CN110871060B - Foamed ceramic carrier, titanium dioxide photocatalyst and preparation method thereof - Google Patents
Foamed ceramic carrier, titanium dioxide photocatalyst and preparation method thereof Download PDFInfo
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- CN110871060B CN110871060B CN201811005071.5A CN201811005071A CN110871060B CN 110871060 B CN110871060 B CN 110871060B CN 201811005071 A CN201811005071 A CN 201811005071A CN 110871060 B CN110871060 B CN 110871060B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 239000000919 ceramic Substances 0.000 title claims abstract description 122
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 96
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 91
- 239000002131 composite material Substances 0.000 claims abstract description 66
- 239000002002 slurry Substances 0.000 claims abstract description 52
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 41
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 239000006260 foam Substances 0.000 claims abstract description 28
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002791 soaking Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 85
- 238000000034 method Methods 0.000 claims description 52
- 239000013078 crystal Substances 0.000 claims description 46
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 25
- 238000005470 impregnation Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 23
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052719 titanium Inorganic materials 0.000 claims description 22
- 239000010936 titanium Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 239000003292 glue Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 239000005995 Aluminium silicate Substances 0.000 claims description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000007581 slurry coating method Methods 0.000 claims description 4
- TYKCBTYOMAUNLH-MTOQALJVSA-J (z)-4-oxopent-2-en-2-olate;titanium(4+) Chemical group [Ti+4].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O TYKCBTYOMAUNLH-MTOQALJVSA-J 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000001699 photocatalysis Effects 0.000 abstract description 37
- 238000007146 photocatalysis Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 description 20
- 239000000758 substrate Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 241000191963 Staphylococcus epidermidis Species 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000000356 contaminant Substances 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000007619 statistical method Methods 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- 238000009423 ventilation Methods 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000003491 array Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011538 cleaning material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8634—Ammonia
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses a foamed ceramic carrier and a foamed ceramic carrier loaded TiO 2 A photocatalyst and a preparation method thereof. The foamed ceramic carrier comprises foamed ceramic and composite oxide, the foamed ceramic is of an open-cell foam structure, three-dimensional through micron-sized pore channels are contained in pore edges of the foamed ceramic, and the composite oxide is distributed on the surfaces of the pore edges and in the pore channels. The preparation method of the foamed ceramic carrier comprises the following steps: and (3) soaking the foam ceramic in the composite oxide precursor slurry to prepare the foam ceramic carrier. The TiO prepared by the foamed ceramic carrier 2 The photocatalyst has high photocatalytic activity, titanium dioxide is not easy to lose, and the activity stability is good, so that the photocatalyst is particularly suitable for purifying gas or liquid by photocatalysis.
Description
Technical Field
The invention relates to a foamed ceramic carrier, a titanium dioxide photocatalyst and a preparation method thereof, in particular to a foamed ceramic carrier-loaded titanium dioxide photocatalyst and a preparation method thereof, belonging to the field of photocatalytic materials.
Background
Semiconductor photocatalytic oxidation is a novel technology that can decompose organic substances into carbon dioxide and water through photocatalysis at normal temperature and normal pressure, and does not cause secondary pollution, and thus has attracted great attention from researchers in various countries in the world. Researches show that various organic pollutants in water and air can be effectively degraded by utilizing a semiconductor photocatalysis method, such as halogenated hydrocarbon, nitroaromatic, phenol, organic pigment, pesticide, surfactant and the like; cyanide, nitrite, thiocyanate and the like can also be converted into non-toxic or low-toxic compounds; can also be applied to the fields of antibiosis, deodorization, air purification, self-cleaning materials and the like. Eyes of a personThe semiconductor photocatalysts which have been studied previously mainly include metal oxides, sulfides and the like, among which titanium dioxide (TiO) 2 ) Has the characteristics of good chemical stability, safety, no toxicity, low cost and the like, and is widely researched and applied in the photocatalytic oxidation direction.
The titanium dioxide photocatalyst is generally used in the form of powder, but this causes a suspension system in a fluid, thereby causing technical problems of difficulty in separation and difficulty in recovery, and thus limiting practical use. The titanium dioxide is fixed on the carrier, so that the defect of the suspension phase titanium dioxide photocatalyst can be overcome. Therefore, finding a suitable carrier and an efficient loading method to fix the catalyst and improve the photocatalytic efficiency of the catalyst are key points in realizing the industrialization of the titanium dioxide photocatalyst, and are hot spots in the research field of the photocatalytic technology in recent years.
At present, when a ceramic carrier is adopted as a carrier material, a titanium dioxide loading method is generally adopted as a titanium glue loading method or a method of adding titanium oxide crystal grains into a binder loading method, and then the titanium oxide crystal grains are sintered at high temperature to prepare the supported photocatalyst. The ceramic supported photocatalyst has the technical problems that: first, the use of non-catalytic materials such as binders can affect the amount of titanium dioxide on the surface during loading and sintering, thereby affecting catalytic activity; secondly, when the ceramic carrier is loaded with titanium dioxide, high-temperature roasting is generally adopted to increase the firmness of the titanium dioxide load, but the titanium dioxide is easy to be sintered and generates a crystal phase with non-photocatalytic activity, so that the catalytic activity is influenced, and the problem that the titanium dioxide is easy to run off even if the titanium dioxide is roasted at high temperature, so that the activity stability of the catalyst is influenced; thirdly, the ceramic carrier is easy to have a problem of uneven distribution when loading titanium dioxide, thereby further influencing the catalytic activity and stability of the ceramic carrier.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a foamed ceramic carrier, a titanium dioxide photocatalyst and a preparation method thereof. The catalyst has high photocatalytic activity, and the titanium dioxide is not easy to run off and has good activity stability.
The foamed ceramic carrier provided by the first aspect of the invention comprises foamed ceramic and composite oxide, wherein the foamed ceramic is an open-cell foam structure, the pore edges of the foamed ceramic contain three-dimensional through micron-sized pore channels, the surface of the pore edges and the interior of the pore channels are distributed with the composite oxide, and preferably, at least part of the composite oxide is embedded in and/or penetrates through the pore channels.
In the foamed ceramic carrier of the present invention, the composite oxide comprises alumina and titania, and may be a homogeneously distributed composite oxide or a heterogeneously distributed composite oxide, and preferably, the titania content on the surface of the carrier is higher than the titania content in the interior of the carrier. The composite oxide accounts for 10-50% of the weight of the foamed ceramic carrier, and the weight content of titanium oxide in the composite oxide is 10-90%.
The alumina in the composite oxide is preferably gamma-Al 2 O 3 The composite oxide obtained by low-temperature roasting is further preferably adopted, and the roasting temperature of the low-temperature roasting is 400-700 ℃, and the preferred roasting temperature is 450-700 ℃.
In the foamed ceramic carrier of the present invention, the foamed ceramic may be conventional foamed ceramic used for photocatalyst carriers, and the composition thereof may include one or more of alumina, zirconia, silicon carbide and silica, preferably alumina, and the alumina is α -Al 2 O 3 。
In the foamed ceramic carrier, the open porosity of the foamed ceramic is 40-90%, preferably 60-80%, the diameter of a pore is 1-5 mm, the pore density is 8-60 ppi, and preferably 8-30 ppi.
In the foamed ceramic carrier, the pore edges of the foamed ceramic have three-dimensional through micron-sized pore channels. The pore volume of the foamed ceramic is 0.1-0.5 mL/g, the pore volume occupied by the pore diameter of less than 20 mu m is less than 20% of the total pore volume, the pore volume occupied by the pore diameter of 20-80 mu m is 50-95% of the total pore volume, and the pore volume occupied by the pore diameter of more than 80 mu m is less than 10% of the total pore volume. The pore volume and the pore distribution of the foamed ceramic are micropore parameters measured by a mercury intrusion method. The outer surface of the foamed ceramic is provided with micron-sized pore openings which are uniformly distributed, and the diameters of the pore openings can be 1-100 mu m.
The composite oxide can also contain modification aids such as silicon, zirconium, magnesium, calcium, manganese and the like, and the content of the modification aids in terms of oxides accounts for less than 15 percent of the weight of the foamed ceramic carrier.
The invention provides a foamed ceramic carrier loaded with TiO in a second aspect 2 The photocatalyst adopts the foamed ceramic carrier provided by the first aspect and TiO distributed on the surface of the foamed ceramic carrier 2 Crystal grain of TiO 5-50 μm in particle size 2 The crystal grains account for 70% or more, preferably 80% or more, and more preferably TiO with a particle size of 15 to 45 μm 2 The crystal grains account for 70% or more, preferably 80% or more.
In the catalyst of the present invention, TiO is used as a catalyst support 2 The total content of (A) is 5 to 40%, preferably 8 to 35%.
In the catalyst of the invention, the weight of the titanium dioxide contained in the composite oxide in the foamed ceramic carrier accounts for the weight of the TiO in the catalyst 2 5 to 50 percent of the total weight.
In the catalyst of the present invention, the TiO 2 Mainly anatase type.
The third aspect of the invention provides a method for preparing a foamed ceramic carrier, which comprises the following steps: and (3) soaking the foam ceramic into the composite oxide precursor slurry to prepare the foam ceramic carrier.
In the preparation method of the foam ceramic carrier, the composite oxide precursor slurry comprises the following components: nano titanium dioxide powder, alumina dry glue powder, peptizing acid, kaolin and water, wherein the nano titanium dioxide powder comprises the following components in percentage by weight: the alumina dry glue powder is calculated by alumina: peptizing acid: kaolin: the weight ratio of water is 1-9: 10: 1-5: 0.1 to 0.7: 3.0-10.0, wherein the alumina dry glue powder is dry powder obtained by drying aluminum hydroxide precipitate and can be prepared by a conventional neutralization method, an alcoholysis method and the like. The peptization acid can be one or more of inorganic acids such as nitric acid, hydrochloric acid and the like. Polyethylene glycol is preferably added into the composite oxide precursor slurry, and the addition amount of the polyethylene glycol accounts for 1-3% of the weight of the composite oxide precursor slurry. The molecular weight of the polyethylene glycol is 200-4000. The particle size of the nano titanium dioxide powder is less than 100nm, and preferably 10-100 nm.
In the preparation method of the foamed ceramic carrier, the method for impregnating the composite oxide precursor slurry by the foamed ceramic can adopt a vacuum impregnation method, and can adopt one or more times of impregnation, preferably multiple times of impregnation, when multiple times of impregnation are adopted, the composite oxide precursor slurry can be the same or different, and the content of the nano titanium dioxide in the slurry subjected to the subsequent impregnation is preferably higher than that in the slurry subjected to the prior impregnation. After each impregnation, the excess slurry is removed, the slurry in the large pore passage is removed by blowing, and then the drying treatment is carried out. And finally, drying for the first time and roasting to obtain the foamed ceramic carrier. The drying can be carried out at room temperature, and then the drying is carried out for 4-24 hours at the temperature of 40-90 ℃. The roasting can be performed in multiple stages by adopting a temperature programming mode, wherein the roasting is performed for 1-8 hours at 200-300 ℃, then for 1-6 hours at 400-700 ℃, preferably for 2-8 hours at 200-300 ℃, and for 2-5 hours at 450-700 ℃.
In the preparation method of the foamed ceramic carrier, the composite oxide precursor slurry used in the last impregnation is preferably prepared by mixing the nano titanium dioxide and the polyethylene glycol, and then mixing the mixture with the alumina dry glue powder, the peptized acid and the water, so that at least part of the polyethylene glycol enters the nano titanium dioxide, more surfaces of the nano titanium dioxide are exposed outside the carrier in the subsequent treatment process, an easily enriched area is formed, the post-loaded titanium dioxide is more easily distributed around the nano titanium dioxide, the dispersity and the dispersion amount of the titanium dioxide on the surface of the carrier are improved, the size of titanium dioxide grains can be better controlled, the firmness of the titanium dioxide in the catalyst is improved, and the activity and the stability of the catalyst are further improved.
The invention provides a foamed ceramic carrier loaded with TiO in the fourth aspect 2 A method of preparing a photocatalyst, comprising:
(1) preparing titanium sol;
(2) immersing the foamed ceramic carrier into the titanium sol obtained in the step (1) for slurry coating, removing excessive slurry, drying,
(3) repeating the dipping process for 0-5 times, preferably 1-4 times;
(4) and (4) carrying out heat treatment on the material obtained in the step (3) to obtain the photocatalyst.
In the method of the present invention, the titanium sol prepared in step (1) can be prepared by a conventional method, and preferably, the following method is adopted: dissolving the titanium oxide precursor in an organic solvent, and uniformly mixing to obtain the titanium sol. The titanium oxide precursor may be titanium (IV) acetylacetonate.
In the step (1) of the method, carboxymethyl cellulose is preferably added in the mixing process, and the molar ratio of the addition amount of the carboxymethyl cellulose to titanium atoms is 1-7: 100.
in step (1) of the method of the present invention, the organic solvent is a lower alcohol, such as an alcohol having a carbon number of from 1 to 5, preferably one or more of methanol, ethanol, and propanol, and more preferably isopropanol. The molar concentration of titanium in the titanium sol is 0.5-4.0 mol/L.
In the method, the slurry coating and the excess slurry removal in the step (2) can be carried out by adopting a conventional method, for example, the slurry coating by adopting an immersion method, normal pressure immersion or vacuum immersion, and the excess slurry removal by adopting a roll pressing method is adopted.
In the method, the drying in the step (2) is carried out for 4-24 hours at the temperature of 50-95 ℃.
In the method of the present invention, the heat treatment conditions in step (4) are as follows: in the presence of water vapor and/or inert gas, roasting in sections, namely roasting at 200-300 ℃ for 3-8 hours, then roasting at 400-750 ℃ for 1-6 hours, preferably roasting at 200-300 ℃ for 3-8 hours, and roasting at 450-700 ℃ for 2-5 hours. The inert gas may be nitrogen.
The foamed alumina-based carrier of the invention loads TiO 2 The application of photocatalyst, the photocatalyst can be used for the purification treatment of gas or liquid (such as waste water), is particularly suitable for the photocatalytic reaction under the action of ultraviolet light, and the purification is to remove organic matters.
The foamed alumina-based carrier of the invention loads TiO 2 The photocatalyst can remove various Volatile Organic Compounds (VOC) such as toluene, xylene, benzene, formaldehyde, acetaldehyde and homologues thereof, can also remove various sulfur and nitrogen-containing gases such as sulfur dioxide, hydrogen sulfide, ammonia and the like, and can also play a role in sterilization. The foamed alumina-based carrier of the invention loads TiO 2 The photocatalyst can be used for purifying indoor air, industrial polluted gas and haze pollutants, has good photocatalytic degradation performance, is stable in performance, and has good application prospect.
The foamed alumina-based carrier of the invention loads TiO 2 The photocatalyst is made into a convenient and practical photocatalytic unit according to application conditions, can be applied to the existing electrical equipment, such as an air purifier, a refrigerator, an air conditioner and the like, can also be applied to pipelines with gas flowing, such as air exhaust, ventilation equipment, tail gas emission equipment, ventilation equipment and the like, and can also be used for transportation tools, such as automobiles, cruise ships, submarines, airplanes and the like.
A fifth aspect of the present invention provides a photocatalytic unit, including:
the photocatalyst of the present invention is a photocatalyst,
an ultraviolet light source device having a light emitting portion facing a photocatalyst.
The photocatalyst adopts a photocatalyst plate, the ultraviolet light source device adopts an ultraviolet LED lamp panel, one surface or two surfaces of the photocatalyst plate are provided with the ultraviolet LED lamp panels, and further, the ultraviolet LED lamp panels are symmetrically arranged on the two surfaces of the photocatalyst plate. The photocatalyst plate and the ultraviolet LED lamp plate are arranged in parallel.
In the ultraviolet light source device, an ultraviolet LED lamp panel comprises a substrate and a plurality of LED ultraviolet light-emitting particles arranged on the substrate, namely a Uv-LED point light source.
In the ultraviolet light source device, the LED ultraviolet light-emitting particles on the ultraviolet LED lamp panel can be arranged in an array form, the vent holes can be arranged between the adjacent arrays, or the vent holes are not arranged, namely, a non-porous entity is arranged between the adjacent arrays, and the arrangement is determined according to the use condition.
The substrate can be in a fence type, namely LED ultraviolet light-emitting particles which can be arranged in an array mode are arranged on the fence strips, and vent holes are formed among the fence strips. The ultraviolet LED lamp plate can set up the LED lamp simultaneously, also can both sides set up the LED lamp.
In the photocatalysis unit, N photocatalyst boards are arranged, ultraviolet LED lamp panels are arranged on two sides of each photocatalyst board and are arranged in parallel, wherein N is an integer larger than or equal to 1. The ultraviolet LED lamp panels arranged between the two adjacent photocatalyst boards are back to back and arranged on the two ultraviolet LED lamp panels of the single-sided LED lamp, and one ultraviolet LED lamp panel of the double-sided LED lamp can be selected.
The photocatalytic unit also comprises a fixing frame for fixing the photocatalyst plate and the ultraviolet LED lamp plate.
The sixth aspect of the invention provides a gas purification method, which can adopt a photocatalytic unit, wherein the gas to be purified passes through the photocatalytic unit to perform photocatalytic reaction under the action of ultraviolet light and a catalyst, so as to obtain purified gas.
In the photocatalysis method of the invention, the air inlet direction of the gas to be purified can be adjusted according to the requirement, and the air can be vertically fed, obliquely fed and the like.
In the photocatalysis method of the invention, N photocatalysis units can be adopted, and the N photocatalysis units can be arranged in parallel or in series. The plurality of photocatalytic units can be arranged in a flat plate shape or in a V shape. The arrangement modes of the N photocatalytic units can be the same or different.
In the photocatalysis method, the wavelength of ultraviolet light emitted by the ultraviolet LED lamp is 280-390 nm, which can be a single wavelength or a mixed wavelength, and is preferably a single wavelength, such as 365 nm.
In the photocatalysis method, the distance between the ultraviolet LED lamp panel and the photocatalyst plate is 0-10 cm. Further, the thickness is 0 to 5cm, preferably 0.5 to 3.5 cm. Further, the thickness of the photocatalyst plate can be 0.3-3.0 cm.
In the photocatalytic method of the present invention, the radiation on the photocatalyst plateThe intensity is 0.01-500 mW/cm 2 Preferably 0.5-70 mW/cm 2 。
In the photocatalysis method of the invention, the gas to be purified is the gas containing volatile organic pollutants and/or sulfur and nitrogen-containing gas, such as indoor air, industrial gas and the like.
Compared with the prior art, the photocatalyst has the following advantages:
1. for a unit amount of TiO 2 The smaller the crystallite size, the larger the specific surface area, the higher the catalytic activity, while the smaller the crystallite size, the less easy to support, and even if supported, the loss or coverage by inactive components is likely to occur, thereby affecting the activity and stability of the catalyst. The inventor finds that the TiO through a large amount of experiments 2 The crystal grains grow on the foamed ceramic carrier in proper micron size and form high active phase titania, which is favorable to decomposing organic matter under the catalysis of ultraviolet light and has high activity 2 The base of the crystal grain is integrated with the foamed ceramic carrier, and the TiO can be greatly improved by the structure 2 Fixed strength of grains, TiO 2 Crystal grains are not easy to lose, and TiO is also used 2 The crystal grains have smooth crystal faces and are not easily covered by inactive components, so that the stability of the catalyst is greatly improved.
The photocatalyst has the advantages of higher specific surface area, higher mechanical strength, higher aperture ratio and good adsorption and desorption performance, and meanwhile, TiO 2 The crystal grains are distributed on the surface of the carrier in proper micron-sized sizes, so that the contact chance of the crystal grains with organic matters in water or gas is increased, and the photocatalyst has higher photocatalytic reaction activity.
2. The foamed ceramic carrier adopts an open-cell foam structure, three-dimensional through micron-sized pore channels are distributed in pore edges of the foamed ceramic, composite oxides are distributed on the surfaces of the pore edges and in the pore channels of the foamed ceramic, at least one part of the composite oxides are embedded and/or penetrated through the pore channels, and the main crystal phase of the composite oxides is gamma-Al 2 O 3 So that on the one hand it is sufficientBy utilizing the connectivity of the open-cell foamed ceramic cell channels, on the other hand, the micron-sized pore channels in the pore edges are fully utilized, and the composite oxide is embedded or penetrated according to the trend of micropores, so that not only can the strength of the foamed ceramic be enhanced and larger external specific surface area be provided, but also when titanium sol is subsequently utilized to load titanium dioxide, low-temperature roasting can be adopted, the growth and aggregation of titanium dioxide crystal grains can be easily carried out on the basis of the composite oxide, the micron-sized crystal grains with uniformly distributed and high active phase are formed, the base part of the micron-sized crystal grains and a foamed ceramic carrier are integrated, and the TiO can be improved 2 The firmness of the photocatalyst improves the stability of the photocatalyst.
3. The heat treatment is preferably carried out by staged heat treatment with steam and/or inert gas to promote the formation of suitable TiO 2 Grain growth, and improvement of TiO 2 The dispersion degree of crystal grains on the surface of the carrier is improved, and TiO is also improved 2 The pore structure on the carrier promotes the contact area of water or gas and the photocatalyst easily, and simultaneously, the water or gas can rapidly pass through the photocatalyst, thereby improving the treatment efficiency.
Drawings
FIG. 1 shows a TiO supported foamed alumina-based carrier according to the present invention 2 An appearance view of the photocatalyst;
FIG. 2 is a 500-fold enlarged view of a foamed alumina-based carrier A of the present invention by a scanning electron microscope;
FIG. 3 is an enlarged cross-sectional view of a photocatalyst according to the present invention; wherein, 1-TiO 2 Crystalline, 2-photocatalyst;
FIG. 4 is an XRD pattern of catalyst A obtained in example 1;
fig. 5 is a schematic view of an ultraviolet LED lamp panel according to an embodiment of the present invention, where the lamp panel includes a 3-ultraviolet LED lamp panel, a 31-substrate, 32-LED ultraviolet light-emitting particles, and 33-vents;
FIG. 6 is a schematic view of a photocatalytic unit according to an embodiment of the present invention; the LED light source comprises 4-a photocatalytic unit, 3-an ultraviolet LED lamp panel, 5-a photocatalyst plate and 6-a fixed frame;
FIG. 7 is a schematic view of a device for testing the performance of a photocatalytic unit of the catalyst of the present invention; wherein, 4-the photocatalytic unit, 7-the wind channel.
Detailed Description
The technical solution of the present invention is described in detail below with reference to examples, but the scope of the present invention is not limited by the examples. In the present invention, wt% is a mass fraction.
In the present invention, TiO is used 2 The crystal form of the crystal is measured by an XRD method, the instrument is a Rigaku D/max-2500X-ray diffractometer, a Cu target (0.15406nm) is adopted, graphite single crystal filtering is adopted, the operating tube voltage is 40kV, the tube current is 30mA, the scanning step length is 0.026 degrees, and the scanning range is 5-70 degrees.
In the present invention, on the surface of the catalyst, TiO 2 The grain size and grain distribution are measured with scanning electron microscope, observed with Hitachi X650 scanning electron microscope, operating voltage 15kV, nitrogen protection and intermittent gold spraying.
In the catalyst of the present invention, TiO 2 The content of (b) is measured by a chemical method. In the support of the invention, TiO 2 The content of (B) is measured by a chemical method.
In the present invention, the open cell content of the organic foam and the foamed alumina-based support is determined according to ASTM D6226-2005, the pore density is expressed in terms of number of pores per inch of length, in ppi.
As shown in fig. 5, the ultraviolet LED lamp panel 3 includes a substrate 31 and a plurality of ultraviolet LED light emitting particles 32 disposed on the substrate 31, and the substrate 31 is further provided with a vent 33. The shape of the lamp panel 3 may be square, and as an alternative embodiment, may also be square, circular, oval or other shapes. The shape of the vent hole 33 is rectangular. As an alternative embodiment, a square, circular, oval or other shape is also possible. It should be understood that the shapes of the ultraviolet LED lamp panel 3 and the ventilation holes 33 can be determined by those skilled in the art according to the needs and the use place, the ventilation requirement, and the like, and the invention is not limited thereto. The ultraviolet LED luminescent particles 32 are arranged in an array on the substrate, with vents 33 between adjacent arrays. The substrate 31 is of a fence type, that is, the fence bars are provided with LED ultraviolet light emitting particles which are arranged in an array manner, and ventilation holes 33 are formed between the fence bars. The number of the ultraviolet LED luminescent particles 32 can be adjusted according to the illumination intensity required by the photocatalyst.
As shown in fig. 6, the photocatalytic unit 4 includes an ultraviolet LED lamp panel 3, a photocatalyst panel 5, and a fixing frame 6. Wherein, two ultraviolet LED lamp panels 3 are respectively arranged on two sides of the photocatalyst plate 5 in parallel, and the photocatalyst plate 5 and the ultraviolet LED lamp panels 3 are fixed by adopting a fixing frame 6 to form a photocatalytic unit 4.
The foam ceramics used in the examples of the present invention and the comparative examples were alpha-Al 2 O 3 The hole edges of the foamed ceramic are provided with three-dimensional through micron-sized pore channels, and the diameter of an orifice on the outer surface of the foamed ceramic is 1-100 micrometers.
The preparation process of the titanium sol is as follows: adding titanium (IV) acetylacetonate solid powder and carboxymethyl cellulose into isopropanol, and uniformly mixing to obtain a titanium sol with the titanium molar concentration of 3mol/L, wherein the molar ratio of the addition amount of the carboxymethyl cellulose to titanium atoms is 3: 100.
example 1
According to the nano titanium dioxide powder (the particle size is less than 100nm, the same is as below): alumina dry glue powder (in alumina): peptizing acid: kaolin: the weight ratio of water is 1.5: 10: 2.5: 0.4: 6.0, mixing to prepare composite oxide precursor slurry A1;
mixing nano titanium dioxide powder with polyethylene glycol 600, and then mixing with alumina dry glue powder, peptized acid and water according to the proportion of the nano titanium dioxide powder: alumina dry glue powder (in alumina): peptizing acid: kaolin: the weight ratio of water is 3: 10: 2.5: 0.3: 6.5, mixing to prepare composite oxide precursor slurry A2, wherein the addition of the polyethylene glycol accounts for 2% of the weight of the composite oxide precursor slurry;
the length of the foamed ceramic is 15cm, the width of the foamed ceramic is 15cm, the thickness of the foamed ceramic is 1cm, the opening rate of the foamed ceramic is 70%, the diameter of a pore of the foamed ceramic is 1-5 mm, and the pore density of the foamed ceramic is 10 ppi. The pore volume of the foamed ceramic is 0.31mL/g, the pore volume occupied by the pore diameter of less than 20 micrometers is 10% of the total pore volume, the pore volume occupied by the pore diameter of 20-80 micrometers is 80% of the total pore volume, and the pore volume occupied by the pore diameter of more than 80 micrometers is 10% of the total pore volume. The pore volume and the pore distribution of the foamed ceramic are micropore parameters measured by a mercury intrusion method. Vacuum impregnating composite oxide precursor slurry A1 in the foamed ceramic twice, drying for 6 hours at 70 ℃ after impregnation, then vacuum impregnating composite oxide precursor slurry A2, drying for 6 hours at 70 ℃, roasting for two sections, namely roasting for 4 hours at 200 ℃, and roasting for 3 hours at 650 ℃ to obtain a foamed ceramic carrier A; wherein the composite oxide accounts for 30 percent of the weight of the foamed ceramic carrier;
soaking the foamed ceramic carrier A into titanium sol for vacuum impregnation and slurry hanging, removing excessive slurry, drying at 70 ℃ for 6 hours, repeating the impregnation twice, then carrying out sectional roasting in the presence of water vapor and nitrogen, namely roasting at 200 ℃ for 4 hours, and then roasting at 650 ℃ for 3 hours to obtain the foamed ceramic carrier supported TiO 2 The photocatalyst A is a square plate. Wherein, in the catalyst A, TiO 2 The total content of (A) is 12%.
In the obtained catalyst A, TiO was measured by XRD 2 Mainly anatase, see fig. 3.
Foamed ceramic carrier loaded TiO 2 The graph of photocatalyst A magnified 500 times by an optical microscope is shown in FIG. 1, and it can be seen from FIG. 1 that TiO is on the outer surface of the catalyst 2 Distributed in small grains.
Measuring the prepared TiO on the surface of the catalyst by adopting a scanning electron microscope 2 Crystal grains and obtaining TiO by a statistical method 2 Grain size, wherein a representative catalyst surface is selected, the statistical area is about 20000 μm 2 Statistical TiO 2 The total number of crystal grains exceeds 500. The TiO with the particle size of 5-50 mu m accounting for 90 percent and the particle size of 15-45 mu m on the surface of the catalyst A is measured 2 The grains account for about 84%.
Observing the cross section of the catalyst by a scanning electron microscope, TiO 2 The crystal grains 1 are partially embedded in the catalyst 2, the non-embedded parts are distributed on the outer surface of the catalyst 2, the schematic diagram is shown in figure 2, and the observation of the pore edge parts shows that the three-dimensional through micron-sized pore channels of the pore edges of the foamed ceramic are embedded and penetrated with alumina and titanium oxide composite oxides.
Example 2
Preparing nano titanium dioxide powder: alumina dry glue powder (in alumina): peptizing acid: kaolin: the weight ratio of water is 2.0: 10: 2.0: 0.5: 6.0, preparing composite oxide precursor slurry B1;
mixing nano titanium dioxide powder with polyethylene glycol 600, and then mixing with alumina dry glue powder, peptized acid and water according to the proportion of the nano titanium dioxide powder: alumina dry glue powder (in alumina): peptizing acid: kaolin: the weight ratio of water is 2.5: 10: 2.5: 0.3: 6.5, mixing to prepare composite oxide precursor slurry B2, wherein the addition of the polyethylene glycol accounts for 2% of the weight of the composite oxide precursor slurry;
taking square foamed ceramic, wherein the length is 15cm, the width is 15cm, the thickness is 1cm, the opening rate is 70%, the diameter of a pore is 1-5 mm, and the pore density is 20 ppi. The pore volume of the foamed ceramic is 0.26mL/g, the pore volume occupied by the pore diameter of less than 20 micrometers is 8 percent of the total pore volume, the pore volume occupied by the pore diameter of 20-80 micrometers is 82 percent of the total pore volume, and the pore volume occupied by the pore diameter of more than 80 micrometers is 10 percent of the total pore volume. The pore volume and the pore distribution of the foamed ceramic are micropore parameters measured by a mercury intrusion method. Vacuum impregnating composite oxide precursor slurry B1 in the foamed ceramic twice, drying for 6 hours at 70 ℃ after impregnation, then vacuum impregnating composite oxide precursor slurry B2, drying for 6 hours at 70 ℃, roasting for two sections, namely roasting for 4 hours at 200 ℃, and roasting for 3 hours at 650 ℃ to obtain a foamed ceramic carrier B; wherein the composite oxide accounts for 30% of the weight of the foamed ceramic carrier;
soaking the foamed ceramic carrier B into the titanium sol for vacuum impregnation and slurry hanging, removing excessive slurry, drying for 6 hours at 70 ℃, repeatedly soaking twice, then roasting in sections in the presence of water vapor and nitrogen, namely roasting for 4 hours at 200 ℃, and then roasting for 3 hours at 650 ℃ to obtain the foamed ceramic carrier supported TiO 2 And the photocatalyst B is a square plate. Wherein, in the catalyst B, TiO 2 The total content of (A) is 15%.
In the obtained catalyst B, TiO was measured by XRD 2 Mainly anatase.
Measuring the prepared TiO on the surface of the catalyst by adopting a scanning electron microscope 2 Crystal grains and obtaining TiO by adopting a statistical method 2 Size of crystal grainWherein a representative catalyst surface is selected, and the statistical area is about 20000 mu m 2 Statistical TiO 2 The total number of crystal grains exceeds 500. The TiO with the particle size of 5-50 mu m accounting for 88% on the surface of the catalyst B and the particle size of 15-45 mu m is measured 2 The grain size is about 83%.
Observing the cross section of the catalyst by a scanning electron microscope, TiO 2 The crystal grains 1 are partially embedded in the catalyst 2, and the non-embedded part is distributed on the outer surface of the catalyst 2, and the schematic diagram is shown in figure 2; by observing the hole edge part, the aluminum oxide and titanium oxide composite oxide is embedded and penetrated in the three-dimensional through micron-sized pore canal of the foam ceramic hole edge
Example 3
Preparing nano titanium dioxide powder: alumina dry glue powder (in alumina): peptizing acid: kaolin: the weight ratio of water is 1.0: 10: 2.0: 0.5: 6.0, and preparing composite oxide precursor slurry C1.
Mixing nano titanium dioxide powder with polyethylene glycol 600, and then mixing with alumina dry glue powder, peptized acid and water according to the proportion of the nano titanium dioxide powder: alumina dry glue powder (in alumina): peptizing acid: kaolin: the weight ratio of water is 3.0: 10: 3.0: 0.3: 8.0, preparing composite oxide precursor slurry C2, wherein the addition amount of the polyethylene glycol accounts for 2.5 percent of the weight of the composite oxide precursor slurry;
the same procedure as in example 1 was repeated. Vacuum impregnating composite oxide precursor slurry C1 twice in the foamed ceramic, drying for 6 hours at 70 ℃ after impregnation, then vacuum impregnating composite oxide precursor slurry C2, drying for 6 hours at 70 ℃, roasting for two sections, namely roasting for 3 hours at 220 ℃, and roasting for 4 hours at 600 ℃ to obtain a foamed ceramic carrier C; wherein the composite oxide accounts for 25 percent of the weight of the foamed ceramic carrier;
soaking the foamed ceramic carrier C into titanium sol for vacuum impregnation and slurry hanging, removing excessive slurry, drying at 70 ℃ for 6 hours, repeating the impregnation twice, then carrying out sectional roasting in the presence of water vapor and nitrogen, namely roasting at 220 ℃ for 3 hours, and then roasting at 600 ℃ for 4 hours to obtain the foamed ceramic carrier supported TiO 2 And the photocatalyst C is a square plate. Wherein, in the catalyst C, TiO 2 The total content of (A) is 18%.
In the obtained catalyst C, TiO was measured by XRD 2 Mainly anatase.
Measuring the prepared TiO on the surface of the catalyst by adopting a scanning electron microscope 2 Crystal grains and obtaining TiO by adopting a statistical method 2 Grain size, wherein a representative catalyst surface is selected, the statistical area is about 20000 μm 2 Statistical TiO 2 The total number of crystal grains exceeds 500. The measured result shows that the TiO with the particle size of 5-50 mu m accounts for 89% and the particle size of 15-45 mu m on the surface of the catalyst C 2 The grains account for about 84%.
Observing the cross section of the catalyst by a scanning electron microscope, TiO 2 The crystal grains 1 are partially embedded in the catalyst 2, and the non-embedded parts are distributed on the outer surface of the catalyst 2, and the schematic diagram is shown in figure 2; by observing the hole edge part, the alumina and titanium oxide composite oxide is embedded and penetrated in the three-dimensional through micron-sized pore canal of the foam ceramic hole edge.
Comparative example 1
The ceramic foam support A of example 1 was replaced with the α -Al used in example 1 2 O 3 Foamed ceramic is used as the carrier DA. Soaking the carrier DA in titanium sol for vacuum impregnation and slurry hanging, removing excessive slurry, drying at 70 ℃ for 6 hours, repeating the impregnation twice, then roasting in the presence of water vapor and nitrogen in sections, namely roasting at 200 ℃ for 4 hours, and then roasting at 650 ℃ for 3 hours to obtain the foamed ceramic carrier supported TiO 2 And (3) a photocatalyst DA. In the catalyst DA, TiO 2 Is 10% of total content, TiO on the outer surface 2 The crystal grains are nano-scale titanium oxide.
Example 4
This embodiment is basically the same as embodiment 1, except that: adding no polyethylene glycol 600 into the composite oxide precursor slurry A2 to obtain the foamed ceramic carrier-supported TiO 2 And (3) a photocatalyst D. In the catalyst D, the mass content of titanium oxide was 12%.
In the obtained catalyst D, TiO was measured by XRD 2 Mainly anatase.
Measuring the prepared TiO on the surface of the catalyst by adopting a scanning electron microscope 2 Crystal grains and obtaining TiO by adopting a statistical method 2 Grain size, wherein a representative catalyst surface is selected, the statistical area is about 20000 μm 2 Statistical TiO 2 The total number of crystal grains exceeds 500. The TiO particles with the particle size of 5-50 mu m accounting for 85% and the particle size of 15-45 mu m on the surface of the catalyst D is measured 2 The grains account for about 81%.
Observing the cross section of the catalyst by a scanning electron microscope, TiO 2 The crystal grains are partially embedded into the catalyst, and the non-embedded parts are distributed on the outer surface of the catalyst, and the schematic diagram is shown in figure 2; by observing the hole edge part, the alumina and titanium oxide composite oxide is embedded and penetrated in the three-dimensional through micron-sized pore canal of the foam ceramic hole edge.
Example 5
This embodiment is basically the same as embodiment 1, except that: soaking the obtained carrier A into titanium sol for vacuum soaking and slurry hanging, removing excessive slurry, drying at 75 ℃ for 6 hours, and repeating the step for 1 time; then adopting single-stage roasting in the presence of water vapor and nitrogen, namely roasting at 650 ℃ for 5 hours to obtain the foam ceramic carrier supported TiO 2 And (3) a photocatalyst E. In the catalyst E, the mass content of titanium oxide was 12.0%.
In the obtained catalyst E, TiO was determined by XRD 2 Mainly anatase.
Measuring the prepared TiO on the surface of the catalyst by adopting a scanning electron microscope 2 Crystal grains and obtaining TiO by a statistical method 2 Grain size, wherein the statistical area is about 20000 μm 2 Statistical TiO 2 The total number of crystal grains exceeds 1000. The particle size of the catalyst E on the surface is 5-50 mu mTiO 2 TiO with grain size of 15-45 μm accounting for 84% 2 The grains account for about 80%.
Observing the cross section of the catalyst by a scanning electron microscope, TiO 2 The crystal grains are partially embedded into the catalyst, and the non-embedded parts are distributed on the outer surface of the catalyst, and the schematic diagram is shown in figure 2; universal jointAnd observing the hole edge part, and finding that the alumina and titanium oxide composite oxide is embedded and penetrated in the three-dimensional through micron-sized pore channel of the foam ceramic hole edge.
Example 6
The test is to test the photocatalytic performance of the photocatalyst A, wherein the test conditions are as follows:
(1) testing raw materials: air with toluene, xylene, benzene, ammonia, formaldehyde, acetaldehyde, sulfur dioxide, and hydrogen sulfide as contaminants was used as the test feed.
(2) Testing equipment: as shown in FIG. 6, the photocatalyst A is taken out to be made into a photocatalytic unit, and then the photocatalytic unit is fixed in an air duct with a fan of a corresponding specification to form a testing device, as shown in FIG. 7. The parameters of the photocatalyst A and the LED lamp are set as follows:
the photocatalyst a is plate-shaped: the length is 15cm, the width is 15cm, and the thickness is 1 cm;
the ultraviolet LED lamp panel comprises a substrate and 48 LED ultraviolet light-emitting particles on the substrate, the LED ultraviolet light-emitting particles are evenly distributed on the substrate in an array manner, 8 LED ultraviolet light-emitting particles are distributed on each array, 6 rows of the array are formed, and the appearance of the substrate is in a fence shape as shown in figure 5. The ultraviolet LED luminous particles face to the photocatalyst A, the wavelength of the emitted light is 365nm ultraviolet light, the length of the substrate is 15cm, the width of the substrate is 15cm, the two ultraviolet LED lamp panels are placed on the two sides of the photocatalyst A board in parallel, the distance between the two ultraviolet LED lamp panels is 2cm, and the single-side ultraviolet intensity on the photocatalyst A reaches 10m W/cm 2 ；
The cross section of the air duct is square, and the photocatalyst unit is hermetically placed in the air duct;
(3) test method and test conditions: preparing a sample experiment chamber and a blank experiment chamber;
the test device was placed at 1m 3 And sealing the sample experiment chamber, and filling pollutants into the experiment chamber. Starting the test equipment and the LED lamp, wherein the feeding speed is 0.5L/min, the test temperature is 26 ℃, the normal pressure is realized, the test time is 1 hour, and the results are shown in a table 1;
the blank experiment chamber and the sample experiment chamber are operated differently by only starting the test equipment and not starting the LED lamp, and the results are shown in table 1;
(4) the detection of the pollutant acetaldehyde is carried out according to GB/T18883-2002, the detection method of the benzene and the benzene series is carried out according to GB/T11737-1989, and the detection method of the formaldehyde is carried out according to GB/T18204.26-2000;
(5) the results of the catalyst sterilization test using a staphylococcus albus-containing gas as a raw material are shown in table 3.
Table 1 results of contaminant detection using catalyst a prepared in example 1
Examples 7 to 10
The detection method for contaminants purified and the detection method for sterilization were the same as in example 6 except that the catalyst samples were replaced with the catalysts B to E prepared in examples 2 to 5, respectively, and the results are shown in tables 2 and 3.
Comparative example 2
The detection method for contaminants purified and the detection method for sterilization were the same as in example 6 except that the catalyst sample was replaced with the catalyst DA prepared in comparative example 1, and the results are shown in tables 2 and 3.
Table 2 results of contaminant detection in the purification of catalyst prepared in examples 2 to 5 and comparative example 1
TABLE 3 test results of sterilization using catalysts prepared in examples and comparative examples
| Catalyst numbering | Testing microorganisms | Treatment time, 0h | Treatment time, 1h | Removal Rate (%) |
| Catalyst A | Staphylococcus albus | 6.5×10 4 | 85 | 99.87 |
| Catalyst B | Staphylococcus albus | 6.5×10 4 | 97 | 99.85 |
| Catalyst C | Staphylococcus albus | 6.5×10 4 | 92 | 99.86 |
| Catalyst D | Staphylococcus albus | 6.5×10 4 | 101 | 99.84 |
| Catalyst E | Staphylococcus albus | 6.5×10 4 | 103 | 99.84 |
| Catalyst DA | Staphylococcus albus | 6.5×10 4 | 108 | 99.83 |
Example 11
This example is a catalyst stability test.
Putting the catalyst A into a container provided with ultrasonic waves, wherein the ultrasonic treatment conditions are as follows: the volume ratio of water to catalyst is 4: 1, the ultrasonic frequency is 30kHz, the power is 20W/L according to the volume of the solution, the temperature is 30 ℃, the treatment times are 5 times, the treatment time is 30min each time, then the catalyst A is used for the photocatalytic performance test, the test method is the same as that in example 6, the removal rate of each test pollutant is reduced, the reduction rate is less than 1%, and the removal rate of the staphylococcus albus is 99.01%.
Examples 12 and 13
The stability of catalysts B and C was tested as in example 11, resulting in a reduction in the removal of each tested contaminant of less than 1.5% and a reduction in the removal of Staphylococcus albus of less than 1.5%.
Examples 14 and 15
The stability of catalysts D and E was tested as in example 11, resulting in a reduction in the removal of each contaminant tested, between 2% and 3%, and about 2% reduction in the removal of Staphylococcus albus.
Comparative example 3
The stability of catalyst DA was tested in accordance with the method of example 11, and as a result, the removal rate of each of the tested contaminants was reduced to a value of 10% or more, and the removal rate of Staphylococcus albus was 84%.
Example 16
In the same example 6, only two ultraviolet LED lamp panels in the test condition (2) were placed in parallel on both sides of the photocatalyst A plate at an interval of 2cm, and on the photocatalyst A plateThe single-side ultraviolet intensity of the ultraviolet ray reaches 10m W/cm 2 "; two ultraviolet LED lamp panels are placed on two sides of a photocatalyst A plate in parallel, the distance is 5cm, and the single-side ultraviolet intensity on the photocatalyst A reaches 0.8m W/cm 2 ", the results are shown in Table 4.
Table 4 example 16 test results for decontamination of contaminants
Claims (27)
1. Foamed ceramic carrier loaded TiO 2 The photocatalyst is characterized by comprising a foamed ceramic carrier and TiO distributed on the outer surface of the catalyst 2 Crystal grain of 5 to 50 μm TiO 2 The crystal grains account for more than 70 percent; the foamed ceramic carrier comprises foamed ceramic and composite oxides, the foamed ceramic is of an open-cell foamed structure, three-dimensional through micron-sized pore channels are contained in pore edges of the foamed ceramic, the composite oxides are distributed on the surfaces of the pore edges and in the pore channels, and the composite oxides comprise aluminum oxide and titanium dioxide.
2. The photocatalyst of claim 1, wherein the TiO disposed on the outer surface of the catalyst 2 Crystal grain of 5 to 50 μm TiO 2 The crystal grains account for more than 80 percent.
3. The photocatalyst as defined in claim 1, wherein the TiO is distributed on the outer surface of the catalyst 2 Crystal grains of TiO 15 to 45 μm in particle size 2 The crystal grains account for more than 70 percent.
4. The photocatalyst as defined in claim 1, wherein the TiO is distributed on the outer surface of the catalyst 2 Crystal grain of TiO 15-45 μm in particle size 2 The crystal grains account for more than 80 percent.
5. The photocatalyst as claimed in claim 1, wherein at least a part of the composite oxide is embedded in and/or penetrates the pores.
6. The photocatalyst of claim 1, wherein the TiO is based on the weight of the photocatalyst 2 The total content of the component (A) is 5 to 40 percent, and the weight of titanium dioxide contained in the composite oxide in the foamed ceramic carrier accounts for the weight of TiO in the photocatalyst 2 5 to 50 percent of the total weight.
7. The photocatalyst of claim 6, wherein the TiO is based on the weight of the photocatalyst 2 The total content of (A) is 8% -35%.
8. The photocatalyst of claim 1, wherein the TiO 2 Mainly anatase type.
9. The photocatalyst as claimed in claim 1, wherein the complex oxide is a homogeneously distributed complex oxide or a heterogeneously distributed complex oxide.
10. The photocatalyst as claimed in claim 9, wherein the content of titanium dioxide in the surface of the composite oxide support is higher than the content of titanium dioxide in the interior of the support.
11. The photocatalyst as set forth in claim 1, wherein said composite oxide accounts for 10 to 50% by weight of the foamed ceramic support, and the content of titanium oxide in said composite oxide is 10 to 90% by weight; the alumina in the composite oxide is gamma-Al 2 O 3 。
12. The photocatalyst of claim 1, wherein the composition of the ceramic foam comprises one or more of alumina, zirconia, silicon carbide, and silica.
13. According to the claimThe photocatalyst as set forth in claim 12, wherein the composition of the ceramic foam comprises α -Al 2 O 3 。
14. The photocatalyst as defined in claim 12, wherein the cell edges of said ceramic foam have micron-sized cell channels running therethrough in three dimensions; the foam ceramic has a pore volume of 0.1-0.5 mL/g, a pore volume of 20 μm or less of the total pore volume, a pore volume of 50-95% of the total pore volume, and a pore volume of 80 μm or more of the total pore volume of 0.1-0.5 mL/g.
15. The photocatalyst as set forth in claim 12, wherein the outer surface of the ceramic foam has micron-sized pore openings uniformly distributed therein, and the pore openings have a diameter of 1 to 100 μm.
16. The photocatalyst as set forth in claim 1, wherein the ceramic foam has an open cell content of 40 to 90%, a cell diameter of 1 to 5mm, and a pore density of 8 to 60 ppi.
17. The photocatalyst as set forth in claim 1, wherein the ceramic foam has an open cell content of 60 to 80%, a cell diameter of 1 to 5mm, and a pore density of 8 to 30 ppi.
18. The foamed ceramic support of any of claims 1-17 loaded with TiO 2 A method of preparing a photocatalyst, comprising:
(1) preparing titanium sol;
(2) immersing the foamed ceramic carrier into the titanium sol obtained in the step (1) for slurry coating, removing excessive slurry, drying,
(3) repeating the dipping process for 0-5 times;
(4) and (4) carrying out heat treatment on the material obtained in the step (3) to obtain the photocatalyst.
19. The method according to claim 18, wherein in the step (3), the impregnation process is repeated 1 to 4 times.
20. The method of claim 18, wherein: at least one of the following methods is adopted:
the method comprises the following steps: the preparation method of the titanium sol in the step (1) comprises the following steps: dissolving titanium oxide precursor in an organic solvent, and uniformly mixing to obtain titanium sol; the titanium oxide precursor is titanium (IV) acetylacetonate; wherein the organic solvent adopts isopropanol; the molar concentration of titanium in the titanium sol is 0.5-4.0 mol/L;
the second method comprises the following steps: the heat treatment conditions in the step (4) are as follows: and (2) in the presence of water vapor and/or inert gas, performing sectional roasting, namely roasting for 3-8 hours at 200-300 ℃, and then roasting for 1-6 hours at 400-750 ℃.
21. The method of claim 20, wherein:
the method comprises the following steps: adding carboxymethyl cellulose in the mixing process of the step (1), wherein the molar ratio of carboxymethyl cellulose to titanium atoms is (1-7): 100, respectively;
the second method comprises the following steps: the step (4) of roasting in sections comprises roasting at 200-300 ℃ for 3-8 hours and roasting at 450-700 ℃ for 2-5 hours.
22. The method of claim 18, wherein the method of preparing the ceramic foam support comprises: soaking the foam ceramic in the composite oxide precursor slurry to prepare a foam ceramic carrier; the composite oxide precursor slurry comprises: nano titanium dioxide powder, alumina dry glue powder, peptized acid, kaolin and water, wherein the nano titanium dioxide powder comprises the following components in percentage by weight: the alumina dry glue powder is calculated by alumina: peptizing acid: kaolin: the weight ratio of water is 1-9: 10: 1-5: 0.1 to 0.7: 3.0 to 10.0; the particle size of the nano titanium dioxide powder is less than 100 nm.
23. The preparation method according to claim 22, wherein polyethylene glycol is added to the composite oxide precursor slurry, the addition amount of polyethylene glycol accounts for 1-3% of the weight of the composite oxide precursor slurry, and the molecular weight of the polyethylene glycol is 200-4000; the particle size of the nano titanium dioxide powder is 10-100 nm.
24. The production method according to claim 22, wherein in the production method of the ceramic foam carrier, the method of impregnating the composite oxide precursor slurry with the ceramic foam employs a vacuum impregnation method for a plurality of times; removing redundant slurry after each impregnation, removing the slurry in the large pore passage by blowing, drying, and roasting after the final drying to obtain a foamed ceramic carrier; wherein the drying is carried out at room temperature, and then the drying is carried out for 4-24 hours at the temperature of 40-90 ℃; the roasting is performed in a programmed heating mode for multiple sections, roasting is performed for 1-8 hours at 200-300 ℃, and then roasting is performed for 1-6 hours at 400-700 ℃.
25. The process according to claim 24, wherein when a plurality of impregnations are employed, the content of nano titanium dioxide in the slurry after impregnation is higher than that in the slurry before impregnation; the roasting is firstly carried out for 2-8 hours at 200-300 ℃, and then is carried out for 2-5 hours at 450-700 ℃.
26. The preparation method according to claim 24, wherein the composite oxide precursor slurry used in the last impregnation is prepared by mixing the nano titanium dioxide and the polyethylene glycol, and then mixing the mixture with the alumina dry glue powder, the peptized acid and the water.
27. A method of photocatalytically purifying a gas or liquid, comprising: use of a photocatalyst as claimed in any one of claims 1 to 17, said photocatalyst being carried out under the influence of ultraviolet light.
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| US4810685A (en) * | 1986-09-10 | 1989-03-07 | Imperial Chemical Industries Plc | Foam catalysts, method of manufacture and method of using |
| CN1712131A (en) * | 2005-06-09 | 2005-12-28 | 上海交通大学 | Production of TiO2 naometer light catalyzing net from foam metal carrier |
| CN102744049A (en) * | 2012-07-06 | 2012-10-24 | 长安大学 | Process for preparing TiO2 (titanium dioxide) film on aluminum-oxide foamed ceramic |
| CN105289298A (en) * | 2015-10-27 | 2016-02-03 | 展宗城 | Catalytic module capable of removing formaldehyde at room temperature and preparation method thereof |
| CN107008240A (en) * | 2017-04-18 | 2017-08-04 | 南京理工大学 | Nano crystal titanium dioxide light catalyst of aluminum oxide open celled foam ceramic load Si doping and preparation method thereof |
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| US4810685A (en) * | 1986-09-10 | 1989-03-07 | Imperial Chemical Industries Plc | Foam catalysts, method of manufacture and method of using |
| CN1712131A (en) * | 2005-06-09 | 2005-12-28 | 上海交通大学 | Production of TiO2 naometer light catalyzing net from foam metal carrier |
| CN102744049A (en) * | 2012-07-06 | 2012-10-24 | 长安大学 | Process for preparing TiO2 (titanium dioxide) film on aluminum-oxide foamed ceramic |
| CN105289298A (en) * | 2015-10-27 | 2016-02-03 | 展宗城 | Catalytic module capable of removing formaldehyde at room temperature and preparation method thereof |
| CN107008240A (en) * | 2017-04-18 | 2017-08-04 | 南京理工大学 | Nano crystal titanium dioxide light catalyst of aluminum oxide open celled foam ceramic load Si doping and preparation method thereof |
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