CN107051511A - The preparation method of ozone Heterogeneous oxidation solid catalyst - Google Patents
The preparation method of ozone Heterogeneous oxidation solid catalyst Download PDFInfo
- Publication number
- CN107051511A CN107051511A CN201710275744.8A CN201710275744A CN107051511A CN 107051511 A CN107051511 A CN 107051511A CN 201710275744 A CN201710275744 A CN 201710275744A CN 107051511 A CN107051511 A CN 107051511A
- Authority
- CN
- China
- Prior art keywords
- weight
- component
- iii
- dimethyl
- solid catalyst
- 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- Withdrawn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 24
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 24
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 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 26
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 18
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims abstract description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 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
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 11
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 10
- 229960000892 attapulgite Drugs 0.000 claims abstract description 10
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052637 diopside Inorganic materials 0.000 claims abstract description 10
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 10
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-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 9
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010436 fluorite Substances 0.000 claims abstract description 9
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 9
- 239000011029 spinel Substances 0.000 claims abstract description 9
- -1 sulfonic acid thulium (III) Rare-earth Chemical class 0.000 claims abstract description 9
- 241000723346 Cinnamomum camphora Species 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
- 239000010970 precious metal Substances 0.000 claims abstract description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 229930008380 camphor Natural products 0.000 claims abstract description 7
- 235000002332 ferrous fumarate Nutrition 0.000 claims abstract description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 7
- 230000007704 transition Effects 0.000 claims abstract description 7
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 6
- 229910021538 borax Inorganic materials 0.000 claims abstract description 6
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
- 239000011591 potassium Substances 0.000 claims abstract description 6
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 6
- AUZRORBINHVFFD-UHFFFAOYSA-N [Rh]N=O Chemical compound [Rh]N=O AUZRORBINHVFFD-UHFFFAOYSA-N 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
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- 239000011773 ferrous fumarate Substances 0.000 claims abstract description 5
- 229960000225 ferrous fumarate Drugs 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
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 238000002604 ultrasonography Methods 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
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000005594 diketone group Chemical group 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 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
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- KPQDSKZQRXHKHY-UHFFFAOYSA-N gold potassium Chemical compound [K].[Au] KPQDSKZQRXHKHY-UHFFFAOYSA-N 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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims 1
- FLNKWZNWHZDGRT-UHFFFAOYSA-N azane;dihydrochloride Chemical compound [NH4+].[NH4+].[Cl-].[Cl-] FLNKWZNWHZDGRT-UHFFFAOYSA-N 0.000 claims 1
- 239000001530 fumaric acid Substances 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 16
- 239000011148 porous material Substances 0.000 abstract description 7
- 238000001994 activation Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 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
- 230000004913 activation Effects 0.000 description 4
- 230000008901 benefit Effects 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
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 125000003438 dodecyl group Chemical group [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])C([H])([H])C([H])([H])* 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
- 239000002671 adjuvant Substances 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
- 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
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 2
- 229910000510 noble metal Inorganic materials 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
- 229910052566 spinel group Inorganic materials 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 description 1
- 229910020252 KAuCl4 Inorganic materials 0.000 description 1
- 241000254158 Lampyridae Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- OLGPDUKUFCIQPH-UHFFFAOYSA-N [Na].[Na].[Na].N(=O)[Rh] Chemical compound [Na].[Na].[Na].N(=O)[Rh] OLGPDUKUFCIQPH-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004556 brain Anatomy 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
- 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
- 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
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 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
- WCWKKSOQLQEJTE-UHFFFAOYSA-N praseodymium(3+) Chemical compound [Pr+3] WCWKKSOQLQEJTE-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 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
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- PWWGCBMGIAPMHQ-UHFFFAOYSA-N thulium(3+) Chemical compound [Tm+3] PWWGCBMGIAPMHQ-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J23/8946—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 alkali or alkaline earth metals
-
- 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 to use attapulgite, diopside, fluorite, glauberite, magnesia spinel and peridotite porous material make carrier, carrier is modified through lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add the bay ammonium chloride of surfactant three 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 (3 trifluoroacetyl group D camphors) praseodymium (III), three cyclopentadiene promethiums, three (6, 6, 7, 7, 8, 8, 8 seven fluorine 2, 2 dimethyl 3, 5 octene diketone) dysprosium (III), trifluoromethayl sulfonic acid thulium (III) Rare-earth chemicals, catalytic active center component predecessor normal transition metallo-organic compound ferrous fumarate, citric acid nickel and the golden potassium of precious metal chemical complex tetrachloro, six nitroso rhodium trisodiums, hydro-thermal reaction is carried out under the effect of the hydroxypropyl dichloride ammonium of emulsifying agent N dodecyl dimethyl N ' dodecyl dimethyls 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 attapulgite, diopside, fluorite, glauberite, magnesium point crystalline substance
Stone, peridotite composition, by weight, attapulgite:Diopside:Fluorite:Glauberite:Magnesia spinel:The weight ratio of peridotite=
（5~15）:（7~17）:（9~19）:（11~21）:（13~23）:（15~25）, by weight, component A:The weight of B component
The ratio between=1:（10~20）, component C is three bay ammonium chlorides, by weight, component C:The weight ratio of reaming modified support=
1:（5~10）, D components are by composite mineralizer borax, the potassium sulfate, (3- trifluoroacetyl group-D- camphor trees of catalytic activity auxiliary agent predecessor three
Brain) praseodymium (III), three cyclopentadiene promethiums, three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosiums
(III), trifluoromethayl sulfonic acid thulium (III) Rare-earth chemicals, catalytic active center predecessor normal transition metal has
The golden potassium of machine compound ferrous fumarate, citric acid nickel and precious metal chemical complex tetrachloro, six nitroso rhodium trisodiums, emulsifying agent N- 12
Alkyl dimethyl-N '-dodecyl-dimethyl -2- hydroxypropyl dichlorides ammonium composition, by weight, borax:Potassium sulfate:Three (3-
Trifluoroacetyl group-D- camphors) praseodymium (III):Three cyclopentadiene promethiums:Three (the fluoro- 2,2- dimethyl -3,5- of 6,6,7,7,8,8,8- seven
Octene diketone) dysprosium (III):Trifluoromethayl sulfonic acid thulium (III):Ferrous fumarate:Citric acid nickel:Tetrachloro gold potassium:Six nitroso rhodiums
Trisodium:The weight ratio of N- dodecyl dimethyls-N '-dodecyl-dimethyl -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）.Institute
Attapulgite, diopside, fluorite, glauberite, magnesia spinel, the peridotite for stating B component are crushed respectively, deionized water washing
Dry and remove after moisture, -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
Attapulgite, diopside, fluorite, glauberite, magnesia spinel and peridotite porous material carrier, in certain temperature and stirring bar
Under part, 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 increasing
Plus, filtering dries the reaming modified support input ultrasound reactor after constant weight, adds three bay ammonium chloride [(C12H25)3NCH3]+Cl-The aqueous solution, control ultrasonic power density, ultrasonic frequency, temperature and sonic oscillation time, is turned into ultrasonic air
Under, three bay ammonium chloride [(C12H25)3NCH3]+Cl-It is easy to escape into reaming modified support duct or attachment from the aqueous solution
On reaming modified support surface, it is beneficial to being interconnected and carrier surface activation for carrier duct, enhances adsorptivity；Ultrasound is living
After the completion of change, ultrasonic surface activated carrier mixed liquor is transferred in hydrothermal reaction kettle, with borax Na2B4O7·10H2O, potassium sulfate
K2SO4Composite mineralizer, catalytic activity auxiliary agent predecessor three (3- trifluoroacetyl group-D- camphors) praseodymium (III) C36H42F9O6Pr, three
Cyclopentadiene promethium Pm (C5H5)3, three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosiums (III)
C30H30DyF21O6, trifluoromethayl sulfonic acid thulium (III) C3F9O9S3Before Tm Rare-earth chemicals, catalytic active center component
Drive thing normal transition metallo-organic compound ferrous fumarate C4H2O4Fe, citric acid nickel C12H10O14Ni3With the golden potassium of tetrachloro
KAuCl4, six nitroso rhodium trisodium Na3Rh(NO2)6Precious metal chemical complex, in emulsifying agent N- dodecyl dimethyls-N '-ten two
Alkyl-dimethyl -2- hydroxypropyl dichloride ammoniums [C12H25N(CH3)2CH2CH(OH)CH2N(CH3)2C12H25]2 +Cl2Effect is lower to be carried out
Hydro-thermal reaction-, mineralizer accelerates diffusion, activates reactant lattice, promotes the progress of solid phase reaction, ultrasonic surface is lived
Change carrier and Rare-earth chemicals, normal transition metallo-organic compound, precious metal chemical complex Uniform Doped, emulsifying agent
N- dodecyl dimethyls-N '-dodecyl-dimethyl -2- hydroxypropyl dichloride ammoniums make reaction solution form quasi-stationary emulsion
Separation of solid and liquid, sedimentation are prevented, while to the further surface active of porous carrier, by anti-in certain temperature, the hydro-thermal of time
Should, drying obtains the fine silt thing of Uniform Doped；The fine silt thing of Uniform Doped is therein through high temperature sintering in Muffle furnace
Organic matter carbonization further enhances the microcellular structure of porous carrier, obtain porous carrier supported rare earth metal oxide,
The ozone Heterogeneous oxidation solid catalyst of transition metal oxide and the catalytic active center of noble metal formation, improves catalysis
The mithridatism and catalytic activity of agent.
Relative to art methods, outstanding feature of the present invention is that attapulgite, diopside, firefly are used in technology of preparing
Stone, glauberite, magnesia spinel, peridotite porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) berylliums
C10H14BeO4Reaming effect, three bay ammonium chloride [(C12H25)3NCH3]+Cl-, N- dodecyl dimethyls-N '-dodecane
Base-dimethyl -2- hydroxypropyl dichloride ammoniums [C12H25N(CH3)2CH2CH(OH)CH2N(CH3)2C12H25]2 +Cl2 -Duct it is mutual
Connection and surface activation；By hydro-thermal reaction make Rare-earth chemicals, normal transition metallo-organic compound and
Precious metal chemical complex reaches Uniform Doped and is attached in carrier surface and duct that high temperature sintering strengthens organic matter carbonization
With form multi-level microcellular structure, porous carrier supported rare earth metal oxide, transition metal oxide and noble metal shape
Into multi-element metal catalytic active center more firm, the ozone Heterogeneous oxidation solid catalyst of preparation is combined with porous carrier
With stronger adsorptivity, the cooperative effect of multi-element metal, particularly the doped precious metal stability and high activity that have can be with
Suppress liquating out for metal catalytic activity component, the mithridatism and catalytic activity of catalyst are improved, with good Environmental Effect
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 attapulgites of 400 mesh standard sieves, 3.75g diopsides, 4.75g fluorites, 5.75g glauberite, 6.75g magnesia spinels,
The weight of 7.75g peridotites, 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, the bay ammonium chlorides of 3.25g tri- 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, three bay ammonium chlorides（3.25g）:Reaming, which is modified, to be carried
Body（31g ）=1:9.5；It is 0.4 W/m to control ultrasonic power density3, ultrasonic frequency 21kHz, 41 DEG C of temperature, sonic oscillation
2.2h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor is transferred to 500ml hydro-thermals anti-
Answer in kettle, add by 2.1g boraxs, 3.05g potassium sulfates, 1.6g tri- (3- trifluoroacetyl group-D- camphors) praseodymium (III), 2.05g
Three cyclopentadiene promethiums, 2.6g tri- (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosium (III), 3.05g
The golden potassium of trifluoromethayl sulfonic acid thulium (III), 5.05g ferrous fumarates, 6.1g citric acids nickel, 2.05g tetrachloros, the nitroso rhodiums of 3.1g six
Trisodium, 3.05gN- dodecyl dimethyls-N '-dodecyl-dimethyl -2- hydroxypropyl dichloride 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 attapulgites of 400 mesh standard sieves, 1.65g diopsides, 1.85g fluorites, 2.05g glauberite, 2.25g magnesia spinels,
The weight of 2.45g peridotites, 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, the bay ammonium chlorides of 2.2g tri- is added and is dissolved in 26ml
The aqueous solution of ionized water, the weight concentration of the aqueous solution is 7.8%, is uniformly mixed, three bay ammonium chlorides（2.2g）:Expand
Hole modified support（11.5g ）=1:5.2；It is 0.7 W/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 is transferred to
In 100ml hydrothermal reaction kettles, add by 0.78g boraxs, 0.97g potassium sulfates, 0.58g tri- (3- trifluoroacetyl group-D- camphors)
Praseodymium (III), the cyclopentadiene promethiums of 0.67g tri-, 0.78g tri- (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven)
The golden potassium of dysprosium (III), 0.87g trifluoromethayl sulfonic acids thulium (III), 1.48g ferrous fumarates, 1.77g citric acids nickel, 0.68g tetrachloros,
The nitroso rhodium trisodiums of 0.87g six, 1.98gN- dodecyl dimethyls-N '-dodecyl-dimethyl -2- hydroxypropyl dichloride 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
Divide and be made up of attapulgite, diopside, fluorite, glauberite, magnesia spinel, peridotite, by weight, attapulgite:Diopside:
Fluorite:Glauberite:Magnesia spinel:The weight ratio of peridotite=（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 three bay ammonium chlorides,
By weight, component C:Weight ratio=1 of reaming modified support:（5~10）, D components by composite mineralizer borax, potassium sulfate,
Catalytic activity auxiliary agent predecessor three (3- trifluoroacetyl group-D- camphors) praseodymium (III), three cyclopentadiene promethiums, three (6,6,7,7,8,8,
Fluoro- 2,2- dimethyl -3, the 5- octene diketone of 8- seven) dysprosium (III), trifluoromethayl sulfonic acid thulium (III) Rare-earth chemicals,
Catalytic active center predecessor normal transition metallo-organic compound ferrous fumarate, citric acid nickel and precious metal chemical complex tetrachloro
Golden potassium, six nitroso rhodium trisodiums, emulsifying agent N- dodecyl dimethyls-N '-dodecyl-dimethyl -2- hydroxypropyl dichlorides
Ammonium is constituted, by weight, borax:Potassium sulfate:Three (3- trifluoroacetyl group-D- camphors) praseodymiums (III):Three cyclopentadiene promethiums:Three (6,
The fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,7,7,8,8,8- seven) dysprosium (III):Trifluoromethayl sulfonic acid thulium (III):Fumaric acid is sub-
Iron:Citric acid nickel:Tetrachloro gold potassium:Six nitroso rhodium trisodiums:N- dodecyl dimethyls-N '-dodecyl-dimethyl -2- hydroxyls
The weight ratio of propyl group dichloride 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 attapulgite, diopside, fluorite, glauberite, magnesia spinel, peridotite group according to claim 1
Into attapulgite, diopside, fluorite, glauberite, magnesia spinel, peridotite 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 |
|---|---|---|---|
| CN201710275744.8A CN107051511A (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 |
|---|---|---|---|
| CN201710275744.8A CN107051511A (en) | 2017-04-25 | 2017-04-25 | The preparation method of ozone Heterogeneous oxidation solid catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107051511A true CN107051511A (en) | 2017-08-18 |
Family
ID=59604582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710275744.8A Withdrawn CN107051511A (en) | 2017-04-25 | 2017-04-25 | The preparation method of ozone Heterogeneous oxidation solid catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107051511A (en) |
-
2017
- 2017-04-25 CN CN201710275744.8A patent/CN107051511A/en not_active Withdrawn
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106984330A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051486A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008414A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051511A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107159253A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008428A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051503A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051506A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008435A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051512A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107088430A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107020131A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008437A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051505A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008398A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107159254A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051520A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008439A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107159243A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051533A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN106984329A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107159250A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107042118A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107029747A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008438A (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 |
Application publication date: 20170818 |
|
| WW01 | Invention patent application withdrawn after publication |