CN104548951A - Antibacterial composite nanofiltration membrane with high salt rejection rate and preparation method of antibacterial composite nanofiltration membrane - Google Patents
Antibacterial composite nanofiltration membrane with high salt rejection rate and preparation method of antibacterial composite nanofiltration membrane Download PDFInfo
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Abstract
The invention discloses an antibacterial composite nanofiltration membrane with high salt rejection rate and a preparation method of the antibacterial composite nanofiltration membrane. The composite nanofiltration membrane contains attapulgite modified by a chitosan quaternary ammonium salt. The preparation method comprises the following steps: (1) enabling a porous support layer to be in contact with a water phase solution of a compound containing two or more reactive amino groups; (2) removing the excess water phase solution on the porous support layer after water phase infiltration; (3) enabling the porous support layer after the treatment in step (2) to be in contact with an organic phase solution of an acyl chloride compound containing two or more acyl chloride groups; (4) volatilizing the organic phase solution and further enabling the porous support layer to be in contact with the water phase solution of the compound containing two or more reactive amino groups and the attapulgite modified by the chitosan quaternary ammonium salt; (5) performing heat treatment and washing with water to obtain the antibacterial composite nanofiltration membrane. The antibacterial composite nanofiltration membrane disclosed by the invention can improve antibacterial performance and salt rejection rate on the basis of keeping considerable water flux.
Description
Technical field
The present invention relates to technical field of membrane, furtherly, relate to antibacterial composite nanometer filtering film of a kind of high salt-stopping rate and preparation method thereof.
Background technology
UF membrane, as a kind of novel isolation technics, compared with the isolation technics such as traditional distillation, rectifying, has the advantages such as low energy consumption, high separating efficiency, environmental protection.Nanofiltration Membrane Separation Technology is a kind of power-actuated membrane separation technique of a kind of Novel pressure between counter-infiltration and ultrafiltration.It is to divalence or multivalent ion, and the rejection that molecular weight is greater than the organic molecule of 200 is generally greater than 90%, can realize the Selective Separation to different material.Therefore, NF membrane, by feat of the separation characteristic of its uniqueness, has now been widely used in water correction, solution has decoloured, dye desalination is concentrated and biochemical substances purified concentration, creates certain economic benefit and social benefit.Wherein, composite nanometer filtering film because of its performance optimizations such as the rejection of film, water flux, stability can be become current development the fastest, apply maximum film kinds, the NF membrane in the market more than 90% is composite nanometer filtering film.
Composite nanometer filtering film refers to that on the support counterdie of porous compound one deck is very thin, different materials that is fine and close, that have special separation function.Compared with the NF membrane of integration, the surface compact layer thickness of composite nanometer filtering film is thinner, thus makes film have high solute separation rate and the transmission rates of water simultaneously, and optimizable physicalchemical structure, can meet various different Selective Separation demand.The composite nanometer filtering film of current application is mainly taked the mode of interfacial polymerization to prepare, and common technical process has detailed introduction in US Patent No. 4277344.First polysulfones being coated in the micropore counterdie that polyester non-woven fabric is formed is immersed in diamines or the polyamines aqueous solution, then film excess surface amine aqueous solution is removed by methods such as wind pouring, roll-ins, be immersed in again in organic non-polar solution of polynary acyl chlorides with acyl chlorides generation interface polymerization reaction, thus the fine and close polyamide ultrathin active layer with separation function is formed on surface, after film forming, fully washing and suitable heat cure process can increase film properties.
But one of application bottleneck affecting composite nanometer filter membrane separation technique is membrane biological pollution, membrane biological pollution seriously constrains large-scale application and the popularization of composite nanometer filter membrane technology.Membrane biological pollution significantly declines directly causing the permeation flux of film, and the production efficiency of system reduces, operating cost and energy consumption increase; Membrane biological pollution also by causing that the frequent clean of system, device can not run well, the retaining characteristic serious deterioration, produce water water degradation of film, membrane lifetime reduce and the frequent replacing of film.
Therefore, people adopt multiple method to improve the anti-microbial property of film in recent years.US Patent No. 2002013972 describes a kind of preparation method of sticking the antibacterial film of water-insoluble propolis on basement membrane, utilizes the adsorptivity of propolis by the bacterium in water, virus sweep.Its shortcoming bacterium, virus thoroughly can not be removed, and will carry out reprocessing after propolis adsorption capacity reaches capacity could re-use, and uses and comparatively bother.Chinese patent CN102527252A " a kind of antibacterial composite reverse osmosis membrane ", the sericin with antibacterial functions is coated in complex reverse osmosis membrane surface, the hydrophily of complex reverse osmosis membrane and anti-microbial property are greatly enhanced, there is good stable against biological contamination performance.Chinese patent CN101695636A " aromatic polyamide composite reverse osmosis membrane of graft modification and preparation method thereof ", this patent take PS membrane as support membrane, is prepared the aromatic polyamide composite reverse osmosis membrane of grafting by interfacial polymerization; Rapidly will containing 3-methylol-5, the graft modification solution of 5-DMH with treat that graft copolymer membrane surface contact is reacted, heat treatment obtains the modified aromatic polyamide complex reverse osmosis membrane of hydantoin derivative grafting, and the resisting microbial contamination performance of the reverse osmosis membrane finally obtained is significantly improved.
Although achieve larger progress at present in the research in antimicrobial compound film field, the composite membrane that preparation has resisting microbial contamination function is still one of target of film academia and the pursuit of film industrial quarters.
Summary of the invention
In order to solve the problems of the prior art, the invention provides antibacterial composite nanometer filtering film of a kind of high salt-stopping rate and preparation method thereof.By the second layer polyamide surface layer of the attapulgite of preparation containing chitosan quaternary ammonium salt modification on polyamide surface layer, improve the anti-microbial property of composite nanometer filtering film; Meanwhile, keeping, on the basis that water flux is suitable, the rejection of composite nanometer filtering film can being improved again.
An object of the present invention is to provide the antibacterial composite nanometer filtering film of a kind of high salt-stopping rate.
Attapulgite containing chitosan quaternary ammonium salt modification in described antibacterial composite nanometer filtering film, attapulgite has in bar-shaped or filamentary structure, and has the nanoscale duct of hollow, and the diameter of attapulgite is between 10 ~ 20nm.
Attapulgite (Attapulgite) is also known as palygorskite (Palygorskite), it is a kind of nanometer porous road lenticular water zeopan, be different from the phyllosilicates such as imvite, crystal is bar-shaped or filamentary structure, diameter 10 ~ 20nm, there is rule in its crystal structure inside, fixed-size one-dimensional channels, water molecule energy enters duct.Simultaneously, because single crystal is tiny bar-shaped, needle-like and threadiness, when disperseing, rod-like fibre can keep multi-faceted irregularly deposit drying in felted thing after, form the inhomogenous secondary pore of size between agglomerate, make more hydrone can through hole.
Although attapulgite is a kind of natural nano material, but it often can not play the advantage as nano material in application process, mainly because the specific area of attapulgite is large, surface-active is high, easy reunion, and the hydroxyl of surface containing polarity, although have certain dispersiveness in aqueous phase solution, does not also reach desirable dispersion effect.
Carrying out modification by water-soluble chitosan quaternary ammonium salt to attapulgite can make the dispersiveness of attapulgite in aqueous phase solution strengthen further, because quaternary ammonium salt cationic is had an effect by ion-exchange absorption and attapulgite, generate attapulgite-chitosan quaternary ammonium salt complex, and chitosan quaternary ammonium salt surface is containing abundant hydroxyl, thus the dispersiveness of attapulgite in aqueous phase solution is enhanced.Moreover chitosan quaternary ammonium salt has stronger anti-microbial property, loaded in NF membrane by convex Attapulgite, thus the antibiotic property of Nano filtering composite membrane can be improved.
Two of object of the present invention is to provide the preparation method of the antibacterial composite nanometer filtering film of a kind of high salt-stopping rate.
Comprise:
(1) aqueous phase solution of porous support layer with the compound containing two or more reactive amino is contacted;
(2) aqueous phase solution of the porous support layer excess surface of removing after aqueous phase infiltrates;
(3) porous support layer after step (2) process is contacted with the organic phase solution of the chloride compounds containing two or more acid chloride group;
(4) contact with the aqueous phase solution of the attapulgite of chitosan quaternary ammonium salt modification with the compound containing two or more reactive amino again after organic phase solution volatilization;
(5) obtained described antibacterial composite nanometer filtering film after heat treatment, washing;
Described porous support layer is the one in polysulfone porous supporting layer, polyether sulfone porous support layer, sulfonated polyether sulfone porous support layer, polypropylene porous support layer; Molecular cut off is preferably 3-5 ten thousand.
The described compound containing two or more reactive amino is one or more in aromatic series, aliphatic, alicyclic polyfunctional amine, polyhydric alcohol amine;
Described aromatic series polyfunctional amine can be selected from m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine (PPD), 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 3,5-diaminobenzoic acids, 2, at least one in 4-diaminotoluene, 2,4-diamino anisoles, amidol, xylylene diamine; Described aliphatic polyfunctional amine can be selected from least one in ethylenediamine, propane diamine, butanediamine, pentanediamine, three (2-aminoethyl) amine, diethylenetriamine; Described alicyclic polyfunctional amine can be selected from least one in 1,2-DACH, Isosorbide-5-Nitrae-DACH, piperazine, 1,3-two piperidyl propane, 4-aminomethylpiperazine; Described polyhydric alcohol amine can be selected from least one in monoethanolamine, diethanol amine, hexylene glycol amine, diglycolamine.
The described chloride compounds containing two or more acid chloride group be aromatic series, aliphatic, alicyclic multifunctional chloride compounds one or more;
The multifunctional chloride compounds of described aromatic series can be selected from least one in paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride, biphenyl dimethyl chloride, benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride; The multifunctional chloride compounds of described aliphatic can be selected from least one in fourth three acyl chlorides, succinyl chloride, penta 3 acyl chlorides, glutaryl chlorine, oneself three acyl chlorides, Adipoyl Chloride, sebacoyl chloride, the last of the ten Heavenly stems three acyl chlorides; Described alicyclic multifunctional chloride compounds can be selected from least one in cyclopropane three acyl chlorides, cyclobutane diacid chloride, cyclobutane four acyl chlorides, pentamethylene diacid chloride, pentamethylene three acyl chlorides, pentamethylene four acyl chlorides, cyclohexane diacid chloride, cyclohexane three acyl chlorides, cyclohexane four acyl chlorides, oxolane diacid chloride, oxolane four acyl chlorides.
The organic solvent of described organic phase solution can be selected from least one in n-hexane, cyclohexane, trifluorotrichloroethane, normal heptane, normal octane, toluene, ethylbenzene, ISOPAR solvent naphtha;
The concentration of the compound containing two or more reactive amino in described aqueous phase solution is 1-30g/L;
The concentration of the chloride compounds containing two or more acid chloride group in described organic phase solution is 0.5-5g/L;
In the aqueous phase solution of step (4), the content of the attapulgite that shitosan is quaternary ammonium salt-modified is 0.001-0.2g/L.
Surfactant and/or acid absorbent can also be contained in the aqueous phase solution of step (1) and step (4); Surfactant and acid absorbent can adopt this area usually to adopt, as
Described surfactant can be preferably at least one in lauryl sodium sulfate, neopelex, DTAB, laurate sodium sulfonate, Qu Latong-100,1-METHYLPYRROLIDONE;
Described acid absorbent can be preferably triethylamine, sodium carbonate, sodium acid carbonate, phosphoric acid hydrogen that, at least one in sodium phosphate, NaOH, potassium hydroxide.
The concentration of described surfactant is preferably 1-5g/L; The concentration of described acid absorbent is preferably 1-10g/L.
Above-described time of contact is 10-150 second.
In step (5), heat treatment temperature is 30-90 DEG C, and heat treatment time is 3-10 minute.
The present invention can be achieved through the following technical solutions:
(1) first, the polysulfone supporting layer of porous contacted with the solution A containing two or more reactive amino compounds, time of contact is 10-150 second;
(2) the polysulfone porous supporting layer rubber rollers roll extrusion after solution A infiltrates, removes unnecessary solution A, forms solution A layer on the surface in polysulfone supporting layer;
(3) this (with solution A layer) polysulfone supporting layer contact 10-150 second with the chloride compounds B solution containing two or more reactive acid chloride group, formation ground floor polyamide surface layer;
(4) contact 10-150 second with the compound containing two or more reactive amino with the C solution of the attapulgite of chitosan quaternary ammonium salt modification again after organic solution volatilization, form second layer polyamide surface layer;
(5) finally above-mentioned film is put into the baking oven heat treatment 3-10 minute of 30-90 DEG C, after washing, namely obtain composite nanometer filtering film.In the present invention, in the antibacterial composite nanometer filtering film functional layer of described high rejection, contain the attapulgite of polymer and chitosan quaternary ammonium salt modification.
The attapulgite of chitosan quaternary ammonium salt modification obtains through purification and modification two steps preparations.Attapulgite through purification and modification just can be dispersed in aqueous phase solution better.Purification and modification can adopt the method for common purification and modification in prior art.
In the present invention, the purification of attapulgite can preferably according to the following steps:
(1) take a certain amount of attapulgite, make attapulgite mass concentration be 10% after adding distilled water, then add a certain amount of sodium hexametaphosphate dispersant, mechanical agitation 30 minutes;
(2) ultrasonic wave process 30 minutes;
(3) then centrifugal treating is carried out by centrifuge 2000r/min;
(4) upper liquid is discarded, dry in 80 DEG C of baking ovens;
The attapulgite of more than purifying is placed in drier and stores for future use.
The attapulgite modified method of chitosan quaternary ammonium salt can preferably be carried out according to the following steps:
(1) take a certain amount of attapulgite of having purified, add distilled water and make its mass concentration reach 10%, add the chitosan quaternary ammonium salt of a certain amount of (quality is 20% of attapulgite quality);
(2) at 70 DEG C, magnetic agitation reacts 2 hours;
(3), after above-mentioned reactant liquor processes certain hour by centrifugal (2000r/min), supernatant liquor is discarded;
(4) modified attapulgite puts into 80 DEG C of oven for drying, cools rear mortar grinder for subsequent use.
Compared with prior art, the present invention takes the aqueous phase solution of porous support membrane with the compound containing two or more reactive amino to contact, then contact with the organic phase solution of the chloride compounds containing two or more reactive acid chloride group, contact with the attapulgite aqueous phase solution of chitosan quaternary ammonium salt modification with containing the compound of two or more reactive amino again, by interfacial polymerization by the attapulgite loaded of chitosan quaternary ammonium salt modification in composite nanometer filtering film functional layer.The experimentation of the composite nanometer filtering film of the attapulgite of preparation containing chitosan quaternary ammonium salt modification is simple, reaction condition is gentle, simultaneously, the anti-microbial property that chitosan quaternary ammonium salt is good makes composite nanometer filtering film anti-microbial property be enhanced, double-deck aramid layer has the salt-stopping rate making composite nanometer filtering film to be promoted further, the water flux that the multi-pore channel structure of attapulgite can make again composite nanometer filtering film keep suitable.
Detailed description of the invention
Below in conjunction with embodiment, further illustrate the present invention.
Nano filtering composite membrane prepared by the present invention is used for desalination, and salt rejection rate and water flux are two important parameters evaluating Nano filtering composite membrane, and salt rejection rate R is defined as:
Wherein, C
frepresent the concentration of salt in the front water of process; C
prepresent the concentration of salt in the rear permeate of process.
Water flux is defined as: under certain operating conditions, and through the volume of the water of per membrane area in the unit interval, its unit is L/m
2h.
The test condition adopted in the present invention is: the aqueous sodium persulfate solution of 1000ppm, and operating pressure is 0.6Mpa, and operating temperature is 25 DEG C.
NF membrane of the present invention has anti-microbial property, and NF membrane antibacterial effect quantitatively detects:
Quantitatively antibacterial effect is detected with fask oscillating method.Antibacterial composite nanometer filtering film is cut into the sample of 10mm × 30mm, above-mentioned sample is put into the triangular flask of 150ml, add the Escherichia coli bacteria liquid of 70ml PBS buffer solution and 500ul respectively, triangular flask is fixed on vibration bed, sways 24 hours with 120r/min.Get the sample liquid after 500ul vibration, carry out viable bacteria after doing suitably dilution with PBS buffer solution and cultivate counting.Contrast test is carried out to common composite nanometer filter diaphragm (not containing antimicrobial component) simultaneously.Sterilizing rate is calculated as follows:
Sterilizing rate (%)=((A-B)/A) × 100%
In formula: A-common composite nanometer filter membrane sample viable count
B-antibacterial composite nanometer filter membrane sample viable count
The present invention is set forth further below in conjunction with embodiment, but not as limitation of the present invention.
Raw materials usedly in embodiment be commercially available, in embodiment, the draw ratio of attapulgite used is greater than 20, between diameter 10-20nm.
Embodiment 1
The concrete purification step of the attapulgite used in the present embodiment is as follows:
Be made into the attapulgite aqueous solution that mass concentration is 10%, adding quality is mechanical agitation 30 minutes after the sodium hexametaphosphate dispersant of 10% of attapulgite quality, ultrasonic wave process 30 minutes, carries out centrifugal treating by centrifuge 2000r/min; Discard upper liquid, dry in 80 DEG C of baking ovens.
Attapulgite modified concrete steps after purifying in the present embodiment are as follows:
Being made into the attapulgite aqueous solution through purifying that mass concentration is 10%, adding the chitosan quaternary ammonium salt powder that quality is 20% of attapulgite quality; At 70 DEG C, magnetic agitation reacts 2 hours; Above-mentioned reactant liquor discards supernatant liquor after processing certain hour by centrifugal (2000r/min); Modified attapulgite puts into 80 DEG C of oven for drying, cools rear mortar grinder for subsequent use.
Use molecular cut off is 3-5 ten thousand polysulfone porous support membrane, the 4-aminomethylpiperazine aqueous phase solution being 30g/L with concentration contacts 150 seconds, wherein 4-aminomethylpiperazine aqueous phase solution contains the triethylamine of 5g/L, the lauryl sodium sulfate of 1g/L, and the polysulfones support membrane rubber rollers after 4-aminomethylpiperazine aqueous phase solution infiltrates removes redundant solution.Then the hexane solution being the pyromellitic trimethylsilyl chloride of 5g/L by this support membrane and concentration contacts 10 seconds; The aramid layer of formation is dried in atmosphere, be that the 4-aminomethylpiperazine aqueous phase solution of 5g/L contacts about 30 seconds again with concentration, wherein 4-aminomethylpiperazine aqueous phase solution contains the sodium carbonate of 5g/L, the lauryl sodium sulfate of 5g/L, the chitin modified attapulgite of 0.001g/L, then above-mentioned film is placed in the baking oven of 30 DEG C and processes 10min, then rinsing 10 minutes in the water of 40 DEG C, obtain the polyamide composite nanofiltration membrane of the quaternary ammonium salt-modified attapulgite of chitosan-containing, the composite nanometer filtering film prepared is preserved in deionized water.
Operating pressure be 0.6Mpa, under temperature is 25 DEG C, pH value is the test condition of 6.5-7.5, the aqueous sodium persulfate solution of 1000ppm is used to test the infiltration cutoff performance of the composite nanometer filtering film of above-mentioned preparation, and press the anti-microbial property of aforesaid antibacterial test method test compound film, the test result of gained lists in table 1.
Embodiment 2
Except in the aqueous phase again added on the aramid layer generated, the concentration of the attapulgite of chitosan quaternary ammonium salt modification being become except 0.004g/L, other processing step and test condition are all identical with embodiment 1, and the test result of prepared composite nanometer filtering film lists in table 1.
Embodiment 3
Except in the aqueous phase again added on the aramid layer generated, the concentration of the attapulgite of chitosan quaternary ammonium salt modification being become except 0.008g/L, other processing step and test condition are all identical with embodiment 1, and the test result of prepared composite nanometer filtering film lists in table 1.
Embodiment 4
Except becoming except 0.02g/L by the concentration of the attapulgite of chitosan quaternary ammonium salt modification in the aqueous phase again added on the aramid layer generated, other processing step and test condition are all identical with embodiment 1, and the test result of prepared composite nanometer filtering film lists in table 1.
Embodiment 5
Except becoming except 0.1g/L by the concentration of the attapulgite of chitosan quaternary ammonium salt modification in the aqueous phase again added on the aramid layer generated, other processing step and test condition are all identical with embodiment 1, and the test result of prepared composite nanometer filtering film lists in table 1.
Comparative example 1
Do not contain except the attapulgite of chitosan quaternary ammonium salt modification except in the aqueous phase again added on the aramid layer generated, other processing step and test condition are all identical with embodiment 1, and the test result of prepared composite nanometer filtering film lists in table 1.
Embodiment 6
The purification of the attapulgite used in the present embodiment and modification procedure are with embodiment 1.
Use the polyether sulfone porous support membrane that molecular cut off is 3-5 ten thousand, piperazine (PIP) aqueous phase solution being 5g/L with concentration contacts about 60 seconds, wherein piperazine aqueous phase solution contains the triethylamine of 5g/L, the neopelex of 2g/L, and the polysulfones support membrane rubber rollers after piperazine aqueous phase solution infiltrates removes redundant solution.Then be that the Isopar G solution of the pyromellitic trimethylsilyl chloride of 0.5g/L contacts 80 seconds by this support membrane and concentration; Then the aramid layer of formation is dried in atmosphere, the piperazine aqueous phase solution being 1g/L with concentration contacts 10 seconds, the triethylamine of 5g/L, the neopelex of 2g/L, wherein, the attapulgite of chitosan quaternary ammonium salt modification containing 0.02g/L in this aqueous phase solution, is then placed on this film in the baking oven of 90 DEG C and places 3min, then rinsing 10 minutes in the water of 40 DEG C, obtain the polypiperazine-amide composite nanometer filtering film containing attapulgite, the composite nanometer filtering film prepared is preserved in deionized water.By infiltration cutoff performance and the anti-microbial property of the method for testing test membrane identical with embodiment 1, the results are shown in table 1.
Comparative example 2
Do not contain except the attapulgite of chitosan quaternary ammonium salt modification except in the aqueous phase again added on the aramid layer generated, other processing step and test condition are all identical with embodiment 6, and the test result of prepared composite nanometer filtering film lists in table 1.
Table 1
As can be seen from Table 1, composite nanometer filtering film prepared by the present invention has the water flux suitable with corresponding comparative example and the salt-stopping rate of Geng Gao, and its anti-microbial property will significantly better than comparative example.
Embodiment 7
The purification of the attapulgite used in the present embodiment and modification procedure are with embodiment 1.
Polysulfone porous support membrane, the p-phenylenediamine (PPD) aqueous phase solution being 30g/L with concentration contacts about 100 seconds, wherein p-phenylenediamine (PPD) aqueous phase solution contains the triethylamine of 10g/L, the lauryl sodium sulfate of 1g/L, and the polysulfones support membrane rubber rollers after p-phenylenediamine (PPD) aqueous phase solution infiltrates removes redundant solution.Then this support membrane is contacted 60 seconds with the hexane solution of cyclopropane three acyl chlorides containing 1g/L; Then the aramid layer of formation is dried in atmosphere, be that p-phenylenediamine (PPD) (PPDA) aqueous phase solution of 30g/L contacts about 60 seconds again with concentration, wherein p-phenylenediamine (PPD) aqueous phase solution contains the triethylamine (TEA) of 10g/L, the lauryl sodium sulfate of 1g/L, the attapulgite of the chitosan quaternary ammonium salt modification of 0.04g/L, then the baking oven this film being put into 40 DEG C keeps 8 minutes, rinsing 10 minutes in the water of 40 DEG C, obtain polyamide composite nanofiltration membrane, the composite nanometer filtering film prepared is preserved in deionized water.By infiltration cutoff performance and the anti-microbial property of the method for testing test membrane identical with embodiment 1, the results are shown in table 2.
Embodiment 8
The purification of the attapulgite used in the present embodiment and modification procedure are with embodiment 1.
Polysulfone porous support membrane, the pentanediamine aqueous phase solution being 30g/L with concentration contacts about 60 seconds, wherein pentanediamine aqueous phase solution contains the triethylamine (TEA) of 10g/L, the lauryl sodium sulfate (SDS) of 1g/L, and the polysulfones support membrane rubber rollers after pentanediamine aqueous phase solution infiltrates removes redundant solution.Then this support membrane is contacted 60 seconds with the hexane solution of fourth three acyl chlorides containing 1g/L; Then the aramid layer of formation is dried in atmosphere, pentanediamine (PPDA) aqueous phase solution being 30g/L with concentration contacts about 60 seconds, wherein pentanediamine aqueous phase solution contains the triethylamine (TEA) of 10g/L, the lauryl sodium sulfate (SDS) of 1g/L, the attapulgite of the chitosan quaternary ammonium salt modification of 0.2g/L, then the baking oven this film being put into 60 DEG C keeps 5 minutes, rinsing 10 minutes in the water of 40 DEG C, obtain polyamide composite nanofiltration membrane, the composite nanometer filtering film prepared is preserved in deionized water.By infiltration cutoff performance and the anti-microbial property of the method for testing test membrane identical with embodiment 1, the results are shown in table 2.
Comparative example 3
Do not contain except the attapulgite of chitosan quaternary ammonium salt modification except in the aqueous phase again added on the aramid layer generated, other processing step and test condition are all identical with embodiment 7, and the test result of prepared composite nanometer filtering film lists in table 2.
Comparative example 4
Do not contain except the attapulgite of chitosan quaternary ammonium salt modification except in the aqueous phase again added on the aramid layer generated, other processing step and test condition are all identical with embodiment 8, and the test result of prepared composite nanometer filtering film lists in table 2.
Table 2
As can be seen from Table 2, the composite nanometer filtering film obtained by embodiment 7-8 there is the water flux suitable with corresponding comparative example and the salt-stopping rate of Geng Gao, and its anti-microbial property significantly will be better than comparative example.
Claims (7)
1. the antibacterial composite nanometer filtering film of high salt-stopping rate, is characterized in that:
Containing the attapulgite of chitosan quaternary ammonium salt modification in described antibacterial composite nanometer filtering film, attapulgite has in bar-shaped or filamentary structure and has the nanoscale duct of hollow, and the diameter of attapulgite is between 10 ~ 20nm.
2. the antibacterial composite nanometer filtering film of high salt-stopping rate as claimed in claim 1, is characterized in that:
Described antibacterial composite nanometer filtering film is prepared by the method comprised the following steps:
(1) aqueous phase solution of porous support layer with the compound containing two or more reactive amino is contacted;
(2) aqueous phase solution of the porous support layer excess surface of removing after aqueous phase infiltrates;
(3) porous support layer after step (2) process contacts with the organic phase solution of the chloride compounds containing two or more acid chloride group;
(4) contact with the aqueous phase solution of the attapulgite of chitosan quaternary ammonium salt modification with the compound containing two or more reactive amino again after organic phase solution volatilization;
(5) obtained described antibacterial composite nanometer filtering film after heat treatment, washing;
Described porous support layer is the one in polysulfone porous supporting layer, polyether sulfone porous support layer, sulfonated polyether sulfone porous support layer, polypropylene porous support layer;
The described compound containing two or more reactive amino is one or more in aromatic series, aliphatic, alicyclic polyfunctional amine, polyhydric alcohol amine;
The described chloride compounds containing two or more acid chloride group be aromatic series, aliphatic, alicyclic multifunctional chloride compounds one or more;
The organic solvent of described organic phase solution is one or more in n-hexane, cyclohexane, trifluorotrichloroethane, normal heptane, normal octane, toluene, ethylbenzene, ISOPAR solvent naphtha;
The concentration of the compound containing two or more reactive amino in described aqueous phase solution is 1-30g/L;
The concentration of the chloride compounds containing two or more acid chloride group in described organic phase solution is 0.5-5g/L;
In the aqueous phase solution of step (4), the content of the attapulgite that shitosan is quaternary ammonium salt-modified is 0.001-0.2g/L.
3. a preparation method for the antibacterial composite nanometer filtering film of high salt-stopping rate as claimed in claim 1 or 2, is characterized in that described method comprises:
(1) aqueous phase solution of porous support layer with the compound containing two or more reactive amino is contacted;
(2) aqueous phase solution of the porous support layer excess surface of removing after aqueous phase infiltrates;
(3) porous support layer after step (2) process contacts with the organic phase solution of the chloride compounds containing two or more acid chloride group;
(4) contact with the aqueous phase solution of the attapulgite of chitosan quaternary ammonium salt modification with the compound containing two or more reactive amino again after organic phase solution volatilization;
(5) obtained described antibacterial composite nanometer filtering film after heat treatment, washing;
Described porous support layer is the one in polysulfone porous supporting layer, polyether sulfone porous support layer, sulfonated polyether sulfone porous support layer, polypropylene porous support layer;
The described compound containing two or more reactive amino is one or more in aromatic series, aliphatic, alicyclic polyfunctional amine, polyhydric alcohol amine;
The described chloride compounds containing two or more acid chloride group be aromatic series, aliphatic, alicyclic multifunctional chloride compounds one or more;
The organic solvent of described organic phase solution is one or more in n-hexane, cyclohexane, trifluorotrichloroethane, normal heptane, normal octane, toluene, ethylbenzene, ISOPAR solvent naphtha;
The concentration of the compound containing two or more reactive amino in described aqueous phase solution is 1-30g/L;
The concentration of the chloride compounds containing two or more acid chloride group in described organic phase solution is 0.5-5g/L;
In the aqueous phase solution of step (4), the content of the attapulgite that shitosan is quaternary ammonium salt-modified is 0.001-0.2g/L.
4. preparation method as claimed in claim 3, is characterized in that:
Described aromatic series polyfunctional amine is m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine (PPD), 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 3,5-diaminobenzoic acids, 2, at least one in 4-diaminotoluene, 2,4-diamino anisoles, amidol, xylylene diamine;
Described aliphatic polyfunctional amine is at least one in ethylenediamine, propane diamine, butanediamine, pentanediamine, three (2-aminoethyl) amine, diethylenetriamine;
Described alicyclic polyfunctional amine is at least one in 1,2-DACH, Isosorbide-5-Nitrae-DACH, piperazine, 1,3-two piperidyl propane, 4-aminomethylpiperazine;
Described polyhydric alcohol amine is at least one in monoethanolamine, diethanol amine, hexylene glycol amine, diglycolamine.
5. preparation method as claimed in claim 3, is characterized in that:
The multifunctional chloride compounds of described aromatic series is at least one in paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride, biphenyl dimethyl chloride, benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride;
The multifunctional chloride compounds of described aliphatic is at least one in fourth three acyl chlorides, succinyl chloride, penta 3 acyl chlorides, glutaryl chlorine, oneself three acyl chlorides, Adipoyl Chloride, sebacoyl chloride, the last of the ten Heavenly stems three acyl chlorides;
Described alicyclic multifunctional chloride compounds is at least one in cyclopropane three acyl chlorides, cyclobutane diacid chloride, cyclobutane four acyl chlorides, pentamethylene diacid chloride, pentamethylene three acyl chlorides, pentamethylene four acyl chlorides, cyclohexane diacid chloride, cyclohexane three acyl chlorides, cyclohexane four acyl chlorides, oxolane diacid chloride, oxolane four acyl chlorides.
6. the preparation method as described in one of claim 3 ~ 5, is characterized in that:
Time of contact is 10-150 second.
7. preparation method as claimed in claim 6, is characterized in that:
In step (5), heat treatment temperature is 30-90 DEG C, and heat treatment time is 3-10 minute.
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