CN113976108B - Ceramic catalytic membrane and preparation method and application thereof - Google Patents
Ceramic catalytic membrane and preparation method and application thereof Download PDFInfo
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- CN113976108B CN113976108B CN202111395450.1A CN202111395450A CN113976108B CN 113976108 B CN113976108 B CN 113976108B CN 202111395450 A CN202111395450 A CN 202111395450A CN 113976108 B CN113976108 B CN 113976108B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 210
- 239000012528 membrane Substances 0.000 title claims abstract description 202
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 140
- 238000002360 preparation method Methods 0.000 title abstract description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 115
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 53
- 231100000719 pollutant Toxicity 0.000 claims abstract description 53
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 36
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 36
- 239000011148 porous material Substances 0.000 claims abstract description 32
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011572 manganese Substances 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 30
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 50
- 239000002243 precursor Substances 0.000 claims description 39
- 150000002696 manganese Chemical class 0.000 claims description 34
- 150000003839 salts Chemical class 0.000 claims description 24
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 13
- 230000004907 flux Effects 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 150000000703 Cerium Chemical class 0.000 claims description 5
- 239000000356 contaminant Substances 0.000 claims description 5
- 150000002505 iron Chemical class 0.000 claims description 5
- 238000006479 redox reaction Methods 0.000 claims description 5
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 claims description 3
- MMOXZBCLCQITDF-UHFFFAOYSA-N N,N-diethyl-m-toluamide Chemical compound CCN(CC)C(=O)C1=CC=CC(C)=C1 MMOXZBCLCQITDF-UHFFFAOYSA-N 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 229960001673 diethyltoluamide Drugs 0.000 claims description 3
- 229960001680 ibuprofen Drugs 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 36
- -1 hydroxyl radicals Chemical class 0.000 description 28
- 239000000243 solution Substances 0.000 description 26
- 230000001976 improved effect Effects 0.000 description 22
- 238000010586 diagram Methods 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000000089 atomic force micrograph Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000027756 respiratory electron transport chain Effects 0.000 description 5
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 229940071125 manganese acetate Drugs 0.000 description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 4
- 238000006385 ozonation reaction Methods 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000003642 reactive oxygen metabolite Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- WYCDUUBJSAUXFS-UHFFFAOYSA-N [Mn].[Ce] Chemical compound [Mn].[Ce] WYCDUUBJSAUXFS-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—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
- B01J23/16—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/653—500-1000 nm
-
- 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
- B01J37/08—Heat treatment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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- Catalysts (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
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Abstract
The invention discloses a ceramic catalytic membrane and a preparation method and application thereof, wherein the ceramic catalytic membrane comprises: a ceramic membrane; and a manganese-based composite metal oxide supported on the surface and/or in the pores of the ceramic film, the manganese-based composite metal oxide including at least one of cerium, iron, and cobalt. Therefore, the ceramic catalytic membrane has efficient ozone catalytic performance, improves the ozone utilization rate, can effectively improve the removal effect of the ozone refractory pollutants by applying the ceramic catalytic membrane to the treatment of the ozone refractory pollutants, and reduces the ozone adding amount, thereby reducing the actual operation cost.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a ceramic catalytic membrane and a preparation method and application thereof.
Background
The heterogeneous ozone catalytic oxidation technology promotes the decomposition of ozone to generate hydroxyl radicals (OH) by adding a catalyst into water, thereby improving the utilization rate of ozone and reducing the operation energy consumption, and is an important technology for preparing high-quality reclaimed water and ensuring the recycling safety of the reclaimed water. However, since the catalyst is dispersed in water in this process, there are problems in that the catalyst is difficult to recover and agglomerated. The ceramic catalytic membrane not only effectively solves the problems, but also realizes the synergistic effect of membrane filtration and catalytic ozonation by loading a catalyst on a ceramic membrane, and is widely concerned by researchers. In addition, the ceramic catalytic membrane has high chemical stability and large specific surface area, so that the ceramic catalytic membrane is used as a nano reactor in ozone catalytic oxidation, and the mass transfer rate of pollutants reaching active sites and the catalytic performance of the ceramic catalytic membrane are improved.
The previous researches mainly focus on single metal oxide as a catalyst-loaded ceramic membrane, wherein the manganese oxide modified ceramic catalytic membrane is researched more, but the actual secondary effluent has complex components, the single metal oxide modified ceramic catalytic membrane has limited ozone utilization efficiency, the ozone adding amount is increased, the operation cost is increased, and the requirements of actual engineering cannot be met.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, one purpose of the invention is to provide a ceramic catalytic membrane, a preparation method and an application thereof, wherein the ceramic catalytic membrane has high ozone catalytic performance, improves the ozone utilization rate, can effectively improve the removal effect of the ozone refractory pollutants when being applied to the treatment of the ozone refractory pollutants, and reduces the ozone addition amount, thereby reducing the actual operation cost.
In one aspect of the invention, a ceramic catalytic membrane is provided. According to an embodiment of the invention, the ceramic catalytic membrane comprises:
a ceramic membrane;
and a manganese-based composite metal oxide supported on the surface and/or in the pores of the ceramic film, the manganese-based composite metal oxide including at least one of cerium, iron, and cobalt.
According to the ceramic catalytic membrane provided by the embodiment of the invention, the manganese-based composite metal oxide containing at least one of cerium, iron and cobalt is loaded on the surface and/or in the membrane pores of the ceramic membrane, and the multiple redox electron pairs on the surface of the manganese-based composite metal oxide act synergistically, so that the oxygen hole content and the electron transfer rate on the surface of the ceramic catalytic membrane are increased, and the ozone is promoted to decompose to generate hydroxyl radicals and superoxide anions to degrade ozone-refractory pollutants. In this process, hydroxyl radicals are the predominant active oxygen species and superoxide anions also participate in the process. Therefore, the ceramic catalytic membrane has high-efficiency ozone catalytic performance, improves the ozone utilization rate, is applied to the ozone degradation-resistant pollutants, can effectively improve the removal effect of the ozone degradation-resistant pollutants (the removal effect of the ceramic catalyst is improved by 50 percent and the removal rate is more than 99 percent relative to a single metal oxide), and reduces the ozone addition amount, thereby reducing the actual operation cost.
In addition, the ceramic catalytic membrane according to the above embodiment of the present invention may also have the following additional technical features:
in some embodiments of the present invention, the ceramic membrane has a pore size of 100 to 900nm. Therefore, the effect of removing the pollutants which are difficult to degrade by ozone can be effectively improved.
In some embodiments of the invention, the ceramic membrane has a filtration area of 0.01 to 0.1m 2 . Therefore, the effect of removing the pollutants which are difficult to degrade by ozone can be effectively improved.
In some embodiments of the present invention, the manganese-based composite metal oxide is supported in an amount of 0.4 to 0.6mg based on 1g of the ceramic membrane. Therefore, the effect of removing the pollutants which are difficult to degrade by ozone can be effectively improved.
In a second aspect of the invention, the invention provides a method of preparing the above ceramic catalytic membrane. According to an embodiment of the invention, the method comprises:
(1) Loading a first precursor comprising a manganese salt and an auxiliary salt on a ceramic membrane and then aging, wherein the auxiliary salt comprises at least one of a cerium salt, an iron salt and a cobalt salt;
(2) Loading a second precursor containing high-valence manganese salt on the ceramic membrane obtained in the step (1), so that the manganese salt in the first precursor and the permanganate in the second precursor are subjected to oxidation-reduction reaction, and then aging;
(3) And (3) calcining the ceramic membrane obtained in the step (2) so as to obtain the ceramic catalytic membrane.
According to the method for preparing the ceramic catalytic membrane, the first precursor comprising manganese salt and auxiliary salt (the auxiliary salt comprises at least one of cerium salt, iron salt and cobalt salt) is loaded on the ceramic membrane and then aged, the manganese salt and the auxiliary salt in the first precursor can be adsorbed on the surface and/or in the membrane pores of the ceramic membrane, then the second precursor containing high-valence manganese salt is loaded on the aged ceramic membrane and then aged, and the manganese salt in the first precursor and the permanganate in the second precursor can generate oxidation-reduction reaction, so that manganese composite metal oxide is generated in situ on the surface and in the membrane pores of the ceramic membrane. And finally calcining the obtained ceramic membrane to enable a catalyst MnMeOx (Me is at least one of Ce, fe and Co) to be deposited on the surface and in the membrane pores of the ceramic membrane, thereby obtaining the manganese-based composite metal oxide-loaded ceramic catalytic membrane. The multiple redox electron pairs on the surface of the manganese-based composite metal oxide on the ceramic catalytic membrane act synergistically, so that the oxygen hole content and the electron transfer rate on the surface of the ceramic catalytic membrane are increased, and further, the ozone decomposition is promoted to generate hydroxyl radicals and superoxide anions to degrade ozone pollutants which are difficult to degrade. In this process, hydroxyl radicals are the primary reactive oxygen species and superoxide anions also participate in the process. Therefore, the ceramic catalytic membrane obtained by the method has a high-efficiency ozone catalytic function, improves the ozone utilization rate, can be applied to treating ozone refractory pollutants, can effectively improve the removal effect of the ozone refractory pollutants (the removal effect of the ceramic catalyst is improved by 50% and the removal rate is more than 99% compared with that of a single metal oxide), and reduces the ozone addition amount, thereby reducing the actual operation cost.
In addition, the method for preparing a ceramic catalytic membrane according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the molar ratio of the manganese salt to the co-salt in the first precursor is (2-4): (0.5-1.5). Therefore, the effect of removing the pollutants which are difficult to degrade by ozone can be effectively improved.
In some embodiments of the invention, the molar ratio of the permanganate salt to the manganese salt is (3-5): (2-4). Therefore, the effect of removing the pollutants which are difficult to degrade by ozone can be effectively improved.
In some embodiments of the invention, the temperature ramp rate of the calcination process is 2 to 20 ℃. Therefore, the effect of removing the pollutants which are difficult to degrade by ozone can be effectively improved.
In some embodiments of the invention, the calcination temperature is 300-400 ℃ and the holding time is 1-3 h. Therefore, the effect of removing the pollutants which are difficult to degrade by ozone can be effectively improved.
In a third aspect of the invention, a method for removing ozone refractory pollutants is provided. According to an embodiment of the invention, the method comprises: mixing the ceramic catalytic membrane, ozone and the solution containing the ozone non-degradable pollutants. Therefore, the ceramic catalytic membrane with high ozone catalytic performance, the ozone and the solution containing the ozone hardly-degradable pollutants are mixed, the ceramic catalytic membrane promotes the ozone to be decomposed to generate hydroxyl radicals and superoxide anions to degrade the ozone hardly-degradable pollutants, the removal effect of the ozone hardly-degradable pollutants can be effectively improved (the removal effect is improved by 50 percent and the removal rate is more than 99 percent compared with that of a ceramic catalyst of a single metal oxide), the ozone adding amount is reduced, and the actual operation cost is reduced.
In addition, the method for removing the ozone degradation-resistant pollutants according to the embodiment of the invention can also have the following additional technical characteristics:
in some embodiments of the invention, the ozone refractory contaminant comprises at least one of atrazine, benzotriazole, ibuprofen, and diethyltoluamide.
In some embodiments of the invention, the ceramic catalytic membrane has a permeation flux of 50 to 70LMH, the ozone dosage is 0.6 to 0.9mg/min, and the initial pH of the solution containing the ozone refractory pollutant is 6 to 9. Therefore, the effect of removing the pollutants which are difficult to degrade by ozone can be effectively improved.
In some embodiments of the invention, the concentration of the ozone-containing refractory pollutant is 0 to 10000mg/L.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a method of making a ceramic catalytic membrane according to one embodiment of the invention;
FIG. 2 (a) is an AFM diagram of CM; FIG. 2 (b) is an AFM image of a ceramic catalytic film of a comparative example; FIG. 2 (c) is an AFM image of the ceramic catalytic film of example 1; FIG. 2 (d) is an AFM image of the ceramic catalytic film of example 2; FIG. 2 (e) is an AFM image of the ceramic catalytic film of example 3; FIG. 2 (f) is Ra data for ceramic catalytic membranes of examples 1-3 and comparative example;
FIG. 3 (a) is an SEM photograph of the surface of example 1; FIG. 3 (b) is an SEM photograph of the internal channels of the ceramic catalytic membrane of example 1; FIG. 3 (c) is an EDX diagram of the ceramic catalytic membrane of example 1;
FIG. 4 (a) is an SEM photograph of the surface of the ceramic catalytic membrane of example 2; FIG. 4 (b) is an SEM photograph of the internal channels of the ceramic catalytic membrane of example 2; FIG. 4 (c) is an EDX diagram of the ceramic catalytic membrane of example 2;
FIG. 5 (a) is an SEM photograph of the surface of the ceramic catalytic membrane of example 3; FIG. 5 (b) is an SEM photograph of internal channels of the ceramic catalytic membrane of example 3; FIG. 5 (c) is an EDX diagram of the ceramic catalytic membrane of example 3;
FIG. 6 (a) is an SEM image of the surface of the ceramic catalytic membrane of the comparative example; FIG. 6 (b) is an SEM image of internal channels of the ceramic catalytic membrane of the comparative example; FIG. 6 (c) is an EDX diagram of a ceramic catalytic membrane of a comparative example;
FIG. 7 is a graph showing the adsorption effect of the ceramic catalytic membranes of examples 1 to 3 and comparative example on atrazine;
FIG. 8 is a graph showing the effect of the ceramic catalytic membrane coupled ozone oxidation process on the removal of atrazine in examples 1 to 3 and comparative example;
FIG. 9 is a graph of the ozone utilization (Ru) in water for the ceramic catalytic membrane coupled ozonation process of examples 1-3 and comparative example;
[O 3 ] I 、[O 3 ] O 、[O 3 ] R respectively representing the concentration of inlet ozone, outlet ozone and residual ozone in water, wherein F is the flow rate, and V is the volume of the solution;
FIG. 10 is a graph showing the comparison of the effect of the ceramic catalytic membrane coupled with the ozonation process on the atrazine removal under different operating conditions, according to one embodiment of the present invention, wherein the formula is
ln(C t /C 0 )＝-kt；
C 0 Is the initial atrazine concentration, C t Is the atrazine concentration after time t (min), k (min) -1 ) Is the degradation rate constant of atrazine.
Detailed Description
The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the invention, a ceramic catalytic membrane is provided. According to an embodiment of the invention, the ceramic catalytic membrane comprises: a ceramic membrane; and a manganese-based composite metal oxide supported on the surface and/or in the pores of the ceramic film, the manganese-based composite metal oxide including at least one of cerium, iron, and cobalt.
The inventor finds that by loading the manganese-based composite metal oxide comprising at least one of cerium, iron and cobalt on the surface and/or in the pores of the ceramic membrane, the oxygen hole content and the electron transfer rate of the surface of the ceramic catalytic membrane are increased by the synergistic effect of a plurality of redox electron pairs on the surface of the manganese-based composite metal oxide, and then the ozone decomposition is promoted to generate hydroxyl radicals and superoxide anions so as to degrade the ozone refractory pollutants. In this process, hydroxyl radicals are the predominant active oxygen species and superoxide anions also participate in the process. Therefore, the ceramic catalytic membrane has efficient ozone catalytic performance, improves the ozone utilization rate, is applied to treating ozone refractory pollutants, can effectively improve the removal effect of the ozone refractory pollutants (the removal effect of the ceramic catalyst is improved by 50% and the removal rate is more than 99% relative to a single metal oxide), reduces the ozone addition amount, and reduces the actual operation cost.
Further, the pore diameter of the ceramic film is 100 to 900nm. The inventor finds that if the pore diameter of the membrane pores of the ceramic membrane is too low, the ceramic membrane is more easily polluted, so that the membrane pores are blocked and the filtration efficiency is reduced, and if the pore diameter of the membrane pores of the ceramic membrane is too high, the confinement effect of the membrane pores for strengthening the catalytic ozonation reaction is reduced, and the effect of the catalytic membrane for degrading pollutants is reduced. In a specific embodiment of the invention, the ceramic membrane is a flat ultrafiltration membrane, and the membrane layer and the support layer are both made of alpha-crystal alumina.
Further, the ceramic membrane has a filtration area of 0.01 to 0.1m 2 . According to an embodiment of the present invention, the manganese-based composite metal oxide is supported in an amount of 0.4 to 0.6mg based on 1g of the ceramic film. The inventors have found that if the manganese-based composite metal oxide supporting amount is too high, the membrane flux decreases, and if the manganese-based composite metal oxide supporting amount is too low, the effect of the ceramic membrane in catalyzing the ozone oxidation decreases.
According to an embodiment of the present invention, the molar ratio of the manganese element to the other element (at least one of cerium, iron, and cobalt) in the manganese-based composite metal oxide is (2 to 4): (0.5-1.5). The inventors have found that if the molar ratio of manganese to other elements is higher than the above range or lower than the above range, the oxygen vacancies generated on the surface of the manganese-based composite metal oxide are very limited, the amount of hydroxyl radicals and other oxygen species generated is limited, and the effect of catalyzing ozone to oxidize trace pollutants is not desirable.
In a second aspect of the invention, a method of making a ceramic catalytic membrane is provided. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: loading a first precursor comprising manganese salt and auxiliary salt on a ceramic membrane and then aging
In the step, a first precursor comprising manganese salt and auxiliary salt is loaded on the ceramic membrane and then aged, and the manganese salt and the auxiliary salt in the first precursor are adsorbed on the surface and/or in pores of the ceramic membrane, wherein the auxiliary salt comprises at least one of cerium salt, iron salt and cobalt salt.
The specific manner of supporting the first precursor including the manganese salt and the co-salt on the ceramic film is not particularly limited as long as the above function is achieved, and the first precursor may be supported on the ceramic film by, for example, filtration. Specifically, the dried ceramic membrane is slowly placed into a first precursor containing manganese salt and auxiliary salt, a peristaltic pump is started to enable the ceramic membrane to be in a filtering mode, the filtering speed is adjusted to be 8-12 mL/min, filtering is continuously carried out for 15-17 h (based on 1L of the first precursor), the first precursor is adsorbed on the surface and/or in membrane pores of the ceramic membrane in the membrane filtering process, and then the loaded ceramic membrane is taken out and placed at room temperature for aging for 8-10 h. In addition, the person skilled in the art can select the specific salt types of the manganese salt and the auxiliary salt according to actual needs, as long as the manganese salt is a soluble salt, for example, manganese acetate, manganese nitrate, manganese chloride, etc. are used as the manganese salt, and corresponding acetate, nitrate, chloride, etc. are used as the auxiliary salt.
Further, the molar ratio of the manganese salt to the auxiliary salt is (2-4): (0.5-1.5). The inventor finds that if the addition amount of the auxiliary salt is too high, oxygen vacancies generated on the surface of the composite metal are very limited, the generated hydroxyl radicals and other oxygen species are limited, and the effect of catalyzing ozone to oxidize trace pollutants is not ideal.
S200: loading a second precursor containing a high-valence manganese salt on the ceramic film obtained in step S100
In the step, a second precursor containing high-valence manganese salt is loaded on the ceramic membrane obtained in the step S100 and then is aged, and the manganese salt in the first precursor and the permanganate in the second precursor perform oxidation-reduction reaction, so that MnMeOx (Me is at least one of Ce, fe and Co) is generated in situ on the surface of the ceramic membrane and in the membrane pores, and the ceramic catalytic membrane containing the bimetallic oxide in-situ load is obtained.
The specific manner of supporting the second precursor containing the high-valence manganese salt on the ceramic film obtained in step S100 is not particularly limited as long as the above function can be achieved, and the supporting of the second precursor on the ceramic film may be achieved by, for example, filtration. Specifically, the ceramic membrane obtained in the step S100 is slowly placed in a second precursor, a peristaltic pump is turned on to enable the ceramic membrane to be in a filtration mode, the filtration speed is adjusted to be 173-500 μ L/min, filtration is continued for 15-17 h (based on 1L of the second precursor), then, high valence manganese in the second precursor reacts with manganese salt in the first precursor in the membrane filtration process, and meox (Me is at least one of Ce, fe, and Co) is generated in situ on the surface and the pores of the ceramic membrane, and then the loaded ceramic membrane is taken out and placed at room temperature for aging for 6-10 h.
Further, the second precursor containing a high-valence manganese salt is prepared by mixing a permanganate salt and a manganese salt in a molar ratio of (3-5): (2-4), and the inventor finds that the catalytic performance of the manganese oxide can be exerted to the maximum extent within the range, and the degradation capability of the pollutants difficult to degrade by ozone can be effectively improved.
S300: calcining the ceramic membrane obtained in the step S200
In this step, the ceramic membrane obtained in step S200 is calcined, so that a catalyst MnMeOx (Me is at least one of Ce, fe, and Co) is deposited on the surface and in the pores of the ceramic membrane, thereby obtaining the ceramic catalytic membrane supporting the manganese-based composite metal oxide. The multiple redox electron pairs on the surface of the manganese-based composite metal oxide on the ceramic catalytic membrane act synergistically, so that the oxygen hole content and the electron transfer rate on the surface of the ceramic catalytic membrane are increased, and further, the ozone decomposition is promoted to generate hydroxyl radicals and superoxide anions to degrade ozone pollutants which are difficult to degrade.
Furthermore, the temperature rise rate in the calcining process is 2-20 ℃. The inventor finds that if the temperature rise rate in the calcining process is too fast or too slow, the crystal form of the composite metal oxide is difficult to regulate, the temperature in the calcining process is 300-400 ℃, and the heat preservation time is 1-3 hours.
According to the method for preparing the ceramic catalytic membrane, a first precursor comprising manganese salt and auxiliary salt (the auxiliary salt comprises at least one of cerium salt, iron salt and cobalt salt) is loaded on the ceramic membrane and then aged, the manganese salt and the auxiliary salt in the first precursor can be adsorbed on the surface and/or in membrane pores of the ceramic membrane, then a second precursor comprising high-valence manganese salt is loaded on the aged ceramic membrane and then aged, and the manganese salt in the first precursor and the permanganate in the second precursor can perform oxidation-reduction reaction, so that MnMeOx (Me is at least one of Ce, fe and Co) is generated on the surface and in the membrane pores of the ceramic membrane in situ, and the ceramic catalytic membrane containing the bimetal oxide in situ load is obtained. And finally, calcining the obtained ceramic membrane to enable a catalyst MnMeOx (Me is at least one of Ce, fe and Co) to be deposited on the surface and in the pores of the ceramic membrane, thereby obtaining the ceramic catalytic membrane loaded with the manganese-based composite metal oxide. The multiple redox electron pairs on the surface of the manganese-based composite metal oxide on the ceramic catalytic membrane act synergistically to increase the oxygen hole content and the electron transfer rate on the surface of the ceramic catalytic membrane, so that the ozone is promoted to decompose and generate hydroxyl radicals and superoxide anions to degrade pollutants difficult to degrade by ozone. In this process, hydroxyl radicals are the primary reactive oxygen species and superoxide anions also participate in the process. Therefore, the ceramic catalytic membrane obtained by the method has high-efficiency ozone catalytic performance, improves the ozone utilization rate, can effectively improve the removal effect of the ozone degradation-resistant pollutants (the removal effect is improved by 50 percent compared with the ceramic catalyst of a single metal oxide, and the removal rate is more than 99 percent) by applying the ceramic catalytic membrane to the treatment of the ozone degradation-resistant pollutants, and reduces the ozone adding amount, thereby reducing the actual operation cost.
It should be noted that the features and advantages described above for the ceramic catalytic membrane also apply to the method for preparing the ceramic catalytic membrane, and are not described herein again.
In a third aspect of the invention, a method for removing ozone nondegradable pollutants is provided. According to an embodiment of the invention, the method comprises: mixing the ceramic catalytic membrane, ozone and the solution containing the ozone non-degradable pollutants. Therefore, the ceramic catalytic membrane with the efficient ozone catalytic performance is mixed with the solution containing the ozone hardly-degradable pollutants, the ceramic catalytic membrane promotes the decomposition of ozone to generate hydroxyl radicals and superoxide anions to degrade the ozone hardly-degradable pollutants, the removal effect of the ozone hardly-degradable pollutants can be effectively improved (the removal effect is improved by 50 percent compared with that of a ceramic catalyst of a single metal oxide, and the removal rate is more than 99 percent), the ozone adding amount is reduced, and the actual operation cost is reduced.
It should be noted that the type of the ozone-hardly degradable pollutant is not particularly limited, and can be selected by those skilled in the art according to actual needs, for example, at least one of atrazine, benzotriazole, ibuprofen and diethyltoluamide is included. And the concentration of the solution containing the ozone degradation-resistant pollutants is 0-10000 mg/L.
Further, the ceramic catalytic membrane has a permeation flux of 50-70LMH, the ozone addition amount is 0.6-0.9mg/min, and the initial pH of the solution containing the ozone refractory pollutants is 6-9. The inventor finds that if the permeation flux of the ceramic catalytic membrane is too low, the normal water yield and the actual application effect of the ceramic catalytic membrane are influenced; if the permeation flux of the ceramic catalytic membrane is too high, the contact time of the ceramic catalytic membrane and ozone is too short, so that the degradation of trace pollutants by the coupling technology is influenced; if the ozone adding amount is too low, the catalyst on the surface and in the ceramic membrane cannot be catalyzed sufficiently, so that the removal effect of the coupling technology on pollutants is influenced, and if the ozone adding amount is too high, the problem of excessive ozone adding is caused, so that the application cost of the ceramic membrane is improved; if the pH value of the solution is too low or too high, the catalysis of the ceramic catalytic membrane on the pollutants which are difficult to degrade by ozone is not facilitated.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way. The examples do not specify particular techniques or conditions, and are performed according to techniques or conditions described in literature in the art or according to the product specification. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
The method for preparing the ceramic catalytic membrane comprises the following steps:
(1) Soaking the ceramic membrane in deionized water for 20min, and baking in an oven at 80 deg.C for 2h to obtain cleaned and dried ceramic membrane, and marking as CM (its AMF diagram is shown in FIG. 2 (a), and porosity and average pore diameter data are shown in Table 1), wherein the ceramic membrane is usedThe ceramic membrane has size of 100mm (length) × 50mm (width) × 5mm (thickness), pore diameter of 100nm, and filtration area of 0.01m 2 Flat ultrafiltration membranes;
(2) 0.03 mol/L -1 With 0.01 mol/L of manganese acetate -1 And (3) mixing the cerium nitrate solution to 1L, then putting the dried ceramic membrane obtained in the step (1) into a mixed solution containing a manganese acetate solution and the cerium nitrate solution, starting a peristaltic pump to enable the ceramic membrane to be in a filtration mode, adjusting the filtration speed to 12mL/min, and filtering for 16h. Taking out the ceramic membrane after filtration, and aging for 8 hours at room temperature;
(3) 0.04 mol.L of the mixture is prepared -1 Slowly putting the treated ceramic membrane obtained in the step (2) into the potassium permanganate solution until the potassium permanganate solution is 1L, starting a peristaltic pump to enable the ceramic membrane to be in a filtering mode, adjusting the filtering speed to be 173 mu L/min, filtering for 16h, taking out the ceramic membrane, and then aging for 8h.
(4) And (4) putting the treated ceramic membrane obtained in the step (3) into a muffle furnace, heating at a rate of 5 ℃/min, carrying out heat preservation and calcination at 300 ℃ for 2h, taking out the calcined ceramic membrane, further cleaning with deionized water to remove impurities, and obtaining the ceramic catalytic membrane with a high-efficiency ozone catalytic function, wherein an AFM diagram of the ceramic catalytic membrane is represented as MnCe-CM (porosity and average pore diameter data are shown in table 1), a surface SEM diagram of the ceramic catalytic membrane is shown in fig. 2 (c), an SEM diagram of an internal channel of the ceramic catalytic membrane is shown in fig. 3 (a), an SEM diagram of an internal channel of the ceramic catalytic membrane is shown in fig. 3 (b), and an EDX diagram of the ceramic catalytic membrane is shown in fig. 3 (c).
Example 2
In the step (2), the cerium nitrate solution is replaced by an iron nitrate solution, and the rest of the preparation process is the same as that of the example 1, so that a ceramic catalytic film with a high-efficiency ozone catalytic function is finally obtained, which is marked as MnFe-CM (the porosity and average pore diameter data are shown in Table 1), the AFM diagram of the ceramic catalytic film is shown in fig. 2 (d), the surface SEM diagram of the ceramic catalytic film is shown in fig. 4 (a), the internal channel SEM diagram of the ceramic catalytic film is shown in fig. 4 (b), and the EDX diagram of the ceramic catalytic film is shown in fig. 4 (c).
Example 3
In the step (2), the cerium nitrate solution is replaced by a cobalt nitrate solution, and the rest of the preparation process is the same as that in example 1, and finally the ceramic catalytic membrane with a high-efficiency ozone catalytic function is obtained, which is marked as MnCo-CM (the porosity and average pore size data are shown in table 1), and the AFM image of the ceramic catalytic membrane is shown in fig. 2 (e), the surface SEM image of the ceramic catalytic membrane is shown in fig. 5 (a), the internal channel SEM image of the ceramic catalytic membrane is shown in fig. 5 (b), and the EDX image of the ceramic catalytic membrane is shown in fig. 5 (c).
Comparative example
In the step (2), 1L and 0.03 mol. L are taken -1 The rest of the preparation process of the manganese acetate solution is the same as that of example 1, and finally, a ceramic catalytic membrane is obtained, which is marked as Mn-CM (the porosity and average pore diameter data are shown in Table 1), and the AFM picture is shown in FIG. 2 (b), the surface SEM picture is shown in FIG. 6 (a), the internal channel SEM picture is shown in FIG. 6 (b), and the EDX picture is shown in FIG. 6 (c).
TABLE 1
Ra measurements were performed on the ceramic catalytic membranes obtained in examples 1 to 3 and comparative example, and the results are shown in FIG. 2 (f).
The ceramic catalytic membranes obtained in examples 1 to 3 and comparative examples were mixed with atrazine solution, wherein the amount of atrazine solution added was 1mg/L, the pH was 7.0, and the permeation flux of the ceramic catalytic membranes was 60LMH. The adsorption effect of the ceramic catalytic membrane on atrazine was measured, and the results are shown in fig. 7. As can be seen from fig. 7, for atrazine, the removal effect of the manganese-based composite metal oxide-supported ceramic catalytic membranes of examples 1 to 3 was improved to a different degree than that of Mn — CM in both the ceramic membrane and the comparative example, wherein the manganese cerium bimetal-supported ceramic catalytic membrane of example 1 had the best removal effect and the adsorption removal rate was 48%.
The ceramic catalytic membrane obtained in examples 1 to 3 and comparative examples was mixed with ozone and atrazine solution, wherein the amount of atrazine solution added was 1mg/L, the permeation flux of the ceramic catalytic membrane was 60LMH, the amount of ozone added was 0.9mg/min, and the pH of atrazine solution was 7.0. And (3) measuring the removal effect of the ceramic catalytic membrane on the atrazine. The results are shown in FIG. 8. The ozone utilization rate of the ceramic catalytic membrane was measured, and the results are shown in fig. 9. As can be seen from fig. 8, the removal rate of atrazine and the utilization rate of ozone by the ceramic catalytic membrane coupling ozone oxidation process of the manganese-based composite metal oxide obtained in examples 1 to 3 are both higher than Mn-CM in the ceramic membrane and the comparative example, and the removal rate of atrazine by the ceramic catalytic membrane coupling ozone oxidation process of examples 1 to 3 is more than 99%, and the utilization rate of ozone is as high as 60%.
Mixing the ceramic catalytic membrane obtained in the example 1 with ozone and atrazine solution, and measuring the atrazine removal rate and the degradation rate constant of the ceramic catalytic membrane: the pH value of the atrazine solution is 2-9, the permeation flux of the ceramic catalytic membrane is 30-180LMH, and the ozone adding amount is 0-0.8mg/min. The results are shown in FIG. 10.
From the above measurement results, it can be seen that the ceramic catalytic membranes obtained in the embodiments 1 to 3 of the present invention have an improved effect of removing trace pollutants by 50% and a removal rate of 99% compared to the unmodified ceramic membranes, and simultaneously, the utilization rate of ozone is improved, and the operation cost is reduced for practical application. In addition, the invention obtains the optimal operating parameter range of the ceramic catalytic membrane for degrading trace pollutants: the ceramic catalytic membrane has a permeation flux of 50-70LMH, an ozone addition amount of 0.6-0.9mg/min, and a pH value of trace pollutants of 6-9.
In the description of the specification, reference to the description of "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that changes, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (12)
1. A method of making a ceramic catalytic membrane, comprising:
(1) Loading a first precursor comprising a manganese salt and an auxiliary salt on a ceramic membrane and then aging, wherein the auxiliary salt comprises at least one of a cerium salt, an iron salt and a cobalt salt;
(2) Loading a second precursor containing high-valence manganese salt on the ceramic membrane obtained in the step (1), so that the manganese salt in the first precursor and the permanganate in the second precursor are subjected to oxidation-reduction reaction, and then aging;
(3) Calcining the ceramic membrane obtained in the step (2) to obtain a ceramic catalytic membrane,
the ceramic catalytic membrane includes:
a ceramic membrane;
and a manganese-based composite metal oxide supported on the surface and/or in the pores of the ceramic film, the manganese-based composite metal oxide including at least one of cerium, iron, and cobalt.
2. The method according to claim 1, wherein in step (1), the molar ratio of the manganese salt to the co-salt in the first precursor is (2-4): (0.5-1.5).
3. The method according to claim 1, wherein in step (2), the molar ratio of the permanganate salt to the manganese salt is (3-5): (2-4).
4. The method of claim 1, wherein in step (3), the temperature increase rate of the calcination process is 2-20 ℃.
5. The method according to claim 1, wherein the calcination temperature is 300-400 ℃ and the holding time is 1-3 h.
6. The method according to claim 1, wherein the ceramic membrane has a pore size of 100 to 900nm.
7. The method according to claim 1 or 6, wherein the ceramic membrane has a filtration area of 0.01 to 0.1m 2 。
8. The method according to claim 1, wherein the manganese-based composite metal oxide is supported in an amount of 0.4 to 0.6mg based on 1g of the ceramic membrane.
9. A method for removing ozone refractory pollutants, comprising: mixing a ceramic catalytic membrane prepared by the method of any one of claims 1-8, ozone, and a solution containing ozone refractory contaminants.
10. The method of claim 9, wherein the ozone refractory contaminant comprises at least one of atrazine, benzotriazole, ibuprofen, and diethyltoluamide.
11. The method of claim 9, wherein the ceramic catalytic membrane has a permeation flux of 50 to 70LMH, the ozone is added in an amount of 0.6 to 0.9mg/min, and the solution containing the ozone refractory contaminant has an initial pH of 6 to 9.
12. The method of claim 9, wherein the concentration of the solution containing the ozone refractory contaminant is 0 to 10000mg/L.
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