CN107008421A - 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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- CN107008421A CN107008421A CN201710276068.6A CN201710276068A CN107008421A CN 107008421 A CN107008421 A CN 107008421A CN 201710276068 A CN201710276068 A CN 201710276068A CN 107008421 A CN107008421 A CN 107008421A
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- ozone heterogeneous
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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 42
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- -1 diatom is pure Substances 0.000 claims abstract description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 14
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000012222 talc Nutrition 0.000 claims abstract description 12
- INJRKJPEYSAMPD-UHFFFAOYSA-N aluminum;silicic acid;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O INJRKJPEYSAMPD-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 229910052623 talc 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
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 9
- 125000003963 dichloro group Chemical group Cl* 0.000 claims abstract description 8
- 229910052675 erionite Inorganic materials 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 8
- BYDILAVGJRCJOJ-UHFFFAOYSA-N O.O.[Y+3] Chemical class O.O.[Y+3] BYDILAVGJRCJOJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021538 borax Inorganic materials 0.000 claims abstract description 7
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 7
- 229910052779 Neodymium Inorganic materials 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
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-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
- 229930195712 glutamate Natural products 0.000 claims abstract description 5
- 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
- 238000001354 calcination Methods 0.000 claims abstract description 4
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- VSIRWAYMNHKLOS-UHFFFAOYSA-N [V].C(C1=CC=NC=C1)(=O)NN=C(C(=O)O)C Chemical compound [V].C(C1=CC=NC=C1)(=O)NN=C(C(=O)O)C VSIRWAYMNHKLOS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
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- 230000035484 reaction time Effects 0.000 claims description 4
- ZGGPNDKKJIWQJU-UHFFFAOYSA-N 2-(pyridine-4-carbonylhydrazinylidene)propanoic acid Chemical compound OC(=O)C(C)=NNC(=O)C1=CC=NC=C1 ZGGPNDKKJIWQJU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052773 Promethium Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- 210000000481 breast Anatomy 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 229910052706 scandium Inorganic materials 0.000 claims 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000010457 zeolite Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 239000012752 auxiliary agent Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 238000001994 activation Methods 0.000 abstract description 5
- 239000003995 emulsifying agent Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
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- 239000010419 fine particle Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000007788 liquid Substances 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
- 229910052723 transition metal Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000206761 Bacillariophyta Species 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 150000002306 glutamic acid derivatives Chemical class 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 150000007857 hydrazones Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 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
- 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
- JTABHYSLUVGCPP-UHFFFAOYSA-N CC(=O)C.C(C)(=O)F Chemical compound CC(=O)C.C(C)(=O)F JTABHYSLUVGCPP-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 240000000203 Salix gracilistyla Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- FLNKWZNWHZDGRT-UHFFFAOYSA-N azane;dihydrochloride Chemical compound [NH4+].[NH4+].[Cl-].[Cl-] FLNKWZNWHZDGRT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 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
- 239000007789 gas 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
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing 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
- 150000003870 salicylic acids Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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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 erionite, garnet, diatom is pure, kyanite, talcum and sal soda masonry carrier are after lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add surfactant dodecyltrimethyl 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 (hexafluoroacetylacetone) yttrium (III) dihydrates, 1, 1, 1 trifluoroacetylacetone (TFA) neodymium, three cyclopentadiene promethiums, catalytic active center predecessor titanocenes ring substituted salicylic acid complex, pyruvic acid isonicotinoyl hydrazone vanadium, cupric glutamate and the ammino platinum of dichloro two, hydro-thermal reaction is carried out under the effect of emulsifying agent N octadecyldimethyl N ' thmethylpropyl dichlorides ammonium, calcination obtains ozone Heterogeneous oxidation solid catalyst in Muffle furnace after 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 by erionite, garnet, pure diatom, kyanite, talcum,
Sal soda stone is constituted, by weight, erionite:Garnet:Diatom is pure:Kyanite:Talcum:The weight ratio of sal soda stone=（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 dodecyltrimethyl, 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
(hexafluoroacetylacetone) yttrium (III) dihydrate, 1,1,1- trifluoroacetylacetone (TFA)s neodymium, three cyclopentadiene promethium rare earth metals are organic
Compound, catalytic active center predecessor normal transition metallo-organic compound titanocenes ring substituted salicylic acid complex, acetone
Sour isonicotinoyl hydrazone vanadium, cupric glutamate and the ammino platinum of precious metal chemical complex dichloro two, emulsifying agent N- octadecyldimethyls-N '-three
MethyI-oropvD dichloride ammonium is constituted, by weight, borax:Potassium sulfate:Isopropyl scandium oxide (III):Three (hexafluoroacetylacetone) yttriums
(III) dihydrate:1,1,1- trifluoroacetylacetone (TFA) neodymiums:Three cyclopentadiene promethiums:Titanocenes ring substituted salicylic acid complex:Third
Ketone acid isonicotinoyl hydrazone vanadium:Cupric glutamate:The ammino platinum of dichloro two:N- octadecyldimethyls-N '-trimethyl-propyl dichloride 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）.Erionite, garnet in the B component, pure diatom, kyanite, talcum, sal soda stone enter respectively
Row is crushed, and deionized water washing, which is dried, to be removed after moisture, and -200 mesh ,+400 mesh sieves point are carried out through standard screen, controls the particle diameter to be
The mm of 0.0370mm~0.0750.
What the technical method of the present invention was realized in：Lithium hypochlorite LiClO, double (second can be being added in closed reactor
Acyl acetone) beryllium C10H14BeO4The aqueous solution is prepared with deionized water stirring, it is 0.0370mm~0.0750mm to add particle diameter after screening
Erionite, garnet, pure diatom, kyanite, talcum and sal soda stone porous material carrier, in certain temperature and stirring condition
Under, the small Be of aqueous solution Ionic Radius2+（0.31Å）、Li+（0.60Å）Displace part ion radius in porous material big
Ca2+（0.99Å）、K+（1.33Å）、Ba2+（1.35Å）Plasma, the aperture of porous material carrier becomes big, surface roughness increase,
Filtering, dries the reaming modified support input ultrasound reactor after constant weight, adds dodecyltrimethyl
[C12H25N(CH3)3] +Cl-The aqueous solution, control ultrasonic power density, ultrasonic frequency, temperature and sonic oscillation time, in ultrasound
Under ripple cavitation, dodecyltrimethyl [C12H25N(CH3)3] +Cl-It is easy to escape into reaming from the aqueous solution and changes
Property carrier duct or be attached to reaming modified support surface, be beneficial to being interconnected and carrier surface activation for carrier duct, increase
Strong 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 isopropyl scandium oxide (III) C9H21O3Sc, three (six
Acetyl fluoride acetone) yttrium (III) dihydrate C15H3F18O6Y·2H2O, 1,1,1- trifluoroacetylacetone (TFA) neodymium C15H12F9NdO6, three
Cyclopentadiene promethium Pm (C5H5)3Rare-earth chemicals, catalytic active center component transition metal organic compound titanocenes
Ring substituted salicylic acid complex (C10H10)Ti(C7H4O3), pyruvic acid isonicotinoyl hydrazone vanadium [VO2(C9H8N3O5)] (C5H5N), paddy ammonia
Sour copper C5H7NO4The Cu and ammino platinum Pt (NH of dichloro two3)2Cl2Precious metal chemical complex, emulsifying agent N- octadecyldimethyls-N '-
Trimethyl-propyl dichloride ammonium C18H37N+(CH3)2CH2CH2CH2N+(CH3)3Cl2 -Effect is lower to carry out hydro-thermal reaction, and mineralizer adds
Fast diffusion, make reactant lattice activate, promote the progress of solid phase reaction, ultrasonic surface activated carrier has with rare earth metal
Machine compound, normal transition metallo-organic compound, precious metal chemical complex Uniform Doped, emulsifying agent N- octadecyldimethyls-
N '-trimethyl-propyl dichloride ammonium make reaction solution formed quasi-stationary emulsion prevent separation of solid and liquid, sedimentation, while to porous
The further surface active of carrier, by the way that in certain temperature, the hydro-thermal reaction of time, drying obtains the fine silt thing of Uniform Doped；
The fine silt thing of Uniform Doped is in Muffle furnace, through high temperature sintering, and organic matter carbonization therein further enhances porous
The microcellular structure of carrier, obtains urging for porous carrier supported rare earth metal oxide, transition metal oxide and noble metal formation
Change the ozone Heterogeneous oxidation solid catalyst in activated centre, improve the mithridatism and catalytic activity of catalyst.
Relative to art methods, outstanding advantages of the present invention are that erionite, garnet, diatom are used in technology of preparing
Pure, kyanite, talcum and sal soda stone porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) berylliums
C10H14BeO4Reaming effect, dodecyltrimethyl [C12H25N(CH3)3] +Cl-, N- octadecyldimethyls-N '-
Trimethyl-propyl dichloride ammonium C18H37N+(CH3)2CH2CH2CH2N+(CH3)3Cl2 -To being interconnected and surface active work for duct
With organic matter carbonization enhances the microcellular structure of porous carrier；Rare-earth chemicals are made by hydro-thermal reaction, it is general
Logical transition metal organometallic compound and precious metal chemical complex reach Uniform Doped and are attached in carrier surface and duct that high temperature burns
Burning makes organic matter carbonization strengthen and form multi-level microcellular structure, porous carrier supported rare earth metal oxide, mistake
Cross metal oxide and noble metal formation multi-element metal catalytic active center combined with porous carrier it is more firm, preparation it is smelly
Oxygen Heterogeneous oxidation solid catalyst has stronger adsorptivity, the particularly cooperative effect of multi-element metal, doped precious metal tool
Some stability and high activity, can suppress liquating out for metal catalytic activity component, improve the mithridatism of catalyst and urge
Change activity, with good environmental benefit and economic benefit.
Embodiment
Embodiment 1:1.4g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 1.7g, 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 2.2%, 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 2.8g erionites of 400 mesh standard sieves, 3.8g garnets, 4.7g diatoms are pure, 5.8g kyanites, 6.7g talcums, 7.8g sal soda stones,
The weight of lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（3.1g）:The weight of porous material（31.6g）=1:10.2,36 DEG C are warming up to,
Reaming modified support 30g is obtained after continuing stirring reaction 3.2h, filtering, 103 DEG C of dry constant weights；In 500ml ultrasound reactors
In, reaming modified support 30g is put into, 3.3g dodecyltrimethyls is added and is dissolved in the water-soluble of 100ml deionized waters
Liquid, the weight concentration of the aqueous solution is 3.2%, is uniformly mixed, dodecyltrimethyl（3.3g）:Reaming is modified
Carrier（30g ）=1:9.1；It is 0.4W/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, 3.1g potassium sulfates, 1.6g isopropyls scandium oxide (III), 2.1g tri- (hexafluoroacetylacetone) yttrium
(III) dihydrate, 2.6g1,1,1- trifluoroacetylacetone (TFA)s neodymium, the cyclopentadiene promethiums of 3.1g tri-, 5.1g titanocenes ring substitution bigcatkin willow
Sour complex, 6.1g pyruvic acid isonicotinoyl hydrazones vanadium, 2g cupric glutamates, the ammino platinum of 3.1g dichloros two, 3.1gN- hexadecyldimethylamines
The aqueous solution that base-N '-trimethyl-propyl dichloride ammonium and 50ml deionized waters are prepared, the weight concentration of the aqueous solution is
40.5%, the weight of the aqueous solution:Weight=84g of ultrasonic surface activated carrier mixed liquor:133.3g=1:1.6, control temperature
125 DEG C, 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, 620 DEG C, burns
Burn after 3.2h, 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 erionites of 400 mesh standard sieves, 1.65g garnets, 1.85g diatoms are pure, 2.05g kyanites, 2.25g talcums, 2.45g
The weight of sal soda stone, 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 dodecyltrimethyls 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, dodecyltrimethyl（2.2g）:
Many reaming modified supports（11.5g ）=1:5.2；It is 0.7W/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-
(hexafluoroacetylacetone) yttrium (III) dihydrate, 0.78g1,1,1- trifluoroacetylacetone (TFA)s neodymium, the cyclopentadiene promethiums of 0.87g tri-,
1.48g titanocenes ring substituted salicylic acids complex, 1.77g pyruvic acid isonicotinoyl hydrazones vanadium, 0.68g cupric glutamates, 0.87g dichloros two
It is water-soluble that ammino platinum, 1.98gN- octadecyldimethyls-N '-trimethyl-propyl dichloride ammonium and 10ml deionized waters are prepared
Liquid, the weight concentration of the aqueous solution is 53.3%, the weight of the aqueous solution:The weight of ultrasonic surface activated carrier mixed liquor=
21.4g: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, can obtain the ozone Heterogeneous oxidation of fine particle shape
Solid catalyst.
Comparative example 1:Preparation process is not added with lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, dodecyltrimethyl, N-
Outside octadecyldimethyl-N '-trimethyl-propyl dichloride ammonium, 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.
Application Example 1:Ozone Heterogeneous oxidation solid catalyst point prepared by embodiment 1, embodiment 2 and comparative example 1
The waste water for being used for Potassium Hydrogen Phthalate, ethylenediamine and the directly preparation of Huang 142 under the same conditions carries out the heterogeneous oxygen of ozone
Change is handled.Treatment conditions are：Rate of charge=1000L of organic wastewater and catalyst:1g, organic wastewater CODCrValue 725.5mg/
L, ozone dosage 60mg/L, processing time 1hr, ozone tail gas KI solution absorption detecting ozone utilization rates.Test data is arranged
Enter 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 boiled by hair
Stone, garnet, diatom are pure, kyanite, talcum, sal soda stone composition, by weight, erionite:Garnet:Diatom is pure:Kyanite:
Talcum:The weight ratio of sal soda stone=（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 dodecyltrimethyl, 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 (hexafluoroacetylacetone) yttrium (III) dihydrates, 1,1,1- trifluoroacetylacetone (TFA)s
Neodymium, three cyclopentadiene promethium Rare-earth chemicals, catalytic active center predecessor normal transition metallo-organic compound two
Luxuriant titanacycle substituted salicylic acid complex, pyruvic acid isonicotinoyl hydrazone vanadium, cupric glutamate and the ammino platinum of precious metal chemical complex dichloro two, breast
Agent N- octadecyldimethyls-N '-trimethyl-propyl dichloride ammonium composition, by weight, borax:Potassium sulfate:Isopropyl oxygen
Change scandium (III):Three (hexafluoroacetylacetone) yttrium (III) dihydrates:1,1,1- trifluoroacetylacetone (TFA) neodymiums:Three cyclopentadiene promethiums:
Titanocenes ring substituted salicylic acid complex:Pyruvic acid isonicotinoyl hydrazone vanadium:Cupric glutamate:The ammino platinum of dichloro two:N- octadecyls two
The weight ratio of methyl-N '-trimethyl-propyl 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 made up of erionite, garnet, pure diatom, kyanite, talcum, sal soda stone according to claim 1, hair
Zeolite, garnet, diatom are pure, kyanite, talcum, sal soda stone 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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