, it is applied widely, it is easy to amplify and promote.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of commercial polyamine complex reverse osmosis membrane in the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of M1RO type antipollution ant-scaling seperation film in the embodiment of the present invention 1；
Fig. 3 is that commercial polyamine is compound after bovine serum albumin for 24 hours and siliceous solution composite pollution in the embodiment of the present invention 1 The scanning electron microscope (SEM) photograph of reverse osmosis membrane；
Fig. 4 is that M1RO type antipollution is anti-after bovine serum albumin for 24 hours and siliceous solution composite pollution in the embodiment of the present invention 1 The scanning electron microscope (SEM) photograph of fouling seperation film.
Specific embodiment
The present invention provides a kind of preparation method of antipollution ant-scaling seperation film, the preparation method includes following step It is rapid:
Step (1) contacts the active layer of basement membrane with metal salt solution, and adsorption of metal ions is made to form gold on active layer Belong to adsorption layer；
Step (2) contacts metal adsorption layer with multicomponent organic acid solution, and it is more to be self-assembly of metal-by complexing Layer is complexed in first organic acid；
Step (3) is to repeat step (1) and step (2), is self-assembly of the N layers of organic polyacid complexed layer of metal-, is made The antipollution ant-scaling seperation film；Wherein N is the integer more than or equal to 1；
Preferably, the N is the integer between 1 to 20.
Specifically, the active layer of basement membrane and the time of contact of metal salt solution are 5~120min, contact temperature in step (1) Degree is 10~30 DEG C.
Specifically, in step (1), contact of the active layer of basement membrane with metal salt solution, " contact " operation for infiltration or Dipping.
Specifically, step (1) further includes washing the remaining metal salt solution of metal adsorption layer surface, room with deionized water The operation being dried with nitrogen under temperature.
Specifically, the metal ion in the metal salt solution includes bivalent metal ion, trivalent metal ion or four One or more of valence metal ion；Preferred metal ion includes calcium, magnesium, iron, aluminium, copper, cobalt, nickel, zirconium, titanium, tin One of ion is a variety of.
Specifically, the molar concentration of metal salt solution is 0.01mol/L~0.5mol/L；Preferably 0.02mol/L~ 0.3mol/L。
Specifically, the time of contact of metal adsorption layer and multicomponent organic acid solution is 5~120min, contact in step (2) Temperature is 10~30 DEG C.
Specifically, the contact of metal adsorption layer and multicomponent organic acid solution, " contact " operation is infiltration in step (2) Or dipping.
Specifically, step (2) further includes that wash the organic polyacid complexed layer surface of metal-with deionized water remaining more First organic acid soln, the operation being dried with nitrogen at room temperature.
Specifically, the multicomponent organic acid in step (2) the multicomponent organic acid solution includes polybasic carboxylic acid, polynary organic sulphur One or more of sour or polynary organic phosphoric acid；Preferably, wherein polybasic carboxylic acid includes citric acid, two gallic acids, 3, One or more of 3 ', 5,5 '-biphenyltetracarboxyacid acids or ethylenediamine tetra-acetic acid；Preferably, wherein polynary organic sulfonic acid packet Include one or more of sulfosalicylic acid or 2- acrylamide-2-methyl propane sulfonic；Preferably, polynary organic phosphoric acid packet Include ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, calgon, sodium tripolyphosphate, phytic acid, second two Four methylenephosphonic acid of amine, 5,3-3- triphosphine acidic group valeric acid, 4,4- '-diphosphono -1,7- pimelic acid, 1- amino-ethylidene -1,1- diphosphine One of acid or 1- hydroxyl-ethylidene -1,1- di 2 ethylhexyl phosphonic acid are a variety of.
Specifically, the molar concentration of step (2) described multicomponent organic acid is 0.01mol/L~0.5mol/L；Preferably 0.02mol/L~0.3mol/L.
Specifically, N is the integer between 1 to 20 in step (3).
Wherein at self assembly initial stage, the self assembly number of plies is bigger, and antipollution ant-scaling effect is better, and flux fall It is small；In the self assembly later period, with being gradually increased for the self assembly number of plies, the variation of antipollution ant-scaling effect is little, but flux meeting Sharp fall.Preferably, self assembly number of plies N is the integer between 1~20.
Specifically, basement membrane is product film or is film-made certainly that the film thickness of basement membrane is 200~300 μm in step (1)；
Specifically, product film includes polyamide composite reverse osmosis membrane, polyamide composite nanofiltration membrane, cellulose acetate reverse osmosis Film or cellulose acetate nano filter-membrane；
Specifically, including making polyamide composite reverse osmosis membrane or self-control polyamide composite nanofiltration membrane by oneself from film.
Specifically, basement membrane is selected from being film-made, further include before the step (1) from the preparation step of film, specifically include as Lower sub-step:
The aqueous phase solution including diamine monomer, water phase additive is respectively configured in sub-step (1-1), and including aromatic series The organic phase solution of polynary acyl chlorides monomer, organic phase additive and organic solvent；
Support membrane liquid compatible with water is contacted, diamine monomer and water phase additive is made to be adsorbed on support membrane by sub-step (1-2) On, obtain the support membrane for being adsorbed with diamine monomer and water phase additive；
Sub-step (1-3) contacts the support membrane for being adsorbed with diamine monomer and water phase additive with organic phase solution, support The aromatic polyvalent acyl chlorides monomer and organic phase additive hair in diamine monomer and water phase additive and organic phase solution on film Raw interface polymerization reaction forms the aromatic polyamides active layer with polybasic Brnsted acid groups in support film surface, obtains nascent state virtue Fragrant polyamide composite film；
Sub-step (1-4) obtains being film-made certainly by nascent state aromatic polyamides composite membrane through Overheating Treatment.
Specifically, support membrane liquid time of contact compatible with water is 1~5min in sub-step (1-2)；
Preferably, in sub-step (1-3), the support membrane for being adsorbed with diamine monomer and water phase additive connects with organic phase solution The touching time is 1~5min；
Preferably, in sub-step (1-4), heat treatment temperature is 50~90 DEG C, and heat treatment time is 3~10min；
Specifically, wherein aqueous phase solution includes that mass fraction adds for 0.5~5% diamine monomer, 0.01~2% water phase Add agent and water, the gross mass of aqueous phase solution is 100%；
Organic phase solution includes the aromatic polyvalent acyl chlorides monomer that mass fraction is 0.1~0.5%, 0.01~0.2% Organic phase additive and organic solvent, the gross mass of organic phase solution are 100%.
Specifically, diamine monomer includes one of m-phenylene diamine (MPD), piperazine, p-phenylenediamine or o-phenylenediamine or a variety of.
Specifically, water phase additive includes sulfamic acid, 2,4- diamino benzene sulfonic acid, 2,5- diamino benzene sulfonic acid, 2- ammonia Base benzene sulfonic acid, 3- aminobenzenesulfonic acid, p-aminobenzene sulfonic acid, 3,5- diaminobenzoic acid, 5- aminovaleric acid, 5- amino orotic acid, 2- amino terephthalic acid (TPA), 2- amino -4- bromobenzoic acid, 3,4- diaminobenzoic acid, 5- amino isophthalic acid, alpha-amido oneself Diacid, asparatate, PAS, 6-aminocaprolc acid, tranexamic acid, 3- Aminopyrazine -2- carboxylic acid, 4- (amino first Base) benzoic acid, folic acid, (aminomethyl) phosphonic acids, 2- aminoethyl phosphonic acid, (3- aminophenyl) phosphonic acids, (4- aminophenyl) phosphonic acids, Alendronic acid sodium trihydrate, polyamino polyether base methylenephosphonic acid, 4- 4-aminophenyl phosphate sodium salt, taurine, 4,4 '-diamino two One of 2,2 '-disulfonic acid of styrene -, aniline -2,5- disulfonic acid, N- tri- (methylol) methylamino -2- hydroxy-propanesulfonic acid or It is a variety of.
Specifically, aromatic polyvalent acyl chlorides monomer includes pyromellitic trimethylsilyl chloride.
Specifically, organic phase additive includes phenylsuccinic acid acid anhydride, 2,3- dimethyl maleic anhydride, 2,3- pyridinedicarboxylic acid Acid anhydride, 2,2- dimethyl succinic anhydride, 2- sulfosalicylic acid acid anhydride, 1,2,4-tricarboxylic anhydride, maleic anhydride, chlorendic anhydride, oneself One of diacid chloride, glutaryl chlorine, sebacoyl chloride, pyrophosphoryl chloride, 1,3- benzene-disulfo-chloride are a variety of.
Specifically, organic solvent includes the first organic solvent and the second organic solvent, the first organic solvent includes acetic acid second Ester, benzene, toluene, methylene chloride, the second organic solvent include one of n-hexane, normal heptane, hexamethylene or a variety of；
Specifically, the first organic solvent is the 2~15% of organic solvent quality.
Specifically, support membrane is commercial polysulfones support membrane.
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this hair It is bright to be described in further detail.
Material
The present invention is not particularly limited the source of all raw materials, is commercially available.
Bovine serum albumin is commercially available, purity 95%, the ox blood for the use of concentration being 500mg/L in embodiment and comparative example Albumin aqueous solution；
Siliceous solution is the Na of concentration 300mg/L2SiO3Aqueous solution；
Bovine serum albumin and siliceous solution are mixed into the bovine serum albumin and concentration 300mg/L that concentration is 500mg/L Na2SiO3Mixed solution.
Test method
Contact angle detection method:
Using video optics contact angle measurement test film surface contact angle, hanging drop measurement pattern, pure water are specially used Droplet size is that 3 μ L record the stabilization pattern and contact angle numerical value of drop after drop contacts 10 seconds with film surface.
Streaming potential detection method:
Film surface Zeta potential is measured using SurPASS surface of solids Zeta potential analyzer, electrolyte solution is 1mmol/L KCl solution adjusts the pH value of electrolyte solution in measurement process using dilute HCl solution and dilute KOH solution.
Membrane flux detection method:
Using laboratory from film permselective property energy test system and test membrane flux and salt rejection rate, test macro by every The components such as membrane pump, membrane cisterna, water phase, pipeline, regulating valve, pressure and flow detector composition, wherein the effective membrane area tested is 24cm2, feed liquid flow 1.0L/min, test pressure is 1.55MPa, and test temperature is 25 ± 0.5 DEG C.
Embodiment 1
By the AlCl of the active layer of commercial polyamine complex reverse osmosis membrane and 0.5mol/L3Aqueous solution contacts 30min, then uses Deionized water rinses out extra AlCl3Aqueous solution is dried with nitrogen；Further, by metal adsorption layer surface and 0.1mol/L sulphur Base salicylic acid solution contacts 60min, then rinses out extra sulfosalisylic acid solution with deionized water, is dried with nitrogen, and completes primary Self assembly circulation.Self assembling process is repeated 10 times at 25 DEG C, obtains M1RO type antipollution ant-scaling seperation film.
After tested, compared with commercial polyamine complex reverse osmosis membrane, the surface of M1RO type antipollution ant-scaling seperation film is connect Feeler declines 19 °, and Zeta potential drops to -45mV by -20mV under neutrallty condition.Under transmembrane pressure 1.55MPa, 2000ppm chlorine Change the water flux decline 10% of sodium solution, sodium chloride rejection improves 2%.Compared with commercial polyamine complex reverse osmosis membrane, In Under the conditions of constant initial flux, after bovine serum albumin pollution for 24 hours, attenuation rate reduces 16%, flux recovery rate after cleaning Improve 15%.After the pollution for 24 hours of siliceous solution, attenuation rate reduces 16%.It is dirty through bovine serum albumin and the mixing of siliceous solution After contaminating for 24 hours, attenuation rate reduces 11%, and flux recovery rate improves 13% after cleaning.
It is anti-to commercial polyamine complex reverse osmosis membrane obtained in the present embodiment 1 and M1RO type using scanning electron microscope Pollution ant-scaling seperation film compares and analyzes, and respectively obtains its scanning electron microscope (SEM) photograph, as depicted in figs. 1 and 2.Through analysis it is found that Film surface all shows foliaceous peak and valley structure after before modified, but compares commercial polyamine complex reverse osmosis membrane, and M1RO type is anti- Pollution ant-scaling separation membrane surface shows slightly smooth, shows that the organic polyacid complexed layer of the metal-by modification, being self-assembly of covers It covers in film surface and very thin, therefore not will cause very big decaying to flux.
To the commercial polyamine complex reverse osmosis membrane and M1RO type after bovine serum albumin and siliceous solution composite pollution Antipollution ant-scaling seperation film is analyzed, its scanning electron microscope (SEM) photograph is respectively obtained, as shown in Figure 3 and Figure 4, through analysis it is found that dirty Commercial polyamine complex reverse osmosis membrane surface after dye is covered with one layer of apparent silicon dirt layer, and the M1RO type antipollution after polluting Ant-scaling separation membrane surface only has a little particle, this shows that the anti-silicon dirt performance of modified antipollution ant-scaling seperation film obtains Improve.
Embodiment 2
By the FeCl of the active layer of commercial polyamine composite nanometer filtering film and 0.3mol/L3Aqueous solution contacts 60min, then spends Ionized water rinses out extra FeCl3Aqueous solution is dried with nitrogen；Further, by metal adsorption layer surface and 0.2mol/L inositol Six phosphoric acid solutions contact 60min, then rinse out extra phytic acid solution with deionized water, are dried with nitrogen, and complete once certainly Assembling circulation.Self assembling process is repeated 5 times at 20 DEG C, obtains M2NF type antipollution ant-scaling seperation film.
After tested, compared with commercial polyamine composite nanometer filtering film, the surface of M2NF type antipollution ant-scaling seperation film is contacted Angle declines 16 °, and Zeta potential drops to -40mV by -15mV under neutrallty condition.Under transmembrane pressure 1.55MPa, 2000ppm chlorination The water flux decline 15% of sodium solution, sodium chloride rejection improves 3%.Compared with commercial polyamine composite nanometer filtering film, constant Under the conditions of initial flux, after bovine serum albumin pollution for 24 hours, attenuation rate reduces 20%, and flux recovery rate improves after cleaning 20%.After the pollution for 24 hours of siliceous solution, attenuation rate reduces 18%.For 24 hours through bovine serum albumin and siliceous solution composite pollution Afterwards, attenuation rate reduces 13%, and flux recovery rate improves 14% after cleaning.
Embodiment 3
By the Cu (NO of the active layer of commodity cellulose acetate nano filter-membrane and 0.05mol/L3)2Aqueous solution contacts 30min, then Extra Cu (NO is rinsed out with deionized water3)2Aqueous solution is dried with nitrogen；Further, by metal adsorption layer surface and 0.1mol/ L sulfosalisylic acid solution contacts 60min, then rinses out extra sulfosalisylic acid solution with deionized water, is dried with nitrogen, and completes one Secondary assembling circulation.Self assembling process is repeated 10 times at 25 DEG C, obtains M3NF type antipollution ant-scaling seperation film.
After tested, compared with commodity cellulose acetate nano filter-membrane, the surface of M3NF type antipollution ant-scaling seperation film is contacted Angle declines 17 °, and Zeta potential drops to -39mV by -18mV under neutrallty condition.Under transmembrane pressure 1.55MPa, 2000ppm chlorination The water flux decline 7% of sodium solution, sodium chloride rejection improves 1.5%.Compared with making polyamide composite reverse osmosis membrane by oneself, in perseverance Under the conditions of determining initial flux, after bovine serum albumin pollution for 24 hours, attenuation rate reduces 15%, and flux recovery rate mentions after cleaning It is high by 13%.After the pollution for 24 hours of siliceous solution, attenuation rate reduces 12%.Through bovine serum albumin and siliceous solution composite pollution After for 24 hours, attenuation rate reduces 11%, and flux recovery rate improves 12% after cleaning.
Embodiment 4
Make the preparation method of polyamide composite reverse osmosis membrane by oneself: configuration contains 3% m-phenylene diamine (MPD), 0.2% piperazine and 0.5% The aqueous solution of sulfamic acid, and contain 0.2% pyromellitic trimethylsilyl chloride, 3% ethyl acetate and 0.2%2- sulfosalicylic acid acid anhydride N-heptane solution；Polysulfones support membrane liquid compatible with water is contacted into 1min, extra aqueous phase solution is removed, is connect later with organic phase solution 1min is touched, 90 DEG C of heat treatment 3min obtain self-control polyamide composite reverse osmosis membrane.
The NiSO of the active layer and 0.02mol/L of polyamide composite reverse osmosis membrane will be made by oneself4Aqueous solution contacts 30min, then Extra NiSO is rinsed out with deionized water4Aqueous solution is dried with nitrogen；Further, by metal adsorption layer surface and 0.05mol/L 4,4- '-diphosphono -1,7- pimelic acid solution contact 120min, then rinse out extra 4,4- '-diphosphono -1,7- with deionized water Pimelic acid solution, is dried with nitrogen, and completes self assembly circulation.Self assembling process is repeated 10 times at 30 DEG C, obtains M4RO type Antipollution ant-scaling seperation film.
After tested, compared with making polyamide composite reverse osmosis membrane by oneself, the surface of M4RO type antipollution ant-scaling seperation film is connect Feeler declines 20 °, and Zeta potential drops to -48mV by -18mV under neutrallty condition.Under transmembrane pressure 1.55MPa, 2000ppm chlorine Change the water flux decline 13% of sodium solution, sodium chloride rejection improves 2%.Compared with making polyamide composite reverse osmosis membrane by oneself, In Under the conditions of constant initial flux, after bovine serum albumin pollution for 24 hours, attenuation rate reduces 18%, flux recovery rate after cleaning Improve 18%.After the pollution for 24 hours of siliceous solution, attenuation rate reduces 16%.It is dirty through bovine serum albumin and the mixing of siliceous solution After contaminating for 24 hours, attenuation rate reduces 10%, and flux recovery rate improves 12% after cleaning.
Embodiment 5
It makes the preparation method of polyamide composite nanofiltration membrane by oneself: configuring water-soluble containing 3% piperazine and 0.5% sulfamic acid Liquid, and contain 0.1% pyromellitic trimethylsilyl chloride, 5% toluene and 0.13%1, the hexane solution of 3- benzene-disulfo-chloride；By polysulfones Support membrane liquid compatible with water contacts 5min, removes extra aqueous phase solution, contacts 5min, 50 DEG C of heat treatments with organic phase solution later 10min obtains self-control polyamide composite nanofiltration membrane.
The CaCl of the active layer and 0.1mol/L of polyamide composite nanofiltration membrane will be made by oneself2Aqueous solution contacts 100min, then uses Deionized water rinses out extra CaCl2Aqueous solution is dried with nitrogen；Further, by metal adsorption layer surface and 0.1mol/L bis- Times acid solution contacts 90min, then rinses out extra two times of acid solutions with deionized water, is dried with nitrogen, and completes primary assembling circulation. Self assembling process is repeated 8 times at 10 DEG C, obtains M5NF type antipollution ant-scaling seperation film.
After tested, compared with making polyamide composite nanofiltration membrane by oneself, the surface of M5NF type antipollution ant-scaling seperation film is contacted Angle declines 16 °, and Zeta potential drops to -45mV by -10mV under neutrallty condition.Under transmembrane pressure 1.55MPa, 2000ppm chlorination The water flux decline 10% of sodium solution, sodium chloride rejection improves 3%.Compared with making polyamide composite nanofiltration membrane by oneself, constant Under the conditions of initial flux, after bovine serum albumin pollution for 24 hours, attenuation rate reduces 22%, and flux recovery rate improves after cleaning 22%.After the pollution for 24 hours of siliceous solution, attenuation rate reduces 20%.For 24 hours through bovine serum albumin and siliceous solution composite pollution Afterwards, attenuation rate reduces 14%, and flux recovery rate improves 15% after cleaning.
Embodiment 6
Make the preparation method of polyamide composite reverse osmosis membrane by oneself: configuration contains 2% m-phenylene diamine (MPD), 0.5% piperazine and 0.5% The aqueous solution of 2- amino terephthalic acid (TPA), and contain 0.5% pyromellitic trimethylsilyl chloride, 3% benzene and 0.2% maleic anhydride Cyclohexane solution；Polysulfones support membrane liquid compatible with water is contacted into 2min, extra aqueous phase solution is removed, is connect later with organic phase solution 2min is touched, 80 DEG C of heat treatment 5min obtain self-control polyamide composite reverse osmosis membrane.
Zr (the NO of the active layer and 0.01mol/L of polyamide composite reverse osmosis membrane will be made by oneself3)4Aqueous solution contacts 30min, Extra Zr (NO is rinsed out with deionized water again3)4Aqueous solution is dried with nitrogen；Further, by metal adsorption layer surface with 0.02mol/L sodium hexametaphosphate solution contacts 90min, then rinses out extra sodium hexametaphosphate solution with deionized water, and nitrogen is blown It is dry, complete primary assembling circulation.Self assembling process is repeated 20 times at 25 DEG C, obtains M6RO type antipollution ant-scaling seperation film.
After tested, compared with making polyamide composite reverse osmosis membrane by oneself, the surface of M6RO type antipollution ant-scaling seperation film is connect Feeler declines 20 °, and Zeta potential drops to -42mV by -20mV under neutrallty condition.Under transmembrane pressure 1.55MPa, 2000ppm chlorine Change the water flux decline 6% of sodium solution, sodium chloride rejection improves 1.5%.Compared with making polyamide composite reverse osmosis membrane by oneself, In Under the conditions of constant initial flux, after bovine serum albumin pollution for 24 hours, attenuation rate reduces 12%, flux recovery rate after cleaning Improve 13%.After the pollution for 24 hours of siliceous solution, attenuation rate reduces 15%.It is dirty through bovine serum albumin and the mixing of siliceous solution After contaminating for 24 hours, attenuation rate reduces 9%, and flux recovery rate improves 9.5% after cleaning.
Comparative example 1
By the FeCl of the active layer of commercial polyamine complex reverse osmosis membrane and 0.5mol/L3Aqueous solution contacts 30min, then uses Deionized water rinses out extra FeCl3Aqueous solution is dried with nitrogen；Further, by metal adsorption layer surface and 0.5mol/L flesh Six phosphoric acid solution of alcohol contacts 60min, then rinses out extra phytic acid solution with deionized water, is dried with nitrogen, and completes primary Self assembly circulation.Self assembling process repeats 30 times at 25 DEG C, obtains the modified reverse osmosis membrane of M7RO type.
After tested, the modified reverse osmosis membrane of M7RO is compared with commercial polyamine complex reverse osmosis membrane, the modified reverse osmosis membrane of M7RO Surface contact angle decline 22 °, Zeta potential drops to -37mV by -18mV under neutrallty condition.Under transmembrane pressure 1.55MPa, The water flux decline 45% of 2000ppm sodium chloride solution, sodium chloride rejection improves 3%.It is compound reverse osmosis with commercial polyamine Film is compared, and under the conditions of constant initial flux, after bovine serum albumin pollution for 24 hours, attenuation rate reduces 12%, is led to after cleaning It measures recovery rate and improves 13%.After the pollution for 24 hours of siliceous solution, attenuation rate reduces 11%.Through bovine serum albumin and siliceous molten After liquid composite pollution for 24 hours, attenuation rate reduces 7%, and flux recovery rate improves 8% after cleaning.
Comparative example 2
The active layer of commercial polyamine complex reverse osmosis membrane is only contacted into 90min with the aqueous citric acid solution of 0.3mol/L, Extra aqueous citric acid solution is rinsed out with deionized water again, is dried with nitrogen, the modified reverse osmosis membrane of M8RO type is obtained.
After tested, the modified reverse osmosis membrane of M8RO type is compared with commercial polyamine complex reverse osmosis membrane, the modified reverse osmosis of M8RO type The surface contact angle of permeable membrane declines 5 °, and Zeta potential drops to -20mV by -18mV under neutrallty condition.Transmembrane pressure 1.55MPa Under, the water flux decline 3% of 2000ppm sodium chloride solution, sodium chloride rejection is identical.With commercial polyamine complex reverse osmosis membrane It compares, under the conditions of constant initial flux, after bovine serum albumin pollution for 24 hours, flux recovery rate after attenuation rate and cleaning It is basically unchanged.After the pollution for 24 hours of siliceous solution, attenuation rate is basically unchanged.It is dirty through bovine serum albumin and the mixing of siliceous solution After contaminating for 24 hours, flux recovery rate is basically unchanged after attenuation rate and cleaning.
It obtains in conjunction with above-described embodiment and comparative example as drawn a conclusion:
It is obtained by contact angle characterization test: compared with basement membrane, antipollution ant-scaling separation membrane surface contact of the invention Angle decline shows that the hydrophilic radical of polyacid improves the hydrophily of its film surface, improves the anti-pollution of antipollution ant-scaling seperation film Metachromia energy；
Obtained by current potential characterization test: compared with basement membrane, current potential decline of the invention shows the sulfonate groups of polyacid The bear for enhancing film surface is electrical, improves the antifouling property of its antipollution ant-scaling seperation film；
Obtained by sodium-chloride water solution separation test: antipollution ant-scaling seperation film of the invention is with respect to basement membrane, chlorine The rejection for changing sodium improves, and shows that rejection effect enhances；
Obtained by bovine serum albumin Contamination measurement: antipollution ant-scaling seperation film of the invention is with respect to basement membrane, anti-pollution Metachromia can improve；
Obtained by siliceous solution Contamination measurement: antipollution ant-scaling seperation film of the invention is with respect to basement membrane, ant-scaling Performance improves；
It tests to obtain by bovine serum albumin and siliceous solution composite pollution: antipollution ant-scaling seperation film phase of the invention To basement membrane, antipollution scaling property can be improved.
It contrasts to obtain by embodiment and comparative example: when self assembly metal-organic polyacid complexed layer number of plies is excessive When, the flux degradation of Modified Membrane can be made, but the increase rate of antipollution scaling property energy is smaller；When the single metal of use When salting liquid or polynary acid solution are modified basement membrane, the antipollution and ant-scaling performance change of membrane flux and Modified Membrane are not Greatly.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in protection of the invention Within the scope of.

Claims (10)

1. a kind of preparation method of antipollution ant-scaling seperation film, which is characterized in that the preparation method includes the following steps:
Step (1) contacts the active layer of basement membrane with metal salt solution, and adsorption of metal ions is made to form metal suction on active layer Attached layer；
Step (2) contacts metal adsorption layer with multicomponent organic acid solution, is self-assembly of that metal-is polynary to be had by complexing Layer is complexed in machine acid；
Step (3) is to repeat step (1) and step (2), is self-assembly of the N layers of organic polyacid complexed layer of metal-, is made described Antipollution ant-scaling seperation film；Wherein N is the integer more than or equal to 1；
Preferably, the N is the integer between 1 to 20.
2. the preparation method of antipollution ant-scaling seperation film as described in claim 1, which is characterized in that in the step (1), The active layer of the basement membrane and the time of contact of metal salt solution are 5~120min, and Contact Temperature is 10~30 DEG C.
3. the preparation method of antipollution ant-scaling seperation film as described in claim 1, which is characterized in that the metal salt solution In metal ion include one of bivalent metal ion, trivalent metal ion or quadrivalent metallic ion or a variety of；
Preferred metal ion includes one of calcium, magnesium, iron, aluminium, copper, cobalt, nickel, zirconium, titanium, tin ion or a variety of.
4. the preparation method of antipollution ant-scaling seperation film as claimed in claim 3, which is characterized in that the metal salt solution Molar concentration be 0.01mol/L~0.50mol/L；
The molar concentration of the preferred metal salt solution is 0.02mol/L~0.30mol/L.
5. the preparation method of antipollution ant-scaling seperation film as described in claim 1, which is characterized in that in the step (2), The time of contact of the metal adsorption layer and the multicomponent organic acid solution is 5~120min, and Contact Temperature is 10~30 DEG C.
6. the preparation method of antipollution ant-scaling seperation film as described in claim 1, which is characterized in that the multicomponent organic acid Multicomponent organic acid in solution includes one of polybasic carboxylic acid, polynary organic sulfonic acid or polynary organic phosphoric acid or a variety of；
Preferably, wherein polybasic carboxylic acid includes citric acid, two gallic acids, 3, in 3 ', 5,5 '-biphenyltetracarboxyacid acids or ethylenediamine tetra-acetic acid It is one or more；
Preferably, wherein polynary organic sulfonic acid include one of sulfosalicylic acid or 2- acrylamide-2-methyl propane sulfonic or It is a variety of；
Preferably, polynary organic phosphoric acid include ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, calgon, Sodium tripolyphosphate, phytic acid, ethylene diamine tetra methylene phosphonic acid, 5,3-3- triphosphine acidic group valeric acid, 4,4- '-diphosphono -1,7- heptan One of diacid, 1- amino-ethylidene -1,1- di 2 ethylhexyl phosphonic acid or 1- hydroxyl-ethylidene -1,1- di 2 ethylhexyl phosphonic acid are a variety of.
7. the preparation method of antipollution ant-scaling seperation film as claimed in claim 6, which is characterized in that the multicomponent organic acid The molar concentration of solution is 0.01mol/L~0.50mol/L；
Preferably, the molar concentration of the multicomponent organic acid solution is 0.02mol/L~0.30mol/L.
8. the preparation method of antipollution ant-scaling seperation film as described in claim 1, which is characterized in that in the step (1), The basement membrane is product film or is film-made certainly that the film thickness of the basement membrane is 200~300 μm；
Preferably, the product film includes polyamide composite reverse osmosis membrane, polyamide composite nanofiltration membrane, cellulose acetate reverse osmosis Film or cellulose acetate nano filter-membrane；
Preferably, described to include self-control polyamide composite reverse osmosis membrane or self-control polyamide composite nanofiltration membrane from film.
9. the preparation method of antipollution ant-scaling seperation film as claimed in claim 8, which is characterized in that the basement membrane is selected certainly Film further includes specifically including following sub-step from the preparation step of film before step (1):
The aqueous phase solution including diamine monomer, water phase additive is respectively configured in sub-step (1-1), and including aromatic polyvalent The organic phase solution of acyl chlorides monomer, organic phase additive and organic solvent；
Support membrane liquid compatible with water is contacted, is adsorbed on diamine monomer and water phase additive on support membrane by sub-step (1-2), Obtain the support membrane for being adsorbed with diamine monomer and water phase additive；
Sub-step (1-3) contacts the support membrane for being adsorbed with diamine monomer and water phase additive with organic phase solution, on support membrane Diamine monomer and water phase additive and organic phase solution in aromatic polyvalent acyl chlorides monomer and organic phase additive boundary occurs Face polymerization reaction forms the aromatic polyamides active layer with polybasic Brnsted acid groups in support film surface, it is poly- to obtain nascent state fragrance Amide composite membrane；
Sub-step (1-4) obtains being film-made certainly by nascent state aromatic polyamides composite membrane through Overheating Treatment.
10. a kind of antipollution ant-scaling seperation film, which is characterized in that using preparation as claimed in any one of claims 1-9 wherein Method is prepared.
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