CN107051531A - 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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- CN107051531A CN107051531A CN201710276368.4A CN201710276368A CN107051531A CN 107051531 A CN107051531 A CN 107051531A CN 201710276368 A CN201710276368 A CN 201710276368A CN 107051531 A CN107051531 A CN 107051531A
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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 31
- 230000003647 oxidation Effects 0.000 title claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 26
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal 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
- 239000004575 stone Substances 0.000 claims abstract description 12
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 11
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052601 baryte Inorganic materials 0.000 claims abstract description 10
- 239000010428 baryte Substances 0.000 claims abstract description 10
- PALNZFJYSCMLBK-UHFFFAOYSA-K magnesium;potassium;trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-].[Cl-].[K+] PALNZFJYSCMLBK-UHFFFAOYSA-K 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 hydroxypropyl dichloride ammonium Chemical compound 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
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 241000723346 Cinnamomum camphora Species 0.000 claims abstract description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 229930008380 camphor Natural products 0.000 claims abstract description 8
- 125000003963 dichloro group Chemical group Cl* 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
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- ITZXULOAYIAYNU-UHFFFAOYSA-N cerium(4+) Chemical compound [Ce+4] ITZXULOAYIAYNU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 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 6
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 125000000858 thiocyanato group Chemical group *SC#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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- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 5
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- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
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- 125000000217 alkyl group Chemical group 0.000 claims description 7
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- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 6
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- RLFOVBVRQCNOMD-UHFFFAOYSA-N lutetium;hydrate Chemical compound O.[Lu] RLFOVBVRQCNOMD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims 1
- 229960000846 camphor Drugs 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims 1
- 239000004576 sand Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- BOLCLFSSFZOGPX-UHFFFAOYSA-N N.[Cl-].C(CCCCCCCCCCC)[NH+](C)C Chemical class N.[Cl-].C(CCCCCCCCCCC)[NH+](C)C BOLCLFSSFZOGPX-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 238000001994 activation Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 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
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 abstract 1
- 239000000306 component Substances 0.000 description 19
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- 230000004913 activation Effects 0.000 description 4
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
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- 125000004005 formimidoyl group Chemical group [H]\N=C(/[H])* 0.000 description 2
- 150000002306 glutamic acid derivatives Chemical class 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002669 lysines Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
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- 229910004835 Na2B4O7 Inorganic materials 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
- AXNBHOOQHIIQFA-UHFFFAOYSA-N [S].C(F)(F)F Chemical compound [S].C(F)(F)F AXNBHOOQHIIQFA-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
- 150000001335 aliphatic alkanes Chemical class 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
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- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
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- WCWKKSOQLQEJTE-UHFFFAOYSA-N praseodymium(3+) Chemical compound [Pr+3] WCWKKSOQLQEJTE-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
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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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 gamma-alumina, barite, activated carbon, carnallite, kaolin and red metal and stone make carrier, carrier is after lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add double dodecyldimethylamine ammonium chlorides and activation process is carried out under ul-trasonic irradiation, then activated carrier in hydrothermal reaction kettle with composite mineralizer borax and potassium sulfate, catalytic activity auxiliary agent predecessor four (2, 2, 6, 6 tetramethyls 3, 5 heptadione acid) cerium (IV), three (3 trifluoroacetyl group D camphors) praseodymiums (III), trifluoromethayl sulfonic acid thulium (III), carbonic acid lutetium hydrate, catalytic active center component predecessor lysine manganese, cupric glutamate, two thiocyanatos silver（I）Sour potassium, the ammino palladium of dichloro four, carry out hydro-thermal reaction under the effect of the hydroxypropyl dichloride ammonium of ten alkyl dimethyl N' trimethyls of emulsifying agent N 2, and drying removes moisture, and 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 chemicals and closes
Thing and precious metal chemical complex are made catalytic active center predecessor and contained with multicomponent porous carrier through hydro-thermal reaction, high temperature sintering preparation
The ozone Heterogeneous oxidation solid catalyst of multi-element metal has to improve the preparation method of catalyst mithridatism and catalytic activity
Larger environmental benefit and higher practical value.
The content of the invention
For existing in current ozone Heterogeneous oxidation solid catalyst preparation method, Catalyst Adsorption is relatively low, mithridatism
Poor to lose catalytic activity problem with easy, exploitation strengthens catalyst using multicomponent porous carrier through reaming, surface active
Adsorptivity, catalytic activity auxiliary agent predecessor, normal transition metallo-organic compound and expensive are made using Rare-earth chemicals
Metallic compound is made catalytic active center predecessor and prepared with multicomponent porous carrier through hydro-thermal reaction, high temperature sintering containing polynary gold
The ozone Heterogeneous oxidation solid catalyst of category to improve the preparation method of catalyst mithridatism and catalytic activity, it is characterized in that
Component A can be added in closed reactor and deionized water stirring prepares the aqueous solution, the weight concentration for control component A is 2%~6%,
After the completion of prepared by solution, B component is added under agitation, 35 DEG C~50 DEG C are warming up to, continues stirring reaction 3h~6h, is filtered, instead
Product is answered to obtain reaming modified support after 102 DEG C~106 DEG C dry constant weights；Reaming modified support puts into ultrasound reactor,
The aqueous solution prepared by component C and deionized water is added, the weight concentration of component C is 3%~8%, is uniformly mixed, and control is super
Sound power density is 0.3~0.8W/m3, frequency 20kHz~30kHz, 40 DEG C~55 DEG C, sonic oscillation 2h~5h obtains ultrasound
Surface active carrier mixed liquor；Ultrasonic surface activated carrier mixed liquor is transferred in hydrothermal reaction kettle, add D components and go from
The aqueous solution that sub- water is prepared, the weight concentration of D components is 40%~55%, by weight, D component deionized water solutions:Ultrasonic table
Weight ratio=1 of face activated carrier mixed liquor:（1.5~2）, control 120 DEG C~180 DEG C of temperature, the hydro-thermal reaction time be 8h~
16h, then dries to obtain fine particle；Fine particle is in Muffle furnace, 600 DEG C~950 DEG C, and calcination 3h~8h obtains ozone non-
Homogeneous oxidizing solid catalyst.The component A is made up of lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, by weight, lithium hypochlorite:
Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B component is by gama-alumina, barite, activated carbon, carnallite, height
Ridge is native, red metal and stone composition, by weight, gama-alumina:Barite:Activated carbon:Carnallite:Kaolin:The weight of red metal and stone
The ratio between amount=（5~15）:（7~17）:（9~19）:（11~21）:（13~23）:（15~25）, by weight, component A:B groups
Weight ratio=1 divided:（10~20）, component C is double dodecyldimethylamine ammonium chlorides, by weight, component C:Reaming is modified
Weight ratio=1 of carrier:（5~10）, D components by composite mineralizer borax, potassium sulfate, catalytic activity auxiliary agent predecessor four (2,
2,6,6- tetramethyl -3,5- heptadione acid) cerium (IV), three (3- trifluoroacetyl group-D- camphors) praseodymiums (III), trifluoromethayl sulfonic acid
Thulium (III), carbonic acid lutetium hydrate Rare-earth chemicals, catalytic active center predecessor normal transition Organometallic are closed
Thing lysine manganese, cupric glutamate and the thiocyanato of precious metal chemical complex two silver（I）Sour potassium, the ammino palladium of dichloro four, emulsifying agent N-
Ten alkyl dimethyl-N'- trimethyl -2- hydroxypropyl dichlorides ammoniums are constituted, by weight, borax:Potassium sulfate:Four (2,2,6,6-
Tetramethyl -3,5- heptadione acid) cerium (IV):Three (3- trifluoroacetyl group-D- camphors) praseodymiums (III):Trifluoromethayl sulfonic acid thulium
(III):Carbonic acid lutetium hydrate:Lysine manganese:Cupric glutamate:Two thiocyanatos silver（I）Sour potassium:The ammino palladium of dichloro four:N- ten
The weight ratio of alkyl dimethyl-N'- trimethyl -2- hydroxypropyl dichloride ammoniums=（4~8）:（6~10）:（3~6）:（4~7）:
（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.Gama-alumina in the B component,
Barite, activated carbon, carnallite, kaolin, red metal and stone are crushed respectively, and deionized water washing, which is dried, to be removed after moisture, warp
Standard screen 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
Gama-alumina, barite, activated carbon, carnallite, kaolin and red metal and stone porous material carrier, in certain temperature and stirring
Under the conditions of, the small Be of aqueous solution Ionic Radius2+（0.31Å）、Li+（0.60Å）Displace part ion radius in porous material
Big Ca2+（0.99Å）、K+（1.33Å）、Ba2+（1.35Å）Plasma, the aperture of porous material carrier becomes big, surface roughness increasing
Plus, filtering dries the reaming modified support input ultrasound reactor after constant weight, adds double dodecyldimethylamine ammonium chlorides
[(C14H29)2N(CH3)2]+Cl-The aqueous solution, control ultrasonic power density, ultrasonic frequency, temperature and sonic oscillation time, super
Under sound wave cavitation, double dodecyldimethylamine ammonium chloride [(C14H29)2N(CH3)2]+Cl-It is easy to escape into from the aqueous solution
Reaming modified support duct is attached to reaming modified support surface, is beneficial to being interconnected and carrier surface work for carrier duct
Change, enhance adsorptivity；After the completion of ultrasonic activation, ultrasonic surface activated carrier mixed liquor is transferred in hydrothermal reaction kettle, with boron
Sand Na2B4O7·10H2O, potassium sulfate K2SO4Composite mineralizer, (2,2,6, the 6- tetramethyls -3,5- of catalytic activity auxiliary agent predecessor four
Heptadione acid) cerium (IV) C22H38CeO4, three (3- trifluoroacetyl group-D- camphors) praseodymium (III) C36H42F9O6Pr, fluoroform sulphur
Sour thulium (III) C3F9O9S3Tm, carbonic acid lutetium hydrate C3H2Lu2O10Before Rare-earth chemicals, catalytic active center component
Drive thing normal transition metallo-organic compound lysine manganese C12H26N4O4, cupric glutamate C5H7NO4Cu and the sulphur of precious metal chemical complex two
Cyanate radical closes silver（I）Sour potassium K [Ag (SCN)2], the ammino palladium Pd (NH of dichloro four3)4Cl2, the alkyl dimethyls of emulsifying agent N- ten-
N'- trimethyl -2- hydroxypropyl dichloride ammoniums C10H21N+(CH3)2CH2CH(OH)CH2N+(CH3)3Cl2 -The lower progress hydro-thermal of effect is anti-
Should, mineralizer accelerates diffusion, activates reactant lattice, promotes the progress of solid phase reaction, ultrasonic surface activated carrier
With Rare-earth chemicals, normal transition metallo-organic compound, precious metal chemical complex Uniform Doped, the alkane of emulsifying agent N- ten
Base dimethyl-N'- trimethyl -2- hydroxypropyl dichloride ammoniums make reaction solution formed quasi-stationary emulsion prevent separation of solid and liquid, it is heavy
Drop, while to the further surface active of porous mineral carrier, by the way that in certain temperature, the hydro-thermal reaction of time, drying is obtained
The fine silt thing of even doping；The fine silt thing of Uniform Doped is in Muffle furnace, through high temperature sintering, organic matter carbonization therein
The microcellular structure of porous carrier is further enhanced, porous carrier supported rare earth metal oxide, transition metal oxide is obtained
With the ozone Heterogeneous oxidation solid catalyst of the catalytic active center of noble metal formation, improve the mithridatism of catalyst and urge
Change activity.
Relative to art methods, outstanding advantages of the present invention are that gama-alumina, barite, work are used in technology of preparing
Property charcoal, carnallite, kaolin, red metal and stone porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) berylliums
C10H14BeO4Reaming effect, double dodecyldimethylamine ammonium chloride [(C14H29)2N(CH3)2]+Cl-The alkyl dimethyls of N- ten-
N'- trimethyl -2- hydroxypropyl dichloride ammoniums C10H21N+(CH3)2CH2CH(OH)CH2N+(CH3)3Cl2 -To duct be interconnected and
Surface activation；Rare-earth chemicals, normal transition metallo-organic compound and noble metal are made by hydro-thermal reaction
Compound reaches Uniform Doped and is attached in carrier surface and duct that high temperature sintering makes organic matter carbonization strengthen and be formed
Multi-level microcellular structure, porous carrier supported rare earth metal oxide, transition metal oxide and noble metal formation it is many
First metal catalytic activity center is combined more firm with porous carrier, and the ozone Heterogeneous oxidation solid catalyst of preparation has more
Strong adsorptivity, the cooperative effect of multi-element metal, stability and high activity that particularly doped precious metal has, can suppress gold
Liquating out for category catalytic active component, improves the mithridatism and catalytic activity of catalyst, with good environmental benefit and warp
Ji benefit.
Embodiment
Embodiment 1:1.35g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 1.65g, 140ml deionized waters, being added to volume is
500ml's can be uniformly mixed in closed reactor, and the weight concentration of the aqueous solution is 2.1%, lithium hypochlorite:Double (levulinics
Ketone) beryllium weight ratio=1:1.2；Add deionized water wash to it is neutral, 103 DEG C dry remove -200 mesh of sieving after moisture~+
The 2.75g gama-aluminas of 400 mesh standard sieves, 3.75g barites, 4.75g activated carbons, 5.75g carnallites, 6.75g kaolin,
The weight of the red metals and stones of 7.75g, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（3g）:The weight of porous material（31.5g）=1:10.5,
36 DEG C are warming up to, reaming modified support 31g is obtained after continuing stirring reaction 3.2h, filtering, 103 DEG C of dry constant weights；It is super in 500ml
In sound wave reactor, reaming modified support 31g is put into, the double dodecyldimethylamine ammonium chlorides of 3.25g is added and is dissolved in 100ml
The aqueous solution of ionized water, the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, double dodecyldimethylamine ammonium chlorides
（3.25g）:Reaming modified support（31g ）=1:9.5；It is 0.4W/m to control ultrasonic power density3, ultrasonic frequency 21kHz, temperature
41 DEG C of degree, sonic oscillation 2.2h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor is turned
Move in 500ml hydrothermal reaction kettles, add by 2.1g boraxs, 3.05g potassium sulfates, (2,2,6, the 6- tetramethyls -3,5- of 1.6g tetra-
Heptadione acid) cerium (IV), 2.05g tri- (3- trifluoroacetyl group-D- camphors) praseodymium (III), 2.6g trifluoromethayl sulfonic acids thulium (III),
3.05g carbonic acid lutetiums hydrate, 5.05g lysines manganese, 6.1g cupric glutamates, the thiocyanatos of 2.05g bis- silver（I）Sour potassium, 3.1g
The ammino palladium of dichloro four, the alkyl dimethyl-N'- trimethyl -2- hydroxypropyl dichloride ammoniums of 3.05gN- ten and 50ml deionized waters are prepared
The aqueous solution, the weight concentration of the aqueous solution is 40.3%, the weight of the aqueous solution:The weight of ultrasonic surface activated carrier mixed liquor
Amount=83.8g:134.25g=1:1.6,125 DEG C of temperature is controlled, the hydro-thermal reaction time is 8.3h, then dries to obtain fine silt for 105 DEG C
Thing；Fine silt thing is in Muffle furnace, 620 DEG C, calcination 3.2h, and after cooling down, the ozone that can obtain fine particle shape is heterogeneous
Oxidized solid catalyst.
Embodiment 2:0.24g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 0.36g, 10ml deionized waters, being added to volume is
100ml's can be uniformly mixed in closed reactor, and the weight concentration of the aqueous solution is 5.7%, lithium hypochlorite:Double (levulinics
Ketone) beryllium weight ratio=1:1.5；Add deionized water wash to it is neutral, 103 DEG C dry remove -200 mesh of sieving after moisture~+
The 1.45g gama-aluminas of 400 mesh standard sieves, 1.65g barites, 1.85g activated carbons, 2.05g carnallites, 2.25g kaolin,
The weight of the red metals and stones of 2.45g, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（0.6g）:The weight of porous material（11.7g）=1:
19.5,48 DEG C are warming up to, reaming modified support 11.5g is obtained after continuing stirring reaction 5.8h, filtering, 105 DEG C of dry constant weights；
In 100ml ultrasound reactors, reaming modified support 11.5g is put into, the double dodecyldimethylamine ammonium chlorides of 2.2g are added molten
In the aqueous solution of 26ml deionized waters, the weight concentration of the aqueous solution is 7.8%, is uniformly mixed, double dodecyldimethylamine bases
Ammonium chloride（2.2g）:Reaming modified support（11.5g ）=1:5.2；It is 0.7W/m to control ultrasonic power density3, ultrasonic frequency
54 DEG C of 29kHz, temperature, sonic oscillation 4.7h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier in ultrasound reactor
Mixed liquor is transferred in 100ml hydrothermal reaction kettles, is added by 0.78g boraxs, 0.97g potassium sulfates, 0.58g tetra- (2,2,6,6-
Tetramethyl -3,5- heptadione acid) cerium (IV), 0.67g tri- (3- trifluoroacetyl group-D- camphors) praseodymium (III), 0.78g fluoroforms
Sulfonic acid thulium (III), 0.87g carbonic acid lutetiums hydrate, 1.48g lysines manganese, 1.77g cupric glutamates, the thiocyanatos of 0.68g bis- silver
（I）Sour potassium, the ammino palladium of 0.87g dichloros four, the alkyl dimethyl-N'- trimethyl -2- hydroxypropyl dichloride ammoniums of 1.98gN- ten and
The aqueous solution that 10ml deionized waters are prepared, the weight concentration of the aqueous solution is 53.3%, the weight of the aqueous solution:Ultrasonic surface is lived
Change weight=21.43g of carrier mixed liquor:39.7g=1:1.9,175 DEG C of temperature is controlled, the hydro-thermal reaction time is 15.5h, then
105 DEG C dry to obtain fine silt thing；Fine silt thing is in Muffle furnace, 930 DEG C, calcination 7.5h, after cooling down, can obtain fine powder
Granular ozone Heterogeneous oxidation solid catalyst.
Comparative example 1:Preparation process be not added with lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, double dodecyldimethylamine ammonium chlorides,
Outside the alkyl dimethyl-N'- trimethyl -2- hydroxypropyl dichlorides ammoniums of N- ten, borax and potassium sulfate, whole preparation process, bar is prepared
Part is 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.
The embodiment of table 1 and comparative example prepare ozone Heterogeneous oxidation solid catalysis agent parameter
Claims (2)
1. a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, it is characterized in that A groups can added in closed reactor
Divide and deionized water stirring prepares the aqueous solution, the weight concentration for controlling component A is 2%~6%, after the completion of prepared by solution, in stirring
Lower addition B component, is warming up to 35 DEG C~50 DEG C, continues stirring reaction 3h~6h, and filtering, reaction product is dry at 102 DEG C~106 DEG C
Reaming modified support is obtained after dry constant weight, reaming modified support input ultrasound reactor, addition is matched somebody with somebody by component C and deionized water
The aqueous solution of system, the weight concentration of component C is 3%~8%, is uniformly mixed, and it is 0.3~0.8W/ to control ultrasonic power density
m3, frequency 20kHz~30kHz, 40 DEG C~55 DEG C, sonic oscillation 2h~5h obtains ultrasonic surface activated carrier mixed liquor, transfer
Into hydrothermal reaction kettle, the aqueous solution that D components and deionized water are prepared is added, the weight concentration of D components is 40%~55%, is pressed
Weight meter, D component deionized water solutions:Weight ratio=1 of ultrasonic surface activated carrier mixed liquor:（1.5~2）, control temperature
120 DEG C~180 DEG C, the hydro-thermal reaction time is 8h~16h, then dries to obtain fine silt thing, fine silt thing is in Muffle furnace, 600
DEG C~950 DEG C, calcination 3h~8h obtains ozone Heterogeneous oxidation solid catalyst；The component A is by lithium hypochlorite, double (acetyl
Acetone) beryllium composition, by weight, lithium hypochlorite:Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B component by γ-
Aluminum oxide, barite, activated carbon, carnallite, kaolin, red metal and stone composition, by weight, gama-alumina:Barite:It is living
Property charcoal:Carnallite:Kaolin:The weight ratio of red metal and stone=（5~15）:（7~17）:（9~19）:（11~21）:（13~
23）:（15~25）, by weight, component A:Weight ratio=1 of B component:（10~20）, component C is double dodecyldimethylamines
Ammonium chloride, by weight, component C:Weight ratio=1 of reaming modified support:（5~10）, D components are by composite mineralizer boron
Sand, potassium sulfate, catalytic activity auxiliary agent predecessor four (2,2,6,6- tetramethyl -3,5- heptadione acid) cerium (IV), three (3- trifluoro second
Acyl group-D- camphors) praseodymium (III), trifluoromethayl sulfonic acid thulium (III), carbonic acid lutetium hydrate Rare-earth chemicals, catalysis
Activated centre predecessor normal transition metallo-organic compound lysine manganese, cupric glutamate and the thiocyanate radical of precious metal chemical complex two
Close silver（I）Sour potassium, the ammino palladium of dichloro four, the alkyl dimethyl-N'- trimethyl -2- hydroxypropyl dichlorides ammoniums of emulsifying agent N- ten composition,
By weight, borax:Potassium sulfate:Four (DPM dpm,dipivalomethane acid) ceriums (IV):Three (3- trifluoroacetyl groups-D-
Camphor) praseodymium (III):Trifluoromethayl sulfonic acid thulium (III):Carbonic acid lutetium hydrate:Lysine manganese:Cupric glutamate:Two thiocyanatos
Silver（I）Sour potassium:The ammino palladium of dichloro four:The weight ratio of the alkyl dimethyl-N'- trimethyl -2- hydroxypropyl dichloride ammoniums of N- ten=
（4~8）:（6~10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6
~20）.
2. B component is by gama-alumina, barite, activated carbon, carnallite, kaolin, red metal and stone according to claim 1
Composition, gama-alumina, barite, activated carbon, carnallite, kaolin, red metal and stone are crushed respectively, deionized water washing
Dry and remove after moisture, sieved through standard screen, it is 0.0370mm~0.0750mm to control particle diameter.
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Application publication date: 20170818 |