CN109925895A - A kind of preparation method of antipollution polyamide film composite membrane - Google Patents
A kind of preparation method of antipollution polyamide film composite membrane Download PDFInfo
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Abstract
The present invention is a kind of preparation method of antipollution polyamide film composite membrane.This method comprises the following steps: water-soluble divalent metal and aqueous phase monomers being separately added into water, the aqueous phase monomers solution containing bivalent metal ion is obtained；Open support layer surface is immersed in the aqueous phase monomers solution containing bivalent metal ion, is put into organic phase monomer solution and impregnates again after taking-up；Maturation process is finally carried out, antipollution polyamide film composite membrane is finally obtained.The present invention has many advantages, such as with strong points, at low cost, nontoxic, simple process, easy to operate, and is easy to large-scale industrial production.
Description
Technical field
The invention belongs to polyamide film technology of composite film preparation fields, and in particular to one kind effectively improves polyamide film
The technical method of composite membrane contamination resistance.
Background technique
With the growth and urbanization of world population and the lasting propulsion of process of industrialization, the water resource in global range is short
Scarce problem is constantly aggravated, and the water treatment technology based on membrane separating process is the powerful for coping with shortage of water resources problem, especially
It is that reverse osmosis, positive infiltration and nanofiltration these three types have the membrane technology of fine separation function even more in bitter desalination, sea water desalination
And all various aspects such as recycling sewage generated by making have played important function.Currently, thin using polyamide prepared by interfacial polymerization method
Film composite membrane (TFC film) is occupied by its excellent separating property and permeance property in reverse osmosis, positive infiltration and nanofiltration field
Leading position, however membrane pollution problem present in actual application becomes the main barrier for limiting the application of its further genralrlization
Hinder.
Dissolved organic matter in water, in sodium alginate (SA), sewage and its two stage biological processing water outlet in seawater
Microorganism extracellular polymeric (EPS) and dissolved phenols (SMP), surface water and bitter in natural organic matter
(NOM) etc., it is easy to adhere to and assemble in TFC film surface, in turn results in TFC fouling membrane.To find out its cause, except TFC film hydrophobicity compared with
Strong outer, another key factor is exactly that TFC film surface contains a large amount of carboxyl functional groups, these carboxyl functional groups can be used as active sites
Point is chemically tied by the complexing bridging action for the calcium and magnesium ion being widely present in water with the dissolved organic matter generation in water
It closes, to promote organic matter in the irreversible deposition of TFC film surface, aggravates the membrane pollution problem of TFC film.
However, the existing open file majority in relation to control membrane fouling is intended to improve film surface hydrophily, and thus strong
Change membrane material to the contamination resistance of hydrophobic organic compound (using bovine serum albumin as representative).For example, Chinese Patent Application No.
201410334374.7 disclosing a kind of antipollution polymer film preparation based on UV graft polymerization acrylic acid epoxy Arrcostab
Method can significantly improve film surface hydrophily and the contamination resistance for bovine serum albumin.Chinese Patent Application No.
201510966664.8 disclosing a kind of anti-pollution reverse osmosis membrane preparation method based on hydrophilic macromolecule cross-linking reaction, the party
Method can effectively improve reverse osmosis membrane to the contamination resistance of bovine serum albumin while keeping and stablizing water flux and salt rejection rate.In
It is anti-that state's number of patent application 201710416654.6 discloses a kind of antipollution based on Amino End Group polyol surface grafting
Membrane preparation method is permeated, this method can improve hydrophily, water flux and the anti-pollution for bovine serum albumin of reverse osmosis membrane simultaneously
Dye ability.Make a general survey of all kinds of data it is found that existing technical measures be broadly divided into TFC film surface grafting and surface coating two major classes,
However its operating process step is complicated, condition is harsh, grafting and coating material used also price with higher in this way will
The preparation cost for dramatically increasing film reduces the feasibility of its large-scale production and application.
Therefore, as contamination resistance that how low in cost and method easy to operate effectively strengthens TFC film be one urgently
Problem to be solved.
Summary of the invention
It is an object of the present invention to be directed to deficiency of the prior art, provide a kind of easy to operate, low-cost anti-
Pollute the preparation method of polyamide film composite membrane.This method originality is proposed is built bridge based on bivalent metal ion inner complexation
The TFC film original position antipollution method of modifying of effect, by drawing during the interface polymerization reaction of TFC film into polynary amine aqueous solution
Entering bivalent metal ion causes to take the lead in being formed in situ stable " bivalent metal ion-carboxyl " complexing bridge formation knot inside PA membrane
Structure to occupy the carboxyl-reactive site of TFC film surface, and then mitigates " organic pollutant-metal ion-film in water treatment procedure
Interaction between the three of surface ", to effectively slow down the membrane pollution problem that TFC film occurs during water treatment applications.
The technical solution of the present invention is as follows:
A kind of preparation method of antipollution polyamide film composite membrane, includes the following steps:
(1) water-soluble divalent metal and aqueous phase monomers are separately added into water, then under constant temperature conditions (20~30
DEG C) continuously stir up to being completely dissolved, obtain the aqueous phase monomers solution containing bivalent metal ion；
Wherein, the quality of water-soluble divalent metal is the 0.2~1.5% of the quality of water；Aqueous phase monomers quality is water
The 0.1~6.0% of quality；Aqueous phase monomers are polyamine；Water-soluble divalent metal is calcium salt, barium salt or magnesium salts；
(2) open support layer surface is immersed in aqueous phase monomers 0.1~5min of solution containing bivalent metal ion, taken out
The macroscopic drop of support layer surface is removed afterwards, then is put into 0.5~10min of immersion in organic phase monomer solution；It obtains
Active layer containing " bivalent metal ion-carboxyl " complexing bridging structure, i.e. TFC film；
Wherein, organic phase monomer is polynary acyl chlorides, and organic phase is organic solvent；The quality of polynary acyl chlorides is organic solvent matter
The 0.1~1.0% of amount；The organic solvent is in n-hexane, hexamethylene, normal heptane, naphthalene, Isopar-G and Isopar-E
One or more of mixtures；The porosity of porous support layer is 50~80%；
(3) the TFC film for obtaining upper step carries out maturation process, finally obtains antipollution polyamide film composite membrane；
The maturation process is the constant temperature baking impregnated 1~10min in the water for be put into 40~90 DEG C, or be put into 40~90 DEG C
Heat 1~10min in case.
The polyamine is specially m-phenylene diamine (MPD), p-phenylenediamine, piperazine, ethylenediamine or polyethyleneimine.
The calcium salt is one or more of calcium chloride, calcium iodide, calcium bromide and calcium lactate；Barium salt be barium chloride,
The one or more of barium nitrate and barium acetate；Magnesium salts is the one or more of magnesium chloride, magnesium nitrate, magnesium sulfate and magnesium acetate.
The material of the porous support layer be polysulfones, sulfonated polysulfone, polyether sulfone, sulfonated polyether sulfone, Kynoar and
One or more of polytetrafluoroethylene (PTFE).
The porous support layer is flat type or hollow fiber form；
The polynary acyl chlorides is specially pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, m-phthaloyl chloride or malonyl chloride.
Substantive distinguishing features of the invention are as follows:
Reaction process of the invention: in step 2, porous support layer adsorbs a part containing bivalent metal ion first
Then polynary amine aqueous solution is contacted with polynary acyl chlorides organic solution, the amino of polyamine and the acid chloride group of high activity occur rapidly
Interface polymerization reaction forms the nascent state polyamide active layer of crosslinking；At the same time, the remaining unreacted acid chloride groups of film surface
Carboxyl is hydrolyzed to form, internal network occurs rapidly for the carboxyl functional group that the calcium ion in polynary amine aqueous solution and film surface are formed at this time
Reaction is closed, and " bivalent metal ion-carboxyl " complexing bridging structure is formed in situ, maturation process process is further to this structure
It is consolidated.
The invention has the benefit that
The present invention uses cheap common water-soluble divalent metal, is realized in the form of additive to polyamide
TFC film it is in-situ modified, " bivalent metal ion-carboxyl " complexing bridging structure has been pre-formed in TFC film activity layer, has allowed two
Valence metal ion occupies the carboxyl-reactive site of active layer surface, so that active layer surface carboxyl groups density reduces by 45%, zeta
Current potential absolute value reduce by 26%, film surface roughness reduce by 45.5%, it is suppressed that in water treatment procedure the carboxyl of organic pollutant with
Combination between active layer carboxyl, so that effective promotion of contamination resistance is realized, so that fouling membrane attenuation rate reduces
35% or more, Membrane cleaning flux recovery rate improves 50% or more.At the same time, appearance of the bivalent metal ion in TFC film is strong
The affinity to hydrone is changed, film surface hydrophily (being characterized with pure water contact angle) is improved 59%, realizes TFC membrane flux
Synchronous lifting, water flux promote amplitude and reach as high as 41.7%.With existing surface grafting method and surface described in current techniques
Coating process is compared, antipollution TFC membrane preparation method of the present invention have with strong points, at low cost, nontoxic, simple process,
The advantages that easy to operate, can be applied to antipollution TFC reverse osmosis membrane, antipollution TFC forward osmosis membrane and antipollution TFC nanofiltration membrane
Preparation process, and it is easy to large-scale industrial production, have for practical application of TFC membrane technology during multiple water treatment
Highly important realistic meaning.
Detailed description of the invention
Fig. 1 is TFC film surface morphology analysis result；Wherein, Fig. 1 (a) is control sample SEM and roughness described in embodiment 1
Analysis is as a result, Fig. 1 (b) is modified sample SEM described in embodiment 1 and Roughness analysis result.
Fig. 2 is TFC film surface XPS and contact angle analyzes result；Wherein, Fig. 2 (a) be embodiment 2 described in control sample with change
Property sample XPS analysis as a result, Fig. 2 (b) be embodiment 2 described in control sample and modified sample contact angle test result.
Fig. 3 is TFC film surface carboxyl density and zeta potentiometric analysis result；Wherein, Fig. 3 (a) is control sample described in embodiment 3
The film surface carboxyl density measurement of product and modified sample is as a result, Fig. 3 (b) is control sample described in embodiment 2 and modified sample
Zeta potential test result.
Fig. 4 is the pure water flux test result of control sample and modified sample described in embodiment 4.
Specific embodiment
Technical solution of the present invention is described further with specific embodiment with reference to the accompanying drawing, it is clear that described
Embodiment is only a part of the invention, and not all embodiment.It is all that technical solution of the present invention is modified or waited
With replacement, without departing from the spirit and scope of the technical solution of the present invention, should all cover within the protection scope of the present invention.
Porous ultrafiltration membrane of the present invention is known substance, can be polysulfones, sulfonated polysulfone, polyether sulfone, sulfonated polyether
One or more of sulfone, Kynoar and polytetrafluoroethylene (PTFE), molecular cut off is in 5~250,000 dalton ranges, hole
Rate is commercially available or known products in 50~80% ranges.
Embodiment 1:
Present embodiments provide a kind of preparation method of antipollution polyamide film complex reverse osmosis membrane (RO), specific steps
It is as follows:
One, it prepares the aqueous phase monomers solution for containing calcium ion: selecting m-phenylene diamine (MPD) (MPD) and anhydrous calcium chloride conduct respectively
M-phenylene diamine (MPD) (MPD) and anhydrous calcium chloride are added to the water, then in constant temperature (25 by water phase film forming monomer and water-soluble Ca salt
DEG C) under the conditions of continuously stir until be completely dissolved, obtain mixed solution, the concentration of MPD is 3.0wt%, CaCl in solution2Concentration
For 1.0wt%；
Two, interfacial polymerization: the molecular cut off by polysulfone material preparation is the porous flat plate ultrafiltration membrane table of 150,000 dalton
Face is immersed in the prepared aqueous phase monomers solution containing calcium ion in step 1, and impregnates 2min, then removes film with air knife
The macroscopic drop in surface, then be put into pyromellitic trimethylsilyl chloride (TMC) hexane solution that concentration is 0.2wt% and react
2min, interface polymerization reaction occurs and forms the active layer containing " calcium ion-carboxyl " complexing bridging structure, i.e. TFC film at this time；
The polyamide active layer that the reaction occurs to be formed in porous flat plate ultrafiltration membrane surface, reaction is incorporated in porous flat plate ultrafiltration membrane
Cooperatively constitute composite membrane；
Three, maturation process: the TFC film formed after the completion of step 2 interface polymerization reaction is put into 70 DEG C of warm water and is impregnated
10min, it is final to obtain the in-situ modified polyamide film complex reverse osmosis membrane of calcium ion with contamination resistance.
Conventional polyamide films complex reverse osmosis membrane of the preparation without calcium ion modification compares test, the control sample
Preparation method it is similar with above-mentioned specific embodiment, be distinguished as aqueous phase monomers solution used and contain only polyamine MPD, do not add
Adding water soluble calcium salt.It is observed using surface topography of the surface sweeping Electronic Speculum (SEM) to two class films, and uses atomic force microscope
(AFM) its surface roughness is tested, as a result as shown in Fig. 1.As seen from the figure, calcium ion is in-situ modified so that film surface is microcosmic
Structure becomes more smooth graininess from original " leaf shape ", and roughness is reduced to 30nm by 55nm, and reduction amplitude reaches
45.5%, this more smooth surface texture is equally beneficial for the raising of contamination resistance.It is with natural organic matter humic acid
Target contaminant compares the contamination resistance of two class reverse osmosis membranes, guarantees identical influent quality feature, initial in operational process
Flux, running temperature and cross-flow velocity, test result is as follows for contamination resistance shown in table, this antipollution is modified known to following table
Process effect is obvious, fouling membrane attenuation rate can be reduced to 39.5%, Membrane cleaning flux recovery rate improves 63.6%.
Embodiment 2:
The preparation method of another antipollution polyamide film complex reverse osmosis membrane (RO) is present embodiments provided, it is specific to walk
It is rapid as follows:
One, it prepares the aqueous phase monomers solution for containing calcium ion: selecting p-phenylenediamine (PPD) and anhydrous calcium iodide conduct respectively
Water phase film forming monomer and water-soluble Ca salt, PPD and anhydrous calcium iodide are added to the water, and are then continuously stirred under constant temperature conditions
Until being completely dissolved, mixed solution is obtained, the concentration of PPD is 2.0wt%, CaI in solution2Concentration is 0.4wt%；
Two, interfacial polymerization: the molecular cut off by polyether sulfone materials preparation is the porous flat plate ultrafiltration membrane of 100,000 dalton
Surface is immersed in the prepared aqueous phase monomers solution containing calcium ion in step 1, and impregnates 1min, is then removed with air knife
Film surface naked eyes drop visible, then be put into anti-in pyromellitic trimethylsilyl chloride (TMC) hexane solution that concentration is 0.15wt%
1min is answered, polymerization reaction occurs and forms the active layer containing " calcium ion-carboxyl " complexing bridging structure at this time；
Three, maturation process: the TFC film after the completion of step 2 interface polymerization reaction is put into 50 DEG C of warm water and is impregnated
10min, it is final to obtain the polyamide composite reverse osmosis membrane with contamination resistance.
Conventional polyamide TFC reverse osmosis membrane of the preparation without calcium ion modification compares test, the system of the control sample
Preparation Method is similar with above-mentioned specific embodiment, is distinguished as aqueous phase monomers solution used and contains only polyamine PPD, does not add water
Dissolubility calcium salt.The active layer of two class films is analyzed using x-ray photoelectron spectroscopy (XPS) and contact angle tester, as a result
As shown in Fig. 2, as seen from the figure, calcium ion is introduced in active layer in situ really, so that going out in film surface elemental analysis result
0.3% calcium constituent is showed, appearance of the calcium ion in active layer effectively reduces film surface contact angle, it is hydrophilic to enhance film surface
Property, it is hydrophilic to improve the promotion for not only contributing to contamination resistance, and facilitate the raising of water flux.With natural organic matter
Humic acid is the contamination resistance that target contaminant compares two class reverse osmosis membranes, guarantees that identical influent quality is special in operational process
Sign, initial flux, running temperature and cross-flow velocity, test result is as follows for contamination resistance shown in table, as seen from table this anti-pollution
It is obvious to contaminate modifying process effect, fouling membrane attenuation rate can be reduced to 35.0%, Membrane cleaning flux recovery rate improves 62.8%.
Embodiment 3:
Unlike specific embodiment 1 and embodiment 2, it is compound to present embodiments provide a kind of antipollution polyamide film
The preparation method of forward osmosis membrane, the specific steps are as follows:
One, prepare the polysulfone porous support membrane without nonwoven layer first: by molecular weight be 14~150,000 dalton at
Membrane polymer polysulfones, additive are mixed with solvent, are stirred for 24 hours, are placed naturally under sealed conditions under conditions of non-tight
Deaeration 16h obtains polysulfones casting solution, then polysulfones casting solution is prepared into the branch of flat type by non-solvent cause phase inversion
Layer is supportted, wherein knifing thickness control is 100 microns；The solvent is N-Methyl pyrrolidone, and additive is ethylene glycol；Polysulfones
The mass fraction of polysulfones is 15wt% in casting solution, and the concentration of ethylene glycol is 17wt%；
Two, it prepares the aqueous phase monomers solution containing bivalent metal ion: selecting m-phenylene diamine (MPD) (MPD) and anhydrous chlorination respectively
M-phenylene diamine (MPD) (MPD) and anhydrous calcium chloride are added to the water, as water phase film forming monomer and water-soluble Ca salt then in perseverance by calcium
It is continuously stirred under the conditions of temperature up to being completely dissolved, obtains mixed solution, the concentration of MPD is 3.4wt%, CaCl in solution2Concentration
For 0.6wt%；
Three, interfacial polymerization: aqueous solution obtained in step 2 is fine and close coated on polysulfone supporting layer obtained in step 1
Side, coating amount are about 0.2ml/cm2, and 3min is contacted, film surface naked eyes drop visible then is removed with nitrogen, then be put into
1min is reacted in pyromellitic trimethylsilyl chloride (TMC) cyclohexane solution that concentration is 0.3wt%, polymerization reaction occurs and formed to contain at this time
There is the active layer of " calcium ion-carboxyl " complexing bridging structure；
Four, maturation process: the TFC film after the completion of interface polymerization reaction is put into 80 DEG C of warm water and impregnates 6min, finally
Obtain the compound forward osmosis membrane of polyamide film with contamination resistance.
It prepares non-modified conventional polyamide TFC forward osmosis membrane and compares test, the preparation method of the control sample
It is similar with above-mentioned specific embodiment, it is distinguished as aqueous phase monomers solution used and contains only polyamine MPD, do not add water-soluble calcium
Salt.Film surface carboxyl density and zeta current potential are tested, as a result shown in attached drawing 3, as seen from the figure, this complexes ira situ of calcium ion is modified
Film surface carboxyl density and zeta current potential absolute value are effectively reduced, wherein carboxyl density reduces by 45%, zeta current potential absolute value drop
Low 26%, this variation will greatly reduce the binding force of organic pollutant and TFC film surface in water treatment procedure, final to realize to film
Effective control of pollution.The contamination resistance of two class forward osmosis membranes, operation are further compared using sodium alginate as target contaminant
Guarantee identical influent quality feature, initial flux, running temperature and cross-flow velocity in the process, contamination resistance test result is such as
Shown in following table, this antipollution modifying process effect is obvious as seen from table, fouling membrane attenuation rate can be reduced by 40.2%, film
It cleans flux recovery rate and improves 63.4%.
Embodiment 4:
The preparation method of another compound forward osmosis membrane of antipollution polyamide film (FO) is present embodiments provided, it is specific to walk
It is rapid as follows:
One, the sulfonated polyether sulfone porous support membrane without nonwoven layer is prepared first: being 170,000 dalton by molecular weight
Film forming polymer sulfonated polyether sulfone, additive are mixed with solvent, are stirred for 24 hours, under conditions of non-tight under sealed conditions
Naturally deaeration 16h is placed, sulfonated polyether sulfone casting solution is obtained, then causes phase inversion by sulfonated polyether sulfone casting film by non-solvent
Liquid is prepared into the supporting layer of flat type, and wherein knifing thickness control is 150 microns；The solvent is N- crassitude
Ketone, additive are ethylene glycol；The mass fraction of polysulfones is 16wt% in sulfonated polyether sulfone casting solution, and the concentration of ethylene glycol is
11wt%；
Two, it prepares the aqueous phase monomers solution for containing calcium ion: selecting m-phenylene diamine (MPD) (MPD) and anhydrous calcium bromide conduct respectively
M-phenylene diamine (MPD) (MPD) and anhydrous calcium bromide are added to the water, then in constant temperature by water phase film forming monomer and water-soluble Ca salt
Under continuously stir until be completely dissolved, obtain mixed solution, the concentration of MPD is 2.5wt%, CaBr in solution2Concentration is
0.8wt%；
Three, interfacial polymerization: aqueous solution obtained in step 2 is supported coated on sulfonated polyether sulfone obtained in step 1
Layer dense side, coating amount is about 0.2ml/cm2, and 3min is contacted, film surface residual droplets then are removed with nitrogen, then set
Enter in pyromellitic trimethylsilyl chloride (TMC) cyclohexane solution that concentration is 0.2wt% and react 1min, polymerization reaction occurs and formed at this time
Active layer containing " calcium ion-carboxyl " complexing bridging structure；
Four, maturation process: the TFC film after the completion of interface polymerization reaction is put into 70 DEG C of warm water and impregnates 8min, finally
Obtain the compound forward osmosis membrane of polyamide film with contamination resistance.
It prepares non-modified conventional polyamide TFC forward osmosis membrane and compares test, the preparation method of the control sample
It is similar with above-mentioned specific embodiment, it is distinguished as aqueous phase monomers solution used and contains only polyamine MPD, do not add water-soluble calcium
Salt.The contamination resistance that two class forward osmosis membranes are compared using sodium alginate as target contaminant, guarantee in operational process it is identical into
Water water quality characteristic, initial flux, running temperature and cross-flow velocity, test result is as follows for contamination resistance shown in table, it is known that this
Antipollution modifying process effect is obvious, fouling membrane attenuation rate can be reduced to 51.1%, Membrane cleaning flux recovery rate improves
61.2%.Two class film pure water fluxs are tested, as a result shown in attached drawing 4, as seen from the figure, this complexes ira situ of calcium ion is modified strong
Pure water flux is improved while changing contamination resistance, water flux is by 18L/m2H is improved to 25.5L/m2H, increase rate are up to
41.7%.
Embodiment 5
A kind of preparation method of antipollution polyamide film composite nanometer filtering film (NF) is present embodiments provided, specific steps are such as
Under:
One, it prepares the aqueous phase monomers solution for containing magnesium ion: selecting piperazine (PIP) and magnesium chloride to form a film as water phase respectively
Monomer and water-soluble magnesium salt, piperazine and magnesium chloride are added to the water, and are then continuously stirred under the conditions of 25 DEG C until completely molten
Solution, obtains mixed solution, and the concentration of PIP is 0.8wt%, MgCl in solution2Concentration is 0.2wt%；
Two, interfacial polymerization: the molecular cut off by polyvinylidene fluoride material preparation is that the porous flat plate of 100,000 dalton surpasses
Filter membrane surface is immersed in the prepared aqueous phase monomers solution containing magnesium ion in step 1, and impregnates 10min, then uses air knife
The macroscopic drop of film surface is removed, then is put into pyromellitic trimethylsilyl chloride (TMC) hexane solution that concentration is 0.1wt%
Middle reaction 1min, interface polymerization reaction occurs and forms the active layer containing " magnesium ion-carboxyl " complexing bridging structure at this time, i.e.,
TFC film；The polyamide active layer formed in porous flat plate ultrafiltration membrane surface, reaction and porous flat plate ultrafiltration membrane occur for the reaction
It is combined together and together constitutes composite membrane；
Three, maturation process: the TFC film formed after the completion of step 2 interface polymerization reaction is put into 50 DEG C of constant temperature oven
10min is heated, it is final to obtain the in-situ modified polyamide film composite nanometer filtering film of magnesium ion with contamination resistance.
It prepares and compares test without the modified conventional polyamide films composite nanometer filtering film of magnesium ion, the control sample
Preparation method is similar with above-mentioned specific embodiment, is distinguished as aqueous phase monomers solution used and contains only piperazine, does not add water-soluble
Property magnesium salts.The contamination resistance of two class nanofiltration membranes is compared using natural organic matter humic acid as target contaminant, is protected in operational process
Demonstrate,prove identical influent quality feature, initial flux, running temperature and cross-flow velocity, contamination resistance test result is as follows table institute
Show, this antipollution modifying process effect known to following table is obvious, fouling membrane attenuation rate can be reduced by 53.3%, Membrane cleaning
Flux recovery rate improves 51.5%.
Embodiment 6
Present embodiments provide the preparation method of another antipollution polyamide film composite nanometer filtering film (NF), specific steps
It is as follows:
One, prepare the aqueous phase monomers solution containing barium ions: selecting molecular weight respectively is 600 polyethyleneimine (PEI
600) and barium chloride is as water phase film forming monomer and water soluble barium salt, PEI 600 and barium chloride is added to the water, then 30
It is continuously stirred under the conditions of DEG C up to being completely dissolved, obtains mixed solution, the concentration of PEI 600 is 0.1wt%, BaCl in solution2
Concentration is 0.1wt%；
Two, interfacial polymerization: the molecular cut off by polysulfone material preparation is the porous flat plate ultrafiltration membrane surface of 80,000 dalton
It is immersed in the prepared aqueous phase monomers solution containing barium ions in step 1, and impregnates 5min, then removes film table with air knife
The macroscopic drop in face, then be put into pyromellitic trimethylsilyl chloride (TMC) hexane solution that concentration is 0.1wt% and react
0.5min, interface polymerization reaction occurs and forms the active layer containing " barium ions-carboxyl " complexing bridging structure, i.e. TFC at this time
Film；The polyamide active layer formed in porous flat plate ultrafiltration membrane surface, reaction and porous flat plate ultrafiltration membrane knot occur for the reaction
It is combined and together constitutes composite membrane；
Three, maturation process: the TFC film formed after the completion of step 2 interface polymerization reaction is put into 70 DEG C of constant temperature oven
5min is heated, it is final to obtain the in-situ modified polyamide film composite nanometer filtering film of barium ions with contamination resistance.
It prepares and compares test without the modified conventional polyamide films composite nanometer filtering film of barium ions, the control sample
Preparation method is similar with above-mentioned specific embodiment, is distinguished as aqueous phase monomers solution used and contains only PEI 600, does not add water
Dissolubility barium salt.Using natural organic matter humic acid as the contamination resistance of target contaminant two class nanofiltration membranes of comparison, in operational process
Guarantee identical influent quality feature, initial flux, running temperature and cross-flow velocity, contamination resistance test result is as follows table institute
Show, this antipollution modifying process effect known to following table is obvious, fouling membrane attenuation rate can be reduced by 44.5%, Membrane cleaning
Flux recovery rate improves 50.2%.
Embodiment 7
For other steps with embodiment 1, difference is that a kind of calcium chloride of step is replaced with barium chloride.Obtained filter membrane
It can be close with embodiment 1.
Embodiment 8
For other steps with embodiment 1, difference is that the porous ultrafiltration membrane of polysulfones plate in step 2 is replaced with sulfonation
Polysulfone porous ultrafiltration membrane.Obtained filter membrane property is close with embodiment 1.
Unaccomplished matter of the present invention is well-known technique.
Claims (6)
1. a kind of preparation method of antipollution polyamide film composite membrane, it is characterized in that this method comprises the following steps:
(1) water-soluble divalent metal and aqueous phase monomers are separately added into water by, then under constant temperature conditions (20~30 DEG C) even
Continuous stirring obtains the aqueous phase monomers solution containing bivalent metal ion up to being completely dissolved；
Wherein, the quality of water-soluble divalent metal is the 0.2~1.5% of the quality of water；Aqueous phase monomers quality is the quality of water
0.1~6.0%；Aqueous phase monomers are polyamine；Water-soluble divalent metal is calcium salt, barium salt or magnesium salts；
(2) open support layer surface is immersed in aqueous phase monomers 0.1~5min of solution containing bivalent metal ion by, after taking-up
The macroscopic drop of support layer surface is removed, then is put into 0.5~10min of immersion in organic phase monomer solution；Contained
There are the active layer of " bivalent metal ion-carboxyl " complexing bridging structure, i.e. TFC film；
Wherein, organic phase monomer is polynary acyl chlorides, and organic phase is organic solvent；The quality of polynary acyl chlorides is organic solvent quality
0.1~1.0%；The organic solvent is one of n-hexane, hexamethylene, normal heptane, naphthalene, Isopar-G and Isopar-E
Or several mixture；The porosity of porous support layer is 50~80%；
(3) the TFC film that obtains upper step carries out maturation process, finally obtains antipollution polyamide film composite membrane；
The maturation process is 1~10min to be impregnated in the water for be put into 40~90 DEG C, or be put into 40~90 DEG C of constant temperature oven
Heat 1~10min.
2. the preparation method of antipollution polyamide film composite membrane as described in claim 1, it is characterized in that the polyamine
Specially m-phenylene diamine (MPD), p-phenylenediamine, piperazine, ethylenediamine or polyethyleneimine.
3. the preparation method of antipollution polyamide film composite membrane as described in claim 1, it is characterized in that the calcium salt is
One or more of calcium chloride, calcium iodide, calcium bromide and calcium lactate；Barium salt is one in barium chloride, barium nitrate and barium acetate
Kind is several；Magnesium salts is one or more of magnesium chloride, magnesium nitrate, magnesium sulfate and magnesium acetate.
4. the preparation method of antipollution polyamide film composite membrane as described in claim 1, it is characterized in that the porous branch
Support layer material be one of polysulfones, sulfonated polysulfone, polyether sulfone, sulfonated polyether sulfone, Kynoar and polytetrafluoroethylene (PTFE) or
It is several.
5. the preparation method of antipollution polyamide film composite membrane as described in claim 1, it is characterized in that the porous branch
Supportting layer is flat type or hollow fiber form.
6. the preparation method of antipollution polyamide film composite membrane as described in claim 1, it is characterized in that the polynary acyl
Chlorine is specially pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, m-phthaloyl chloride or malonyl chloride.
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