CN107008466A - The preparation method of ozone Heterogeneous oxidation solid catalyst - Google Patents
The preparation method of ozone Heterogeneous oxidation solid catalyst Download PDFInfo
- Publication number
- CN107008466A CN107008466A CN201710275437.XA CN201710275437A CN107008466A CN 107008466 A CN107008466 A CN 107008466A CN 201710275437 A CN201710275437 A CN 201710275437A CN 107008466 A CN107008466 A CN 107008466A
- Authority
- CN
- China
- Prior art keywords
- component
- weight
- double
- acetylacetone
- 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- Withdrawn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 31
- 230000003647 oxidation Effects 0.000 title claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 27
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 70
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 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 16
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 12
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 11
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 11
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims abstract description 11
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 claims abstract description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 10
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052601 baryte Inorganic materials 0.000 claims abstract description 10
- 239000010428 baryte Substances 0.000 claims abstract description 10
- PALNZFJYSCMLBK-UHFFFAOYSA-K magnesium;potassium;trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-].[Cl-].[K+] PALNZFJYSCMLBK-UHFFFAOYSA-K 0.000 claims abstract description 10
- 239000001103 potassium chloride Substances 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 claims abstract description 9
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 8
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 8
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 239000011591 potassium Substances 0.000 claims abstract description 8
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 8
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 7
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims abstract description 6
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004472 Lysine Substances 0.000 claims abstract description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 6
- ITZXULOAYIAYNU-UHFFFAOYSA-N cerium(4+) Chemical compound [Ce+4] ITZXULOAYIAYNU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229930195712 glutamate Natural products 0.000 claims abstract description 6
- 229910052779 Neodymium 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
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- -1 dodecyldimethylamines Ammonium chloride Chemical class 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000010970 precious metal Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000004576 sand Substances 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- BOLCLFSSFZOGPX-UHFFFAOYSA-N N.[Cl-].C(CCCCCCCCCCC)[NH+](C)C Chemical class N.[Cl-].C(CCCCCCCCCCC)[NH+](C)C BOLCLFSSFZOGPX-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 238000001994 activation Methods 0.000 abstract description 5
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000036571 hydration Effects 0.000 abstract description 4
- 238000006703 hydration reaction Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 150000002910 rare earth metals Chemical class 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 235000018977 lysine Nutrition 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000007787 solid Substances 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
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002306 glutamic acid derivatives Chemical class 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002669 lysines Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 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
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002242 deionisation method 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
- 230000009931 harmful effect Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 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
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007790 solid phase Substances 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
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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.With gamma-alumina, barite, activated carbon, carnallite, it is modified through lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings that montmorillonite and sylvite make carrier, add the double dodecyldimethylamine ammonium chlorides of surfactant 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 four (2, 2, 6, 6 tetramethyls 3, 5 heptadione acid) cerium (IV), 1, 1, 1 trifluoroacetylacetone (TFA) neodymium, three cyclopentadiene promethiums, acetylacetone,2,4-pentanedione samarium, catalytic active center predecessor lysine manganese, cupric glutamate and two thiocyanatos silver（I）Sour potassium, the hydration iridium of tetrachloro two, it is double in emulsifying agent diethyl maleate base（Chlorination dodecyl dimethyl ammonium）Calcination obtains ozone Heterogeneous oxidation solid catalyst in Muffle furnace after the lower progress hydro-thermal reaction of effect, drying removing moisture.
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 gama-alumina, barite, activated carbon, carnallite, illiteracy
De- soil, sylvite composition, by weight, gama-alumina:Barite:Activated carbon:Carnallite:Montmorillonite:The weight of sylvite it
Than=（5~15）:（7~17）:（9~19）:（11~21）:（13~23）:（15~25）, by weight, component A:B component
Weight ratio=1:（10~20）, component C is double dodecyldimethylamine ammonium chlorides, by weight, component C:Reaming modified support
Weight ratio=1:（5~10）, D components by composite mineralizer borax, potassium sulfate, catalytic activity auxiliary agent predecessor four (2,2,6,
6- tetramethyl -3,5- heptadione acid) cerium (IV), 1,1,1- trifluoroacetylacetone (TFA)s neodymium, three cyclopentadiene promethiums, acetylacetone,2,4-pentanedione samarium rare earth
Metallo-organic compound, catalytic active center predecessor normal transition metallo-organic compound lysine manganese, cupric glutamate and expensive
The thiocyanato of metallic compound two silver（I）Sour potassium, the hydration iridium of tetrachloro two, emulsifying agent diethyl maleate base are double（Chlorination 12
Alkyl dimethyl ammonium）Composition, by weight, borax:Potassium sulfate:Four (DPM dpm,dipivalomethane acid) ceriums (IV):
1,1,1- trifluoroacetylacetone (TFA) neodymiums:Three cyclopentadiene promethiums:Acetylacetone,2,4-pentanedione samarium:Lysine manganese:Cupric glutamate:Two thiocyanatos silver
（I）Sour potassium:Tetrachloro two is hydrated iridium:Diethyl maleate base is double（Chlorination dodecyl dimethyl ammonium）Weight ratio=（4~8）:
（6~10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.
Gama-alumina, barite, activated carbon, carnallite, montmorillonite, sylvite in the B component are crushed respectively, deionization
Water washing, which is dried, to be removed after moisture, and -200 mesh ,+400 mesh sieves point are carried out through standard screen, and it is 0.0370mm~0.0750 to control particle diameter
mm。
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
Gama-alumina, barite, activated carbon, carnallite, montmorillonite and sylvite porous material carrier, in certain temperature and stirring
Under the conditions of, 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 double dodecyldimethylamine ammonium chlorides
[(C14H29)2N(CH3)2]+Cl-The aqueous solution, control ultrasonic power density, ultrasonic frequency, temperature and sonic oscillation time, super
Under sound wave cavitation, double dodecyldimethylamine ammonium chloride [(C14H29)2N(CH3)2]+Cl-It is easy to escape into from the aqueous solution
Reaming modified support duct is attached to reaming modified support surface, is beneficial to being interconnected and carrier surface work for carrier duct
Change, enhance adsorptivity；After the completion of ultrasonic activation, ultrasonic surface activated carrier mixed liquor is transferred in hydrothermal reaction kettle, with boron
Sand Na2B4O7·10H2O, potassium sulfate K2SO4Composite mineralizer, (2,2,6, the 6- tetramethyls -3,5- of catalytic activity auxiliary agent predecessor four
Heptadione acid) cerium (IV) C22H38CeO4, 1,1,1- trifluoroacetylacetone (TFA) neodymiums C15H12F9NdO6, three cyclopentadiene promethium Pm (C5H5)3、
Acetylacetone,2,4-pentanedione samarium C15H25O8Sm Rare-earth chemicals, catalytic active center component predecessor normal transition Organometallic
Compound lysine manganese C12H26N4O4, cupric glutamate C5H7NO4Cu and the thiocyanato of precious metal chemical complex two silver（I）Sour potassium K [Ag
(SCN)2], the hydration of tetrachloro two iridium Ir (H2O)2Cl4, it is double in emulsifying agent diethyl maleate base（Chlorination dodecyl dimethyl ammonium）
C36H72N2O4Cl2Effect is lower to carry out hydro-thermal reaction, and mineralizer accelerates diffusion, activates reactant lattice, promotes solid phase
The progress of reaction, ultrasonic surface activated carrier and Rare-earth chemicals, normal transition metallo-organic compound, noble metal
Compound Uniform Doped, emulsifying agent diethyl maleate base is double（Chlorination dodecyl dimethyl ammonium）Make reaction solution formation quasi-steady state
Emulsion prevent separation of solid and liquid, sedimentation, while to the further surface active of porous mineral carrier, by certain temperature, when
Between hydro-thermal reaction, drying obtains the fine silt thing of Uniform Doped；The fine silt thing of Uniform Doped burns in Muffle furnace through high temperature
Burn, organic matter carbonization therein further enhances the microcellular structure of porous carrier, obtain porous carrier supported rare earth gold
Belong to the ozone Heterogeneous oxidation solid catalyst of the catalytic active center of oxide, transition metal oxide and noble metal formation,
Improve the mithridatism and catalytic activity of catalyst.
Relative to art methods, outstanding advantages of the present invention are that gama-alumina, barite, work are used in technology of preparing
Property charcoal, carnallite, montmorillonite, sylvite porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) berylliums
C10H14BeO4Reaming effect, double dodecyldimethylamine ammonium chloride [(C14H29)2N(CH3)2]+Cl-Diethyl maleate base is double
（Chlorination dodecyl dimethyl ammonium）C36H72N2O4Cl2To being interconnected and surface activation for duct；Pass through hydro-thermal reaction
Rare-earth chemicals, normal transition metallo-organic compound and precious metal chemical complex is set to reach Uniform Doped and be attached to
In carrier surface and duct, high temperature sintering makes organic matter carbonization strengthen and form multi-level microcellular structure, porous load
The multi-element metal catalytic active center of body supported rare earth metal oxide, transition metal oxide and noble metal formation is carried with porous
Body combination is more firm, and the ozone Heterogeneous oxidation solid catalyst of preparation has stronger adsorptivity, the collaboration of multi-element metal
Effect, stability and high activity that particularly doped precious metal has, can suppress liquating out for metal catalytic activity component, carry
The mithridatism and catalytic activity of high 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 gama-aluminas of 400 mesh standard sieves, 3.75g barites, 4.75g activated carbons, 5.75g carnallites, 6.75g montmorillonites,
The weight of 7.75g sylvites, 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 double dodecyldimethylamine ammonium chlorides of 3.25g is added and is dissolved in 100ml
The aqueous solution of ionized water, the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, double dodecyldimethylamine ammonium chlorides
（3.25g）:Reaming modified support（31g ）=1:9.5；It is 0.4W/m to control ultrasonic power density3, ultrasonic frequency 21kHz, temperature
41 DEG C of degree, sonic oscillation 2.2h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor is turned
Move in 500ml hydrothermal reaction kettles, add by 2.1g boraxs, 3.05g potassium sulfates, (2,2,6, the 6- tetramethyls -3,5- of 1.6g tetra-
Heptadione acid) cerium (IV), 2.05g1,1,1- trifluoroacetylacetone (TFA)s neodymium, the cyclopentadiene promethiums of 2.6g tri-, 3.05g acetylacetone,2,4-pentanediones samarium,
5.05g lysines manganese, 6.1g cupric glutamates, the thiocyanatos of 2.05g bis- silver（I）Sour potassium, the hydration of 3.1g tetrachloros two iridium, 3.05g
Diethyl maleate base is double（Chlorination dodecyl dimethyl ammonium）The aqueous solution prepared with 50ml deionized waters, the weight of the aqueous solution
It is 40.3%, the weight of the aqueous solution to measure concentration:Weight=83.8g of ultrasonic surface activated carrier mixed liquor:134.25g=1:
1.6,125 DEG C of temperature is controlled, the hydro-thermal reaction time is 8.3h, then dries to obtain fine silt thing for 105 DEG C；Fine silt thing is in Muffle furnace
Interior, 620 DEG C, calcination 3.2h after cooling down, can obtain the ozone Heterogeneous oxidation solid catalyst of fine particle shape.
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 gama-aluminas of 400 mesh standard sieves, 1.65g barites, 1.85g activated carbons, 2.05g carnallites, 2.25g montmorillonites,
The weight of 2.45g sylvites, 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 double dodecyldimethylamine ammonium chlorides of 2.2g are added molten
In the aqueous solution of 26ml deionized waters, the weight concentration of the aqueous solution is 7.8%, is uniformly mixed, double dodecyldimethylamine bases
Ammonium chloride（2.2g）:Reaming modified support（11.5g ）=1:5.2；It is 0.7W/m to control ultrasonic power density3, ultrasonic frequency
54 DEG C of 29kHz, temperature, sonic oscillation 4.7h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier in ultrasound reactor
Mixed liquor is transferred in 100ml hydrothermal reaction kettles, is added by 0.78g boraxs, 0.97g potassium sulfates, 0.58g tetra- (2,2,6,6-
Tetramethyl -3,5- heptadione acid) cerium (IV), 0.67g1,1,1- trifluoroacetylacetone (TFA)s neodymium, the cyclopentadiene promethiums of 0.78g tri-, 0.87g
Acetylacetone,2,4-pentanedione samarium, 1.48g lysines manganese, 1.77g cupric glutamates, the thiocyanatos of 0.68g bis- silver（I）Sour potassium, 0.87g tetrachloros two
It is hydrated iridium, 1.98g diethyl maleates base double（Chlorination dodecyl dimethyl ammonium）The aqueous solution prepared with 10ml deionized waters,
The weight concentration of the aqueous solution is 53.3%, the weight of the aqueous solution:Weight=21.43g of ultrasonic surface activated carrier mixed liquor:
39.7g=1:1.9,175 DEG C of temperature is controlled, the hydro-thermal reaction time is 15.5h, then dries to obtain fine silt thing for 105 DEG C；Fine silt
Thing is in Muffle furnace, 930 DEG C, calcination 7.5h, after cooling down, and the ozone Heterogeneous oxidation solid that can obtain fine particle shape is urged
Agent.
Comparative example 1:Preparation process be not added with lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, double dodecyldimethylamine ammonium chlorides,
Diethyl maleate base is double（Chlorination dodecyl dimethyl ammonium）, outside borax and potassium sulfate, whole preparation process, preparation condition and
Embodiment 1 is identical.
The parameter of ozone Heterogeneous oxidation solid catalyst prepared by embodiment 1, embodiment 2 and comparative example 1 is included in table 1.
The embodiment of table 1 and comparative example prepare ozone Heterogeneous oxidation solid catalysis agent parameter
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 is by lithium hypochlorite, double (acetyl
Acetone) beryllium composition, by weight, lithium hypochlorite:Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B component by γ-
Aluminum oxide, barite, activated carbon, carnallite, montmorillonite, sylvite composition, by weight, gama-alumina:Barite:It is living
Property charcoal:Carnallite:Montmorillonite:The weight ratio of sylvite=（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 double dodecyldimethylamines
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 four (2,2,6,6- tetramethyl -3,5- heptadione acid) cerium (IV), 1,1,1- trifluoro
Acetylacetone,2,4-pentanedione neodymium, three cyclopentadiene promethiums, acetylacetone,2,4-pentanedione samarium Rare-earth chemicals, catalytic active center predecessor are common
Transition metal organometallic compound lysine manganese, cupric glutamate and the thiocyanato of precious metal chemical complex two silver（I）Sour potassium, tetrachloro two
Iridium is hydrated, emulsifying agent diethyl maleate base is double（Chlorination dodecyl dimethyl ammonium）Composition, by weight, borax:Potassium sulfate:
Four (DPM dpm,dipivalomethane acid) ceriums (IV):1,1,1- trifluoroacetylacetone (TFA) neodymiums:Three cyclopentadiene promethiums:Acetyl
Acetone samarium:Lysine manganese:Cupric glutamate:Two thiocyanatos silver（I）Sour potassium:Tetrachloro two is hydrated iridium:Diethyl maleate base
It is double（Chlorination dodecyl dimethyl ammonium）Weight ratio=（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 gama-alumina, barite, activated carbon, carnallite, montmorillonite, sylvite according to claim 1
Composition, gama-alumina, barite, activated carbon, carnallite, montmorillonite, sylvite are crushed respectively, deionized water washing
Dry and remove 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 |
|---|---|---|---|
| CN201710275437.XA CN107008466A (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 |
|---|---|---|---|
| CN201710275437.XA CN107008466A (en) | 2017-04-25 | 2017-04-25 | The preparation method of ozone Heterogeneous oxidation solid catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107008466A true CN107008466A (en) | 2017-08-04 |
Family
ID=59447241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710275437.XA Withdrawn CN107008466A (en) | 2017-04-25 | 2017-04-25 | The preparation method of ozone Heterogeneous oxidation solid catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107008466A (en) |
-
2017
- 2017-04-25 CN CN201710275437.XA patent/CN107008466A/en not_active Withdrawn
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107051529A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008395A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008400A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107042115A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008466A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107159234A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008391A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051531A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008401A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051536A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051530A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008393A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051535A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008309A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008434A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008392A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008297A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008441A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008345A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008307A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008440A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008361A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051526A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008310A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051534A (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: 20170804 |