CN106693724B - Asymmetric structure in-situ ultrasonic anti-pollution membrane with piezoelectric material as separation layer and preparation method thereof - Google Patents
Asymmetric structure in-situ ultrasonic anti-pollution membrane with piezoelectric material as separation layer and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 83
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 41
- 238000000926 separation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims description 44
- 230000005684 electric field Effects 0.000 claims abstract description 27
- 230000010287 polarization Effects 0.000 claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 27
- 239000004020 conductor Substances 0.000 claims abstract description 16
- 239000000919 ceramic Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 17
- 238000010792 warming Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 229910052451 lead zirconate titanate Inorganic materials 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- BOUHOYYXLIKKRM-UHFFFAOYSA-N [Pb].[Nb].[Mn] Chemical compound [Pb].[Nb].[Mn] BOUHOYYXLIKKRM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 claims description 7
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229920002545 silicone oil Polymers 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 229910002113 barium titanate Inorganic materials 0.000 claims description 5
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000001238 wet grinding Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000007888 film coating Substances 0.000 claims description 2
- 238000009501 film coating Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- -1 metaniobate Chemical compound 0.000 claims 1
- 230000009471 action Effects 0.000 abstract description 12
- 238000002604 ultrasonography Methods 0.000 abstract description 9
- 238000001035 drying Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 description 11
- 230000004907 flux Effects 0.000 description 11
- 238000001471 micro-filtration Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 230000003373 anti-fouling effect Effects 0.000 description 8
- 238000000108 ultra-filtration Methods 0.000 description 7
- 230000010358 mechanical oscillation Effects 0.000 description 6
- 239000002562 thickening agent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
-
- 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
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
-
- 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
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/2603—Application of an electric field, different from the potential difference across the membrane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to an asymmetric structure in-situ ultrasonic anti-pollution membrane with a piezoelectric material as a separation layer, which is characterized in that a support body is a porous conductive material, and the average pore diameter is 1-20 um; the separation layer is porous piezoelectric ceramic with an average pore diameter of 1-1000 nm. Preparing a separation layer on the surface of a conductive support body by taking a piezoelectric material as a raw material, airing, drying and calcining a wet film, and naturally cooling to prepare an asymmetric structure film; and (4) carrying out high-voltage polarization on the asymmetric membrane to obtain the in-situ ultrasonic anti-pollution membrane with the asymmetric structure. The aperture of the separation membrane prepared by the invention can be regulated and controlled within 1-1000nm so as to meet the requirements of different separation systems; meanwhile, under the action of an electric field, the piezoelectric separation layer can generate in-situ ultrasound in the separation process, and the anti-pollution effect is remarkable.
Description
Technical field
The present invention relates to ultrasonic pollution-resistant membranes in situ and preparation method thereof, more particularly to using conductive material as supporter, with
Piezoelectric material is the unsymmetric structure of separating layer ultrasonic pollution-resistant membrane in situ and preparation method thereof.
Background technique
Membrane separation technique, by applying certain motive force on film both sides, makes feed side using selective permeable membrane as separating medium
Film is penetrated to component selection, to reach separating-purifying purpose.It has without phase-change, low energy consumption, high efficiency, simple process etc. it is excellent
Point, and inoranic membrane has many advantages, such as acid-alkali-corrosive-resisting, organic solvent-resistant, high temperature high voltage resistant, therefore has boundless answer
Use prospect.However, fouling membrane is the general character problem that membrane separation technique faces in actual application, pollutant can be deposited in film
Fouling membrane phenomenon is caused in surface or fenestra road, not only makes Membrane Filtration Flux deep fades, it is also possible to influence film to isolate
The cutoff performance of matter directly affects the economy and reliability of membrane separating process.
Piezoelectric material is that one kind is under pressure when acting on and the crystalline material of voltage can occurs at both ends, and piezoelectric material is through excessively high
The crystal grain of internal original random orientation can be oriented in applied field direction under DC voltage effect after pressure polarization, and remove in electric field
The state of positive and negative anodes separation is kept after pin.Applying AC field at its both ends at this time can make piezoelectric material generate mechanical vibration
The characteristics of moving, alternating current being made to be converted to mechanical oscillation according to piezoelectric material, can be prepared into seperation film for piezoelectric material, make
Membrane material becomes ultrasound emission in situ source, generates mechanical oscillation during the separation process, to play alleviation or even avoid fouling membrane
Effect.
Currently, mainly having Darestani (J Membrane using the report that piezoelectric material prepares anti-pollution separation membrane as raw material
Sci, 2013,435:226-232) aperture is prepared for by raw material of PVDF for 220nm, with a thickness of 123 μm of symmetrical structure PVDF
Organic vibrating membrane；Qiu (J Membrane Sci, 2015,44:120-135) and by raw material of lead zirconate-titanate ceramic it is prepared for aperture
For the symmetrical structure PZT electricity Tao Zhendong porcelain film of 365nm.The ultrasonic film in situ of both symmetrical structures shows good anti-
Pollutant performance, both films are all symmetrical structures, and the film of unsymmetric structure has better permeance property and separating property, because
In situ ultrasonic pollution-resistant membrane of this preparation with unsymmetric structure has great meaning.
Summary of the invention
The technical problems to be solved by the present invention are: existing original position mechanical oscillation film is symmetrical structure, in order to improve
The separating property and permeance property of mechanical oscillation film need to prepare the mechanical oscillation film in situ of unsymmetric structure；It thus provides
Using piezoelectric material as the unsymmetric structure of separating layer ultrasonic pollution-resistant membrane in situ, it is former that the present invention also provides above-mentioned unsymmetric structures
The preparation and application of the ultrasonic pollution-resistant membrane in position, reduce the average pore size of film while ensuring ultrasonic antifouling property in situ,
Improve the separation accuracy of film.
The technical solution of the present invention is as follows: being raw material in porous, electrically conductive supporting body surface preparative separation layer using piezoelectric ceramics, change
Transformation electric material particle size is to adjust film layer pore size.Conductive support can provide higher mechanical strength, simultaneously
It can be used as electrode and play electric action；The separation accuracy of anisotropic membrane can be improved in piezoelectricity separating layer, while after polarization
Have piezoelectric property, can produce ultrasound in situ under DC Electric Field and play anti-pollution.
It is of the invention the specific scheme is that a kind of using piezoelectric material as the unsymmetric structure of separating layer ultrasonic antipollution in situ
Film, it is characterised in that supporter is porous conductive material, average pore size 1-20um；Separating layer is porous piezoceramics, average
Aperture is 1-1000nm.
It is preferred that above-mentioned porous conductive material is porous carbon, porous metals titanium, nickel foam, foam copper, foamed aluminium, stainless steel
Or one of alloy；Supporter porous conductive material is sheet or tubular structure.Unsymmetric structure ultrasonic pollution-resistant membrane in situ
Resonant frequency be 20-500kHz.
It is preferred that the material of above-mentioned porous piezoceramics be barium titanate, lead titanates, lead zirconate titanate, zinc oxide, metaniobate,
One of manganese niobium lead acid, lead zinc niobate or quartz or its mixture；The number of plies of separating layer is 1-5 layers.
The present invention also provides the preparation method of above-mentioned unsymmetric structure ultrasonic pollution-resistant membrane in situ, specific steps
Are as follows: porous piezoelectric film A, is prepared on supporter porous conductive material surface, is warming up to 300-1200 DEG C, calcines 1-4 hours and forms,
Prepare porous piezoelectric film；B or the repetition step A1-4 times porous piezoelectric film layer with preparation more small-bore；C, by the more of preparation
Hole piezoelectric film polarizes under high voltage electric field, and porous piezoceramics separating layer is made to have piezoelectric property, and unsymmetric structure is made
Ultrasound pollution-resistant membrane in situ.
Calcination environment in preferred steps A is one of air atmosphere, argon atmosphere, helium atmosphere or nitrogen atmosphere.
It is preferred that the above-mentioned preparation method for preparing porous piezoelectric film on supporter porous conductive material surface is cement-dipping method, dry-pressing
One of method or wet-milling spray mo(u)lding method.
It is preferred that the piezoelectric ceramics average grain diameter for preparing porous piezoelectric film is 5-3000nm.
Above-mentioned cement-dipping method is that piezoelectric ceramics dispersion is prepared finely dispersed preparation liquid in aqueous solution and is coated in branch
Support body surface, wherein soaking paste preparation liquid quality solid content is 2-20%；Wet film coating time is 30-180s.
Above-mentioned wet-milling spray coating method is that piezoelectric ceramics dispersion is prepared finely dispersed preparation liquid in aqueous solution and is sprayed
In supporting body surface, wherein preparation liquid quality solid content is 2-20%；Spray time is 5-25s.
It is preferred that above-mentioned piezoelectric ceramics is film-made liquid and preparation method thereof, dispersing agent or dispersing agent can be added and thickener promotes preparation liquid
It is uniformly dispersed, dispersing agent can be ammonium hydroxide or polyethyleneimine, and dispersing agent quality solid content is no more than 2.2%；Thickener is
One of hydroxymethyl cellulose, polyvinyl alcohol or ethylene glycol, thickener qualities solid content are no more than 2%.
The polarization condition of anisotropic membrane in preferred steps C are as follows: polarization environment is insulation white oil, insulation silicone oil or air；
Polarized electric field intensity is 1-3kV/mm；Poling temperature is 80-150 DEG C, polarization time 0.5-2h.
The ultrasonic pollution-resistant membrane in situ of unsymmetric structure prepared by the present invention can be in separation of solid and liquid, gas solid separation or liquid liquid point
Application from.Stabilized flux can promote 0.5-20 times.
It is preferred that wet film flash-off time is 10-20 hours；It is 10-20 hours dry at 60-120 DEG C.
The ultrasonic pollution-resistant membrane in situ of unsymmetric structure prepared by the present invention has 1-5 tunic layer, and film layer has stronger
Piezoelectric property can produce ultrasound in situ and play anti-pollution；Separating layer average pore size scope is 1-1000nm, be can satisfy
The separation requirement of different systems.
Beneficial effect
1. the piezoelectricity separating layer in anisotropic membrane can convert electrical energy into mechanical energy after both ends apply alternating current, generate
Mechanical oscillation can slow down the concentration polarization phenomenon of film surface, slow down the accumulation of pollutant, play anti-pollution.
2. anisotropic membrane using porous conductive material as supporter, passes through the method successively prepared on its surface, it can be ensured that
The precision of separating layer prevents the generation of defect.
3. porous conductive material is used to provide higher mechanical strength as supporter for composite membrane, original can simultaneously serve as
Position electrode plays electric action, avoids additional traveling electrode.
Detailed description of the invention
It is supporter using piezoelectric material as the unsymmetric structure of separating layer ultrasonic pollution-resistant membrane in situ that Fig. 1, which is using conductive material,
And preparation method thereof schematic diagram.
Fig. 2 is that the unsymmetric structure ultrasonic pollution-resistant membrane (example one) in situ that underwater ultrasound detector detects vibrates song
Line.
Fig. 3 is unsymmetric structure ultrasonic pollution-resistant membrane (example one) antipollution curve in situ.
It is supporter using piezoelectric material as the unsymmetric structure of separating layer ultrasonic pollution-resistant membrane in situ that Fig. 4, which is using conductive material,
Surface surface sweeping Electronic Speculum (SEM) photo of (example two).
Specific embodiment
Embodiment one: using porous metals titanium as the lead zirconate titanate piezoelectric seperation film of supporter and its preparation
5g PZT powder (partial size 2-3um) is pressed by dry pressing in porous metals titanium (average pore size 20um)
Type is made, is warming up to 1200 DEG C under argon atmosphere protection and calcines 4 hours, the double-deck knot that average pore size is 1000nm is prepared
Structure microfiltration membranes, it is as shown in Figure 1 to prepare schematic diagram.Anisotropic membrane is subjected to high voltage polarization, polarized electric field electricity in 150 DEG C of insulation silicone oil
Pressure is 1kV/mm, and polarization obtains ultrasonic pollution-resistant membrane in situ after 2 hours, piezoelectric film ultrasonic resonance frequency is as shown in Fig. 2, piezoelectric film
Ultrasonic resonance frequency is 190-210kHz.The piezoelectricity seperation film is filtered experiment, permeance property in particle aqueous solution
It changes over time as shown in figure 3, piezoelectricity seperation film generates ultrasonic vibration under electric field action, has embodied good resistance tocrocking
Can, stabilized flux promotes 6-7 times.
Embodiment two: being separated using porous metals titanium as the barium titanate piezoelectricity of supporter and its preparation
On the basis of average pore size prepared by embodiment one is the lead titanates microfiltration membranes of 1000nm, by 20g manganese niobium lead acid pressure
Electroceramics powder (partial size 900nm) is dispersed in 100g aqueous solution, and 2.2g ammonium hydroxide is added as dispersing agent, 1.5g ethylene glycol conduct
The preparation liquid that quality solid content is 20% is prepared in thickener, 3min is coated on the manganese niobium lead acid surface of 1000nm, by wet film
It is warming up to 100 DEG C to dry 20 hours in hot air drier, then the film of drying is warming up to 800 DEG C in helium, calcine 2 hours
The manganese niobium lead acid microfiltration membranes that the average pore size with three-decker is 500nm, microfiltration membranes surface microscopic topographic such as Fig. 4 is prepared
It is shown.Anisotropic membrane is subjected to high voltage polarization in 100 DEG C of insulation white oil environment, polarized electric field voltage is 2.5kV/mm, pole
Ultrasonic pollution-resistant membrane in situ is obtained after changing 1.5 hours, piezoelectric film ultrasonic resonance frequency is 230-250kHz.By the piezoelectricity seperation film
Experiment is filtered in grease system, piezoelectricity seperation film generates ultrasonic vibration under electric field action, has embodied good anti-
Pollutant performance, stabilized flux promote 8-10 times.
Embodiment three: using porous metals titanium as the lead zinc niobate piezoelectricity seperation film of supporter and its preparation
On the basis of average pore size prepared by embodiment two is the manganese niobium lead acid microfiltration membranes of 500nm, by 10g lead zinc niobate pressure
Electroceramics powder (partial size 200nm) is dispersed in 100g water, 1.2g polyethyleneimine is added as dispersing agent, 1g polyvinyl alcohol is made
For thickener, the preparation liquid that quality solid content is 10% is prepared, is coated in the manganese niobium lead acid microfiltration membranes of 500nm
1.5min.Wet film is warming up to 90 DEG C in hot air drier to dry 10 hours, then by the film of drying in atmosphere temperature rising to 650
DEG C, the lead zinc niobate ultrafiltration membrane that the average pore size with four-layer structure is 50nm is prepared for 1 hour in calcining.Anisotropic membrane is existed
High voltage polarization is carried out in 100 DEG C of insulation white oil environment, polarized electric field voltage is 2kV/mm, and polarization obtained original position after 1.5 hours
Ultrasonic pollution-resistant membrane, piezoelectric film ultrasonic resonance frequency are 470-500kHz.By the piezoelectricity seperation film in nanometer dusty gas into
Row filtration experiment, piezoelectricity seperation film generate ultrasonic vibration under electric field action, have embodied good antifouling property, stablize logical
Amount promotes 0.5-2 times.
Example IV: using porous metals titanium as the metaniobate piezoelectricity seperation film of supporter and its preparation
On the basis of average pore size prepared by embodiment three is the lead zinc niobate ultrafiltration membrane of 50nm, by 6g lead meta-columbute piezoelectricity
Ceramic powder (partial size 20nm) is dispersed in 100g water, and 1.2g polyethyleneimine is added as dispersing agent, 1g polyvinyl alcohol conduct
Thickener is prepared the preparation liquid that quality solid content is 6%, coats 1min on the lead zinc niobate ultrafiltration membrane of 50nm.It will be wet
Film is warming up to 80 DEG C and dries 10 hours in hot air drier, then the film of drying is warming up to 500 DEG C in air, and calcining 1 is small
When be prepared the average pore size with five-layer structure be 5nm lead meta-columbute ultrafiltration membrane.Insulation by anisotropic membrane at 100 DEG C
High voltage polarization is carried out in silicone oil environment, polarized electric field voltage is 1.5kV/mm, and polarization obtains ultrasonic antipollution in situ after 1 hour
Film, piezoelectric film ultrasonic resonance frequency are 310-330kHz.The piezoelectricity seperation film is filtered experiment in glucan aqueous solution,
Piezoelectricity seperation film generates ultrasonic vibration under electric field action, has embodied good antifouling property, and stabilized flux promotes 15-17
Times.
Embodiment five: using porous metals titanium as the zinc oxide piezoelectric seperation film of supporter and its preparation
On the basis of the average pore size of example IV preparation is the lead meta-columbute ultrafiltration membrane of 5nm, by 2g zinc oxide (partial size
5nm) ceramic powder is dispersed in 1000g deionized water, 1.5g polyethyleneimine is added as dispersing agent, 2g ethylene glycol is as increasing
It thick dose, is uniformly dispersed and the preparation liquid that quality solid content is 2% is prepared, in the lead meta-columbute ultrafiltration membrane that average pore size is 5nm
Upper coating 30s.Wet film is warming up to 60 DEG C in hot air drier to dry 10 hours, then by the film of drying atmosphere temperature rising extremely
300 DEG C, the zinc oxide nano filter membrane that the average pore size with six layer structure is 1nm is prepared for 1 hour in calcining.Anisotropic membrane is existed
High voltage polarization is carried out in 80 DEG C of insulating silicon oil environment, polarized electric field voltage is 1kV/mm, and polarization obtained ultrasound in situ after 2 hours
Pollution-resistant membrane, piezoelectric film ultrasonic resonance frequency are 390-410kHz.The piezoelectricity seperation film is carried out in polyethylene glycol solution
Filtration experiment, piezoelectricity seperation film generate ultrasonic vibration under electric field action, have embodied good antifouling property, stabilized flux
Promote 19-20 times.
Embodiment six: using nickel foam as the lead titanates piezoelectricity seperation film of supporter and its preparation
2g lead titanate powder (partial size 2-3um) is dry-pressing formed on circular shaped foam nickel supporter, and nickel foam diameter is
30mm, with a thickness of 5mm, average pore size 15um.Film is warming up to 600 DEG C in air, calcining is prepared with two for 2 hours
The microfiltration membranes that the average pore size of layer structure is 1000nm.Anisotropic membrane is subjected to high voltage polarization, pole in 140 DEG C of air environment
Change voltage of electric field is 2.1kV/mm, and polarization obtains ultrasonic pollution-resistant membrane in situ after 1 hour, piezoelectric film ultrasonic resonance frequency is 390-
410kHz.The piezoelectricity seperation film is filtered experiment in particle aqueous solution, piezoelectricity seperation film generates super under electric field action
Acoustic vibration, has embodied good antifouling property, and stabilized flux promotes 2-5 times.
Embodiment seven: using porous carbon as the zinc oxide piezoelectric seperation film of supporter and its preparation
15g PZT powder (partial size 500nm) is dispersed in 100g water, 1.2g ammonium hydroxide is added as dispersing agent, divides
Dissipate the preparation liquid that uniformly preparation quality solid content is 15%.5s is sprayed on the surface porous carbon (average pore size 1um) by spray coating method
Lead zirconate titanate separating layer is prepared, wet film is warming up to 80 DEG C in hot air drier and is dried 12 hours, then by the film of drying in nitrogen
900 DEG C are warming up in gas atmosphere, the microfiltration membranes that the average pore size of double-layer structure is 300nm are prepared for 2 hours in calcining.By 2g oxygen
Change zinc powder body (partial size 100nm) to be dispersed in 100g water, 1ml ammonium polyacrylate is added as dispersing agent, is uniformly dispersed and prepares matter
Amount solid content is 2% preparation liquid, coats the 25s preparation smaller oxygen in aperture in the lead zirconate titanate film layer of 300nm by spray coating method
Change zinc layers, wet film is warming up to 80 DEG C in hot air drier and is dried 12 hours, then the film of drying is heated up in argon atmosphere
To 750 DEG C, the ultrafiltration membrane that the average pore size of three-decker is 30nm is prepared for 2 hours in calcining.By anisotropic membrane at 140 DEG C
High voltage polarization is carried out in air environment, polarized electric field voltage is 1.6kV/mm, and polarization obtains ultrasonic antipollution in situ after 1 hour
Film, piezoelectric film ultrasonic resonance frequency are 20-50kHz.The piezoelectricity seperation film is filtered reality in nano particle dusty gas
It tests, piezoelectricity seperation film generates ultrasonic vibration under electric field action, has embodied good antifouling property, and stabilized flux is promoted
0.5-2 times.
Embodiment eight: using foamed aluminium as the lead zirconate titanate piezoelectric seperation film of supporter and its preparation
By 5g PZT powder (partial size 2-3um), by dry pressing, in foamed aluminium, (average pore size 16um, diameter are
30mm, with a thickness of 5mm) compression moulding, 1200 DEG C are warming up under argon atmosphere protection and is calcined 4 hours, and average hole is prepared
Diameter is the double-layer structure microfiltration membranes of 1000nm, and it is as shown in Figure 1 to prepare schematic diagram.Anisotropic membrane is carried out in 150 DEG C of insulation silicone oil
High voltage polarization, polarized electric field voltage are 1kV/mm, and polarization obtains ultrasonic pollution-resistant membrane in situ after 0.5 hour, piezoelectric film ultrasound is total
Vibration frequency is 70-90kHz.The piezoelectricity seperation film is filtered experiment in particle aqueous solution, piezoelectricity seperation film is made in electric field
With lower generation ultrasonic vibration, good antifouling property is embodied, stabilized flux promotes 10-12 times.
Embodiment nine: using 316L type porous stainless steel as the barium titanate piezoelectricity seperation film of supporter and its preparation
20g barium carbonate powder (partial size 500nm) is dispersed in 100g water, 1.2g ammonium hydroxide is added as dispersing agent, dispersion
The uniformly preparation liquid that preparation quality solid content is 20%, prepares barium titanate in 316L type stainless steel surface by wet-milling spray coating method
Layer, spray time 25s；Wet film is dried and is warming up to 80 DEG C after 12h and is dried 12 hours in hot air drier, then by drying
Composite membrane under argon gas protection, is warming up to 700 DEG C in tube furnace, calcines the average pore size for double-layer structure being prepared in 2 hours and is
The composite membrane of 200nm.Composite membrane is subjected to high voltage polarization in 140 DEG C of air environment, polarized electric field voltage is 2.1kV/mm,
Polarization obtains ultrasonic pollution-resistant membrane in situ after 1 hour, piezoelectric film ultrasonic resonance frequency is 130-150kHz.By the piezoelectricity seperation film
Experiment is filtered in grease system, piezoelectricity seperation film generates ultrasonic vibration under electric field action, has embodied good anti-
Pollutant performance, stabilized flux promote 7-9 times.
Embodiment ten: using foam copper as the lead zirconate titanate piezoelectric seperation film of supporter and its preparation
By 5g PZT powder (partial size 2-3um), by dry pressing, in foam copper, (average pore size 15um, diameter are
30mm, with a thickness of 5mm) compression moulding, 1200 DEG C are warming up under argon atmosphere protection and is calcined 4 hours, and average hole is prepared
Diameter is the double-layer structure microfiltration membranes of 1000nm.Anisotropic membrane is subjected to high voltage polarization, polarized electric field electricity in 150 DEG C of insulation silicone oil
Pressure is 1kV/mm, and polarization obtains ultrasonic pollution-resistant membrane in situ after 0.5 hour, piezoelectric film ultrasonic resonance frequency is 230-250kHz.
The piezoelectricity seperation film is filtered experiment in particle aqueous suspension, piezoelectricity seperation film generates ultrasound vibration under electric field action
It is dynamic, good antifouling property is embodied, stabilized flux promotes 8-10 times.
Claims (10)
1. a kind of using piezoelectric material as the unsymmetric structure of separating layer ultrasonic pollution-resistant membrane in situ, it is characterised in that supporter is more
Hole conductive material, average pore size 1-20um；Separating layer is porous piezoceramics, average pore size 1-1000nm.
2. unsymmetric structure according to claim 1 ultrasonic pollution-resistant membrane in situ, it is characterised in that the porous, electrically conductive
Material is one of porous carbon, porous metals titanium, nickel foam, foam copper, foamed aluminium, stainless steel or alloy；Supporter is porous
Conductive material is sheet or tubular structure.
3. unsymmetric structure according to claim 1 ultrasonic pollution-resistant membrane in situ, it is characterised in that the porous piezoelectric
The material of ceramics is in barium titanate, lead titanates, lead zirconate titanate, zinc oxide, metaniobate, manganese niobium lead acid, lead zinc niobate or quartz
One kind or its mixture；The number of plies of separating layer is 1-5 layers；The resonant frequency of unsymmetric structure pollution-resistant membrane in situ ultrasonic is
20-500kHz。
4. a kind of method for preparing unsymmetric structure as described in claim 1 ultrasonic pollution-resistant membrane in situ, the specific steps are that:
A, porous piezoelectric film is prepared on supporter porous conductive material surface, is warming up to 300-1200 DEG C, calcined 1-4 hours and form, system
Standby porous piezoelectric film；B or repeat step A1-4 times；C, the porous piezoelectric film of preparation is polarized under high voltage electric field, is made
Porous piezoceramics separating layer has piezoelectric property, and unsymmetric structure ultrasonic pollution-resistant membrane in situ is made.
5. according to the method described in claim 4, it is characterized in that calcination environment in step A be air atmosphere, argon atmosphere,
One of helium atmosphere or nitrogen atmosphere.
6. according to the method described in claim 4, it is characterized in that preparing porous piezoelectric on supporter porous conductive material surface
The preparation method of film is one of cement-dipping method, dry pressing or wet-milling spray mo(u)lding method.
7. according to the method described in claim 6, it is characterized in that the cement-dipping method is that piezoelectric ceramics is dispersed in aqueous solution
Middle to prepare finely dispersed preparation liquid and be coated in supporting body surface, wherein soaking paste preparation liquid quality solid content is 2-20%；It is wet
Film coating time is 30-180s.
8. according to the method described in claim 6, it is characterized in that the wet-milling spray mo(u)lding method is to disperse piezoelectric ceramics
Finely dispersed preparation liquid is prepared in aqueous solution and is sprayed on supporting body surface, and wherein preparation liquid quality solid content is 2-
20%；Spray time is 5-25s.
9. according to the method described in claim 4, it is characterized in that in step C polarize environment be insulation white oil, insulation silicone oil or
Person's air；Polarized electric field intensity is 1-3kV/mm；Poling temperature is 80-150 DEG C, polarization time 0.5-2h.
10. a kind of unsymmetric structure as described in claim 1 ultrasonic pollution-resistant membrane in situ is in separation of solid and liquid, gas solid separation or liquid
Application in liquid separation.
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