CN105457500A - Carbon nano tube/porous ceramic hollow fiber composite ultrafiltration membrane as well as preparation method and application thereof - Google Patents
Carbon nano tube/porous ceramic hollow fiber composite ultrafiltration membrane as well as preparation method and application thereof Download PDFInfo
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- CN105457500A CN105457500A CN201511002441.6A CN201511002441A CN105457500A CN 105457500 A CN105457500 A CN 105457500A CN 201511002441 A CN201511002441 A CN 201511002441A CN 105457500 A CN105457500 A CN 105457500A
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/08—Thickening liquid suspensions by filtration
- B01D17/085—Thickening liquid suspensions by filtration with membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
- B01D46/543—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
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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
- B01D67/0072—Inorganic membrane manufacture by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
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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
- B01D69/08—Hollow fibre membranes
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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
Abstract
The invention discloses a carbon nano tube/porous ceramic hollow fiber composite ultrafiltration membrane as well as a preparation method and application thereof. The preparation method comprises the following steps: carrying out ultrasonic vibration on a hollow fiber ceramic membrane used as a carrier with absolute ethyl alcohol and washing the hollow fiber ceramic membrane with de-ionized water until the hollow fiber ceramic membrane is neutral; drying to obtain the treated carrier; coating a Ni(NO3)2 solution onto the treated carrier by using an impregnation coating method; after drying, putting the carrier into a muffle furnace to be roasted to obtain a hollow fiber membrane loaded with a nickel oxide catalyst; putting the hollow fiber membrane into a quartz reaction tube and introducing N2 and H2 into the quartz reaction tube to reduce a catalyst; and switching into hydrogen gas and raising the temperature, switching a gas flow into pure methane gas and carrying out a high-temperature reaction to obtain the product. The carbon nano tube/porous ceramic hollow fiber composite ultrafiltration membrane can be used for separating liquid-water emulsion liquid and bacteria, and has a very good effect of removing PM1 fine particles in atmosphere.
Description
Technical field
The present invention relates to inoranic membrane field, particularly relate to a kind of CNT/porous ceramics doughnut composite hyperfiltration membrane, Preparation method and use.
Background technology
Environmental problem is the focus of countries in the world common concern all the time, and water pollution, atmosphere pollution at every moment threaten the living environment of the mankind.Water pollution: Oil spills and oil-containing industrial water discharge have been worldwide problems, this brings many noxious materials to ocean, be delivered to higher mammal by marine food chain from rudimentary plant algae to comprise in each species body of the mankind, organism species and human health are on the hazard.Nowadays, there is more and more organic matter and the high low quality waters of content of microorganisms in the whole world, the demand that rational utilization of water resources converts it into clean drinking water constantly increases.Atmosphere pollution: along with process of industrialization deeply and fast-developing, the dust granules thing be discharged in air sharply increases, wherein PM
2.5(particulate pollutant that particle diameter is less than 2.5 μm) can cause serious injury the health of the mankind, directly can enter bronchus after it is inhaled into human body, causes the diseases such as asthma, bronchitis, pneumoconiosis and cardiovascular disease.In addition, PM
2.5haze weather also can be caused to take place frequently and the significantly increase of poisonous and harmful substance concentration in mist, affect the normal trip of people and serious harm is caused to vegeto-animal normal growth.Fine particle (PM
2.5) in, PM
1proportion is up to 80%-90%.And research shows, at PM
2.5in, PM
1be only the arch-criminal affecting vision visibility and health.Therefore, effectively to reduce the filtering material of particulate pollutant in air significant for design and preparation.
CNT has great draw ratio, and (its length is more than micron order, diameter only has several nanometer or tens nanometers), there is unique mechanical property, as tensile strength reaches 100 gpa, modulus is up to 1800 gpa, and resistance to strong acid, highly basic, less than 600 DEG C are substantially not oxidized, and these features make CNT become a kind of excellent filtering material.For existing CNT filter membrane, film-forming process needs first to be distributed into preparation liquid to CNT, because of carbon nano tube surface inertia, difficult dispersion, generally need carbon pipe to be carried out to the process such as strong acid oxidation to be beneficial to be dispersed in solvent, but this meeting destroying carbon nanometer tube structure, affect its performance.And prepare carbon nano-tube film by the method for vacuum drying, condition is comparatively complicated, is awkward.And raw materials used unfavorable to environment, cause and have certain limitation with the preparation of this regulation modelling.And the carbon nanotube diameter in this carbon nano-tube film comparatively large (being generally greater than 15 nanometers), make the micropore size in the filter membrane prepared comparatively large, filter effect is poor.Due to the filter membrane toughness of carbon nano-tube film and self-supporting poor, must be supported on filter substrate during use, how overcoming the adhesion of carbon nano-tube film and substrate weak is a key technical problem, and this is also to the simplification of membrane module, miniaturization and intensive very unfavorable.Therefore the difficulties in dispersion problem of CNT preparation liquid and the rete of preparation and these deficiencies of supporter adhesion problem all govern the application of this kind of carbon nano-tube film.
In view of this, provide the bond strength of a kind of supportive better, between carbon film and carrier high and carbon nano-tube compound film that is that be easy to prepare has great importance.Utilize chemical vapour deposition technique (CVD) in-situ growing carbon nano tube rete can ensure the combination of carbon nanotube layer and substrate, also effectively can ensure the electric property etc. of composite membrane.This method mainly uses the transition metal of nanoscale as catalyst, the source of the gas in-situ preparation of carbon nanotube rete of pyrolysis carbon containing.Preparation is suitable for the carbon nano-tube film of practical application, and CNT first will be enable to grow on suitable carrier, because the method preparation process is carried out usually at higher temperatures, so this supporter must be high temperature resistant, and stable in properties in the environment of high temperature; Environmental protection as far as possible in preparation process, reduces production and the discharge of harmful substance.The cellular ceramic substrate prepared through high-temperature roasting has good mechanical strength, and is suitable for using under high temperature harsh conditions, is the good carrier preparing CNT rete.Although utilize vapour deposition process to prepare carbon film layer based on ceramic bases can ensure enough mechanical performances, but the structure and morphology of ceramic monolith also has impact to carbon film, conventional symmetrical ceramic membrane structure is the symmetrical structure be made up of particle packing, on the one hand, because of particle and shaping restriction, pore size can limit the growth of CNT, and the hole of composite membrane entirety, gas and liquid mass transfer resistance also can be caused on the other hand to increase, and permeance property decays.
The asymmetric ceramic hollow fibrous membrane prepared by inversion of phases-sintering technology one-step shaping has finger-like pore structure, finger-like pore structure, and the first, greatly reduce the mass transport resistance of carbon-source gas, be easy to diffuse to ceramic grain surface and carry out CNT nucleation and growth; The second, for CNT provides enough growing spaces, be convenient in finger-like pore, form interlaced carbon nanotube mesh structures.3rd, form network structure because CNT is all staggered in finger-like pore, make permeance property attenuation rate not high, ensure that enough gas and liquid flux, and filter to retain and also can occur in carbon nanotube network.
In synthesizing carbon nanotubes rete course of reaction, byproduct hydrogen gas is as a kind of secondary energy sources carrier of high-efficiency cleaning, is considered to the clean energy resource source that the following mankind are important.Traditional oil and fossil energy consume problems such as causing greenhouse effects of the earth, environmental pollution and energy shortage excessively.In this context, the low-carbon economy based on low energy consumption, low stain is just becoming the focus of global concern and research.Hydrogen is as the energy, and the product after burning is water, is no pollution substantially.And the energy density of hydrogen is large, liberated heat is about three times of homogenous quantities gasoline.21 century, Hydrogen Energy likely occupied very important status on world energy sources stage.
Summary of the invention
The object of the present invention is to provide a kind of thickness thin, energy oil-water separation emulsion, bacterium, and to the PM in air
1fine particle has the CNT/porous ceramics doughnut composite hyperfiltration membrane of good removal effect.
For achieving the above object, the invention provides the preparation method of a kind of CNT/porous ceramics doughnut composite hyperfiltration membrane, it is characterized in that, step is,
The pretreatment of carrier: using the hollow fiber ceramic membrane absolute ethyl alcohol ultrasonic vibration as carrier, then also dries to neutral the carrier obtaining handling well by washed with de-ionized water;
Prepare the hollow-fibre membrane of supported catalyst: with dip coating method by Ni (NO
3)
2solution is coated on the carrier handled well, and drying is placed on roasting in Muffle furnace, obtains the hollow-fibre membrane of load nickel oxide catalyst;
Ventilatory response: the hollow-fibre membrane of described load nickel oxide catalyst is placed in crystal reaction tube, passes into N in crystal reaction tube
2and H
2, reducing catalyst, then switches to hydrogen and heats up, and air-flow is switched to pure methane gas, obtains CNT/porous ceramics doughnut composite hyperfiltration membrane.
Further, the pretreatment of described carrier is using the hollow fiber ceramic membrane absolute ethyl alcohol ultrasonic vibration 1h as carrier, then extremely neutral by washed with de-ionized water, and dries 2h in 100 DEG C, obtains the carrier handled well;
Preferably, described hollow fiber ceramic membrane is mullite hollow fiber ceramic membrane, Al
2o
3, ZrO
2or TiO
2hollow fiber ceramic membrane.
Further, describedly prepare in the hollow-fibre membrane step of supported catalyst, Ni (NO
3)
2the solution of solution to be mass concentration be 10-30%; Preferably, described Ni (NO
3)
2solution to be mass concentration be 20% solution.Concentration is too low, needs repeatedly dip-coating, takes time and effort; Concentration is too high, the nickel oxide particle size heterogeneity obtained after roasting, and nickel oxide particle is uneven in fibre pipe surface distributed, thus causes the CNT thicknesses of layers of generation uneven.
Further, the described hollow-fibre membrane step preparing supported catalyst is by Ni (NO with dip coating method
3)
2solution is coated on the carrier handled well, and 80 DEG C of dry 1h to be placed in Muffle furnace in 300-400 DEG C of roasting 2h, obtain the hollow-fibre membrane of load nickel oxide catalyst.
Further, in described ventilatory response step, N
2, H
2, pure methane gas flow be all 10-30ml/min; Preferably, described N
2, H
2, pure methane gas flow be all 20ml/min.Flow is excessive, reactant gas and catalyst exposure react produce CNT time just too short, cause reaction to be carried out insufficient, waste resource; Flow is too small, and the time of reactant gas and catalyst exposure is just long, easily causes back-mixing, and flow is too low simultaneously needs the long period to form CNT rete.
Further, described ventilatory response is that the hollow-fibre membrane of described load nickel oxide catalyst is placed in crystal reaction tube, in crystal reaction tube, pass into N
2and H
2, N
2, H
2flow be all 10-30ml/min, 400-600 DEG C of reducing catalyst 1h, then switch to the H of 10-30ml/min flow
2and being warming up to required reaction temperature 550-750 DEG C, (time is too short, is not enough to film forming air-flow to be switched to the pure methane solid/liquid/gas reactions 2-6h of 10-30ml/min flow; Time, oversize then film was too thick, and CNT Diameter distribution broadens, uneven), obtain CNT/porous ceramics doughnut composite hyperfiltration membrane;
Preferably, described ventilatory response is that the hollow-fibre membrane of described load nickel oxide catalyst is placed in crystal reaction tube, in crystal reaction tube, pass into N
2and H
2, N
2, H
2flow be all 20ml/min, 500 DEG C of reducing catalyst 1h, then switch to the H of 20ml/min flow
2and be warming up to required reaction temperature 650 DEG C, air-flow is switched to the pure methane solid/liquid/gas reactions 4h of 20ml/min flow, obtain CNT/porous ceramics doughnut composite hyperfiltration membrane.
Another aspect of the present invention, provides CNT/porous ceramics doughnut composite hyperfiltration membrane that the preparation method of described CNT/porous ceramics doughnut composite hyperfiltration membrane prepares.
Further, the thickness 2-8 μm of described CNT/porous ceramics doughnut composite hyperfiltration membrane, membrane aperture is 10-100nm.
Another aspect of the present invention, provides described CNT/porous ceramics doughnut composite hyperfiltration membrane for the purposes of Industrial Wastewater Treatment.
Another aspect of the present invention, provide described CNT/porous ceramics doughnut composite hyperfiltration membrane for dedusting, degerming, except virus, except colloid, except algae, purposes except larger molecular organics and water-oil separating.
CNT of the present invention/porous ceramics doughnut composite hyperfiltration membrane, its carrier (being supporter again) is porous ceramics hollow fiber conduit, the present invention utilizes CVD technology carbon nano-tube on hollow fiber conduit, separating layer is intermeshed by CNT and forms the network structure of porous, aperture is 10-100nm, average pore size is about 40nm, belongs to milipore filter scope.
The present invention utilizes chemical vapour deposition (CVD) (CVD) method directly fabricated in situ one deck carbon nano-tube compound film in ceramic hollow fibrous membrane, effectively improves the bond strength between CNT and carrier.CNT/porous ceramics doughnut composite hyperfiltration membrane utilizes CNT to have staggered hole as the network structure that functional layer material is formed, and the adsorptivity of CNT self and chemical property strengthen the separating property of film further.And hollow fiber conduit finger-like pore structure both ensure that high flux and the separating effect of CNT/porous ceramics doughnut composite hyperfiltration membrane; The supporting condition of high strength, high stable can be provided again to ensure, and composite membrane under high pressure normally runs.CNT/porous ceramics doughnut composite hyperfiltration membrane prepared by the method can be separated oil-water emulsion, bacterium, and to the PM in air
1fine particle has good removal effect.Protection of the environment, maintenance ecosystem balance are had very important significance.This prepares the secondary energy sources carrier of carbon nano-tube compound film layer process byproduct hydrogen gas as a kind of high-efficiency cleaning, has important application at energy field.Utilize chemical vapour deposition technique (CVD) technique directly carbon nano-tube in situ film on ceramic monolith, due to the method, to have adjustable sex change strong, large area deposition can be realized, the feature such as reproducible, the new direction of carbon nanotube composite membrane structure design and film preparation will be opened up, simultaneously also by the preparation field of expansion inoranic membrane.
The present invention utilizes CNT for film functional layer, porous mullite, Al
2o
3, ZrO
2or TiO
2hollow fiber ceramic membrane is carrier, adopt chemical vapour deposition technique (CVD) cracking methane preparing carbon nanometer tube rete, and the hydrogen produced in preparation process directly can use as the energy.The network structure interpenetrated that CNT (CNTs) rete is interweaved by CNT in addition forms, and porosity is high; Thickness is 2-8 μm of scope, and filter membrane is thin, and thus flow resistance is little, and permeation flux is large; Membrane aperture, in 10-100nm scope, belongs to optimal experimental design technology.This CNT/porous ceramics doughnut composite hyperfiltration membrane has good strainability and selective, has good removal effect by the fine particle in the bacterium in water body and most of virus, colloid, algae, larger molecular organics and air.Invention enhances the adhesion between carbon nano-tube film and ceramic membrane, have preparation technology simple, equipment cost is low, is easy to the advantage of control and large-scale production.Can a step fabricated in situ thickness thin, only containing the CNT/porous ceramics doughnut composite hyperfiltration membrane of the desirable structure of composite membrane of the effective separating layer of one deck and porous support layer,
CNT/porous ceramics doughnut composite hyperfiltration membrane prepared by the method can be separated oil-water emulsion, bacterium, and to the PM in air
1fine particle has good removal effect.Protection of the environment, maintenance ecosystem balance are had very important significance.
Accompanying drawing explanation
Fig. 1 is mullite hollow-fibre membrane (left side) and CNT/porous ceramics doughnut composite hyperfiltration membrane (right side) pictorial diagram.
Fig. 2 is the section low power stereoscan photograph of mullite hollow fiber ceramic membrane;
Fig. 3 is the surface scan electromicroscopic photograph of the CNT/porous ceramics doughnut composite hyperfiltration membrane of embodiment 1 gained;
Fig. 4 is the section high power stereoscan photograph of the CNT/porous ceramics doughnut composite hyperfiltration membrane of embodiment 1 gained;
Fig. 5 is the transmission electron microscope photo of the CNT/porous ceramics doughnut composite hyperfiltration membrane of embodiment 1 gained.
Fig. 6 is that CNT of the present invention/porous ceramics doughnut composite hyperfiltration membrane is to the rejection figure of various pollutant.
Detailed description of the invention
Be described below in detail embodiments of the invention, the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or has element that is identical or similar functions from start to finish.Exemplary below by the embodiment be described with reference to the drawings.Unreceipted concrete technology or condition person in embodiment, according to the technology described by the document in this area or condition or carry out according to product description.Agents useful for same or the unreceipted production firm person of instrument, being can by the conventional products of commercial acquisition.
Embodiment 1: prepare CNT/porous ceramics doughnut composite hyperfiltration membrane
With average pore size be the mullite hollow fiber ceramic membrane of 1.0 μm as carrier, preparation aperture <100nm CNT/porous ceramics doughnut composite hyperfiltration membrane, step is:
The first step, the pretreatment of carrier
To be mullite hollow fiber ceramic membrane (see Fig. 1 left side figure) the absolute ethyl alcohol ultrasonic vibration 1h of 1.0 μm as the aperture of carrier, then by washed with de-ionized water to neutral, dry 2h in 100 DEG C, obtain the carrier handled well;
Second step, by Ni (NO
3)
2be mixed with the solution that mass concentration is 20%, by dip-coating (immersion coating) method by Ni (NO
3)
2solution is coated on the carrier handled well, and 80 DEG C of dry 1h are placed in Muffle furnace in 400 DEG C of roasting 2h.Reached a conclusion by X-ray diffraction instrument (XRD) analysis: this step obtains the mullite hollow fiber conduit of load NiO catalyst.
3rd step, is placed in crystal reaction tube by the mullite hollow-fibre membrane of load nickel oxide catalyst, in crystal reaction tube, passes into N
2and H
2(flow is all 20ml/min) mullite hollow fiber conduit to load NiO catalyst, in 500 DEG C of reducing catalyst 1h, then switches to H
2and be warming up to required reaction temperature 650 DEG C, air-flow is switched to the pure methane gas of 20ml/min.CNT/porous ceramics doughnut composite hyperfiltration membrane is obtained after reaction 4h.As can be seen from Figure 1: the material (the right figure of Fig. 1) that mullite hollow fiber conduit carrier (the left figure of Fig. 1) deposited one deck black is multi-walled carbon nano-tubes through Raman spectrum analysis (Ramanspectra) and transmission electron microscope analysis (TEM) this atrament.
Exporting hydrogen adopts Agilent4890D gas chromatograph (TCD and fid detector) to carry out on-line analysis.Obtain Fout (H
2) data.
In course of reaction, the generating rate of CNT is:
Rate＝Fout(H
2)/2(mol/h)
Wherein Fout (H
2) be the throughput rate of ml/min in course of reaction.The growing amount of last CNT is then obtained reaction time integral and calculating by the generating rate of CNT.
Result: the surface porosity factor of CNT/porous ceramics doughnut composite hyperfiltration membrane reaches 50 ~ 80%, liquid-liquid displacement method is utilized to record film average pore size for about 40nm, and Effective Regulation can be carried out by the CVD reaction time in this aperture, realize effectively removing different target thing.Stereoscan photograph is shown in Fig. 2-5.Wherein Fig. 2 is the section low power stereoscan photograph of mullite hollow fiber ceramic membrane, this hollow-fibre membrane has asymmetric " sandwich " structure, close surfaces externally and internally is finger-like pore structure and mid portion is spongy layer structure, improve the defect causing porosity low by inorganic particle closs packing film forming, make that tunica fibrosa has high porosity, effective film thickness is little, resistance to mass tranfer is little, have good gas permeation flux, thus be conducive to the transmission of carbon containing source of the gas at support film interlayer, improve the productive rate of CNT; Fig. 3 is the surface scan electromicroscopic photograph of CNT/porous ceramics doughnut composite hyperfiltration membrane.Fig. 4 is the section high power stereoscan photograph of the CNT/porous ceramics doughnut composite hyperfiltration membrane of the present embodiment gained; Fig. 5 is transmission electron microscope photo in the CNT/porous ceramics doughnut composite hyperfiltration membrane of the present embodiment gained.Can find out, even carbon nanotube is covered in ceramic bases, and without defects such as cracking and pin holes, interlaced formation network structure between carbon pipe, therefore this carbon nano-tube film has better toughness.This rete has flourishing gap structure, makes this kind of ceramic base carbon nano composite separating film have high porosity, high flux.Thicknesses of layers about 6 μm, CNT is combined comparatively firm with ceramic bases hollow-fibre membrane, effectively can improve the mechanical strength of composite membrane, improve the crisp frangible defect of conventional carbon film quality and be suitable for practical application.CNT productive rate is 40-100mgCg
-1fibre pipe h
-1, H
2exit concentration is 5-10vol%.
Embodiment 2: prepare CNT/porous ceramics doughnut composite hyperfiltration membrane
With the Al that average pore size is 1.0 μm
2o
3hollow fiber ceramic membrane is as carrier, and prepare the CNT/porous ceramics doughnut composite hyperfiltration membrane of aperture <100nm, step is:
The first step, the pretreatment of carrier
To be the Al of 1.0 μm as the aperture of carrier
2o
3hollow fiber ceramic membrane absolute ethyl alcohol ultrasonic vibration 1h, then extremely neutral by washed with de-ionized water, dry 2h in 100 DEG C, obtain the carrier handled well;
Second step, by Ni (NO
3)
2be mixed with the solution that mass concentration is 10%, by dip-coating (immersion coating) method by Ni (NO
3)
2solution is coated on the carrier handled well, and 80 DEG C of dry 1h are placed in Muffle furnace in 350 DEG C of roasting 2h.Reached a conclusion by X-ray diffraction instrument (XRD) analysis: this step obtains the Al of load NiO catalyst
2o
3hollow fiber conduit.
3rd step, by the Al of load nickel oxide catalyst
2o
3hollow-fibre membrane is placed in crystal reaction tube, in crystal reaction tube, pass into N
2and H
2(flow is all 10ml/min) Al to load NiO catalyst
2o
3hollow fiber conduit, in 400 DEG C of reducing catalyst 1h, then switches to H
2and be warming up to required reaction temperature 550 DEG C, air-flow is switched to the pure methane gas of 10ml/min.Reaction 2h obtains CNT/porous ceramics doughnut composite hyperfiltration membrane.
Result: the surface porosity factor of CNT/porous ceramics doughnut composite hyperfiltration membrane reaches 50 ~ 80%, liquid-liquid displacement method is utilized to record film average pore size for about 40nm, and Effective Regulation can be carried out by the CVD reaction time in this aperture, realize effectively removing different target thing.
Even carbon nanotube is covered in ceramic bases, and without defects such as cracking and pin holes, interlaced formation network structure between carbon pipe, therefore this carbon nano-tube film has better toughness.This rete has flourishing gap structure, makes this kind of ceramic base carbon nano composite separating film have high porosity, high flux.Thicknesses of layers about 2 μm, CNT is combined comparatively firm with ceramic bases hollow-fibre membrane, effectively can improve the mechanical strength of composite membrane, improve the crisp frangible defect of conventional carbon film quality and be suitable for practical application.CNT productive rate is 40-100mgCg
-1fibre pipe h
-1, H
2exit concentration is 5-10vol%.
Embodiment 3: prepare CNT/porous ceramics doughnut composite hyperfiltration membrane
With the ZrO that average pore size is 1.0 μm
2hollow fiber ceramic membrane is as carrier, and prepare the CNT/porous ceramics doughnut composite hyperfiltration membrane of aperture <100nm, step is:
The first step, the pretreatment of carrier
To be the ZrO of 1.0 μm as the aperture of carrier
2hollow fiber ceramic membrane absolute ethyl alcohol ultrasonic vibration 1h, then extremely neutral by washed with de-ionized water, dry 2h in 100 DEG C, obtain the carrier handled well;
Second step, by Ni (NO
3)
2be mixed with the solution that mass concentration is 30%, by dip-coating (immersion coating) method by Ni (NO
3)
2solution is coated on the carrier handled well, and 80 DEG C of dry 1h are placed in Muffle furnace in 300-400 DEG C of roasting 2h.Reached a conclusion by X-ray diffraction instrument (XRD) analysis: this step obtains the ZrO of load NiO catalyst
2hollow fiber conduit.
3rd step, by the ZrO of load nickel oxide catalyst
2hollow-fibre membrane is placed in crystal reaction tube, in crystal reaction tube, pass into N
2and H
2(flow is all 30ml/min) ZrO to load NiO catalyst
2hollow fiber conduit, in 600 DEG C of reducing catalyst 1h, then switches to H
2and be warming up to required reaction temperature 750 DEG C, air-flow is switched to the pure methane gas of 30ml/min.CNT/porous ceramics doughnut composite hyperfiltration membrane is obtained after reaction 6h.
Result: the surface porosity factor of CNT/porous ceramics doughnut composite hyperfiltration membrane reaches 50 ~ 80%, liquid-liquid displacement method is utilized to record film average pore size for about 40nm, and Effective Regulation can be carried out by the CVD reaction time in this aperture, realize effectively removing different target thing.
Even carbon nanotube is covered in ceramic bases, and without defects such as cracking and pin holes, interlaced formation network structure between carbon pipe, therefore this carbon nano-tube film has better toughness.This rete has flourishing gap structure, makes this kind of ceramic base carbon nano composite separating film have high porosity, high flux.Thicknesses of layers about 8 μm, CNT is combined comparatively firm with ceramic bases hollow-fibre membrane, effectively can improve the mechanical strength of composite membrane, improve the crisp frangible defect of conventional carbon film quality and be suitable for practical application.CNT productive rate is 40-100mgCg
-1fibre pipe h
-1, H
2exit concentration is 5-10vol%.
Embodiment 4: the application test in CNT/porous ceramics doughnut composite hyperfiltration membrane and environmental project
1, oil-water emulsion (200mgL is prepared
-1) and bacterial suspension (1*10
7cFUml
-1e. coli suspension) as model pollutant, embodiment 1 gained CNT/porous ceramics doughnut composite hyperfiltration membrane is fixed on filter, and driven by lower intake pressure (0.05MPa) and be separated.By oil-water emulsion and bacterial suspension (E. coli suspension) respectively by after filter, measure oil content in filtrate respectively by Ultravioblet spectrophotometer, colony counting method counts the bacterium in filtered fluid.Result shows: can't detect any pollutant in filtered fluid, CNT/porous ceramics doughnut composite hyperfiltration membrane to the filter efficiency of two kinds of pollutants clearly, reaches the rejection of 100%.On the one hand by this ultrafiltration membrane technique process industrial wastewater can some useful component (oil) in waste water be concentrated, be reclaimed.Can go being stripped of again being back to use in relevant operation through water of various impurity, to economize on resources and to avoid environmental pollution on the other hand.
2, by particle diameter be the SiO of 1 μm
2ball and air form PM
1dusty gas, PM
1dusty gas after CNT/porous ceramics doughnut Compound Ultrafiltration membrane filtration, by aerosol detector measure unstripped gas and infiltration gas in dust content, calculate CNT/porous ceramics doughnut composite hyperfiltration membrane to PM
1the PM of dusty gas
1rejection.Result display CNT/porous ceramics doughnut composite hyperfiltration membrane is to PM
1filter efficiency clearly, reach the rejection of 100%.
As can be seen from Figure 6, CNT/porous ceramics doughnut composite hyperfiltration membrane is to oil emulsion, bacterium, PM
1the rejection of fine particle all reaches 100%, and rejection is high, effective.
Although illustrate and describe embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, those of ordinary skill in the art can change above-described embodiment within the scope of the invention when not departing from principle of the present invention and aim, revising, replacing and modification.
Claims (10)
1. a preparation method for CNT/porous ceramics doughnut composite hyperfiltration membrane, is characterized in that, step is,
The pretreatment of carrier: using the hollow fiber ceramic membrane absolute ethyl alcohol ultrasonic vibration as carrier, then also dries to neutral the carrier obtaining handling well by washed with de-ionized water;
Prepare the hollow-fibre membrane of supported catalyst: with dip coating method by Ni (NO
3)
2solution is coated on the carrier handled well, and drying is placed on roasting in Muffle furnace, obtains the hollow-fibre membrane of load nickel oxide catalyst;
Ventilatory response: the hollow-fibre membrane of described load nickel oxide catalyst is placed in crystal reaction tube, passes into N in crystal reaction tube
2and H
2, reducing catalyst, then switches to hydrogen and heats up, and air-flow is switched to pure methane gas, obtains CNT/porous ceramics doughnut composite hyperfiltration membrane.
2. the preparation method of CNT/porous ceramics doughnut composite hyperfiltration membrane according to claim 1, it is characterized in that, the pretreatment of described carrier is using the hollow fiber ceramic membrane absolute ethyl alcohol ultrasonic vibration 1h as carrier, then extremely neutral by washed with de-ionized water, and dry 2h in 100 DEG C, obtain the carrier handled well;
Preferably, described hollow fiber ceramic membrane is mullite hollow fiber ceramic membrane, Al
2o
3, ZrO
2or TiO
2hollow fiber ceramic membrane.
3. the preparation method of CNT/porous ceramics doughnut composite hyperfiltration membrane according to claim 1, is characterized in that, describedly prepares in the hollow-fibre membrane step of supported catalyst, Ni (NO
3)
2the solution of solution to be mass concentration be 10-30%; Preferably, described Ni (NO
3)
2solution to be mass concentration be 20% solution.
4. the preparation method of CNT/porous ceramics doughnut composite hyperfiltration membrane according to claim 1, is characterized in that, the described hollow-fibre membrane step preparing supported catalyst for dip coating method by Ni (NO
3)
2solution is coated on the carrier handled well, and 80 DEG C of dry 1h to be placed in Muffle furnace in 300-400 DEG C of roasting 2h, obtain the hollow-fibre membrane of load nickel oxide catalyst.
5. the preparation method of CNT/porous ceramics doughnut composite hyperfiltration membrane according to claim 1, is characterized in that, in described ventilatory response step, and N
2, H
2, pure methane gas flow be all 10-30ml/min; Preferably, described N
2, H
2, pure methane gas flow be all 20ml/min.
6. the preparation method of CNT/porous ceramics doughnut composite hyperfiltration membrane according to claim 1, it is characterized in that, described ventilatory response is that the hollow-fibre membrane of described load nickel oxide catalyst is placed in crystal reaction tube, in crystal reaction tube, pass into N
2and H
2, N
2, H
2flow be all 10-30ml/min, 400-600 DEG C of reducing catalyst 1h, then switch to the H of 10-30ml/min flow
2and be warming up to required reaction temperature 550-750 DEG C, air-flow is switched to the pure methane solid/liquid/gas reactions 2-6h of 10-30ml/min flow, obtain CNT/porous ceramics doughnut composite hyperfiltration membrane;
Preferably, described ventilatory response is that the hollow-fibre membrane of described load nickel oxide catalyst is placed in crystal reaction tube, in crystal reaction tube, pass into N
2and H
2, N
2, H
2flow be all 20ml/min, 500 DEG C of reducing catalyst 1h, then switch to the H of 20ml/min flow
2and be warming up to required reaction temperature 650 DEG C, air-flow is switched to the pure methane solid/liquid/gas reactions 4h of 20ml/min flow, obtain CNT/porous ceramics doughnut composite hyperfiltration membrane.
7. CNT/porous ceramics doughnut composite hyperfiltration membrane of preparing of the preparation method of CNT described in any one of 1-6/porous ceramics doughnut composite hyperfiltration membrane according to claim 1.
8. CNT described in claim 7/porous ceramics doughnut composite hyperfiltration membrane, is characterized in that, the thickness 2-8 μm of described CNT/porous ceramics doughnut composite hyperfiltration membrane, membrane aperture is 10-100nm.
9. CNT described in claim 7/porous ceramics doughnut composite hyperfiltration membrane is used for the purposes of Industrial Wastewater Treatment.
10. CNT described in claim 7/porous ceramics doughnut composite hyperfiltration membrane be used for dedusting, degerming, except virus, except colloid, except algae, purposes except larger molecular organics and water-oil separating.
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