CN117960251A - Catalytic filter element, preparation method and application thereof - Google Patents
Catalytic filter element, preparation method and application thereof Download PDFInfo
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- CN117960251A CN117960251A CN202410383517.7A CN202410383517A CN117960251A CN 117960251 A CN117960251 A CN 117960251A CN 202410383517 A CN202410383517 A CN 202410383517A CN 117960251 A CN117960251 A CN 117960251A
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002243 precursor Substances 0.000 claims abstract description 59
- 239000000084 colloidal system Substances 0.000 claims abstract description 44
- 238000004132 cross linking Methods 0.000 claims abstract description 39
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010000 carbonizing Methods 0.000 claims abstract description 14
- 229910052786 argon Inorganic materials 0.000 claims abstract description 10
- 238000011068 loading method Methods 0.000 claims abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 66
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- 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 claims description 36
- 239000007788 liquid Substances 0.000 claims description 31
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- -1 polypropylene Polymers 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 239000004743 Polypropylene Substances 0.000 claims description 14
- 229920002125 Sokalan® Polymers 0.000 claims description 14
- 239000004584 polyacrylic acid Substances 0.000 claims description 14
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 14
- 229920001155 polypropylene Polymers 0.000 claims description 14
- 229920001661 Chitosan Polymers 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229920002492 poly(sulfone) Polymers 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- AZKVWQKMDGGDSV-BCMRRPTOSA-N Genipin Chemical compound COC(=O)C1=CO[C@@H](O)[C@@H]2C(CO)=CC[C@H]12 AZKVWQKMDGGDSV-BCMRRPTOSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- AZKVWQKMDGGDSV-UHFFFAOYSA-N genipin Natural products COC(=O)C1=COC(O)C2C(CO)=CCC12 AZKVWQKMDGGDSV-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 5
- 229920002301 cellulose acetate Polymers 0.000 claims description 5
- 239000003651 drinking water Substances 0.000 claims description 5
- 235000020188 drinking water Nutrition 0.000 claims description 5
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 5
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000004065 wastewater treatment Methods 0.000 claims description 4
- 239000010840 domestic wastewater Substances 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000010865 sewage Substances 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000001514 detection method Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 229920000875 Dissolving pulp Polymers 0.000 description 2
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003864 humus Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
Classifications
-
- 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
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/0205—Impregnation in several steps
-
- 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
- B01J37/0213—Preparation of the impregnating solution
-
- 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
- B01J37/06—Washing
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The application belongs to the technical field of sewage treatment, and solves the problems of low catalyst loading efficiency and unstable action in the catalytic oxidation technology in the water treatment in the prior art. The application provides a preparation method of a catalytic filter element, which comprises the following steps of: preparing a precursor colloid of the crosslinking reaction; crosslinking: immersing the filter element into the precursor colloid for crosslinking reaction to obtain a precursor filter element; load: carrying out metal ion loading on the precursor filter element to obtain a loaded filter element; drying and carbonizing: and drying the loaded filter element, and carbonizing in an argon environment to obtain the ozone catalytic filter element. The application also claims a catalytic filter element prepared by the preparation method and application thereof. The catalytic filter element provided by the application has the advantages of improved metal ion adsorption capacity and enhanced ozone catalytic performance.
Description
Technical Field
The application belongs to the technical field of water advanced treatment, and particularly relates to a catalytic filter element, a preparation method and application thereof.
Background
Industrial and agricultural production and domestic wastewater contains a large amount of organic pollutants, including some refractory toxic pollutants such as antibiotics, organic halides and the like, which are not only highly toxic, but also difficult to be effectively treated by the traditional treatment method, so that the high-performance sewage catalytic oxidation treatment process is widely applied. The ozone catalytic oxidation technology becomes a sewage catalytic oxidation treatment technology with wide application prospect due to the strong oxidation performance and low treatment cost.
The catalyst and the load are the cores of the ozone catalytic oxidation technology, and the catalyst usually exists in the form of powder and plays a role in application, but the catalyst in the form of powder is difficult to recover and is easy to run off along with water, so that the catalyst load has low action efficiency and unstable action effect.
Disclosure of Invention
The application aims to solve the problems of low catalyst loading action efficiency and unstable action effect in the catalytic oxidation technology in the technical field of water treatment in the prior art.
In order to achieve the above purpose, the application adopts the following technical scheme: a method of preparing a catalytic filter cartridge comprising:
Colloid preparation: preparing a precursor colloid of the crosslinking reaction;
Crosslinking: immersing the filter element into the precursor colloid for crosslinking reaction to obtain a precursor filter element;
load: carrying out metal ion loading on the precursor filter element to obtain a loaded filter element;
Drying and carbonizing: and drying the loaded filter element, and carbonizing in an argon environment to obtain the ozone catalytic filter element.
Specifically, the colloid formulation includes:
preparing an impregnating solution: mixing the coating agent solution and the flocculant solution according to the volume ratio of 1:0.5-2, and adding a cross-linking agent to obtain an impregnating solution;
precursor colloid preparation: adding methanol and acetic acid into the impregnating solution to obtain the precursor colloid.
Specifically, crosslinking includes:
impregnation and crosslinking: immersing the filter element into the precursor colloid, standing for 1-5h, drying at 30-120 ℃ and carrying out crosslinking reaction;
Metal adsorption: repeating the dipping and crosslinking operation for 3-10 times to obtain the precursor filter element.
Specifically, the load includes:
preparing a load solution: adding cerium nitrate into a manganese nitrate solution with the concentration of 0.1-1.0M to ensure that the quantity ratio of the manganese nitrate to the final substance of cerium nitrate is 2-6:1, thus obtaining a load solution;
Impregnation load: and immersing the precursor filter element in the load liquid for 8-24h to obtain the load filter element.
Further, the preparation method of the catalytic filter element provided by the application further comprises the following steps before colloid preparation:
Purifying: washing the filter element with water and alcohol, and drying at 30-80deg.C to obtain purified filter element;
Pretreatment: immersing the purification filter element into pretreatment liquid, and standing for 1-5h to obtain a pretreatment filter element; wherein the pretreatment liquid is one of polyacrylic acid solution, polyvinylpyrrolidone solution and polyethylene glycol solution, and the volume concentration of the pretreatment liquid is 1-10%.
Optionally, in the preparation method of the catalytic filter element provided by the application, the filter element is made of one of polypropylene, polysulfone, polyvinylidene fluoride, polyacrylonitrile and activated carbon.
Optionally, in the preparation method of the catalytic filter element provided by the application, the coating agent is one or a combination of more of cellulose acetate, polyacrylic acid, polyacrylonitrile and polyvinyl alcohol, and the volume concentration of the coating agent solution is 1% -10%; the flocculant is one or the combination of more of chitosan, sodium alginate and hydroxypropyl cellulose, and the volume concentration of the flocculant solution is 1-10%; the cross-linking agent is one or the combination of more of genipin, epichlorohydrin, N-methylene bisacrylamide and glutaraldehyde, and the volume concentration of the cross-linking agent in the impregnating solution after the addition is 1-10%; the volume concentration of methanol in the precursor colloid after adding methanol and acetic acid is 0.05-0.2%, and the volume concentration of acetic acid is 0.05-0.2%.
Furthermore, the application claims a catalytic filter element prepared by the preparation method.
Further, the application claims the application of the catalytic filter element in water treatment, including domestic wastewater treatment, industrial wastewater treatment and drinking water treatment.
Compared with the prior art, the application has the following beneficial effects:
The preparation method of the catalytic filter element provided by the application is simple in preparation method and low in cost by preparing the metal adsorption and ozone catalyst through in-situ crosslinking polymerization and a secondary impregnation method.
The catalytic filter element prepared by the preparation method of the catalytic filter element provided by the application adsorbs a large amount of colloid particles, exists on the filter element in the form of carbon particles after being dried and carbonized, has larger specific surface area, high catalyst loading efficiency, and can perform physical catalysis and chemical catalysis simultaneously, so that the catalytic effect is more stable, the metal ion adsorption capacity is improved, and the ozone catalytic performance is enhanced.
Drawings
Fig. 1 is a flowchart of a method for preparing a catalytic filter element according to an embodiment of the present application.
Fig. 2 is a flowchart of a colloid preparation step in the preparation method of the catalytic filter element provided by the embodiment of the application.
Fig. 3 is a flowchart of a crosslinking step in the preparation method of the catalytic filter element according to the embodiment of the present application.
Fig. 4 is a flowchart of a loading step in a preparation method of a catalytic filter element according to an embodiment of the present application.
Fig. 5 is a flowchart of purification and pretreatment steps in the preparation method of the catalytic filter element according to the embodiment of the present application.
Detailed Description
The following describes the technical aspects of the present application with reference to examples, but the present application is not limited to the following examples.
The experimental methods and the detection methods in the following embodiments are all conventional methods unless otherwise specified; the medicaments and materials are commercially available unless specified; the index data are all conventional measurement methods unless specified.
The embodiment of the application provides a preparation method of a catalytic filter element, the flow of which is shown in figure 1, comprising the following steps:
Colloid preparation: preparing a precursor colloid of the crosslinking reaction;
Crosslinking: immersing the filter element into the precursor colloid for crosslinking reaction to obtain a precursor filter element;
load: carrying out metal ion loading on the precursor filter element to obtain a loaded filter element;
Drying and carbonizing: and drying the loaded filter element, and carbonizing in an argon environment to obtain the ozone catalytic filter element.
Specifically, the process of colloid preparation is shown in fig. 2, and includes:
preparing an impregnating solution: mixing the coating agent solution and the flocculant solution according to the volume ratio of 1:0.5-2, and adding a cross-linking agent to obtain an impregnating solution;
precursor colloid preparation: adding methanol and acetic acid into the impregnating solution to obtain the precursor colloid.
The coating agent can increase the specific surface area of the filter element, the flocculant provides negatively charged groups in the colloid-forming reaction, the cross-linking agent provides positively charged metal ions in the colloid-forming reaction, and the methanol and the acetic acid serve as catalysts in the colloid-forming reaction.
Specifically, the cross-linking process is shown in fig. 3, and includes:
impregnation and crosslinking: immersing the filter element into the precursor colloid, standing for 1-5h, drying at 30-120 ℃ and carrying out crosslinking reaction;
Metal adsorption: repeating the dipping and crosslinking operation for 3-10 times to obtain the precursor filter element.
Repeating the impregnation cross-linking operation allows the cartridge to carry more colloid.
Specifically, as shown in fig. 4, the load flow includes:
preparing a load solution: adding cerium nitrate into a manganese nitrate solution with the concentration of 0.1-1.0M to ensure that the quantity ratio of the manganese nitrate to the final substance of cerium nitrate is 2-6:1, thus obtaining a load solution;
Impregnation load: and immersing the precursor filter element in the load liquid for 8-24h to obtain the load filter element.
Manganese ions and cerium ions are used as catalysts in the catalytic purification treatment of water.
The drying carbonization operation can make the carried colloid exist and act in the form of carbon spheres to increase the specific surface area.
Further, the preparation method of the catalytic filter element provided by the application further comprises the following steps of:
Purifying: washing the filter element with water and alcohol, and drying at 30-80deg.C to obtain purified filter element;
Pretreatment: immersing the purification filter element into pretreatment liquid, and standing for 1-5h to obtain a pretreatment filter element; wherein the pretreatment liquid is one of polyacrylic acid solution, polyvinylpyrrolidone solution and polyethylene glycol solution, and the volume concentration of the pretreatment liquid is 1-10%. The solute of the pretreatment liquid is a high polymer material, so that the adhesive capacity of the filter element can be improved, and the dispersion performance of the solute in the subsequent reaction can be improved.
Optionally, in the preparation method of the catalytic filter element provided by the application, the filter element material is one of polypropylene, polysulfone, polyvinylidene fluoride, polyacrylonitrile and active carbon, and in some other application examples, the filter element material can also be ceramic, resin and the like.
Optionally, in the preparation method of the catalytic filter element provided by the application, the coating agent is one or a combination of more of cellulose acetate, polyacrylic acid, polyacrylonitrile and polyvinyl alcohol, and the volume concentration of the coating agent solution is 1% -10%; the flocculant is one or the combination of more of chitosan, sodium alginate and hydroxypropyl cellulose, and the volume concentration of the flocculant solution is 1-10%; the cross-linking agent is one or the combination of more of genipin, epichlorohydrin, N-methylene bisacrylamide and glutaraldehyde, and the volume concentration of the cross-linking agent in the impregnating solution after the addition is 1-10%; the volume concentration of methanol in the precursor colloid after adding methanol and acetic acid is 0.05-0.2%, and the volume concentration of acetic acid is 0.05-0.2%.
Further, the embodiment of the application provides the catalytic filter element prepared by the preparation method.
Furthermore, the application provides an application test of the catalytic filter element in water treatment.
The embodiment of the application provides preparation of an ozone catalytic polypropylene filter element-1, an ozone catalytic polypropylene filter element, an ozone catalytic polysulfone filter element, an ozone catalytic polyvinylidene fluoride filter element, an ozone catalytic polyacrylonitrile filter element and an ozone catalytic activated carbon filter element, wherein the preparation process is as follows:
example 1
Dissolving cellulose acetate in water to prepare a cellulose acetate solution with the volume concentration of 5%, dissolving chitosan in water to prepare a chitosan solution with the volume concentration of 5%, fully mixing the coating solution and the flocculant solution with the volume ratio of 1:1, adding genipin, adding 5% of genipin to obtain an impregnating solution, adding methanol and acetic acid to the impregnating solution, and adding 0.1% of methanol and acetic acid to obtain a precursor colloid;
Adding cerium nitrate into a manganese nitrate solution with the concentration of 0.5M to ensure that the quantity ratio of the manganese nitrate to the final substance of cerium nitrate is 4:1, thereby obtaining a load solution;
A blank filter element made of polypropylene is quickly immersed into a precursor colloid, and is dried at 80 ℃ after standing for 3 hours, so that a crosslinking reaction is carried out;
Repeating the dipping and crosslinking step for 7 times to obtain a precursor polypropylene filter element;
Immersing the precursor polypropylene filter element in a load liquid for 16 hours to obtain a load filter element;
Drying the load filter element at 90 ℃ to obtain a dried load filter element;
And carbonizing the dried load filter element in a tubular furnace at 600 ℃ in an argon environment to obtain the ozone catalyzed polypropylene filter element-1.
Example 2
Washing a blank filter element made of polypropylene with 200mL of water and 200mL of alcohol, and drying at 30 ℃ for later use;
Taking polyacrylic acid to be dissolved in water to prepare a polyacrylic acid solution with volume concentration of 1 percent as pretreatment liquid, immersing the dried blank filter element into the pretreatment liquid, and standing for 1h to obtain a pretreatment filter element;
Dissolving cellulose acetate in water to prepare a cellulose acetate solution with volume concentration of 1%, dissolving chitosan in water to prepare a chitosan solution with volume concentration of 1%, fully mixing the coating solution with the flocculant solution according to the volume ratio of 1:0.5, adding genipin with volume concentration of 1% to obtain an impregnating solution, adding methanol and acetic acid into the impregnating solution, and adding methanol and acetic acid with volume concentrations of 0.05% to obtain a precursor colloid;
Adding cerium nitrate into a manganese nitrate solution with the concentration of 0.1M to ensure that the quantity ratio of the manganese nitrate to the final substance of cerium nitrate is 2:1, thereby obtaining a load solution;
Rapidly immersing the pretreatment filter element into the precursor colloid, standing for 1h, drying at 30 ℃ and carrying out crosslinking reaction;
repeating the dipping and crosslinking step for 3 times to obtain a precursor polypropylene filter element;
Immersing the precursor polypropylene filter element in a load liquid for 8 hours to obtain a load filter element;
drying the load filter element at 60 ℃ to obtain a dried load filter element;
and carbonizing the dried load filter element in a tubular furnace at the temperature of 500 ℃ in an argon environment to obtain the ozone catalyzed polypropylene filter element.
Example 3
Washing 200mL of polysulfone blank filter element with 200mL of water, washing with 200mL of alcohol, and drying at 50 ℃ for later use;
Dissolving polyvinylpyrrolidone in water to prepare polyvinylpyrrolidone solution with volume concentration of 3%, taking the polyvinylpyrrolidone solution as pretreatment liquid, immersing the dried blank filter element in the pretreatment liquid, and standing for 2h to obtain a pretreatment filter element;
Dissolving polyacrylic acid into water to prepare a polyacrylic acid solution with the volume concentration of 3%, dissolving sodium alginate into water to prepare a sodium alginate solution with the volume concentration of 3%, fully mixing the coating agent solution and the flocculant solution according to the volume ratio of 1:0.9, adding epichlorohydrin, wherein the volume concentration of the epichlorohydrin is 3% after the addition to obtain an impregnating solution, adding methanol and acetic acid into the impregnating solution, and the volume concentrations of the methanol and the acetic acid are 0.09% after the addition to obtain a precursor colloid;
Adding cerium nitrate into a manganese nitrate solution with the concentration of 0.3M to ensure that the quantity ratio of the manganese nitrate to the final substance of cerium nitrate is 3:1, thereby obtaining a load solution;
rapidly immersing the pretreatment filter element into the precursor colloid, standing for 2 hours, drying at 50 ℃ and carrying out crosslinking reaction;
repeating the dipping and crosslinking step for 5 times to obtain a precursor polysulfone filter element;
Immersing the precursor polysulfone filter element in a load liquid for 13h to obtain a load filter element;
Drying the load filter element at 75 ℃ to obtain a dried load filter element;
And carbonizing the dried loaded filter element in a tubular furnace at 550 ℃ in an argon environment to obtain the ozone catalytic polysulfone filter element.
Example 4
Washing a blank filter element made of polyvinylidene fluoride with 200mL of water and 200mL of alcohol, and drying at 60 ℃ for later use;
Dissolving polyethylene glycol into water to prepare polyethylene glycol solution with volume concentration of 5%, taking the polyethylene glycol solution as pretreatment liquid, immersing the dried blank filter element into the pretreatment liquid, and standing for 3 hours to obtain a pretreatment filter element;
Dissolving polyacrylonitrile in water to prepare a polyacrylonitrile solution with the volume concentration of 5%, dissolving hydroxypropyl cellulose in water to prepare a hydroxypropyl cellulose solution with the volume concentration of 5%, fully mixing the coating agent solution and the flocculant solution according to the volume ratio of 1:1.3, adding N, N-methylene bisacrylamide, wherein the volume concentration of the added N, N-methylene bisacrylamide is 5%, obtaining an impregnating solution, adding methanol and acetic acid into the impregnating solution, and the volume concentrations of the added methanol and acetic acid are 0.13%, thus obtaining a precursor colloid;
Adding cerium nitrate into a manganese nitrate solution with the concentration of 0.5M to ensure that the quantity ratio of the manganese nitrate to the final substance of cerium nitrate is 4:1, thereby obtaining a load solution;
rapidly immersing the pretreatment filter element into the precursor colloid, standing for 3h, drying at 80 ℃ and carrying out crosslinking reaction;
repeating the dipping and crosslinking step for 7 times to obtain a precursor polyvinylidene fluoride filter element;
immersing the precursor polyvinylidene fluoride filter element in the load liquid for 16 hours to obtain a load filter element;
Drying the load filter element at 90 ℃ to obtain a dried load filter element;
And carbonizing the dried load filter element in a tubular furnace at 600 ℃ in an argon environment to obtain the ozone catalytic polyvinylidene fluoride filter element.
Example 5
Washing a blank filter element made of polyacrylonitrile with 200mL of water and 200mL of alcohol, and drying at 70 ℃ for later use;
Dissolving polyacrylic acid in water to prepare a polyacrylic acid solution with the volume concentration of 7 percent as pretreatment liquid, immersing the dried blank filter element into the pretreatment liquid, and standing for 4 hours to obtain a pretreatment filter element;
dissolving polyvinyl alcohol into water to prepare a polyvinyl alcohol solution with the volume concentration of 7%, dissolving chitosan into water to prepare a chitosan solution with the volume concentration of 7%, fully mixing the coating agent solution and the flocculant solution with the volume ratio of 1:1.7, adding glutaraldehyde, wherein the volume concentration of glutaraldehyde is 7%, so as to obtain an impregnating solution, adding methanol and acetic acid into the impregnating solution, and the volume concentrations of methanol and acetic acid are 0.17%, so as to obtain a precursor colloid;
adding cerium nitrate into a manganese nitrate solution with the concentration of 0.7M to ensure that the quantity ratio of manganese nitrate to cerium nitrate is 5:1, thereby obtaining a load solution;
Rapidly immersing the pretreatment filter element into the precursor colloid, standing for 4 hours, drying at 100 ℃, and carrying out crosslinking reaction;
Repeating the dipping and crosslinking step for 9 times to obtain a precursor polyacrylonitrile filter element;
Immersing the precursor polyacrylonitrile filter element in the load liquid for 20 hours to obtain a load filter element;
Drying the load filter element at 105 ℃ to obtain a dried load filter element;
And carbonizing the dried load filter element in a tubular furnace at 650 ℃ in an argon environment to obtain the ozone-catalyzed polyacrylonitrile filter element.
Example 6
Washing 200mL of water with 200mL of alcohol, and drying at 80 ℃ for later use;
Dissolving polyacrylic acid in water to prepare a polyacrylic acid solution with the volume concentration of 10 percent as pretreatment liquid, immersing the dried blank filter element into the pretreatment liquid, and standing for 5 hours to obtain a pretreatment filter element;
Dissolving polyvinyl alcohol into water to prepare a polyvinyl alcohol solution with the volume concentration of 10%, dissolving chitosan into water to prepare a chitosan solution with the volume concentration of 10%, fully mixing the coating agent solution and the flocculant solution with the volume ratio of 1:2, adding glutaraldehyde, adding the glutaraldehyde with the volume concentration of 10%, obtaining an impregnating solution, adding methanol and acetic acid into the impregnating solution, and adding methanol and acetic acid with the volume concentrations of 0.2%, thereby obtaining a precursor colloid;
adding cerium nitrate into a manganese nitrate solution with the concentration of 1.0M to ensure that the quantity ratio of the manganese nitrate to the final substance of cerium nitrate is 6:1, thereby obtaining a load solution;
rapidly immersing the pretreatment filter element into the precursor colloid, standing for 5 hours, drying at 120 ℃, and carrying out crosslinking reaction;
repeating the dipping and crosslinking step for 10 times to obtain a precursor activated carbon filter element;
immersing the precursor active carbon filter element in the load liquid for 24 hours to obtain a load filter element;
Drying the load filter element at 120 ℃ to obtain a dried load filter element;
and carbonizing the dried loaded filter element in a tubular furnace at 700 ℃ in an argon environment to obtain the ozone catalytic activated carbon filter element.
The embodiment of the application also provides an application test of the ozone catalytic filter element.
Chemical Oxygen Demand (COD) refers to the amount of oxidant consumed when the reducing substances in water are oxidized and decomposed under the action of the externally added strong oxidant, and expressed in mg/L of oxygen, and the COD reflects the pollution degree of the reducing substances in water and can be used as a comprehensive index of the relative content of organic substances. UV 254 is the absorbance of some organic matters in water under 254nm wavelength ultraviolet light, reflects the amount of humus macromolecular organic matters and aromatic compounds containing C=C double bonds and C=O double bonds naturally existing in water, and is expressed in mg/L of the contained substances after conversion.
The ozone catalytic polypropylene filter element, the ozone catalytic polysulfone filter element, the ozone catalytic polyvinylidene fluoride filter element, the ozone catalytic polyacrylonitrile filter element and the ozone catalytic activated carbon filter element which are prepared by the embodiment of the application are respectively assembled into a sewage reactor; and respectively carrying out Hg 2+ ion removal rate detection, COD reduction rate detection and UV 254 reduction rate detection.
The Hg 2+ ion removal rate detection method comprises the following steps: the water with Hg 2+ ion concentration of 5ppb is used as treatment liquid, the treatment liquid is pumped into the water inlet of a sewage reactor provided with the five ozone catalytic filter elements respectively by a constant flow pump, the flow rate is 0.5L/h, and continuous water inlet treatment is carried out; continuously sampling at a water outlet, continuously monitoring the concentration of Hg 2+ ions in the water outlet, and detecting the concentration of Hg 2+ ions in the water outlet, wherein the detection result is shown in a table 1;
The COD reduction rate detection method comprises the following steps: the water with the COD value of 1000mg/L is used as treatment fluid, the treatment fluid is pumped into the water inlet of the sewage reactor provided with the five ozone catalytic filter elements by a constant flow pump, the flow rate is 0.5L/h, and continuous water inlet treatment is carried out; continuously sampling at a water outlet, continuously monitoring the COD value in the water outlet, and detecting the COD value, wherein the detection result is shown in Table 2;
UV 254 reduction rate detection method: the water with the UV 254 content of 0.5 mg/L is used as treatment fluid, the treatment fluid is pumped into the water inlet of the sewage reactor provided with the five ozone catalytic filter elements respectively by a constant flow pump, the flow rate is 0.5L/h, and continuous water inlet treatment is carried out; samples were continuously taken at the water outlet, the value of UV 254 in the water was continuously monitored, and the detection results are shown in table 3.
Table 1 results of test for removal rate of Hg 2+ from ozone catalytic cartridge
As can be seen from Table 1, the five ozone catalytic filter elements provided by the embodiment of the application can effectively remove Hg 2+ in water, the removal rate is more than 90%, and the Hg 2+ content in the effluent accords with the content specified in the national sanitary standard of drinking water. The catalytic filter element prepared by the preparation method of the catalytic filter element provided by the application is applied to sewage treatment, can effectively remove metal ions in water, and has higher metal ion adsorption capacity.
Table 2 COD reduction test results for ozone catalyzed cartridges
As can be seen from Table 2, the ozone catalytic filter element provided by the application can effectively reduce the COD of water body, the reduction rate is more than 70%, and the COD value in the effluent accords with the value specified in the national sanitary standard of drinking water. The catalytic filter element prepared by the preparation method of the catalytic filter element provided by the application is applied to sewage treatment, can effectively remove the reducing substances in the water body, and has stronger catalytic oxidation performance.
TABLE 3 UV 254 degradation test results for ozone catalytic cartridges
As can be seen from Table 3, the ozone catalytic filter element provided by the application can effectively reduce UV 254 of water, the reduction rate is more than 95%, and the UV 254 value in the effluent accords with the value specified in the national sanitary standard of drinking water. The catalytic filter element prepared by the preparation method of the catalytic filter element provided by the application is applied to sewage treatment, can effectively remove humus macromolecular organic matters and aromatic compounds containing C=C double bonds and C=O double bonds in water, and has stronger catalytic oxidation performance.
The present application may be better implemented as described above, and the above examples are merely illustrative of preferred embodiments of the present application and not intended to limit the scope of the present application, and various changes and modifications made by those skilled in the art to the technical solution of the present application should fall within the scope of protection defined by the present application without departing from the spirit of the design of the present application.
Claims (10)
1. A method of preparing a catalytic filter cartridge comprising:
Colloid preparation: preparing a precursor colloid of the crosslinking reaction;
crosslinking: immersing the filter element into the precursor colloid for crosslinking reaction to obtain a precursor filter element;
Load: carrying out metal ion loading on the precursor filter element to obtain a loaded filter element;
drying and carbonizing: and drying the load filter element, and carbonizing in an argon environment to obtain the ozone catalytic filter element.
2. The method of preparing a catalytic filter cartridge of claim 1, wherein the colloidal formulation comprises:
preparing an impregnating solution: mixing the coating agent solution and the flocculant solution according to the volume ratio of 1:0.5-2, and adding a cross-linking agent to obtain an impregnating solution;
precursor colloid preparation: and adding methanol and acetic acid into the impregnating solution to obtain a precursor colloid.
3. The method of preparing a catalytic filter cartridge of claim 2, wherein the cross-linking comprises:
impregnation and crosslinking: immersing the filter element into the precursor colloid, standing for 1-5h, drying at 30-120 ℃ and carrying out crosslinking reaction;
Metal adsorption: repeating the dipping cross-linking operation for 3-10 times to obtain the precursor filter element.
4. A method of preparing a catalytic filter cartridge according to claim 3, wherein the loading comprises:
preparing a load solution: adding cerium nitrate into a manganese nitrate solution with the concentration of 0.1-1.0M to ensure that the quantity ratio of the manganese nitrate to the final substance of cerium nitrate is 2-6:1, thus obtaining a load solution;
impregnation load: and immersing the precursor filter element in the load liquid for 8-24h to obtain the load filter element.
5. The method of preparing a catalytic filter cartridge of claim 1, further comprising, prior to said colloid formulation:
purifying: washing the filter element with water and alcohol, and drying at 30-80deg.C to obtain a purified filter element;
Pretreatment: immersing the purification filter element into pretreatment liquid, and standing for 1-5h to obtain a pretreatment filter element; wherein the pretreatment liquid is one of polyacrylic acid solution, polyvinylpyrrolidone solution and polyethylene glycol solution, and the volume concentration of the pretreatment liquid is 1% -10%.
6. The method for preparing a catalytic filter cartridge according to any one of claims 1-5, wherein the filter cartridge material is one of polypropylene, polysulfone, polyvinylidene fluoride, polyacrylonitrile and activated carbon.
7. The method for preparing the catalytic filter element according to claim 2, wherein the coating agent is one or a combination of several of cellulose acetate, polyacrylic acid, polyacrylonitrile and polyvinyl alcohol, and the volume concentration of the coating agent solution is 1% -10%;
The flocculant is one or a combination of more of chitosan, sodium alginate and hydroxypropyl cellulose, and the volume concentration of the flocculant solution is 1-10%;
the cross-linking agent is one or the combination of more of genipin, epichlorohydrin, N-methylene bisacrylamide and glutaraldehyde, and the volume concentration of the cross-linking agent in the impregnating solution is 1-10% after the cross-linking agent is added;
The volume concentration of methanol in the precursor colloid is 0.05-0.2% after methanol and acetic acid are added, and the volume concentration of acetic acid in the precursor colloid is 0.05-0.2%.
8. A catalytic filter element prepared by the method of any one of claims 1-7.
9. The use of the catalytic filter element of claim 8 in water treatment.
10. The use according to claim 9, wherein the water treatment comprises domestic wastewater treatment, process wastewater treatment and drinking water treatment.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4797380A (en) * | 1986-03-06 | 1989-01-10 | Satoshi Motoo | Method for producing highly dispersed catalyst |
| JP2005046701A (en) * | 2003-07-31 | 2005-02-24 | Kurosaki Harima Corp | Porous material for highly efficient ozonolysis |
| US20090272698A1 (en) * | 2008-05-01 | 2009-11-05 | John Hill | Bromate suppression |
| CN105948159A (en) * | 2016-06-07 | 2016-09-21 | 中国科学院新疆理化技术研究所 | Manufacturing method for heavy metal adsorption filter element |
| CN106732643A (en) * | 2016-11-16 | 2017-05-31 | 天津碧水源膜材料有限公司 | A kind of modified ozone oxidation catalyst carrier and preparation method thereof |
| US20180093260A1 (en) * | 2016-05-20 | 2018-04-05 | The Hong Kong Research Institute Of Textiles And Apparel Limited | Catalysts for degradation of organic pollutants in printing and dyeing wastewater and method of preparation thereof |
| CN109453672A (en) * | 2018-11-27 | 2019-03-12 | 成都新柯力化工科技有限公司 | A kind of use in waste water treatment ceramic catalytic film and preparation method |
| CN111229248A (en) * | 2020-03-03 | 2020-06-05 | 清华大学 | Preparation method of supported metal oxide particle catalyst |
| US20220111362A1 (en) * | 2020-03-30 | 2022-04-14 | Chinese Research Academy Of Environment Sciences | Supported two-component metal oxide catalyst for advanced treatment of petrochemical wastewater and method for preparing same |
| CN115055174A (en) * | 2022-06-29 | 2022-09-16 | 北京化工大学 | Ca-based ozone catalytic oxidation catalyst for advanced treatment of salt-containing organic wastewater and preparation method thereof |
-
2024
- 2024-04-01 CN CN202410383517.7A patent/CN117960251A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4797380A (en) * | 1986-03-06 | 1989-01-10 | Satoshi Motoo | Method for producing highly dispersed catalyst |
| JP2005046701A (en) * | 2003-07-31 | 2005-02-24 | Kurosaki Harima Corp | Porous material for highly efficient ozonolysis |
| US20090272698A1 (en) * | 2008-05-01 | 2009-11-05 | John Hill | Bromate suppression |
| US20180093260A1 (en) * | 2016-05-20 | 2018-04-05 | The Hong Kong Research Institute Of Textiles And Apparel Limited | Catalysts for degradation of organic pollutants in printing and dyeing wastewater and method of preparation thereof |
| CN105948159A (en) * | 2016-06-07 | 2016-09-21 | 中国科学院新疆理化技术研究所 | Manufacturing method for heavy metal adsorption filter element |
| CN106732643A (en) * | 2016-11-16 | 2017-05-31 | 天津碧水源膜材料有限公司 | A kind of modified ozone oxidation catalyst carrier and preparation method thereof |
| CN109453672A (en) * | 2018-11-27 | 2019-03-12 | 成都新柯力化工科技有限公司 | A kind of use in waste water treatment ceramic catalytic film and preparation method |
| CN111229248A (en) * | 2020-03-03 | 2020-06-05 | 清华大学 | Preparation method of supported metal oxide particle catalyst |
| US20220111362A1 (en) * | 2020-03-30 | 2022-04-14 | Chinese Research Academy Of Environment Sciences | Supported two-component metal oxide catalyst for advanced treatment of petrochemical wastewater and method for preparing same |
| CN115055174A (en) * | 2022-06-29 | 2022-09-16 | 北京化工大学 | Ca-based ozone catalytic oxidation catalyst for advanced treatment of salt-containing organic wastewater and preparation method thereof |
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