CN106621850A - Antibacterial composite nanofiltration membrane, and preparation method and application thereof - Google Patents
Antibacterial composite nanofiltration membrane, and preparation method and application thereof Download PDFInfo
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- CN106621850A CN106621850A CN201510711256.8A CN201510711256A CN106621850A CN 106621850 A CN106621850 A CN 106621850A CN 201510711256 A CN201510711256 A CN 201510711256A CN 106621850 A CN106621850 A CN 106621850A
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Abstract
The invention relates to an antibacterial composite nanofiltration membrane. The antibacterial composite nanofiltration membrane comprises a porous supporting layer and a polyamide functional layer, wherein the polyamide functional layer comprises attapulgite-nanometer silver composite inorganic powder; and in the attapulgite-nanometer silver composite inorganic powder, the mass ratio of silver to attapulgite is 10/100 to 100/100, and the particle size of the nanometer silver is 3 to 100 nm. The invention also relates to a preparation method and an application of the above-mentioned antibacterial composite nanofiltration membrane. The antibacterial composite nanofiltration membrane provided by the invention has the advantages of high flux, high rejection rate, good antibacterial properties, stable membrane structure, high operation efficiency and long service life.
Description
Technical field
The present invention relates to technical field of membrane separation, is to be related to a kind of antibacterial Nano filtering composite membrane furtherly.This
Invention further relates to the preparation method and application of the antibacterial Nano filtering composite membrane.
Background technology
NF membrane is a kind of novel separation film of the aperture between reverse osmosis membrane and milipore filter, is received because it has
It is how electrically charged on the membrane aperture of meter level, film, it is allowed to which that low molecule salt passes through the organic matter of rear retention higher molecular weight
And multivalent ion, with unique separating property, higher separation accuracy.Compared with other seperation films, nanofiltration
Film has that membrane flux is bigger, process infiltration is forced down, low, system power is wanted to select to separate ion, operating pressure
Seek low feature.At present Nanofiltration-membrane technique be widely used in water soften and brackish water desalination, drink water purifying,
The fields such as feed separation is purified and concentrated, wastewater treatment and Treated sewage reusing, clean manufacturing, achieve good Jing
Ji and social benefit.
However, the fouling membrane of NF membrane has seriously constrained the large-scale application of NF membrane and has promoted, especially in height
Application in the fields such as contamination data analysis, Water circulation and chemical separating.Fouling membrane will result directly in the infiltration of film
Flux is remarkably decreased, and membrane separation efficiency declines, and the production efficiency of system is reduced, operating cost and energy consumption increase；
Fouling membrane will also cause the frequent clean of system, device to run well, producing water water quality is deteriorated, membrane lifetime drop
The problems such as frequent replacing of low and film.
Pollution is divided into inorganic matter pollution, Organic Pollution, particle and colloidal sol and pollutes and micro- according to polluter property
Biological pollution, wherein microorganism pollution form thin by the microorganism adsorption being present in water in the surface of seperation film
Produced by biomembrane, remove extremely difficult.In order to improve the antifouling property of NF membrane, researcher is anti-
Pollution NF membrane research and development aspect has carried out substantial amounts of research work, mainly to be coated by film surface,
The Chemical Physics method such as surface chemical modification, surface grafting, changes the chemical physical property of composite membrane, such as surface
Hydrophily, surface roughness and surface charge etc., improve the antifouling property of NF membrane.Existing antimicrobial dirt
Focus are coated antibacterial by the research of dye seperation film on the surface grafting of composite membrane, surface treatment, surface substantially
Agent.As document report in the polyamide macromolecule desalination layer by surface coating technique compound one layer there is antibacterial
The sericin of function so that the hydrophily and bacteriostasis property of complex reverse osmosis membrane is greatly enhanced, with very
Good stable against biological contamination performance.Document " a kind of complex reverse osmosis membrane of microbial contamination resistance and preparation method thereof " exists
The modified polynary amine aqueous solution of useful nano inorganic antibacterial granule and polynary acyl chloride reaction on ground floor polyamide surface layer
The second layer polyamide surface layer containing nano inorganic antibacterial granule for preparing, improves the resistance to microorganism of reverse osmosis membrane
Pollutant performance, and the thickness on reverse osmosis membrane surface is increased, the performance that the mechanical resistant of reverse osmosis membrane is damaged is enhanced,
The service life of counter-infiltration is extended, contained inorganic antibacterial particle includes that silver ion class antiseptic, copper ion class resist
Microbial inoculum, Nano Silver etc..Kill by the solidification of hydroxyl group polymer and containing hydroxyl nanometer in document report
The crosslinking of bacterium particulate, through high-temperature process, on reverse osmosis membrane surface the fine and close netted coating of crosslinking is formed, sterilized micro-
Grain is uniformly distributed and is crosslinked with coating in face, had not only improved antibacterial ability but also had extended antibacterial timeliness.But
During composite membrane use, coat or the second layer aramid layer containing antiseptic can gradually ablation,
Anti-microbial property is caused to decline.There is document to disclose and the trichloro-benzenes oxygen formyl chloride of biocidal property group is added into organic phase
In, by interfacial polymerization so that the group is connected in composite membrane polymer mesh structure in the form of covalent bond, institute
The film of preparation has strong biocidal property, is difficult the antibacterial group during NF membrane use and is lost in.There is document to disclose
By the way that the desalination layer of reverse osmosis composite membrane is soaked in the persulfate solution of pbz polymer antibacterial material, then
Drying, obtains good antibacterial antioxidative composite reverse osmosis membrane.Although these methods can be greatly improved compound
The anti-inorganic matter pollution of film and the performance of anti-Organic Pollution, but due to without the accompanying bacterium of killing, suppressing it
The function of breeding, therefore suppress caused by the institute such as pollution or the secondary pollution that is induced by it due to biogenetic derivation
The effect that membrane property is reduced is poor.
At present, to the research of NF membrane resisting microbial contamination also in the starting stage.Microorganism pollution is still to be received
The problem of most common and most serious, has had a strong impact on the application and popularization of NF membrane in filter membrane application.Thus, such as
What improves the antibacterial and anti-microbial property of existing NF membrane, is to improve NF membrane operational efficiency, extend its service life
Key.
The content of the invention
In order to solve the problems of the prior art, the invention provides a kind of antibacterial composite nanometer filtering film, its preparation side
Method and its application.During interfacial polymerization prepares composite nanometer filtering film, by adding in organic phase solution
Plus homemade attapulgite-nanometer silver antimicrobial composite inorganic powder, after water phase and the polymerization of organic phase monomer interface, obtain
To polyamide functional layer in contain homodisperse attapulgite-nanometer silver antimicrobial composite powder, prepared answers
Closing NF membrane can be on the basis of keeping flux and rejection suitable, and its anti-microbial property is improved.
According to an aspect of the invention, there is provided a kind of antibacterial composite nanometer filtering film, including：Porous support layer and
Polyamide functional layer, includes attapulgite-Nano Silver composite inorganic powder, described in the polyamide functional layer
In composite inorganic powder, silver is 10/100-100/100 with the mass ratio of attapulgite, and the particle diameter of Nano Silver is
3-100nm。
According to antibacterial composite nanometer filtering film of the present invention, in the composite inorganic powder, it is preferably silver-colored with it is concavo-convex
The mass ratio of rod soil is 30/100-80/100.
It is recessed in the composite inorganic powder containing Nano Silver according to antibacterial composite nanometer filtering film of the present invention
Convex rod soil has in bar-shaped or filamentary structure and has hollow nanoscale duct, the rod crystalline substance diameter of attapulgite
For 10-80nm.
According to the present invention provide NF membrane, the attapulgite-Nano Silver composite inorganic powder as antiseptic,
In being dispersed in the polyamide functional layer, attapulgite-Nano Silver can preferably give play to anti-microbial property, make
Obtain composite nanometer filtering film anti-microbial property to improve a lot.
According to another aspect of the present invention, a kind of method for preparing antibacterial composite nanometer filtering film is additionally provided, is wrapped
Include：
(1) attapulgite and water are mixed and made into attapulgite suspension；
(2) silver nitrate is added in the attapulgite suspension described in step (1), is then stirred heat
Process；
(3) by step (2) heat treatment after attapulgite suspension carry out spray drying obtain attapulgite answer
Close powder；
(4) attapulgite clay compounded powder obtained in step (3) is carried out into roasting, obtains attapulgite-Nano Silver
Composite inorganic powder；
(5) attapulgite obtained in step (4)-Nano Silver composite inorganic powder is dispersed in containing at least
In the organic solution of the compound of two acid chloride groups, mixed liquor is obtained；
(6) porous support layer is contacted with the aqueous solution of the compound containing at least two amino, is then removed many
The remaining aqueous solution；
(7) mixed liquor obtained in porous support layer and the step (5) Jing after step (6) process is connect
Touch, the polyamide functional layer comprising attapulgite-Nano Silver composite inorganic powder is formed on the porous support layer
Composite nanometer filtering film.
(8) step (7) gained composite nanometer filtering film is heat-treated, washes and obtain final product containing attapulgite-Nano Silver
The composite nanometer filtering film of composite inorganic powder.
In one preferred embodiment of the method provided according to the present invention, the attapulgite is commercially available concavo-convex
Rod is native through thermal activation and the attapulgite of decentralized processing, without the need for acid activation process step.Using through thermal activation
And the attapulgite of decentralized processing can improve its dispersiveness in the solution.Thermal activation and decentralized processing can be adopted
Usual way in prior art.For example preferably according to the following steps：A certain amount of attapulgite is put into Muffle
In stove, the roasting 30min at 400 DEG C；Above-mentioned roasting attapulgite is put into ball mill, in 500rpm
Lower ball milling 3h；The attapulgite of a certain amount of above-mentioned process is weighed, to be added and be configured to attapulgite quality after distilled water
Concentration is 5% suspension, first mechanical agitation 1h, then ultrasonication 30min；Then it is outstanding by what is handled well
Supernatant liquid is centrifuged by centrifuge under 12000r/min；Supernatant liquor is finally discarded, thermal activation is obtained final product and is divided
Dissipate the attapulgite for processing.
According to the method that the present invention is provided, the decentralized processing of the attapulgite can be using of the prior art normal
Rule method, for example：Ultrasonic disperse, mechanical agitation dispersion (such as ball milling dispersion, high-speed stirred dispersion) etc..
One specific embodiment of the method provided according to the present invention, the attapulgite suspension described in step (1)
In, the concentration of attapulgite is less than 10wt%, preferred 1-10wt%.
One specific embodiment of the method provided according to the present invention, in the step (2), the nitric acid
Silver is 17/100-170/100 with the mass ratio of attapulgite, and preferred preferred mass ratio is 50/100-135/100.Institute
Heat treatment temperature is stated for more than 50 DEG C, preferably 50-90 DEG C, the heat treatment time is more than 1h, preferably
1h-10h.Stirring heat treatment in step (2), enables to carbanion and the silver contained in attapulgite
Ionic reaction generates silver carbonate, and the silver carbonate of generation adsorbs on the surface of attapulgite.
One specific embodiment of the method provided according to the present invention, in step (3), the spray drying
Temperature be 150-200 DEG C.In step (4), the roasting can be conventional method of roasting, for example will be concavo-convex
Rod soil composite powder is in Muffle kiln roasting.The temperature of the roasting is 200-500 DEG C；The too high meeting of sintering temperature
Make attapulgite duct cave in so as to cause adsorption capacity to be deteriorated, and be easily caused attapulgite reunion, temperature mistake
It is low, Nano Silver simple substance cannot be obtained.The roasting time is more than 5min, preferably 5-180min.It is made
In the composite inorganic powder (or claiming attapulgite-Nano Silver composite inorganic powder) containing Nano Silver for obtaining, concave convex rod
Native area load has Nano silver grain, and the particle diameter of silver is 3-100nm.Obtained attapulgite-Nano Silver is combined
In inorganic powder, silver is 10/100-100/100 with the mass ratio of attapulgite, and preferred mass ratio is
30/100-80/100.Obtained attapulgite-Nano Silver composite inorganic powder is used as antiseptic.The present invention
In step (1)-(4) to prepare the antiseptic the step of.In patent application CN201510262409.5,
It is incorporated into herein about the content of attapulgite-Nano Silver composite inorganic powder.And confirmed by wide-angle XRD,
In the attapulgite clay compounded powder obtained after spray drying, silver nitrate reacts and finishes, obtains silver carbonate.
In the present invention, silver nitrate and attapulgite are stirred at a certain temperature after mixing, needed dry by spraying
Dry mode obtains treating the composite powder of roasting.Using other sides for example filtered and be dried with convection oven
Method, it is impossible to obtain and be spray-dried identical technique effect.Inventors believe that in the Nano Silver for preparing the present invention
During attapulgite clay compounded powder, attapulgite suspension and silver nitrate solution mixing are stirred through heating
Mix, the carbanion in attapulgite in carbonate can be promoted to dissolve and silver carbonate suction is generated with silver ion reaction
It is attached to attapulgite's surface.In spray-drying process, unreacted silver nitrate solution and solution is dispersed in
In attapulgite plus thermal current in the presence of can further react generation silver carbonate.By wide-angle
XRD confirms that in the attapulgite clay compounded powder obtained after spray drying, silver nitrate reacts and finishes, obtains
To silver carbonate.During follow-up baking heat, silver carbonate is decomposed into silver-colored simple substance, finally with the shape of Nano Silver
Formula is equably supported on attapulgite's surface.
Attapulgite is natural monodimension nanometer material, with very big specific surface area, absorption property and chemical reaction
The nano effects such as activity so that the Nano Silver formed after roasting can firmly adsorb in attapulgite's surface, this
Sample forms equally distributed nano level Argent grain in attapulgite's surface.Although by the side for directly heating calcining
Method decomposes silver nitrate can also obtain Nano Silver simple substance, but its decomposition temperature is high, high energy consumption, and preparation is received
Rice silver particles are susceptible to reunite, and particle diameter is than larger.By heating, then it is spray-dried and causes silver nitrate
Fully react with the contained carbonate in attapulgite the inside, then can make less than roasting under silver nitrate decomposition temperature
Nano Silver is obtained, the environmental pollution brought using reducing agent or other chemical reactions, and carbonic acid is not only avoid
The decomposition temperature of silver is relatively low, and roasting at relatively low temperatures can generate silver-colored simple substance, and silver-colored simple substance is with nanometer
The form of silver uniformly absorption in attapulgite's surface, this absorption attapulgite's surface nano silver active very
Greatly, the silver ion with antibacterial effect can be slowly released, and nano-Ag particles are combined jail with attapulgite
Gu.
Another specific embodiment of the invention, it is described to contain at least two acyls in the step (5)
The compound of cl radical includes the multifunctional acyl chlorides of aromatic series, the multifunctional acyl chlorides of aliphatic and alicyclic multifunctional acyl chlorides
In at least one.In a preferred embodiment, the compound for containing at least two acid chloride groups includes
Paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride, biphenyl dimethyl chloride, benzene-disulfo-chloride,
The formyl chloride of benzene three, the acyl chlorides of fourth three, succinyl chloride, penta 3 acyl chlorides, glutaryl chlorine, oneself three acyl chlorides, Adipoyl Chloride,
Sebacoyl chloride, the acyl chlorides of the last of the ten Heavenly stems three, the acyl chlorides of cyclopropane three, cyclobutane diacid chloride, the acyl chlorides of cyclobutane four, pentamethylene two
Acyl chlorides, the acyl chlorides of pentamethylene three, the acyl chlorides of pentamethylene four, hexamethylene diacid chloride, the acyl chlorides of hexamethylene three, hexamethylene four
At least one in acyl chlorides, tetrahydrofuran diacid chloride and the acyl chlorides of tetrahydrofuran four.Above-mentioned multifunctional acyl chlorides can be with
Using one kind, it is also possible to using 2 kinds and more than.Fragrant multifunctional acyl chlorides is preferably used, to obtain high rejection
Functional layer.
Another specific embodiment of the invention, in the step (5), in the organic solution
Organic solvent include n-hexane, hexamethylene, trifluorotrichloroethane, normal heptane, normal octane, toluene, ethylbenzene and
At least one in ISOPAR solvent naphthas.In the organic solution, the chemical combination containing at least two or acid chloride group
The concentration of thing is 0.5-5g/L.The content of the attapulgite-Nano Silver composite inorganic powder is 0.001-0.5g/L,
It is preferred that 0.001-0.1g/L.
According to the present invention, the porous support layer is in the art conventional.For example it is polysulfone porous supporting layer, poly-
At least one in ether sulfone porous support layer, sulfonated polyether porous support layer and polypropylene porous support layer.
Another specific embodiment of the invention, it is described to contain at least two ammonia in the step (6)
The compound of base includes aromatic series polyfunctional amine, aliphatic polyfunctional amine, alicyclic polyfunctional amine and polyhydric alcohol amine
In at least one, it is possible to use wherein a kind, it is also possible to use two or more.Preferably, it is described containing at least
The compound of two amino includes m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine, 1,3,5- triaminobenzenes, 1,2,4-
Triaminobenzene, 3,5- diaminobenzoic acids, 2,4 di amino toluene, 2,4- diamino anisoles, amidol, benzene
Dimethyl-p-phenylenediamine, ethylenediamine, propane diamine, butanediamine, pentanediamine, three (2- aminoethyls) amine, diethylenetriamine,
1,2- DACHs, 1,4- DACHs, piperazine, 1,3- bipiperidine base propane, 4- amino methyl piperazines
At least one in piperazine, monoethanolamine, diethanol amine, hexylene glycol amine and diglycolamine.In the aqueous solution, contain
The concentration of the compound of at least two amino is 1-30g/L.Described amino is reactive amino.
Another specific embodiment of the invention, in the step (6), may be used also in the aqueous solution
With containing surfactant, acid absorbent for generally adopting in the art etc..The surfactant can be cloudy
Ionic surface active agent, cationic surfactant or nonionic surfactant, for example, can select dodecane
Base sodium sulphate, neopelex, DTAB, bay disulfonate acid, Qula are led to
- 100, at least one in 1-METHYLPYRROLIDONE.The acid absorbent is triethylamine, sodium carbonate, bicarbonate
At least one in disodium, sodium phosphate, NaOH, potassium hydroxide.The concentration of the surfactant is preferred
For 0-5g/L.The concentration of the acid absorbent is preferably 0-10g/L.In the step (6), the contact
Time be 5-300s.It is described to remove the unnecessary aqueous solution, for example can be by way of being rolled using squeegee
Carry out.
Another specific embodiment of the invention, in the step (7), the time of the contact is
5-300s, preferred 5-120s.By the contact in this step, interfacial polymerization is carried out.By acid chloride groups and ammonia
The reaction of base, forms polyamide functional layer.In the step (8), the temperature of the heat treatment is 30-120
DEG C, the time of the heat treatment is 1-10min.Amine diffusion velocity can be improved by heat treatment, increase polymerization
The amine content of reaction zone, promotes interface polymerization reaction completely, improves polyamide molecular weight and crosslinking degree.Pass through
Washing, for example, wash, and can remove unreacted monomer.
According to a specific embodiment of the inventive method, the antibacterial in the present invention is prepared by said method
Composite nanometer filtering film.
Compared with prior art, the present invention takes and for self-control antiseptic attapulgite-Nano Silver to be dispersed in organic phase
In, by interfacial polymerization by the functional layer of attapulgite-nano-silver loaded to composite nanometer filtering film.Attapulgite
- Nano Silver can be uniformly scattered in organic solution through ultrasonic disperse process, and the self-control antiseptic for being used is recessed
The convex rod soil-simple energy-conservation of Nano Silver preparation process, anti-microbial property is good, and by interfacial polymerization composite nanometer filter is loaded to
Film functional layer so that the anti-microbial property of composite nanometer filtering film is greatly improved；Prepare and contain attapulgite-nanometer
The method of silver-colored composite antibacterial NF membrane is simple, and reaction condition is gentle；The self-control antiseptic attapulgite for being used-
Nano Silver low production cost, with the basic and wide application prospect of good industrialized production.
According to another aspect of the present invention, above-mentioned antibacterial composite nanometer filtering film or said method system are additionally provided
Application of the standby antibacterial composite nanometer filtering film in UF membrane.Antibacterial composite nanometer filtering film of the invention, not only leads to
Amount is high, rejection is high and anti-microbial property is good, and the Stability Analysis of Structures of film, and operational efficiency is high, long service life.
Specific embodiment
The present invention is described in further detail with reference to embodiments, however, these embodiments are only to provide
It is of the invention by way of illustration and not limitation.
Composite nanometer filter membrane separating property is evaluated：
Salt rejection rate R is defined as：Under the conditions of certain operating pressure, feeding liquid salinity (Cf) and penetrating fluid
Middle salinity (Cp) difference, then divided by feeding liquid salinity.
Water flux is defined as：Under certain operating conditions, the body of the water of per membrane area is passed through in the unit interval
Product, its unit is L/ (m2·h)。
The test condition adopted in the present invention for：Concentration is the Na of 1000ppm2SO4·10H2The O aqueous solution,
Operating pressure is 0.6MPa, and test temperature is 25 DEG C, and pH value of water solution is 6.8.
NF membrane antibacterial effect quantitative determination：
Antibacterial examination criteria：The evaluation third portion of GB/T 20944.3-2008 antibacterial textile performances：Succusion.
Antibacterial NF membrane is cut into the sample of 10mm × 30mm, above-mentioned sample is put into the triangular flask of 150ml,
The Escherichia coli bacteria liquid of 70ml PBSs and 500ul is separately added into, triangular flask is fixed on vibration bed,
24h is swayed with 120r/min.The sample liquid after 500ul vibrations is taken, is made to be carried out after appropriate dilution with PBS
Viable bacteria culture is counted.Simultaneously contrast test is carried out to common NF membrane (not containing antimicrobial component).Sterilizing rate is calculated
It is as follows：
Sterilizing rate (%)=((A-B)/A) × 100
In formula：A-common nanofiltration membrane sample viable count
B-antibacterial nanofiltration membrane sample viable count
Embodiment is raw materials used
Raw materials used in embodiment to be commercially available, attapulgite used in embodiment, rod crystalline substance diameter is in 30-80nm
Between.
In following examples, using, commercially available attapulgite is carried out the concave convex rod of thermal activation and decentralized processing
Soil, comprises the following steps that：A certain amount of attapulgite is put into Muffle furnace, the roasting 30min at 400 DEG C；
Above-mentioned roasting attapulgite is put into ball mill, at 500 rpm ball milling 3h；Weigh a certain amount of above-mentioned
The attapulgite of process, to add and be configured to the suspension that attapulgite mass concentration is 5%, first chance after distilled water
Tool stirs 1h, then ultrasonication 30min；Then the suspension handled well is passed through into centrifuge in 12000r/min
Under be centrifuged；Supernatant liquor is finally discarded, the attapulgite of thermal activation and decentralized processing is obtained final product.
Embodiment 1
The preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent in the present embodiment is comprised the following steps that：(1) claim
The attapulgite (AT) of thermal activation and the decentralized processing of learning from else's experience, is configured to the water that attapulgite mass concentration is 1%
Suspension, (2) and then by silver nitrate solution (AgNO3/ AT=17/100) it is added to attapulgite suspension,
At 50 DEG C, magnetic agitation 1h, (3) are again spray-dried attapulgite suspension at 200 DEG C,
Collect spray-dried obtained composite powder, (4) finally by the composite powder for obtaining in Muffle furnace at 500 DEG C
Lower roasting 5min, obtains final product attapulgite-Nano Silver composite inorganic antimicrobial agent.Will be above-mentioned spray-dried obtained
Obtained composite powder carries out respectively XRD and TEM signs after composite powder and roasting, as a result shows：Spraying
Silver after drying in composite powder is with Ag2CO3Form exist, it is fired after be decomposed into Ag, and silver/attapulgite
Mass ratio be 10/100, the particle diameter of Nano Silver is 3-100nm, and attapulgite is not reunited.
The preparation of antibacterial composite nanometer filtering film in the present embodiment is comprised the following steps that：(5) prepare aforementioned
Attapulgite-Nano Silver composite inorganic antimicrobial agent is added in the Isopar G solution of pyromellitic trimethylsilyl chloride, and ultrasound
30min, in the organic solution, the content of attapulgite-Nano Silver composite inorganic powder is 0.001g/L；(6)
Piperazine aqueous phase solution by the front of polyether sulfone porous support membrane with concentration for 30g/L contacts about 300s, uses rubber
Roller removes the aqueous phase solution of the polyether sulfone support membrane excess surface Jing after the infiltration of piperazine aqueous phase solution；(7) will be poly-
The concentration that the front of ether sulfone support membrane prepares with step (5) is molten for the Isopar G of the pyromellitic trimethylsilyl chloride of 5g/L
Liquid contact 120s forms aramid layer, wherein containing the recessed of 0.001g/L in the organic solution of pyromellitic trimethylsilyl chloride
Convex rod soil-Nano Silver；(8) it is put into after is dried in atmosphere the aramid layer of formation in 120 DEG C of baking oven and locates
Reason 1min, after then washing in deionized water, obtains the polyamides amine composite nanofiltration containing attapulgite-Nano Silver
Film, finally preserves composite nanometer filtering film in deionized water in case characterizing.By aforementioned NF membrane separating property and
The method of testing of anti-microbial property is tested the performance of composite membrane, and the test result of gained is listed in table 1.
Embodiment 2
The preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent in the present embodiment is comprised the following steps that：(1) claim
The attapulgite (AT) of thermal activation and the decentralized processing of learning from else's experience, is configured to attapulgite quality dense after addition distilled water
The suspension for 5% is spent, (2) and then silver nitrate solution (AgNO3/ AT=135/100) it is added to concave convex rod
In native suspension, at 90 DEG C, magnetic agitation 3h, (3) are again carried out attapulgite suspension in 170 DEG C
It is spray-dried, collects spray-dried obtained composite powder, (4) is finally by the composite powder for obtaining in 400 DEG C
Roasting 15min, obtains final product attapulgite-Nano Silver composite inorganic antimicrobial agent.Will be above-mentioned spray-dried obtained multiple
Closing obtained composite powder after powder and roasting carries out respectively XRD and TEM signs, as a result shows：Spraying is dry
Silver in dry rear composite powder is with Ag2CO3Form is present, it is fired after be decomposed into Ag, and silver/attapulgite
Mass ratio is 80/100, and the particle diameter of silver is 3-100nm, and attapulgite is not reunited.
The preparation of antibacterial composite nanometer filtering film in the present embodiment is comprised the following steps that：(5) prepare aforementioned
Attapulgite-Nano Silver composite inorganic antimicrobial agent is added in the Isopar E solution of pyromellitic trimethylsilyl chloride, and ultrasound
30min, in the organic solution, the content of attapulgite-Nano Silver composite inorganic powder is 0.005g/L；(6)
P-phenylenediamine aqueous phase solution by the front of polyether sulfone porous support membrane with concentration for 1g/L contacts about 60s, wherein
The also dodecyl sodium sulfate (SBS) of the triethylamine containing 4g/L (TEA), 2g/L in the aqueous phase solution；Use rubber
Rubber roll removes the aqueous phase solution of the polyether sulfone support membrane excess surface Jing after the infiltration of p-phenylenediamine aqueous phase solution；(7)
Isopar E solution by the front of polyether sulfone support membrane with concentration for the pyromellitic trimethylsilyl chloride of 0.5g/L contacts 60s
Form aramid layer, the attapulgite-nanometer containing 0.005g/L wherein in the organic solution of pyromellitic trimethylsilyl chloride
Silver；(8) it is put into after is dried in atmosphere the aramid layer of formation in 65 DEG C of baking oven and processes 3min, then
After washing in deionized water, the polyamide composite nanofiltration membrane containing attapulgite-Nano Silver is obtained, finally will be compound
NF membrane is preserved in deionized water in case characterizing.Separating property and the test of anti-microbial property by aforementioned NF membrane
Method is tested the performance of composite membrane, and the test result of gained is listed in table 1.
Embodiment 3
The preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent in the present embodiment is comprised the following steps that：(1) claim
The attapulgite (AT) of thermal activation and the decentralized processing of learning from else's experience, adds distilled water to be configured to attapulgite mass concentration
For 10% suspension, (2) and then silver nitrate solution (AgNO3/ AT=170/100) it is added to attapulgite
In suspension, at 60 DEG C, 1h is stirred, it is dry that attapulgite suspension is carried out spraying in 150 DEG C by (3) again
It is dry, spray-dried obtained composite powder is collected, (4) are finally by the composite powder for obtaining in 200 DEG C of roastings
180min, obtains final product attapulgite-Nano Silver composite inorganic powder.By above-mentioned spray-dried obtained composite powder
XRD and TEM is carried out respectively with obtained composite powder after roasting to characterize, and is as a result shown：It is multiple after spray drying
The silver in powder is closed with Ag2CO3Form exist, it is fired after be decomposed into Ag, and the mass ratio of silver/attapulgite
For 100/100, the particle diameter of silver is 3-100nm, and attapulgite is not reunited.
The preparation of antibacterial composite nanometer filtering film in the present embodiment is comprised the following steps that：(5) prepare aforementioned
Attapulgite-Nano Silver composite inorganic antimicrobial agent is added in the hexane solution of paraphthaloyl chloride, and ultrasound
30min, in the organic solution, the content of attapulgite-Nano Silver composite inorganic powder is 0.01g/L；(6)
Piperazine aqueous phase solution by the front of polyether sulfone porous support membrane with concentration for 1g/L contacts about 60s, wherein the water
Also contain ethylenediamine, the lauryl sodium sulfate (SDS) of 1g/L of 30g/L in phase solution, with rubber rollers Jing is removed
The aqueous phase solution of the polyether sulfone support membrane excess surface after the infiltration of piperazine aqueous phase solution；(7) polyether sulfone is supported
The front of film contacts 60s and forms aramid layer with concentration for the hexane solution of the paraphthaloyl chloride of 0.5g/L,
Attapulgite-Nano Silver containing 0.01g/L wherein in the organic solution of paraphthaloyl chloride；(8) will be formed
Aramid layer dry in atmosphere after be put into 30 DEG C of baking oven and process 10min, then wash in deionized water
After washing, the polyamide composite nanofiltration membrane containing attapulgite-Nano Silver is obtained, be finally stored in composite nanometer filtering film
In case characterizing in ionized water.
The performance of composite membrane is tested by the separating property of aforementioned NF membrane and the method for testing of anti-microbial property,
The test result of gained is listed in table 1.
Embodiment 4
Except the content of attapulgite-Nano Silver in organic solution is other processing steps and test-strips in addition to 0.05g/L
Part is same as Example 2, and the test result of prepared NF membrane is listed in table 1.
Embodiment 5
Except the content of attapulgite-Nano Silver in organic solution is other processing steps and test-strips in addition to 0.1g/L
Part is same as Example 2, and the test result of prepared NF membrane is listed in table 1.
Comparative example 1
Except the content of attapulgite-Nano Silver in organic solution is other processing steps and test-strips in addition to 0.2g/L
Part is same as Example 2, and the test result of prepared NF membrane is listed in table 1.
Comparative example 2
The preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent in this comparative example is comprised the following steps that：Weigh Jing hot
Activation and the attapulgite (AT) of decentralized processing, with silver nitrate according to AgNO after heat drying3/ AT=135/100
Ratio mixing, it is then broken with mortar grinder, finally by the composite powder for obtaining in Muffle furnace at 550 DEG C
Roasting 30min, obtains final product attapulgite-silver composite inorganic antimicrobial agent.By above-mentioned fired rear obtained composite powder
XRD and TEM is carried out respectively to characterize, and is as a result shown：Ag is decomposed into after composite powder is fired, and it is silver-colored/recessed
The mass ratio of convex rod soil is 80/100, and silver is micron order, and attapulgite there occurs reunion.
The preparation concrete steps of composite nanometer filtering film are same as Example 2 with test condition in this comparative example, made
The test result of standby NF membrane is listed in table 1.
Comparative example 3
Except without in addition to attapulgite-Nano Silver, other processing steps and test condition are and embodiment in organic solution
2 is identical, and the test result of prepared NF membrane is listed in table 1.
Embodiment 1-5 and comparative example 1-3 prepare composite nanometer filtering film Jing test after obtain water flux, cut salt
Rate and anti-microbial property are listed in Table 1 below.
Table 1
From the data of table 1 as can be seen that during interfacial polymerization prepares composite nanometer filtering film, pass through
Add homemade attapulgite-nanometer silver antimicrobial composite inorganic powder, prepared polyamide in organic phase solution
The NF membrane containing homodisperse attapulgite-nanometer silver antimicrobial composite powder is keeping rejection in functional layer
On the basis of quite, flux is improved (embodiment 1-5 and comparative example 2).With attapulgite-Nano Silver
The increase of antiseptic addition, the anti-microbial property of composite nanometer filtering film gradually increases, but antiseptic addition is excessive, by
Easily reunite for nano material in attapulgite, although the flux and anti-microbial property of composite nanometer filtering film is increased
Plus, but the rejection of composite membrane is greatly lowered (comparative example 1).In addition, by traditional roasting direct
Attapulgite carrying silver antimicrobials obtained in method are incorporated into composite nanometer filtering film polyamide functional layer, in functional layer
Introduce the homemade attapulgite-nano silver antimicrobials of the present inventor to compare (embodiment 4), it is prepared compound to receive
The flux of filter membrane is improved (comparative example 3), but because in antiseptic silver be micron order, and attapulgite is easy
Reunite, sterilizing rate and rejection are relatively low.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to the present invention's
Any restriction.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein used
Word is descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by regulation in the claims in the present invention
In the range of the present invention is modified, and the present invention is carried out in without departing substantially from scope and spirit of the present invention
Revision.Although the present invention described in it is related to specific method, material and embodiment, it is not intended that
The present invention is limited to wherein disclosed particular case, conversely, the present invention to can be extended to other all with identical function
Methods and applications.
Claims (11)
1. a kind of antibacterial composite nanometer filtering film, including：Porous support layer and polyamide functional layer, the polyamide
In functional layer include attapulgite-Nano Silver composite inorganic powder, in the composite inorganic powder, it is silver-colored with it is concavo-convex
The mass ratio of rod soil is 10/100-100/100, and the particle diameter of Nano Silver is 3-100nm.
2. NF membrane according to claim 1, it is characterised in that in the composite inorganic powder, silver
It is 30/100-80/100 with the mass ratio of attapulgite.
3. a kind of method for preparing antibacterial composite nanometer filtering film, including：
(1) attapulgite and water are mixed and made into attapulgite suspension；
(2) silver nitrate is added in the attapulgite suspension described in step (1), is then stirred heat
Process；
(3) by step (2) heat treatment after attapulgite suspension carry out spray drying obtain attapulgite answer
Close powder；
(4) attapulgite clay compounded powder obtained in step (3) is carried out into roasting, obtains attapulgite-Nano Silver
Composite inorganic powder；
(5) attapulgite obtained in step (4)-Nano Silver composite inorganic powder is dispersed in containing at least
In the organic solution of the compound of two acid chloride groups, mixed liquor is obtained；
(6) porous support layer is contacted with the aqueous solution of the compound containing at least two amino, then removes and prop up
The unnecessary aqueous solution of support layer surface；
(7) mixed liquor obtained in porous support layer and the step (5) Jing after step (6) process is connect
Touch, the polyamide functional layer comprising attapulgite-Nano Silver composite inorganic powder is formed on the porous support layer
Composite nanometer filtering film.
(8) step (7) gained composite nanometer filtering film is heat-treated, washes and obtain final product containing attapulgite-Nano Silver
The composite nanometer filtering film of composite inorganic powder.
4. method according to claim 3, it is characterised in that in the step (1) is described outstanding
In supernatant liquid, the concentration of attapulgite is less than 10wt%, preferably 1-10wt%.
5. the method according to claim 3 or 4, it is characterised in that in the step (2), institute
The temperature for stating heat treatment is higher than 50 DEG C, preferred 50-90 DEG C；The time of the heat treatment is more than 1h, preferably
1-10h；And/or, the silver nitrate is 17/100-170/100 with the mass ratio of attapulgite, preferably
50/100-135/100。
6. the method according to any one in claim 3-5, it is characterised in that in step (3),
The temperature of the spray drying is 150-200 DEG C；And/or, in step (4), the temperature of the roasting is
200-500 DEG C, the time of the roasting is more than 5min, preferred 5-180min.
7. the method according to any one in claim 3-6, it is characterised in that in the step (4)
In, in the attapulgite-Nano Silver composite inorganic powder, the particle diameter of silver is 3-100nm；And/or silver with it is recessed
The mass ratio of convex rod soil is 10/100-100/100, preferred 30/100-80/100.
8. the method according to any one in claim 3-7, it is characterised in that in the step (5)
In, the compound for containing at least two acid chloride groups includes the multifunctional acyl chlorides of aromatic series, the multifunctional acyl of aliphatic
At least one in chlorine and alicyclic multifunctional acyl chlorides, preferably include paraphthaloyl chloride, m-phthaloyl chloride,
O-phthaloyl chloride, biphenyl dimethyl chloride, benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride, the acyl chlorides of fourth three, succinyl
Chlorine, penta 3 acyl chlorides, glutaryl chlorine, oneself three acyl chlorides, Adipoyl Chloride, sebacoyl chloride, the acyl chlorides of the last of the ten Heavenly stems three, cyclopropane
Three acyl chlorides, cyclobutane diacid chloride, the acyl chlorides of cyclobutane four, pentamethylene diacid chloride, the acyl chlorides of pentamethylene three, pentamethylene
Four acyl chlorides, hexamethylene diacid chloride, the acyl chlorides of hexamethylene three, the acyl chlorides of hexamethylene four, tetrahydrofuran diacid chloride and tetrahydrochysene
At least one in the acyl chlorides of furans four；And/or in the mixed liquor, the attapulgite-Nano Silver composite inorganic
The content of powder is 0.001-0.5g/L, preferred 0.001-0.1g/L；And/or containing at least two in the organic solution
The concentration of the compound of acid chloride group is 0.5-5g/L.
9. the method according to any one in claim 3-8, it is characterised in that in the step (6)
In, the compound for containing at least two amino includes aromatic series polyfunctional amine, aliphatic polyfunctional amine, alicyclic ring
At least one in race's polyfunctional amine and polyhydric alcohol amine, preferably include m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine,
1,3,5- triaminobenzenes, 1,2,4- triaminobenzenes, 3,5- diaminobenzoic acids, 2,4 di amino toluene, 2,4- diaminourea
Methyl phenyl ethers anisole, amidol, xylylene diamine, ethylenediamine, propane diamine, butanediamine, pentanediamine, three (2- ammonia second
Base) amine, diethylenetriamine, 1,2- DACHs, 1,4- DACHs, piperazine, 1,3- bipiperidine bases
At least one in propane, 4- aminomethylpiperazines, monoethanolamine, diethanol amine, hexylene glycol amine and diglycolamine；
It is preferred that the concentration of the compound containing at least two amino in the aqueous solution is 1-30g/L；And/or, the water
Further comprising surfactant and acid absorbent in solution.
10. the method according to any one in claim 3-9, it is characterised in that in the step (7)
In, the time of the contact is 5-300s, preferred 5-120s；And/or, it is described in the step (8)
The temperature of heat treatment is 30-120 DEG C, and the time of the heat treatment is 1-10min.
Any one in 11. antibacterial composite nanometer filtering films according to claim 1 and 2 or claim 3-10
The application of antibacterial composite nanometer filtering film prepared by methods described in UF membrane.
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| CN109433029A (en) * | 2018-11-15 | 2019-03-08 | 山东大学 | A kind of preparation method of the reverse osmosis membrane of anti-pollution type doped cerium oxide and silver nano-grain |
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| CN112516799A (en) * | 2020-12-18 | 2021-03-19 | 山东建筑大学 | Reverse osmosis membrane and preparation method thereof |
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