CN106582295B - Piezoelectric ceramic filter membrane and application device - Google Patents
Piezoelectric ceramic filter membrane and application device Download PDFInfo
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- CN106582295B CN106582295B CN201611060410.0A CN201611060410A CN106582295B CN 106582295 B CN106582295 B CN 106582295B CN 201611060410 A CN201611060410 A CN 201611060410A CN 106582295 B CN106582295 B CN 106582295B
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- 239000012465 retentate Substances 0.000 claims description 40
- 239000012466 permeate Substances 0.000 claims description 33
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 28
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 22
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- 229910002113 barium titanate Inorganic materials 0.000 claims description 11
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- 238000002156 mixing Methods 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 8
- 230000007704 transition Effects 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D35/00—Filtering devices having features not specifically covered by groups B01D24/00 - B01D33/00, or for applications not specifically covered by groups B01D24/00 - B01D33/00; Auxiliary devices for filtration; Filter housing constructions
- B01D35/06—Filters making use of electricity or magnetism
-
- 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
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5041—Titanium oxide or titanates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5049—Zinc or bismuth oxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/20—By influencing the flow
- B01D2321/2066—Pulsated flow
- B01D2321/2075—Ultrasonic treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/22—Electrical effects
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2325/26—Electrical properties
Abstract
The invention discloses a piezoelectric ceramic filter membrane and a using device, wherein the piezoelectric ceramic filter membrane with a piezoelectric layer is prepared by coating a mixture of a piezoelectric material and an additive on the surface of a ceramic membrane and sintering the mixture; or adding piezoelectric materials and additives in the existing ceramic membrane preparation process to prepare the piezoelectric ceramic membrane containing the piezoelectric materials and the additives; the membrane is used in the fluid separation process, and the piezoelectric effect and the inverse piezoelectric effect of the piezoelectric material are utilized to force particles and charged bodies to be far away from the ceramic filter membrane under the action of an external power supply or ultrasonic synergism, so that the effects of preventing the filter pore canal of the ceramic filter membrane from being blocked, realizing the self-cleaning function and inhibiting the pollution of the ceramic filter membrane are achieved, and the service life of the ceramic membrane is obviously prolonged; the piezoelectric ceramic filter membrane prepared by the invention has strong pollution resistance, high pollutant rejection rate, wide application range, reasonable design of the piezoelectric ceramic filter membrane running device and simple and convenient operation.
Description
Technical Field
The invention belongs to the technical field of functional ceramic filter membrane separation, and particularly relates to a piezoelectric ceramic filter membrane and a using device.
Background
The ceramic membrane separation technology is an advanced separation concentration technology in recent years, and the ceramic membrane is widely used in various fields of environmental protection, biological medicine, chemical manufacturing, energy protection and the like. The ceramic membrane has the advantages of acid and alkali corrosion resistance, high temperature resistance, stable structure, uniform pore size distribution, good chemical stability, high separation efficiency, high mechanical strength and the like. Making it an irreplaceable place in the field of liquid as well as gas separation and concentration.
The ceramic membrane is a layered composite membrane composed of a support layer, an intermediate transition layer, a separation layer and a modified separation layer, and the separation layer has good separation interception performance and plays a main role in the filtration process. Research work on inorganic ceramic membranes for water treatment has been widely conducted, but the application of the inorganic ceramic membranes in industrial test stages is difficult, mainly because separation layers of the inorganic ceramic membranes are easy to be polluted when the inorganic ceramic membranes are applied to separation and concentration of substances, pore channels are blocked, the separation layers play a main role in the filtration process, and the flux of the polluted ceramic membranes is attenuated, the membrane pressure difference is increased, the rejection rate is reduced, and the service life of the ceramic membranes is greatly shortened.
At present, aiming at the problem of easy pollution caused by the blockage of a ceramic membrane pore canal, the pollution of the ceramic membrane is delayed mainly by pretreatment, optimization of operation conditions and cleaning of the ceramic membrane, and although the measures can play a certain role, the operation cost is increased intangibly, and if the operation is improper, the separation concentration efficiency is even reduced, and even secondary pollution is caused. Therefore, by modifying the ceramic membrane separation layer, the anti-pollution performance of the ceramic membrane is improved, which is also recognized as a method for overcoming the root cause of membrane pollution.
In Chinese patent application CN104128101A, it is proposed to modify the separation layer of ceramic membrane by doping silver in proper amount to obtain a separation membrane material with metal-ceramic composite structure, which has a certain antibacterial property due to water treatment, especially when the matrix is TiO 2 When the ceramic membrane is used, the ceramic membrane has certain photocatalytic performance and self-cleaning function, so that the anti-pollution performance is realized, but silver is relatively expensive, silver poisoning can be caused by improper use, the anti-pollution performance of the ceramic membrane is single, the realization condition is harsh, the self-cleaning efficiency is low, and the general applicability is not high.
Disclosure of Invention
In order to solve the problems, the invention provides a self-cleaning piezoelectric ceramic filter membrane, which is prepared by coating a piezoelectric material and an additive mixture on the surface of a ceramic membrane and sintering the mixture on the surface of the ceramic membrane to form a piezoelectric layer, wherein the ceramic membrane is a commercially available membrane or a ceramic membrane prepared by a conventional process;
or the membrane is prepared by adding piezoelectric materials and additives in the existing ceramic membrane preparation process to prepare a piezoelectric ceramic filter membrane containing the piezoelectric materials and the additives; namely, a piezoelectric ceramic filter membrane containing a piezoelectric material and an additive in the separation layer and the transition layer, or a piezoelectric ceramic filter membrane containing a piezoelectric material and an additive in the whole membrane is produced.
The piezoelectric ceramic filter membrane is used in the fluid separation and purification process, under the combined action of pulse current or pulse current and ultrasound, the piezoelectric effect and inverse piezoelectric effect of the piezoelectric material are utilized to force particles and charged bodies to be far away from the ceramic filter membrane, so that the effects of preventing the filter pore canal of the ceramic filter membrane from being blocked, realizing the self-cleaning function and inhibiting the pollution of the ceramic filter membrane are achieved.
When the coating is prepared, the mixture of the piezoelectric material and the additive is prepared by mixing the piezoelectric material and the additive according to the mass ratio of 4-6:1, the coating thickness is 10-80 mu m, and the sintering temperature is 1000-1500 ℃.
When the piezoelectric material and the additive are added in the existing ceramic membrane preparation process, the addition amount of the piezoelectric material is 25-60% of the mass of the inorganic ceramic raw material, and the addition amount of the additive is 5-20% of the mass of the inorganic ceramic raw material.
The piezoelectric material is one of zinc oxide, barium titanate, lead zirconate titanate, doped modified zinc oxide conductive material and doped modified barium titanate conductive material.
Preferably, the piezoelectric material is a nano material, and the prepared piezoelectric ceramic filter membrane has an antibacterial effect and greatly enhances the anti-biological pollution capability when being used for liquid separation and concentration.
The additive is one or more of polystyrene, polyethylene glycol, polyacrylic alcohol and polyethylene oxide.
The doped modified zinc oxide conductive material and the doped modified barium titanate conductive material are piezoelectric materials with conductive performance, which are prepared by adopting a conventional process, for example, conductive aluminum-doped nano zinc oxide is prepared by referring to a method in the section of Xiong Yu Al doped nano zinc oxide conductive powder performance and structure, conductive aluminum-doped nano zinc oxide is prepared by referring to a method in the section of Yue Renliang aluminum doped nano zinc oxide liquid-phase flame combustion synthesis and conductivity research thereof, and conductive doped barium titanate is prepared by referring to a method in the section of Zhang Hao doped barium titanate/conductive polymer composite wave-absorbing material preparation and performance; but is not limited to the above method.
Zinc oxide and barium titanate are not only remarkable in piezoelectric effect, but also good in conductivity through doping modification, zinc oxide is not only a piezoelectric material, but also a semiconductor with a material valence of the zinc oxide, the forbidden band width can be reduced through doping, the conductivity is improved, and the barium titanate can form a gap impurity level through doping, so that the conductivity is improved. The doped conductive piezoelectric material is applied to the preparation of the piezoelectric ceramic filter membrane, and the prepared piezoelectric ceramic filter membrane can combine the electrophoresis effect and the inverse piezoelectric effect in the operation process, so that the self-cleaning anti-pollution effect of the piezoelectric ceramic filter membrane is enhanced.
The ceramic filter membrane has 3 configurations of flat plate, tube and multi-channel.
The piezoelectric ceramic filter membrane is used in the fluid separation process and is carried out under the combined action of pulse current or pulse current and ultrasound, wherein the piezoelectric ceramic filter membrane is placed in an ultrasound environment, and mechanical vibration is generated along with the ultrasound, so that charges are generated on the surface of the piezoelectric ceramic filter membrane by the mechanical vibration, the conductivity of the piezoelectric ceramic filter membrane is increased, the electric field effect of the piezoelectric ceramic filter membrane is enhanced, and the self-cleaning function of the piezoelectric ceramic filter membrane is enhanced.
The self-cleaning piezoelectric ceramic filter membrane disclosed by the invention realizes a self-cleaning function in the following two modes:
(1) When the self-cleaning piezoelectric ceramic filter membrane is prepared by adding piezoelectric materials such as zinc oxide, barium titanate, lead zirconate titanate and the like into cross-flow filtration, the self-cleaning piezoelectric ceramic filter membrane is used for separating and concentrating fluid, a power supply is directly connected with the self-cleaning piezoelectric ceramic filter membrane to form a closed circuit, when particles in the fluid are close to the piezoelectric ceramic filter membrane, high-frequency pulse current is applied to a ceramic filter membrane separation layer or the whole piezoelectric layer of the ceramic filter membrane under the action of the pulse current, a reverse piezoelectric effect is generated by the piezoelectric layer of the ceramic filter membrane, the piezoelectric ceramic filter membrane is caused to mechanically vibrate, the particles close to the piezoelectric ceramic filter membrane are sprung off, and the particles are far away from the piezoelectric ceramic filter membrane under the scouring action of the fluid, so that the self-cleaning function is realized; when the doped modified zinc oxide conductive material and the doped modified barium titanate conductive material are added to prepare the self-cleaning piezoelectric ceramic filter membrane, the self-cleaning piezoelectric ceramic filter membrane is used for separating and concentrating fluid, a power supply is respectively connected with an auxiliary electrode and the self-cleaning piezoelectric ceramic filter membrane to form a complete circuit through the fluid, particles in the fluid are charged, when the fluid is filtered through the ceramic filter membrane, an electric field formed by the piezoelectric ceramic filter membrane promotes the particles in the fluid to be far away from the ceramic membrane, meanwhile, due to the inverse piezoelectric effect, the piezoelectric layer aggravates vibration, the particles close to the piezoelectric ceramic filter membrane are sprung away, and the particles flow away along with the fluid, so that the self-cleaning function is realized.
(2) When the piezoelectric ceramic filter membrane is used for separating and concentrating fluid in a dead-end filtering mode, a power supply is directly connected with the self-cleaning piezoelectric ceramic filter membrane to form a closed circuit, the fluid is filtered through the piezoelectric ceramic filter membrane, substances trapped by the piezoelectric ceramic filter membrane are left on one side of the piezoelectric ceramic filter membrane, high-frequency current pulses are applied to the piezoelectric ceramic filter membrane, particles are far away from the ceramic filter membrane due to the inverse piezoelectric effect of the piezoelectric ceramic filter membrane and the action of gravity, and the particles are deposited and discharged along with concentrated substances.
The pulse current is generated by connecting a high-frequency power supply of the piezoelectric ceramic filter membrane, when the piezoelectric ceramic filter membrane is in a tubular and flat type, the piezoelectric ceramic filter membrane is directly connected with the power supply, when the piezoelectric ceramic filter membrane is in a multi-channel type, the piezoelectric ceramic filter membrane can be connected with the power supply after being connected in parallel in multiple channels through metal sheets, the metal sheets are platinum sheets and titanium sheets or multiple channels, the metal sheets are in a structure consistent with the cross section shape of the multi-channel piezoelectric ceramic filter membrane, and the metal sheets are covered at the end parts of the piezoelectric ceramic filter membrane when in use.
The invention further aims to provide a device utilizing the piezoelectric ceramic filter membrane, which comprises a fluid conveying pipe, a pulsation damper, a back pressure valve, a flowmeter, a separation box, the piezoelectric ceramic filter membrane and a power supply; the fluid delivery pipe is communicated with a fluid inlet on the separation box, the piezoelectric ceramic filter membrane is fixed in the separation box to divide the separation box into a permeate storage chamber and a retentate storage chamber, a permeate discharge port is arranged on the permeate storage chamber, a retentate discharge port is arranged on the retentate storage chamber, the power supply is directly connected with the piezoelectric ceramic filter membrane to form a closed circuit, or two stages of the power supply are respectively connected with the auxiliary electrode and the piezoelectric ceramic filter membrane to form a closed circuit through fluid, and the pulsation damper, the back pressure valve and the flowmeter are sequentially arranged on the fluid delivery pipe.
The separation tank is placed in an ultrasonic device.
The fluid conveying pipe is provided with a pressure gauge.
The auxiliary electrode is used when the piezoelectric ceramic filter membrane has conductivity, the two poles of the high-frequency power supply are respectively connected with the piezoelectric ceramic filter membrane and the auxiliary electrode, and the auxiliary electrode is one of a stainless steel electrode, a platinum electrode or a titanium electrode.
The device can complete fluid separation in a cross-flow filtration mode or a dead-end filtration mode.
Compared with the prior art, the invention has the beneficial effects that:
1. the piezoelectric material is added in the preparation process of the ceramic membrane, so that the piezoelectric ceramic filter membranes with different shapes can be prepared according to the filter requirement, the separation and concentration requirements of gas and liquid microfiltration, ultrafiltration and nanofiltration can be met, and the application range is wide; 2. the invention realizes the self-cleaning function in the membrane separation process, so that the separation and concentration efficiency is high and durable, the stable filtering performance can be maintained for a long time, and the used device has reasonable design, simple and convenient operation and convenient popularization and use; 3. the invention utilizes the organic combination of the piezoelectric material and the ceramic membrane, utilizes the synergistic effect of the piezoelectric material and the reverse piezoelectric effect and the ceramic membrane filtration to effectively reduce the pollution of the ceramic membrane, and the nano piezoelectric material used by the invention can effectively inhibit biological pollution, and the ultrasonic effect can strengthen the self-cleaning anti-pollution performance of the piezoelectric ceramic filter membrane, effectively remove the substances remained on the tubular piezoelectric ceramic membrane, and furthest improve the service life of the piezoelectric ceramic filter membrane; 4. the method has the advantages that the low-cost and easily-obtained piezoelectric materials are used in the preparation process of the ceramic filter membrane, the sintering temperature is low, the filtering performance is stable and efficient, the service life is long, and the preparation cost is reduced to a certain extent.
Drawings
FIG. 1 is a schematic diagram of a piezoelectric ceramic filter membrane cross-flow filtration type self-cleaning device;
FIG. 2 is a schematic illustration of the use of a self-cleaning apparatus in combination with an ultrasonic device;
FIG. 3 is a schematic diagram of a dead-end filtration type self-cleaning device for a piezoelectric ceramic filter membrane;
in the figure: 1-a fluid delivery tube; 2-pulsation damper; 3-back pressure valve; 4-a flow meter; 5-a separation box; 6-piezoelectric ceramic filter membrane; 7-fluid inlet; 8-a power supply; 9-permeate discharge port; 10-retentate discharge port; 11-a pressure gauge; 12-electrode; 13-a regulating valve; 14-a pump; 15-a fluid storage tank; 16-a stirrer; 17-an ultrasound device; 18-check valve; 19-permeate storage chamber; 20-retentate storage chamber.
Detailed Description
The technical solution of the present invention will be further described with reference to the specific embodiments, but the scope of the present invention is not limited to the above description.
Example 1: the piezoelectric ceramic filter membrane is prepared by coating a mixture of an aluminum-modified zinc oxide conductive material and polystyrene on the surface of a conventional commercial ceramic membrane and sintering at 1200 ℃; in the preparation of the coating, the mixture of the aluminum-doped modified zinc oxide conductive material and the polystyrene is prepared by mixing the aluminum-doped modified zinc oxide conductive material and the polystyrene according to the mass ratio of 5:1, the coating thickness is 20 mu m, and the aluminum-doped modified zinc oxide conductive material is prepared by the method in the section of the research on the conductivity of the aluminum-doped nano zinc oxide by referring to Yue Renliang.
As shown in fig. 1, the device using the piezoelectric ceramic filter membrane comprises a fluid delivery pipe 1, a pulsation damper 2, a back pressure valve 3, a flowmeter 4, a separation tank 5, a piezoelectric ceramic filter membrane 6, a power supply 8 and a fluid storage tank 15; the fluid storage tank 15 is connected with the fluid delivery pipe 1 through the pump 14, the fluid delivery pipe 1 is communicated with the fluid inlet 7 on the separation tank 5 by the stirrer 16 arranged in the fluid storage tank 15, the piezoelectric ceramic filter membrane 6 is fixed in the separation tank 5 to divide the separation tank 5 into a permeate storage chamber 19 and a retentate storage chamber 20, the permeate storage chamber is provided with a permeate discharge port 9, the retentate storage chamber is provided with a retentate discharge port 10, the two stages of power supplies are respectively connected with the auxiliary electrode 12 and the piezoelectric ceramic filter membrane through fluid to form a closed circuit, the fluid delivery pipe is sequentially provided with the pulsation damper 2, the back pressure valve 3 and the flowmeter 4, the retentate discharge port 10 is communicated with the fluid storage tank 15 through a pipeline, and a check valve 18 and a regulating valve 13 are sequentially arranged on the pipeline; the auxiliary electrode 12 is a stainless steel electrode, the separation box 5 is hollow and cylindrical, the piezoelectric ceramic filter membrane is tubular, a permeate storage chamber is formed by sealing the outer sides of two ends of the tube body and the separation box 5, and the fluid conveying pipe 1 is provided with a pressure gauge 11;
the device is adopted to filter and separate 1g/L bovine serum albumin liquid, the to-be-separated material is placed in a fluid storage tank 15, a stainless steel electrode 12 is connected to the positive electrode of a high-frequency alternating current power supply, a tubular piezoelectric ceramic membrane 6 piezoelectric layer is connected to the negative electrode of the high-frequency alternating current power supply, the high-frequency alternating current power supply is turned on, the fixed current frequency is 5MHz, the regulating potential is 30V, a stirrer 16 is started to stir the bovine serum albumin liquid, a circulating pump 14 is turned on, the bovine serum albumin liquid is pumped into the separation tank 5 through a fluid conveying pipe 1 through a fluid inlet 7, a back pressure valve 3 and a pulsation damper 2 are regulated, a pressure gauge 11 on the fluid conveying pipe 1 is displayed to be 0.5MPa, a regulating flowmeter 4 controls the flow rate of the bovine serum albumin liquid to be 0.1m/s, the bovine serum albumin liquid is subjected to cross-flow filtration through the tubular piezoelectric ceramic membrane 6, the bovine serum albumin liquid is controlled through a regulating valve 13 on a retentate outlet 10, the bovine serum albumin liquid is discharged into the fluid storage tank 15 through the retentate outlet 10 for circulation, a retentate 10 is also provided with a permeate valve 18, and the bovine serum permeate liquid is discharged through a permeate outlet 9.
The tubular piezoelectric ceramic membrane self-cleaning device runs continuously for 1h according to the scheme,the permeation flux of the tubular piezoelectric ceramic membrane prepared by the method is 1140 L.m -2 ·h -1 ·bar -1 And the permeation flux of the tubular piezoelectric ceramic membrane after continuous operation for 2 hours is 860 L.m -2 ·h -1 ·bar -1 Under the same conditions, the tubular ceramic filter membrane prepared without adding piezoelectric material is used for filtering and separating, and the permeation flux of the tubular ceramic filter membrane is 1080 L.m after 2 hours of filtering -2 ·h -1 ·bar -1 Down to 560 L.m -2 ·h -1 ·bar -1 . Compared with the common ceramic filter membrane, the piezoelectric ceramic filter membrane has obvious self-cleaning anti-pollution effect, and the content of bovine serum albumin in the retentate of the bovine serum albumin wastewater is measured to be 5g/L, so that the interception efficiency is high.
According to example 1, the self-cleaning piezoelectric ceramic filter membrane prepared in example 1 was used in combination with an ultrasonic apparatus, as shown in FIG. 2, for separation of 1g/L bovine serum albumin feed liquid, the ultrasonic apparatus 17 (ultrasonic apparatus) was turned on, other operation conditions were the same as those of example 1, and the operation was continued for 2 hours, and the permeation flux of the tubular piezoelectric ceramic membrane prepared by dip coating was 1120 L.m -2 ·h -1 ·bar -1 And the permeation flux of the tubular piezoelectric ceramic membrane after continuous operation for 2 hours is 980 L.m -2 ·h -1 ·bar -1 Under the same conditions, the tubular ceramic filter membrane prepared without adding piezoelectric material is used for filtering and separating, and the permeation flux of the tubular ceramic filter membrane is 1055 L.m after 2 hours of filtering -2 ·h -1 ·bar -1 Down to 590 L.m -2 ·h -1 ·bar -1 . The result shows that the ultrasonic effect can relieve the pollution of the ceramic filter membrane, but the ultrasonic effect is combined in the running process of the self-cleaning piezoelectric ceramic membrane, so that the anti-pollution effect of the self-cleaning piezoelectric ceramic can be effectively enhanced.
The feed liquid in the filter device is cleaned, 1g/L of bovine serum albumin feed liquid is added into the filter device again, the ceramic filter membrane is continuously operated for 2 hours again according to the separation and filtration process, and the permeation flux of the tubular piezoelectric ceramic filter membrane is measured to be 860 L.m -2 ·h -1 ·bar -1 Down to 726 L.m -2 ·h -1 ·bar -1 Whereas common ceramicsThe permeation flux of the filter membrane is 560L m -2 ·h -1 ·bar -1 Down to 208L m -2 ·h -1 ·bar -1 When the same self-cleaning piezoelectric ceramic filter membrane is used in combination with ultrasonic equipment, the permeation flux of the self-cleaning piezoelectric ceramic filter membrane is 980L m -2 ·h -1 ·bar -1 Down to 895L m -2 ·h -1 ·bar -1 The results show that the piezoelectric ceramic filter membrane can maintain stable filtering performance for a long time, and particularly has little attenuation of permeation flux when being used together with ultrasound, and can maintain optimal filtering performance for a long time.
Example 2: the piezoelectric ceramic filter membrane is prepared by coating a mixture of barium titanate and polyethylene glycol on the surface of a conventional commercially available micro-filtration ceramic membrane and sintering at 1000 ℃; in the coating preparation, the mixture of barium titanate and polyethylene glycol is prepared by mixing barium titanate and polyethylene glycol according to the mass ratio of 4:1, and the coating thickness is 50 mu m.
As shown in fig. 3, the device using the piezoelectric ceramic filter membrane comprises a fluid delivery pipe 1, a pulsation damper 2, a back pressure valve 3, a flowmeter 4, a separation tank 5, a piezoelectric ceramic filter membrane 6, a power supply 8 and an ultrasonic device 17; the fluid delivery pipe 1 is communicated with a fluid inlet 7 on the separation box 5, the piezoelectric ceramic filter membrane 6 is fixed in the separation box 5 to divide the separation box 5 into a permeate storage chamber 19 and a retentate storage chamber 20, the piezoelectric ceramic filter membrane is in a flat plate shape, a permeate discharge port 9 is arranged on the permeate storage chamber, a retentate discharge port 10 is arranged on the retentate storage chamber, a power supply is connected with the piezoelectric ceramic filter membrane to form a closed circuit, the fluid delivery pipe is sequentially provided with the pulsation damper 2, the back pressure valve 3 and the flowmeter 4, and a regulating valve 13 is arranged at the retentate discharge port 10; a pressure gauge 11 is arranged on the fluid conveying pipe 1;
the device is used for filtering and separating dust-containing waste gas (the average grain diameter of dust is 8.9 mu m, the density is 10 mg/m), a flat plate-shaped piezoelectric ceramic micro-filtration membrane 6 is installed in a separation box 5 and is fixed, a power supply 8 (high-frequency alternating current) is connected to the flat plate-shaped piezoelectric ceramic micro-filtration membrane 6, the power supply 8 is turned on, the fixed current frequency is 3MHz, an ultrasonic device 17 is turned on, at the moment, the dust-containing waste gas is introduced into the separation box 5 through a fluid conveying pipe 1 through a fluid inlet 7, a backpressure valve 3 and a pulsation damper 2 are regulated, a pressure gauge 11 on the fluid conveying pipe 1 is enabled to be 0.05MPa, a flow rate of the dust-containing waste gas is regulated to be 0.05m/s, the dust-containing waste gas is filtered through the piezoelectric ceramic micro-filtration membrane 6, dust is trapped, the gas is discharged and collected through a permeate discharge port 9 after the gas is filtered, the trapped dust-containing particulate matters are discharged and collected through a regulating valve 13 on a retentate discharge port 10 along with partial gas discharged and collected from the retentate 10.
The operation is continued for 8 hours, the retention rate of dust is up to 89% through measurement, and the permeation flux of the piezoelectric ceramic micro-filtration membrane is only 2720L m -2 ·h -1 ·bar -1 Down to 2680L m -2 ·h -1 ·bar -1 The flat plate type piezoelectric ceramic filter membrane has high separation performance, obvious self-cleaning effect in the separation process and long-time stable operation.
According to example 2, the dust-containing waste gas (dust having an average particle diameter of 8.9 μm and a density of 10 mg/m. Mu.m) was again filtered and separated by using a plate-shaped piezoelectric ceramic filter membrane prepared under the same conditions, and at this time, the ultrasonic device 17 was turned off, and other operation conditions were the same as those described above, and the retention rate of dust was 82% by continuous operation for 8 hours, while the permeation flux of the piezoelectric ceramic microfiltration membrane was 2690L. Mu.m -2 ·h -1 ·bar -1 Down to 2430L m -2 ·h -1 ·bar -1 The ultrasonic effect has a certain reinforcing effect on the anti-pollution performance of the self-cleaning piezoelectric ceramic membrane.
Example 3: referring to the method of example 2, a conventional commercially available micro-filtration ceramic membrane was coated with a mixture of lead zirconate titanate and polyethylene oxide, which was prepared by sintering at 1150 c, in which case the mixture of lead zirconate titanate and polyethylene oxide was prepared by mixing lead zirconate titanate and polyethylene oxide in a mass ratio of 4.5:1, and a coating thickness of 80 μm was prepared to obtain a piezoelectric ceramic membrane with a piezoelectric layer.
The dust-laden exhaust gas (dust average particle diameter 8.9 μm, density 10mg +.m) are filtered and separated, the operation conditions are consistent, the continuous operation is carried out for 8 hours, the retention rate of dust is up to 96% after being measured, and the permeation flux of the flat plate type piezoelectric ceramic micro-filtration membrane is 2370 L.m under the cooperation of ultrasonic equipment -2 ·h -1 ·bar -1 Down to 2230L m -2 ·h -1 ·bar -1 Under the condition of no ultrasonic equipment, the device continuously runs for 8 hours, the dust rejection rate is 83 percent, and the permeation flux of the flat plate type piezoelectric ceramic micro-filtration membrane is L m -2 ·h -1 ·bar -1 Down to 2230L m -2 ·h -1 ·bar -1 It is also proved that the piezoelectric ceramic filter membrane can stably operate for a long time, and the anti-pollution performance of the piezoelectric ceramic filter membrane can be enhanced by the ultrasonic action, however, when the piezoelectric layer is coated, the permeation flux is reduced due to too thick coating.
Example 4: the piezoelectric ceramic filter membrane is prepared by adding nano zinc oxide and polyethylene glycol in the existing ceramic membrane preparation process, and an ultrafiltration piezoelectric ceramic filter membrane containing piezoelectric materials and additives in a separation layer and a transition layer is prepared; in the preparation of the separation layer and the transition layer, the addition amount of the nano zinc oxide is 60% of the mass of the inorganic ceramic raw material, and the addition amount of the polyethylene glycol is 10% of the mass of the inorganic ceramic raw material;
the specific preparation method of the piezoelectric ceramic filter membrane comprises the following steps:
(1) Preparing a tubular alumina ceramic membrane support by referring to a method in Chen Jugong preparation and characterization of a porous alumina ceramic membrane support;
(2) Immersing the support body prepared in the step (1) in saturated sodium hydroxide-ethanol solution for 0.5h, taking out, cleaning the immersed support body by using ultrapure water until the cleaning solution is neutral, placing the cleaned support body in a vacuum drying oven at 60 ℃, and drying for 4h to obtain a dried porous support body for later use;
(3) Al is added with 2 O 3 Adding nanometer zinc oxide powder (particle diameter 40-80 nm) and polyethylene glycol into ultrapure water, mixing, stirring for 3 hr, and mixing to obtain coating solution, wherein the addition amounts of nanometer zinc oxide powder and polyethylene glycol are respectively Al 2 O 3 6 of mass0% and 10%;
(4) Placing the coating liquid in an ultrasonic bath, sealing the outer wall of the tubular support body dried in the step (2) by using a preservative film, immersing the tubular support body in the coating liquid for 90s, taking out, repeatedly dip-coating for 10 times, taking out the coated tubular support body, drying for 2h at room temperature, transferring to a drying box at 100 ℃ for drying for 0.5h, sintering at 1250 ℃ for 0.2h, and introducing N at a constant rate in the sintering process 2 Cooling at a cooling rate of 5 ℃ per minute to obtain the tubular piezoelectric ceramic filter membrane.
As shown in fig. 2, the device using the piezoelectric ceramic filter membrane comprises a fluid delivery pipe 1, a pulsation damper 2, a back pressure valve 3, a flowmeter 4, a separation tank 5, a piezoelectric ceramic filter membrane 6, a power supply 8, a fluid storage tank 15 and an ultrasonic device 17; the fluid storage tank 15 is connected with the fluid delivery pipe 1 through the pump 14, the fluid delivery pipe 1 is communicated with the fluid inlet 7 on the separation tank 5 through the stirrer 16 arranged in the fluid storage tank 15, the piezoelectric ceramic filter membrane 6 is fixed in the separation tank 5 to divide the separation tank 5 into a permeate storage chamber 19 and a retentate storage chamber 20, the permeate storage chamber is provided with a permeate discharge port 9, the retentate storage chamber is provided with a retentate discharge port 10, a power supply is directly connected with the self-cleaning piezoelectric ceramic filter membrane to form a closed circuit, the fluid delivery pipe is sequentially provided with the pulsation damper 2, the back pressure valve 3 and the flowmeter 4, the retentate discharge port 10 is communicated with the fluid storage tank 15 through a pipeline, and a check valve 18 and a regulating valve 13 are sequentially arranged on the pipeline; the separation box 5 is placed in ultrasonic equipment, the separation box 5 is hollow and cylindrical, the piezoelectric ceramic filter membrane is tubular, a permeate storage chamber is formed by sealing the outer sides of two ends of the tube body and the separation box 5, and the fluid conveying pipe 1 is provided with a pressure gauge 11;
the device is adopted to filter and separate oily wastewater (100 mg/L of oil and 6mg/L of cetyltrimethylammonium bromide), the to-be-separated matter is placed into a fluid storage tank 15, a piezoelectric layer of a tubular piezoelectric ceramic membrane 6 is connected to the positive electrode and the negative electrode of a power supply 8, the power supply 8 is turned on, the fixed current frequency is 5MHz, the regulating potential is 30V, an ultrasonic device 17 is turned on, a stirrer 16 is started to stir the oily wastewater, a circulating pump 14 is turned on, the oily wastewater is pumped into the separation tank 5 through a fluid conveying pipe 1 through a fluid inlet, a backpressure valve 3 and a pulsation damper 2 are regulated, the pressure gauge 11 on the fluid conveying pipe 1 shows 0.5MPa, a flow meter 4 is regulated to control the flow rate of the oily wastewater to be 0.1m/s, the oily wastewater is subjected to cross-flow filtration through the tubular piezoelectric ceramic membrane 6, the oily wastewater is controlled through a regulating valve 13 on a retentate outlet 10, the oily wastewater is discharged into the fluid storage tank 15 through the retentate outlet 10 to circulate, a check valve 18 is further arranged on the retentate outlet 10, and the permeate is discharged through the permeate outlet 9.
The tubular piezoelectric ceramic nanofiltration membrane self-cleaning device continuously runs for 2 hours according to the scheme, and the permeation flux of the tubular piezoelectric ceramic nanofiltration membrane prepared by the method is 912L m after measurement -2 ·h -1 ·bar -1 And the permeation flux of the tubular piezoelectric ceramic membrane after continuous operation for 2 hours is L.m -2 ·h -1 ·bar -1 The permeability flux attenuation is very small, and the prepared tubular piezoelectric ceramic filter membrane has excellent self-cleaning anti-pollution performance, and the removal rate of COD is as high as 88 percent, which is mainly due to the reverse piezoelectric effect of the tubular piezoelectric ceramic filter membrane, and oil drops attached to the piezoelectric ceramic filter membrane are sprung off the surface of the tubular piezoelectric ceramic filter membrane, so that the self-cleaning function in the running process is realized.
According to the above, the oily wastewater (100 mg/L oil and 6mg/L cetyltrimethylammonium bromide) was again separated and filtered using the tubular piezoelectric ceramic filter membrane prepared under the same conditions, the other operating conditions were the same, the ultrasonic equipment 17 was turned off, the oily wastewater was filtered in the apparatus shown in FIG. 1, and the operation was continued for 2 hours, and the permeation flux of the tubular piezoelectric ceramic filter membrane prepared by the above method was 930L.m, as measured -2 ·h -1 ·bar -1 And the permeation flux of the tubular piezoelectric ceramic membrane after continuous operation for 2 hours is 863L m -2 ·h -1 ·bar -1 The permeate flux attenuation was slightly increased compared to the combined ultrasonic device and the removal rate for COD was also reduced to 82%.
The feed liquid in the filter device is cleaned, and oily wastewater (100 mg/L oil and 6mg/L cetyltrimethylammonium bromide) is added into the filter device again, and is separated according to the aboveThe filtration process is that the ceramic filter membrane is continuously operated for 2 hours again, and the permeation flux of the tubular piezoelectric ceramic filter membrane is 863L m after measurement -2 ·h -1 ·bar -1 Down to 786L m -2 ·h -1 ·bar -1 When the same self-cleaning piezoelectric ceramic filter membrane is used in combination with ultrasonic equipment, the permeation flux of the self-cleaning piezoelectric ceramic filter membrane is from 894L m -2 ·h -1 ·bar -1 Down to 845L m -2 ·h -1 ·bar -1 The removal rates of COD are 78% and 83%, respectively, and the results also show that the piezoelectric ceramic filter membrane can maintain stable filtering performance for a long time.
Example 5: the piezoelectric ceramic filter membrane is a nanofiltration piezoelectric ceramic filter membrane prepared by adding doped modified barium titanate conductive material, polyacrylic alcohol and polyethylene oxide in the existing ceramic membrane preparation process, wherein the doped modified barium titanate conductive material is prepared according to Zhang Hao 'preparation and performance of doped barium titanate/conductive polymer composite wave absorbing material', and the support layer, the transition layer and the separation layer all contain piezoelectric materials and additives; the addition amount of the doped modified barium titanate conductive material in the preparation of the supporting layer is 40% of the mass of the inorganic ceramic raw material, and the addition amount of the polyacrylic alcohol is 8% of the mass of the inorganic ceramic raw material; the addition of the doped modified barium titanate conductive material in the preparation of the transition layer and the separation layer is 60% of the mass of the inorganic ceramic raw material, and the addition of polyethylene oxide is 8% of the mass of the inorganic ceramic raw material;
the specific preparation method of the piezoelectric ceramic filter membrane comprises the following steps:
(1) According to the method in Zhu Qingpeng 'preparation of porous alumina ceramic membrane support and performance characterization', when preparing the seven-channel alumina ceramic membrane support, adding a doped modified barium titanate conductive material and polyacrylic alcohol, wherein the doped modified barium titanate conductive material is 40% of the mass of alumina, and the polyacrylic alcohol is 8% of the mass of alumina;
(2) Immersing the support body prepared in the step (1) in saturated sodium hydroxide-ethanol solution for 0.5h, taking out, cleaning the immersed support body by using ultrapure water until the cleaning solution is neutral, placing the cleaned support body in a vacuum drying oven at 60 ℃, and drying for 4h to obtain a dried porous support body for later use;
(3) Al is added with 2 O 3 Adding the doped modified barium titanate conductive material and polyethylene oxide into ultrapure water, mixing and stirring for 3 hours, and uniformly mixing to obtain coating liquid, wherein the addition amounts of the doped modified barium titanate conductive material and the polyethylene oxide are respectively Al 2 O 3 60% and 8% by mass;
(4) And (3) placing the coating liquid in an ultrasonic bath, sealing the outer wall of the support body dried in the step (2) by using a preservative film, immersing the support body in the coating liquid for 90s, taking out, repeatedly dip-coating for 6 times, taking out the coated support body, drying for 2h at room temperature, transferring to a drying oven at 100 ℃ for drying for 0.8h, sintering at 1050 ℃ for 0.2h, and cooling at a cooling rate of 5 ℃/min to obtain the seven-channel piezoelectric ceramic filter membrane.
As shown in fig. 1, the device using the piezoelectric ceramic filter membrane comprises a fluid delivery pipe 1, a pulsation damper 2, a back pressure valve 3, a flowmeter 4, a separation tank 5, a piezoelectric ceramic filter membrane 6, a power supply 8 and a fluid storage tank 15; the fluid storage tank 15 is connected with the fluid delivery pipe 1 through the pump 14, the fluid delivery pipe 1 is communicated with the fluid inlet 7 on the separation tank 5 by the stirrer 16 arranged in the fluid storage tank 15, the piezoelectric ceramic filter membrane 6 is fixed in the separation tank 5 to divide the separation tank 5 into a permeate storage chamber 19 and a retentate storage chamber 20, the permeate storage chamber is provided with a permeate discharge port 9, the retentate storage chamber is provided with a retentate discharge port 10, the two poles of the power supply 8 are respectively connected with the auxiliary electrode 12 and the piezoelectric ceramic filter membrane through fluid to form a closed circuit, the fluid delivery pipe is sequentially provided with the pulsation damper 2, the back pressure valve 3 and the flowmeter 4, the retentate discharge port 10 is communicated with the fluid storage tank 15 through a pipeline, and a check valve 18 and a regulating valve 13 are sequentially arranged on the pipeline; wherein the auxiliary electrode 12 is a titanium electrode, the separation box 5 is hollow and cylindrical, the piezoelectric ceramic filter membrane is tubular, a permeate storage chamber is formed by sealing the outer sides of the two ends of the tube body and the separation box 5, and the fluid conveying pipe 1 is provided with a pressure gauge 11;
the device is adopted to filter and separate oily wastewater (100 mg/L of oil and 6mg/L of cetyltrimethylammonium bromide), the to-be-separated matter is placed into a fluid storage tank 15, a titanium electrode 12 is connected to the positive electrode of a power supply 8, a seven-channel piezoelectric ceramic membrane 6 is connected in parallel through a platinum sheet (the platinum sheet structure is the same as the cross section structure of the seven-channel piezoelectric ceramic membrane, when the device is used, one end of the seven-channel piezoelectric ceramic membrane is covered) and then connected to the negative electrode of the power supply 8, the power supply 8 is turned on, the fixed current frequency is 5MHz, the adjustment potential is 30V, a stirrer 16 is started to stir the oily wastewater, a circulating pump 14 is turned on, the oily wastewater is pumped into a separation tank 5 through a fluid inlet, a backpressure valve 3 and a pulsation damper 2 are adjusted, a pressure gauge 11 on the fluid storage tank 1 is shown as 0.5MPa, the flow rate of the oily wastewater is controlled to be 0.1m/s by a flow meter 4, the oily wastewater is filtered through the seven-channel piezoelectric ceramic membrane 6, the oily wastewater is controlled by a regulating valve 13 on a control retentate 10, the retentate is discharged from the retentate 10 through a retentate 10, a permeate drain outlet 9 is also arranged on the retentate 10, and the retentate is discharged from the retentate 10 through the permeate drain outlet.
The seven-channel piezoelectric ceramic ultrafiltration membrane self-cleaning device continuously runs for 2 hours according to the scheme, and the permeation flux of the seven-channel piezoelectric ceramic membrane prepared by the method is 830L m after measurement -2 ·h -1 ·bar -1 The permeation flux of the seven-channel piezoelectric ceramic membrane after continuous operation for 2 hours is 794L m -2 ·h -1 ·bar -1 The permeation flux attenuation is little, the COD removal rate also reaches 90%, and the prepared seven-channel piezoelectric ceramic membrane has excellent self-cleaning and pollution resistance.
According to the above operation, the seven-channel piezoelectric ceramic filter membrane prepared under the same conditions is used for separating and filtering the oily wastewater (100 mg/L of oil and 6mg/L of cetyltrimethylammonium bromide) again, other operation conditions are consistent, the ultrasonic equipment 17 is combined, the device shown in the figure 2 is used for filtering the oily wastewater, the operation is carried out continuously for 2 hours, and the permeation flux of the seven-channel piezoelectric ceramic filter membrane prepared by the method is 846L m after the measurement -2 ·h -1 ·bar -1 The permeation flux of the seven-channel piezoelectric ceramic membrane after continuous operation for 2 hours is L.m -2 ·h -1 ·bar -1 The permeate flux attenuation was reduced compared to the absence of the ultrasonic device, and the removal rate for COD was also increased to 93%.
The feed liquid in the filter device is cleaned, oily wastewater (100 mg/L oil and 6mg/L cetyltrimethylammonium bromide) is added into the filter device again, the ceramic filter membrane is continuously operated for 2 hours again according to the separation and filtration process, and the permeation flux of the seven-channel piezoelectric ceramic filter membrane is measured from 863L m -2 ·h -1 ·bar -1 Down to 786L m -2 ·h -1 ·bar -1 When the same self-cleaning piezoelectric ceramic filter membrane is used in combination with ultrasonic equipment, the permeation flux of the self-cleaning piezoelectric ceramic filter membrane is from 894L m -2 ·h -1 ·bar -1 Down to 845L m -2 ·h -1 ·bar -1 The removal rates of COD before and after the ultrasonic equipment are combined are 88% and 90%, and the results also show that the piezoelectric ceramic filter membrane can keep stable filtering performance for a long time.
Claims (6)
1. A piezoelectric ceramic filter membrane for treating bovine serum albumin feed liquid, oily wastewater and dust-containing waste gas is characterized in that: coating a mixture of a piezoelectric material and an additive on the surface of the ceramic membrane, and sintering to prepare a piezoelectric ceramic filter membrane with a piezoelectric layer; or adding piezoelectric materials and additives in the existing ceramic membrane preparation process to prepare the piezoelectric ceramic membrane containing the piezoelectric materials and the additives;
when the coating is prepared, the mixture of the piezoelectric material and the additive is prepared by mixing the piezoelectric material and the additive according to the mass ratio of 4-6:1, and the coating thickness is 10-80 mu m; the piezoelectric material and the additive are added in the preparation process, the addition amount of the piezoelectric material is 25-60% of the mass of the inorganic ceramic raw material, and the addition amount of the additive is 5-20% of the mass of the inorganic ceramic raw material;
the piezoelectric material is one of zinc oxide, barium titanate, lead zirconate titanate, doped modified zinc oxide conductive material and doped modified barium titanate conductive material; the additive is one or more of polystyrene, polyethylene glycol, polyacrylic alcohol and polyethylene oxide in any ratio;
the sintering temperature in the preparation is 1000-1500 ℃.
2. The piezoelectric ceramic filter membrane according to claim 1, wherein: the piezoelectric ceramic filter membrane containing the piezoelectric material and the additive refers to a piezoelectric ceramic filter membrane containing the piezoelectric material and the additive in a separation layer and a transition layer, or a piezoelectric ceramic filter membrane containing the piezoelectric material and the additive in the whole membrane.
3. The piezoelectric ceramic filter membrane according to claim 1, wherein: the piezoelectric ceramic filter membrane is used in the fluid separation process under the combined action of pulse current or pulse current and ultrasound.
4. An apparatus using the piezoelectric ceramic filter membrane of claim 1, characterized in that: the device comprises a fluid conveying pipe (1), a pulsation damper (2), a back pressure valve (3), a flowmeter (4), a separation box (5), a piezoelectric ceramic filter membrane (6) and a power supply (8); the fluid delivery pipe (1) is communicated with a fluid inlet (7) on the separation box (5), the piezoelectric ceramic filter membrane (6) is fixed in the separation box (5) to divide the separation box (5) into a permeate storage chamber (19) and a retentate storage chamber (20), a permeate discharge port (9) is arranged on the permeate storage chamber, a retentate discharge port (10) is arranged on the retentate storage chamber, a power supply is directly connected with the piezoelectric ceramic filter membrane to form a closed circuit or two poles of the power supply are respectively connected with the auxiliary electrode (12) and the piezoelectric ceramic filter membrane to form a closed circuit through fluid, and the pulsation damper (2), the back pressure valve (3) and the flowmeter (4) are sequentially arranged on the fluid delivery pipe.
5. The apparatus according to claim 4, wherein: the device also comprises an ultrasonic device (17) in which the separation tank (5) is placed.
6. The apparatus according to claim 4, wherein: a pressure gauge (11) is arranged on the fluid conveying pipe (1).
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