CN107008400A - 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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- CN107008400A CN107008400A CN201710275669.5A CN201710275669A CN107008400A CN 107008400 A CN107008400 A CN 107008400A CN 201710275669 A CN201710275669 A CN 201710275669A CN 107008400 A CN107008400 A CN 107008400A
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- component
- weight
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- solid catalyst
- ozone heterogeneous
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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 27
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 27
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 239000000126 substance 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
- 229910021532 Calcite Inorganic materials 0.000 claims abstract description 10
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000010428 baryte Substances 0.000 claims abstract description 10
- 229910052601 baryte Inorganic materials 0.000 claims abstract description 10
- -1 holmium oxalate Rare-earth Chemical class 0.000 claims abstract description 10
- 235000019362 perlite Nutrition 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
- 229910052656 albite Inorganic materials 0.000 claims abstract description 9
- 239000010459 dolomite Substances 0.000 claims abstract description 9
- 229910000514 dolomite Inorganic materials 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
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- 229930008380 camphor Natural products 0.000 claims abstract description 7
- ITZXULOAYIAYNU-UHFFFAOYSA-N cerium(4+) Chemical compound [Ce+4] ITZXULOAYIAYNU-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZCPCLAPUXMZUCD-UHFFFAOYSA-M dihexadecyl(dimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCC ZCPCLAPUXMZUCD-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000010970 precious metal Substances 0.000 claims abstract description 7
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 7
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 6
- SHFGJEQAOUMGJM-UHFFFAOYSA-N dialuminum dipotassium disodium dioxosilane iron(3+) oxocalcium oxomagnesium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Na+].[Na+].[Al+3].[Al+3].[K+].[K+].[Fe+3].[Fe+3].O=[Mg].O=[Ca].O=[Si]=O SHFGJEQAOUMGJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229930195712 glutamate Natural products 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
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004472 Lysine Substances 0.000 claims abstract description 5
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 5
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021538 borax Inorganic materials 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
- 239000004328 sodium tetraborate 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
- 238000001354 calcination Methods 0.000 claims abstract description 4
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- 238000003756 stirring Methods 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- DYYFBWLZDJSPGO-UHFFFAOYSA-H holmium(3+);oxalate Chemical class [Ho+3].[Ho+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DYYFBWLZDJSPGO-UHFFFAOYSA-H 0.000 claims description 5
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- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 5
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- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 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
- 230000036571 hydration Effects 0.000 claims description 3
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- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 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
- KPQDSKZQRXHKHY-UHFFFAOYSA-N gold potassium Chemical compound [K].[Au] KPQDSKZQRXHKHY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 125000002252 acyl group Chemical group 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 239000004576 sand Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 16
- 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
- 239000011148 porous material Substances 0.000 abstract description 7
- 238000001994 activation Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 235000018977 lysine Nutrition 0.000 description 5
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- 239000003643 water by type Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
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- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
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- 150000002306 glutamic acid derivatives Chemical class 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
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
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- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 210000004556 brain Anatomy 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
- 238000009792 diffusion process Methods 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical class CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-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
- 125000002524 organometallic group Chemical group 0.000 description 1
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- 239000012071 phase Substances 0.000 description 1
- WCWKKSOQLQEJTE-UHFFFAOYSA-N praseodymium(3+) Chemical compound [Pr+3] WCWKKSOQLQEJTE-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—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
- 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
- B01J23/8986—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 with manganese, technetium or rhenium
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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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.The preparation method is to use gamma-alumina, barite, perlite, albite, dolomite and calcite porous material make carrier, carrier is modified through lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add the double dodecyldimethylamine ammonium chlorides of surfactant and surface activation process is carried out under ul-trasonic irradiation, then ultrasonic surface 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), it is hydrated three acetic acid terbiums, ten water holmium oxalate Rare-earth chemicals, catalytic active center component predecessor normal transition metallo-organic compound lysine manganese, cupric glutamate, zirconium carbonate ammonium and the golden potassium of precious metal chemical complex tetrachloro, hydro-thermal reaction is carried out under the effect of emulsifying agent Varisoft 432PPG, reaction product drying is removed after moisture, in Muffle furnace, calcination obtains ozone Heterogeneous oxidation solid catalyst under certain temperature.
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, perlite, albite, white
Marble, calcite composition, by weight, gama-alumina:Barite:Perlite:Albite:Dolomite:The weight of calcite
The ratio between=（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 double dodecyldimethylamine ammonium chlorides, by weight, component C:Reaming, which is modified, to be carried
Weight ratio=1 of body:（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), hydration three acetic acid terbiums, ten
Water holmium oxalate Rare-earth chemicals, catalytic active center predecessor normal transition metallo-organic compound lysine manganese,
The golden potassium of cupric glutamate, zirconium carbonate ammonium and precious metal chemical complex tetrachloro, emulsifying agent Varisoft 432PPG composition, by weight
Gauge, borax:Potassium sulfate:Four (DPM dpm,dipivalomethane acid) ceriums (IV):Three (3- trifluoroacetyl group-D- camphor trees
Brain) praseodymium (III):It is hydrated three acetic acid terbiums:Ten water holmium oxalates:Lysine manganese:Cupric glutamate:Zirconium carbonate ammonium:Tetrachloro gold potassium:Double 16
The weight ratio of alkyl dimethyl ammonium chloride=（4~8）:（6~10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~
15）:（12~18）:（4~7）:（6~9）:（6~20）.Gama-alumina, barite, perlite, sodium in the B component is long
Stone, dolomite, calcite are crushed respectively, deionized water washing dry remove moisture after, through standard screen carry out -200 mesh ,+
400 mesh sieves point, it is the mm of 0.0370mm~0.0750 control particle diameter.
What the technical method of the present invention was realized in：Lithium hypochlorite LiClO, double (second can be being added in closed reactor
Acyl acetone) beryllium C10H14BeO4The aqueous solution is prepared with deionized water stirring, it is 0.0370mm~0.0750mm to add particle diameter after screening
Gama-alumina, barite, perlite, albite, dolomite and calcite 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, three acetic acid of hydration
Terbium C6H11O7Tb, ten water holmium oxalate C6Ho2O12Rare-earth chemicals, catalytic active center component predecessor normal transition
Metallo-organic compound lysine manganese C12H26N4O4, cupric glutamate C5H7NO4Cu, zirconium carbonate ammonium (NH4)2·C2H2O8Zr and your gold
Belong to the golden potassium KAuCl of compound tetrachloro4, in emulsifying agent Varisoft 432PPG [(C16H33)2N(CH3)2]+Cl-Effect
Lower carry out hydro-thermal reaction, mineralizer accelerates diffusion, activates reactant lattice, promotes the progress of solid phase reaction, ultrasound
Surface active carrier and Rare-earth chemicals, normal transition metallo-organic compound, precious metal chemical complex Uniform Doped,
Emulsifying agent Varisoft 432PPG make reaction solution formed quasi-stationary emulsion prevent separation of solid and liquid, sedimentation, simultaneously
To the further surface active of porous mineral carrier, by the way that in certain temperature, the hydro-thermal reaction of time, drying obtains Uniform Doped
Fine silt thing；The fine silt thing of Uniform Doped is in Muffle furnace, through high temperature sintering, and organic matter carbonization therein is further strong
Change the microcellular structure of porous carrier, obtain porous carrier supported rare earth metal oxide, transition metal oxide and noble metal
The ozone Heterogeneous oxidation solid catalyst of the catalytic active center of formation, improves the mithridatism and catalytic activity of catalyst.
Relative to art methods, outstanding advantages of the present invention are that gama-alumina, barite, treasure are used in technology of preparing
Zhu Yan, albite, dolomite, calcite 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-Di-cetyl dimethyl
Ammonium chloride [(C16H33)2N(CH3)2]+Cl-To being interconnected and surface activation for duct；Rare earth gold is made by hydro-thermal reaction
Category organic compound, normal transition metallo-organic compound and precious metal chemical complex reach Uniform Doped and are attached to carrier surface
In duct, high temperature sintering makes organic matter carbonization strengthen and form multi-level microcellular structure, and porous carrier load is dilute
The multi-element metal catalytic active center of soil metal oxide, transition metal oxide and noble metal formation is combined more with porous carrier
Plus firmly, the ozone Heterogeneous oxidation solid catalyst of preparation has a stronger adsorptivity, the cooperative effect of multi-element metal, especially
It is stability and high activity that doped precious metal has, liquating out for metal catalytic activity component can be suppressed, improves catalysis
The mithridatism and catalytic activity of agent, 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 gama-aluminas of 400 mesh standard sieves, 3.75g barites, 4.75g perlites, 5.75g albites, 6.75g dolomites,
The weight of 7.75g calcites, 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 be hydrated three acetic acid terbiums, 3.05g ten
The golden potassium of water holmium oxalate, 5.05g lysines manganese, 6.1g cupric glutamates, 2.05g zirconium carbonate ammoniums, 3.1g tetrachloros, the double hexadecanes of 3.05g
The aqueous solution that base alkyl dimethyl ammonium chloride and 50ml deionized waters are prepared, the weight concentration of the aqueous solution is 40.3%, the aqueous solution
Weight:Weight=83.8g of ultrasonic surface activated carrier mixed liquor:134.25g=1:1.6, control 125 DEG C of temperature, 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, cooling down
Afterwards, it can obtain the ozone Heterogeneous oxidation solid catalyst of fine particle shape.
Embodiment 2:0.24g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 0.36g, 10ml deionized waters, being added to volume is
100ml's can be uniformly mixed in closed reactor, and the weight concentration of the aqueous solution is 5.7%, lithium hypochlorite:Double (levulinics
Ketone) beryllium weight ratio=1:1.5；Add deionized water wash to it is neutral, 103 DEG C dry remove -200 mesh of sieving after moisture~+
The 1.45g gama-aluminas of 400 mesh standard sieves, 1.65g barites, 1.85g perlites, 2.05g albites, 2.25g dolomites,
The weight of 2.45g calcites, 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 be hydrated three vinegar
The golden potassium of sour terbium, the water holmium oxalates of 0.87g ten, 1.48g lysines manganese, 1.77g cupric glutamates, 0.68g zirconium carbonate ammoniums, 0.87g tetrachloros,
The aqueous solution that 1.98g Varisoft 432PPGs and 10ml deionized waters are prepared, the weight concentration of the aqueous 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, control temperature
175 DEG C, 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, burns
Burn after 7.5h, cooling down, can obtain the ozone Heterogeneous oxidation solid catalyst of fine particle shape.
Comparative example 1:Preparation process be not added with lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, double dodecyldimethylamine ammonium chlorides,
Outside Varisoft 432PPG, 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.
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, perlite, albite, dolomite, calcite composition, by weight, gama-alumina:Barite:It is precious
Zhu Yan:Albite:Dolomite:The weight ratio of calcite=（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), hydration three acetic acid terbiums, ten water holmium oxalate Rare-earth chemicals, catalytic active center
The golden potassium of predecessor normal transition metallo-organic compound lysine manganese, cupric glutamate, zirconium carbonate ammonium and precious metal chemical complex tetrachloro,
Emulsifying agent Varisoft 432PPG is constituted, by weight, borax:Potassium sulfate:Four (2,2,6,6- tetramethyls -3,5-
Heptadione acid) cerium (IV):Three (3- trifluoroacetyl group-D- camphors) praseodymiums (III):It is hydrated three acetic acid terbiums:Ten water holmium oxalates:Rely ammonia
Sour manganese:Cupric glutamate:Zirconium carbonate ammonium:Tetrachloro gold potassium:The weight ratio of Varisoft 432PPG=（4~8）:（6~
10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.
2. B component is by gama-alumina, barite, perlite, albite, dolomite, calcite group according to claim 1
Into gama-alumina, barite, perlite, albite, dolomite, calcite are crushed respectively, deionized water washing drying
Remove after moisture, sieved through standard screen, it is 0.0370mm~0.0750mm to control particle diameter.
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