CN102527253A - Antibacterial antioxidative composite reverse osmosis membrane - Google Patents
Antibacterial antioxidative composite reverse osmosis membrane Download PDFInfo
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- CN102527253A CN102527253A CN2012100072119A CN201210007211A CN102527253A CN 102527253 A CN102527253 A CN 102527253A CN 2012100072119 A CN2012100072119 A CN 2012100072119A CN 201210007211 A CN201210007211 A CN 201210007211A CN 102527253 A CN102527253 A CN 102527253A
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- 239000012528 membrane Substances 0.000 title claims abstract description 91
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 81
- 230000000844 anti-bacterial Effects 0.000 title claims abstract description 45
- 230000003078 antioxidant Effects 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title abstract description 25
- 239000004952 Polyamide Substances 0.000 claims abstract description 22
- 238000010612 desalination reaction Methods 0.000 claims abstract description 22
- 229920002647 polyamide Polymers 0.000 claims abstract description 22
- 239000011528 polyamide (building material) Substances 0.000 claims abstract description 22
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims description 20
- 235000006708 antioxidants Nutrition 0.000 claims description 20
- 229920002521 Macromolecule Polymers 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 239000004760 aramid Substances 0.000 claims description 7
- 229920003235 aromatic polyamide Polymers 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 229920000591 gum Polymers 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N Ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L Potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L Sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- 108010022355 Fibroins Proteins 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 25
- 238000002360 preparation method Methods 0.000 abstract description 10
- 230000004907 flux Effects 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000002791 soaking Methods 0.000 abstract description 2
- 206010034133 Pathogen resistance Diseases 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 19
- 239000000460 chlorine Substances 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 230000003115 biocidal Effects 0.000 description 8
- LRJAGMBMPSXEFP-UDPUMDPQSA-N 2-[[[(1R)-1-[[(2R)-2-[3-acetamido-2-[[[(2R,3S,4R)-3,4-dihydroxy-5-(5-iodo-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy-hydroxyphosphoryl]oxy-hydroxyphosphoryl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxypropanoyl]amino]ethyl]-hydroxyphosphoryl]methyl]penta Chemical compound CC(=O)NC1C(O[C@H](C)C(=O)N[C@@H](C)P(O)(=O)CC(CCC(O)=O)C(O)=O)C(O)C(CO)OC1OP(O)(=O)OP(O)(=O)OC[C@@H]1[C@@H](O)[C@@H](O)C(N2C(NC(=O)C(I)=C2)=O)O1 LRJAGMBMPSXEFP-UDPUMDPQSA-N 0.000 description 6
- 229940088710 Antibiotic Drugs 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 6
- 230000003026 anti-oxygenic Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 230000003373 anti-fouling Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- -1 alkyl phenol Chemical compound 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 125000005395 methacrylic acid group Chemical class 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 229920002492 poly(sulfones) Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000001954 sterilising Effects 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-M 2-methylpropanimidate Chemical compound CC(C)C([O-])=N WFKAJVHLWXSISD-UHFFFAOYSA-M 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 108010013296 Sericins Proteins 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N Sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive Effects 0.000 description 1
- 230000000845 anti-microbial Effects 0.000 description 1
- 230000003064 anti-oxidating Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000011030 bottleneck Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N n-methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- 230000000149 penetrating Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229960002668 sodium chloride Drugs 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Abstract
The invention relates to a polymeric separation membrane, in particular to an antibacterial antioxidative composite reverse osmosis membrane for water treatment. The antibacterial antioxidative composite reverse osmosis membrane consists of a non-woven layer, a porous supporting layer and a polyamide polymeric desalination layer arranged on the porous supporting layer and is characterized by being prepared by soaking the polymeric desalination layer into a persulfate solution containing a polymeric antibacterial material and drying. The conventional composite reverse osmosis membrane containing the polyamide polymeric desalination layer is treated by the persulfate solution containing the antibacterial material, so that hydrophilicity, bacterial resistance and oxidation resistance of the composite reverse osmosis membrane are greatly improved and high antibacterial antioxidative performance is achieved. The antibacterial antioxidative composite reverse osmosis membrane has the characteristics of simplicity in preparation, high desalination rate and high water flux. The reverse osmosis membrane has wide application.
Description
Technical field
The invention belongs to water treatment field, specifically be meant a kind of antibacterial anti-oxidant complex reverse osmosis membrane that is used for water treatment.
Technical background
Reverse osmosis technology is a kind of efficient, energy-conservation green new separation technology; Have outstanding features such as equipment is simple, operating condition is gentle, treating capacity is big, separative efficiency height; Separate with resource, biological products with brackish water desalination, wastewater treatment at seawater, environmental project, food, medicine and other fields be used widely, and obtained good economic and social benefit; In recent years, along with the water globe shortage of resources is serious day by day, water pollutes and increases the weight of day by day, reverse osmosis technology has obtained using widely and paying attention in desalinization and water reuse field.
But one of reverse osmosis membrane separation The Application of Technology bottleneck is a film to be polluted, and film pollutes large-scale application and the popularization that has seriously restricted reverse osmosis technology, especially in Application for Field such as high pollution water treatment, water reuse and chemical separating.Film pollutes and will directly cause the permeation flux of film significantly to descend, and the production efficiency reduction of system, operating cost and energy consumption increase; Film pollutes that frequent clean, the device also will cause system can not run well, the holding back the serious deterioration of characteristic, produce water water quality variation of film, membrane lifetime reduces and the frequent change of film.
Biological pollution is to cause one of major reason of reverse osmosis membrane performance deterioration at present, is control and the effective way of eliminating biological pollution and use oxidizing biocide.But the antioxygenic property of anti-chlorine of widely used polyamide-based complex reverse osmosis membrane is relatively poor at present, has seriously restricted reverse osmosis technology in Application for Field such as high pollution water treatment, water reuse and chemical separating.Thereby, how to improve the antibacterial and antioxygenic property that has reverse osmosis membrane now, be the key that improves compound counter-infiltration operational efficiency, prolongs its service life.
Aspect the polyamide-based complex reverse osmosis membrane antifouling property of raising; To pass through Chemical Physics methods such as film surface applied, surface chemical modification, surface grafting; Change chemical physical property such as surface hydrophilicity, surface roughness and the surface charge etc. of reverse osmosis membrane, improve the antifouling property of reverse osmosis composite membrane.Uemura and Kuriharal are through improving the hydrophily and the stain resistance of reverse osmosis membrane at the compound counter-infiltration surface applied of polyamide polyvinyl alcohol (PVA) protective layer; Jennifer etc. are through improving resistance tocrocking at polyamide reverse osmosis composite film surface-coated polyether-amide block copolymers; Two kinds of T-X series of usefulness such as Wilbert and P series are gathered oxireme type non-ionic surface active agent, handle commercial polyamide reverse osmosis composite film, improve the anti-protein-contamination ability of film.People such as Kang have reduced the film surface roughness again, thereby have improved the antifouling property of film at nascent state polyamide reverse osmosis composite film surface grafting polyethylene glycol when improving the film surface hydrophilicity; Freger and Gilron etc. all adopt oxidation-reduction method (with K
2S
2O
8And K
2S
2O
5As initator) at side chains such as the acrylic acid of polyamide reverse osmosis composite film surface grafting possess hydrophilic property, methacrylic acids; The film surface roughness is reduced, thereby weakened the absorption of pollutant on the film surface, the film contact angle reduces simultaneously; The film hydrophily strengthens, so the stain resistance of film strengthens; Belfer etc. adopt radiation graft process at commercial polyamide composite film surface difference grafting methacrylic acid side chain and polyethylene glycol methacrylic acid side chain; Because the existence of hydrophilic radical-COOH; Film all has higher negative Zeta potential in whole pH value scope, thereby has improved the contamination resistance of film; Equally, Belfer etc. are grafted propylene nitrile side chain on the polyamide reverse osmosis composite film surface, has also obtained the better pollution resistance effect.
Aspect raising limitation type complex reverse osmosis membrane non-oxidizability; Chinese patent 200610051219.X (publication number:, make the chlorine-resistant property of complex reverse osmosis membrane and antifouling property obtain improving greatly CN101147846A) through the aramid layer of polyamide composite reverse osmosis membrane being handled with persulfate solution.
Thereby although obtaining very big progress aspect the research and development of antipollution and resistance to oxidation reverse osmosis membrane at present, preparation has antibacterial and complex reverse osmosis membrane anti-oxidation function, is still one of target of film academia and film industrial quarters pursuit.
Summary of the invention
The objective of the invention is,, a kind of antibacterial anti-oxidant complex reverse osmosis membrane is provided to deficiency of the prior art.Improve antibacterial, the anti-oxidant and anti-fouling performance of reverse osmosis membrane, prolong the service life of reverse osmosis membrane
The present invention is achieved through following technical proposals:
A kind of antibacterial anti-oxidant complex reverse osmosis membrane; Comprise nonwoven layer, porous support layer and the macromolecule desalination layer on porous support layer; It is characterized in that: macromolecule desalination layer is soaked in the persulfate solution of the antibacterial material of pbz polymer; Oven dry obtains antibacterial anti-oxidant complex reverse osmosis membrane then.
As preferably, in the above-mentioned antibacterial anti-oxidant complex reverse osmosis membrane, described macromolecule desalination layer is polyamide-based macromolecule; As better selection, described polyamide-based macromolecule is a Wholly aromatic polyamide, or aromatic polyamides-urea, or aromatic polyamides-carbamate, or the aromatic-aliphatic mixed polyamide;
Concrete molecular formula is represented as follows:
A: Wholly aromatic polyamide
X is :-H or-Cl or-NO
2Or-CH
3
B: aromatic polyamides-urea
Y is :-H or-Cl or-NO
2Or-CH
3
C: aromatic polyamides-carbamate
Z is :-H or-Cl or-NO
2Or-CH
3
D: or the aromatic-aliphatic mixed polyamide
W is :-H or-Cl or-NO
2Or-CH
3
As preferably, in the above-mentioned antibacterial anti-oxidant complex reverse osmosis membrane, described high-molecular anti-bacteria material is a silk gum, or fibroin, or their mixture.
As preferably, in the above-mentioned antibacterial anti-oxidant complex reverse osmosis membrane, described persulfate is a potassium peroxydisulfate, or ammonium persulfate, or sodium peroxydisulfate, or their mixture.
As preferably, in the above-mentioned antibacterial anti-oxidant complex reverse osmosis membrane, the antibacterial concentration of material of described macromolecule is 0.1-10.0wt%, and the concentration of persulfate is 0.1-10.0wt%, and pH value of solution is 7.0-9.0, and soak time is 10-120 minute; As better selection, the antibacterial concentration of material of described macromolecule is 0.2-5.0wt%, and the concentration of persulfate is 0.2-5.0wt%, and pH value of solution is 7.5-8.5, and soak time is 10-120 minute.
Reverse osmosis membrane described in the present invention is a flat sheet membrane, or hollow-fibre membrane, or tubular membrane.
Beneficial effect: the present invention is through handling the polyamide macromolecule desalination layer of complex reverse osmosis membrane with the persulfate solution that contains anti-biotic material; Make hydrophily, anti-microbial property and the oxidation resistent susceptibility of complex reverse osmosis membrane be greatly enhanced, have good antibacterial antioxygenic property.The salt rejection rate of antibacterial antipollution complex reverse osmosis membrane of the present invention and water flux are not less than existing complex reverse osmosis membrane, and the preparation method is also simpler.
The specific embodiment
Specify in the face of enforcement of the present invention down:
Porous support membrane preparation: by the conventional method preparation; The present invention is the UDEL PS3500LCD polysulfones with 16.0wt%; The water of 0.2wt% and the surfactant of 0.05wt% are dissolved in the polar organic solvent; Be coated with and scrape on polyester non-woven fabric, immerse then in the water remove desolvate with additive after to obtain molecular cut off (MWCO) be about 40,000 porous support membrane.Wherein, surfactant comprises alkyl phenol polyoxy Acetoxon acid esters at least, a kind of in dodecyl sodium sulfate and the alkyl phenol polyoxy Acetoxon hydrochlorate; Polar organic solvent is N, N-dimethylacetylamide, or N, dinethylformamide, or N-methyl pyrrolidone, or their mixture.
Macromolecule desalination layer preparation: the polysulfones support membrane single face of hygrometric state is immersed in the polyamine solution, after extracting with squeegee roll extrusion support membrane surface, contacts with polynary solution of acid chloride single face and to carry out interface polymerization reaction.Composite membrane dried in the shade in air 3-5 minute, and again through two step heat treatments: the first step is to handle 5～10 minutes down at 40～70 ℃, and second step was to handle 5～10 minutes down at 80～110 ℃.Then carry out two step rinsings again: the first step is to be rinsing 10～15 minutes in the aqueous solution of 20.0wt% at 40～50 ℃ methyl alcohol part by weight, and second step was rinsing 10～15 minutes in 30～40 ℃ water.
The antibacterial anti-oxidant treatment of desalination layer:
To use solution soaking time 10-120 minute of pH through the complex reverse osmosis membrane of pure water rinsing and extrusion process as the persulfate of 7.0-9.0, the high-molecular anti-bacteria material that contains 0.1-10.0wt% and 0.1-10.0wt%; Composite membrane is taken out, in the baking oven of 120 degree, kept 5 minutes, obtain antibacterial anti-oxidant complex reverse osmosis membrane.
Film properties is tested:
1, salt rejection rate and water flux evaluation:
Salt rejection rate and water flux are two important parameters estimating the reverse osmosis membrane separation performance.Through the cross-flow permeability test, reverse osmosis membrane is carried out the separating property evaluation.
Salt rejection rate (R) is defined as: under certain operating condition, and feeding liquid salinity (C
f) with penetrating fluid in salinity (C
p) poor, again divided by the feeding liquid salinity.
Water flux is defined as: under certain operating condition, see through the volume of the water of elementary membrane area in the unit interval, its unit is l/m
2.h.
The operating condition that reverse osmosis membrane performance mensuration adopts among the present invention is: feed liquor is the sodium-chloride water solution of 1000ppm, and operating pressure is 225psi, and operating temperature is 20 ℃, and aqueous solution pH is 6.8.
2, antibacterial effect detection by quantitative:
With fask oscillating method detection by quantitative antibacterial effect.Antibiotic complex reverse osmosis membrane is cut into the sample of 10mm * 30mm; Above-mentioned sample is put into the conical flask of 150mL; The Escherichia coli bacteria suspension that adds 70mL PBS buffer solution and 500 μ L respectively is fixed in conical flask on the vibration shaking table, sways 24 hours with 120r/min.Appearance liquid after getting 500 μ L and swaying is done to carry out after the suitably dilution viable bacteria with the PBS buffer solution and is cultivated and count.Simultaneously common complex reverse osmosis membrane sheet (not containing surperficial high-molecular anti-bacteria material layer) is made an experiment.Sterilizing rate calculates as follows:
Sterilizing rate (%)=((A-B)/A) * 100%
In the formula: A---common reverse osmosis membrane sample viable count;
B---antibiotic reverse osmosis membrane sample viable count.
3, chlorine-resistant property evaluation:
With the aqueous sodium hypochlorite solution of 2000mg/L, be 4.5 times at pH, the counter-infiltration diaphragm was soaked 25 hours, estimate its salt rejection rate and water flux then.
The result:
Comparative example 1-4
Adopt the prior art for preparing complex reverse osmosis membrane, the desalination layer is not carried out immersion treatment with the persulfate solution that contains anti-biotic material.The separating property of complex reverse osmosis membrane, bacteriostasis property and chlorine-resistant property are as shown in table 1.
Table 1: comparative example 1-4
Above-mentioned comparative example shows: the complex reverse osmosis membrane that contains different polyamide family macromolecule desalination layer with prior art for preparing does not have bacteriostasis property, and the chlorine-resistant property of film is also relatively poor.
Embodiment 5-8
Adopt the prior art for preparing complex reverse osmosis membrane, use pH to be 8.0, to contain 2.0wt% silk gum and 2.0wt% persulfate aqueous solution to the desalination layer then, soaked 30 minutes.The separating property of prepared composite reverse osmosis membrane, bacteriostasis property and chlorine-resistant property are as shown in table 2.
Table 2: embodiment 5-8
Above-mentioned instance shows: with the persulfate solution that contains anti-biotic material the desalination layer of polyamide-based complex reverse osmosis membrane is carried out immersion treatment, not only can significantly improve the antioxygenic property of complex reverse osmosis membrane, also given the bacteriostasis property of reverse osmosis membrane simultaneously.
Embodiment 9-12
Except the anti-biotic material difference, adopt to prepare complex reverse osmosis membrane with embodiment 5 identical preparation methods.The separating property of prepared composite reverse osmosis membrane, bacteriostasis property and chlorine-resistant property are as shown in table 3.
Table 3: embodiment 9-12
Above-mentioned instance shows: the persulfate solution with containing different anti-biotic materials carries out Wholly aromatic polyamide composite membrane desalination layer, all can prepare antibacterial anti-oxidant complex reverse osmosis membrane.
Embodiment 13-18
Except anti-biotic material content difference, adopt to prepare complex reverse osmosis membrane with embodiment 6 identical preparation methods.The separating property of prepared composite reverse osmosis membrane, bacteriostasis property and chlorine-resistant property are as shown in table 4.
Table 4: embodiment 13-18
Above-mentioned instance shows: the persulfate solution with containing variable concentrations silk gum carries out aromatic polyamides-urea composite membrane desalination layer, all can improve the antibacterial and antioxygenic property of complex reverse osmosis membrane, and wherein silk gum concentration is best in the 0.2-5.0wt% effect.
Embodiment 19-12
Except the persulfate difference, adopt to prepare complex reverse osmosis membrane with embodiment 5 identical preparation methods.The separating property of prepared composite reverse osmosis membrane, bacteriostasis property and chlorine-resistant property are as shown in table 5.
Table 5: embodiment 19-21
Above-mentioned instance shows: the solution with containing 2.0wt% silk gum and different persulfates carries out Wholly aromatic polyamide composite membrane desalination layer, all can prepare antibacterial anti-oxidant complex reverse osmosis membrane.
Embodiment 22-27
Except persulfate content difference, adopt to prepare complex reverse osmosis membrane with embodiment 5 identical preparation methods.The separating property of prepared composite reverse osmosis membrane, bacteriostasis property and chlorine-resistant property are as shown in table 6.
Table 6: embodiment 22-27
Above-mentioned instance shows: usefulness contains the sericin of 2.0wt% and the potassium peroxydisulfate liquid of variable concentrations carries out composite membrane desalination layer; All can improve the antibacterial and antioxygenic property of Wholly aromatic polyamide complex reverse osmosis membrane, wherein potassium peroxydisulfate concentration is best in the 0.2-5.0wt% effect.
Claims (5)
1. antibacterial anti-oxidant complex reverse osmosis membrane; Comprise nonwoven layer, porous support layer and the macromolecule desalination layer on porous support layer; It is characterized in that: described macromolecule desalination layer is in the persulfate aqueous solution at the antibacterial material of pbz polymer, to soak; Oven dry obtains antibacterial anti-oxidant complex reverse osmosis membrane then;
Wherein: the mass concentration of the antibacterial material of macromolecule is 0.1-10.0wt%, and the mass concentration of persulfate is 0.1-10.0wt%, and pH value of solution is 7.0-9.0, and soak time is 10-120 minute;
The antibacterial material of macromolecule is a silk gum, or fibroin, or their mixture;
Macromolecule desalination layer is polyamide-based macromolecule.
2. antibacterial anti-oxidant complex reverse osmosis membrane according to claim 1 is characterized in that: described polyamide-based macromolecule is a Wholly aromatic polyamide, or aromatic polyamides-urea, or aromatic polyamides-carbamate, or the aromatic-aliphatic mixed polyamide.
3. antibacterial anti-oxidant complex reverse osmosis membrane according to claim 1, it is characterized in that: described persulfate is a potassium peroxydisulfate, or ammonium persulfate, or sodium peroxydisulfate, or their mixture.
4. antibacterial anti-oxidant complex reverse osmosis membrane according to claim 1; It is characterized in that: the mass concentration of the antibacterial material of macromolecule is 0.2-5.0wt%; The mass concentration of persulfate is 0.2-5.0wt%, and pH value of solution is 7.5-8.5, and soak time is 10-120 minute.
5. antibacterial anti-oxidant complex reverse osmosis membrane according to claim 1 is characterized in that said reverse osmosis membrane is a flat sheet membrane, or hollow-fibre membrane, or tubular membrane.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143270A (en) * | 2013-03-19 | 2013-06-12 | 中国科学院长春应用化学研究所 | Hydrophilic antiosmosis composite membrane and preparation method thereof |
| CN104998559A (en) * | 2015-06-29 | 2015-10-28 | 苏州佑君环境科技有限公司 | Filtration sterilization membrane and preparation method thereof |
| CN106725633A (en) * | 2017-01-11 | 2017-05-31 | 温州中壹技术服务有限公司 | A kind of genetic test special sampler |
| CN111871223A (en) * | 2020-07-23 | 2020-11-03 | 华中科技大学 | High-flux antibacterial nanofiltration membrane and preparation method thereof |
| CN114307685A (en) * | 2021-11-16 | 2022-04-12 | 中国科学院生态环境研究中心 | High-flux modification method of polyamide composite membrane based on small molecular alcohol free radicals |
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| CN106725633A (en) * | 2017-01-11 | 2017-05-31 | 温州中壹技术服务有限公司 | A kind of genetic test special sampler |
| CN106725633B (en) * | 2017-01-11 | 2019-07-09 | 温州中壹技术研究院有限公司 | A kind of genetic test special sampler |
| CN111871223A (en) * | 2020-07-23 | 2020-11-03 | 华中科技大学 | High-flux antibacterial nanofiltration membrane and preparation method thereof |
| CN111871223B (en) * | 2020-07-23 | 2021-10-08 | 华中科技大学 | High-flux antibacterial nanofiltration membrane and preparation method thereof |
| CN114307685A (en) * | 2021-11-16 | 2022-04-12 | 中国科学院生态环境研究中心 | High-flux modification method of polyamide composite membrane based on small molecular alcohol free radicals |
| CN114307685B (en) * | 2021-11-16 | 2022-11-11 | 中国科学院生态环境研究中心 | High-flux modification method of polyamide composite membrane based on small molecular alcohol free radicals |
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