CN113318608A - Dynamically catalyzed water treatment ceramic membrane and application thereof - Google Patents

Dynamically catalyzed water treatment ceramic membrane and application thereof Download PDF

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CN113318608A
CN113318608A CN202110533035.1A CN202110533035A CN113318608A CN 113318608 A CN113318608 A CN 113318608A CN 202110533035 A CN202110533035 A CN 202110533035A CN 113318608 A CN113318608 A CN 113318608A
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membrane
ceramic membrane
water treatment
ozone
titanium dioxide
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CN113318608B (en
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王俊杰
陈锋涛
方泽
吕汪洋
陈文兴
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Zhejiang University of Technology ZJUT
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Zhejiang University of Technology ZJUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • 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
    • 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
    • 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
    • B01D71/025—Aluminium oxide
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention relates to the technical field of porous ceramic materials and membrane separation, in particular to a dynamic catalytic ceramic membrane and application thereof in water treatment. The invention relates to a dynamic catalytic water treatment ceramic membrane, which mainly comprises a ceramic membrane and a dynamic catalytic functional layer formed on the surface of the ceramic membrane; the dynamic catalytic function layer is a film formed by coating a layer of metal alkoxide on the surface of titanium dioxide particles; and the use of the membrane in the water treatment industry. The invention has the advantages that the filtering function of the ceramic membrane layer is not damaged, the filtering resistance and the permeation flux of the ceramic membrane are not influenced, the utilization efficiency of ozone is improved, the ozone is catalyzed and activated to generate hydroxyl free radicals, the organic pollution which is difficult to degrade in water is not selectively oxidized, the formation of membrane pollutants is effectively relieved, and the membrane water treatment technology is efficient, safe and stable.

Description

Dynamically catalyzed water treatment ceramic membrane and application thereof
Technical Field
The invention relates to the technical field of water treatment, in particular to the technical field of ozone catalysis and ceramic membrane filtration, and specifically relates to a dynamic catalytic ceramic membrane water treatment method.
Background
The problem of water pollution has become a major environmental problem affecting the sustainable development of China. With the acceleration of industrialization and population urbanization, the problems of water resource shortage and water source pollution in China become more and more serious. The main pollution sources are industrial wastewater and domestic sewage, but the pollution of drinking water also becomes the focus of attention in recent years. At present, micro-pollution of drinking water sources becomes a common problem in China and continues to exist for a long time in the future. Besides visible rust and silt, drinking water pollution also causes pathogenic microorganisms such as 'two worms' (giardia and recessive sporozoans) and new pollutants such as Endocrine Disruptors (EDCs), medicines and personal care products (PPCPs) to cause diarrhea of human bodies to be detected in water bodies and tap water plants, so that the risk brought by the pollution is more worthy of attention.
At present, the construction of treatment facilities of industrial wastewater, domestic sewage and water works is continuously improved, but tail water treated by the traditional biochemical treatment process still contains a plurality of substances which are toxic and harmful to human bodies, such as refractory organic pollutants, bacteria, heavy metals and the like, and can not reach the standards of discharge, reuse and drinking. Membrane separation technology can intercept solid suspended matters, colloids, proteins, bacteria, viruses, microorganisms and some organic pollutants in water. Compared with the traditional water separation technology, the method has the advantages of low energy consumption, no phase change, no secondary pollution, simple equipment, convenience in operation, no need of additionally adding a medicament, small equipment floor area, high automation degree, high separation speed and the like. The membrane pollution is an inevitable problem in the membrane water treatment technology and also an important problem influencing the wide application of the membrane technology. Membrane fouling can lead to reduced membrane permeate flux, increased transmembrane pressure differentials, increased membrane cleaning and replacement frequency, reduced membrane service life, increased operating and maintenance costs, and the like. The technologies of strengthening pretreatment, aeration, cross flow filtration, water-gas back flushing and the like can slow down membrane pollution to a certain degree, but also increase the operation cost of membrane separation.
Membrane elements can be classified into organic membranes and ceramic membranes according to the material. Compared with organic membranes, ceramic membranes have better mechanical properties and chemical stability, can stably run under higher membrane permeation flux, and can bear high backwashing strength to obtain better backwashing effect, and the ceramic membranes also have the most important characteristic of being resistant to ozone oxidation. Patent (CN 107673504A) reports that ozone oxidation and ceramic membrane separation technology are combined to maintain stable high permeation flux, slow down membrane pollution process, and oxidize and degrade pollutants which are difficult to degrade in water, especially has prominent removing effect on EDCs and PPCPs, and fully ensures the biological safety of produced water.
However, in the technology of integrating pure ozone oxidation and ceramic membrane filtration, the mass transfer rate of ozone in the large-flux ceramic membrane filtration process is limited, the concentration of ozone dissolved in water is low, the ozone is not fully contacted with pollutants, and the oxidation degradation effect is not obvious. Patent (CN 106630391a) reports that doping manganese dioxide in ceramic particles to prepare ceramic membrane with ozone catalytic function by high temperature sintering technique, indeed obviously improves the utilization efficiency of ozone. However, the ceramic membrane prepared by the doping modification method has the phenomenon that a manganese dioxide catalyst is embedded, so that the efficiency of catalyzing ozone is not sufficient; secondly, doping of manganese dioxide causes the increase of film defects formed by stacking of ceramic particles, the distribution of the film pore diameter is wide, and the filtering precision is poor; most importantly, when the membrane is seriously polluted, the manganese dioxide particles are corroded by acid by adopting chemical cleaning, and the filtering function of the membrane layer can be possibly disabled. Patent (CN 104803512A) reports that a catalytic functional layer of titanium manganese or titanium cerium is prepared on the surface of a ceramic membrane by a dip coating method, and ozone dissolved in water is catalyzed to realize the catalytic self-cleaning function of the ceramic membrane. But has the problems that the catalytic function has the risk of blocking the pore diameter of the ceramic membrane, so that the membrane permeation resistance is increased, the membrane permeation flux is reduced, the transmembrane pressure difference is increased and the filtration efficiency is reduced; also, the catalytic function layer may have a risk of falling off during backwashing, which may result in poor stability of the catalytic function layer of the membrane.
Disclosure of Invention
The invention aims to solve the problems that in the integration process of ozone oxidation and ceramic membrane separation technology, the following steps occur: the catalytic degradation efficiency is low due to pure ozone oxidation and ceramic membrane filtration; the catalyst-doped modified ceramic membrane has the defects of unobvious catalytic effect, more membrane layer defects and poor membrane filtration precision; the coating of the catalyst functional layer on the surface of the ceramic membrane has a series of problems of low membrane separation efficiency, poor stability of the catalyst functional layer and the like. The method for dynamically catalyzing the ceramic membrane water treatment is provided, the filtering function of the ceramic membrane layer is not damaged, the filtering resistance and the permeation flux of the ceramic membrane are not influenced, the utilization efficiency of ozone is improved, the ozone is catalyzed and activated to generate hydroxyl radicals, the organic pollution which is difficult to degrade in water is not selectively oxidized, the formation of membrane pollutants is effectively relieved, and the membrane water treatment technology is efficient, safe and stable.
The invention is realized by the following technical scheme: a dynamically catalyzed water treatment ceramic membrane characterized by: mainly comprises a ceramic membrane and a dynamic catalytic function layer formed on the surface of the ceramic membrane; the dynamic catalytic function layer is a film formed by coating a layer of metal alkoxide on the surface of titanium dioxide particles.
Preferably, the dynamic catalytic function layer in the dynamically catalyzed ceramic membrane for water treatment is prepared by preparing alkoxide sol formed by metal salt and ethanol from titanium dioxide particles, soaking, performing centrifugal separation and drying; coating a layer of nano-particles with an ozone catalysis function on the surface of titanium dioxide particles by using metal alkoxide;
preferably, in the dynamically catalyzed water treatment ceramic membrane, commercial titanium dioxide particles with the particle size range of 0.1-10 mu m are modified into nano-scale microspheres with round particles and uniform size by a ball-milling shaping technology;
preparing metal alkoxide sol formed by metal salt and ethanol; then soaking the titanium dioxide nano-scale microspheres in the metal alkoxide sol for 1-24 h, and drying the titanium dioxide nano-scale microspheres subjected to centrifugal separation in an oven at the temperature of 25-110 ℃ for 1-24 h; and finally, preserving the dried titanium dioxide nano-scale microspheres in a muffle furnace for 1-4 h at the temperature of 300-800 ℃.
Preferably, the metal element in the metal alkoxide in the one dynamically catalyzed ceramic water treatment membrane is one or a mixture of more than one of manganese, iron, nickel, cobalt, or cerium.
Preferably, the material of the ceramic membrane in the dynamic catalytic water treatment ceramic membrane is alumina, zirconia, titania, silica, silicon carbide or a composite ceramic membrane prepared from the above ceramic membranes, and the aperture range of the ceramic membrane is 0.04-1 μm.
The application of a dynamic catalytic water treatment ceramic membrane in water treatment is characterized in that:
(1) mixing the titanium dioxide nanoparticles impregnated with the metal alkoxide with ozone to form ozone catalytic particles;
(2) coating ozone catalytic particles on the surface of a ceramic membrane to form a dynamic catalytic functional layer; wherein the ozone catalytic particles are dispersed in 1-10 wt% of the weight of water to be treated which can be contained in the feeding tank or the membrane pool;
(3) a water treatment process integrating ozone catalysis and ceramic membrane filtration processes; blowing ozone with the concentration range of 0.1-5 mg/L into a feeding tank or a membrane pool; the filtration treatment is carried out under pressure. Under the drive of pressure or negative pressure, before entering a membrane hole, water for dissolving ozone firstly enters a dynamic catalytic function layer of a three-dimensional catalytic pore formed by piling up titanium dioxide rigid particles coated on the surface of a membrane, and the nano particles coated on the surface of titanium dioxide microspheres and having the function of catalyzing ozone catalyze ozone to generate hydroxyl radicals, so that pollutants which are difficult to degrade in water are not selectively oxidized, and a filter cake layer is not formed on the surface of the membrane, so that the permeation flux of the membrane always keeps higher filtering efficiency. The water to be treated in the present application is the tail water after biochemical treatment of industrial wastewater or domestic sewage, the deep purification treatment of river and lake water or water produced by waterworks.
Preferably, the dynamic catalytic ceramic membrane for water treatment is applied to water treatment and is subjected to backwashing by a membrane filtration backwashing system after being treated for a certain time in the step (3), because some pollutants which are not degraded are deposited on the surface or in pores of the dynamic catalytic functional layer after long-time operation; by adopting a membrane filtration backwashing system, the dynamic catalytic function layer blocked by serious pollution can be damaged; and then, the dynamic catalytic function layer is formed again according to the step (1) and the step (2), and the regeneration of the dynamic catalytic function layer can be obtained.
Preferably, the ceramic membrane for dynamic catalysis in water treatment is in a tubular membrane cross-flow filtration mode in the step (2), before water to be treated enters, a suspension liquid in which ozone catalytic particles are dispersed is subjected to cross-flow circulation for 1-30 min under the pressure of 0.1-0.5 MPa, a membrane penetrating liquid flows back into the feeding tank, and a dynamic catalysis function layer is coated on the surface of the tubular ceramic membrane under the condition that the volume of the suspension liquid in the whole feeding tank is ensured to be unchanged;
or the ceramic membrane is in a dead-end filtration mode of the flat plate type membrane, before water to be treated enters the membrane pool, turbid liquid with dispersed ozone catalytic particles is firstly sucked under the negative pressure of 0.01-0.05 MPa for 1-30 min, membrane penetrating fluid flows back into the membrane pool, and a layer of dynamic catalytic function layer is coated on the surface of the flat plate type ceramic membrane under the condition that the volume of the turbid liquid in the whole membrane pool is unchanged.
Has the advantages that:
1. the method for treating the water by the ozone catalysis and ceramic membrane filtration integrated process does not affect the performance of the ceramic membrane while catalyzing ozone, and does not cause the defect of the ceramic membrane separation layer.
2. The ozone catalysis and ceramic membrane filtration integrated process water treatment method provided by the invention can catalyze ozone without causing the resistance increase of the ceramic membrane and the reduction of permeation flux.
3. The ozone catalysis and ceramic membrane filtration integrated process water treatment method has high mass transfer efficiency for catalyzing ozone and oxidizing pollution under the driving of pressure, so that the utilization rate of the organic pollutants catalyzed and oxidized by ozone is high.
4. The water treatment method of the ozone catalysis and ceramic membrane filtration integrated process has the advantages that the formation process of the dynamic catalysis function layer is very simple and convenient, the ball-milling shaping titanium dioxide microspheres load the function nano catalyst, the ozone water can be completely catalyzed and dissolved, and the catalysis efficiency is high.
5. According to the ozone catalysis and ceramic membrane filtration integrated process water treatment method, the dynamic functional layer formed by the titanium dioxide microspheres subjected to ball milling and shaping by the supported functional nano catalyst through the filtration method has high porosity and small water permeation resistance, and the permeation of the membrane is not influenced; the filter cake layer can be effectively prevented from being formed on the surface of the membrane, and the seriously polluted dynamic catalytic function layer can be damaged by a back washing method and regenerated again by a filtering method.
The specific implementation mode is as follows:
the invention is further illustrated by the following examples, which are not intended to limit the scope of the present disclosure in any way.
Example 1
Modifying commercialized titanium dioxide particles with the particle size range of 0.1-0.5 mu m into microspheres with round particles and uniform size by a ball milling and shaping technology; preparing alkoxide sol of metal manganese; soaking titanium dioxide microspheres with the medium particle size of 0.3 mu m in the metal manganese alkoxide sol for 4h, and drying the titanium dioxide microspheres subjected to centrifugal separation in an oven at 100 ℃ for 3 h; and finally, preserving the heat of the dried titanium dioxide microspheres in a muffle furnace for 3 hours at the temperature of 600 ℃, and coating a layer of nano-particles of manganese metal on the surfaces of the titanium dioxide particles.
Dispersing the titanium dioxide microspheres coated with the manganese metal nanoparticles prepared in the step (1) in a 500L feeding tank according to 1 wt%; adopting a silicon carbide tubular ceramic membrane with the aperture of 0.1 mu m for cross-flow filtration, carrying out cross-flow circulation on a suspension of titanium dioxide microspheres coated by dispersed manganese metal nanoparticles for 10min under the pressure of 0.2MPa before entering biochemical tail water of an industrial wastewater treatment plant, directly refluxing a membrane penetrating fluid into a feeding tank, and coating a dynamic catalytic functional layer on the surface of the tubular ceramic membrane under the condition of ensuring that the volume of the suspension in the whole feeding tank is unchanged.
And (3) blowing ozone with the concentration range of 2mg/L into a feeding tank, under the drive of pressure, before water for dissolving the ozone enters a membrane hole, firstly entering a dynamic catalytic functional layer of three-dimensional catalytic pores formed by piling up titanium dioxide rigid particles coated on the surface of the membrane, and catalyzing the ozone by metal manganese nanoparticles coated on the surface of titanium dioxide microspheres and having the function of catalyzing the ozone to generate hydroxyl radicals, so that pollutants which are difficult to degrade in the water are not selectively oxidized, and a filter cake layer is not formed on the surface of the membrane, so that the permeation flux of the membrane always keeps higher filtering efficiency.
Step (4) is that after the step (3) is operated for a long time, some pollutants which are not degraded are deposited on the surface or in the pores of the dynamic catalytic function layer; and a membrane filtration backwashing system is adopted, and the dynamic catalytic function layer which is seriously polluted and blocked can be destroyed after backwashing for 3 min.
And (5) repeating the step (2) to obtain the regeneration of the dynamic catalytic function layer.
Example 2
Modifying commercialized titanium dioxide particles with the particle size range of 0.1-0.5 mu m into microspheres with round particles and uniform size by a ball milling and shaping technology; preparing alkoxide sol of metal manganese; soaking titanium dioxide microspheres with the medium particle size of 0.3 mu m in the metal manganese alkoxide sol for 4h, and drying the titanium dioxide microspheres subjected to centrifugal separation in an oven at 100 ℃ for 3 h; and finally, preserving the heat of the dried titanium dioxide microspheres in a muffle furnace for 3 hours at the temperature of 600 ℃, and coating a layer of nano-particles of manganese metal on the surfaces of the titanium dioxide particles.
Dispersing the titanium dioxide microspheres coated with the manganese metal nanoparticles prepared in the step (1) in a 1000L membrane pool according to 1 wt%; the method adopts a negative pressure suction type dead-end filtration of a silicon carbide flat plate type ceramic membrane with the aperture of 0.1 mu m, before biochemical tail water enters a domestic sewage treatment plant, firstly, a suspension of titanium dioxide microspheres coated with dispersed manganese metal nanoparticles is sucked by a negative pressure pump with the pressure of 0.02MPa for 20min, membrane penetrating fluid directly flows back to a membrane pool, and a dynamic catalytic functional layer is coated on the surface of the flat plate silicon carbide ceramic membrane under the condition that the volume of the suspension in the whole membrane pool is not changed.
And (3) blowing ozone with the concentration range of 3mg/L into the membrane pool, under the suction of negative pressure, before water for dissolving the ozone enters the membrane hole, firstly entering a dynamic catalytic functional layer of three-dimensional catalytic pores formed by piling up titanium dioxide rigid particles coated on the surface of the membrane, and catalyzing the ozone by the manganese metal nanoparticles coated on the surface of the titanium dioxide microspheres and having the function of catalyzing the ozone to generate hydroxyl radicals, so that pollutants which are difficult to degrade in the water are not selectively oxidized, and a filter cake layer is not formed on the surface of the membrane, so that the permeation flux of the membrane always keeps higher filtration efficiency.
Step (4) is that after the step (3) is operated for a long time, some pollutants which are not degraded are deposited on the surface or in the pores of the dynamic catalytic function layer; and a membrane filtration backwashing system is adopted, and the dynamic catalytic function layer which is seriously polluted and blocked can be destroyed after backwashing for 5 min.
And (5) repeating the step (2) to obtain the regeneration of the dynamic catalytic function layer.
Example 3
Only the metal manganese is changed into the metal cobalt in the embodiment 2, the treated domestic sewage is changed into river water in Zhejiang, and other conditions are not changed.
Example 4
Only the metal manganese is changed into the metal nickel in the embodiment 2, the treated domestic sewage is changed into river water in Zhejiang, and other conditions are not changed.
Example 5
Only the metal manganese is changed into the metal iron in the embodiment 2, the treated domestic sewage is changed into the water produced by a certain tap water plant in Zhejiang, and other conditions are not changed.
Example data comparison:
Figure BDA0003068683470000061
the above description is only a preferred embodiment of the present invention, and should not be taken as limiting the scope of the invention, which is defined by the appended claims.

Claims (8)

1. A dynamically catalyzed water treatment ceramic membrane characterized by: mainly comprises a ceramic membrane and a dynamic catalytic function layer formed on the surface of the ceramic membrane; the dynamic catalytic function layer is a film formed by coating a layer of metal alkoxide on the surface of titanium dioxide particles.
2. A dynamically catalyzed water treatment ceramic membrane according to claim 1, wherein: preparing titanium dioxide particles into alkoxide sol formed by metal salt and ethanol, soaking, performing centrifugal separation and drying; the metal alkoxide coats a layer of nano-particles with ozone catalysis function on the surface of the titanium dioxide particles.
3. A dynamically catalyzed water treatment ceramic membrane according to claim 2, wherein: modifying commercialized titanium dioxide particles with the particle size range of 0.1-10 mu m into nano-scale microspheres with round particles and uniform size by a ball milling shaping technology;
preparing metal alkoxide sol formed by metal salt and ethanol; then soaking the titanium dioxide nano-scale microspheres in the metal alkoxide sol for 1-24 h, and drying the titanium dioxide nano-scale microspheres subjected to centrifugal separation in an oven at the temperature of 25-110 ℃ for 1-24 h; and finally, preserving the dried titanium dioxide nano-scale microspheres in a muffle furnace for 1-4 h at the temperature of 300-800 ℃.
4. A dynamically catalyzed water treatment ceramic membrane according to claim 1, wherein: the metal element in the metal alkoxide is one or a mixture of more than one of manganese, iron, nickel, cobalt and cerium.
5. A dynamically catalyzed water treatment ceramic membrane according to claim 1, wherein: the ceramic membrane is made of alumina, zirconia, titanium oxide, silicon carbide or a composite ceramic membrane prepared from the above materials, and the aperture range of the ceramic membrane is 0.04-1 mu m.
6. Use of a dynamically catalysed ceramic membrane for water treatment according to claims 1 to 5, wherein:
(1) mixing the titanium dioxide nanoparticles impregnated with the metal alkoxide with ozone to form ozone catalytic particles;
(2) coating ozone catalytic particles on the surface of a ceramic membrane to form a dynamic catalytic functional layer; wherein the ozone catalytic particles are dispersed in 1-10 wt% of the weight of water to be treated which can be contained in the feeding tank or the membrane pool;
(3) a water treatment process integrating ozone catalysis and ceramic membrane filtration processes; blowing ozone with the concentration range of 0.1-5 mg/L into a feeding tank or a membrane pool; the filtration treatment is carried out under pressure.
7. The use of a dynamically catalyzed water treatment ceramic membrane in water treatment according to claim 6, wherein after a certain time of treatment in step (3), backwashing is performed by a membrane filtration backwashing system; and then, the dynamic catalytic function layer is formed again according to the steps (1) and (2).
8. The application of a dynamically catalyzed ceramic membrane for water treatment in water treatment according to claim 6, wherein the ceramic membrane in step (2) is in a tubular membrane cross-flow filtration mode, before water to be treated enters, a suspension liquid in which ozone catalytic particles are dispersed is subjected to cross-flow circulation for 1-30 min under the pressure of 0.1-0.5 MPa, a membrane penetrating fluid flows back into a feeding tank, and a dynamic catalytic functional layer is coated on the surface of the tubular ceramic membrane under the condition that the volume of the suspension liquid in the whole feeding tank is ensured to be unchanged;
or the ceramic membrane is in a dead-end filtration mode of the flat plate type membrane, before water to be treated enters the membrane pool, turbid liquid with dispersed ozone catalytic particles is firstly sucked under the negative pressure of 0.01-0.05 MPa for 1-30 min, membrane penetrating fluid flows back into the membrane pool, and a layer of dynamic catalytic function layer is coated on the surface of the flat plate type ceramic membrane under the condition that the volume of the turbid liquid in the whole membrane pool is unchanged.
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