CN113332975A - Honeycomb ceramic etching supported catalyst and preparation method and application thereof - Google Patents
Honeycomb ceramic etching supported catalyst and preparation method and application thereof Download PDFInfo
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- CN113332975A CN113332975A CN202110406475.0A CN202110406475A CN113332975A CN 113332975 A CN113332975 A CN 113332975A CN 202110406475 A CN202110406475 A CN 202110406475A CN 113332975 A CN113332975 A CN 113332975A
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- honeycomb ceramic
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- 239000000919 ceramic Substances 0.000 title claims abstract description 210
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000005530 etching Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000001035 drying Methods 0.000 claims abstract description 37
- 238000001354 calcination Methods 0.000 claims abstract description 36
- 230000003197 catalytic effect Effects 0.000 claims abstract description 36
- 238000005406 washing Methods 0.000 claims abstract description 29
- 238000011068 loading method Methods 0.000 claims abstract description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 16
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 16
- 230000007935 neutral effect Effects 0.000 claims abstract description 14
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 14
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006385 ozonation reaction Methods 0.000 claims abstract description 10
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 8
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 7
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000005260 corrosion Methods 0.000 claims abstract description 4
- 230000007797 corrosion Effects 0.000 claims abstract description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 44
- 238000007254 oxidation reaction Methods 0.000 claims description 27
- 239000002957 persistent organic pollutant Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 18
- 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 10
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 10
- 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 6
- 239000000356 contaminant Substances 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 description 22
- 239000011737 fluorine Substances 0.000 description 22
- 229910052751 metal Inorganic materials 0.000 description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 21
- 239000002184 metal Substances 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 10
- 239000008399 tap water Substances 0.000 description 10
- 235000020679 tap water Nutrition 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 7
- -1 hydroxyl free radical Chemical class 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- MUDSDYNRBDKLGK-UHFFFAOYSA-N 4-methylquinoline Chemical compound C1=CC=C2C(C)=CC=NC2=C1 MUDSDYNRBDKLGK-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- SRUWWOSWHXIIIA-UKPGNTDSSA-N Cyanoginosin Chemical compound N1C(=O)[C@H](CCCN=C(N)N)NC(=O)[C@@H](C)[C@H](C(O)=O)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)NC(=O)C(=C)N(C)C(=O)CC[C@H](C(O)=O)N(C)C(=O)[C@@H](C)[C@@H]1\C=C\C(\C)=C\[C@H](C)[C@@H](O)CC1=CC=CC=C1 SRUWWOSWHXIIIA-UKPGNTDSSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000005562 Glyphosate Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- ZAIPMKNFIOOWCQ-UEKVPHQBSA-N cephalexin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@@H]3N(C2=O)C(=C(CS3)C)C(O)=O)=CC=CC=C1 ZAIPMKNFIOOWCQ-UEKVPHQBSA-N 0.000 description 3
- 229940106164 cephalexin Drugs 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 3
- 229940097068 glyphosate Drugs 0.000 description 3
- 108010067094 microcystin Proteins 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid Chemical compound CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 description 1
- 239000005561 Glufosinate Substances 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- YYQRGCZGSFRBAM-UHFFFAOYSA-N Triclofos Chemical compound OP(O)(=O)OCC(Cl)(Cl)Cl YYQRGCZGSFRBAM-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229960001147 triclofos Drugs 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- B01J23/83—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 rare earths or actinides
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- 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
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Abstract
The invention discloses a honeycomb ceramic etching supported catalyst, a preparation method thereof and application thereof in catalytic ozonation water treatment. The preparation method comprises the following steps: (1) pretreatment of the honeycomb ceramic: washing the honeycomb ceramic with water, drying, soaking in 0.2-5 mol/L nitric acid solution for 1-2 h, taking out, drying, and calcining at 300-750 ℃ for 1-5 h to obtain pretreated honeycomb ceramic; (2) etching the honeycomb ceramic: putting the pretreated honeycomb ceramic into a fluoride solution for corrosion for 1-7 h, taking out, washing with an alkali solution or water to be neutral, drying, and calcining at 300-750 ℃ for 1-5 h to obtain etched honeycomb ceramic; the concentration of the fluoride in the fluoride solution is 0.1-5 mol/L, and the fluoride is one or more of ammonium fluoride, sodium fluoride and potassium fluoride; (3) active component loading the etched honeycomb ceramic is immersed in nitrate solution of the active component, taken out, dried and calcined to obtain the honeycomb ceramic etching supported catalyst.
Description
Technical Field
The invention relates to the technical field of water pollution control and water treatment, in particular to a honeycomb ceramic etching supported catalyst and a preparation method and application thereof.
Background
With the improvement of sewage discharge standard and drinking water standard and the increasing shortage of water resources, the treatment of organic pollutants in water has higher and higher requirements, and some traditional water and sewage treatment processes are difficult to meet the requirements. Organic contaminants, including a wide range of organic chemicals, also include naturally occurring organic substances, such as cephalexin, octylphenol, bisphenol a, trichloroethyl phosphate, glufosinate, glyphosate, microcystin, and the like. Some of these organisms are toxic to humans and living beings, some threaten public health safety, and some pollute the water body, which is usually an important object for deep water treatment. The common water depth technology mainly comprises an adsorption method, a membrane separation method, an advanced oxidation method and the like. Wherein the advanced oxidation method refers to that under the excitation of sound, light, electricity, catalyst and other conditions, the oxidant is decomposed to generate strong oxidizing free radicals, such as hydroxyl free radical (. OH), superoxide free radical (O)2 -) Hydrogen peroxide radical (HO)2 -) The organic pollutants are oxidized by free radical reaction, and the method is characterized by high reaction rate, strong oxidizing ability, wide application range and the like, and can quickly degrade and mineralize the organic pollutants.
Currently, the more studied advanced oxidation methods mainly include an ultrasonic oxidation method, a photocatalytic oxidation method, an ozone oxidation method, and the like. The catalytic ozonation technology is to enhance ozonation with the help of a catalyst, so as to achieve the purpose of degrading and removing dissolved organic pollutants. The search for high-efficiency catalysts which promote the formation of more strongly oxidizing radicals in an ozone-water system is the key to the application and development of catalytic ozonation technology. The solid catalyst can be used for multiple times, thereby reducing the cost of catalyzing ozone oxidation treatment water and sewage. Conventional catalysts and supports have been activated carbon, molecular sieves, alumina and active components supported thereon, usually metals and their oxides. The type of active component has a significant influence on the catalytic activity of the catalyst, S.Imamura et al (Imamura S, Ikebata M, Ito T.Decomposion of ozone on a silver catalyst [ J].Industrial&Engineering Chemistry Research,1991,30(1): 217-: ag2O>NiO>Fe2O3>Co3O4>CeO2>MnO3>CuO>Pb2O3>Bi2O3>SnO2>MnO3>V2O5>SiO2. Dhandapani and Oyama (Dhandapani B, Oyama S T. gas phase ozone composition locations [ J ]]Applied Catalysis B, Environmental,1997,11(2):129-166.) the order of the ability of metal oxides on activated alumina to obtain the catalytic ozonolysis of common metal oxides is: MnO2>Co3O4>NiO>Fe2O3>Ag2O>Cr2O3>CeO2>V2O5>CuO>MoO3. Jianjun Lin and Akimasa Kawai (Lin J, Kawai A, Nakajima T. efficient catalysts for composition of aqueous ozone [ J]Applied Catalysis B, Environmental,2002,39(2):157-165.) the best catalytic performance of Pt and Pd was found when different metals were supported on activated alumina.
The honeycomb ceramic is a ceramic material with strong stability and honeycomb-shaped pore passages, and is widely applied to the chemical industry, the electric power industry, the mechanical industry and the environmental protection industry. Hydroxyl groups adsorbed on the surface of the honeycomb ceramic are beneficial to improving the generation of hydroxyl radicals; the honeycomb ceramic has stable physical and chemical properties, no adverse effect on water quality, high strength, difficult abrasion and easy recovery.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a preparation method of a honeycomb ceramic etching supported catalyst, which takes honeycomb ceramic as a substrate, prepares the catalyst through fluorine etching and active component loading, is used for catalyzing organic pollutants in ozone oxidation water, achieves the effect of quickly degrading and mineralizing the organic pollutants, and achieves the purpose of deeply purifying water.
A preparation method of a honeycomb ceramic etching supported catalyst comprises the following steps:
(1) pretreatment of honeycomb ceramics
And washing the honeycomb ceramic with water, drying, soaking in a 0.2-5 mol/L nitric acid solution for 1-2 h, taking out, drying, and calcining at 300-750 ℃ for 1-5 h to obtain the pretreated honeycomb ceramic.
(2) Honeycomb ceramic etching
And putting the pretreated honeycomb ceramic into a fluoride solution for corrosion for 1-7 h, taking out, washing with an alkali solution or water to be neutral, drying, and calcining at 300-750 ℃ for 1-5 h to obtain the etched honeycomb ceramic.
The concentration of the fluoride in the fluoride solution is 0.1-5 mol/L, and the fluoride is one or more of ammonium fluoride, sodium fluoride and potassium fluoride.
(3) Active ingredient loading
And soaking the etched honeycomb ceramic into a nitrate solution of an active component, taking out, drying and calcining to obtain the honeycomb ceramic etching supported catalyst.
The key point of the invention is that the synergistic effect between the active components is strengthened by etching the honeycomb ceramics by fluorine, the reaction of decomposing ozone and generating strong oxidizing free radicals is initiated and promoted, and the reaction is unselectively reacted with organic pollutants in water.
In the preparation method, firstly, small particles and powder on the surface are taken out by washing, the honeycomb ceramic is pretreated by nitric acid solution with specific concentration, and impurities in the pore channel of the honeycomb ceramic are dissolved and removed, so that the pore channel is smoother, the subsequent fluorine etching can be fully carried out, and the catalytic ozonation reaction can be carried out; and then the honeycomb ceramic is etched by fluoride solution with specific concentration and specific species, and an acid site is introduced, so that a powerful condition is provided for promoting the generation of hydroxyl radicals in an ozone-water system, and the reaction activity of the catalyst is remarkably improved. The fluorine etching can also increase the roughness of the surface of the honeycomb ceramic, is beneficial to loading active metal components, and further strengthens the catalytic activity of the honeycomb ceramic by optimizing the ratio of the metal components to the fluorine components.
In the preparation method of the present invention, the Al and Si-containing honeycomb ceramics commonly used in the art, such as cordierite type honeycomb ceramics, etc., can be used.
In the step (1), the mesh number of the honeycomb ceramics is preferably 100-400 meshes.
From the comprehensive consideration of the catalytic effect, the manufacturing cost and the control of secondary pollution, the invention selects common metal elements as active components, namely heavy metals and noble metals are eliminated. In the step (3), the nitrate in the nitrate solution is preferably at least one of manganese nitrate, iron nitrate, magnesium nitrate, lanthanum nitrate, cerium nitrate and ytterbium nitrate.
In the step (2), the alkali solution is preferably 1-2 mol/L NaOH solution.
In the step (3), the concentration of the nitrate in the nitrate solution is preferably 0.1-5 mol/L.
In the step (3), the calcining temperature is preferably 300-750 ℃, and the time is preferably 1-5 h.
The catalytic ozone oxidation activity of the honeycomb ceramic can be further enhanced by optimizing the types of the metal active components, the proportion of the metal active components to the fluorine components, and the temperature and time of calcination after loading.
The invention also provides the honeycomb ceramic etching supported catalyst prepared by the preparation method.
The invention also provides application of the honeycomb ceramic etching supported catalyst in catalyzing ozone oxidation treatment water.
As a general inventive concept, the present invention also provides a method for treating organic pollutants in water, comprising: adding the honeycomb ceramic etching supported catalyst into a catalytic oxidation reactor, then adding water containing organic pollutants into the catalytic oxidation reactor, and simultaneously adding ozone to carry out ozone catalytic oxidation reaction.
The reaction mechanism of the honeycomb ceramic etching supported catalyst for catalyzing ozone to oxidize organic matters to treat water is shown in figure 1:
1) the fluorine etching process makes the honeycomb ceramic obtain abundant surface electron holes.
2) After the metal active component is loaded, an electron transfer cycle is formed between the variable-valence metal ions and main cation Al ions of the honeycomb ceramic, so that the reaction of ozone and water on the surface of the honeycomb ceramic etching supported catalyst is promoted, and the reaction is converted into free radicals.
3) At the catalyst surface, the free radicals react with organic contaminant contaminants.
4) The organic pollutants are oxidized, degraded and even mineralized, and the concentration of the organic pollutants is reduced and the COD is reduced.
The pH value of the water containing the organic pollutants is preferably 5-10.
The addition amount of the honeycomb ceramic etching supported catalyst is preferably 50-200 g/L of water.
The addition amount of the ozone is preferably 1-1000 mg/L of water.
The residence time of the water containing the organic pollutants in the catalytic oxidation reactor is preferably 1-240 min, and more preferably 5-120 min.
The catalytic ozonation reaction can be carried out at normal temperature and normal pressure.
The processing method comprises the following steps: adjusting the pH value of water, adding a catalyst, introducing ozone, and degrading organic pollutants by catalytic oxidation.
The detection finds that the adsorption of the honeycomb ceramic etching supported catalyst on organic pollutants in water is very little, which indicates that the honeycomb ceramic etching supported catalyst of the invention mainly removes and mineralizes the organic pollutants in the water in a catalytic ozone oxidation mode, but not simply adsorbs the organic pollutants in the water to the inner surface and the outer surface of the catalyst.
Compared with the prior art, the invention has the main advantages that:
the preparation method of the catalyst is characterized in that on the basis of nitric acid pretreatment, fluorine ions are doped by an etching method, better conditions are created for loading other active components, and metal active components are loaded by an immersion method to obtain the etching-loaded honeycomb ceramic catalyst. Based on the synergistic promotion effect of fluorine and metal active components, the efficiency of ozone and water action and decomposition into free radicals is improved by preferably doping fluorine and metal active components, and further organic pollutants are oxidatively degraded and mineralized, namely COD is reduced. The honeycomb ceramic etching supported catalyst prepared by the preparation method has the advantages of good strength, high catalytic efficiency, stable performance and the like.
Drawings
FIG. 1 is a schematic diagram of the reaction mechanism of the honeycomb ceramic etching supported catalyst for catalyzing ozone to oxidize organic matters to treat water according to the invention;
FIG. 2 is a schematic flow chart of a preparation method of the honeycomb ceramic etching supported catalyst of the present invention.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
As shown in FIG. 1, the preparation method of the honeycomb ceramic etching supported catalyst of the invention comprises the following steps:
(1) pretreatment of honeycomb ceramics
The method comprises the steps of washing the honeycomb ceramic with water, drying, soaking in 0.2-5 mol/L nitric acid solution for 1-2 hours, taking out, drying, and calcining at 300-750 ℃ for 1-5 hours to obtain the pretreated honeycomb ceramic, namely the acid modified honeycomb ceramic.
(2) Honeycomb ceramic etching
Putting the pretreated honeycomb ceramic into a fluoride solution for corrosion for 1-7 h, taking out, washing with an alkali solution (such as a 1-2 mol/L NaOH solution) or water to be neutral, drying, and calcining at 300-750 ℃ for 1-5 h to obtain the etched honeycomb ceramic, namely the fluorine etched honeycomb ceramic.
The concentration of the fluoride in the fluoride solution is 0.1-5 mol/L, and the fluoride is one or more of ammonium fluoride, sodium fluoride and potassium fluoride.
(3) Active ingredient loading
And soaking the etched honeycomb ceramic into a nitrate solution of an active component, taking out, drying and calcining to obtain the honeycomb ceramic etching supported catalyst, namely the fluorine etching metal supported honeycomb ceramic.
Example 1
(1) Pretreatment of honeycomb ceramics
The honeycomb ceramics (phi 35 multiplied by 30mm) are washed by tap water or deionized water and dried in an oven. The dried honeycomb ceramics with 100 meshes is immersed in 5.0mol/L nitric acid solution and is placed in a shaking table to be shaken for 1 h. Taking out and drying in a 105 ℃ oven, and then placing in a muffle furnace to calcine for 5h at 300 ℃.
(2) Fluorine etching
Immersing the honeycomb ceramic treated in the step (1) in 0.1mol/L ammonium fluoride solution, placing the honeycomb ceramic in a shaking table, oscillating for 2 hours, taking out the honeycomb ceramic, ultrasonically washing the honeycomb ceramic with 1mol/L NaOH solution until the washing liquid is neutral, drying the honeycomb ceramic in a 105 ℃ oven, and calcining the honeycomb ceramic in a muffle furnace at 300 ℃ for 5 hours.
(3) Metal active component loading
Immersing the fluorine-etched honeycomb ceramic treated in the step (2) in a 0.2mol/L manganese nitrate solution, placing the honeycomb ceramic in a shaking table, oscillating for 2 hours, taking out the honeycomb ceramic, drying the honeycomb ceramic in an oven at 105 ℃, and then calcining the honeycomb ceramic in a muffle furnace at 300 ℃ for 5 hours.
The water to be treated contains 2.0mg/L of formaldehyde, the pH value of the solution is adjusted to 6.4, the adding amount of ozone is 5mg/L, the adding amount of a catalyst is 100g/L, and the catalytic ozonation reaction time is 7 min. After the treatment, the concentration of formaldehyde in the water was 0.05 mg/L.
Example 2
(1) Pretreatment of honeycomb ceramics
The honeycomb ceramics (phi 50 multiplied by 30mm) are washed by tap water or deionized water and dried in an oven. The dried 200-mesh honeycomb ceramic is immersed in 0.2mol/L nitric acid solution and placed in a shaking table to be shaken for 2 hours. Taken out and dried in an oven at 105 ℃, and then calcined in a muffle furnace at 400 ℃ for 3 h.
(2) Fluorine etching
Immersing the honeycomb ceramic treated in the step (1) in 0.2mol/L sodium fluoride solution, placing the honeycomb ceramic in a shaking table, oscillating for 2 hours, taking out the honeycomb ceramic, ultrasonically washing the honeycomb ceramic with water until the washing liquid is neutral, drying the honeycomb ceramic in an oven at 105 ℃, and then calcining the honeycomb ceramic in a muffle furnace at 400 ℃ for 2.5 hours.
(3) Metal active component loading
Immersing the fluorine-etched honeycomb ceramic treated in the step (2) in a 0.5mol/L magnesium nitrate solution, placing the honeycomb ceramic in a shaking table, oscillating for 2 hours, taking out the honeycomb ceramic, drying the honeycomb ceramic in an oven at 105 ℃, and then calcining the honeycomb ceramic in a muffle furnace at 500 ℃ for 2.5 hours.
The water to be treated contains 1.2mg/L of glyphosate, the pH of the solution is adjusted to be 7.1, the adding amount of ozone is 3mg/L, the adding amount of a catalyst is 156g/L, and the catalytic ozonation reaction time is 11 min. After treatment, the water contains 0.01mg/L of glyphosate.
Example 3
(1) Pretreatment of honeycomb ceramics
The purchased honeycomb ceramics (Φ 35 × 30mm) were washed with tap water or deionized water and dried in an oven. The dried 300-mesh honeycomb ceramic is immersed in 4mol/L nitric acid solution and placed in a shaking table to be shaken for 1 h. Taking out and drying in a 105 ℃ oven, and then calcining in a muffle furnace at 500 ℃ for 2 h.
(2) Fluorine active component loading
Immersing the honeycomb ceramic treated in the step (1) in 0.5mol/L potassium fluoride solution, placing the honeycomb ceramic in a shaking table, oscillating for 2 hours, taking out the honeycomb ceramic, ultrasonically washing the honeycomb ceramic with water until the washing liquid is neutral, drying the honeycomb ceramic in an oven at 105 ℃, and calcining the honeycomb ceramic in a muffle furnace at 500 ℃ for 3 hours.
(3) Metal active component loading
Immersing the fluorine-etched honeycomb ceramic treated in the step (2) in 1mol/L manganese nitrate solution, placing the honeycomb ceramic in a shaking table for oscillation for 2 hours, taking out the honeycomb ceramic, drying the honeycomb ceramic in a 105 ℃ oven, and calcining the honeycomb ceramic in a muffle furnace at 400 ℃ for 3 hours.
0.6mg/L atrazine is contained in the water to be treated, the pH value of the solution is adjusted to be 7.7, the adding amount of ozone is 5mg/L, 65g/L of catalyst is added, and the reaction time of catalyzing ozone oxidation is 21 min. After treatment, the water contained 0.006mg/L atrazine.
Example 4
(1) Pretreatment of honeycomb ceramics
The honeycomb ceramics (phi 50 multiplied by 25mm) are washed by tap water or deionized water and dried in an oven. The dried 400-mesh honeycomb ceramic is immersed in 1mol/L nitric acid solution, placed in a shaking table, shaken for 2 hours, taken out and dried in an oven at 105 ℃, and then calcined in a muffle furnace at 600 ℃ for 1.5 hours.
(2) Fluorine active component loading
Immersing the honeycomb ceramic treated in the step (1) in 0.7mol/L ammonium fluoride solution, placing the honeycomb ceramic in a shaking table, oscillating for 2 hours, taking out the honeycomb ceramic, ultrasonically washing the honeycomb ceramic with 1mol/L NaOH solution until the washing liquid is neutral, drying the honeycomb ceramic in an oven at 105 ℃, and then calcining the honeycomb ceramic in a muffle furnace at 600 ℃ for 2 hours.
(3) Metal active component loading
Immersing the fluorine-etched honeycomb ceramic treated in the step (2) in 1.5mol/L ferric nitrate solution, placing the honeycomb ceramic in a shaking table, oscillating for 2 hours, taking out the honeycomb ceramic, drying the honeycomb ceramic in a 105 ℃ oven, and calcining for 4 hours in a muffle furnace at 600 ℃.
The water to be treated contains 56 mu g/L of microcystin, the pH value of the water is 7.2, the adding amount of ozone is 1mg/L, the adding amount of a catalyst is 105g/L, and the catalytic ozone oxidation reaction time is 4 min. After treatment, the water contains 0.03 mu g/L of microcystin.
Example 5
(1) Pretreatment of honeycomb ceramics
The honeycomb ceramics (phi 35 multiplied by 30mm) are washed by tap water or deionized water and dried in an oven. The dried 400-mesh honeycomb ceramic is immersed in 0.5mol/L nitric acid solution, placed in a shaking table to be shaken for 2 hours, taken out and dried in an oven at 105 ℃, and then calcined in a muffle furnace at 750 ℃ for 1.5 hours.
(2) Fluorine etching
Immersing the honeycomb ceramic treated in the step (1) in 1.5mol/L potassium fluoride solution, placing the honeycomb ceramic in a shaking table, oscillating for 4 hours, taking out the honeycomb ceramic, ultrasonically washing the honeycomb ceramic with water until the washing liquid is neutral, drying the honeycomb ceramic in an oven at 105 ℃, and then calcining the honeycomb ceramic in a muffle furnace at 750 ℃ for 4 hours.
(3) Metal active component loading
Immersing the fluorine-etched honeycomb ceramic treated in the step (2) in a 2mol/L cerium nitrate solution, placing the honeycomb ceramic in a shaking table, oscillating for 2 hours, taking out the honeycomb ceramic, drying the honeycomb ceramic in an oven at 105 ℃, and then calcining the honeycomb ceramic in a muffle furnace at 750 ℃ for 2 hours.
The water to be treated contains 1.3mg/L of cefalexin, the pH value of the solution is adjusted to 9.4, the adding amount of the catalyst is 55g/L, the adding amount of the ozone is 1.5mg/L, and the ozone reaction time is 9 min. After the ozone oxidation reaction, the concentration of the cefalexin in the water is 0.01 mg/L.
Example 6
(1) Pretreatment of honeycomb ceramics
The honeycomb ceramics (phi 35 multiplied by 20mm) are washed by tap water or deionized water and dried in an oven. And immersing the dried 300-mesh honeycomb ceramic into 1mol/L nitric acid solution, and placing the honeycomb ceramic in a shaking table for oscillation for 3 hours. Taken out and dried in an oven at 105 ℃, and then calcined in a muffle furnace at 600 ℃ for 3 h.
(2) Fluorine etching
Immersing the honeycomb ceramic treated in the step (1) in a 2mol/L sodium fluoride solution, placing the honeycomb ceramic in a shaking table, oscillating for 1h, taking out, ultrasonically washing the honeycomb ceramic with water until the washing liquid is neutral, drying the honeycomb ceramic in an oven at 105 ℃, and calcining the honeycomb ceramic in a muffle furnace at 500 ℃ for 3 h.
(3) Metal active component loading
Immersing the fluorine-etched honeycomb ceramic treated in the step (2) in a solution of 0.3mol/L cerium nitrate and 3mol/L manganese nitrate, placing the honeycomb ceramic in a shaking table, oscillating for 1 hour, taking out the honeycomb ceramic, drying the honeycomb ceramic in an oven at 105 ℃, and then calcining the honeycomb ceramic in a muffle furnace at 720 ℃ for 4.5 hours.
The water to be treated contains 5.3mg/L of 4-methylquinoline, the pH value is 8.1, the adding amount of ozone is 16mg/L, the adding amount of a catalyst is 105g/L, and the catalytic ozonation reaction time is 32 min. After treatment, the water contained 0.12mg/L of 4-methylquinoline.
Example 7
(1) Pretreatment of honeycomb ceramics
The honeycomb ceramics (phi 100 multiplied by 100mm) is cleaned by tap water or deionized water and dried in an oven. The dried 300-mesh honeycomb ceramic is immersed in 2.5mol/L nitric acid solution and placed in a shaking table to be shaken for 2 h. Taken out and dried in an oven at 105 ℃, and then calcined in a muffle furnace at 400 ℃ for 3 h.
(2) Fluorine etching
Immersing the honeycomb ceramic treated in the step (1) in a potassium fluoride solution of 3mol/L, placing the honeycomb ceramic in a shaking table, oscillating for 1h, taking out, ultrasonically washing the honeycomb ceramic with water until the washing liquid is neutral, drying the honeycomb ceramic in an oven at 105 ℃, and then calcining the honeycomb ceramic in a muffle furnace at 600 ℃ for 2 h.
(3) Metal active component loading
Immersing the fluorine-etched honeycomb ceramic treated in the step (2) in a solution of 4.5mol/L magnesium nitrate, 2mol/L ferric nitrate and 0.6mol/L lanthanum nitrate, placing the honeycomb ceramic in a shaking table, oscillating for 2 hours, taking out the honeycomb ceramic, drying the honeycomb ceramic in an oven at 105 ℃, and then calcining the honeycomb ceramic in a muffle furnace at 700 ℃ for 5 hours.
The water to be treated contains 11mg/L of carboxymethyl cellulose, the pH of the solution is adjusted to 6.7, the adding amount of the catalyst is 178g/L, the adding amount of ozone is 29mg/L, and the reaction time of the catalytic ozone is 47 min. After the catalytic ozone oxidation reaction, the concentration of the carboxymethyl cellulose is 2.4 mg/L.
Example 8
(1) Pretreatment of honeycomb ceramics
The honeycomb ceramics (phi 35 multiplied by 30mm) are washed by tap water or deionized water and dried in an oven. And immersing the dried 300-mesh honeycomb ceramic into 3mol/L nitric acid solution, and placing the honeycomb ceramic in a shaking table for 2 hours. Taken out and dried in an oven at 105 ℃, and then calcined in a muffle furnace at 600 ℃ for 2 h.
(2) Fluorine etching
Immersing the honeycomb ceramic treated in the step (1) in 5.0mol/L ammonium fluoride solution, placing the honeycomb ceramic in a shaking table, oscillating for 4 hours, taking out the honeycomb ceramic, ultrasonically washing the honeycomb ceramic with 1mol/L NaOH solution until the washing liquid is neutral, drying the honeycomb ceramic in a 105 ℃ oven, and calcining the honeycomb ceramic in a muffle furnace at 750 ℃ for 3 hours.
(3) Metal active component loading
Immersing the fluorine-etched honeycomb ceramic treated in the step (2) in 3mol/L magnesium nitrate and 1mol/L ytterbium nitrate solution, placing the honeycomb ceramic in a shaking table, oscillating for 4 hours, taking out the honeycomb ceramic, drying the honeycomb ceramic in a 105 ℃ oven, and calcining the honeycomb ceramic in a muffle furnace at 650 ℃ for 3 hours.
0.11mg/L of volatile phenol in the water to be treated, the pH value of the solution is adjusted to 9.3, the adding amount of the catalyst is 60g/L, the adding amount of the ozone is 2.7mg/L, and the reaction time of the catalytic ozone is 10 min. After the catalytic ozone oxidation reaction, the concentration of volatile phenol in water is 0.001 mg/L.
Example 9
(1) Pretreatment of honeycomb ceramics
The honeycomb ceramics (phi 35 multiplied by 30mm) are washed by tap water or deionized water and dried in an oven. And immersing the dried 300-mesh honeycomb ceramic into a 3mol/L nitric acid solution, and placing the honeycomb ceramic in a shaking table for oscillation for 1 h. Taken out and dried in an oven at 105 ℃, and then calcined in a muffle furnace at 500 ℃ for 2 h.
(2) Fluorine etching
Immersing the honeycomb ceramic treated in the step (1) in a 2.5mol/L potassium fluoride solution, placing the honeycomb ceramic in a shaking table, oscillating for 1h, taking out, ultrasonically washing the honeycomb ceramic until the washing liquid is neutral, drying the honeycomb ceramic in an oven at 105 ℃, and then calcining the honeycomb ceramic in a muffle furnace at 750 ℃ for 1.5 h.
(3) Metal active component loading
Immersing the fluorine-etched honeycomb ceramic treated in the step (2) in a 4.1mol/L ferric nitrate and 0.18mol/L lanthanum nitrate solution, placing the honeycomb ceramic in a shaking table, oscillating for 5 hours, taking out, drying in an oven at 105 ℃, and then calcining for 4 hours in a muffle furnace at 600 ℃.
1.6mg/L of anthraquinone is contained in the water to be treated, the pH value of the solution is adjusted to 8.1, the adding amount of the catalyst is 64g/L, the adding amount of the ozone is 8mg/L, and the reaction time of the catalytic ozone is 52 min. After the catalytic ozone oxidation reaction, the concentration of anthraquinone in water is 0.11 mg/L.
Example 10
(1) Pretreatment of honeycomb ceramics
The honeycomb ceramics (phi 60 multiplied by 30mm) is cleaned by tap water or deionized water and dried in an oven. And immersing the dried 300-mesh honeycomb ceramic into 2mol/L nitric acid solution, and placing the honeycomb ceramic in a shaking table for 2 hours. Taken out and dried in an oven at 105 ℃ and then calcined in a muffle furnace at 600 ℃ for 1 h.
(2) Fluorine etching
Immersing the honeycomb ceramic treated in the step (1) in a 5mol/L sodium fluoride solution, placing the honeycomb ceramic in a shaking table, oscillating for 1h, taking out, ultrasonically washing the honeycomb ceramic with water until the washing liquid is neutral, drying the honeycomb ceramic in an oven at 105 ℃, and calcining the honeycomb ceramic in a muffle furnace at 600 ℃ for 3 h.
(3) Metal active component loading
Immersing the fluorine-etched honeycomb ceramic treated in the step (2) in a solution of 4mol/L manganese nitrate, 2mol/L ferric nitrate and 0.1mol/L cerium nitrate, placing the honeycomb ceramic in a shaking table, oscillating for 5 hours, taking out, drying the honeycomb ceramic in an oven at 105 ℃, and calcining for 1 hour at 740 ℃ in a muffle furnace.
The water to be treated contains 0.52mg/L of 2,4, 6-trichlorophenol, the pH value of the solution is adjusted to 6.6, the adding amount of the catalyst is 110g/L, the adding amount of the ozone is 2.5mg/L, and the reaction time of the catalytic ozone is 16 min. After the catalytic ozone oxidation reaction, the concentration of the 2,4, 6-trichlorophenol in the water is 0.12 mg/L.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a honeycomb ceramic etching supported catalyst is characterized by comprising the following steps:
(1) pretreatment of honeycomb ceramics
Washing the honeycomb ceramic with water, drying, soaking in 0.2-5 mol/L nitric acid solution for 1-2 h, taking out, drying, and calcining at 300-750 ℃ for 1-5 h to obtain pretreated honeycomb ceramic;
(2) honeycomb ceramic etching
Putting the pretreated honeycomb ceramic into a fluoride solution for corrosion for 1-7 h, taking out, washing with an alkali solution or water to be neutral, drying, and calcining at 300-750 ℃ for 1-5 h to obtain etched honeycomb ceramic;
the concentration of fluoride in the fluoride solution is 0.1-5 mol/L, and the fluoride is one or more of ammonium fluoride, sodium fluoride and potassium fluoride;
(3) active ingredient loading
And soaking the etched honeycomb ceramic into a nitrate solution of an active component, taking out, drying and calcining to obtain the honeycomb ceramic etching supported catalyst.
2. The preparation method according to claim 1, wherein in the step (1), the mesh number of the honeycomb ceramic is 100-400 meshes.
3. The method according to claim 1, wherein in the step (3), the nitrate in the nitrate solution is at least one of manganese nitrate, iron nitrate, magnesium nitrate, lanthanum nitrate, cerium nitrate and ytterbium nitrate.
4. The preparation method according to claim 1, wherein in the step (3), the concentration of the nitrate in the nitrate solution is 0.1 to 5 mol/L.
5. The preparation method according to claim 1, wherein in the step (3), the calcining temperature is 300-750 ℃ and the calcining time is 1-5 h.
6. The honeycomb ceramic etching supported catalyst prepared by the preparation method of any one of claims 1 to 5.
7. Use of the honeycomb ceramic etching supported catalyst of claim 6 in the catalytic ozonation treatment of water.
8. A method for treating organic pollutants in water is characterized by comprising the following steps: adding the honeycomb ceramic etching supported catalyst of claim 6 into a catalytic oxidation reactor, and then adding water containing organic pollutants into the catalytic oxidation reactor, and simultaneously adding ozone to carry out ozone catalytic oxidation reaction.
9. The treatment method according to claim 8, wherein the pH of the water containing organic contaminants is 5 to 10.
10. The treatment method according to claim 8, wherein the honeycomb ceramic etching supported catalyst is added in an amount of 50-200 g/L of water, the ozone is added in an amount of 1-1000 mg/L of water, the retention time of the water containing organic pollutants in the catalytic oxidation reactor is 1-240 min, and the ozone catalytic oxidation reaction is carried out at normal temperature and normal pressure.
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