CN108525527A - Carbon fiber O3 catalytic oxidation composite separating film and its preparation method and application - Google Patents
Carbon fiber O3 catalytic oxidation composite separating film and its preparation method and application Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
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- 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
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0067—Inorganic membrane manufacture by carbonisation or pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- 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
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
A kind of carbon fiber O3 catalytic oxidation composite separating film and its preparation method and application, the composite separating film is constituted by carbon fibre composite is interlaced with each other, carbon fibre composite is loading titanium oxide and/or silica on carbon fiber, and carbon fiber is 1: 0.04~0.49 with the mass ratio of titanium oxide and/or silica；The thickness of a diameter of 200~1000nm of carbon fibre composite, seperation film are 200~700 μm, membrane aperture ranging from 20~150nm.Preparation method is to prepare the pan based fibers composite separating film containing titanium oxide and/or siliconoxide precursor first using electrical spinning method, is then handled by high temperature cabonization under pre-oxidation and inert gas shielding.The composite separating film has higher O3 catalytic oxidation performance and excellent membrane permeability energy, and realizes to be carried out at the same time O3 catalytic oxidation decomposition and film to sewage and recycled water and retain and be separated by filtration the integrated deep purifying function of pollutant.
Description
Technical field
The present invention relates to a kind of seperation films and its preparation method and application, and in particular to is with carbon fiber and its composite material
Carrier, the Separation membrane for water treatment and its preparation method and application for having O3 catalytic oxidation function, belong to technical field of membrane.
Background technology
Municipal sewage ingredient is sufficiently complex, and length of conventional biological treatment processing time, hold facility area are big, to part
Organic pollution is difficult to handle, the existing recycled water produced from the processing water-break of municipal wastewater treatment plant qualified discharge or regeneration water factory
In contain a certain amount of persistent organic pollutants, including multiring aromatic hydrocarbon, heterocyclic, organic cyanogen compound, Polychlorinated biphenyls, agriculture
Medicine, dyestuff, environmental hormone and personal care articles etc. have very big harm to the mankind and environment.Pass through novel pollution control technology
It thoroughly destroys organic pollution difficult to degrade and inactivation is easy the pathogenic microorganism of activation again, reach less toxic harmless emission, one
It is directly the major issue that recycling sewage generated by making field is constantly studied.
Membrane separation technique has become the current world because of the features such as floor space is small, flexible process design, high degree of automation
One of upper most important water technology.Wherein, Nanofiltration Membrane Separation Technology is due to can efficiently the overwhelming majority is small in quick separating water
Molecular contaminants, it has also become the hot spot of profound purification research.Due to the smaller pore diameter range of NF membrane (1~5nm) and half
Permeable membrane characteristic so that it can retain most of polluter in water body, to applied to the softening of the water of various industries and only
Change, substance separation and concentration, decoloration and taste removal etc..However in actual application, there are still following key technologies to ask for nanofiltration
Topic：(1) NF membrane is easy to pollute and cleaning is difficult；(2) membrane flux still needs to be further improved；(3) part small molecule is polluted
Object removal effect is limited；(4) concentrated water need to be further processed.
Catalytic ozonation is the high-level oxidation technology based on ozone, it is by the strong oxidizing property of ozone and catalyst
Absorption, catalysis characteristics combine, and can more efficiently solve the problems, such as that organic matter degradation is incomplete.Ozone high grade oxidation is catalyzed
Agent is divided into homogeneous catalysis ozonisation by the phase of catalyst and multi-phase catalytic ozonation is urged in homogeneous catalysis ozonation technique
Agent is evenly distributed and catalytic activity is high, but disadvantage is apparent, and catalyst is easy to run off, is not easily recycled and generate secondary pollution, operation
It is costly, increase cost of water treatment；Multi-phase catalytic ozonation method accelerates liquid phase oxidation under normal pressure using solid catalyst
Reaction, catalyst exist with solid-state, are easy to be separated from water, and secondary pollution is few, but catalyst service efficiency is relatively low.
Advantage and disadvantage based on membrane technology and catalytic ozonation, the patent skill of Patent No. ZL201310603496.7
Art " method of heterogeneous catalytic ozonation-nanofiltration combination unit and its water purifying and disinfection " using heterogeneous catalytic ozonation process with
Separation process of nanofiltration membrane series coupled realizes the deep purifying function of degrading and detach pollutant, and there is raising dissolved oxygen to contain
Amount improves the effects that subsequent film producing water ratio and mitigation fouling membrane.But this process combination purification method is in practical applications still
So have the following disadvantages：1. it is low that technique produces water efficiency；2. NF membrane is vulnerable to the destruction of ozone molecule.
Invention content
The purpose of the present invention is to provide carbon fiber O3 catalytic oxidation composite separating film and its preparation side of a kind of self-supporting
Method and application, which has higher O3 catalytic oxidation performance and excellent membrane permeability energy, and realizes pair
Sewage and recycled water are carried out at the same time the integrated deep purifying work(that O3 catalytic oxidation decomposition is separated by filtration pollutant with film retention
Energy.
To achieve the above object, the present invention takes following technical scheme：
A kind of carbon fiber O3 catalytic oxidation composite separating film is to constitute separation by carbon fibre composite is interlaced with each other
Film, the carbon fibre composite are loading titanium oxide and/or silica on carbon fiber, carbon fiber and titanium oxide and/or silica
Mass ratio be 1: 0.04~0.49；A diameter of 200~1000nm of carbon fibre composite, the thickness of seperation film is 200~
700 μm, membrane aperture ranging from 20~150nm.
Carbon fiber O3 catalytic oxidation composite separating film as described above, it is preferable that the carbon fiber is by polyacrylonitrile
Fiber sintering forms.
Carbon fiber O3 catalytic oxidation composite separating film as described above, it is preferable that the carbon fibre composite be by
Polyacrylonitrile fibre containing titanium oxide and/or siliconoxide precursor is sintered.
Carbon fiber O3 catalytic oxidation composite separating film as described above, it is preferable that the titania precursor body is titanium alcohol
Salt, the siliconoxide precursor are silicon alkoxide；Preferably, the Titanium alkoxides are butyl titanate or isopropyl titanate, the silanol
Salt is methyl orthosilicate or ethyl orthosilicate.
On the other hand, the present invention provides the preparation method of carbon fiber O3 catalytic oxidation composite separating film as described above, should
Method includes the following steps：
I. composite spinning liquid is prepared
Polyacrylonitrile, titanium oxide and/or siliconoxide precursor and n,N-Dimethylformamide are uniformly mixed, wherein poly-
The mass percent of acrylonitrile is 6%~18%, and the mass percent of titanium oxide and/or siliconoxide precursor is 1%~9%,
Surplus is n,N-Dimethylformamide；
II. pan based fibers film is prepared
The composite spinning liquid that step I is prepared is made by pan based fibers film, polyacrylonitrile-radical using electrical spinning method
A diameter of 250~2000nm of fiber is prepared per square meter tunica fibrosa, and the dosage of composite spinning liquid is 100~250mL；
III. heat treatment is dry and carbonizes
Then pan based fibers film heat drying prepared by step II keeps the temperature 0.5~5h in 150~280 DEG C, into
One step is passed through inert gas, is warming up to 600~1000 DEG C of 0.5~5h of heat preservation, is down to room temperature to get carbon fiber O3 catalytic oxidation
Composite separating film.
Preparation method as described above, it is preferable that the concrete operations of the step II are as follows：
The composite spinning liquid that step I is prepared is added in the feed liquid device of Electrospun instrument, feed liquid device is equipped with needle-like metal
Nozzle；The operating condition of Electrospun instrument is：Feed liquid device driving velocity is 1~2mL/h, and spinning voltage is 10~20 kilovolts, nozzle
Be 9~16cm at a distance from receiver board, it is 100~250mL to prepare the dosage per square meter tunica fibrosa composite spinning liquid.
Another aspect, the present invention provide a kind of carbon fiber O3 catalytic oxidation composite separating film, are using as described above
Method prepare.
In another aspect, the present invention provides carbon fiber O3 catalytic oxidation composite separating film as described above in removing sewage
The application in hazardous contaminant field, with the carbon fiber O3 catalytic oxidation composite separating film treat purifying water body simultaneously into
Row Interfacial Adsorption, retention filtering and O3 catalytic oxidation.
Application as described above, it is preferable that the water body to be clean is micro-polluted surface water, source water or recycled water.
Application as described above, it is preferable that the specific method of the application is：Treatment sewage is passed through into compound-split
The pressure difference of film, film both sides is 0.02~0.20MPa, and composite separating film adsorbs organic pollutants and retain separation；
Be carried out at the same time it is ozonation aerated, compound-split film layer be activated generate hydroxyl radical free radical isoreactivity substance, to film absorption it is same
When retention substance occur redox reaction realize degradation.
When for the water treatment or micro-polluted surface Water warfare, composite separating film should be strengthened to not during film preparation
The absorption of generic pollutant and cutoff performance, preferably use lower quality than polyacrylonitrile (PAN) powder, better quality than
Ethyl orthosilicate is simultaneously dissolved in n,N-Dimethylformamide (DMF) as composite spinning formula of liquid.In practical water purifying process,
To ensure that film producing water ratio and pollutant removal, both sides differential pressure of membrane are preferably greater than 0.05Mpa.
When for recycled water advanced treating, composite separating film should be strengthened to the organic dirt of difficult for biological degradation during film preparation
Catalysis and the cutoff performance for contaminating object, preferably use lower quality than polyacrylonitrile (PAN) powder and butyl titanate and be dissolved in
N,N-Dimethylformamide (DMF) solution is as composite spinning formula of liquid.In practical water purifying process, to take into account film producing water ratio
And catalytic degradation effect, both sides differential pressure of membrane are preferably greater than 0.1Mpa.
When for earth's surface water pretreatment or stain disease advanced treating, it should be strengthened to different classes of dirt during film preparation
The catalytic performance for contaminating object, preferably uses polyacrylonitrile (PAN) powder of better quality percentage, the titanium oxide of better quality percentage
It is compounded with the presoma of silica, and is dissolved in n,N-Dimethylformamide (DMF) solution as composite spinning formula of liquid.In reality
In border pretreatment or advanced treatment process, to ensure Interfacial Adsorption effect, extending catalysis reaction time, raising catalytic degradation
Can, both sides differential pressure of membrane is preferably less than 0.1Mpa.
The beneficial effects of the present invention are the present invention is prepared first using electrical spinning method containing before titanium oxide and/or silica
Polyacrylonitrile (PAN) base fiber composite seperation film of body is driven, is then passed through under pre-oxidation and inert gas shielding at high temperature cabonization
Reason forms carbon fiber O3 catalytic oxidation composite separating film.Since membrane material is the function separation being made of nano-fiber material
Film not only increases permeability of the membrane energy, and the carbon fibre composite formed has higher Catalytic Ozonation Activity.
Therefore, carbon fiber O3 catalytic oxidation composite separating film of the invention has catalytic degradation and film compared with traditional seperation film
Multifunctional integrated property is detached, and has ensured higher producing water ratio.
The membrane aperture of composite separating film of the present invention ranging from 20~150nm, room temperature lower film infiltration coefficient up to 2000~
7000L/(m2hMPa).It, can be as the main of flow in terms of micro-polluted surface water process, sewage and regeneration advanced water treatment
The pretreating process of technique unit or main technique unit is used with advanced treatment process.When accessing pending water passes through compound-split
When film, the pressure differences of film both sides is 0.02~0.20MPa, and composite separating film adsorbs organic pollutants and retains point
From；Be carried out at the same time it is ozonation aerated, compound-split film layer be activated generate hydroxyl radical free radical isoreactivity substance, to film absorption
Substance is retained simultaneously, and redox reaction realization degradation occurs.It is total organic for micro-polluted surface water, source water or recycled water
Carbon removal rate is up to 90%, CODCrConcentration reduces by 66~72%, is gone to dirt (useless) water pollutant containing single organic pollution
Except rate is 75~83%.The composite separating film realizes the integration of the multiple-units such as UF membrane, catalytic degradation and sterilizing, reduces throwing
Money and floor space, while preparation and technique for applying are simple, are easy to large-scale industrial production and application.
Description of the drawings
Fig. 1 a are the scanning electron microscope front view of the carbon fiber composite separating film of PAN a concentration of 6% in composite spinning liquid, carbon fiber
It is about 200nm to tie up composite material average diameter.
Fig. 1 b are the scanning electron microscope front view of the carbon fiber composite separating film of PAN a concentration of 18% in composite spinning liquid, carbon
Fibrous composite average diameter is about 1000nm.
Fig. 2 a are scanning electron microscope (SEM) photo of carbon fiber O3 catalytic oxidation composite separating film prepared by comparative example 1.
Fig. 2 b are scanning electron microscope (SEM) photo of carbon fiber O3 catalytic oxidation composite separating film prepared by embodiment 1.
Fig. 2 c are scanning electron microscope (SEM) photo of carbon fiber O3 catalytic oxidation composite separating film prepared by embodiment 2.
Fig. 2 d are scanning electron microscope (SEM) photo of carbon fiber O3 catalytic oxidation composite separating film prepared by embodiment 3.
Fig. 3 a are cross section scanning electron microscope (SEM) of carbon fiber O3 catalytic oxidation composite separating film prepared by comparative example 1
Figure.
Fig. 3 b are cross section scanning electron microscope (SEM) of carbon fiber O3 catalytic oxidation composite separating film prepared by embodiment 1
Figure.
Fig. 3 c are cross section scanning electron microscope (SEM) of carbon fiber O3 catalytic oxidation composite separating film prepared by embodiment 2
Figure.
Fig. 3 d are cross section scanning electron microscope (SEM) of carbon fiber O3 catalytic oxidation composite separating film prepared by embodiment 3
Figure.
Specific implementation mode
Below by specific embodiment, further illustrate carbon fiber O3 catalytic oxidation compound-split membrane preparation method and its
Using.
Embodiment 1
It is net for the water treatment containing natural organic matter (NOMs), pathogenic bacteria, algae etc. or micro-polluted surface water
When change, carbon fiber loaded silica O3 catalytic oxidation composite separating film can be prepared using the following conditions.Step is：
The first step, composite spinning liquid are prepared
Measure polyacrylonitrile (PAN) powder, 9% ethyl orthosilicate and 83% N, N- bis- that mass percent is 8%
Methylformamide (DMF), three mixes is heated to 40 DEG C while stirring, until polyacrylonitrile powder all dissolves, prepares
Go out uniform composite spinning liquid.
Second step, PAN base fiber composites detach film preparation
The spinning solution configured is added to Electrospun instrument (manufacturer：Beijing new master one hundred receives Science and Technology Ltd.；Type
Number：TEADFS-101 types) feed liquid device in, feed liquid device is equipped with needle-like metal nozzle.The operating condition that Electrospun instrument is arranged is：
Feed liquid device driving velocity is 2mL/h, and spinning voltage is 20 kilovolts, is 16cm at a distance from receiver board.It prepares per square meter tunica fibrosa
The dosage of composite spinning liquid is 150mL.
Third walks, and heat treatment is dry and carbonizes
It is put into the PAN base fiber composite seperation films drying 1h prepared in vacuum drying oven, is then put into Muffle furnace
Composite separating film after drying is further passed through inert gas, rises from room temperature to 280 DEG C of heat preservation 5h in air atmosphere
Then temperature is down to room temperature with 500 DEG C/h, prepares and complete to 1000 DEG C of heat preservation 5h.
Testing result：Carbon fiber loaded silica O3 catalytic oxidation composite separating film average pore size is 50~100nm,
Composite membrane infiltration coefficient is about 3500L/ (m2hMPa).Film surface is smooth and is in netted chi structure, is covered with carbon fiber loaded dioxy
Change titanium composite fibre.
Fig. 2 b are scanning electron microscope (SEM) photo of the carbon fiber O3 catalytic oxidation composite separating film prepared, scanning electron microscope
Accelerating potential is 10kV, and 5000 times of amplification factor is shot along perpendicular to composite membrane direction.Photo is as it can be seen that due to preparing spinning solution
The PAN mass percents of Shi Caiyong are relatively low, are prepared through electrostatic spinning, after heat treatment drying and charing, it is negative to be formed by carbon fiber
It is about 500nm to carry average fibre diameter on silica O3 catalytic oxidation composite separating film, due to silicon alkoxide (positive silicic acid second
Ester) mass percent in spinning solution is higher, and the film surface composite fibre diameter distribution after carbonization is relatively uneven but still by fibre
Netted chi structure is tieed up to constitute.
Fig. 3 (b) is scanning electron microscope (SEM) cross-sectional view of the carbon fiber O3 catalytic oxidation composite separating film prepared.Figure
Middle scanning electron microscope accelerating potential is 10kV, and 75-200 times of amplification factor is shot along composite membrane direction is parallel to.As seen from the figure, by
The PAN mass percents used when preparing spinning solution are relatively low, prepared through electrostatic spinning, after heat treatment drying and charing, institute's shape
At carbon fiber loaded silica O3 catalytic oxidation composite separating film it is relatively thin, film average thickness is about 200 μm, due to silanol
Mass percent of the salt (ethyl orthosilicate) in spinning solution is higher, and the film section after carbonization is by the netted cross knot of multi-layer fiber
It is configured to.
Embodiment 2
Water depth is given off for containing sewage treatment plants such as persistence organic pollutant, environmental hormone, personal care articles
When processing, carbon fiber loaded Titanium Dioxide ozone oxidation composite separating film can be prepared with the following conditions.Step is：
The first step, composite spinning liquid are prepared
Polyacrylonitrile (PAN) powder, 1% solution of tetrabutyl titanate and 91% N that mass percent is 8% are measured,
Dinethylformamide (DMF) solution, three mixes is heated to 80 DEG C while stirring, until polyacrylonitrile powder is all molten
Solution, prepares uniform composite spinning liquid.
Second step, PAN base fiber composites detach film preparation
The spinning solution configured is added to Electrospun instrument (manufacturer：Beijing new master one hundred receives Science and Technology Ltd.；Type
Number：TEADFS-101 types) feed liquid device in, feed liquid device is equipped with needle-like metal nozzle.The operating condition that Electrospun instrument is arranged is：
Feed liquid device driving velocity is 1mL/h, and spinning voltage is 10 kilovolts, is 9cm at a distance from receiver board, is prepared multiple per square meter tunica fibrosa
The dosage for closing spinning solution is 250mL.
Third walks, and heat treatment is dry and carbonizes
It is put into the PAN base fiber composite seperation films drying 5h prepared in vacuum drying oven, is then put into Muffle furnace
Composite separating film after drying is further passed through inert gas from room temperature to 150 DEG C of heat preservation 0.5h in air atmosphere,
600 DEG C of heat preservation 0.5h are warming up to, room temperature is then down to 50 DEG C/h, prepares and completes.
Testing result：Carbon fiber loaded Titanium Dioxide ozone oxidation compound-split membrane aperture be average pore size be 20~
50nm, composite membrane infiltration coefficient are about 2000L/ (m2hMPa).Film surface is smooth and is in netted chi structure, is covered with carbon fiber loaded
Titanium dioxide composite fibre.
Fig. 2 c are scanning electron microscope (SEM) photo of the carbon fiber O3 catalytic oxidation composite separating film prepared, scanning electron microscope
Accelerating potential is 10kV, and 5000 times of amplification factor is shot along perpendicular to composite membrane direction.As seen from the figure, due to preparing spinning solution
The PAN mass percents of Shi Caiyong are relatively low, are prepared through electrostatic spinning, after heat treatment drying and charing, it is negative to be formed by carbon fiber
It is about 500nm to carry average fibre diameter on silica O3 catalytic oxidation composite separating film, and the film surface fiber after carbonization is straight
Diameter is still more single, the features such as being made of fibrous web-like chi structure.
Fig. 3 (c) is scanning electron microscope (SEM) cross-sectional view of the carbon fiber O3 catalytic oxidation composite separating film prepared.Figure
Middle scanning electron microscope accelerating potential is 10kV, and 75-200 times of amplification factor is shot along composite membrane direction is parallel to.As seen from the figure, by
The PAN mass percents used when preparing spinning solution are relatively low, prepared through electrostatic spinning, after heat treatment drying and charing, institute's shape
At carbon fiber loaded silica O3 catalytic oxidation compound-split film thickness it is moderate, film average thickness is about 500 μm, through carbon
Film section after change is formed by the netted chi structure of multi-layer fiber.
Embodiment 3
For the micro-polluted surface water pretreatment containing suspended solid particles, NOMs, bacterium, algae etc. or difficult to degrade organic
When the stain disease advanced treating of pollutant, it is smelly that carbon fiber loaded titania/silica catalysis can be prepared with the following conditions
Oxygen aoxidizes composite separating film.Step is：
The first step, composite spinning liquid are prepared
Measurement mass percent is 18% polyacrylonitrile (PAN) powder, 1.5% methyl orthosilicate solution, 7.5%
Titanium isopropoxide solution and 73% n,N-Dimethylformamide (DMF) solution, four mix and are heated to 60 DEG C while stirring,
Until polyacrylonitrile powder all dissolves, uniform composite spinning liquid is prepared.
Second step, PAN base fiber composites detach film preparation
The spinning solution configured is added to Electrospun instrument (manufacturer：Beijing new master one hundred receives Science and Technology Ltd.；Type
Number：TEADFS-101 types) feed liquid device in, feed liquid device is equipped with needle-like metal nozzle.The operating condition that Electrospun instrument is arranged is：
Feed liquid device driving velocity is 1.5mL/h, and spinning voltage is 15 kilovolts, is 13cm at a distance from receiver board, prepares per square meter fiber
The dosage of film composite spinning liquid is 100mL.
Third walks, and heat treatment is dry and carbonizes
It is put into the PAN base fiber composite seperation films drying 2h prepared in vacuum drying oven, is then put into Muffle furnace
Composite separating film after drying is further passed through inert gas, rises from room temperature to 200 DEG C of heat preservation 2h in air atmosphere
Then temperature is down to room temperature with 100 DEG C/h, prepares and complete to 800 DEG C of heat preservation 2h.
Testing result：Carbon fiber loaded Titanium Dioxide ozone oxidation compound-split membrane aperture be average pore size be 50~
150nm, the infiltration coefficient under composite membrane room temperature are 7000L/ (m2hMPa).Film surface is smooth and is in netted chi structure, is covered with carbon
Fiber-loaded titanium dioxide composite fibre.
Fig. 2 d are scanning electron microscope (SEM) photo of the carbon fiber O3 catalytic oxidation composite separating film prepared, scanning electron microscope
Accelerating potential is 10kV, and 5000 times of amplification factor is shot along perpendicular to composite membrane direction.As seen from the figure, due to preparing spinning solution
The PAN mass percents of Shi Caiyong are higher, are prepared through electrostatic spinning, after heat treatment drying and charing, it is negative to be formed by carbon fiber
It is about 1000nm to carry average fibre diameter on silica O3 catalytic oxidation composite separating film, despite the use of methyl orthosilicate
Solution, titanium isopropoxide solution as compounded formula, but film surface fibre diameter after carbonization it is still more single, by fibrous web-like
The features such as chi structure is constituted.
Fig. 3 (d) is scanning electron microscope (SEM) cross-sectional view of the carbon fiber O3 catalytic oxidation composite separating film prepared.Figure
Middle scanning electron microscope accelerating potential is 10kV, and 75-200 times of amplification factor is shot along composite membrane direction is parallel to.As seen from the figure, by
The PAN mass percents used when preparing spinning solution are higher, prepared through electrostatic spinning, after heat treatment drying and charing, institute's shape
At carbon fiber loaded silica O3 catalytic oxidation composite separating film it is thicker, film average thickness is about 600 μm, after carbonization
Film section formed by the netted chi structure of multi-layer fiber.
Embodiment 4 prepares carbon fiber O3 catalytic oxidation composite separating film
The first step, composite spinning liquid are prepared
Measure polyacrylonitrile (PAN) powder, 1% ethyl orthosilicate and 93% N, N- bis- that mass percent is 6%
Methylformamide (DMF), three mixes is heated to 40 DEG C while stirring, until polyacrylonitrile powder all dissolves, prepares
Go out uniform composite spinning liquid.
Second step, PAN base fiber composites detach film preparation
The spinning solution configured is added to Electrospun instrument (manufacturer：Beijing new master one hundred receives Science and Technology Ltd.；Type
Number：TEADFS-101 types) feed liquid device in, feed liquid device is equipped with needle-like metal nozzle.The operating condition that Electrospun instrument is arranged is：
Feed liquid device driving velocity is 2mL/h, and spinning voltage is 20 kilovolts, is 16cm at a distance from receiver board.
Third walks, and heat treatment is dry and carbonizes
It is put into the PAN base fiber composite seperation films drying 1h prepared in vacuum drying oven, is then put into Muffle furnace
Composite separating film after drying is further passed through inert gas, rises from room temperature to 280 DEG C of heat preservation 5h in air atmosphere
Then temperature is down to room temperature with 500 DEG C/h, prepares and complete to 1000 DEG C of heat preservation 5h.
Testing result：Carbon fiber loaded silicon dioxide composite material average diameter is about 200nm.
Fig. 1 (a) is that the scanning electron microscope of the PAN base fiber composite seperation films of PAN a concentration of 6% in composite spinning liquid is faced
Figure.
Embodiment 5 prepares carbon fiber O3 catalytic oxidation composite separating film
The first step, composite spinning liquid are prepared
Polyacrylonitrile (PAN) powder, 3% solution of tetrabutyl titanate and 79% N that mass percent is 18% are measured,
Dinethylformamide (DMF) solution, three mixes is heated to 80 DEG C while stirring, until polyacrylonitrile powder is all molten
Solution, prepares uniform composite spinning liquid.
Second step, PAN base fiber composites detach film preparation
The spinning solution configured is added to Electrospun instrument (manufacturer：Beijing new master one hundred receives Science and Technology Ltd.；Type
Number：TEADFS-101 types) feed liquid device in, feed liquid device is equipped with needle-like metal nozzle.The operating condition that Electrospun instrument is arranged is：
Feed liquid device driving velocity is 1mL/h, and spinning voltage is 10 kilovolts, is 9cm at a distance from receiver board.
Third walks, and heat treatment is dry and carbonizes
It is put into the PAN base fiber composite seperation films drying 5h prepared in vacuum drying oven, is then put into Muffle furnace
Composite separating film after drying is further passed through inert gas from room temperature to 150 DEG C of heat preservation 0.5h in air atmosphere,
600 DEG C of heat preservation 0.5h are warming up to, room temperature is then down to 50 DEG C/h, prepares and completes.
Testing result：Carbon fiber loaded silicon dioxide composite material average diameter is about 1000nm.
Fig. 1 (b) is that the scanning electron microscope of the PAN base fiber composite seperation films of PAN a concentration of 18% in composite spinning liquid is faced
Figure.
Comparative example 1：
As a comparison, while non-loaded carbon fiber O3 catalytic oxidation composite separating film is prepared, step is：
The first step, PAN preparation of spinning solution
It is 12% polyacrylonitrile (PAN) powder and 88% n,N-Dimethylformamide (DMF) to measure mass percent
Solution, the two mixes is heated to 80 DEG C while stirring, until polyacrylonitrile powder all dissolves, prepares uniform PAN
Spinning solution.
Second step, PAN fiber detach film preparation
The spinning solution configured is added to Electrospun instrument (manufacturer：Beijing new master one hundred receives Science and Technology Ltd.；Type
Number：TEADFS-101 types) feed liquid device in, feed liquid device is equipped with needle-like metal nozzle.The operating condition that Electrospun instrument is arranged is：
Feed liquid device driving velocity is 1.5mL/h, and spinning voltage is 15 kilovolts, is 13cm at a distance from receiver board, prepares per square meter fiber
The dosage of film composite spinning liquid is 200mL.
Third walks, and heat treatment is dry and carbonizes
The PAN fiber seperation film drying 2h prepared is put into vacuum drying oven, after drying is then put into Muffle furnace
Seperation film, in air atmosphere from room temperature to 200 DEG C heat preservation 2h, be further passed through inert gas, be warming up to 800 DEG C of guarantors
Then warm 2h is down to room temperature with 100 DEG C/h, prepare and complete.
Testing result：Non-loaded carbon fiber O3 catalytic oxidation seperation film average pore size is 50~100nm, and carbon-fiber film oozes
Saturating coefficient is 4000L/ (m2hMPa).Film surface is smooth and is in netted chi structure.
Fig. 2 a are scanning electron microscope (SEM) photo of the non-loaded carbon fiber O3 catalytic oxidation seperation film prepared, scanning
Electronic Speculum accelerating potential is 10kV, and 5000 times of amplification factor is shot along perpendicular to composite membrane direction.As seen from the figure, it is spun due to preparing
The PAN mass percents used when silk liquid are higher, prepare, after heat treatment drying and charing, are formed by without negative through electrostatic spinning
Average fibre diameter is about 1000nm in the carbon fiber O3 catalytic oxidation seperation film of load, and the film surface fibre diameter after carbonization is still
So more single, the features such as being made of fibrous web-like chi structure.
Fig. 3 (a) is scanning electron microscope (SEM) cross-sectional view of the carbon fiber O3 catalytic oxidation composite separating film prepared.Figure
Middle scanning electron microscope accelerating potential is 10kV, and 75-200 times of amplification factor is shot along composite membrane direction is parallel to.As seen from the figure, by
The PAN mass percents used when preparing spinning solution are higher, prepared through electrostatic spinning, after heat treatment drying and charing, institute's shape
At non-loaded carbon fiber O3 catalytic oxidation seperation film it is thicker, film average thickness is about 700 μm, the film section after carbonization
It is formed by the netted chi structure of multi-layer fiber.
6 carbon fiber loaded silica O3 catalytic oxidation composite separating film of embodiment is used for water source water pretreatment
×× reservoir is Beijing City resource of water supply, water quality：Total organic carbon initial concentration is 3.05mg/L, and total plate count is
560/mL, chlorophyll a initial concentration is 3.25mg/m3；Flow of inlet water is 5L/h, and water intaking water is 50.0L.
Carbon fiber loaded silica O3 catalytic oxidation composite separating film pretreatment purification water source in Application Example 1
Water.Under room temperature, pending source water is flowed through into film test cell by pump by the way of cross-flow filtration.In two side pressure of film
While difference is membrane filtration under 0.1Mpa, in compound point of O3 catalytic oxidation in such a way that ozone generator is by jet-flow aeration
It is reacted from film, ozone adds a concentration of 2.5mg/L.1 is the results are shown in Table, effluent quality is basicly stable after processing 1 hour, water outlet
Organic carbon concentration is 0.30mg/L, and total organic carbon treatment effeciency reaches 90% or more, and total plate count is 18/mL, Ye Lv
Plain a concentration of 0.26mg/m of a3.By advanced treating, CODMnDrinking water water has been had reached with total two indexs of microbe colony
Matter standard GB/T5750-2006.
After operation 1 hour, compound-split membrane flux compares the stabilized flux slightly decaying, but and conventional ultrafiltration after membrane pressure reality
Film (membrane aperture 0.22um) is compared, and the decline of membrane flux degree significantly slows down, and shows the film to source water preprocessing process
In have certain self-cleaning antifouling property；Composite separating film is taken out from membrane module and further through microscopic examination,
Film surface structural integrity, film surface have part microorganism corpse and bacterium remains etc. to adhere to film surface, it is micro- to containing to demonstrate the film
The source water of biology, bacterium etc. has stronger sterilization ability.
1 carbon fiber loaded silica O3 catalytic oxidation composite separating film of table is used for source water pretreating effect
7 carbon fiber loaded Titanium Dioxide ozone oxidation composite separating film of embodiment is for regenerating advanced water treatment
Beijing ×× recycled water plant effluent, water quality：CODCrA concentration of 24.9mg/L, concentration of suspension 26.0mg/L, ammonia
Nitrogen concentration is 2.26mg/L；Flow of inlet water is 10L/h, and water intaking water is 50L.
Carbon fiber loaded Titanium Dioxide ozone oxidation composite separating film deep purifying regeneration in Application Example 2
Water.Under room temperature, pending recycled water is flowed through into film test cell by pump by the way of cross-flow filtration.It is in pressure difference
Under 0.2Mpa while membrane filtration, in O3 catalytic oxidation composite separating film in such a way that ozone generator is by jet-flow aeration
It is reacted, ozone adds a concentration of 5.0mg/L.2 are the results are shown in Table, is handled 2 hours, effluent quality is basicly stable, CODCrConcentration
For 8.51mg/L, concentration of suspension 7.0mg/L, ammonia nitrogen concentration 0.82mg/L；CODCrIt has been reached with two water quality index of ammonia nitrogen
To surface water Group III standard, high-quality recycled water can be used as to carry out circulating and recovering.
After operation 2 hours, compound-split membrane flux, without notable decaying, shows the film compared to the stabilized flux after membrane pressure reality
There is preferable self-cleaning antifouling property during regenerating advanced water treatment；Composite separating film is taken out simultaneously from membrane module
Further through microscopic examination, film surface structural integrity, no notable pollution layer is formed, and does not find notable bad point or film surface defect
Point.
2 carbon fiber loaded Titanium Dioxide ozone oxidation composite separating film of table is for regenerating advanced water treatment effect
8 carbon fiber loaded titania/silica O3 catalytic oxidation composite separating film of embodiment is used for dirty (useless) water
Advanced treating
Beijing ×× laboratory phenol wastewater, Pollutant Composition are bisphenol-A, and influent concentration is about 10mg/L；Water inlet
Flow is 5L/h, and water intaking water is 100L.
Carbon fiber loaded titania/silica O3 catalytic oxidation compound-split film process in Application Example 3
Phenol wastewater.Under room temperature, pending earth's surface aqueous solution is flowed through into film test cell by pump by the way of cross-flow filtration.
While membrane filtration under pressure difference is 0.02Mpa, in O3 catalytic oxidation in such a way that ozone generator is by jet-flow aeration
Composite separating film is reacted, and ozone adds a concentration of 7.5mg/L.3 are the results are shown in Table, is handled 4 hours, after stable effluent quality,
Its treatment effeciency reaches 75%.By being further processed, quality of reused water standard is reached.
After operation 4 hours, compound-split membrane flux, without notable decaying, shows the film compared to the stabilized flux after membrane pressure reality
There is preferable operation stability in the dirt of one-component (useless) water depth processing procedure；By composite separating film from membrane module
It is middle taking-up and further through microscopic examination, film surface structural integrity does not find notable bad point or film surface defect point.
3 carbon fiber loaded titania/silica O3 catalytic oxidation composite separating film of table is used for dirty (useless) water depth
Processing
Claims (10)
1. a kind of carbon fiber O3 catalytic oxidation composite separating film, which is characterized in that it is handed over each other by carbon fibre composite
For paramnesia at seperation film, which is loading titanium oxide and/or silica on carbon fiber, carbon fiber and titanium oxide
And/or the mass ratio of silica is 1: 0.04~0.49；A diameter of 200~1000nm of carbon fibre composite, seperation film
Thickness is 200~700 μm, membrane aperture ranging from 20~150nm.
2. carbon fiber O3 catalytic oxidation composite separating film as described in claim 1, which is characterized in that the carbon fiber be by
Polyacrylonitrile fibre is sintered.
3. carbon fiber O3 catalytic oxidation composite separating film as described in claim 1, which is characterized in that the carbon fiber is compound
Material is sintered by the polyacrylonitrile fibre containing titanium oxide and/or siliconoxide precursor.
4. carbon fiber O3 catalytic oxidation composite separating film as described in claim 1, which is characterized in that the titania precursor
Body is Titanium alkoxides, and the siliconoxide precursor is silicon alkoxide；Preferably, the Titanium alkoxides be butyl titanate or isopropyl titanate,
The silicon alkoxide is methyl orthosilicate or ethyl orthosilicate.
5. the preparation method of any one of the claim 1-4 carbon fiber O3 catalytic oxidation composite separating films, feature exist
In this method comprises the following steps：
I. composite spinning liquid is prepared
Polyacrylonitrile, titanium oxide and/or siliconoxide precursor and n,N-Dimethylformamide are uniformly mixed, wherein polypropylene
The mass percent of nitrile is 6%~18%, and the mass percent of titanium oxide and/or siliconoxide precursor is 1%~9%, surplus
For n,N-Dimethylformamide；
II. pan based fibers film is prepared
The composite spinning liquid that step I is prepared is made by pan based fibers film, pan based fibers using electrical spinning method
A diameter of 250~2000nm, prepare per square meter tunica fibrosa, the dosage of composite spinning liquid is 100~250mL；
III. heat treatment is dry and carbonizes
Then pan based fibers film heat drying prepared by step II keeps the temperature 0.5~5h, further in 150~280 DEG C
It is passed through inert gas, 600~1000 DEG C of 0.5~5h of heat preservation is warming up to, it is compound to get carbon fiber O3 catalytic oxidation to be down to room temperature
Seperation film.
6. preparation method as claimed in claim 5, which is characterized in that the concrete operations of the step II are as follows：
The composite spinning liquid that step I is prepared is added in the feed liquid device of Electrospun instrument, feed liquid device is equipped with needle-like metal nozzle；
The operating condition of Electrospun instrument is：Feed liquid device driving velocity is 1~2mL/h, and spinning voltage is 10~20 kilovolts, nozzle and reception
The distance of plate is 9~16cm, and it is 100~250mL to prepare the dosage per square meter tunica fibrosa composite spinning liquid.
7. a kind of carbon fiber O3 catalytic oxidation composite separating film, which is characterized in that it is using described in claim 5 or 6
Prepared by method.
8. the carbon fiber O3 catalytic oxidation composite separating film described in any one of claim 1-4 or 7 has in removing sewage
The application in malicious noxious pollutant field, which is characterized in that with the carbon fiber O3 catalytic oxidation composite separating film to be clean
Water body is carried out at the same time Interfacial Adsorption, retention filtering and O3 catalytic oxidation.
9. application as claimed in claim 8, which is characterized in that the water body to be clean be micro-polluted surface water, source water or
Recycled water.
10. application as claimed in claim 8 or 9, which is characterized in that the specific method of the application is：By treatment sewage
By composite separating film, the pressure difference of film both sides is 0.02~0.20MPa, and composite separating film adsorbs organic pollutants
It is detached with retention；Be carried out at the same time it is ozonation aerated, compound-split film layer be activated generate hydroxyl radical free radical isoreactivity substance, to
Redox reaction realization degradation occurs for retention substance while film adsorbs.
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