CN107051493A - The preparation method of ozone Heterogeneous oxidation solid catalyst - Google Patents
The preparation method of ozone Heterogeneous oxidation solid catalyst Download PDFInfo
- Publication number
- CN107051493A CN107051493A CN201710275136.7A CN201710275136A CN107051493A CN 107051493 A CN107051493 A CN 107051493A CN 201710275136 A CN201710275136 A CN 201710275136A CN 107051493 A CN107051493 A CN 107051493A
- Authority
- CN
- China
- Prior art keywords
- component
- weight
- acetylacetone
- pentanedione
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 230000003647 oxidation Effects 0.000 title claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 25
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 16
- 229910001868 water Inorganic materials 0.000 claims abstract description 16
- -1 holmium oxalate Rare-earth Chemical class 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims abstract description 13
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000019738 Limestone Nutrition 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- INJRKJPEYSAMPD-UHFFFAOYSA-N aluminum;silicic acid;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O INJRKJPEYSAMPD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010459 dolomite Substances 0.000 claims abstract description 10
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 10
- 239000010443 kyanite Substances 0.000 claims abstract description 10
- 229910052850 kyanite Inorganic materials 0.000 claims abstract description 10
- 239000006028 limestone Substances 0.000 claims abstract description 10
- 239000011017 amazonite Substances 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 9
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 8
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 8
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 8
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 8
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 8
- 230000007704 transition Effects 0.000 claims abstract description 8
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims abstract description 7
- BYDILAVGJRCJOJ-UHFFFAOYSA-N O.O.[Y+3] Chemical compound O.O.[Y+3] BYDILAVGJRCJOJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 7
- 229910021538 borax Inorganic materials 0.000 claims abstract description 6
- 229930195712 glutamate Natural products 0.000 claims abstract description 6
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 6
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 5
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 5
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 5
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 5
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- VAIVGJYVKZVQAA-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;nickel Chemical compound [Ni].OC(=O)CC(O)(C(O)=O)CC(O)=O VAIVGJYVKZVQAA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 4
- VSIRWAYMNHKLOS-UHFFFAOYSA-N [V].C(C1=CC=NC=C1)(=O)NN=C(C(=O)O)C Chemical compound [V].C(C1=CC=NC=C1)(=O)NN=C(C(=O)O)C VSIRWAYMNHKLOS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000007795 chemical reaction product Substances 0.000 claims abstract 2
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- DYYFBWLZDJSPGO-UHFFFAOYSA-H holmium(3+);oxalate Chemical class [Ho+3].[Ho+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DYYFBWLZDJSPGO-UHFFFAOYSA-H 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- ZGGPNDKKJIWQJU-UHFFFAOYSA-N 2-(pyridine-4-carbonylhydrazinylidene)propanoic acid Chemical compound OC(=O)C(C)=NNC(=O)C1=CC=NC=C1 ZGGPNDKKJIWQJU-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 claims 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 239000011148 porous material Substances 0.000 abstract description 7
- 239000010970 precious metal Substances 0.000 abstract description 7
- 238000001994 activation Methods 0.000 abstract description 6
- 125000002091 cationic group Chemical group 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000036571 hydration Effects 0.000 abstract description 5
- 238000006703 hydration reaction Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000004913 activation Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 241000206761 Bacillariophyta Species 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000004005 formimidoyl group Chemical group [H]\N=C(/[H])* 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- QOTOCTPPXLYYOY-UHFFFAOYSA-N dodecyl-ethoxy-dimethylazanium Chemical compound CCCCCCCCCCCC[N+](C)(C)OCC QOTOCTPPXLYYOY-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 150000002306 glutamic acid derivatives Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/898—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with vanadium, tantalum, niobium or polonium
-
- B01J35/40—
-
- B01J35/50—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The present invention relates to a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, category environmental protection and technical field of chemical engineering catalysts.The preparation method is pure with diatom, kyanite, cubric niter, dolomite, amazonite and lithium lime stone porous material make carrier, carrier is modified through lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add surfactant Cationic surfucant and surface activation process is carried out under ul-trasonic irradiation, then ultrasonic surface activated carrier in hydrothermal reaction kettle with composite mineralizer borax and potassium sulfate, catalytic activity auxiliary agent predecessor three (hexafluoroacetylacetone) yttrium (III) dihydrate, acetylacetone,2,4-pentanedione samarium, three (4, 4, (2 thiophene) 1 of 4 trifluoro 1, 3 diacetyl) europium, ten water holmium oxalate Rare-earth chemicals, catalytic active center component predecessor normal transition metallo-organic compound pyruvic acid isonicotinoyl hydrazone vanadium, citric acid nickel, cupric glutamate and the hydration iridium of precious metal chemical complex tetrachloro two, hydro-thermal reaction is carried out under the effect of the hydroxypropyl dichloride ammonium of emulsifying agent N dodecyl dimethyl N ' trimethyls 2, reaction product drying is removed after moisture, in Muffle furnace, calcination obtains ozone Heterogeneous oxidation solid catalyst under certain temperature.
Description
Technical field
The present invention relates to a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, category environmental protection and chemical catalyst skill
Art field.
Background technology
Ozonation technology using ozone oxidation ability it is strong the characteristics of, can be by many organic pollution oxidation Decompositions, extensively
For wastewater treatment.Catalytic ozonation technology is divided into ozone homogeneous catalytic oxidation and ozone heterogeneous catalytic oxidation, and ozone is equal
Phase catalysis oxidation has that the more difficult separation and recovery of catalyst is reused, ozone utilization rate is low causes water process operating cost higher,
Organic pollutant removal rate is relatively low simultaneously and easily causing secondary pollution of water is limited to its application；Ozone heterogeneous catalysis oxygen
There is change technology catalyst to be easily isolated and recycled and reusable, ozone utilization rate is high, organic pollutant removal rate is higher, drop
Low water process operating cost and receive significant attention its application the advantages of do not result in secondary pollution.Ozone heterogeneous catalysis
It is to reach local organic matter enrichment by catalyst surface absorption organic matter that oxidation of organic compounds, which is decomposed, while ozone molecule absorption exists
The hydroxyl radical free radical that catalyst surface produces high activity under catalyst action decomposes organic matter.Ozone heterogeneous catalytic oxidation
Handle in waste water technology, core technology is the preparation of ozone Heterogeneous oxidation solid catalyst.
Ozone Heterogeneous oxidation solid catalyst is generally made up of carrier, activated centre and auxiliary agent.Due to being polluted in waste water
Species are various, complex chemical composition feature, can produce harmful effect to performance such as absorption, the mithridatism of catalyst.
Prepare that the carrier structure that ozone Heterogeneous oxidation solid catalyst uses is more single at present, adsorptivity is relatively low；Activated centre is universal
Using normal transition metal salt, mithridatism is poor；Preparation method mainly has infusion process, the precipitation method, mixing method and collosol and gel etc.
Method attachment activity center and adjuvant component are easily liquated out in carrier surface, activated centre and adjuvant component, cause catalyst
Easily lose catalytic activity.For exist in current ozone Heterogeneous oxidation solid catalyst preparation method Catalyst Adsorption compared with
Low, mithridatism is poor and easily loses catalytic activity problem, and exploitation is strengthened using multicomponent porous carrier through reaming, surface active
Catalyst Adsorption, makees catalytic activity auxiliary agent predecessor, normal transition Organometallic using Rare-earth chemicals and closes
Thing and precious metal chemical complex are made catalytic active center predecessor and contained with multicomponent porous carrier through hydro-thermal reaction, high temperature sintering preparation
The ozone Heterogeneous oxidation solid catalyst of multi-element metal has to improve the preparation method of catalyst mithridatism and catalytic activity
Larger environmental benefit and higher practical value.
The content of the invention
For existing in current ozone Heterogeneous oxidation solid catalyst preparation method, Catalyst Adsorption is relatively low, mithridatism
Poor to lose catalytic activity problem with easy, exploitation strengthens catalyst using multicomponent porous carrier through reaming, surface active
Adsorptivity, catalytic activity auxiliary agent predecessor, normal transition metallo-organic compound and expensive are made using Rare-earth chemicals
Metallic compound is made catalytic active center predecessor and prepared with multicomponent porous carrier through hydro-thermal reaction, high temperature sintering containing polynary gold
The ozone Heterogeneous oxidation solid catalyst of category to improve the preparation method of catalyst mithridatism and catalytic activity, it is characterized in that
Component A can be added in closed reactor and deionized water stirring prepares the aqueous solution, the weight concentration for control component A is 2%~6%,
After the completion of prepared by solution, B component is added under agitation, 35 DEG C~50 DEG C are warming up to, continues stirring reaction 3h~6h, is filtered, instead
Product is answered to obtain reaming modified support after 102 DEG C~106 DEG C dry constant weights；Reaming modified support puts into ultrasound reactor,
The aqueous solution prepared by component C and deionized water is added, the weight concentration of component C is 3%~8%, is uniformly mixed, and control is super
Sound power density is 0.3~0.8W/m3, frequency 20kHz~30kHz, 40 DEG C~55 DEG C, sonic oscillation 2h~5h obtains ultrasound
Surface active carrier mixed liquor；Ultrasonic surface activated carrier mixed liquor is transferred in hydrothermal reaction kettle, add D components and go from
The aqueous solution that sub- water is prepared, the weight concentration of D components is 40%~55%, by weight, D component deionized water solutions:Ultrasonic table
Weight ratio=1 of face activated carrier mixed liquor:（1.5~2）, control 120 DEG C~180 DEG C of temperature, the hydro-thermal reaction time be 8h~
16h, then dries to obtain fine particle；Fine particle is in Muffle furnace, 600 DEG C~950 DEG C, and calcination 3h~8h obtains ozone non-
Homogeneous oxidizing solid catalyst.The component A is made up of lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, by weight, lithium hypochlorite:
Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B component is by diatom is pure, kyanite, cubric niter, dolomite, the Milky Way
Stone, lithium lime stone composition, by weight, diatom is pure:Kyanite:Cubric niter:Dolomite:Amazonite:The weight ratio of lithium lime stone=（5
~15）:（7~17）:（9~19）:（11~21）:（13~23）:（15~25）, by weight, component A:The weight of B component it
Than=1:（10~20）, component C is Cationic surfucant, by weight, component C:Reaming modified support
Weight ratio=1:（5~10）, D components are by composite mineralizer borax, potassium sulfate, (the hexafluoro acetyl of catalytic activity auxiliary agent predecessor three
Acetone) yttrium (III) dihydrate, acetylacetone,2,4-pentanedione samarium, three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europiums, ten water
Holmium oxalate Rare-earth chemicals, the different nicotinoyl of catalytic active center predecessor normal transition metallo-organic compound pyruvic acid
Hydrazone vanadium, citric acid nickel, cupric glutamate and the hydration iridium of precious metal chemical complex tetrachloro two, emulsifying agent N- dodecyl dimethyls-N '-three
Methyl -2- hydroxypropyl dichlorides ammonium is constituted, by weight, borax:Potassium sulfate:Three (hexafluoroacetylacetone) yttriums (III) two are hydrated
Thing:Acetylacetone,2,4-pentanedione samarium:Three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europiums:Ten water holmium oxalates:The different nicotinoyl of pyruvic acid
Hydrazone vanadium:Citric acid nickel:Cupric glutamate:Tetrachloro two is hydrated iridium:N- dodecyl dimethyls-N '-trimethyl -2- hydroxypropyl dichlorides
The weight ratio of ammonium=（4~8）:（6~10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~18）:（4
~7）:（6~9）:（6~20）.The diatom of the B component is pure, kyanite, cubric niter, dolomite, amazonite, lithium lime stone difference
Crushed, deionized water washing, which is dried, to be removed after moisture, and -200 mesh ,+400 mesh sieves point are carried out through standard screen, control the particle diameter to be
The mm of 0.0370mm~0.0750.
What the technical method of the present invention was realized in：Lithium hypochlorite LiClO, double (second can be being added in closed reactor
Acyl acetone) beryllium C10H14BeO4The aqueous solution is prepared with deionized water stirring, it is 0.0370mm~0.0750mm to add particle diameter after screening
Diatom is pure, kyanite, cubric niter, dolomite, amazonite and lithium lime stone porous material carrier, in certain temperature and stirring condition
Under, the small Be of aqueous solution Ionic Radius2+（0.31Å）、Li+（0.60Å）Displace part ion radius in porous material big
Ca2+（0.99Å）、K+（1.33Å）、Ba2+（1.35Å）Plasma, the aperture of porous material carrier becomes big, surface roughness increase,
Filtering, dries the reaming modified support input ultrasound reactor after constant weight, adds chlorination dodecyl dimethyl ethoxy
Ammonium [C12H25N(CH3)2CH2CH2OH]+Cl-The aqueous solution, when control ultrasonic power density, ultrasonic frequency, temperature and sonic oscillation
Between, under ultrasonic cavitation effect, Cationic surfucant [C12H25N(CH3)2CH2CH2OH]+Cl-It is easy to
Reaming modified support duct is escaped into from the aqueous solution or reaming modified support surface is attached to, and is beneficial to the mutual of carrier duct
Connection and carrier surface activation, enhance adsorptivity；After the completion of ultrasonic activation, ultrasonic surface activated carrier mixed liquor is transferred to water
In thermal response kettle, with borax Na2B4O7·10H2O, potassium sulfate K2SO4The composite mineralizer, (hexafluoro of catalytic activity auxiliary agent predecessor three
Acetylacetone,2,4-pentanedione) yttrium (III) dihydrate C15H3F18O6Y·2H2O, acetylacetone,2,4-pentanedione samarium C15H25O8Sm, three (the fluoro- 1- of 4,4,4- tri-
(2- thiophene) -1,3- diacetyl) europium C24H18EuF9O6S3, ten water holmium oxalate C6Ho2O12Rare-earth chemicals, catalysis is lived
Property center component predecessor normal transition metallo-organic compound pyruvic acid isonicotinoyl hydrazone vanadium [VO2(C9H8N3O5)] (C5H5N)、
Citric acid nickel C12H22O14Co, cupric glutamate C6H7O4The Cu and hydration iridium Ir of precious metal chemical complex tetrachloro two (H2O) 2Cl4, in emulsification
Agent N- dodecyl dimethyls-N '-trimethyl -2- hydroxypropyl dichloride ammoniums C12H25N+(CH3)2CH2CH (OH)CH2N+(CH3)3Cl2 -Effect is lower to carry out hydro-thermal reaction, and mineralizer accelerates diffusion, activates reactant lattice, promotes entering for solid phase reaction
OK, ultrasonic surface activated carrier and Rare-earth chemicals, normal transition metallo-organic compound, precious metal chemical complex are equal
Even doping, emulsifying agent N- dodecyl dimethyls-N '-trimethyl -2- hydroxypropyl dichloride ammoniums form reaction solution is quasi-stationary
Emulsion prevents separation of solid and liquid, sedimentation, while to the further surface active of porous carrier, passing through the water in certain temperature, time
Thermal response, drying obtains the fine silt thing of Uniform Doped；The fine silt thing of Uniform Doped is in Muffle furnace, through high temperature sintering, its
In organic matter carbonization further enhance the microcellular structure of porous carrier, obtain the oxidation of porous carrier supported rare earth metal
The ozone Heterogeneous oxidation solid catalyst of the catalytic active center of thing, transition metal oxide and noble metal formation, is improved
The mithridatism and catalytic activity of catalyst.
Relative to art methods, outstanding feature of the present invention is using diatom is pure, kyanite, saliter in technology of preparing
Stone, dolomite, amazonite, lithium lime stone porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) berylliums
C10H14BeO4Reaming effect, Cationic surfucant [C12H25N(CH3)2 CH2CH2OH]+Cl-, N- 12
Alkyl dimethyl-N '-trimethyl -2- hydroxypropyl dichloride ammoniums C12H25N+(CH3)2CH2CH (OH)CH2N+(CH3)3Cl2 -Duct
Be interconnected and surface activation；Rare-earth chemicals, normal transition Organometallic are made by hydro-thermal reaction
Compound and precious metal chemical complex reach Uniform Doped and are attached in carrier surface and duct that high temperature sintering makes the complete carbon of organic matter
Change reinforcing and form multi-level microcellular structure, porous carrier supported rare earth metal oxide, transition metal oxide and expensive
The multi-element metal catalytic active center of metal formation is combined more firm, the ozone Heterogeneous oxidation solid of preparation with porous carrier
Catalyst has stronger adsorptivity, and the cooperative effect of multi-element metal, the stability that particularly doped precious metal has and height are lived
Property, liquating out for metal catalytic activity component can be suppressed, the mithridatism and catalytic activity of catalyst is improved, with good
Environmental benefit and economic benefit.
Embodiment
Embodiment 1:1.35g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 1.65g, 140ml deionized waters, being added to volume is
500ml's can be uniformly mixed in closed reactor, and the weight concentration of the aqueous solution is 2.1%, lithium hypochlorite:Double (levulinics
Ketone) beryllium weight ratio=1:1.2；Add deionized water wash to it is neutral, 103 DEG C dry remove -200 mesh of sieving after moisture~+
The 2.75g diatoms of 400 mesh standard sieves are pure, 3.75g kyanites, 4.75g cubric niters, 5.75g dolomites, 6.75g amazonites,
The weight of 7.75g lithium lime stones, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（3g）:The weight of porous material（31.5g）=1:10.5,
36 DEG C are warming up to, reaming modified support 31g is obtained after continuing stirring reaction 3.2h, filtering, 103 DEG C of dry constant weights；It is super in 500ml
In sound wave reactor, reaming modified support 31g is put into, 3.25g Cationic surfucants is added and is dissolved in
The aqueous solution of 100ml deionized waters, the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, chlorination dimethyl
Base hydroxyethyl ammonium（3.25g）:Reaming modified support（31g ）=1:9.5；It is 0.4W/m to control ultrasonic power density3, ultrasonic wave frequency
41 DEG C of rate 21kHz, temperature, sonic oscillation 2.2h；After the completion of ultrasonic activation, the ultrasonic surface in ultrasound reactor is activated and carried
Body mixed liquor is transferred in 500ml hydrothermal reaction kettles, is added by 2.1g boraxs, 3.05g potassium sulfates, (the hexafluoro acetyl of 1.6g tri-
Acetone) yttrium (III) dihydrate, 2.05g acetylacetone,2,4-pentanediones samarium, (4,4,4- tri- fluoro- 1- (2- the thiophene) -1,3- fourths two of 2.6g tri-
Ketone) europium, the water holmium oxalates of 3.05g ten, 5.05g pyruvic acid isonicotinoyl hydrazones vanadium, 6.1g citric acids nickel, 2.05g cupric glutamates, 3.1g tetra-
The hydration of chlorine two iridium, 3.05gN- dodecyl dimethyls-N '-trimethyl -2- hydroxypropyl dichloride ammoniums and 50ml deionized waters are prepared
The aqueous solution, the weight concentration of the aqueous solution is 40.3%, the weight of the aqueous solution:The weight of ultrasonic surface activated carrier mixed liquor
Amount=83.8g:134.25g=1:1.6,125 DEG C of temperature is controlled, the hydro-thermal reaction time is 8.3h, then dries to obtain fine silt for 105 DEG C
Thing；Fine silt thing is in Muffle furnace, 620 DEG C, calcination 3.2h, and after cooling down, the ozone that can obtain fine particle shape is heterogeneous
Oxidized solid catalyst.
Embodiment 2:0.24g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 0.36g, 10ml deionized waters, being added to volume is
100ml's can be uniformly mixed in closed reactor, and the weight concentration of the aqueous solution is 5.7%, lithium hypochlorite:Double (levulinics
Ketone) beryllium weight ratio=1:1.5；Add deionized water wash to it is neutral, 103 DEG C dry remove -200 mesh of sieving after moisture~+
The 1.45g diatoms of 400 mesh standard sieves are pure, 1.65g kyanites, 1.85g cubric niters, 2.05g dolomites, 2.25g amazonites,
The weight of 2.45g lithium lime stones, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（0.6g）:The weight of porous material（11.7g）=1:
19.5,48 DEG C are warming up to, reaming modified support 11.5g is obtained after continuing stirring reaction 5.8h, filtering, 105 DEG C of dry constant weights；
In 100ml ultrasound reactors, reaming modified support 11.5g is put into, 2.2g chlorination dodecyl dimethyl ethoxys are added
Ammonium is dissolved in the aqueous solution of 26ml deionized waters, and the weight concentration of the aqueous solution is 7.8%, is uniformly mixed, chlorination dodecyl
Dimethyl hydroxyethyl ammonium（2.2g）:Reaming modified support（11.5g ）=1:5.2；It is 0.7W/m to control ultrasonic power density3, it is super
54 DEG C of frequency of sound wave 29kHz, temperature, sonic oscillation 4.7h；After the completion of ultrasonic activation, the ultrasonic surface in ultrasound reactor
Activated carrier mixed liquor is transferred in 100ml hydrothermal reaction kettles, is added by 0.78g boraxs, 0.97g potassium sulfates, 0.58g tri-
(hexafluoroacetylacetone) yttrium (III) dihydrate, 0.67g acetylacetone,2,4-pentanediones samarium, 0.78g tri- (the fluoro- 1- of 4,4,4- tri- (2- thiophene)-
1,3- diacetyl) europium, the water holmium oxalates of 0.87g ten, 1.48g pyruvic acid isonicotinoyl hydrazones vanadium, 1.77g citric acids nickel, 0.68g glutamic acid
Copper, the hydration of 0.87g tetrachloros two iridium, 1.98gN- dodecyl dimethyls-N '-trimethyl -2- hydroxypropyl dichloride ammoniums and 10ml are gone
The aqueous solution that ionized water is prepared, the weight concentration of the aqueous solution is 53.3%, the weight of the aqueous solution:Ultrasonic surface activated carrier
Weight=21.43g of mixed liquor:39.7g=1:1.9,175 DEG C of temperature is controlled, the hydro-thermal reaction time is 15.5h, then 105 DEG C of bakings
Do to obtain fine silt thing；Fine silt thing is in Muffle furnace, 930 DEG C, calcination 7.5h, after cooling down, can obtain fine particle shape
Ozone Heterogeneous oxidation solid catalyst.
Claims (2)
1. a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, it is characterized in that A groups can added in closed reactor
Divide and deionized water stirring prepares the aqueous solution, the weight concentration for controlling component A is 2%~6%, after the completion of prepared by solution, in stirring
Lower addition B component, is warming up to 35 DEG C~50 DEG C, continues stirring reaction 3h~6h, and filtering, reaction product is dry at 102 DEG C~106 DEG C
Reaming modified support is obtained after dry constant weight, reaming modified support input ultrasound reactor, addition is matched somebody with somebody by component C and deionized water
The aqueous solution of system, the weight concentration of component C is 3%~8%, is uniformly mixed, and it is 0.3~0.8W/ to control ultrasonic power density
m3, frequency 20kHz~30kHz, 40 DEG C~55 DEG C, sonic oscillation 2h~5h obtains ultrasonic surface activated carrier mixed liquor, transfer
Into hydrothermal reaction kettle, the aqueous solution that D components and deionized water are prepared is added, the weight concentration of D components is 40%~55%, is pressed
Weight meter, D component deionized water solutions:Weight ratio=1 of ultrasonic surface activated carrier mixed liquor:（1.5~2）, control temperature
120 DEG C~180 DEG C, the hydro-thermal reaction time is 8h~16h, then dries to obtain fine silt thing, fine silt thing is in Muffle furnace, 600
DEG C~950 DEG C, calcination 3h~8h obtains ozone Heterogeneous oxidation solid catalyst；The component A by expanding agent lithium hypochlorite,
Double (acetylacetone,2,4-pentanedione) beryllium compositions, by weight, lithium hypochlorite:Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B groups
Point by diatom is pure, kyanite, cubric niter, dolomite, amazonite and lithium lime stone are constituted, by weight, diatom is pure:Kyanite:
Cubric niter:Dolomite:Amazonite:The weight ratio of lithium lime stone=（5~15）:（7~17）:（9~19）:（11~21）:
（13~23）:（15~25）, by weight, component A:Weight ratio=1 of B component:（10~20）, component C is chlorination dodecane
Base dimethyl hydroxyethyl ammonium, by weight, component C:Weight ratio=1 of reaming modified support:（5~10）, D components are by being combined
Mineralizer borax, potassium sulfate, catalytic activity auxiliary agent predecessor three (hexafluoroacetylacetone) yttrium (III) dihydrate, acetylacetone,2,4-pentanedione
Samarium, three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europiums, ten water holmium oxalate Rare-earth chemicals, catalysis are lived
Property center predecessor normal transition metallo-organic compound pyruvic acid isonicotinoyl hydrazone vanadium, citric acid nickel, cupric glutamate and noble metal
Compound tetrachloro two is hydrated iridium, and emulsifying agent N- dodecyl dimethyls-N '-trimethyl -2- hydroxypropyl dichlorides ammonium composition is pressed
Weight meter, borax:Potassium sulfate:Three (hexafluoroacetylacetone) yttrium (III) dihydrates:Acetylacetone,2,4-pentanedione samarium:Three (4,4,4- tri-
Fluoro- 1- (2- thiophene) -1,3- diacetyl) europium:Ten water holmium oxalates:Pyruvic acid isonicotinoyl hydrazone vanadium:Citric acid nickel:Cupric glutamate:
Tetrachloro two is hydrated iridium:The weight ratio of N- dodecyl dimethyls-N '-trimethyl -2- hydroxypropyl dichloride ammoniums=（4~8）:
（6~10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.
2. according to claim 1 B component by diatom is pure, kyanite, cubric niter, dolomite, amazonite and lithium lime stone group
Into diatom is pure, kyanite, cubric niter, dolomite, amazonite and lithium lime stone are crushed respectively, and deionized water washing drying is removed
Go after moisture, sieved through standard screen, it is 0.0370mm~0.0750mm to control particle diameter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710275136.7A CN107051493A (en) | 2017-04-25 | 2017-04-25 | The preparation method of ozone Heterogeneous oxidation solid catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710275136.7A CN107051493A (en) | 2017-04-25 | 2017-04-25 | The preparation method of ozone Heterogeneous oxidation solid catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107051493A true CN107051493A (en) | 2017-08-18 |
Family
ID=59603513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710275136.7A Withdrawn CN107051493A (en) | 2017-04-25 | 2017-04-25 | The preparation method of ozone Heterogeneous oxidation solid catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107051493A (en) |
-
2017
- 2017-04-25 CN CN201710275136.7A patent/CN107051493A/en not_active Withdrawn
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107042115A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051486A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107159234A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008414A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107020096A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107088431A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051493A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN106984328A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051474A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008345A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107042114A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107088422A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107042116A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008341A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008344A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN106984327A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008352A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008356A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008369A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008342A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107088421A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008394A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107020105A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051497A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051477A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20170818 |