CN107008306A - The preparation method of ozone Heterogeneous oxidation solid catalyst - Google Patents
The preparation method of ozone Heterogeneous oxidation solid catalyst Download PDFInfo
- Publication number
- CN107008306A CN107008306A CN201710276076.0A CN201710276076A CN107008306A CN 107008306 A CN107008306 A CN 107008306A CN 201710276076 A CN201710276076 A CN 201710276076A CN 107008306 A CN107008306 A CN 107008306A
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- Prior art keywords
- weight
- component
- solid catalyst
- ozone heterogeneous
- heterogeneous oxidation
- Prior art date
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 230000003647 oxidation Effects 0.000 title claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 21
- 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 46
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 239000004575 stone Substances 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
- 239000010881 fly ash Substances 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
- 239000000126 substance Substances 0.000 claims abstract description 11
- 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 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
- 235000010339 sodium tetraborate 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
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 9
- 239000010456 wollastonite Substances 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
- 239000011591 potassium Substances 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 8
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 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 7
- 229910021538 borax Inorganic materials 0.000 claims abstract description 7
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 7
- 235000000193 zinc lactate Nutrition 0.000 claims abstract description 7
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 6
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-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
- 239000010970 precious metal Substances 0.000 claims abstract description 6
- 229960004889 salicylic acid Drugs 0.000 claims abstract description 6
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 claims abstract description 6
- 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 5
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- 229940050168 zinc lactate Drugs 0.000 claims abstract description 5
- 239000011576 zinc lactate Substances 0.000 claims abstract description 5
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 claims abstract description 4
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- -1 carbonic acid lutetium hydrate Rare-earth Chemical class 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
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- KNFUDJRDHMKNRO-UHFFFAOYSA-N acetic acid;terbium Chemical compound [Tb].CC(O)=O KNFUDJRDHMKNRO-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims description 2
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- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 2
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- 235000012054 meals Nutrition 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 238000001994 activation Methods 0.000 abstract description 6
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- GDJKGUGXMBNRHL-UHFFFAOYSA-N O.[Lu].C(O)(O)=O Chemical compound O.[Lu].C(O)(O)=O GDJKGUGXMBNRHL-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- HRLJRVRWYAHDFN-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC.CN Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC.CN HRLJRVRWYAHDFN-UHFFFAOYSA-N 0.000 abstract 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 abstract 1
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- 230000000052 comparative effect Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- 238000005245 sintering Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000008569 process Effects 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
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- FQBVXOKFIMQGGF-UHFFFAOYSA-N 17-hexadecyltritriacontan-17-ylazanium;chloride Chemical class [Cl-].CCCCCCCCCCCCCCCCC([NH3+])(CCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCC FQBVXOKFIMQGGF-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- BHWMZEPWQUFLLQ-UHFFFAOYSA-N 2-hydroxypropanoic acid;zinc Chemical compound [Zn].CC(O)C(O)=O BHWMZEPWQUFLLQ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 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
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 239000002956 ash Substances 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 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
- 230000002708 enhancing effect Effects 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
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- ADALIFAVBBCNGP-UHFFFAOYSA-N heptadecan-1-amine;hydrochloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCC[NH3+] ADALIFAVBBCNGP-UHFFFAOYSA-N 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- RLFOVBVRQCNOMD-UHFFFAOYSA-N lutetium;hydrate Chemical compound O.[Lu] RLFOVBVRQCNOMD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 125000001421 myristyl 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])[H] 0.000 description 1
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- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
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- DTMHTVJOHYTUHE-UHFFFAOYSA-N thiocyanogen Chemical compound N#CSSC#N DTMHTVJOHYTUHE-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- GYOFRJOMHLYJNZ-UHFFFAOYSA-N tributyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](CCCC)(CCCC)CCCC GYOFRJOMHLYJNZ-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000011701 zinc Substances 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 medical stone, wollastonite, activated carbon, carnallite, flyash and taking coal gangue as 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, it is hydrated three acetic acid terbiums, carbonic acid lutetium hydrate, catalytic active center predecessor titanocenes ring substituted salicylic acid complex, zinc lactate, zirconium carbonate ammonium and the thiocyanato of precious metal chemical complex two silver（I）Sour potassium, hydro-thermal reaction is carried out under the effect of emulsifying agent hexatriacontane methyl ammonium, and drying removes after moisture that calcination obtains ozone Heterogeneous oxidation solid catalyst in Muffle furnace.
Description
Technical field
The present invention relates to a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, category environmental protection and chemical catalyst skill
Art field.
Background technology
Ozonation technology using ozone oxidation ability it is strong the characteristics of, can be by many organic pollution oxidation Decompositions, extensively
For wastewater treatment.Catalytic ozonation technology is divided into ozone homogeneous catalytic oxidation and ozone heterogeneous catalytic oxidation, and ozone is equal
Phase catalysis oxidation has that the more difficult separation and recovery of catalyst is reused, ozone utilization rate is low causes water process operating cost higher,
Organic pollutant removal rate is relatively low simultaneously and easily causing secondary pollution of water is limited to its application；Ozone heterogeneous catalysis oxygen
There is change technology catalyst to be easily isolated and recycled and reusable, ozone utilization rate is high, organic pollutant removal rate is higher, drop
Low water process operating cost and receive significant attention its application the advantages of do not result in secondary pollution.Ozone heterogeneous catalysis
It is to reach local organic matter enrichment by catalyst surface absorption organic matter that oxidation of organic compounds, which is decomposed, while ozone molecule absorption exists
The hydroxyl radical free radical that catalyst surface produces high activity under catalyst action decomposes organic matter.Ozone heterogeneous catalytic oxidation
Handle in waste water technology, core technology is the preparation of ozone Heterogeneous oxidation solid catalyst.
Ozone Heterogeneous oxidation solid catalyst is generally made up of carrier, activated centre and auxiliary agent.Due to being polluted in waste water
Species are various, complex chemical composition feature, can produce harmful effect to performance such as absorption, the mithridatism of catalyst.
Prepare that the carrier structure that ozone Heterogeneous oxidation solid catalyst uses is more single at present, adsorptivity is relatively low；Activated centre is universal
Using normal transition metal salt, mithridatism is poor；Preparation method mainly has infusion process, the precipitation method, mixing method and collosol and gel etc.
Method attachment activity center and adjuvant component are easily liquated out in carrier surface, activated centre and adjuvant component, cause catalyst
Easily lose catalytic activity.For exist in current ozone Heterogeneous oxidation solid catalyst preparation method Catalyst Adsorption compared with
Low, mithridatism is poor and easily loses catalytic activity problem, and exploitation is strengthened using multicomponent porous carrier through reaming, surface active
Catalyst Adsorption, makees catalytic activity auxiliary agent predecessor, normal transition Organometallic using rare earth 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 is by medical stone, wollastonite, activated carbon, carnallite, flyash
, gangue composition, by weight, medical stone:Wollastonite:Activated carbon:Carnallite:Flyash:The weight ratio of gangue=（5
~15）:（7~17）:（9~19）:（11~21）:（13~23）:（15~25）, by weight, component A:The weight of B component it
Than=1:（10~20）, component C is myristyl tributyl ammonium chloride, by weight, component C:The weight of reaming modified support it
Than=1:（5~10）, D components 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) europiums, three acetic acid terbiums of hydration, carbonic acid lutetium hydrate rare earth metal are organic
Compound, catalytic active center predecessor normal transition metallo-organic compound titanocenes ring substituted salicylic acid complex, lactic acid
Zinc, zirconium carbonate ammonium and the thiocyanato of precious metal chemical complex two silver（I）Sour potassium, emulsifying agent three-cetylmethylammonium chloride group
Into, by weight, borax:Potassium sulfate:Isopropyl scandium oxide (III):Three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl)
Europium:It is hydrated three acetic acid terbiums:Carbonic acid lutetium hydrate:Titanocenes ring substituted salicylic acid complex:Zinc lactate:Zirconium carbonate ammonium:Two sulphur
Cyanate radical closes silver（I）Sour potassium:The weight ratio of three-cetylmethylammonium chloride=（4~8）:（6~10）:（3~6）:（4~
7）:（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.The medical stone of B component, silicon ash
Stone, activated carbon, carnallite, flyash, gangue are crushed respectively, and deionized water washing, which is dried, to be removed after moisture, through mark
Quasi- sieve carries out -200 mesh ,+400 mesh sieves point, and 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, flyash and gangue porous material carrier, in certain temperature and stirring bar
Under part, the small Be of aqueous solution Ionic Radius2+（0.31Å）、Li+（0.60Å）Displace part ion radius in porous material big
Ca2+（0.99Å）、K+（1.33Å）、Ba2+（1.35Å）Plasma, the aperture of porous material carrier becomes big, surface roughness increasing
Plus, filtering dries the reaming modified support input ultrasound reactor after constant weight, adds 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, hydration three acetic acid terbium C6H11O7Tb, carbonic acid lutetium
Hydrate C3H2Lu2O10Rare-earth chemicals, catalytic active center predecessor normal transition metallo-organic compound two
Luxuriant titanacycle substituted salicylic acid complex (C10H10)Ti(C7H4O3), zinc lactate C6H10O6Zn, zirconium carbonate ammonium (NH4)2·C2H2O8Zr
With two thiocyanatos silver（I）Sour potassium K [Ag (SCN)2] precious metal chemical complex, in three-cetylmethylammonium chloride of emulsifying agent
[(C16H33)3NCH3]+Cl-Effect is lower to carry out hydro-thermal reaction, and mineralizer accelerates diffusion, activates reactant lattice, promotes
The progress of solid phase reaction, it is ultrasonic surface activated carrier and Rare-earth chemicals, normal transition organo-metallic compound, expensive
Metallic compound Uniform Doped, three-cetylmethylammonium chloride of emulsifying agent makes reaction solution form quasi-stationary emulsion to prevent
Separation of solid and liquid, sedimentation, while to the further surface active of porous carrier, by certain temperature, the hydro-thermal reaction of time, drying
Obtain 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 therein is complete
Full carbonization further enhances the microcellular structure of porous carrier, obtains porous carrier supported rare earth metal oxide, transition metal
The ozone Heterogeneous oxidation solid catalyst of oxide and the catalytic active center of noble metal formation, improves the antitoxin of catalyst
Property and catalytic activity.
Relative to art methods, outstanding feature of the present invention is that medical stone, wollastonite, activity are used in technology of preparing
Charcoal, carnallite, flyash, gangue porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) berylliums
C10H14BeO4Reaming effect, myristyl tributyl ammonium chloride C14H29N+(C4H9)3Cl-, three-cetylmethylammonium chloride
[(C16H33)3NCH3]+Cl- To being interconnected and surface activation for duct；Rare earth organometallic is made by hydro-thermal reaction
Compound, normal transition metallo-organic compound and precious metal chemical complex reach Uniform Doped and are attached to carrier surface and duct
Interior, high temperature sintering makes organic matter carbonization strengthen and form multi-level microcellular structure, porous carrier supported rare earth metal
The multi-element metal catalytic active center of oxide, transition metal oxide and noble metal formation is combined more firm with porous carrier
Gu, the ozone Heterogeneous oxidation solid catalyst of preparation has a stronger adsorptivity, the cooperative effect of multi-element metal, particularly mixes
Stability and high activity that miscellaneous noble metal has, 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
2.75g medical stones, 3.75g wollastonites, 4.75g activated carbons, 5.75g carnallites, 6.75g flyash, the 7.75g bastard coals of standard screen
The weight of stone, 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 be hydrated three acetic acid terbiums, 3.05g carbonic acid lutetiums hydrate, 5.05g titanocenes rings
Substituted salicylic acid complex, 6.1g zinc lactates, 2.05g zirconium carbonate ammoniums, the thiocyanatos of 3.1g bis- silver（I）Sour potassium, 3.05g
The aqueous solution that three-cetylmethylammonium chloride and 50ml deionized waters are prepared, the weight concentration of the aqueous solution is 40.3%, should
The weight of the aqueous solution: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, 620 DEG C, calcination 3.2h,
After cooling down, the ozone Heterogeneous oxidation solid catalyst of fine particle shape can obtain.
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 medical stones of 400 mesh standard sieves, 1.65g wollastonites, 1.85g activated carbons, 2.05g carnallites, 2.25g flyash,
The weight of 2.45g gangues, 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, 2.2g myristyl tributyl ammonium chlorides is added and is dissolved in
The aqueous solution of 26ml deionized waters, the weight concentration of the aqueous solution is 7.8%, is uniformly mixed, myristyl tributyl chlorination
Ammonium（2.2g）:Reaming modified support（11.5g ）=1:5.2；It is 0.7 W/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 isopropyl scandium oxides
(III), 0.67g tri- (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europium, 0.78g are hydrated three acetic acid terbiums, 0.87g carbon
Sour lutetium hydrate, 1.48g titanocenes ring substituted salicylic acids complex, 1.77g zinc lactates, 0.68g zirconium carbonate ammoniums, the sulphur of 0.87g bis-
Cyanate radical closes silver（I）The aqueous solution that sour potassium, tri--cetylmethylammonium chlorides of 1.98g and 10ml deionized waters are prepared, the water
The weight concentration of 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, myristyl tributyl ammonium chloride, three-
Outside cetylmethylammonium 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
Ethylenediamine it is not used under the same conditions, the waste water that directly black 19 and active golden yellow K-2RA is prepared carries out ozone Heterogeneous oxidation
Processing.Treatment conditions are：Rate of charge=1000L of organic wastewater and catalyst:1g, organic wastewater CODCrValue 853.9mg/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, flyash, gangue composition, by weight, medical stone:Wollastonite:Activated carbon:Light halogen
Stone:Flyash:The weight ratio of gangue=（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 myristyl tributyl ammonium chloride, is pressed
Weight meter, component C:Weight ratio=1 of reaming modified support:（5~10）, D components are urged by composite mineralizer borax, potassium sulfate
Change coagent predecessor isopropyl scandium oxide (III), three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europiums, hydration three
Acetic acid terbium, carbonic acid lutetium hydrate Rare-earth chemicals, catalytic active center predecessor normal transition Organometallic are closed
Thing titanocenes ring substituted salicylic acid complex, zinc lactate, zirconium carbonate ammonium and the thiocyanato of precious metal chemical complex two silver（I）Acid
Potassium, three-cetylmethylammonium chloride of emulsifying agent composition, by weight, borax:Potassium sulfate:Isopropyl scandium oxide (III):Three (4,
4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europium:It is hydrated three acetic acid terbiums:Carbonic acid lutetium hydrate:Titanocenes ring replaces water
Poplar acid complex:Zinc lactate:Zirconium carbonate ammonium:Two thiocyanatos silver（I）Sour potassium:The weight of three-cetylmethylammonium chloride
The ratio between=（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, flyash, gangue according to claim 1,
Medical stone, wollastonite, activated carbon, carnallite, flyash, gangue are crushed respectively, and deionized water washing, which is dried, removes water
After point, sieved through standard screen, it is 0.0370mm~0.0750mm to control particle diameter.
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