CN108993171A - Attapulgite is improving the application in polyvinylidene fluoride (PVDF) ultrafiltration membrane filtration flux - Google Patents
Attapulgite is improving the application in polyvinylidene fluoride (PVDF) ultrafiltration membrane filtration flux Download PDFInfo
- Publication number
- CN108993171A CN108993171A CN201810768133.1A CN201810768133A CN108993171A CN 108993171 A CN108993171 A CN 108993171A CN 201810768133 A CN201810768133 A CN 201810768133A CN 108993171 A CN108993171 A CN 108993171A
- Authority
- CN
- China
- Prior art keywords
- attapulgite
- carbon nitride
- phase carbon
- class graphite
- graphite phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/06—Flat membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to attapulgites to improve the application in polyvinylidene fluoride (PVDF) ultrafiltration membrane filtration flux, belongs to separation membrane technical field.In the present invention, utilize the carrier property that attapulgite is excellent, the dispersion of class graphite phase carbon nitride is immobilized on attapulgite surface by chemical bonding effect, the deficiencies of avoiding the reunion and difficult separation of class graphite phase carbon nitride, and the evenly dispersed class graphite phase carbon nitride for being immobilized on attapulgite surface has photocatalysis performance, class graphite phase carbon nitride in ultrafiltration membrane surface and ontology makes to be film-made with photocatalysis performance, realize the coupling of photocatalytic process and UF membrane, make film that there is antipollution and self-cleaning performance, promotes the economy of membrane separating process.
Description
Technical field
Present patent application is that number of patent application is 2017102390068, and entitled " a kind of antipollution automatically cleaning is poly- inclined
Fluoride flat ultrafiltration membrane and its preparation method and application " divisional application.The present invention relates to attapulgites to gather inclined fluorine in raising
Application in ethylene ultrafiltration membrance filter flux, belongs to separation membrane technical field.
Background technique
In recent years, it prepares ultrafiltration membrane with Kynoar (PVDF) for main material to receive much attention, PVDF material has machine
Many advantages, such as tool function admirable, stable chemical performance, antiacid caustic corrosion, preparation process are simply, cost is relatively low.But PVDF
Surface can it is extremely low, hydrophobicity is stronger, cause its form a film after water flux it is lower, trapped substance is easily adsorbed on film table in use
Cause Pore Blocking in face and fenestra, makes membrane body antipollution, flux decline quickly, reduces the service life of film, and cleans
It is very difficult.So improving the hydrophilicity of PVDF film to expand the application range and service life of PVDF film, avoiding
Fouling membrane is particularly important.
Currently, the method modified to pvdf membrane mainly has surface modified and blending and modifying two major classes.Surface modification mainly has
Surface coating and surface grafting.The modified material that the former easy to operate but modifying agent is easy to run off in film use process, and falls off
Also film can be polluted；The latter need to post-process and be modified not enough uniformly, or even can block die hole, damage film properties.Blending changes
Property be then that membrane modifying is completed during preparing casting solution, be not required to cumbersome last handling process, and modifying agent can cover film simultaneously
Surface and fenestra inner wall, will not cause the destruction of membrane structure.There are three types of common alloying agents: hydrophilic polymer, parents' polymerization
Object, inorganic nano-particle.
In recent years, inorganic nano-particle can be to avoid it since inorganic nano-particle is hydrophilic but not soluble in water by favor
It is lost from membrane material and easy to operate, it is modified that uniformly effect is lasting, inorganic nano-particle is blended with macromolecule member material,
Membrane structure can be improved and it is made to have both the heat-resisting quantity of the toughness of polymeric membrane and inoranic membrane.But inorganic nano-particle
Specific surface area is larger, it is easy to reunite together, and hydrophilic inorganic nano-particle and macromolecule member material poor compatibility.It passes
Unite inorganic nano-particle (Al2O3, TiO2Deng) easily fall off in film preparation and in, influence the performance and modified effect of film.
The monodimension nanometer materials such as carbon nanotube can improve self stability, but its higher cost by the winding of macromolecular chain.Middle promulgated by the State Council
Bright patent (CN201410439685.X), which discloses, prepares attapulgite/polyvinylidene fluoride for nano-attapulgite stone introducing polymeric membrane
Nano combined ultrafiltration membrane of alkene and preparation method thereof.By the way that nano-attapulgite stone is introduced polyvinylidene fluoride (PVDF) ultrafiltration membrane, bumps are utilized
It is super that the unique nanofibrous structures of stick stone and its tridimensional network formed with Kynoar are effectively improved Kynoar
The structure and intensity of filter membrane, while improving using the high water-wet behavior of attapulgite the permeability, hydrophilic of polyvinylidene fluoride (PVDF) ultrafiltration membrane
Property and contamination resistance.
The technology for coupling photocatalysis and UF membrane that developed recently gets up can carry out polluter using photochemical catalyst
Oxidative degradation makes flux depression problem caused by fouling membrane be addressed or mitigate, and assigns film self-cleaning performance.In crowd
Class graphite phase carbon nitride g-C in more photochemical catalysts3N4As it is a kind of cheap, stablize, with good visible light-responded polymer half
Conductor photochemical catalyst, gets more and more extensive concerning of people.But in existing g-C3N4In photocatalytic system, require
Catalyst dispersion comes into full contact in a solvent and with object, and active particle acts on object through catalyst surface, so g-
C3N4Specific surface area and microscopic appearance also affect its photocatalysis performance.By g-C3N4Polymer acts on jail by chemical bonding
Admittedly being supported on other carriers, efficient, stable coupled mode g-C can get3N4Composite material.CN106179447A discloses one
The preparation method of kind close coupling type attapulgite-KHX-g-C3N4 composite material, close coupling type attapulgite-KHX-g-C3N4 are multiple
Condensation material has good catalytic performance.In blending and modifying, since nano particle is wrapped in macromolecule member material, seriously
The performance of its photocatalysis performance is influenced, and compared to blending and modifying, ultrafiltration membrane surface is carried out using nano particle in situ implantation
Modification can be such that nano particle exposes to the open air in film surface, directly act on polluter, but the implantation of nano particle only change it is super
The surface topography of filter membrane, structure and performance to its ontology do not improve.
Summary of the invention
The object of the present invention is to provide a kind of antipollution self-cleaning type polyvinylidene fluoride (PVDF) ultrafiltration membranes and preparation method thereof, utilize
The tridimensional network that the unique nanofibrous structures of attapulgite and Kynoar are formed pure gathers inclined fluorine to be effectively improved
The structure and intensity of ethylene ultrafiltration membrane improve permeability of the membrane and hydrophily using attapulgite high-hydrophilic；Amphiphilic is utilized
Property copolymer improve the hydrophily of polyvinylidene fluoride film, while improving attapulgite-class graphite phase carbon nitride composite wood feed powder
Dispersibility of the body in casting solution；The carrier property for also utilizing attapulgite excellent simultaneously is acted on by chemical bonding by class stone
The deficiencies of black phase carbon nitride dispersion is immobilized on attapulgite surface, avoids the reunion and difficult separation of class graphite phase carbon nitride,
And the evenly dispersed class graphite phase carbon nitride for being immobilized on attapulgite surface has photocatalysis performance, in ultrafiltration membrane surface and
The class graphite phase carbon nitride of ontology makes to be film-made with photocatalysis performance, realizes the coupling of photocatalytic process and UF membrane, makes film
With antipollution and self-cleaning performance, the economy of membrane separating process is promoted.
To solve the above problems, using following technological means:
The first aspect of the invention:
A kind of preparation method of antipollution automatically cleaning vinylidene difluoride planar ultrafiltration membrane, includes the following steps:
Step 1, it is by weight, attapulgite -75~85 parts of class graphite phase carbon nitride composite material powder addition is organic molten
In agent, ultrasonic disperse is uniform to mixed system；
Step 2 adds 15~25 parts of Kynoar powder, amphipathic copolymer and additive, obtains casting solution after stirring and dissolving,
Standing and defoaming；
Step 3, the casting solution that step 2 is obtained are applied on plate with scraper, using being immersed in coagulating bath, using immersion precipitation
Phase inversion processing, obtains flat plate ultrafiltration membrane；
The attapulgite-class graphite phase carbon nitride composite material quality is the 0.5~10% of Kynoar powder；
The quality of the additive is the 3~6% of Kynoar powder and organic solvent gross mass；
The quality of the amphipathic copolymer is the 2~4% of Kynoar powder.
Class graphite phase carbon nitride is acted on by chemical bonding in the attapulgite-class graphite phase carbon nitride composite material
It is immobilized on attapulgite surface, quality is the 2~50% of attapulgite.
The atapulgite fibres length is 0.5~2 μm, and diameter is 30~70nm, and purity is greater than 95%.
In the step 1, it is sub- that the organic solvent is selected from n-methyl-2-pyrrolidone, tetrahydrofuran, dimethyl
Sulfone, amide solvent, esters solvent or lactone solvent；The amide solvent is selected from dimethyl acetamide or dimethyl methyl
Amide；The esters solvent is selected from trimethyl phosphate or triethyl phosphate etc.；The lactone solvent is selected from γ-Ding Nei
Ester.
In the step 2, the additive is selected from polyvinylpyrrolidone, polyacrylic acid, polyethylene glycol, polyethylene
Alcohol, lithium chloride, sodium chloride, calcium chloride, lithium nitrate or formamide.
In the step 2, at 75~85 DEG C, the time of stirring and dissolving is controlled 20~40 for the temperature control of stirring and dissolving
Hour.
In the step 2, the temperature of standing and defoaming is 75~85 DEG C, and the time is 12~24 hours.
In the step 2, the amphipathic copolymer is poly- (methyl methacrylate-vinyl alcohol).
In the step 3, attapulgite-class graphite phase carbon nitride composite material powder aqueous suspension is used in phase inversion
Liquid is coagulating bath, in coagulating bath attapulgite-class graphite phase carbon nitride composite material powder mass percent be 0.01~
0.05%, coagulation bath temperature is 5~30 DEG C.
The second aspect of the invention:
The flat plate ultrafiltration membrane being directly prepared by the above method.
The third aspect of the invention:
Flat plate ultrafiltration membrane is being applied to filtering containing the application in organic wastewater.
Described refers to the humic acid solution containing 20mg/L containing organic wastewater.
The application is filtered under the irradiation of 500W xenon lamp.
The fourth aspect of the invention:
The Kynoar ultrafiltration that attapulgite is adulterated as the carrier of class graphite phase carbon nitride in raising class graphite phase carbon nitride
The application of the film filtering filtration flux of when containing organic wastewater.
Beneficial effect
1. the antipollution self-cleaning type polyvinylidene fluoride (PVDF) ultrafiltration membrane had both promoted using the nanoparticle of attapulgite as nucleus poly-
Vinylidene crystallization, the palygorskite nano fiber being dispersed in inside film, the tridimensional network formed with Kynoar have
Effect improves the structure and intensity of polyvinylidene fluoride (PVDF) ultrafiltration membrane, enhances the close performance of membrane pressure；It is again hydrophilic using the height of attapulgite
Property effectively improves the permeability and hydrophily of pure polyvinylidene fluoride film.
2. compared with traditional inorganic nano-particle, attapulgite is a kind of typical monodimension nanometer material, internal multichannel,
High-specific surface area, and it is big in China's reserves, low in cost, to environment without negative effect, cost performance is substantially better than artificial synthesized
1-dimention nano fibrous material.
3. by chemical bonding effect that the dispersion of class graphite phase carbon nitride is immobilized using the carrier property that attapulgite is excellent
On attapulgite surface, the deficiencies of avoiding the reunion and difficult separation of class graphite phase carbon nitride, and evenly dispersed be immobilized on
The class graphite phase carbon nitride on attapulgite surface has photocatalysis performance, nitrogenizes in the class graphite-phase of ultrafiltration membrane surface and ontology
Carbon makes to be film-made with photocatalysis performance, realizes the coupling of photocatalytic process and UF membrane, and film is made to have antipollution and automatically cleaning
Performance promotes the economy of membrane separating process.
4. attapulgite-class graphite phase carbon nitride composite material is introduced ultrafiltration membrane body by being blended, pass through simultaneously
The attapulgite being dispersed in coagulating bath-class graphite phase carbon nitride composite material powder is implanted into ultrafiltration membrane surface in situ, makes ultrafiltration
Membrane body and surface introduce attapulgite-class graphite phase carbon nitride composite material powder simultaneously, and it is super to greatly improve Kynoar
The antipollution self-cleaning performance of filter membrane.
5. the hydrophily of film can be improved in the addition using amphiphilic copolymer, at the same can also be improved inorganic particle with
Compatibility between Kynoar.
Specific embodiment
Below by specific embodiment, the invention will be further described.It should be noted that following embodiments are only used
In illustrating the present invention, the scope of the present invention is not constituted a limitation.In the examples where no specific technique or condition is specified, by this field
Technology or conditions described in interior document are carried out by product description.Reagents or instruments used without specified manufacturer,
Being can be with conventional products that are commercially available.
Natural nano attapulgite has one-dimensional nano-scale structure on the external appearance characteristics such as form, size, and it comes
Source is wide, at low cost.The present invention is by the way that attapulgite-class graphite phase carbon nitride composite material powder to be introduced into Kynoar and surpass
In filter membrane, the tridimensional network formed using the unique nanofibrous structures of attapulgite with Kynoar is to effectively change
It is apt to the structure and intensity of pure polyvinylidene fluoride (PVDF) ultrafiltration membrane, improves permeability of the membrane and hydrophily using attapulgite high-hydrophilic；
The dispersion of class graphite phase carbon nitride is immobilized on bumps by chemical bonding effect by carrier property excellent using attapulgite simultaneously
It is the deficiencies of avoiding the reunion and difficult separation of class graphite phase carbon nitride, evenly dispersed to be immobilized on attapulgite table on stick stone surface
The class graphite phase carbon nitride in face has photocatalysis performance；Again by being blended attapulgite-class graphite phase carbon nitride composite material
Ultrafiltration membrane body is introduced, while the attapulgite by being dispersed in coagulating bath-class graphite phase carbon nitride composite material powder is former
Position implantation ultrafiltration membrane surface, makes ultrafiltration membrane body and surface while introducing attapulgite-class graphite phase carbon nitride composite wood feed powder
Body, the class graphite phase carbon nitride in ultrafiltration membrane surface and ontology make to be film-made with photocatalysis performance, realize photocatalytic process
With the coupling of UF membrane, the antipollution and self-cleaning performance of polyvinylidene fluoride (PVDF) ultrafiltration membrane are greatly improved, membrane separating process is promoted
Economy.This method is easy to operate, and modified uniformly membrane aperture is controllable, can be used for drink water purifying, milk separation, and waste water returns
With etc..
For the fibre length of the nano-attapulgite stone used in following embodiment for 500~2000nm, diameter is 30~70nm,
Attapulgite content is not less than 95%.
The ultrafiltration membrane provided in the present invention is using Kynoar (PVDF) as substrate, wherein again added with amphipathic
Attapulgite-class graphite phase carbon nitride composite material, attapulgite-class is all distributed in its inside and outer surface in copolymer
Graphite phase carbon nitride composite material is using attapulgite as carrier, in its area load class graphite phase carbon nitride composite material.
Attapulgite-class graphite phase carbon nitride composite material preparation method, can be refering to patent document CN106179447A: first
It is coupling agent modified that attapulgite is subjected to silane surface, then by melamine in its Surface grafting reaction, by air or oxygen
After sintering under atmosphere, make the Surface Creation class graphite phase carbon nitride of attapulgite, wherein the weight of carbonitride is concave convex rod
The 2~50% of stone.
The raw material for preparing of the ultrafiltration membrane includes following components: Kynoar powder, amphipathic copolymer, organic solvent are recessed
Convex stick stone-class graphite phase carbon nitride composite material powder, additive, coagulating bath.
Organic solvent herein is the solvent for referring to dissolution Kynoar powder, such as: n-methyl-2-pyrrolidone,
Tetrahydrofuran, dimethyl sulfoxide；The amides such as dimethyl acetamide, dimethylformamide；Trimethyl phosphate or triethyl phosphate etc.
Esters solvent；The lactones solvent such as gamma-butyrolacton；And their mixed solvent.
The additive is the aperture that can refer to adjusting film and the additive of porosity, such as polyvinylpyrrolidine
The water soluble polymers such as ketone, polyacrylic acid, polyethylene glycol, polyvinyl alcohol；Lithium chloride, sodium chloride, calcium chloride, lithium nitrate etc. are inorganic
Salt；Formamide, formaldehyde etc..Using polyethylene glycol 400 as pore-foaming agent in following embodiment.
The coagulating bath refers to non-solvent, i.e., cannot dissolve the solvent of Kynoar, such as: water, hexane, three chloroethenes
Alkene, benzene and their mixed solvent etc. since water is more environmentally friendly, therefore preferentially select water as coagulating bath, while in order to will be recessed
Convex stick stone-class graphite phase carbon nitride composite material powder is implanted to ultrafiltration membrane surface in situ, therefore uses attapulgite-class graphite-phase
Nitridation carbon composite water slurry is coagulating bath.
Class graphite phase carbon nitride is acted on by chemical bonding in above-mentioned attapulgite-class graphite phase carbon nitride composite material
It is immobilized on attapulgite surface, quality is the 2 ~ 50% of attapulgite, and the fibre length of attapulgite used is 0.5~2 μm,
Diameter is 30~70nm, and purity is greater than 95%.
The preparation method of the ultrafiltration membrane is to form a film using scraper film, then using immersion precipitation inversion of phases.
In the present invention, membrane aperture is characterized using liquid liquid exclusive method.Determination step is as follows, first infiltrates film different
In butanol for 24 hours, it is reloaded into membrane module, the isobutanol in film is squeezed out with the water phase saturated solution of isobutanol and water, utilizes hole
Diameter analyzes software and carries out membrane aperture calculating.
In the present invention, film pure water flux is tested using end-filtration device, first by film under the pressure of 0.2MPa
Precompressed 30min, then use the operating pressure of 0.1MPa instead and tested, runing time 30min.
In the present invention, investigation can be carried out using antipollution self-cleaning property of the cross-flow filtration device to film.Steps are as follows, in room
Under the pressure of mild 0.1MPa, crossflow velocity 0.3m/s replaces pure water to carry out with mass concentration by the humic acid solution of 20mg/L
The measurement of antipollution self-cleaning performance is led to respectively at measuring its permeation flux in different time under no light and the irradiation of 500W xenon lamp
After amount is stablized, its attenuation rate, attenuation rate=(1- steady seepage flux/initial pure water flux) × 100% are measured.
The preparation of 1 attapulgite of embodiment-class graphite phase carbon nitride composite material
It weighs the silane coupler modified attapulgite of 3.02g to be dispersed in the deionized water of 1000mL, ultrasonic disperse；Then plus
Enter 6.01g melamine, stirs, 80 DEG C of condensing reflux 2h；Then it is freeze-dried 48h, is added in quartz boat after grinding, by stone
Ying Zhou is placed in tube furnace, in air atmosphere temperature programming in tube furnace, the program of heating are as follows: 0.5 h of room temperature is warming up to 500
DEG C, continue 2 min after 500 DEG C of 2 h of holding and be warming up to 520 DEG C, keeps Temperature fall after 2 h, be fully ground to powdery, obtain concave-convex
(preparation method is refering to patent document CN106179447A) for class graphite phase carbon nitride composite material for stick stone-.
Embodiment 2
Respectively by 1%, quality of 4%, the 7%(relative to Kynoar powder) the attapulgite-class stone that is prepared of embodiment 1
Black phase carbon nitride is added in 48g triethyl phosphate, and after ultrasonic disperse is uniform, 12g Kynoar powder and 3% poly- (methyl is added
Methyl acrylate-vinyl alcohol) (quality relative to Kynoar powder) at 80 DEG C stirring and dissolving for 24 hours, add 3g
Polyethylene glycol 400 stirring obtains standing and defoaming at casting solution, with 80 DEG C for 24 hours and for 24 hours, obtains casting solution；Casting solution is applied with scraper again
It on plate, is formed a film using immersion precipitation phase inversion process, coagulating bath is attapulgite-class graphite-phase that mass fraction is 0.05%
Carbonitride water slurry, water temperature are 25 DEG C, obtain antipollution self-cleaning type attapulgite-class graphite phase carbon nitride/mixed poly- inclined
Fluoride ultrafiltration membrane.
Reference examples 1
The difference from example 2 is that: attapulgite-class graphite phase carbon nitride powder is not added.
In 48g triethyl phosphate, 12g Kynoar powder and 3% poly- (methyl methacrylate-vinyl alcohol) (phase is added
For the quality of Kynoar powder) at 80 DEG C stirring and dissolving for 24 hours, add the stirring of 3g polyethylene glycol 400 for 24 hours
Standing and defoaming for 24 hours, obtains casting solution at casting solution, with 80 DEG C；Casting solution is applied on plate with scraper again, using immersion precipitation
Forming film with phase transformation method, coagulating bath are attapulgite-class graphite phase carbon nitride water slurry that mass fraction is 0.05%, and water temperature is
25 DEG C, obtain antipollution self-cleaning type attapulgite-class graphite phase carbon nitride/mixed polyvinylidene fluoride (PVDF) ultrafiltration membrane.
Reference examples 2
The difference from example 2 is that: attapulgite-class graphite phase carbon nitride particle is not added in casting solution, but uses class
Graphite phase carbon nitride nano particle and attapulgite are separately added into.
It respectively will be relative to the attapulgite powder of the quality 1.6% and 2.4% of Kynoar powder and the nitridation of class graphite-phase
Carbon nano-particle is added in 48g triethyl phosphate, and after ultrasonic disperse is uniform, 12g Kynoar powder and 3% poly- (methyl is added
Methyl acrylate-vinyl alcohol) (quality relative to Kynoar powder) at 80 DEG C stirring and dissolving for 24 hours, add 3g
Polyethylene glycol 400 stirring obtains standing and defoaming at casting solution, with 80 DEG C for 24 hours and for 24 hours, obtains casting solution；Casting solution is applied with scraper again
It on plate, is formed a film using immersion precipitation phase inversion process, coagulating bath is attapulgite-class graphite-phase that mass fraction is 0.05%
Carbonitride water slurry, water temperature are 25 DEG C, obtain antipollution self-cleaning type attapulgite-class graphite phase carbon nitride/mixed poly- inclined
Fluoride ultrafiltration membrane.
Reference examples 3
The difference from example 2 is that: attapulgite-class graphite phase carbon nitride particle is added not in coagulating bath.
Quality by 4%(relative to Kynoar powder) the attapulgite-class graphite-phase nitrogen that is prepared of embodiment 1
Change carbon to be added in 48g triethyl phosphate, after ultrasonic disperse is uniform, 12g Kynoar powder and 3% poly- (methacrylic acid is added
Methyl esters-vinyl alcohol) (quality relative to Kynoar powder) at 80 DEG C stirring and dissolving for 24 hours, add the poly- second two of 3g
The stirring of alcohol 400 obtains standing and defoaming at casting solution, with 80 DEG C for 24 hours and for 24 hours, obtains casting solution；Casting solution is applied to plate with scraper again
On, it is formed a film using immersion precipitation phase inversion process, coagulating bath is deionized water, and water temperature is 25 DEG C, obtains antipollution self-cleaning type
Attapulgite-class graphite phase carbon nitride/mixed polyvinylidene fluoride (PVDF) ultrafiltration membrane.
The performance of different films is as shown in the table:
As can be seen from the table, influence of attapulgite-class graphite phase carbon nitride addition to membrane aperture is little, but makes film
Attapulgite-class graphite phase carbon nitride film is much larger, and flux recovery rate has also obtained being obviously improved compared with being not added for pure water flux
Illustrate that modified film hydrophily and permeance property have all obtained apparent improvement, embodies preferable antifouling property.Pass through
Reference examples 2 can be seen that and class graphite phase carbon nitride is carried on attapulgite, can use attapulgite and plays preferable point
The effect with carrier is dissipated, improves its applied to the self-cleaning effect to organic solution filtering after ultrafiltration membrane；Pass through reference examples 3
Compared with Example 1 relatively as can be seen that passing through blending and bumps made from surface in situ implantation joint in the case where there is illumination condition
Attenuation rate significantly reduces under stick stone-class graphite phase carbon nitride/polyvinylidene fluoride (PVDF) ultrafiltration membrane illumination, shows blending and surface
Implantation in situ combines attapulgite-class graphite phase carbon nitride/polyvinylidene fluoride (PVDF) ultrafiltration membrane antipollution self-cleaning property obtained
Attapulgite-class graphite phase carbon nitride obtained/mixed polyvinylidene fluoride (PVDF) ultrafiltration membrane can be blended better than simple, can have by illumination
Effect mitigates film surface pollution.
Claims (5)
1. attapulgite is improving the application in polyvinylidene fluoride (PVDF) ultrafiltration membrane filtration flux, which is characterized in that the described application is
Refer to attapulgite as the carrier of class graphite phase carbon nitride in the polyvinylidene fluoride (PVDF) ultrafiltration membrane for improving the doping of class graphite phase carbon nitride
Filter the application of the filtration flux of when containing organic wastewater.
2. application according to claim 1, which is characterized in that filtering when containing organic wastewater is under the irradiation of 500W xenon lamp
It is filtered.
3. application according to claim 1, which is characterized in that refer to that the humic acid containing 20mg/L is molten containing organic wastewater
Liquid.
4. application according to claim 1, which is characterized in that the preparation method of the polyvinylidene fluoride (PVDF) ultrafiltration membrane, packet
Include following steps: attapulgite-class graphite phase carbon nitride composite material powder is added 75~85 parts by weight by step 1
In organic solvent, ultrasonic disperse is uniform to mixed system；Step 2 adds 15~25 parts of Kynoar powder, amphipathic copolymerization
Object and additive, after stirring and dissolving casting solution, standing and defoaming；Casting solution that step 2 obtains is applied to scraper flat by step 3
On plate, using being immersed in coagulating bath, is handled using immersion precipitation phase inversion process, obtain flat plate ultrafiltration membrane；The attapulgite-
The quality of class graphite phase carbon nitride composite material is the 0.5~10% of Kynoar powder；The quality of the additive is to gather inclined fluorine
The 3~6% of ethylene powder and organic solvent gross mass；The quality of the amphipathic copolymer is the 2~4% of Kynoar powder.
5. application according to claim 4, which is characterized in that the attapulgite-class graphite phase carbon nitride composite wood
Class graphite phase carbon nitride is immobilized on attapulgite surface by chemical bonding effect in material, quality be attapulgite 2~
50%；The atapulgite fibres length is 0.5~2 μm, and diameter is 30~70nm, and purity is greater than 95%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810768133.1A CN108993171B (en) | 2017-04-13 | 2017-04-13 | Application of attapulgite in improving filtering flux of polyvinylidene fluoride ultrafiltration membrane |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810768133.1A CN108993171B (en) | 2017-04-13 | 2017-04-13 | Application of attapulgite in improving filtering flux of polyvinylidene fluoride ultrafiltration membrane |
| CN201710239006.8A CN106902650B (en) | 2017-04-13 | 2017-04-13 | A kind of antipollution automatically cleaning vinylidene difluoride planar ultrafiltration membrane and its preparation method and application |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710239006.8A Division CN106902650B (en) | 2017-04-13 | 2017-04-13 | A kind of antipollution automatically cleaning vinylidene difluoride planar ultrafiltration membrane and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108993171A true CN108993171A (en) | 2018-12-14 |
| CN108993171B CN108993171B (en) | 2021-06-11 |
Family
ID=59209436
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710239006.8A Active CN106902650B (en) | 2017-04-13 | 2017-04-13 | A kind of antipollution automatically cleaning vinylidene difluoride planar ultrafiltration membrane and its preparation method and application |
| CN201810768071.4A Active CN108993170B (en) | 2017-04-13 | 2017-04-13 | Preparation method of polyvinylidene fluoride flat ultrafiltration membrane |
| CN201810768133.1A Active CN108993171B (en) | 2017-04-13 | 2017-04-13 | Application of attapulgite in improving filtering flux of polyvinylidene fluoride ultrafiltration membrane |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710239006.8A Active CN106902650B (en) | 2017-04-13 | 2017-04-13 | A kind of antipollution automatically cleaning vinylidene difluoride planar ultrafiltration membrane and its preparation method and application |
| CN201810768071.4A Active CN108993170B (en) | 2017-04-13 | 2017-04-13 | Preparation method of polyvinylidene fluoride flat ultrafiltration membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN106902650B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108246110B (en) * | 2018-01-08 | 2019-05-28 | 淮阴师范学院 | A kind of attapulgite modified PVDF ultrafiltration membrane, preparation method and its application in protein solution filtration |
| CN110292865B (en) * | 2019-06-27 | 2022-08-30 | 三达膜科技（厦门）有限公司 | Preparation method of self-cleaning carbon nitride/titanium dioxide/polyvinyl alcohol composite nanofiltration membrane |
| CN110961132A (en) * | 2019-11-14 | 2020-04-07 | 济南市环境研究院 | C3N4Preparation method and application of modified organic membrane |
| CN111467963B (en) * | 2020-03-16 | 2022-02-25 | 淮阴师范学院 | Polyvinylidene fluoride/Fe3O4-attapulgite composite ultrafiltration membrane and preparation method thereof |
| CN112569807A (en) * | 2020-11-19 | 2021-03-30 | 上海应用技术大学 | Polyvinylidene fluoride mixed matrix membrane with photocatalytic performance and preparation and application thereof |
| CN112569809A (en) * | 2020-11-20 | 2021-03-30 | 上海应用技术大学 | PMIA modified ultrafiltration membrane with photocatalytic performance and preparation and application thereof |
| CN112999889A (en) * | 2021-02-25 | 2021-06-22 | 上海应用技术大学 | Method for preparing PMIA mixed matrix membrane with photocatalytic performance by self-adhesion and application |
| CN117181023B (en) * | 2023-11-06 | 2024-01-26 | 深圳格立菲环境科技有限公司 | Anti-pollution hollow fiber ultrafiltration membrane and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1319415A1 (en) * | 2001-12-13 | 2003-06-18 | Nipro Corporation | Adhesion preventive membrane, method of producing a collagen single strand, collagen nonwoven fabric and method and apparatus for producing the same |
| CN1490440A (en) * | 2003-07-08 | 2004-04-21 | 东华大学 | Inorganic granular soliquoid for modified Nitrilon, preparing method and use thereof |
| CN104971632A (en) * | 2015-07-29 | 2015-10-14 | 淮阴师范学院 | Easy-to-wash PVDF (polyvinylidene fluoride) ultrafiltration membrane and preparation method thereof |
| CN105126643A (en) * | 2015-08-21 | 2015-12-09 | 天津膜天膜科技股份有限公司 | Hollow fiber reverse osmosis membrane and preparation method thereof |
| CN106179447A (en) * | 2016-07-13 | 2016-12-07 | 淮阴师范学院 | Close coupling type attapulgite KHX g C3n4the preparation method of composite |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104209018B (en) * | 2014-09-01 | 2016-06-29 | 淮阴师范学院 | A kind of attapulgite/polyvinylidene fluoride nanometer composite hyperfiltration membrane and preparation method thereof |
-
2017
- 2017-04-13 CN CN201710239006.8A patent/CN106902650B/en active Active
- 2017-04-13 CN CN201810768071.4A patent/CN108993170B/en active Active
- 2017-04-13 CN CN201810768133.1A patent/CN108993171B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1319415A1 (en) * | 2001-12-13 | 2003-06-18 | Nipro Corporation | Adhesion preventive membrane, method of producing a collagen single strand, collagen nonwoven fabric and method and apparatus for producing the same |
| CN1490440A (en) * | 2003-07-08 | 2004-04-21 | 东华大学 | Inorganic granular soliquoid for modified Nitrilon, preparing method and use thereof |
| CN104971632A (en) * | 2015-07-29 | 2015-10-14 | 淮阴师范学院 | Easy-to-wash PVDF (polyvinylidene fluoride) ultrafiltration membrane and preparation method thereof |
| CN105126643A (en) * | 2015-08-21 | 2015-12-09 | 天津膜天膜科技股份有限公司 | Hollow fiber reverse osmosis membrane and preparation method thereof |
| CN106179447A (en) * | 2016-07-13 | 2016-12-07 | 淮阴师范学院 | Close coupling type attapulgite KHX g C3n4the preparation method of composite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108993171B (en) | 2021-06-11 |
| CN106902650B (en) | 2018-09-14 |
| CN106902650A (en) | 2017-06-30 |
| CN108993170A (en) | 2018-12-14 |
| CN108993170B (en) | 2021-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106902650B (en) | A kind of antipollution automatically cleaning vinylidene difluoride planar ultrafiltration membrane and its preparation method and application | |
| CN104971632B (en) | Easy-to-wash PVDF (polyvinylidene fluoride) ultrafiltration membrane and preparation method thereof | |
| Vatanpour et al. | Enhancing the permeability and antifouling properties of cellulose acetate ultrafiltration membrane by incorporation of ZnO@ graphitic carbon nitride nanocomposite | |
| CN109847586B (en) | High-flux reverse osmosis membrane and preparation method and application thereof | |
| CN104353366B (en) | A kind of polymeric film with antifouling and antibiosis function and preparation method thereof | |
| CN106902638B (en) | A kind of attapulgite-class graphite phase carbon nitride-polyvinylidene fluoride nanometer composite hyperfiltration membrane and its preparation method and application | |
| CN105457504A (en) | Novel titanium dioxide nano-particle/polymer hybrid membrane and preparation method thereof | |
| Malik et al. | Design and synthesis of polymeric membranes using water-soluble pore formers: An overview | |
| CN1973972A (en) | Prepn process of reinforced hybrid organic-inorganic film | |
| CN101837249A (en) | Composite polrvinyl chloride hollow fiber ultrafiltration membrane and preparation method thereof | |
| JP4243293B2 (en) | Polyvinyl chloride hollow filter membrane and process for producing the same | |
| CN104209018A (en) | Attapulgite/polyvinylidene fluoride nano-composite ultra-filtration membrane and preparation method thereof | |
| CN107433141A (en) | A kind of multi-walled carbon nanotube hybrid membranes for possessing antipollution automatically cleaning, anti-microbial property | |
| EP3471864A1 (en) | Periodic mesoporous organosilica-doped nanocomposite membranes and systems including same | |
| CN104383818A (en) | Composite microporous diaphragm, preparation method and application thereof | |
| Kumar et al. | Efficacy of polymeric nanofibrous membranes for proficient wastewater treatment | |
| CN103172898B (en) | Preparation method of polyetherimide/silicon dioxide hybrid membrane | |
| CN112295421B (en) | Surface-bonded TiO2/PVDF ultrafiltration membrane for photocatalysis | |
| Vatanpour et al. | Defected Ag/Cu-MOF as a modifier of polyethersulfone membranes for enhancing permeability, antifouling properties and heavy metal and dye pollutant removal | |
| CN108097062A (en) | It is a kind of for hollow fiber compound nanofiltration membrane of water filter purification and preparation method thereof | |
| CN108642861A (en) | A kind of electrostatic spinning prepares the compound film method of conduction absorption of nano-metal-oxide doping | |
| CN102464848B (en) | Composite material of polyacrylonitrile-based copolymer and carbon nanotubes, carbon fiber and preparation method of carbon fiber | |
| JPS6397202A (en) | Polyether sulfone resin semipermeable membrane and its production | |
| CN112473400B (en) | Graphene micro-ultrafiltration membrane and preparation method thereof | |
| CN105833740B (en) | A kind of Kynoar ultrafiltration dry state film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 211799 Duliang Xianglan building, economic development zone, Xuyi county, Huai'an City, Jiangsu Province Patentee after: HUAIYIN NORMAL University Address before: 223300 No. 111 Changjiang West Road, Huaiyin District, Jiangsu, Huaian Patentee before: HUAIYIN NORMAL University |