CN106621851A - Antibacterial reverse osmosis composite membrane and preparation method and application thereof - Google Patents
Antibacterial reverse osmosis composite membrane and preparation method and application thereof Download PDFInfo
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- CN106621851A CN106621851A CN201510712715.4A CN201510712715A CN106621851A CN 106621851 A CN106621851 A CN 106621851A CN 201510712715 A CN201510712715 A CN 201510712715A CN 106621851 A CN106621851 A CN 106621851A
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- reverse osmosis
- attapulgite
- silver
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Abstract
The invention relates to an antibacterial reverse osmosis composite membrane, which comprises a reverse osmosis membrane and a polymer cross-linking coating. An antibacterial agent in the polymer cross-linking coating is composite inorganic powder containing nano-silver. In the composite inorganic powder, mass ratio of silver to attapulgite is 10/100-100/100, and particle size of nano-silver is 3-100 nm. The invention also relates to a preparation method of the antibacterial reverse osmosis composite membrane. The antibacterial reverse osmosis composite membrane provided by the invention has advantages of good antibacterial property, long life, etc.
Description
Technical field
The present invention relates to technical field of membrane, is to be related to a kind of antibacterial reverse osmosis composite membrane furtherly.This Shen
Please further relate to the preparation method and applications of above-mentioned antibacterial reverse osmosis membrane.
Background technology
Reverse osmosis technology is the high-end water technology produced using osmotic pressure principle, realizes water from different solutes
Separation, compared with other technologies, with more succinct mode of operation, can effectively go salt in eliminating water, little point
Organic matter and the colloids such as sub- acid, aldehyde, phenol.With perforated membrane as supporting layer, by between polyamine and polynary acyl chlorides
Interface polymerization reaction, it is the reverse osmosis membrane being most widely used at present that the compound reverse osmosis of the polyamide of preparation closes film,
Have the advantages that permeation flux is big, select separating property good.During reverse osmosis membrane processing sewage, in water
Some organic matters or inorganic matter pollution, the inorganic ions, bacterium, virus, organic matter and glue such as in raw water
The impurity such as body can adsorb on the surface of reverse osmosis membrane, cause counter-infiltration surface to be contaminated, and fouling membrane will result directly in
The permeation flux of film is remarkably decreased, and the production efficiency of system is reduced, operating cost and energy consumption increase；Fouling membrane is also
The frequent clean of system, device will be caused to run well, the rejection characteristic serious deterioration of film, produce water water
Qualitative change is poor, membrane lifetime is reduced and the frequent replacing of film.
Wherein microorganism pollution forms thin biology by the microorganism adsorption being present in water in the surface of seperation film
Produced by film, remove extremely difficult.In order to improve the antifouling property of reverse osmosis membrane, researcher is in anti-soil
Dye reverse osmosis membrane research and development aspect has carried out substantial amounts of research work.
Surface grafting, surface of the research of existing resisting microbial contamination seperation film substantially by focus in composite membrane
Process, surface coats antiseptic.A kind of document such as " antibacterial composite reverse osmosis membrane " is de- in polyamide macromolecule
By the compound one layer of sericin with antibacterial functions of surface coating technique on salt deposit so that complex reverse osmosis membrane
Hydrophily and bacteriostasis property be greatly enhanced, with good stable against biological contamination performance.A kind of " resistance to micro- life
The document of complex reverse osmosis membrane of thing pollution and preparation method thereof " is disclosed, and is had on ground floor polyamide surface layer
The polynary amine aqueous solution being modified with nano inorganic antibacterial granule is prepared with polynary acyl chloride reaction and contains nano inorganic antibacterial
The second layer polyamide surface layer of particle, improves the microbial contamination resistance performance of reverse osmosis membrane, and increased reverse osmosis
The thickness of permeable membrane surface, enhances the performance that the mechanical resistant of reverse osmosis membrane is damaged, and extends the use longevity of counter-infiltration
Life, contained inorganic antibacterial particle includes silver ion class antiseptic, copper ion class antiseptic, Nano Silver etc.." one
The document of kind inorganic pollution resistance antibacterial reverse osmosis membrane and preparation method thereof " is disclosed, poly- by hydroxyl group
The solidification of compound and the crosslinking containing hydroxyl nano-disinfection particulate, through high-temperature process, in reverse osmosis membrane surface shape
Into crosslinking dense mess shape coating, sterilized particulate is uniformly distributed and is crosslinking in coating on film surface, has both improved antibacterial
Ability extends antibacterial timeliness again.But during composite membrane use, coat or containing antiseptic
Two strata amide layers can gradually ablation, cause anti-microbial property to decline." a kind of biocidal property polypiperazine-amide is received
The document of the preparation method of filter membrane " is disclosed, and the trichloro-benzenes oxygen formyl chloride of biocidal property group is added to 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 to cause antibacterial group to be lost in during NF membrane use." one kind suppression
The document of the anti-oxidant complex reverse osmosis membrane of bacterium " is disclosed, by the way that the desalination layer of reverse osmosis composite membrane is being contained into high score
Soak in the persulfate solution of sub- antibacterial material, then dry, obtain biocidal property anti-oxidant compound anti-well
Permeable membrane.
At present microorganism pollution is still modal problem in reverse osmosis composite membrane application, has had a strong impact on reverse osmosis
The application and popularization of composite membrane thoroughly.Thus, the anti-microbial property for how improving existing reverse osmosis composite membrane is to improve anti-
Osmosis composite membrane operational efficiency, the key for extending its service life.Although current grinding in antimicrobial compound film field
Study carefully aspect and achieve larger progress, but it is still hymenology art to prepare the composite membrane with resisting microbial contamination function
One of target that boundary and film industrial quarters are pursued.
The content of the invention
In order to solve the problems of the prior art, the invention provides a kind of antibacterial reverse osmosis composite membrane and its preparation
Method.According to reverse osmosis composite membrane prepared by the method that the present invention is provided, not only with good anti-microbial property；
And can improve the salt-stopping rate of reverse osmosis composite membrane again while the water flux for keeping reverse osmosis composite membrane is suitable.
An object of the present invention, is to provide a kind of antibacterial reverse osmosis composite membrane, including reverse osmosis membrane and macromolecule
Cross-linked coating, the antiseptic in the high molecular crosslink coating is the composite inorganic powder containing Nano Silver, described
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 reverse osmosis composite membrane of the present invention, in the composite inorganic powder, it is preferably silver-colored with it is recessed
The mass ratio of convex rod soil is 30/100-80/100.
According to antibacterial reverse osmosis composite membrane of the present invention, in the composite inorganic powder containing Nano Silver,
Attapulgite has in bar-shaped or filamentary structure and has hollow nanoscale duct, and the rod of attapulgite is brilliant straight
Footpath is 10-80nm.
Easy to understand, as needed, the high molecular crosslink coating can also be able to be multilayer for individual layer.One
In individual specific example, the reverse osmosis membrane includes porous polysulfone supporting layer and polyamide functional layer.It is easy to understand,
The high molecular crosslink coating should contact with functional layer.
According to the present invention, the reverse osmosis membrane can be commercially available, also can be prepared by following known method：It is first
First, the polysulfone supporting layer of porous is connect with the solution A containing two or more reactive amino compounds
Touch, time of contact is 5-300s；Then the polysulfone porous supporting layer after solution A infiltration is rolled with rubber rollers,
To remove unnecessary solution A；Again by the polysulfone supporting layer of unnecessary solution A after aqueous phase solution infiltrates with contain
There is the chloride compounds B solution contact 5-300s of two or more reactive acid chloride groups；Finally by above-mentioned system
The standby reverse osmosis composite membrane for obtaining is put in 30-120 DEG C of baking oven and is heat-treated 1-10min, you can obtain described containing
The reverse osmosis membrane of polyamide functional layer.
According to the present invention, the macromolecular material involved by high molecular crosslink coating is selected from polyethylene glycol, polyether polyols
One kind or many in alcohol, polyetheramine, polyvinyl alcohol, polyacrylic acid, PVP and poly-dopamine
Kind.Macromolecular material used is material well known in the prior art, and its parameter is here is omitted.Its
In, poly-dopamine also can be synthesized by conventional method.The high molecular crosslink coating, can contain institute by being first obtained
The coating liquid of macromolecular material, crosslinking agent, crosslinking catalyst, the composite inorganic powder containing Nano Silver and water is stated,
It is then coated with, on the surface of the reverse osmosis membrane, obtaining by the crosslinking of macromolecular material.
According to the antimicrobial compound film that the present invention is provided, silver-colored simple substance is uniformly adsorbed in concave convex rod in the form of Nano Silver
Native surface, this absorption is very big in the nano silver active of attapulgite's surface, can slowly release with antibacterial
The silver ion of effect, and nano-Ag particles are firmly combined with attapulgite.Composite inorganic powder containing Nano Silver
(or claiming attapulgite-Nano Silver composite powder), used as antiseptic, its anti-microbial property was good, and uniform and jail
Solid be embedded in the polymeric coating layer of crosslinking (as crosslinking PVA coatings) in；The coating layer thickness of crosslinking is several
Hundred nanometers, and coating adopts hydrophilic high molecular material, so affecting on the original water flux of reverse osmosis composite membrane
Less；And the cross-linked structure of coating causes the salt-stopping rate of antibacterial reverse osmosis composite membrane to increase, and overcome painting
Layer holds caducous shortcoming, and to the functional layer top layer (polyamide surface layer) of antibacterial reverse osmosis composite membrane protection is played
Effect, improves the antifouling property of reverse osmosis composite membrane, extends the use of the antibacterial reverse osmosis composite membrane
Life-span.The anti-microbial property of obtained antibacterial reverse osmosis composite membrane is good.
The second object of the present invention, is to provide a kind of preparation method of antibacterial reverse osmosis composite membrane.The antibacterial is anti-
The preparation method of osmosis composite membrane is comprised the following steps：
(1) attapulgite and water are mixed and made into 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 compound containing Nano Silver
Inorganic powder；
(5) by containing for obtaining in hydrophilic high molecular material, crosslinking agent, crosslinking catalyst and step (4)
The composite inorganic powder of Nano Silver mixes with water, obtains coating liquid；
(6) step (5) coating liquid is coated on the surface of reverse osmosis membrane, discharge opeing after contact certain hour；
(7) reverse osmosis membrane that the surface obtained in step (6) is contained into coating liquid carries out at a certain temperature heat
Process, obtain the antibacterial reverse osmosis composite membrane with cross-linked structure coating.
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 into Muffle
In stove, the roasting 30min at 400 DEG C；Above-mentioned roasting attapulgite is put in 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..
In a specific embodiment, in the attapulgite suspension, the mass concentration of attapulgite is less than 10%,
It is preferred that 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.Step (2)
In stirring heat treatment, enable to the carbanion that contains in attapulgite and generate carbonic acid with silver ion reaction
Silver, 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 preferably 150-200 DEG C.In step (4), the roasting can be conventional method of roasting, for example will
Attapulgite clay compounded powder is in Muffle kiln roasting；The temperature of the roasting is 200-500 DEG C；Sintering temperature mistake
Height can make attapulgite duct cave in so as to cause adsorption capacity to be deteriorated, and be easily caused attapulgite reunion, temperature
Spend low, Nano Silver simple substance cannot be obtained.The roasting time is more than 5min, preferably 5-180min.
In the obtained composite inorganic powder (or claiming attapulgite-Nano Silver composite powder) containing Nano Silver, 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.And confirmed by wide-angle XRD, in spraying
In the attapulgite clay compounded powder obtained after drying, silver nitrate reacts and finishes, and what is obtained is 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 be silver carbonate.During follow-up baking heat, silver carbonate is decomposed into silver-colored simple substance, finally with Nano Silver
Form be 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.
One specific embodiment of the method provided according to the present invention, the hydrophilic high molecular material is selected from poly- second
Glycol, PPG, polyetheramine, polyvinyl alcohol, polyacrylic acid, PVP and poly- DOPA
One or more in amine.Hydrophilic high molecular material used is material of the prior art, and its parameter exists
Here is omitted.In a specific example, hydrophilic high molecular material used is polyvinyl alcohol, excellent
Select the polyvinyl alcohol that alcoholysis degree is 75-99%.In the coating liquid, the concentration of hydrophilic high molecular material is
0.1-5wt%, preferably 0.5-2wt%.
According to the present invention provide method another specific embodiment, the crosslinking agent selected from aliphatic dialdehydes,
One or more in polyfunctionality acid, anhydrides and multivalent anions compound, the preferably crosslinking agent is selected from
Glutaraldehyde, butanedial, hexandial, glyoxal, dimethyl glyoxal, lauric aldehyde, citral, boric acid, horse
One or more come in acid anhydrides, maleic acid and oxalic acid.According to a specific embodiment, in the coating liquid,
The concentration of the crosslinking agent is 0.01-0.2wt%.
According to the present invention provide method another specific embodiment, the crosslinking catalyst selected from organic acid,
One or more in inorganic acid and alkali catalyst, be preferably selected from formic acid, acetic acid, propionic acid, butyric acid, hydrochloric acid,
One or more in sulfuric acid, phosphoric acid, nitric acid, NaOH, potassium hydroxide, sodium carbonate and sodium acid carbonate.
In one instantiation, in the coating liquid, the concentration of the crosslinking catalyst is 0.01-0.2wt%.
In an instantiation, in the coating liquid, the attapulgite-Nano Silver composite inorganic powder
Concentration is 0.005-0.2wt%.
Another specific embodiment for the method provided according to the present invention, in step (6), the counter-infiltration
The functional layer of film is aramid layer.The time of contact is more than 5s, more preferably preferred 5-300s, 10-60s.
Painting method has no particular limits, can adopt existing paint-on technique, such as knife coating, silk bar coating method,
Spread coating etc..Easy to understand, the coating liquid should be coated in the function layer surface of the reverse osmosis membrane, such as poly-
On the surface of amide layer.
Withering method has no particular limits after coating.In step (7), the heat treatment
Temperature such as can be 40-150 DEG C, preferred 50-120 DEG C.Suitable process time is not particularly limited, and such as can be
1-10min。
According to the present invention, resulting antibacterial reverse osmosis composite membrane includes reverse osmosis membrane and high molecular crosslink coating,
Antiseptic in the high molecular crosslink coating is the composite inorganic powder containing Nano Silver, in the composite inorganic powder
In end, silver is 10/100-100/100 with the mass ratio of attapulgite, and the particle diameter of Nano Silver is 3-100nm.It is excellent
Choosing silver is 30/100-80/100 with the mass ratio of attapulgite.
According to the antimicrobial compound film that the present invention is provided, silver-colored simple substance is uniformly adsorbed in concave convex rod in the form of Nano Silver
Native surface, this absorption is very big in the nano silver active of attapulgite's surface, can slowly release with antibacterial
The silver ion of effect, and nano-Ag particles are firmly combined with attapulgite.Composite inorganic powder containing Nano Silver
(or claiming attapulgite-Nano Silver composite powder), used as antiseptic, its anti-microbial property was good, and uniform and jail
Solid be embedded in the polymeric coating layer of crosslinking (as crosslinking PVA coatings) in；The coating layer thickness of crosslinking is several
Hundred nanometers, and coating adopts hydrophilic high molecular material, so affecting on the original water flux of reverse osmosis composite membrane
Less；And the cross-linked structure of coating causes the salt-stopping rate of antibacterial reverse osmosis composite membrane to increase, and overcome painting
Layer holds caducous shortcoming, and to the functional layer top layer (polyamide surface layer) of antibacterial reverse osmosis composite membrane protection is played
Effect, improves the antifouling property of reverse osmosis composite membrane, extends the use of the antibacterial reverse osmosis composite membrane
Life-span.The anti-microbial property of obtained antibacterial reverse osmosis composite membrane is good.
The third object of the present invention, is to provide a kind of application of antibacterial reverse osmosis composite membrane in water process, including：
First antibacterial reverse osmosis composite membrane is prepared according to said method, then the antibacterial reverse osmosis composite membrane is used for into water
Process.The method according to the invention prepares antibacterial reverse osmosis composite membrane, improves the anti-microbial property of film；Meanwhile,
On the basis of keeping water flux suitable, the salt-stopping rate of reverse osmosis composite membrane is improved again.
Silver nitrate decomposition can also be obtained into Nano Silver simple substance by directly heating the method for calcining in prior art,
But its decomposition temperature is high, high energy consumption, the nano silver particles of preparation are susceptible to reunite, and particle diameter is than larger.And
Chemical reduction method, needs to carry out pickling to attapulgite, also adds chemical reducing agent to be reduced, and technique is multiple
It is miscellaneous, and cause environmental pollution.Meanwhile, chemical reduction method cannot prepare the attapulgite of high content of nanometer silver-
The composite powder (mass ratio of Nano Silver/attapulgite is generally less than 10/100) of Nano Silver.This is because, institute
When the amount of the silver nitrate for needing is big, amount of reducing agent etc. also increases, and silver particles are reunited seriously in obtained inorganic powder,
Silver particles are micron order or more, and then antibacterial effect is poor.
However, according to the present invention, by heating, being then spray-dried and causing in silver nitrate and attapulgite
Carbonate fully reacts contained by face, then can be prepared by Nano Silver less than roasting under silver nitrate decomposition temperature, no
Only avoid the environmental pollution brought using reducing agent or other chemical reactions, and the decomposition temperature of silver carbonate
Relatively low, roasting at relatively low temperatures can generate silver-colored simple substance, and silver-colored simple substance is uniform in the form of Nano Silver
Absorption in attapulgite's surface, this absorption is very big in the nano silver active of attapulgite's surface, can be slow
The silver ion with antibacterial effect is discharged, and nano-Ag particles are firmly combined with attapulgite.Then will be recessed
Convex rod soil-nano silver antimicrobials are dispersed in the coating liquid containing crosslinking agent and crosslinking catalyst, by the painting for obtaining
Covering liquid is coated to the reverse osmosis membrane surface for having prepared；Attapulgite-nano silver antimicrobials anti-microbial property is good,
And in being dispersed in coating liquid, attapulgite-Nano Silver inorganic powder is firmly embedded in crosslinking after heat treatment
Coating (as crosslinking PVA coatings) in；The coating layer thickness of crosslinking be hundreds of nanometer, and coating adopt
Hydrophilic high molecular material, so affecting little to the original water flux of reverse osmosis composite membrane；And the crosslinking knot of coating
Structure causes the salt-stopping rate of antibacterial reverse osmosis composite membrane to increase, and overcomes the caducous shortcoming of coating appearance, right
Antibacterial reverse osmosis composite membrane polyamide surface layer plays a protective role, and improves the resistance tocrocking of reverse osmosis composite membrane
Can, extend the service life of the antibacterial reverse osmosis composite membrane.
According to the method that the present invention is provided, preparation process is simple, and low production cost, obtained antibacterial counter-infiltration is answered
The anti-microbial property for closing film is good.Thus, according to the method that the present invention is provided, with good industrialized production base
Plinth and wide application prospect.
Description of the drawings
Fig. 1 shows the transmission electricity of the composite inorganic powder containing Nano Silver prepared according to one embodiment of the invention
Sub- microscope (TEM) photo；
Fig. 2 shows the surface sweeping electricity of the composite inorganic powder containing Nano Silver prepared according to one embodiment of the invention
Sub- microscope SEM) photo；
Fig. 3 shows the XRD of the composite inorganic powder containing Nano Silver prepared according to one embodiment of the invention
Spectrogram.
Specific embodiment
With reference to embodiment, the present invention is further illustrated, but be not construed as limiting the invention.
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 operating condition that membrane separating property is adopted in the present invention for：Feeding liquid is the aqueous sodium chloride of 2000ppm
Liquid, operating pressure is 225psi, and operation temperature is 25 DEG C, and pH value of water solution is 6.8.
Antibacterial effect quantitative determination：
Antibacterial examination criteria：The evaluation third portion of GB/T 20944.3-2008 antibacterial textile performances：Succusion.
Antibacterial reverse osmosis composite membrane is cut into into the sample of 10mm × 30mm, above-mentioned sample is put into into the triangle of 150ml
In bottle, Escherichia coli (ATCC 25922) bacterium solution of 70ml PBSs and 500ul is separately added into, will
Triangular flask is fixed on vibration bed, and with 120r/min 24h is swayed.The sample liquid after 500ul vibrations is taken, PBS is used
Buffer solution is made to carry out viable bacteria culture counting after appropriate dilution.Simultaneously to common reverse osmosis composite membrane (do not contain antibacterial into
Point) carry out contrast test.Sterilizing rate is calculated as follows：
Sterilizing rate (%)=((A-B)/A) × 100
In formula：A-common reverse osmosis composite membrane sample viable count
B-antibacterial reverse osmosis composite membrane sample viable count
Embodiment is raw materials used
In embodiment it is raw materials used be it is commercially available, in embodiment attapulgite rod used crystalline substance diameter 30-80nm it
Between.The present invention is by adopting X-ray diffraction analysis (XRD) and transmission electron microscope (TEM) to made
Standby attapulgite-Nano Silver composite inorganic powder is characterized.
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 in Muffle furnace, the roasting 30min at 400 DEG C；
Above-mentioned roasting attapulgite is put in 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.
Reverse osmosis membrane containing nonwoven layer, polysulfone supporting layer and aramid layer prepared by the prior art of comparative example 1
First by homemade molecular cut off for the polysulfone porous support membranes of 3-5 ten thousand front and concentration for 30g/L's
M-phenylene diamine (MPD) aqueous phase solution contacts about 60s, and with rubber rollers the polysulfones Jing after the infiltration of m-phenylene diamine (MPD) aqueous phase solution is removed
The unnecessary solution in support membrane front, then by the front of this support membrane and the pyromellitic trimethylsilyl chloride that concentration is 12g/L
Isopar E solution contact 60s, then unnecessary solution is removed and the solvent on film surface dries in the air in atmosphere
It is dry, it is heat-treated 3min in the baking oven for finally placing it in 70 DEG C, you can obtain polyamide composite reverse osmosis membrane.
Embodiment 1 prepares antibacterial reverse osmosis composite membrane according to following steps：
(1) preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent：Weigh Jing thermal activations and decentralized processing
Attapulgite (AT), is configured to the water slurry that attapulgite mass concentration is 1%, then that silver nitrate is molten
Liquid (AgNO3/ AT=17/100) attapulgite suspension is added to, at 50 DEG C, magnetic agitation 1h, then will
Attapulgite suspension is spray-dried at 200 DEG C, collects spray-dried obtained composite powder, most
Afterwards by the composite powder for obtaining in Muffle furnace the roasting 30min at 500 DEG C, obtain final product attapulgite-Nano Silver multiple
Close inorganic antiseptic.By obtained composite powder difference after above-mentioned spray-dried obtained composite powder and roasting
Carry out XRD and TEM to characterize, as a result show：Silver after spray drying in composite powder is with Ag2CO3Form
Exist, it is fired after be decomposed into Ag, and the mass ratio of silver/attapulgite is 10/100, and the particle diameter of Nano Silver is
3-100nm, attapulgite is not reunited.
(2) preparation of reverse osmosis composite membrane：Method is with comparative example 1.
(3) preparation of antibacterial reverse osmosis composite membrane：By the polyvinyl alcohol prepared, (78%) PVA, alcoholysis degree is
Coating liquid is coated on the aramid layer surface of the reverse osmosis composite membrane prepared by step (2), the wherein matter of PVA
Amount concentration is 0.2%, and the mass concentration of glutaraldehyde is 0.01%, and the mass concentration of hydrochloric acid is 0.01%, concave convex rod
The mass concentration of soil-nano silver antimicrobials is 0.05%, after PVA coating liquids infiltration aramid layer surface 10s,
Unnecessary PVA solution is removed, then reverse osmosis composite membrane is placed in 90 DEG C of baking ovens and is heat-treated 6min, obtains final product anti-
Bacterium reverse osmosis composite membrane, is finally stored in prepared antibacterial reverse osmosis composite membrane in deionized water in case testing
Characterize.It is anti-to prepared antibacterial by the separating property of aforementioned reverse osmosis composite membrane and the method for testing of anti-microbial property
Osmosis composite membrane carries out separating property and anti-microbial property test, and the test result of gained is listed in table 1.
Embodiment 2 prepares antibacterial reverse osmosis composite membrane according to following steps：
(1) preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent：Except by silver nitrate solution and attapulgite
The temperature of magnetic agitation is adjusted to 70 DEG C of outer, other processing steps and XRD and TEM tables after suspension mixing
The result levied is same as Example 1.
(2) preparation of reverse osmosis composite membrane：Method is with comparative example 1.
(3) preparation of antibacterial reverse osmosis composite membrane：Except the quality of PVA (alcoholysis degree is 88%) in coating liquid
Concentration is adjusted to 1%, and the mass concentration of glutaraldehyde is adjusted to 0.1%, and the mass concentration of hydrochloric acid is adjusted to outside 0.1%,
Other processing steps are same as Example 1 with test condition, the test of prepared antibacterial reverse osmosis composite membrane
As a result it is listed in table 1.
Embodiment 3 prepares antibacterial reverse osmosis composite membrane according to following steps：
(1) preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent：Except by silver nitrate solution and attapulgite
The temperature of magnetic agitation is adjusted to 90 DEG C of outer, other processing steps and XRD and TEM tables after suspension mixing
The result levied is same as Example 1.
(2) preparation of reverse osmosis composite membrane：Method is with comparative example 1.
(3) preparation of antibacterial reverse osmosis composite membrane：Except the quality of PVA (alcoholysis degree is 95%) in coating liquid
Concentration is adjusted to 1.5%, and the mass concentration of glutaraldehyde is adjusted to 0.15%, and the mass concentration of hydrochloric acid is adjusted to 0.15%
Outward, other processing steps are same as Example 1 with test condition, prepared antibacterial reverse osmosis composite membrane
Test result is listed in table 1.
Embodiment 4：Antibacterial reverse osmosis composite membrane is prepared according to following steps：
(1) preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent：Processing step and XRD and TEM tables
The result levied is same as Example 1.
(2) preparation of reverse osmosis composite membrane：Method is with comparative example 1.
(3) preparation of antibacterial reverse osmosis composite membrane：Except by the matter of PVA in coating liquid (alcoholysis degree is 99%)
Amount concentration is adjusted to 2%, and the mass concentration of glutaraldehyde is adjusted to 0.2%, and the mass concentration of hydrochloric acid is adjusted to 0.2%
Outward, other processing steps are same as Example 1 with test condition, prepared antibacterial reverse osmosis composite membrane
Test result is listed in table 1.
Comparative example 2：The reverse osmosis composite membrane for being coated with PVA layers is prepared according to following steps
(1) preparation of reverse osmosis composite membrane：Method is with comparative example 1.
(2) it is coated with the preparation of the reverse osmosis composite membrane of PVA layers：Except in PVA coating liquids without concavo-convex
Outside rod soil-nano silver antimicrobials, other processing steps are same as Example 1 with test condition, and prepared is anti-
The test result of osmosis composite membrane is listed in table 1.
Comparative example 3：Antibacterial reverse osmosis composite membrane is prepared according to following steps：
(1) preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent：Weigh Jing thermal activations and decentralized processing
Attapulgite (AT), with silver nitrate according to AgNO after heat drying3The ratio mixing of/AT=17/100, so
Afterwards with mortar grinder it is broken, finally by the composite powder for obtaining in Muffle furnace the roasting 30min at 550 DEG C, i.e.,
Obtain attapulgite-silver composite inorganic antimicrobial agent.Above-mentioned fired rear obtained composite powder is carried out into respectively XRD
Characterize with TEM, as a result show：Ag, and the mass ratio of silver/attapulgite are decomposed into after composite powder is fired
For 10/100, silver is micron order, and attapulgite is reunited.
(2) preparation of reverse osmosis composite membrane：Method is with comparative example 1.
(3) preparation of antibacterial reverse osmosis composite membrane：Processing step is same as Example 1 with test condition,
The test result of prepared antibacterial reverse osmosis composite membrane is listed in table 1.
Reverse osmosis composite membrane prepared by the antibacterial reverse osmosis composite membrane and comparative example 1-3 prepared by embodiment 1-4
The results are shown in Table 1 for water flux, salt-stopping rate and anti-microbial property.
Table 1
As can be seen that with PVA concentration in coating liquid from the data of embodiment 1-4 of table 1 and comparative example 1
Increase, prepared reverse osmosis composite membrane water flux is slightly reduced, and salt-stopping rate gradually increases, and sterilizing rate reaches
To more than 99%, and without the complex reverse osmosis membrane prepared by antiseptic (comparative example 2) in PVA coating liquids
Without antibacterial effect, using traditional roasting direct method obtained in antiseptic be applied in PVA coating liquids,
The antibacterial effect of obtained complex reverse osmosis membrane (comparative example 3) is substantially low.
Embodiment 5：Antibacterial reverse osmosis composite membrane is prepared according to following steps：
(1) preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent：Weigh Jing thermal activations and decentralized processing
Attapulgite (AT), to add and be configured to the suspension that attapulgite mass concentration is 5% after distilled water, then
Silver nitrate solution (AgNO3/ AT=135/100) attapulgite suspension is added to, at 90 DEG C, magnetic force
Stirring 3h, then attapulgite suspension is spray-dried in 170 DEG C, collect spray-dried obtained multiple
Powder is closed, finally by the composite powder for obtaining in 200 DEG C of roasting 15min, attapulgite-Nano Silver is obtained final product and is combined
Inorganic antiseptic.Obtained composite powder after above-mentioned spray-dried obtained composite powder and roasting is entered respectively
Row XRD and TEM are characterized, and are as a result shown：Silver after spray drying in composite powder is with Ag2CO3Form is deposited
, it is fired after be decomposed into Ag, and the mass ratio of silver/attapulgite is 80/100, and the particle diameter of silver is 3-100nm,
Attapulgite is not reunited.
(2) preparation of reverse osmosis composite membrane：Method is with comparative example 1.
(3) preparation of antibacterial reverse osmosis composite membrane：Polyethylene glycol (PEG-1000) coating liquid prepared is applied
The aramid layer surface of the reverse osmosis composite membrane being overlying on prepared by step (2), the wherein mass concentration of PEG is
1%, the mass concentration of butanedial is 0.1%, and the mass concentration of phosphoric acid is 0.1%, and attapulgite-Nano Silver is combined
The mass concentration of inorganic antiseptic is 0.05%, after PEG coating liquids infiltration aramid layer surface 60s, is removed
Unnecessary PEG solution, then reverse osmosis composite membrane is placed in 150 DEG C of baking ovens be heat-treated 1min, obtains final product antibacterial
Reverse osmosis composite membrane, is finally stored in prepared antibacterial reverse osmosis composite membrane in deionized water in case test table
Levy.The test result of prepared antibacterial reverse osmosis composite membrane is listed in table 2.
Embodiment 6：Antibacterial reverse osmosis composite membrane is prepared according to following steps：
(1) preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent：Except by the roasting of powder after spray drying
Temperature be adjusted to 300 DEG C it is outer, the result that other processing steps and XRD and TEM are characterized with the phase of embodiment 5
Together.
(2) preparation of reverse osmosis composite membrane：Method is with comparative example 1.
(3) preparation of antibacterial reverse osmosis composite membrane：Except heat treatment temperature is adjusted to into 120 DEG C, the time is adjusted to
Outside 3min, other processing steps are same as Example 5 with test condition.Prepared antibacterial counter-infiltration is combined
The test result of film is listed in table 2.
Embodiment 7：Antibacterial reverse osmosis composite membrane is prepared according to following steps：
(1) preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent：Except by the roasting of powder after spray drying
Temperature be adjusted to 400 DEG C it is outer, the result that other processing steps and XRD and TEM are characterized with the phase of embodiment 5
Together.
(2) preparation of reverse osmosis composite membrane：Method is with comparative example 1.
(3) preparation of antibacterial reverse osmosis composite membrane：Except heat treatment temperature is adjusted to into 100 DEG C, the time is adjusted to
Outside 5min, other processing steps are same as Example 5 with test condition.Prepared antibacterial counter-infiltration is combined
The test result of film is listed in table 2.
Embodiment 8：Antibacterial reverse osmosis composite membrane is prepared according to following steps：
(1) preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent：Except by the roasting of powder after spray drying
Temperature be adjusted to 500 DEG C it is outer, the result that other processing steps and XRD and TEM are characterized with the phase of embodiment 5
Together.
(2) preparation of reverse osmosis composite membrane：Method is with comparative example 1.
(3) preparation of antibacterial reverse osmosis composite membrane：Except heat treatment temperature is adjusted to into 80 DEG C, the time is adjusted to
Outside 7min, other processing steps are same as Example 5 with test condition.Prepared antibacterial counter-infiltration is combined
The test result of film is listed in table 2.
Embodiment 9：Antibacterial reverse osmosis composite membrane is prepared according to following steps：
(1) preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent：Except by the roasting of powder after spray drying
Temperature is adjusted to 500 DEG C, and roasting time is adjusted to outside 30min, other processing steps and XRD and TEM tables
The result levied is same as Example 5.
(2) preparation of reverse osmosis composite membrane：Method is with comparative example 1.
(3) preparation of antibacterial reverse osmosis composite membrane：Except heat treatment temperature is adjusted to into 40 DEG C, the time is adjusted to
Outside 10min, other processing steps are same as Example 5 with test condition.Prepared antibacterial counter-infiltration is answered
The test result for closing film is listed in table 2.
Comparative example 4：Reverse osmosis composite membrane is prepared according to following steps：
(1) preparation of reverse osmosis composite membrane：Method is with comparative example 1.
(2) it is coated with the preparation of the reverse osmosis composite membrane of PEG layers：Except heat treatment temperature is adjusted to 30 DEG C, when
Between be adjusted to outside 5min, other processing steps reverse osmosis same as Example 5 with test condition, prepared
Thoroughly the test result of composite membrane is listed in table 2.
Comparative example 5：Reverse osmosis composite membrane is prepared according to following steps：
(1) preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent：Weigh Jing thermal activations and decentralized processing
Attapulgite (AT), with silver nitrate according to AgNO after heat drying3The ratio mixing of/AT=135/100, so
Afterwards with mortar grinder it is broken, finally by the composite powder for obtaining in Muffle furnace the roasting 30min at 550 DEG C, i.e.,
Obtain attapulgite-silver composite inorganic antimicrobial agent.Above-mentioned fired rear obtained composite powder is carried out into respectively XRD
Characterize with TEM, as a result show：Ag, and the mass ratio of silver/attapulgite are decomposed into after composite powder is fired
For 80/100, the particle diameter of silver is micron order, and attapulgite is reunited.
(2) preparation of reverse osmosis composite membrane：Method is with comparative example 1.
(3) preparation of antibacterial reverse osmosis composite membrane：Processing step is same as Example 5 with test condition,
The test result of prepared antibacterial reverse osmosis composite membrane is listed in table 2.
Reverse osmosis composite membrane Jing tests prepared by the reverse osmosis composite membrane and comparative example 4-5 prepared by embodiment 5-9
Water flux, salt-stopping rate and the anti-microbial property for obtaining afterwards is listed in Table 2 below.
Table 2
Data from table 2 can be seen that：Heat cross-linking temperature is too low or the time short (comparative example 4), generation
PEG cross-linked structures loosely, easily come off from the surface of reverse osmosis composite membrane, therefore sterilizing rate is low, and are improving
Crosslinking temperature or prolongation crosslinking time (embodiment 5-9) can obtain antimicrobial compound film of the sterilizing rate more than 99%,
Rejection is improved while keeping water flux suitable.Using traditional roasting direct method obtained in antibacterial
Agent is applied in PEG coating liquids, and the antibacterial effect of obtained complex reverse osmosis membrane (comparative example 5) is substantially low.
Embodiment 10：Antibacterial reverse osmosis composite membrane is prepared according to following steps：
(1) preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent：Weigh Jing thermal activations and decentralized processing
Attapulgite (AT), add distilled water be configured to the suspension that attapulgite mass concentration is 10%, then
Silver nitrate solution (AgNO3/ AT=170/100) attapulgite suspension is added to, at 60 DEG C, 1h is stirred,
Attapulgite suspension is spray-dried in 150 DEG C again, is collected spray-dried obtained composite powder,
Finally by the composite powder for obtaining in 200 DEG C of roasting 10min, attapulgite-Nano Silver composite inorganic powder is obtained final product.
By obtained composite powder after above-mentioned spray-dried obtained composite powder and roasting carry out respectively XRD and
TEM is characterized, and is as a result shown：Silver after spray drying in composite powder is with Ag2CO3Form is present, fired
After be decomposed into Ag, and the mass ratio of silver/attapulgite is 100/100, and the particle diameter of silver is 3-100nm, concave convex rod
Soil is not reunited.
(2) preparation of reverse osmosis composite membrane：Method is with comparative example 1.
(3) preparation of antibacterial reverse osmosis composite membrane：Dopamine is dissolved in into Tris-HCl bufferings in conical flask
In solution, it is 8.5 to adjust pH value, and conical flask is placed in shaking table, at 30 DEG C, is shaken under conditions of 50r/min
24h is swung, dopamine generates poly-dopamine (PDA) solution of black by polymerisation.With this poly-dopamine (PDA)
Solution preparation coating liquid, the aramid layer surface of the reverse osmosis composite membrane being coated on prepared by step (2), its
The mass concentration of middle poly-dopamine is 0.75%, and the mass concentration of attapulgite-Nano Silver composite inorganic antimicrobial agent is
0.005%, poly-dopamine solution removes unnecessary poly-dopamine solution after film surface infiltration 30s, is placed on 100 DEG C
5min is heat-treated in baking oven, antibacterial reverse osmosis composite membrane is obtained final product, finally by prepared antibacterial reverse osmosis composite membrane
It is stored in deionized water in case testing sign.The test result of prepared antibacterial reverse osmosis composite membrane is listed in table
3。
Embodiment 11：Antibacterial reverse osmosis composite membrane is prepared according to following steps：
(1) preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent：Except by silver nitrate solution and attapulgite
The time of magnetic agitation is adjusted to outside 2h after suspension mixing, the table of other processing steps and XRD and TEM
As a result it is same as in Example 10.
(2) preparation of reverse osmosis composite membrane：Method is with embodiment 10.
(3) preparation of antibacterial reverse osmosis composite membrane：Except by attapulgite-nano silver antimicrobials in PDA coating liquids
Mass concentration be adjusted to outside 0.01%, other processing steps are same as in Example 10 with test condition, made
The test result of standby antibacterial reverse osmosis composite membrane is listed in table 3.
Embodiment 12：Antibacterial reverse osmosis composite membrane is prepared according to following steps：
(1) preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent：Weigh Jing thermal activations and decentralized processing
Attapulgite, to add and be configured to the suspension that attapulgite mass concentration is 3% after distilled water, then nitric acid
Silver-colored solution (AgNO3/ AT=50/100) attapulgite suspension is added to, at 70 DEG C, magnetic agitation 2h,
Attapulgite suspension is spray-dried at 170 DEG C again, is collected the composite powder after being spray-dried,
Finally by the composite powder for obtaining at 350 DEG C roasting 5min, obtain final product attapulgite-Nano Silver composite inorganic powder
End.Obtained composite powder after above-mentioned spray-dried obtained composite powder and roasting is carried out into respectively XRD
Characterize with TEM, TEM (as shown in Figure 1) is carried out to obtained composite powder after roasting and scanning electron is aobvious
Micro mirror (as shown in Figure 2) and XRD signs (as shown in Figure 3).As a result show：Composite powder after spray drying
Silver in end is with Ag2CO3Form is present, it is fired after be decomposed into Ag, and the mass ratio of silver/attapulgite is
30/100, the particle diameter of silver ion is 3-100nm, and attapulgite is not reunited.
(2) preparation of reverse osmosis composite membrane：Method is with comparative example 1.
(3) preparation of antibacterial reverse osmosis composite membrane：Except by attapulgite-nano silver antimicrobials in PDA coating liquids
Mass concentration be adjusted to outside 0.05%, other processing steps are same as in Example 10 with test condition, made
The test result of standby antibacterial reverse osmosis composite membrane is listed in table 3.
Embodiment 13：Antibacterial reverse osmosis composite membrane is prepared according to following steps：
(1) preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent：Except by the roasting of spray-dried rear powder
The burning time is adjusted to outside 20min, and the characterization result of other processing steps and XRD and TEM is and embodiment
12 is identical.
(2) preparation of reverse osmosis composite membrane：Method is with comparative example 1.
(3) preparation of antibacterial reverse osmosis composite membrane：Except by attapulgite-nano silver antimicrobials in PDA coating liquids
Mass concentration be adjusted to outside 0.1%, other processing steps are same as in Example 10 with test condition, made
The test result of standby antibacterial reverse osmosis composite membrane is listed in table 3.
Embodiment 14：Antibacterial reverse osmosis composite membrane is prepared according to following steps：
(1) preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent：Except by the roasting of spray-dried rear powder
The burning time is adjusted to outside 180min, and the characterization result of other processing steps and XRD and TEM is and embodiment
12 is identical.
(2) preparation of reverse osmosis composite membrane：Method is with comparative example 1.
(3) preparation of antibacterial reverse osmosis composite membrane：Except by attapulgite-nano silver antimicrobials in PDA coating liquids
Mass concentration be adjusted to outside 0.2%, other processing steps are same as in Example 10 with test condition, made
The test result of standby antibacterial reverse osmosis composite membrane is listed in table 3.
Comparative example 6：Reverse osmosis composite membrane is prepared according to following steps：
In addition to attapulgite-nano silver antimicrobials are not contained in PDA coating liquids, other processing steps and test-strips
Part is same as in Example 10, and the test result of prepared reverse osmosis composite membrane is listed in table 3.
Comparative example 7：Reverse osmosis composite membrane is prepared according to following steps：
(1) preparation of attapulgite-Nano Silver composite inorganic antimicrobial agent：Weigh Jing thermal activations and decentralized processing
Attapulgite (AT), with silver nitrate according to AgNO after heat drying3The ratio mixing of/AT=170/100, so
Afterwards with mortar grinder it is broken, finally by the composite powder for obtaining in Muffle furnace the roasting 30min at 550 DEG C, i.e.,
Obtain attapulgite-silver composite inorganic antimicrobial agent.Above-mentioned fired rear obtained composite powder is carried out into respectively XRD
Characterize with TEM, as a result show：Ag, and the mass ratio of silver/attapulgite are decomposed into after composite powder is fired
For 100/100, silver is micron order, and attapulgite there occurs reunion.
(2) preparation of reverse osmosis composite membrane：Method is with comparative example 1.
(3) preparation of antibacterial reverse osmosis composite membrane：Processing step is identical with embodiment 10 with test condition,
The test result of prepared antibacterial reverse osmosis composite membrane is listed in table 3.
Reverse osmosis composite membrane Jing prepared by the reverse osmosis composite membrane and comparative example 6-7 prepared by embodiment 10-14 is surveyed
Water flux, salt-stopping rate and the anti-microbial property obtained after examination is listed in Table 3 below.
Table 3
Can be seen that from the data of table 3：The timing of PDA concentration one of reverse osmosis composite membrane surface coating, instead
The sterilizing rate of osmosis composite membrane increases with the increase of antimicrobial levels, and is all higher than 99%, leads to water is kept
Rejection is improved while measuring suitable.And adopt attapulgite-silver obtained in the method for roasting direct inorganic
The antibiotic rate that powder is added to the antibacterial reverse osmosis composite membrane (comparative example 7) obtained in PDA coating liquids is obvious
It is 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 (12)
1. a kind of antibacterial reverse osmosis composite membrane, including reverse osmosis membrane and high molecular crosslink coating, the macromolecule is handed over
Connection coating in antiseptic be the composite inorganic powder containing Nano Silver, in the composite inorganic powder, it is silver-colored with it is recessed
The mass ratio of convex rod soil is 10/100-100/100, and the particle diameter of Nano Silver is 3-100nm.
2. antibacterial reverse osmosis composite membrane according to claim 1, it is characterised in that in the composite inorganic
In powder, silver is 30/100-80/100 with the mass ratio of attapulgite.
3. a kind of preparation method of antibacterial reverse osmosis composite membrane, comprises the following steps：
(1) attapulgite and water are mixed and made into 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 compound containing Nano Silver
Inorganic powder；
(5) by containing for obtaining in hydrophilic high molecular material, crosslinking agent, crosslinking catalyst and step (4)
The composite inorganic powder of Nano Silver mixes with water, obtains coating liquid；
(6) step (5) coating liquid is coated on the surface of reverse osmosis membrane, discharge opeing after contact certain hour；
(7) reverse osmosis membrane that the surface obtained in step (6) is contained into coating liquid carries out at a certain temperature heat
Process, obtain the antibacterial reverse osmosis composite membrane with cross-linked structure coating.
4. method according to claim 3, it is characterised in that in the step (1) is described outstanding
In supernatant liquid, the concentration of the attapulgite is 1-10wt%；And/or, in the step (2), the nitre
Sour silver is 17/100-170/100, preferred 50/100-135/100 with the mass ratio of attapulgite.
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
1h-10h。
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 composite inorganic powder containing Nano Silver, the particle diameter of silver is 3-100nm；And/or silver and attapulgite
Mass ratio be 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 coating liquid,
The concentration of hydrophilic high molecular material is 0.1-5wt%, preferably 0.5-2wt%；And/or, the crosslinking agent
Concentration is 0.01-0.2wt%；And/or, the concentration of the crosslinking catalyst is 0.01-0.2wt%；And/or, it is described
The concentration of the composite inorganic powder containing Nano Silver is 0.005-0.2wt%.
9. the method according to any one in claim 3-8, it is characterised in that the hydrophily high score
Sub- material is selected from polyethylene glycol, PPG, polyetheramine, polyvinyl alcohol, polyacrylic acid, polyvinyl pyrrole
One or more in pyrrolidone and poly-dopamine, more preferably preferred polyvinyl alcohol, alcoholysis degree are the poly- of 75-99%
Vinyl alcohol；And/or,
The crosslinking agent is in polyfunctionality aldehyde, polyfunctionality acid, anhydrides and multivalent anions compound
One or more, the preferably crosslinking agent is selected from glutaraldehyde, butanedial, hexandial, glyoxal, dimethyl second
One or more in dialdehyde, lauric aldehyde, citral, boric acid, maleic anhydride, maleic acid and oxalic acid；With/
Or,
The crosslinking catalyst is selected from one or more in organic acid, inorganic acid and alkali catalyst, preferred choosing
From formic acid, acetic acid, propionic acid, butyric acid, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, NaOH, potassium hydroxide,
One or more in sodium carbonate and sodium acid carbonate.
10. the method according to any one in claim 3-9, it is characterised in that in step (6),
The time of the contact is more than 5s, more preferably preferred 5-300s, 10-60s；And/or, in step (7),
The temperature of the heat treatment is 40-150 DEG C, preferred 50-120 DEG C.
11. methods according to any one in claim 3-10, it is characterised in that the antibacterial reverse osmosis
Thoroughly composite membrane includes reverse osmosis membrane and high molecular crosslink coating, the antiseptic in the high molecular crosslink coating be containing
The composite inorganic powder of Nano Silver, in the composite inorganic powder, silver is with the mass ratio of attapulgite
10/100-100/100, the particle diameter of Nano Silver is 3-100nm；It is preferred that silver is with the mass ratio of attapulgite
30/100-80/100。
A kind of application of the 12. antibacterial reverse osmosis composite membranes in water process, including：First according to claim 3-11
Middle any one methods described prepares antibacterial reverse osmosis composite membrane, then by the antibacterial reverse osmosis composite membrane
For water process.
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