CN107051478A - The preparation method of ozone Heterogeneous oxidation solid catalyst - Google Patents
The preparation method of ozone Heterogeneous oxidation solid catalyst Download PDFInfo
- Publication number
- CN107051478A CN107051478A CN201710274705.6A CN201710274705A CN107051478A CN 107051478 A CN107051478 A CN 107051478A CN 201710274705 A CN201710274705 A CN 201710274705A CN 107051478 A CN107051478 A CN 107051478A
- Authority
- CN
- China
- Prior art keywords
- weight
- component
- solid catalyst
- glauberite
- astrakanite
- 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- Withdrawn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 23
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 23
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 19
- 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 40
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- -1 monoalky lether trimethyl ammonium chloride Chemical class 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 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
- GYZGFUUDAQXRBT-UHFFFAOYSA-J calcium;disodium;disulfate Chemical compound [Na+].[Na+].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GYZGFUUDAQXRBT-UHFFFAOYSA-J 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
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000010436 fluorite Substances 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
- ILRSCQWREDREME-UHFFFAOYSA-N lauric acid amide propyl betaine Natural products CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 239000011591 potassium Substances 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
- BYDILAVGJRCJOJ-UHFFFAOYSA-N O.O.[Y+3] Chemical compound O.O.[Y+3] BYDILAVGJRCJOJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 7
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- NQNOMXXYKHWVKR-UHFFFAOYSA-N methylazanium;sulfate Chemical compound NC.NC.OS(O)(=O)=O NQNOMXXYKHWVKR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 7
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 7
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 claims abstract description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940009662 edetate Drugs 0.000 claims abstract description 6
- 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 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
- 229910021538 borax Inorganic materials 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 4
- WHELTKFSBJNBMQ-UHFFFAOYSA-L dichlororuthenium;2-pyridin-2-ylpyridine;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ru+2].N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 WHELTKFSBJNBMQ-UHFFFAOYSA-L 0.000 claims abstract description 4
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 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
- 239000007864 aqueous solution Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 230000007704 transition Effects 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052773 Promethium Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000004576 sand Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 6
- 238000001994 activation Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 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
- 239000000126 substance Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 239000010970 precious metal Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000010419 fine particle Substances 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YPUOTXOJCHHZIY-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;ytterbium(3+) Chemical compound [Yb+3].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YPUOTXOJCHHZIY-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229940048820 edetates Drugs 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- MITDXNUXOAYFGC-UHFFFAOYSA-N 1-prop-2-ynylbenzimidazole Chemical compound C1=CC=C2N(CC#C)C=NC2=C1 MITDXNUXOAYFGC-UHFFFAOYSA-N 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- NMOJAXCSURVGEY-UHFFFAOYSA-N N#CC#N.[S] Chemical compound N#CC#N.[S] NMOJAXCSURVGEY-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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229940068911 chloride hexahydrate Drugs 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 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
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- VOAPTKOANCCNFV-UHFFFAOYSA-N hexahydrate;hydrochloride Chemical compound O.O.O.O.O.O.Cl VOAPTKOANCCNFV-UHFFFAOYSA-N 0.000 description 1
- 150000007857 hydrazones Chemical class 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
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 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
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 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
- DTMHTVJOHYTUHE-UHFFFAOYSA-N thiocyanogen Chemical compound N#CSSC#N DTMHTVJOHYTUHE-UHFFFAOYSA-N 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
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- GRTBAGCGDOYUBE-UHFFFAOYSA-N yttrium(3+) Chemical compound [Y+3] GRTBAGCGDOYUBE-UHFFFAOYSA-N 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.It is pure with diatom, kyanite, fluorite, glauberite, basalt and astrakanite make carrier after lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add monoalky lether trimethyl ammonium chloride and carry out activation process through ul-trasonic irradiation, then carrier in hydrothermal reaction kettle with composite mineralizer borax and potassium sulfate, catalytic activity auxiliary agent predecessor three (hexafluoroacetylacetone) yttrium (III) dihydrate, three cyclopentadiene promethiums, three (4, 4, (2 thiophene) 1 of 4 trifluoro 1, 3 diacetyl) europium, three (trifluoromethanesulfonimide) ytterbiums, catalytic active center predecessor pyruvic acid isonicotinoyl hydrazone vanadium, cobalt edetate and two thiocyanatos silver（I）Sour potassium, Tris(2,2'- bipyridyl) ruthenium (II) chloride hexahydrate, hydro-thermal reaction is carried out under the effect of emulsifying agent dodecanamide propyl trimethyl sulfate methyl ammonium, and drying removes after moisture that calcination obtains ozone Heterogeneous oxidation solid catalyst in Muffle furnace.
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, fluorite, glauberite, basalt,
Astrakanite is constituted, and by weight, diatom is pure:Kyanite:Fluorite:Glauberite:Basalt:The weight ratio of astrakanite=（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 monoalky lether trimethyl ammonium chloride, by weight, component C:The weight of reaming modified support it
Than=1:（5~10）, D components are by composite mineralizer borax, potassium sulfate, catalytic activity auxiliary agent predecessor three (hexafluoroacetylacetone)
Yttrium (III) dihydrate, three cyclopentadiene promethiums, three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europiums, three (trifluoros
Sulfonyl methane imines) ytterbium Rare-earth chemicals, catalytic active center predecessor normal transition metallo-organic compound third
Ketone acid isonicotinoyl hydrazone vanadium, cobalt edetate and the thiocyanato of precious metal chemical complex two silver（I）Sour potassium, Tris(2,2'- bipyridyl) ruthenium (II) chloride six
Hydrate, emulsifying agent dodecanamide propyl trimethyl sulfate methyl ammonium composition, by weight, borax:Potassium sulfate:Three (hexafluoro second
Acyl acetone) yttrium (III) dihydrate:Three cyclopentadiene promethiums:Three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europiums:
Three (trifluoromethanesulfonimide) ytterbiums:Pyruvic acid isonicotinoyl hydrazone vanadium:Cobalt edetate:Two thiocyanatos silver（I）Sour potassium:Three
Pyridine ruthenic chloride hexahydrate:The weight ratio of dodecanamide propyl trimethyl sulfate methyl ammonium=（4~8）:（6~10）:（3~
6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.The silicon of the B component
Algae is pure, kyanite, fluorite, glauberite, basalt, astrakanite are crushed respectively, and deionized water washing, which is dried, removes moisture
Afterwards, -200 mesh ,+400 mesh sieves point are carried out through standard screen, it is the mm of 0.0370mm~0.0750 control particle diameter.
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, fluorite, glauberite, basalt and astrakanite 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 monoalky lether trimethyl ammonium chloride
C12H25O(CH2CH2O)3N+(CH3)3Cl-The aqueous solution, when control ultrasonic power density, ultrasonic frequency, temperature and sonic oscillation
Between, under ultrasonic cavitation effect, monoalky lether trimethyl ammonium chloride C12H25O(CH2CH2O)3N+(CH3)3Cl-It is easy to from water-soluble
Liquid escapes into reaming modified support duct or is attached to reaming modified support surface, be beneficial to carrier duct be interconnected and
Carrier surface is activated, and enhances adsorptivity；After the completion of ultrasonic activation, ultrasonic surface activated carrier mixed liquor is transferred to hydro-thermal reaction
In kettle, with borax Na2B4O7·10H2O, potassium sulfate K2SO4The composite mineralizer, (hexafluoroacetylacetonate of catalytic activity auxiliary agent predecessor three
Ketone) yttrium (III) dihydrate C15H3F18O6Y·2H2O, three cyclopentadiene promethium Pm (C5H5)3, three (fluoro- 1- (the 2- thiophenes of 4,4,4- tri-
Fen) -1,3- diacetyl) europium C24H18EuF9O6S3, three (trifluoromethanesulfonimide) ytterbium [(CF3SO2)2N]3Yb rare earth metals are organic
Compound, catalytic active center component predecessor normal transition metallo-organic compound pyruvic acid isonicotinoyl hydrazone vanadium [VO2
(C9H8N3O5)] (C5H5N), cobalt edetate C12H22 O14Co and the thiocyanato of precious metal chemical complex two silver（I）Sour potassium K [Ag
(SCN)2], Tris(2,2'- bipyridyl) ruthenium (II) chloride hexahydrate (C10H8N2)3Cl2Ru·(H2O)6, in emulsifying agent dodecanamide propyl trimethyl
Sulfate methyl ammonium [C11H23COCH2CH2CH2N( CH3)3]+ CH3SO4 -Effect is lower to carry out hydro-thermal reaction, and mineralizer accelerates diffusion to make
With, activate reactant lattice, promote the progress of solid phase reaction, ultrasonic surface activated carrier and rare earth metal organic compound
Thing, normal transition metallo-organic compound, precious metal chemical complex Uniform Doped, emulsifying agent dodecanamide propyl trimethyl sulfuric acid first
Ester ammonium makes reaction solution form quasi-stationary emulsion to prevent separation of solid and liquid, sedimentation, while to the further surface active of porous carrier,
By the way that in certain temperature, the hydro-thermal reaction of time, drying obtains the fine silt thing of Uniform Doped；The fine silt thing of Uniform Doped exists
In Muffle furnace, through high temperature sintering, organic matter carbonization therein further enhances the microcellular structure of porous carrier, obtains many
The ozone of the catalytic active center of the carrier loaded rare-earth oxide in hole, transition metal oxide and noble metal formation is heterogeneous
Oxidized solid catalyst, improves the mithridatism and catalytic activity of catalyst.
Relative to art methods, outstanding feature of the present invention be in technology of preparing using diatom is pure, kyanite, fluorite,
Glauberite, basalt, astrakanite porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) berylliums
C10H14BeO4Reaming effect, monoalky lether trimethyl ammonium chloride C12H25O(CH2CH2O)3N+(CH3)3Cl-, dodecanamide propyl
Trimethyl sulfate methyl ammonium [C11H23COCH2CH2CH2N( CH3)3]+ CH3SO4 -To being interconnected and surface active work for duct
With；Rare-earth chemicals, normal transition metallo-organic compound and precious metal chemical complex are reached by hydro-thermal reaction
Uniform Doped is simultaneously attached in carrier surface and duct, and high temperature sintering makes organic matter carbonization strengthen and form multi-level
Microcellular structure, the multi-element metal catalysis of porous carrier supported rare earth metal oxide, transition metal oxide and noble metal formation
Activated centre is combined more firm with porous carrier, and the ozone Heterogeneous oxidation solid catalyst of preparation has stronger absorption
Property, the cooperative effect of multi-element metal, stability and high activity that particularly doped precious metal has can suppress metal catalytic work
Liquating out for property component, improves the mithridatism and catalytic activity of catalyst, 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 fluorites, 5.75g glauberite, 6.75g basalt, 7.75g
The weight of astrakanite, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（3g）:The weight of porous material（31.5g）=1:10.5, heating
To 36 DEG C, reaming modified support 31g is obtained after continuing stirring reaction 3.2h, filtering, 103 DEG C of dry constant weights；In 500ml ultrasonic waves
In reactor, reaming modified support 31g is put into, 3.25g monoalky lether trimethyl ammonium chlorides is added and is dissolved in 100ml deionized waters
The aqueous solution, the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, monoalky lether trimethyl ammonium chloride（3.25g）:Expand
Hole modified support（31g ）=1:9.5；It is 0.4W/m to control ultrasonic power density3, ultrasonic frequency 21kHz, 41 DEG C of temperature, surpass
Sound oscillation 2.2h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor is transferred to 500ml
In hydrothermal reaction kettle, add and be hydrated by 2.1g boraxs, 3.05g potassium sulfates, 1.6g tri- (hexafluoroacetylacetone) yttrium (III) two
Thing, the cyclopentadiene promethiums of 2.05g tri-, 2.6g tri- (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europium, (trifluoros of 3.05g tri-
Sulfonyl methane imines) ytterbium, 5.05g pyruvic acid isonicotinoyl hydrazones vanadium, 6.1g cobalt edetates, the thiocyanatos of 2.05g bis- silver（I）Acid
Potassium, 3.1g Tris(2,2'- bipyridyl) ruthenium (II) chlorides hexahydrate, 3.05g dodecanamide propyl trimethyl sulfate methyl ammoniums and 50ml deionized waters
The aqueous solution of preparation, the weight concentration of the aqueous solution is 40.3%, the weight of the aqueous solution:Ultrasonic surface activated carrier mixed liquor
Weight=83.8g:134.25g=1:1.6,125 DEG C of temperature is controlled, the hydro-thermal reaction time is 8.3h, then dries carefully for 105 DEG C
Powder material；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 non-
Homogeneous oxidizing 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 fluorites, 2.05g glauberite, 2.25g basalt, 2.45g
The weight of astrakanite, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（0.6g）:The weight of porous material（11.7g）=1:19.5, rise
Temperature obtains reaming modified support 11.5g to 48 DEG C after continuing stirring reaction 5.8h, filtering, 105 DEG C of dry constant weights；It is super in 100ml
In sound wave reactor, put into reaming modified support 11.5g, add 2.2g monoalky lether trimethyl ammonium chlorides be dissolved in 26ml go from
The aqueous solution of sub- water, the weight concentration of the aqueous solution is 7.8%, is uniformly mixed, monoalky lether trimethyl ammonium chloride
（2.2g）:Reaming modified support（11.5g ）=1:5.2；It is 0.7W/m to control ultrasonic power density3, ultrasonic frequency 29kHz,
54 DEG C of temperature, sonic oscillation 4.7h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor
It is transferred in 100ml hydrothermal reaction kettles, adds by 0.78g boraxs, 0.97g potassium sulfates, 0.58g tri- (hexafluoroacetylacetone) yttrium
(III) dihydrate, the cyclopentadiene promethiums of 0.67g tri-, 0.78g tri- (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europium,
0.87g tri- (trifluoromethanesulfonimide) ytterbium, 1.48g pyruvic acid isonicotinoyl hydrazones vanadium, 1.77g cobalt edetates, the sulphur cyanogen of 0.68g bis-
Acid group closes silver（I）Sour potassium, 0.87g Tris(2,2'- bipyridyl) ruthenium (II) chlorides hexahydrate, 1.98g dodecanamide propyl trimethyl sulfate methyl ammoniums
The aqueous solution prepared with 10ml deionized waters, the weight concentration of the aqueous solution is 53.3%, the weight of the aqueous solution:Ultrasonic surface
Weight=21.43g of activated carrier mixed liquor:39.7g=1:1.9,175 DEG C of temperature is controlled, the hydro-thermal reaction time is 15.5h, so
Dry to obtain fine silt thing for 105 DEG C afterwards；Fine silt thing is in Muffle furnace, 930 DEG C, calcination 7.5h, after cooling down, can obtain fine powder
Granular 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, fluorite, glauberite, basalt and astrakanite are constituted, by weight, diatom is pure:Kyanite:
Fluorite:Glauberite:Basalt:The weight ratio of astrakanite=（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 monoalky lether front three
Ammonium chloride, by weight, component C:Weight ratio=1 of reaming modified support:（5~10）, D components are by composite mineralizer boron
Sand, potassium sulfate, catalytic activity auxiliary agent predecessor three (hexafluoroacetylacetone) yttrium (III) dihydrate, three cyclopentadiene promethiums, three
(4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europium, three (trifluoromethanesulfonimide) ytterbium rare earth metal organic compounds
Thing, catalytic active center predecessor normal transition metallo-organic compound pyruvic acid isonicotinoyl hydrazone vanadium, cobalt edetate and your gold
Belong to the thiocyanato of compound two silver（I）Sour potassium, Tris(2,2'- bipyridyl) ruthenium (II) chloride hexahydrate, emulsifying agent dodecanamide propyl trimethyl
Sulfate methyl ammonium is constituted, by weight, borax:Potassium sulfate:Three (hexafluoroacetylacetone) yttrium (III) dihydrates:Three rings penta
Diene promethium:Three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europiums:Three (trifluoromethanesulfonimide) ytterbiums:Pyruvic acid
Isonicotinoyl hydrazone vanadium:Cobalt edetate:Two thiocyanatos silver（I）Sour potassium:Tris(2,2'- bipyridyl) ruthenium (II) chloride hexahydrate:Lauroyl
The weight ratio of amine oxypropyl trimethyl sulfate methyl ammonium=（4~8）:（6~10）:（3~6）:（4~7）:（5~8）:（6~9）:
（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.
2. B component is by diatom is pure, kyanite, fluorite, glauberite, basalt and astrakanite are constituted according to claim 1,
Diatom is pure, kyanite, fluorite, glauberite, basalt and astrakanite are crushed respectively, and deionized water washing, which is dried, removes water
After point, sieved through standard screen, it is 0.0370mm~0.0750mm to control particle diameter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710274705.6A CN107051478A (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 |
|---|---|---|---|
| CN201710274705.6A CN107051478A (en) | 2017-04-25 | 2017-04-25 | The preparation method of ozone Heterogeneous oxidation solid catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107051478A true CN107051478A (en) | 2017-08-18 |
Family
ID=59603474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710274705.6A Withdrawn CN107051478A (en) | 2017-04-25 | 2017-04-25 | The preparation method of ozone Heterogeneous oxidation solid catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107051478A (en) |
-
2017
- 2017-04-25 CN CN201710274705.6A patent/CN107051478A/en not_active Withdrawn
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107020109A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107096534A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051529A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051486A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051478A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107020105A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051474A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107159232A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107020111A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107020114A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107029742A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008352A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107088422A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN106984328A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN106984327A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051506A (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 | |
| CN107008344A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008391A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107020108A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008374A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107088420A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008356A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107088419A (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 |