CN107042109A - The preparation method of ozone Heterogeneous oxidation solid catalyst - Google Patents
The preparation method of ozone Heterogeneous oxidation solid catalyst Download PDFInfo
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- CN107042109A CN107042109A CN201710277035.3A CN201710277035A CN107042109A CN 107042109 A CN107042109 A CN 107042109A CN 201710277035 A CN201710277035 A CN 201710277035A CN 107042109 A CN107042109 A CN 107042109A
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 230000003647 oxidation Effects 0.000 title claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 29
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 46
- 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 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims abstract description 14
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004575 stone Substances 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 11
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000010436 fluorite Substances 0.000 claims abstract description 10
- 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
- 239000010456 wollastonite Substances 0.000 claims abstract description 10
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 10
- 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
- KHFLASRWTYBRDK-UHFFFAOYSA-M tributyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](CCCC)(CCCC)CCCC KHFLASRWTYBRDK-UHFFFAOYSA-M 0.000 claims abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 8
- 150000001413 amino acids Chemical class 0.000 claims abstract description 8
- 235000016768 molybdenum Nutrition 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
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 8
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 claims abstract description 8
- 235000000193 zinc lactate Nutrition 0.000 claims abstract description 8
- 235000005340 Asparagus officinalis Nutrition 0.000 claims abstract description 7
- ZCPCLAPUXMZUCD-UHFFFAOYSA-M dihexadecyl(dimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCC ZCPCLAPUXMZUCD-UHFFFAOYSA-M 0.000 claims abstract description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021538 borax Inorganic materials 0.000 claims abstract description 6
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229960004889 salicylic acid Drugs 0.000 claims abstract description 6
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 6
- 229940050168 zinc lactate Drugs 0.000 claims abstract description 6
- 239000011576 zinc lactate Substances 0.000 claims abstract description 6
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 5
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 5
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims abstract description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 4
- BENADMAVJUZZBP-UHFFFAOYSA-N [O-2].C(C)(C)[Sc+2] Chemical compound [O-2].C(C)(C)[Sc+2] BENADMAVJUZZBP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- -1 sulfonic acid thulium (III) Rare-earth Chemical class 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 230000007704 transition Effects 0.000 claims description 7
- 241000234427 Asparagus Species 0.000 claims description 6
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- 241000209140 Triticum Species 0.000 claims 2
- 235000021307 Triticum Nutrition 0.000 claims 2
- 235000012054 meals Nutrition 0.000 claims 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000004576 sand Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 238000001994 activation Methods 0.000 abstract description 7
- 229910052693 Europium Inorganic materials 0.000 abstract description 6
- 239000012752 auxiliary agent Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 244000003416 Asparagus officinalis Species 0.000 abstract 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 229910001868 water Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 235000007686 potassium Nutrition 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000000052 comparative effect 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
- 239000003643 water by type Substances 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 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
- 238000001179 sorption measurement Methods 0.000 description 3
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229960003019 loprazolam Drugs 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 150000003870 salicylic acids Chemical class 0.000 description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- GYOFRJOMHLYJNZ-UHFFFAOYSA-N tributyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](CCCC)(CCCC)CCCC GYOFRJOMHLYJNZ-UHFFFAOYSA-N 0.000 description 2
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- XJENSLNYTFOSKA-UHFFFAOYSA-M [Cl-].C(CCCCCCCCCCCCCCC)[N+](CC1=CC=CC=C1)(C)C.[Cl-].[NH4+] Chemical compound [Cl-].C(CCCCCCCCCCCCCCC)[N+](CC1=CC=CC=C1)(C)C.[Cl-].[NH4+] XJENSLNYTFOSKA-UHFFFAOYSA-M 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
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- 230000002079 cooperative 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
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- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UTEFBSAVJNEPTR-RGEXLXHISA-N loprazolam Chemical compound C1CN(C)CCN1\C=C/1C(=O)N2C3=CC=C([N+]([O-])=O)C=C3C(C=3C(=CC=CC=3)Cl)=NCC2=N\1 UTEFBSAVJNEPTR-RGEXLXHISA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000010232 propyl p-hydroxybenzoate Nutrition 0.000 description 1
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- 229960003415 propylparaben Drugs 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
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- 241000894007 species Species 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- PWWGCBMGIAPMHQ-UHFFFAOYSA-N thulium(3+) Chemical compound [Tm+3] PWWGCBMGIAPMHQ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/686—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with molybdenum
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- B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
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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 medical stone, wollastonite, activated carbon, carnallite, fluorite and glauberite multichip carrier are after lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add surfactant myristyl tributyl ammonium chloride and activation process is carried out under ul-trasonic irradiation, then carrier in hydrothermal reaction kettle with composite mineralizer borax and potassium sulfate, catalytic activity auxiliary agent predecessor isopropyl scandium oxide (III), three (4, 4, (2 thiophene) 1 of 4 trifluoro 1, 3 diacetyl) europium, three (2, 2, 6, 6 tetramethyls 3, 5 heptadione acid) gadolinium, trifluoromethayl sulfonic acid thulium (III), catalytic active center predecessor titanocenes ring substituted salicylic acid complex, zinc lactate, L lucid asparagus amino acid molybdenums and two thiocyanatos silver（I）Sour potassium, hydro-thermal reaction is carried out under the effect of emulsifying agent Varisoft 432PPG, and drying removes after moisture that calcination obtains ozone Heterogeneous oxidation solid catalyst in Muffle furnace.
Description
Technical field
The present invention relates to a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, category environmental protection and chemical catalyst skill
Art field.
Background technology
Ozonation technology using ozone oxidation ability it is strong the characteristics of, can be by many organic pollution oxidation Decompositions, extensively
For wastewater treatment.Catalytic ozonation technology is divided into ozone homogeneous catalytic oxidation and ozone heterogeneous catalytic oxidation, and ozone is equal
Phase catalysis oxidation has that the more difficult separation and recovery of catalyst is reused, ozone utilization rate is low causes water process operating cost higher,
Organic pollutant removal rate is relatively low simultaneously and easily causing secondary pollution of water is limited to its application；Ozone heterogeneous catalysis oxygen
There is change technology catalyst to be easily isolated and recycled and reusable, ozone utilization rate is high, organic pollutant removal rate is higher, drop
Low water process operating cost and receive significant attention its application the advantages of do not result in secondary pollution.Ozone heterogeneous catalysis
It is to reach local organic matter enrichment by catalyst surface absorption organic matter that oxidation of organic compounds, which is decomposed, while ozone molecule absorption exists
The hydroxyl radical free radical that catalyst surface produces high activity under catalyst action decomposes organic matter.Ozone heterogeneous catalytic oxidation
Handle in waste water technology, core technology is the preparation of ozone Heterogeneous oxidation solid catalyst.
Ozone Heterogeneous oxidation solid catalyst is generally made up of carrier, activated centre and auxiliary agent.Due to being polluted in waste water
Species are various, complex chemical composition feature, can produce harmful effect to performance such as absorption, the mithridatism of catalyst.
Prepare that the carrier structure that ozone Heterogeneous oxidation solid catalyst uses is more single at present, adsorptivity is relatively low；Activated centre is universal
Using normal transition metal salt, mithridatism is poor；Preparation method mainly has infusion process, the precipitation method, mixing method and collosol and gel etc.
Method attachment activity center and adjuvant component are easily liquated out in carrier surface, activated centre and adjuvant component, cause catalyst
Easily lose catalytic activity.For exist in current ozone Heterogeneous oxidation solid catalyst preparation method Catalyst Adsorption compared with
Low, mithridatism is poor and easily loses catalytic activity problem, and exploitation is strengthened using multicomponent porous carrier through reaming, surface active
Catalyst Adsorption, makees catalytic activity auxiliary agent predecessor, normal transition Organometallic using rare earth organo-metallic compound 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 organo-metallic compound
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 by medical stone, wollastonite, activated carbon, carnallite, fluorite,
Glauberite is constituted, by weight, medical stone:Wollastonite:Activated carbon:Carnallite:Fluorite:The weight ratio of glauberite=（5~
15）:（7~17）:（9~19）:（11~21）:（13~23）:（15~25）, by weight, component A:The weight ratio of B component
=1:（10~20）, component C is myristyl tributyl ammonium chloride, by weight, component C:The weight ratio of reaming modified support
=1:（5~10）, D components are by composite mineralizer borax, potassium sulfate, catalytic activity auxiliary agent predecessor isopropyl scandium oxide (III), three
(4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europium, three (DPM dpm,dipivalomethane acid) gadoliniums, trifluoro
Loprazolam thulium (III) Rare-earth chemicals, catalytic active center predecessor normal transition metallo-organic compound two
Luxuriant titanacycle substituted salicylic acid complex, zinc lactate, L- lucid asparagus amino acid molybdenums and the thiocyanato of precious metal chemical complex two silver（I）
Sour potassium, emulsifying agent Varisoft 432PPG composition, by weight, borax:Potassium sulfate:Isopropyl scandium oxide (III):Three
(4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europium:Three (DPM dpm,dipivalomethane acid) gadoliniums:Fluoroform
Alkyl sulfonic acid thulium (III):Titanocenes ring substituted salicylic acid complex:Zinc lactate:L- lucid asparagus amino acid molybdenums:Two thiocyanatos
Silver（I）Sour potassium:The weight ratio of Varisoft 432PPG=（4~8）:（6~10）:（3~6）:（4~7）:（5~
8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.Medical stone, wollastonite in the B component,
Activated carbon, carnallite, fluorite, glauberite are crushed respectively, and deionized water washing, which is dried, to be removed after moisture, is entered through standard screen
- 200 mesh of row ,+400 mesh sieves point, 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
Medical stone, wollastonite, activated carbon, carnallite, fluorite and glauberite porous material carrier, in certain temperature and stirring condition
Under, the small Be of aqueous solution Ionic Radius2+（0.31Å）、Li+（0.60Å）Displace part ion radius in porous material big
Ca2+（0.99Å）、K+（1.33Å）、Ba2+（1.35Å）Plasma, the aperture of porous material carrier becomes big, surface roughness increase,
Filtering, dries the reaming modified support input ultrasound reactor after constant weight, adds myristyl tributyl ammonium chloride
C14H29N+(C4H9)3Cl- The aqueous solution, control ultrasonic power density, ultrasonic frequency, temperature and sonic oscillation time, in ultrasound
Under ripple cavitation, myristyl tributyl ammonium chloride C14H29N+(C4H9)3Cl- It is easy to escape into reaming modification from the aqueous solution
Carrier duct is attached to reaming modified support surface, is beneficial to being interconnected and carrier surface activation for carrier duct, enhancing
Adsorptivity；After the completion of ultrasonic activation, 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 isopropyl scandium oxide (III) C9H21O3Sc、
Three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europium C24H18EuF9O6S3, three (2,2,6,6- tetramethyls -3,5- heptan two
Ketone acid) gadolinium C33H57GdO6, trifluoromethayl sulfonic acid thulium (III) C18H54ErN3Si6Rare-earth chemicals, catalytic active center
Predecessor normal transition metallo-organic compound titanocenes ring substituted salicylic acid complex (C10H10)Ti(C7H4O3), zinc lactate
C5H7NO4Cu, L- lucid asparagus amino acid molybdenum Ir (H2O)2Cl4With two thiocyanatos silver（I）Sour potassium Pt (NH3)2Cl2Noble metal
Compound, in emulsifying agent Varisoft 432PPG [(C14H29)2N(CH3)2]+Cl-Effect is lower to carry out hydro-thermal reaction, mineralising
Agent accelerates diffusion, activates reactant lattice, promotes the progress of solid phase reaction, ultrasonic surface activated carrier and rare earth gold
Belong to organic compound, normal transition organo-metallic compound, precious metal chemical complex Uniform Doped, emulsifying agent double hexadecyl diformazan
Ammonium chloride make reaction solution formed quasi-stationary emulsion prevent separation of solid and liquid, sedimentation, while to the further surface of porous carrier
Activation, by the way that in certain temperature, the hydro-thermal reaction of time, drying obtains the fine silt thing of Uniform Doped；The fine powder of Uniform Doped
Grain thing is in Muffle furnace, and through high temperature sintering, organic matter carbonization therein further enhances the microcellular structure of porous carrier,
Obtain the ozone of the catalytic active center of porous carrier supported rare earth metal oxide, transition metal oxide and noble metal formation
Heterogeneous oxidation solid catalyst, improves the mithridatism and catalytic activity of catalyst.
Relative to art methods, outstanding advantages of the present invention are that medical stone, wollastonite, activity are used in technology of preparing
Charcoal, carnallite, fluorite, glauberite porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) beryllium C10H14BeO4
Reaming effect, myristyl tributyl ammonium chloride C14H29N+(C4H9)3Cl-, Varisoft 432PPG [(C14H29)2N(CH3)2]+Cl- To being interconnected and surface activation for duct；By hydro-thermal reaction make rare earth organo-metallic compound,
Normal transition metallo-organic compound and precious metal chemical complex reach Uniform Doped and be attached in carrier surface and duct, high temperature
Calcination makes organic matter carbonization reinforcing and forms multi-level microcellular structure, porous carrier supported rare earth metal oxide,
Transition metal oxide and noble metal formation multi-element metal catalytic active center combined with porous carrier it is more firm, preparation
Ozone Heterogeneous oxidation solid catalyst has stronger adsorptivity, the particularly cooperative effect of multi-element metal, doped precious metal
The stability and high activity having, can suppress liquating out for metal catalytic activity component, improve catalyst mithridatism and
Catalytic activity, 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 are added to volume for 500ml
Can be uniformly mixed in closed reactor, the weight concentration of the aqueous solution is 2.1%, lithium hypochlorite:Double (acetylacetone,2,4-pentanedione) berylliums
Weight ratio=1:1.2；Add deionized water wash to it is neutral, 103 DEG C dry and remove the mesh of -200 mesh of sieving after moisture~+400
The 2.75g medical stones of standard screen, 3.75g wollastonites, 4.75g activated carbons, 5.75g carnallites, 6.75g fluorites, 7.75g calcium awns
The weight of nitre, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（3g）:The weight of porous material（31.5g）=1:10.5, it is warming up to 36
DEG C, obtain reaming modified support 31g after continuing stirring reaction 3.2h, filtering, 103 DEG C of dry constant weights；In 500ml ultrasonic responses
In device, reaming modified support 31g is put into, the water that 3.25g myristyl tributyl ammonium chlorides are dissolved in 100ml deionized waters is added
Solution, the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, myristyl tributyl ammonium chloride（3.25g）:Reaming
Modified support（31g ）=1:9.5；It is 0.4 W/m to control ultrasonic power density3, ultrasonic frequency 21kHz, 41 DEG C of temperature, ultrasound
Vibrate 2.2h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor is transferred to 500ml water
In thermal response kettle, add by 2.1g boraxs, 3.05g potassium sulfates, 1.6g isopropyls scandium oxide (III), 2.05g tri- (4,4,4- tri-
Fluoro- 1- (2- thiophene) -1,3- diacetyl) europium, 2.6g tri- (DPM dpm,dipivalomethane acid) gadolinium, 3.05g trifluoros
Loprazolam thulium (III), 5.05g titanocenes ring substituted salicylic acids complex, 6.1g zinc lactates, 2.05g L- lucid asparagus amino acid
Molybdenum, the thiocyanatos of 3.1g bis- silver（I）What sour potassium, 3.05g Varisoft 432PPGs and 50ml deionized waters were prepared
The aqueous solution, the weight concentration of the aqueous solution is 40.3%, the weight of the aqueous solution:The weight of ultrasonic surface activated carrier mixed liquor=
83.8g:134.25g =1:1.6,125 DEG C of temperature is controlled, the hydro-thermal reaction time is 8.3h, then dries to obtain fine silt for 105 DEG C
Thing；Fine silt thing is in Muffle furnace, 620 DEG C, calcination 3.2h, and after cooling down, the ozone that can obtain fine particle shape is heterogeneous
Oxidized solid catalyst.
Embodiment 2:0.24g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 0.36g, 10ml deionized waters, being added to volume is
100ml's can be uniformly mixed in closed reactor, and the weight concentration of the aqueous solution is 5.7%, lithium hypochlorite:Double (levulinics
Ketone) beryllium weight ratio=1:1.5；Add deionized water wash to it is neutral, 103 DEG C dry remove -200 mesh of sieving after moisture~+
1.45g medical stones, 1.65g wollastonites, 1.85g activated carbons, 2.05g carnallites, 2.25g fluorites, the 2.45g of 400 mesh standard sieves
The weight of glauberite, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（0.6g）:The weight of porous material（11.7g）=1:19.5, heating
To 48 DEG C, reaming modified support 11.5g is obtained after continuing stirring reaction 5.8h, filtering, 105 DEG C of dry constant weights；In 100ml ultrasounds
In ripple reactor, reaming modified support 11.5g is put into, 2.2g myristyl tributyl ammonium chlorides is added and is dissolved in 26ml deionizations
The aqueous solution of water, the weight concentration of the aqueous solution is 7.8%, is uniformly mixed, myristyl tributyl ammonium chloride（2.2g）:
Reaming modified support（11.5g ）=1:5.2；It is 0.7 W/m to control ultrasonic power density3, ultrasonic frequency 29kHz, temperature 54
DEG C, 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 isopropyls scandium oxide (III), 0.67g tri-
(4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europium, 0.78g tri- (DPM dpm,dipivalomethane acid) gadolinium,
0.87g trifluoromethayl sulfonic acids thulium (III), 1.48g titanocenes ring substituted salicylic acids complex, 1.77g zinc lactates, 0.68g L- days
Door winter amino acid molybdenum, the thiocyanatos of 0.87g bis- silver（I）Sour potassium, 1.98g Varisoft 432PPGs and 10ml are gone
The aqueous solution that ionized water is prepared, the weight concentration of the aqueous solution is 53.3%, the weight of the aqueous solution:Ultrasonic surface activated carrier
Weight=21.43g of mixed liquor:39.7g =1:1.9,175 DEG C of temperature is controlled, the hydro-thermal reaction time is 15.5h, then 105 DEG C
Dry to obtain fine silt thing；Fine silt thing is in Muffle furnace, 930 DEG C, calcination 7.5h, after cooling down, can obtain fine particle shape
Ozone Heterogeneous oxidation solid catalyst.
Comparative example 1:Preparation process is not added with lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, myristyl tributyl ammonium chloride, double
Outside hexadecyldimethyl benzyl ammonium ammonium chloride, borax and potassium sulfate, whole preparation process, preparation condition are identical with embodiment 1.
The parameter of ozone Heterogeneous oxidation solid catalyst prepared by embodiment 1, embodiment 2 and comparative example 1 is included in table 1.
Application Example 1:Ozone Heterogeneous oxidation solid catalyst point prepared by embodiment 1, embodiment 2 and comparative example 1
The waste water progress for being used for ethylenediamine, 4,4 '-diaminourea acardite and propylparaben preparation under the same conditions is smelly
The processing of oxygen Heterogeneous oxidation.Treatment conditions are：Rate of charge=1000L of organic wastewater and catalyst:1g, organic wastewater CODCr
Value 976.8mg/L, ozone dosage 80mg/L, processing time 1hr, ozone tail gas KI solution absorption detecting ozone utilization rates.
Test data is included in table 2.
The embodiment of table 1 and comparative example prepare ozone Heterogeneous oxidation solid catalysis agent parameter
The ozone Heterogeneous oxidation solid catalyst Application Example of table 2
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 is by wheat meal
Stone, wollastonite, activated carbon, carnallite, fluorite, glauberite composition, by weight, medical stone:Wollastonite:Activated carbon:Carnallite:
Fluorite:The weight ratio of glauberite=（5~15）:（7~17）:（9~19）:（11~21）:（13~23）:（15~25）, by weight
Gauge, component A:Weight ratio=1 of B component:（10~20）, component C is myristyl tributyl ammonium chloride, by weight, C
Component:Weight ratio=1 of reaming modified support:（5~10）, D components help by composite mineralizer borax, potassium sulfate, catalytic activity
Agent predecessor isopropyl scandium oxide (III), three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europiums, three (2,2,6,6- tetra-
Methyl -3,5- heptadione acid) gadolinium, trifluoromethayl sulfonic acid thulium (III) Rare-earth chemicals, catalytic active center forerunner
Thing normal transition metallo-organic compound titanocenes ring substituted salicylic acid complex, zinc lactate, L- lucid asparagus amino acid molybdenums and expensive
The thiocyanato of metallic compound two silver（I）Sour potassium, emulsifying agent Varisoft 432PPG composition, by weight, boron
Sand:Potassium sulfate:Isopropyl scandium oxide (III):Three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europiums:Three (2,2,6,6-
Tetramethyl -3,5- heptadione acid) gadolinium:Trifluoromethayl sulfonic acid thulium (III):Titanocenes ring substituted salicylic acid complex:Zinc lactate:
L- lucid asparagus amino acid molybdenums:Two thiocyanatos silver（I）Sour potassium:The weight ratio of Varisoft 432PPG=（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 made up of medical stone, wollastonite, activated carbon, carnallite, fluorite, glauberite according to claim 1, wheat
Meal stone, wollastonite, activated carbon, carnallite, fluorite, glauberite are crushed respectively, and deionized water washing, which is dried, to be removed after moisture,
Sieved through standard screen, it is 0.0370mm~0.0750mm to control particle diameter.
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