CN107051450A - 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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- CN107051450A CN107051450A CN201710275985.2A CN201710275985A CN107051450A CN 107051450 A CN107051450 A CN 107051450A CN 201710275985 A CN201710275985 A CN 201710275985A CN 107051450 A CN107051450 A CN 107051450A
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- solid catalyst
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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 22
- 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 42
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- 239000004575 stone Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
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- 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
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- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims abstract description 10
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 239000010456 wollastonite Substances 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
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- 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
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 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 6
- AUZRORBINHVFFD-UHFFFAOYSA-N [Rh]N=O Chemical compound [Rh]N=O AUZRORBINHVFFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-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
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
- 239000011591 potassium Substances 0.000 claims abstract description 6
- 229960004889 salicylic acid Drugs 0.000 claims abstract description 6
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 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
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- CPSCNTYWVQYNOQ-UHFFFAOYSA-M 2-hydroxyethyl-dimethyl-propylazanium;chloride Chemical compound [Cl-].CCC[N+](C)(C)CCO CPSCNTYWVQYNOQ-UHFFFAOYSA-M 0.000 claims abstract description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- -1 sulfonic acid thulium (III) rare earth metal Chemical class 0.000 claims description 14
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 210000000481 breast Anatomy 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 claims 1
- KPQDSKZQRXHKHY-UHFFFAOYSA-N gold potassium Chemical compound [K].[Au] KPQDSKZQRXHKHY-UHFFFAOYSA-N 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 238000001994 activation Methods 0.000 abstract description 6
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- 229910052688 Gadolinium Inorganic materials 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
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- 238000005245 sintering Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
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- PMUNIMVZCACZBB-UHFFFAOYSA-N 2-hydroxyethylazanium;chloride Chemical compound Cl.NCCO PMUNIMVZCACZBB-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
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- 238000003763 carbonization Methods 0.000 description 2
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- 239000003795 chemical substances by application Substances 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
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
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- 229910000510 noble metal Inorganic materials 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 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
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- BBZDYQUXRFATHZ-UHFFFAOYSA-N 2-(2,5-dimethoxyphenyl)acetic acid Chemical compound COC1=CC=C(OC)C(CC(O)=O)=C1 BBZDYQUXRFATHZ-UHFFFAOYSA-N 0.000 description 1
- YJHSJERLYWNLQL-UHFFFAOYSA-N 2-hydroxyethyl(dimethyl)azanium;chloride Chemical compound Cl.CN(C)CCO YJHSJERLYWNLQL-UHFFFAOYSA-N 0.000 description 1
- USWINTIHFQKJTR-UHFFFAOYSA-N 3-hydroxynaphthalene-2,7-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C=C(S(O)(=O)=O)C(O)=CC2=C1 USWINTIHFQKJTR-UHFFFAOYSA-N 0.000 description 1
- 241001614291 Anoplistes Species 0.000 description 1
- 241001163600 Bathylaco nigricans Species 0.000 description 1
- DCSMHJFYWFUKIZ-UHFFFAOYSA-N CCCCCCCCCCCCCCCl(CCCC)(CCCC)CCCC Chemical compound CCCCCCCCCCCCCCCl(CCCC)(CCCC)CCCC DCSMHJFYWFUKIZ-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
- JTPIELSRLONMBL-UHFFFAOYSA-N [K].[Au].[Cl] Chemical compound [K].[Au].[Cl] JTPIELSRLONMBL-UHFFFAOYSA-N 0.000 description 1
- OLGPDUKUFCIQPH-UHFFFAOYSA-N [Na].[Na].[Na].N(=O)[Rh] Chemical compound [Na].[Na].[Na].N(=O)[Rh] OLGPDUKUFCIQPH-UHFFFAOYSA-N 0.000 description 1
- VIINJADDDFDFQW-UHFFFAOYSA-N [Na].[Na].[Na].[N+](=O)([O-])[Rh] Chemical compound [Na].[Na].[Na].[N+](=O)([O-])[Rh] VIINJADDDFDFQW-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- IOIFRTZBJMZZFO-UHFFFAOYSA-N dysprosium(3+) Chemical compound [Dy+3] IOIFRTZBJMZZFO-UHFFFAOYSA-N 0.000 description 1
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- WSDBZHXOTXNOFK-UHFFFAOYSA-M ethoxy-dimethyl-propylazanium chloride Chemical compound [Cl-].C(CC)[N+](OCC)(C)C WSDBZHXOTXNOFK-UHFFFAOYSA-M 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 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
- 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
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
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Classifications
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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, kaolin, red metal and stone, basalt and astrakanite make carrier 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 (2, 2, 6, 6 tetramethyls 3, 5 heptadione acid) gadolinium, three (6, 6, 7, 7, 8, 8, 8 seven fluorine 2, 2 dimethyl 3, 5 octene diketone) dysprosium (III), trifluoromethayl sulfonic acid thulium (III), catalytic active center predecessor titanocenes ring substituted salicylic acid complex, zinc lactate and the golden potassium of tetrachloro, six nitroso rhodium trisodiums, hydro-thermal reaction is carried out under the effect of emulsifying agent oleamide propyl-dimethyl hydroxyethyl ammonium chloride, 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 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, kaolin, red metal and stone, the Black Warrior
Rock, astrakanite composition, by weight, medical stone:Wollastonite:Kaolin:Red metal and stone:Basalt:The weight of astrakanite it
Than=(5~15):(7~17):(9~19):(11~21):(13~23):(15~25), by weight, component A:B component
Weight ratio=1:(10~20), component C is myristyl tributyl ammonium chloride, by weight, component C:Reaming modified support
Weight ratio=1:(5~10), D components are by composite mineralizer borax, potassium sulfate, catalytic activity auxiliary agent predecessor isopropyl scandium oxide
(III), three (DPM dpm,dipivalomethane acid) gadoliniums, three (the fluoro- 2,2- dimethyl -3,5- of 6,6,7,7,8,8,8- seven
Octene diketone) dysprosium (III), trifluoromethayl sulfonic acid thulium (III) Rare-earth chemicals, catalytic active center predecessor is common
The golden potassium of transition metal organometallic compound titanocenes ring substituted salicylic acid complex, zinc lactate and precious metal chemical complex tetrachloro, six Asias
Nitro rhodium trisodium, emulsifying agent oleamide propyl-dimethyl hydroxyethyl ammonium chloride composition, by weight, borax:Potassium sulfate:Isopropyl oxygen
Change scandium (III):Three (DPM dpm,dipivalomethane acid) gadoliniums:Three (the fluoro- 2,2- dimethyl of 6,6,7,7,8,8,8- seven-
3,5- octenes diketone) dysprosium (III):Trifluoromethayl sulfonic acid thulium (III):Titanocenes ring substituted salicylic acid complex:Zinc lactate:Four
Chlorine gold potassium:Six nitroso rhodium trisodiums:The weight ratio of oleamide propyl-dimethyl hydroxyethyl ammonium chloride=(4~8):(6~10):
(3~6):(4~7):(5~8):(6~9):(10~15):(12~18):(4~7):(6~9):(6~20).The wheat of B component
Meal stone, wollastonite, kaolin, red metal and stone, basalt, astrakanite are crushed respectively, and deionized water washing, which is dried, removes water
After point, -200 mesh ,+400 mesh sieves point are carried out through standard screen, it is the mm of 0.0370mm~0.0750 control particle diameter.
What the technical method of the present invention was realized in:Lithium hypochlorite LiClO, double (second can be being added in closed reactor
Acyl acetone) beryllium C10H14BeO4The aqueous solution is prepared with deionized water stirring, it is 0.0370mm~0.0750mm to add particle diameter after screening
Medical stone, wollastonite, kaolin, red metal and stone, basalt and astrakanite 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 ultrasonic wave
Under cavitation, myristyl tributyl ammonium chloride C14H29N+(C4H9)3Cl-It is easy to escape into reaming modification load from the aqueous solution
Body opening road is attached to reaming modified support surface, is beneficial to being interconnected and carrier surface activation for carrier duct, enhances
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 (2,2,
6,6- tetramethyl -3,5- heptadione acid) gadolinium C33H57GdO6, three (the fluoro- 2,2- dimethyl -3,5- octenes of 6,6,7,7,8,8,8- seven
Diketone) dysprosium (III) C30H30DyF21O6, trifluoromethayl sulfonic acid thulium C3F9O9S3Tm Rare-earth chemicals, catalytic active center
Predecessor normal transition metallo-organic compound titanocenes ring substituted salicylic acid complex (C10H10)Ti(C7H4O3), zinc lactate
C6H10O6The Zn and golden potassium KAuCl of tetrachloro4, six nitroso rhodium trisodium Na3Rh(NO2)6Precious metal chemical complex, in emulsifying agent oleamide third
Base dimethyl hydroxyethyl ammonium chloride [C17H33CONH(CH2)3N(CH3)2CH2CH2OH]+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 oleamide dimethylamine
Base hydroxyethyl ammonium chloride make reaction solution formed quasi-stationary emulsion prevent separation of solid and liquid, sedimentation, while entering one to porous carrier
Surface active is walked, by the way that in certain temperature, the hydro-thermal reaction of time, drying obtains the fine silt thing of Uniform Doped;Uniform Doped
Fine silt thing in Muffle furnace, through high temperature sintering, organic matter carbonization therein further enhances the micro- of porous carrier
In pore structure, the catalytic activity for obtaining porous carrier supported rare earth metal oxide, transition metal oxide and noble metal formation
The ozone Heterogeneous oxidation solid catalyst of the heart, improves the mithridatism and catalytic activity of catalyst.
Relative to art methods, outstanding feature of the present invention is that medical stone, wollastonite, kaolinite are used in technology of preparing
Native, red metal and stone, basalt, astrakanite 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-, oleamide propyl-dimethyl ethoxy
Ammonium chloride [C17H33CONH(CH2)3N(CH3)2CH2CH2OH]+Cl-To being interconnected and surface activation for duct;Pass through water
Thermal response makes rare earth organo-metallic compound, normal transition metallo-organic compound and precious metal chemical complex reach Uniform Doped simultaneously
It is attached in carrier surface and duct, high temperature sintering makes organic matter carbonization strengthen and form multi-level microcellular structure,
Porous carrier supported rare earth metal oxide, transition metal oxide and noble metal formation multi-element metal catalytic active center with
Porous carrier combination is more firm, and the ozone Heterogeneous oxidation solid catalyst of preparation has stronger adsorptivity, multi-element metal
Cooperative effect, particularly the doped precious metal stability and high activity that have, the molten of metal catalytic activity component can be suppressed
Separate out, the mithridatism and catalytic activity of catalyst are improved, with good environmental benefit and economic benefit.
Embodiment
Embodiment 1:1.35g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 1.65g, 140ml deionized waters, being added to volume is
500ml's can be uniformly mixed in closed reactor, and the weight concentration of the aqueous solution is 2.1%, lithium hypochlorite:Double (levulinics
Ketone) beryllium weight ratio=1:1.2;Add deionized water wash to it is neutral, 103 DEG C dry remove -200 mesh of sieving after moisture~+
The 2.75g medical stones of 400 mesh standard sieves, 3.75g wollastonites, 4.75g kaolin, the red metals and stones of 5.75g, 6.75g basalt,
The weight of 7.75g astrakanites, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums(3g):The weight of porous material(31.5g)=1:
10.5,36 DEG C are warming up to, reaming modified support 31g is obtained after continuing stirring reaction 3.2h, filtering, 103 DEG C of dry constant weights;
In 500ml ultrasound reactors, reaming modified support 31g is put into, 3.25g myristyl tributyl ammonium chlorides is added and is dissolved in
The aqueous solution of 100ml deionized waters, the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, myristyl tributyl chlorine
Change ammonium(3.25g):Reaming modified support(31g )=1:9.5;It is 0.4W/m to control ultrasonic power density3, ultrasonic frequency
41 DEG C of 21kHz, temperature, sonic oscillation 2.2h;After the completion of ultrasonic activation, the ultrasonic surface activated carrier in ultrasound reactor
Mixed liquor is transferred in 500ml hydrothermal reaction kettles, is added by 2.1g boraxs, 3.05g potassium sulfates, 1.6g isopropyl scandium oxides
(III), 2.05g tri- (DPM dpm,dipivalomethane acid) gadolinium, (the fluoro- 2,2- bis- of 6,6,7,7,8,8,8- seven of 2.6g tri-
Methyl -3,5- octenes diketone) dysprosium (III), 3.05g trifluoromethayl sulfonic acids thulium (III), 5.05g titanocenes ring substituted salicylic acids
The golden potassium of complex, 6.1g zinc lactates, 2.05g tetrachloros, the nitroso rhodium trisodiums of 3.1g six, 3.05g oleamide propyl-dimethyl hydroxyl second
The aqueous solution that ammonium chloride and 50ml deionized waters are prepared, the weight concentration of the aqueous solution is 40.3%, 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, can after cooling down
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 medical stones of 400 mesh standard sieves, 1.65g wollastonites, 1.85g kaolin, the red metals and stones of 2.05g, 2.25g basalt,
The weight of 2.45g astrakanites, 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 0.7W/m to control ultrasonic power density3, ultrasonic frequency
54 DEG C of 29kHz, temperature, sonic oscillation 4.7h;After the completion of ultrasonic activation, the ultrasonic surface activated carrier in ultrasound reactor
Mixed liquor is transferred in 100ml hydrothermal reaction kettles, is added by 0.78g boraxs, 0.97g potassium sulfates, 0.58g isopropyl scandium oxides
(III), 0.67g tri- (DPM dpm,dipivalomethane acid) gadolinium, (the fluoro- 2,2- of 6,6,7,7,8,8,8- seven of 0.78g tri-
Dimethyl -3,5- octenes diketone) dysprosium (III), 0.87g trifluoromethayl sulfonic acids thulium (III), 1.48g titanocenes ring substitution bigcatkin willow
The golden potassium of sour complex, 1.77g zinc lactates, 0.68g tetrachloros, the nitroso rhodium trisodiums of 0.87g six, 1.98g oleamide propyl-dimethyls
The aqueous solution that hydroxyethyl ammonium chloride and 10ml deionized waters are prepared, the weight concentration of the aqueous solution is 53.3%, the weight of the aqueous solution
Amount:Weight=21.43g of ultrasonic surface activated carrier mixed liquor:39.7g=1:1.9, control 175 DEG C of temperature, the hydro-thermal reaction time
For 15.5h, then fine silt thing is dried to obtain for 105 DEG C;Fine silt thing is in Muffle furnace, 930 DEG C, calcination 7.5h, after cooling down,
It can obtain the ozone Heterogeneous oxidation solid catalyst of fine particle shape.
Comparative example 1:Preparation process is not added with lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, myristyl tributyl ammonium chloride, oil
Outside amido propyl dimethyl hydroxyethyl ammonium chloride, borax and potassium sulfate, whole preparation process, preparation condition and embodiment 1 are complete
It 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
Under the same conditions be used for ethylenediamine, direct red brown R and 2,5- dimethoxyphenylacetic acid prepare waste water carry out ozone it is non-
Phase oxidation is handled.Treatment conditions are:Rate of charge=1000L of organic wastewater and catalyst:1g, organic wastewater CODCrValue
629.5mg/L, ozone dosage 80mg/L, processing time 1hr, ozone tail gas KI solution absorption detecting ozone utilization rates.Examination
Test data and be 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, kaolin, red metal and stone, basalt, astrakanite composition, by weight, medical stone:Wollastonite:Kaolin:It is red
Metal and stone:Basalt:The weight ratio of astrakanite=(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,
By weight, component C:Weight ratio=1 of reaming modified support:(5~10), D components by composite mineralizer borax, potassium sulfate,
Catalytic activity auxiliary agent predecessor isopropyl scandium oxide (III), three (DPM dpm,dipivalomethane acid) gadoliniums, three (6,6,7,
The fluoro- 2,2- dimethyl -3,5- octenes diketone of 7,8,8,8- seven) dysprosium (III), trifluoromethayl sulfonic acid thulium (III) rare earth metal have
Machine compound, catalytic active center predecessor normal transition metallo-organic compound titanocenes ring substituted salicylic acid complex, breast
The golden potassium of sour zinc and precious metal chemical complex tetrachloro, six nitroso rhodium trisodiums, emulsifying agent oleamide propyl-dimethyl hydroxyethyl ammonium chloride
Composition, by weight, borax:Potassium sulfate:Isopropyl scandium oxide (III):Three (DPM dpm,dipivalomethane acid) gadoliniums:
Three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosiums (III):Trifluoromethayl sulfonic acid thulium (III):
Titanocenes ring substituted salicylic acid complex:Zinc lactate:Tetrachloro gold potassium:Six nitroso rhodium trisodiums:Oleamide propyl-dimethyl hydroxyl
The weight ratio of ethyl ammonium chloride=(4~8):(6~10):(3~6):(4~7):(5~8):(6~9):(10~15):(12
~18):(4~7):(6~9):(6~20).
2. B component is by medical stone, wollastonite, kaolin, red metal and stone, basalt, astrakanite group according to claim 1
Into medical stone, wollastonite, kaolin, red metal and stone, basalt, astrakanite are crushed respectively, and deionized water washing drying is removed
Go after moisture, sieved through standard screen, it is 0.0370mm~0.0750mm to control particle diameter.
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Application publication date: 20170818 |