CN113559727A - Anti-biological pollution ultrafiltration membrane and preparation method thereof - Google Patents
Anti-biological pollution ultrafiltration membrane and preparation method thereof Download PDFInfo
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- CN113559727A CN113559727A CN202110832871.XA CN202110832871A CN113559727A CN 113559727 A CN113559727 A CN 113559727A CN 202110832871 A CN202110832871 A CN 202110832871A CN 113559727 A CN113559727 A CN 113559727A
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- ultrafiltration membrane
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- diatomite
- biological pollution
- polyvinyl alcohol
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- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 125
- 238000002360 preparation method Methods 0.000 title abstract description 14
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- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 62
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 62
- 239000011248 coating agent Substances 0.000 claims abstract description 48
- 238000000576 coating method Methods 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 46
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 26
- 150000007973 cyanuric acids Chemical class 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 20
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- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 40
- 239000002033 PVDF binder Substances 0.000 claims description 9
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 claims description 9
- 229920002492 poly(sulfone) Polymers 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- XSXSKSKONCDOMZ-UHFFFAOYSA-N sodium;1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound [Na+].ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O XSXSKSKONCDOMZ-UHFFFAOYSA-N 0.000 claims description 9
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
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- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 claims description 3
- 229950009390 symclosene Drugs 0.000 claims description 3
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- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
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- 239000004408 titanium dioxide Substances 0.000 description 2
- VUWCWMOCWKCZTA-UHFFFAOYSA-N 1,2-thiazol-4-one Chemical class O=C1CSN=C1 VUWCWMOCWKCZTA-UHFFFAOYSA-N 0.000 description 1
- USVZHTBPMMSRHY-UHFFFAOYSA-N 8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]-9-[2-(2-chlorophenyl)ethyl]purin-6-amine Chemical compound C=1C=2OCOC=2C=C(Br)C=1SC1=NC=2C(N)=NC=NC=2N1CCC1=CC=CC=C1Cl USVZHTBPMMSRHY-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
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- YKPUWZUDDOIDPM-SOFGYWHQSA-N capsaicin Chemical class COC1=CC(CNC(=O)CCCC\C=C\C(C)C)=CC=C1O YKPUWZUDDOIDPM-SOFGYWHQSA-N 0.000 description 1
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- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
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- 239000004745 nonwoven fabric Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
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- 230000001376 precipitating effect Effects 0.000 description 1
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- 239000010865 sewage Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/48—Antimicrobial properties
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses an anti-biological pollution ultrafiltration membrane and a preparation method thereof. The preparation method comprises the following steps: (1) loading chlorinated derivatives of isocyanuric acid on diatomite so as to obtain modified diatomite; (2) mixing the modified diatomite, the polyvinyl alcohol solution and the cross-linking agent, and carrying out ultrasonic treatment to obtain an anti-biological pollution coating solution; (3) and (3) dipping the ultrafiltration basement membrane by using the biological pollution resistant coating liquid, and drying to obtain the biological pollution resistant ultrafiltration membrane. The method is simple to operate, low in cost and suitable for large-scale industrial production, the prepared ultrafiltration membrane has good hydrophilicity, antibacterial property and flux, the biological pollution resistance is good, the service life is long, the hydrophilicity promotion rate of the ultrafiltration membrane can be improved by more than 10%, and the bacteriostasis rate can be up to more than 93%.
Description
Technical Field
The invention belongs to the field of ultrafiltration membranes, and particularly relates to an anti-biological-pollution ultrafiltration membrane and a preparation method thereof.
Background
In recent years, ultrafiltration has been widely used in sewage treatment and reuse of reclaimed water. Currently, the main problem faced by ultrafiltration technology is membrane fouling, of which biological fouling is the major one. Since microorganisms can rapidly grow and multiply in a short time, even small amounts present on the membrane surface can cause serious consequences. Microorganisms are widely present in water, air and soil, and the feed liquid to be treated in the membrane technology inevitably contains microorganisms, so that the biological pollution of the membrane is not preventable, and is also called as the only fatal weak point in the membrane process. The biological pollution process of the membrane comprises three steps of adhesion of microorganisms on the surface of the membrane, growth and reproduction of nutrient substances on the surface of the membrane by the microorganisms and expansion and adhesion of microbial colonies into the biological membrane. The properties of the membrane surface can affect the adhesion and growth of microorganisms on the membrane surface, and therefore, the surface modification of the membrane can become an important means for controlling membrane biofouling. Because the adhesion of microorganisms on the membrane surface cannot be completely avoided, the surface antimicrobial adsorption and the growth performance need to be considered simultaneously when the membrane surface is modified so as to obtain better biological pollution resistance effect.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art.
The present invention has been completed based on the following findings of the inventors:
PVA has strong hydrophilicity and good protein pollution resistance, and has wide application prospect in the aspect of pollution-resistant ultrafiltration membranes. The existing methods for preparing ultrafiltration membranes are that a PVA coating is formed on the surface of a hydrophobic membrane through the adsorption action of PVA on the surface of the membrane, borax is mixed into PVA to control the adsorption quantity of PVA on the surface of the membrane and improve the stability of a modified membrane, and hydrophilic polyvinyl alcohol and polyvinylpyrrolidone are uniformly deposited on the surface of the membrane and the inner wall of a membrane pore by a pneumatic deposition method to improve the hydrophilicity of the surface of the membrane, but the methods only consider the antimicrobial adsorption of the surface of the membrane and do not consider the growth resistance; at present, an isothiazolinone derivative is grafted on the surface of a polyvinylidene fluoride membrane, the polyvinylidene fluoride membrane is made to have anti-biological contamination property by using the bactericidal property of isothiazolinone, and a polysulfone ultrafiltration membrane is put into a solution consisting of a capsaicin derivative, an initiator and a hydrophilic monomer with excellent antibacterial property to react to obtain the antibacterial polysulfone ultrafiltration membrane. In addition, a modified coating is formed by utilizing diatomite and titanium dioxide, direct contact between pollutants and an ultrafiltration membrane is reduced through the coating, so that membrane pollution is reduced, and the pollutants are degraded by utilizing titanium dioxide catalysis. Obviously, the existing methods for preparing the ultrafiltration membrane have the defects, and further improvement schemes are needed.
In order to make the ultrafiltration membrane have better surface antimicrobial adsorption property and antimicrobial growth property, the inventor conducts a great deal of research experiments and finds that diatomite with strong adsorption property and a natural porous structure can be used for loading chlorinated derivatives of isocyanuric acid, and the chlorinated derivatives of the isocyanuric acid can be used in the ultrafiltration membrane to improve the hydrophilicity and the antimicrobial property of the membrane surface and achieve the purpose of improving the antimicrobial adsorption property and the antimicrobial growth property.
In view of the above, an object of the present invention is to provide a method for preparing an anti-biofouling ultrafiltration membrane, which considers both the anti-adsorption property and the anti-growth property of microorganisms on the surface of the ultrafiltration membrane, and has a simple preparation process, and is suitable for practical industrial production.
According to one aspect of the invention, a method of preparing an anti-biofouling ultrafiltration membrane is presented. According to an embodiment of the invention, the method comprises:
(1) loading chlorinated derivatives of isocyanuric acid on diatomite so as to obtain modified diatomite;
(2) mixing the modified diatomite, the polyvinyl alcohol solution and the cross-linking agent, and carrying out ultrasonic treatment to obtain an anti-biological pollution coating solution;
(3) and (3) dipping the ultrafiltration basement membrane by using the biological pollution resistant coating liquid, and drying to obtain the biological pollution resistant ultrafiltration membrane.
According to the method for preparing the anti-biofouling ultrafiltration membrane of the above embodiment of the present invention, the inventors have found that increasing the hydrophilicity of the surface of the ultrafiltration membrane reduces the adhesion of microorganisms on the surface of the membrane, and that increasing the antibacterial property of the surface of the ultrafiltration membrane inhibits the growth of microorganisms remaining on the surface of the membrane, that is, increasing the hydrophilicity and antibacterial property of the surface of the membrane greatly improves the anti-biofouling performance of the ultrafiltration membrane. The anti-biological pollution coating liquid formed by the preparation method takes a polyvinyl alcohol solution as a main body, and diatomite loaded with the chlorinated derivatives of isocyanuric acid is mixed, so that on one hand, the polyvinyl alcohol can be used for improving the hydrophilicity of the surface of the ultrafiltration membrane, and the chlorinated derivatives of isocyanuric acid are used for improving the antibacterial property of the surface of the membrane; on the other hand, the diatomite with a porous structure is used as a carrier, so that the contact specific surface area of the isocyanuric acid chloro derivative and microorganisms and the like can be increased, a slow controlled release effect is achieved, the antibacterial efficiency and the antibacterial time are improved, and the flux attenuation caused by coating a polyvinyl alcohol hydrophilic layer on the surface of the ultrafiltration membrane can be relieved.
According to the embodiment of the invention, the loading amount of the chlorinated derivative of isocyanuric acid in the modified diatomite is 4-8 wt%.
According to an embodiment of the invention, said chlorinated derivative of isocyanuric acid comprises at least one selected from the group consisting of sodium trichloroisocyanurate, trichloroisocyanuric acid, sodium dichloroisocyanurate and dichloroisocyanuric acid.
According to the embodiment of the invention, the mesh number of the diatomite is 1000-2000 meshes.
According to an embodiment of the present invention, step (1) comprises: mixing diatomite with the chlorinated derivative solution of isocyanuric acid, stirring and filtering; and roasting the filtered product to obtain the modified diatomite.
According to the embodiment of the invention, the temperature of the roasting treatment is 80-150 ℃.
According to the embodiment of the invention, in the polyvinyl alcohol solution, the molecular weight of the polyvinyl alcohol is not lower than 50000, and the concentration of the polyvinyl alcohol is 0.05-0.2 wt%.
According to the embodiment of the invention, the concentration of the modified diatomite in the anti-biological pollution coating liquid is 0.5-2 wt%.
According to the embodiment of the invention, the concentration of the cross-linking agent in the anti-biological pollution coating liquid is 0.5-1 wt%.
According to the embodiment of the invention, in the anti-biological pollution coating liquid, the concentration of the chlorinated derivative of the isocyanuric acid is 0.02-0.05 wt%; and/or the cross-linking agent is an inorganic cross-linking agent, and the inorganic cross-linking agent comprises at least one selected from sodium sulfate, zinc sulfate and boric acid.
According to the embodiment of the invention, in the step (3), the ultrafiltration bottom membrane is a polysulfone ultrafiltration membrane, a polyethersulfone ultrafiltration membrane or a PVDF ultrafiltration membrane.
According to the embodiment of the invention, in the step (3), the dipping time is 10-20 s.
According to the embodiment of the invention, in the step (3), the drying temperature is 40-80 ℃, and the drying time is 3-10 min.
According to yet another aspect of the present invention, an anti-biofouling ultrafiltration membrane is presented. According to the embodiment of the invention, the anti-biological pollution ultrafiltration membrane is prepared by adopting the method for preparing the anti-biological pollution ultrafiltration membrane. Compared with the prior art, the ultrafiltration membrane has good hydrophilicity, antibacterial property and flux, better biological pollution resistance and longer service life.
The invention has the following beneficial technical effects:
(1) the surface of the ultrafiltration membrane is coated with polyvinyl alcohol, so that the hydrophilic performance of the ultrafiltration membrane can be greatly improved, and the biological adhesion resistance of the surface of the membrane is improved; the cross-linking agent is added into the polyvinyl alcohol solution, so that the adhesion between the polyvinyl alcohol and the surface of the membrane can be improved, and the loss of a polyvinyl alcohol hydrophilic layer in the running process of the membrane is avoided.
(2) The polyethylene hydrophilic layer is mixed with the porous diatomite inside, so that the water permeability of the ultrafiltration membrane is improved, and the flux attenuation caused by coating the polyvinyl alcohol hydrophilic layer on the surface of the ultrafiltration membrane can be relieved.
(3) The chlorinated derivative of the bactericide isocyanuric acid in the polyvinyl alcohol hydrophilic layer enables the ultrafiltration membrane to have excellent antibacterial performance, and the surface of the membrane can resist microbial growth.
(4) The chlorinated derivative of the bactericide isocyanuric acid is loaded on the porous diatomite, so that compared with the method of directly mixing the chlorinated derivative of the bactericide isocyanuric acid into the hydrophilic layer, on one hand, the contact specific surface area of the bactericide can be increased, and the antibacterial efficiency is improved; on the other hand, the sustained-release antibacterial agent can play a role in slowly releasing and controlling the bactericide, and prolong the antibacterial time.
(5) The invention considers the anti-biological adhesion and the antimicrobial growth performance of the membrane surface, the ultrafiltration membrane prepared according to the invention has excellent anti-biological pollution performance, and the attenuation degree of the membrane flux is low, thus meeting the requirements of practical application.
(6) The preparation method is simple in preparation process and low in cost, the interception performance of the ultrafiltration membrane can be adjusted by controlling the concentration of the polyvinyl alcohol and the surface structure of the coating drying temperature control membrane, and the method is suitable for large-scale industrial production.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a flow diagram of a method of preparing an anti-biofouling ultrafiltration membrane according to one embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
According to one aspect of the invention, a method of preparing an anti-biofouling ultrafiltration membrane is presented. According to an embodiment of the invention, with reference to fig. 1, the method comprises: (1) loading chlorinated derivatives of isocyanuric acid on diatomite so as to obtain modified diatomite; (2) mixing modified diatomite, a polyvinyl alcohol solution and a cross-linking agent, and carrying out ultrasonic treatment to obtain an anti-biological pollution coating solution; (3) and (3) dipping the ultrafiltration basement membrane by using the anti-biological pollution coating liquid, and drying to obtain the anti-biological pollution ultrafiltration membrane. The preparation method is simple to operate, low in cost and suitable for large-scale industrial production, and the prepared ultrafiltration membrane has good hydrophilicity, antibacterial property and flux, is good in biological pollution resistance and longer in service life, wherein the hydrophilicity promotion rate of the ultrafiltration membrane can be improved by more than 10%, and the bacteriostasis rate can be up to more than 93%.
The method for preparing an anti-biofouling ultrafiltration membrane according to the above-described embodiment of the present invention is described in detail with reference to fig. 1.
S100, loading chlorinated derivatives of isocyanuric acid on diatomite to obtain modified diatomite
According to the embodiment of the invention, the inventor finds that the chlorinated derivative of isocyanuric acid is loaded on diatomite to form coating liquid for the surface of an ultrafiltration membrane, so that the antibacterial performance of the surface of the membrane can be improved on one hand, and on the other hand, the diatomite is used as a carrier of an antibacterial agent, so that the contact specific surface area of the antibacterial agent can be increased, the antibacterial agent can be slowly controlled and released, and the antibacterial efficiency and the antibacterial time are improved; meanwhile, flux attenuation caused by coating of a polyvinyl alcohol hydrophilic layer on the surface of the ultrafiltration membrane can be relieved.
According to an embodiment of the present invention, the loading amount of the chlorinated derivative of isocyanuric acid in the modified diatomite may be 4 to 8 wt%, for example, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt% or 8 wt%, and the inventors found that, if the loading amount of the chlorinated derivative of isocyanuric acid is too small, the amount of diatomite required to achieve a better antibacterial property is increased, the mechanical property of the functional layer formed on the surface of the ultrafiltration bottom film may be affected due to the increased amount of the inorganic material, and more importantly, the dispersibility of the diatomite in the polyvinyl alcohol solution is poor, and if the amount of the diatomite is increased, the chlorinated derivative of isocyanuric acid is likely to aggregate and agglomerate in the subsequently formed anti-biological contamination coating solution, and the antibacterial effect is affected due to uneven distribution of the chlorinated derivative of isocyanuric acid in the ultrafiltration membrane; further, since the chlorinated derivatives of isocyanuric acid generally have strong oxidizing property, if the loading amount of the chlorinated derivatives of isocyanuric acid in the diatomite is too large, the addition amount of the antibacterial agent is too large, and further, the ultrafiltration membrane can be damaged, the service life of the membrane is influenced, and if the loading capacity of the chlorinated derivative of the isocyanuric acid is too large, the amount of the carrier required on the premise of the same addition amount of the antibacterial agent is less, so that the chlorinated derivative of the isocyanuric acid is not beneficial to uniform dispersion of the chlorinated derivative of the isocyanuric acid in the coating liquid, and the effect of relieving flux attenuation caused by coating a polyvinyl alcohol hydrophilic layer on the surface of the ultrafiltration membrane is not obvious.
According to another embodiment of the present invention, the chlorinated derivatives of isocyanuric acid used in the present invention are not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the chlorinated derivatives of isocyanuric acid may include at least one selected from sodium trichloroisocyanurate, trichloroisocyanuric acid, sodium dichloroisocyanurate and dichloroisocyanuric acid, wherein the chlorinated derivatives of isocyanuric acid are a new type of disinfectant meeting the internationally recognized disinfection standards, and have the advantages of broad-spectrum disinfection, low toxicity, easy degradation, non-flammability, easy storage and transportation, low-concentration, i.e. high-efficiency disinfection, etc., and are the upgrading and upgrading products of the traditional disinfectants such as sodium hypochlorite, chlorine dioxide, etc., which are widely used in the fields of military field disinfection, swimming pool disinfection, water body disinfection, etc., and the chlorinated derivatives of isocyanuric acid are not only easily available as the disinfectant, but also has the advantages of good sterilization effect, high safety and the like.
According to another embodiment of the present invention, the mesh number of the diatomaceous earth used in the present invention may be 1000 to 2000 mesh, for example, 1250 mesh, 1340 mesh or 2000 mesh, and the inventors found that when the mesh number of the diatomaceous earth is less than 1000 mesh, the diatomaceous earth has low porosity and has insignificant effect on alleviating attenuation of membrane flux, and when the mesh number of the diatomaceous earth is greater than 2000 mesh, the diatomaceous earth has small particle size and is easy to block the ultrafiltration membrane pores.
According to another embodiment of the present invention, diatomaceous earth may be mixed with a chlorinated derivative solution of isocyanuric acid in advance, and stirred and filtered; and roasting the filtered product to obtain the modified diatomite, so that the chlorinated derivative of isocyanuric acid can be uniformly loaded on the diatomite. The stirring conditions are not particularly limited, and those skilled in the art can select the stirring conditions according to actual needs, for example, the stirring conditions can be at a rotation speed of 250 to 400r/min for 0.5 to 2 hours, for example, the stirring conditions can be at a rotation speed of 300r/min for 1 hour, so that the sufficient and uniform mixing of the diatomite and the chlorinated derivative solution of isocyanuric acid can be facilitated; further, the temperature of the roasting treatment may be 80 to 150 ℃, for example, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃, and the roasting time may be 1 to 4 hours, for example, 2 hours or 3 hours, and the inventors found that if the roasting temperature is too low, the required roasting time is long, and the efficiency is low, and the roasting efficiency, the roasting effect and the roasting cost can be better considered by adopting the roasting conditions.
S200, mixing the modified diatomite, the polyvinyl alcohol solution and the cross-linking agent, and performing ultrasonic treatment to obtain the anti-biological pollution coating liquid
According to the embodiment of the invention, the inventor finds that the hydrophilicity of the surface of the ultrafiltration membrane can be improved by using polyvinyl alcohol, the loss of free polyvinyl alcohol in the operation process of the membrane can be prevented by using a cross-linking agent, and the stability of the polyvinyl alcohol on the surface of the membrane can be improved; further, ultrasonic treatment can be used for improving the uniform dispersion of the diatomite particles in the polyvinyl alcohol solution and preventing the diatomite particles from agglomerating and precipitating. The modified diatomite, the polyvinyl alcohol solution and the cross-linking agent may be mixed and stirred for a period of time, and then treated with an ultrasonic intensity of 15 to 25 kHz for 5 to 15min, for example, the mixture may be stirred at a speed of 500r/min for 5min, and then treated with an ultrasonic intensity of 20 kHz for 10min, thereby further improving the uniformity and stability of the anti-biofouling coating solution.
According to an embodiment of the present invention, in the polyvinyl alcohol solution, the molecular weight of the polyvinyl alcohol may be not less than 50000, and the concentration of the polyvinyl alcohol may be 0.05 to 0.2 wt%, for example, may be 0.05 wt%, 0.08 wt%, 0.1 wt%, 0.12 wt%, 0.14 wt%, 0.16 wt%, 0.18 wt%, or 0.2 wt%, etc., and the inventors found that, if the molecular weight of the polyvinyl alcohol in the polyvinyl alcohol solution is not less than 50000, the higher the molecular weight is, the stronger the adhesiveness of the polyvinyl alcohol is, and when the molecular weight is less than 50000, the coating solution may hardly satisfy the requirement for the adhesive property of the film; further, when the concentration of the polyvinyl alcohol solution is lower than 0.05%, the hydrophilicity improvement effect on the ultrafiltration membrane is not obvious, and when the concentration of the polyvinyl alcohol solution is higher than 0.2 wt%, a very compact surface coating is formed, although the rejection rate is high, the flux of the ultrafiltration membrane is greatly attenuated.
According to still another embodiment of the present invention, the modified diatomaceous earth may be present in the anti-biofouling coating solution in an amount of 0.5 to 2 wt%, for example, 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.4 wt%, 1.6 wt%, 1.8 wt%, or 2 wt%, and the inventors have found that if the modified diatomaceous earth is present in an excessively low concentration, the content of the chlorinated derivative of the isocyanuric acid as the antibacterial agent is also small, and the effect of improving the antibacterial activity of the ultrafiltration membrane is not significant; meanwhile, flux attenuation caused by coating a polyvinyl alcohol hydrophilic layer on the surface of the ultrafiltration membrane is difficult to relieve; if the concentration of the modified diatomite is too high, on one hand, too much chlorinated derivative of isocyanuric acid can be introduced, the ultrafiltration membrane can be damaged due to too strong oxidability of the antibacterial agent, the service life of the membrane is influenced, and on the other hand, the mechanical property of the functional membrane layer can be influenced due to too much inorganic material; on the other hand, the diatomite is not easy to disperse in the polyvinyl alcohol solution, and if the concentration of the diatomite is too high, the diatomite is aggregated and agglomerated in the anti-biological pollution coating solution, so that the chlorinated derivative of the isocyanuric acid is unevenly distributed in the ultrafiltration membrane, and the antibacterial effect of the ultrafiltration membrane is influenced. According to the invention, by controlling the concentration range of the modified diatomite in the anti-biological pollution coating liquid, the ultrafiltration membrane has better antibacterial property and lower flux attenuation, the uniformity and stability of the membrane can be ensured, and the service life of the membrane is prolonged. Furthermore, the concentration of the chlorinated derivative of the isocyanuric acid in the anti-biological pollution coating liquid can be 0.02-0.05 wt%, so that the damage to the ultrafiltration membrane caused by excessive usage of the antibacterial agent can be further avoided on the basis of ensuring the antibacterial property of the ultrafiltration membrane, and the service life of the ultrafiltration membrane is ensured.
According to another embodiment of the present invention, the concentration of the cross-linking agent in the anti-biological coating solution may be 0.5 to 1 wt%, for example, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, or 1 wt%, etc., and the inventors found that free polyvinyl alcohol may be lost during the operation of the membrane, and that the problem may be effectively prevented by further adding the cross-linking agent, so that the stability of polyvinyl alcohol on the surface of the membrane is improved, and the hydrophilic performance of the membrane is more stable during long-term use, but if the amount of the cross-linking agent is too small, the effect of preventing the loss of free polyvinyl alcohol during the operation of the membrane is not significant, and if the amount of the cross-linking agent is too large, the anti-biological coating solution is easily gelled and is difficult to be coated on the ultrafiltration bottom membrane. It should be noted that the crosslinking agent used in the present invention may be an inorganic crosslinking agent, wherein the kind of the inorganic crosslinking agent is not particularly limited, and those skilled in the art may select the inorganic crosslinking agent according to actual needs as long as the loss of the free polyvinyl alcohol during the operation of the membrane can be prevented, and for example, the inorganic crosslinking agent may include at least one selected from the group consisting of sodium sulfate, zinc sulfate and boric acid.
S300, adopting the anti-biological pollution coating liquid to dip and dry the ultrafiltration basement membrane to obtain the anti-biological pollution ultrafiltration membrane
According to the embodiment of the invention, more anti-biological pollution coating liquid can be attached to the ultrafiltration bottom film through dipping treatment, so that a functional layer with better anti-biological pollution capability is formed on the ultrafiltration bottom film. The time of the dipping treatment can be 10 to 20s, for example, 11s, 13s, 15s or 19s, and the dipping time can be controlled to further ensure that the anti-biological pollution coating liquid which can form a film sufficiently and has the film thickness and the strength meeting the requirements of the ultrafiltration membrane is adhered on the ultrafiltration bottom film. Further, drying can be performed in a drying manner, wherein the temperature can be 40-80 ℃, for example, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃ and the like, and the drying time can be 3-10 min, for example, 5min or 6min and the like, and the inventors find that the higher the drying temperature is, the more compact the surface of the formed ultrafiltration membrane is, the higher the rejection rate is, but the membrane flux can be reduced, and meanwhile, if the drying temperature is too high, the deformation of the non-woven fabric support layer of the ultrafiltration membrane can be caused, and if the drying temperature is too low, sufficient drying is difficult to achieve, and the process is time-consuming and low in efficiency.
According to a specific embodiment of the present invention, the kind of the ultrafiltration membrane is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the ultrafiltration membrane may be a polysulfone ultrafiltration membrane, a polyethersulfone ultrafiltration membrane, or a PVDF ultrafiltration membrane.
In summary, the method for preparing the anti-biological contamination ultrafiltration membrane according to the above embodiment of the present invention has the following beneficial effects: (1) the surface of the ultrafiltration membrane is coated with polyvinyl alcohol, so that the hydrophilic performance of the ultrafiltration membrane can be greatly improved, and the biological adhesion resistance of the surface of the membrane is improved; the cross-linking agent is added into the polyvinyl alcohol solution, so that the adhesion between the polyvinyl alcohol and the surface of the membrane can be improved, and the loss of a polyvinyl alcohol hydrophilic layer in the running process of the membrane is avoided. (2) The polyethylene hydrophilic layer is mixed with the porous diatomite inside, so that the water permeability of the ultrafiltration membrane is improved, and the flux attenuation caused by coating the polyvinyl alcohol hydrophilic layer on the surface of the ultrafiltration membrane can be relieved. (3) The chlorinated derivative of the bactericide isocyanuric acid in the polyvinyl alcohol hydrophilic layer enables the ultrafiltration membrane to have excellent antibacterial performance, and the surface of the membrane can resist microbial growth. (4) The chlorinated derivative of the bactericide isocyanuric acid is loaded on the porous diatomite, so that compared with the method of directly mixing the chlorinated derivative of the bactericide isocyanuric acid into the hydrophilic layer, on one hand, the contact specific surface area of the bactericide can be increased, and the antibacterial efficiency is improved; on the other hand, the sustained-release antibacterial agent can play a role in slowly releasing and controlling the bactericide, and prolong the antibacterial time. (5) The invention considers the anti-biological adhesion and the antimicrobial growth performance of the membrane surface, the ultrafiltration membrane prepared according to the invention has excellent anti-biological pollution performance, and the attenuation degree of the membrane flux is low, thus meeting the requirements of practical application. (6) The preparation method is simple in preparation process and low in cost, the interception performance of the ultrafiltration membrane can be adjusted by controlling the concentration of the polyvinyl alcohol and the surface structure of the coating drying temperature control membrane, and the method is suitable for large-scale industrial production.
According to yet another aspect of the present invention, an anti-biofouling ultrafiltration membrane is presented. According to the embodiment of the invention, the anti-biological pollution ultrafiltration membrane is prepared by adopting the method for preparing the anti-biological pollution ultrafiltration membrane. Compared with the prior art, the ultrafiltration membrane has good hydrophilicity, antibacterial property and flux, better biological pollution resistance and longer service life. It should be noted that the features and effects described for the above method for preparing an anti-biofouling ultrafiltration membrane are also applicable to the anti-biofouling ultrafiltration membrane, and are not described in detail herein.
The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
(1) 1000 meshes of diatomite is dissolved in a sodium trichloroisocyanurate solution with the mass concentration of 0.03 percent, stirred for 1 hour at the rotating speed of 300r/min, filtered and roasted at high temperature to obtain the diatomite particles loaded with the sodium trichloroisocyanurate. The high-temperature roasting temperature is 100 ℃, and the high-temperature roasting time is 2 hours.
(2) And (2) dissolving the sodium trichloroisocyanurate-loaded diatomite particles obtained in the step (1) and sodium sulfate in a polyvinyl alcohol solution with the mass concentration of 0.1% and the molecular weight of 10 ten thousand. Wherein, the mass concentrations of the diatomite particles and the sodium sulfate in the polyvinyl alcohol solution are respectively 0.8 percent and 0.5 percent. The mixed solution is firstly stirred for 5min at the rotating speed of 500r/min and then treated for 10min under the ultrasonic intensity of 20 kilohertz to obtain the anti-biological pollution coating solution.
(3) And (3) immersing the polysulfone base membrane into the biological pollution-resistant coating liquid obtained in the step (2) for 10s, and then drying at the temperature of 60 ℃ for 5min to obtain the biological pollution-resistant polysulfone ultrafiltration membrane.
And respectively testing the hydrophilicity and the antibacterial property of the ultrafiltration membrane by adopting a contact angle measuring method and a flask oscillation method. According to the contact angle measurement result, the contact angle of the anti-biological pollution polysulfone ultrafiltration membrane is reduced from 67 degrees to 58 degrees compared with the blank polysulfone ultrafiltration membrane. According to the test result of the flask oscillation method, the bacteriostasis rate of the anti-biological pollution ultrafiltration membrane on escherichia coli reaches more than 93%.
Example 2
(1) And (2) dissolving 2000-mesh diatomite in 0.04% sodium trichloroisocyanurate solution, stirring at the rotating speed of 300r/min for 1h, filtering, and roasting at high temperature to obtain the diatomite particles loaded with the sodium trichloroisocyanurate. The high-temperature roasting temperature is 100 ℃, and the high-temperature roasting time is 2 hours.
(2) And (2) dissolving the sodium trichloroisocyanurate-loaded diatomite particles obtained in the step (1) and zinc sulfate in a polyvinyl alcohol solution with the mass concentration of 0.2% and the molecular weight of 10 ten thousand. Wherein, the mass concentrations of the diatomite particles and the zinc sulfate in the polyvinyl alcohol solution are respectively 1 percent and 0.8 percent. The mixed solution is firstly stirred for 5min at the rotating speed of 500r/min and then treated for 10min under the ultrasonic intensity of 20 kilohertz to obtain the anti-biological pollution coating solution.
(3) And (3) immersing the polyether sulfone base membrane into the biological pollution-resistant coating liquid obtained in the step (2) for 10s, and then drying at the temperature of 80 ℃ for 5min to obtain the biological pollution-resistant polyether sulfone ultrafiltration membrane.
And respectively testing the hydrophilicity and the antibacterial property of the ultrafiltration membrane by adopting a contact angle measuring method and a flask oscillation method. According to the contact angle measurement result, the contact angle of the anti-biological contamination polyethersulfone ultrafiltration membrane is reduced from 60 degrees to 52 degrees compared with that of a blank polyethersulfone ultrafiltration membrane. According to the test result of the flask oscillation method, the bacteriostasis rate of the anti-biological pollution ultrafiltration membrane on escherichia coli reaches more than 95%.
Example 3
(1) The preparation method comprises the steps of dissolving 2000-mesh diatomite in 0.05% sodium dichloroisocyanurate solution, stirring for 1h at the rotating speed of 300r/min, filtering, and roasting at high temperature to obtain the diatomite particles loaded with the sodium dichloroisocyanurate. The high-temperature roasting temperature is 100 ℃, and the high-temperature roasting time is 2 hours.
(2) Dissolving the sodium dichloroisocyanurate-loaded diatomite particles obtained in the step (1) and boric acid in a polyvinyl alcohol solution with the mass concentration of 0.1% and the molecular weight of 10 ten thousand. Wherein, the mass concentrations of the diatomite particles and the boric acid in the polyvinyl alcohol solution are respectively 1.5 percent and 0.5 percent. The mixed solution is firstly stirred for 5min at the rotating speed of 500r/min and then treated for 10min under the ultrasonic intensity of 20 kilohertz to obtain the anti-biological pollution coating solution.
(3) And (3) immersing a polyvinylidene fluoride base membrane into the biological pollution-resistant coating liquid obtained in the step (2) for 20s, and then drying at the temperature of 80 ℃ for 5min to obtain the biological pollution-resistant polyvinylidene fluoride ultrafiltration membrane.
And respectively testing the hydrophilicity and the antibacterial property of the ultrafiltration membrane by adopting a contact angle measuring method and a flask oscillation method. According to the contact angle measurement result, the contact angle of the anti-biological pollution polyvinylidene fluoride ultrafiltration membrane is reduced from 75 degrees to 67 degrees compared with that of a blank polyvinylidene fluoride ultrafiltration membrane. According to the test result of the flask oscillation method, the bacteriostasis rate of the anti-biological pollution ultrafiltration membrane on escherichia coli reaches more than 95%.
Results and conclusions:
it can be seen from the comprehensive examples 1 to 3 that compared with a blank ultrafiltration membrane, the contact angle of the ultrafiltration membrane obtained by the preparation method is obviously reduced, the hydrophilicity of the membrane is obviously improved, the promotion rate is generally over 10%, and the bacteriostasis rate of the ultrafiltration membrane can reach over 93%.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method of making an anti-biofouling ultrafiltration membrane, comprising:
(1) loading chlorinated derivatives of isocyanuric acid on diatomite so as to obtain modified diatomite;
(2) mixing the modified diatomite, the polyvinyl alcohol solution and the cross-linking agent, and carrying out ultrasonic treatment to obtain an anti-biological pollution coating solution;
(3) and (3) dipping the ultrafiltration basement membrane by using the biological pollution resistant coating liquid, and drying to obtain the biological pollution resistant ultrafiltration membrane.
2. The method of claim 1, wherein step (1) satisfies at least one of the following conditions:
the loading capacity of the chlorinated derivative of the isocyanuric acid in the modified diatomite is 4-8 wt%;
the chlorinated derivative of isocyanuric acid comprises at least one selected from sodium trichloroisocyanurate, trichloroisocyanuric acid, sodium dichloroisocyanurate and dichloroisocyanuric acid;
the mesh number of the diatomite is 1000-2000 meshes.
3. The method of claim 1 or 2, wherein step (1) comprises: mixing diatomite with the chlorinated derivative solution of isocyanuric acid, stirring and filtering; and roasting the filtered product to obtain the modified diatomite.
4. The method according to claim 3, wherein the temperature of the roasting treatment is 80 to 150 ℃.
5. The method according to claim 1 or 4, wherein step (2) satisfies at least one of the following conditions:
in the polyvinyl alcohol solution, the molecular weight of the polyvinyl alcohol is not lower than 50000, and the concentration of the polyvinyl alcohol is 0.05-0.2 wt%;
in the anti-biological pollution coating liquid, the concentration of the modified diatomite is 0.5-2 wt%;
in the anti-biological pollution coating liquid, the concentration of the cross-linking agent is 0.5-1 wt%.
6. The method as claimed in claim 5, wherein the concentration of the chlorinated derivative of isocyanuric acid in the anti-biofouling coating liquid is 0.02 to 0.05 wt%; and/or the presence of a gas in the gas,
the crosslinking agent is an inorganic crosslinking agent, and the inorganic crosslinking agent comprises at least one of sodium sulfate, zinc sulfate and boric acid.
7. The method according to claim 1 or 6, wherein in step (3), the ultrafiltration membrane base membrane is a polysulfone ultrafiltration membrane, a polyethersulfone ultrafiltration membrane or a PVDF ultrafiltration membrane.
8. The method according to claim 7, wherein in the step (3), the dipping time is 10-20 s.
9. The method according to claim 1 or 8, wherein in the step (3), the drying temperature is 40 to 80 ℃ and the drying time is 3 to 10 min.
10. An anti-biofouling ultrafiltration membrane prepared by the method of any one of claims 1 to 9.
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| CN106172437A (en) * | 2016-07-07 | 2016-12-07 | 江苏辉丰农化股份有限公司 | A kind of microbicide compositions |
| CN107213804A (en) * | 2017-07-18 | 2017-09-29 | 宁波日新恒力科技有限公司 | A kind of antibacterial reverse osmosis composite membrane and its preparation method and application |
| CN110870480A (en) * | 2019-12-12 | 2020-03-10 | 潘虹 | Bactericidal composition containing hymexazol and dichloroisocyanuric acid |
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