CN112246268A - Novel efficient ozone catalytic material and preparation method thereof - Google Patents
Novel efficient ozone catalytic material and preparation method thereof Download PDFInfo
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- CN112246268A CN112246268A CN202011083819.0A CN202011083819A CN112246268A CN 112246268 A CN112246268 A CN 112246268A CN 202011083819 A CN202011083819 A CN 202011083819A CN 112246268 A CN112246268 A CN 112246268A
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- transition metal
- oxide
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- ozone catalytic
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- 239000000463 material Substances 0.000 title claims abstract description 59
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 31
- 239000003513 alkali Substances 0.000 claims abstract description 27
- 239000012266 salt solution Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 15
- 239000002585 base Substances 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000011068 loading method Methods 0.000 claims description 16
- -1 transition metal salt Chemical class 0.000 claims description 16
- 239000012876 carrier material Substances 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 229910052878 cordierite Inorganic materials 0.000 claims description 2
- 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 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002657 fibrous material Substances 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 1
- 239000006260 foam Substances 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 239000006262 metallic foam Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract description 2
- 239000002440 industrial waste Substances 0.000 abstract description 2
- 150000004692 metal hydroxides Chemical class 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 230000001804 emulsifying effect Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 150000002815 nickel Chemical class 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 2
- 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 2
- 150000002696 manganese Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
- B01D53/8675—Ozone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a novel efficient ozone catalytic material and a preparation method thereof, wherein the novel efficient ozone catalytic material comprises a base material with high specific surface area and a transition metal oxide-C loaded on the base material3N4Composite material of C3N4Transition metal hydroxide formed by compounding transition metal salt solution and alkali solution-C3N4The mixture is obtained by sintering. The ozone catalytic material of the invention has continuous and efficient catalytic performance,The method has the advantages that the reaction condition is mild, the mass production can be realized under the normal temperature condition, the raw materials with relatively low price can be used, the method is suitable for large-scale production, the ozone can be quickly removed by combining adsorption and catalysis, the method is suitable for most industrial waste gas, ozone tail gas, waste water, ozone and indoor environment, the type and the shape of a carrier are changed, the method can be used for equipment such as a humidifier and a purifier, and the method has good application prospect.
Description
Technical Field
The invention relates to a catalytic material, in particular to a novel efficient ozone catalytic material and a preparation method thereof.
Background
Ozone, as a strong oxidant, has abundant applications in material preparation, space disinfection, wastewater purification, waste gas treatment, and the like. However, since the half-life of ozone is about half an hour, ozone remains in the environment for a short time after use when it is discharged into the atmosphere along with the pipe. The human or animal inhales more high-concentration ozone which is very harmful to human bodies, so that the treatment of the tail gas ozone is indispensable. At present, the ozone tail gas treatment method has several main modes of direct discharge, adsorption, catalyst, heating and catalyst combination, and the use of the catalyst is one of the most efficient and environment-friendly methods. The catalyst used for eliminating ozone at present mainly focuses on noble metals or metal oxides such as manganese oxide, iron oxide, aluminum oxide, zinc oxide, nickel oxide and the like, but the catalysts in the category have the problems of harsh reaction conditions (hydrothermal reaction and high-temperature sintering), poor moisture resistance, capability of only treating low-concentration ozone, insufficient catalytic efficiency and the like in the preparation process.
Disclosure of Invention
The technical problem to be solved by the invention is that the existing catalyst for eliminating ozone mainly focuses on noble metals or metal oxides such as manganese oxide, iron oxide, aluminum oxide, zinc oxide, nickel oxide and the like, and the preparation process has the problems of harsh reaction conditions, poor moisture resistance, capability of only treating low-concentration ozone, insufficient catalytic efficiency and the like.
The invention is realized by the following technical scheme:
the invention provides a novel efficient ozone catalytic material, which comprises a base material with high specific surface area and transition metal oxide-C loaded on the base material3N4Composite material of C3N4Transition metal hydroxide formed by compounding transition metal salt solution and alkali solution-C3N4The mixture is obtained by sintering.
The ozone catalytic material has continuous and efficient catalytic performance, relatively mild reaction conditions, relatively low-price raw materials, suitability for large-scale production, capability of quickly removing ozone by combining adsorption and catalysis, suitability for most of industrial waste gas, ozone tail gas, wastewater, ozone and indoor environment, capability of being used in equipment such as humidifiers, purifiers and the like by changing the type and the shape of a carrier, and good application prospect.
The transition metal oxide is one or more of iron oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, aluminum oxide, tungsten oxide, molybdenum oxide, chromium oxide, zinc oxide and the like.
The metal cation in the transition metal salt is one or more of iron, cobalt, manganese, nickel, copper, vanadium, titanium, niobium, tantalum, molybdenum, chromium, cadmium, tungsten, platinum, zinc and the like.
Preferably, the metal cation in the transition metal salt is one or more of iron, cobalt, manganese, nickel and copper.
The anion in the transition metal salt is sulfate radical, nitrate radical, nitrite radical, acetate radical, oxalate radical, halide ion, phosphate radical or carbonate radical, preferably nickel nitrate.
A preparation method of an ozone catalytic material comprises the following steps: 1) preparing a transition metal salt into a transition metal salt solution, dispersing C3N4 in the metal salt solution, loading the solution on a substrate with a high specific surface area, and then drying to obtain a first carrier material; 2) dissolving alkali in water to form an alkali solution, reacting the alkali solution with the first carrier material, and drying to obtain a second carrier material; 3) finally, washing the surface of the second carrier material for multiple times by using deionized water; 4) and drying the cleaned second carrier material, and sintering to obtain the novel efficient ozone catalytic material.
The transition metal salt solution takes deionized water as a solvent and is prepared into a solution with the concentration of 0.01-5mol/L at normal temperature; the alkali is one or more of potassium hydroxide, sodium hydroxide, calcium hydroxide, ammonia water and barium hydroxide, and C in the solution3N4The mass fraction of (A) is 5-20%; wherein, sodium hydroxide is preferred, deionized water is used as solvent of the alkali solution, and the solution with the concentration of 0.01-5mol/L is prepared at normal temperature.
The substrate with high specific surface area is foamed metal, honeycomb metal, foamed ceramic, honeycomb ceramic, activated carbon material, fiber material, activated carbon, cordierite, zeolite or molecular sieve, and preferably foamed ceramic is adopted.
The loading technique is spray loading, coating loading or dipping loading, preferably dipping loading.
The drying process adopts natural drying, oven drying, freeze drying or vacuum drying; wherein, the preferable drying process is oven drying, the drying temperature is 25-200 ℃, and the preferable drying temperature is 60 ℃.
The sintering process adopts sintering in air, the sintering temperature is 250-600 ℃, and the preferred temperature is 450 ℃.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the novel efficient ozone catalytic material and the preparation method thereof have the advantages of continuous efficient catalytic performance, mild reaction conditions, capability of using relatively cheap raw materials, suitability for large-scale production and good application prospect;
2. the invention relates to a novel efficient ozone catalytic material and a preparation method thereof, and a novel non-metallic material C is used3N4As a complex, C3N4And the precursor of the transition metal oxide is uniformly grown on the surface of the substrateThe dispersibility is improved, and the ozone removal performance is greatly improved;
3. according to the novel efficient ozone catalytic material and the preparation method thereof, the transition metal salt and the alkali solution are adopted, the transition metal salt and the alkali solution can naturally react at normal temperature, the price is low, the prepared transition metal oxide catalyst is high in catalytic efficiency and has continuous efficient catalytic performance, and therefore ozone with high concentration can be continuously treated;
4. the invention relates to a novel efficient ozone catalytic material and a preparation method thereof3N4The transition metal salt solution is loaded with alkali solution, namely the transition metal salt solution and the alkali solution react directly on the base material to generate transition metal hydroxide, and the transition metal hydroxide is dried and sintered to ensure that the catalytic material can be uniformly synthesized and distributed on the base material.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
FIG. 1 is a graph comparing the removal rate of ozone for the catalytic materials prepared in each example.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.
Example 1
Cobalt nitrate is used as transition metal salt, deionized water is used for preparing 2mol/L cobalt salt solution, C is added3N4Adding 10% of cobalt salt solution into the powder by mass ratio, emulsifying and cutting for 1h, loading on the foamed ceramic by a dipping method, and drying at 60 ℃. Soaking the dried material in 2mol/L aqueous alkali prepared from sodium hydroxide as an alkali source and deionized water, taking out, drying at 60 ℃, and cleaning for more than 3 times. Drying at 60 ℃ and sintering at 450 ℃ to obtain the catalytic material.
Example 2
Ferric nitrate is taken as transition metal salt, deionized water is used for preparing 3mol/L ferric salt solution, and C is3N4Adding the iron salt solution into the powder according to the mass ratio of 10%, emulsifying and cutting for 1h, loading on the foamed ceramic by a dipping method, and drying at 60 ℃. Soaking the dried material in 3mol/L alkali solution prepared from sodium hydroxide as an alkali source and deionized water, taking out, drying at 60 ℃, and cleaning for more than 3 times. Drying at 60 ℃ and sintering at 450 ℃ to obtain the catalytic material.
Example 3
Nickel nitrate is used as transition metal salt, deionized water is used for preparing 0.8mol/L nickel salt solution, and C is added3N4Adding the powder into a nickel salt solution in an amount of 20% by mass, emulsifying and cutting for 1h, loading on the foamed ceramic by a dipping method, and drying at 60 ℃. Soaking the dried material in 0.8mol/L aqueous alkali prepared from sodium hydroxide as an alkali source and deionized water, taking out, drying at 60 ℃, and cleaning for more than 3 times. Drying at 60 ℃ and sintering at 450 ℃ to obtain the catalytic material.
Example 4
Manganese nitrate is taken as transition metal salt, deionized water is used for preparing 0.8mol/L manganese salt solution, and C is added3N4Adding the powder into a manganese salt solution in an amount of 20% by mass, emulsifying and cutting for 1h, loading on the foamed ceramic by a dipping method, and drying at 60 ℃. Soaking the dried material in 0.8mol/L aqueous alkali prepared from sodium hydroxide as an alkali source and deionized water, taking out, drying at 60 ℃, and cleaning for more than 3 times. Drying at 60 ℃ and sintering at 450 ℃ to obtain the catalytic material.
Example 5
Preparing 1mol/L nickel salt solution by using nickel nitrate as transition metal salt and deionized water, and adding C3N4Adding the powder into nickel salt solution according to the mass ratio of 10%, emulsifying and cutting for 1h, loading on the foamed ceramic by a dipping method, and drying at 60 ℃. Soaking the dried material in 1mol/L alkali solution prepared from sodium hydroxide as an alkali source and deionized water, taking out, drying at 60 ℃, and cleaning for more than 3 times. Drying at 60 ℃ and sintering at 450 ℃ to obtain the catalytic material.
The above examples are merely preferred examples to fully illustrate the present invention, and the scope of the present invention is not limited thereto, and the addition of the auxiliary components and the change in the preparation method based on the present invention are within the scope of the present invention.
The catalytic material prepared in the above example and a commercial ozone catalytic material (using manganese dioxide as an active material) were tested for their ozone catalytic degradation performance at a temperature of 25 ℃ and a humidity of 60% RH, and the ozone concentration in the gas stream continuously fed into the reactor was about 100ppm, with the following results:
the blank is a control with no catalytic material placed therein.
From the test results and fig. 1, it can be seen that under the test conditions, the ozone catalytic efficiency of the commercial ozone catalyst material is about 87% at most, and the ozone catalytic efficiency is in a significant decline trend along with the increase of the test time, which indicates that the catalytic performance is not good and the duration is not long. The catalytic performance of the ozone catalyst material prepared by the method is obviously superior to that of the catalyst material sold on the market, the catalytic performance is over 90 percent, the lasting effect is good, the performance is still good after continuous testing for 72 hours under the testing condition, the testing sample prepared according to the embodiment 3 is optimal, the catalytic performance is kept at about 99 percent, and the ozone catalyst material has a very good application prospect.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A novel high-efficiency ozone catalytic material is characterized by comprising a base material with high specific surface area and transition metal oxide-C loaded on the base material3N4The transition metal oxide-C3N4The composite material is synthesized and grown in C by a transition metal salt solution and an alkali solution3N4Finally, the base material and the load material are sintered to prepare the novel ozone catalytic material, C3N4Is a novel non-metallic catalytic material.
2. The novel high-efficiency ozone catalytic material as claimed in claim 1, wherein the transition metal oxide is one or more of iron oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, aluminum oxide, tungsten oxide, molybdenum oxide, chromium oxide, zinc oxide, etc.
3. The novel high-efficiency ozone catalytic material as claimed in claim 1, wherein the metal cation in the transition metal salt is one or more of iron, cobalt, manganese, nickel, copper, vanadium, titanium, niobium, tantalum, molybdenum, chromium, cadmium, tungsten, platinum, zinc, etc.
4. The novel high-efficiency ozone catalytic material as claimed in claim 1, wherein the anion in the transition metal salt is sulfate, nitrate, nitrite, acetate, oxalate, halide, phosphate or carbonate.
5. A method for preparing the ozone catalytic material as claimed in any one of claims 1 to 4, characterized in that: the method comprises the following steps: 1) preparing transition metal salt into transition metal salt solution, and adding C3N4Dispersing in the metal salt solution, loading the solution on a substrate with high specific surface area, and then drying to obtain a first carrier material; 2) dissolving alkali in water to form an alkali solution, reacting the alkali solution with the first carrier material, and drying to obtain a second carrier material; 3) finally, washing the surface of the second carrier material for multiple times by using deionized water; 4) and drying the cleaned second carrier material, and sintering to obtain the novel efficient ozone catalytic material.
6. The method for preparing an ozone catalytic material as claimed in claim 5, wherein the transition metal salt solution is prepared as a solution with a concentration of 0.01-5mol/L at room temperature using deionized water as a solvent, and C is contained in the solution3N4The mass fraction of (A) is 5-20%; the alkali is one or more of potassium hydroxide, sodium hydroxide, calcium hydroxide, ammonia water and barium hydroxide; wherein the aqueous alkali takes deionized water as a solvent and is prepared into a solution with the concentration of 0.01-5mol/L at normal temperature.
7. The method of claim 5, wherein the substrate with high specific surface area is a metal foam, a honeycomb metal, a ceramic foam, a honeycomb ceramic, an activated carbon material, a fiber material, activated carbon, cordierite, zeolite or a molecular sieve.
8. The method for preparing an ozone catalytic material as claimed in claim 5, wherein the loading technique is spray loading, coating loading or dipping loading.
9. The method for preparing the ozone catalytic material as claimed in claim 5, wherein the drying process is natural drying, oven drying, freeze drying or vacuum drying, and the drying temperature is 25-200 ℃.
10. The method for preparing an ozone catalytic material as claimed in claim 5, wherein the sintering is sintering in air environment, and the sintering temperature is 250-600 ℃.
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