CN107008385A - The preparation method of ozone Heterogeneous oxidation solid catalyst - Google Patents
The preparation method of ozone Heterogeneous oxidation solid catalyst Download PDFInfo
- Publication number
- CN107008385A CN107008385A CN201710275293.8A CN201710275293A CN107008385A CN 107008385 A CN107008385 A CN 107008385A CN 201710275293 A CN201710275293 A CN 201710275293A CN 107008385 A CN107008385 A CN 107008385A
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- solid catalyst
- ozone heterogeneous
- weight ratio
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- 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 19
- 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 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- -1 polyhalite Substances 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001868 water Inorganic materials 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims abstract description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000004575 stone Substances 0.000 claims abstract description 12
- 235000012222 talc Nutrition 0.000 claims abstract description 12
- 125000001400 nonyl 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])[H] 0.000 claims abstract description 11
- 235000019362 perlite Nutrition 0.000 claims abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 239000000454 talc Substances 0.000 claims abstract description 10
- 229910052623 talc Inorganic materials 0.000 claims abstract description 10
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229940107816 ammonium iodide Drugs 0.000 claims abstract description 9
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- 229910052700 potassium Inorganic materials 0.000 claims abstract description 9
- 239000011591 potassium Substances 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 9
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 9
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000440 bentonite Substances 0.000 claims abstract description 8
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 8
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- 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 abstract description 8
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 8
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 8
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 claims abstract description 8
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- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 5
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 5
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- 229940009662 edetate Drugs 0.000 claims abstract description 5
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- JQDYLDJOLNKPHG-UHFFFAOYSA-N octadecanoate;trimethylazanium Chemical group CN(C)C.CCCCCCCCCCCCCCCCCC(O)=O JQDYLDJOLNKPHG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 4
- VAIVGJYVKZVQAA-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;nickel Chemical compound [Ni].OC(=O)CC(O)(C(O)=O)CC(O)=O VAIVGJYVKZVQAA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007795 chemical reaction product Substances 0.000 claims abstract 2
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 7
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- VOAPTKOANCCNFV-UHFFFAOYSA-N hexahydrate;hydrochloride Chemical compound O.O.O.O.O.O.Cl VOAPTKOANCCNFV-UHFFFAOYSA-N 0.000 claims description 4
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
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- RLFOVBVRQCNOMD-UHFFFAOYSA-N lutetium;hydrate Chemical compound O.[Lu] RLFOVBVRQCNOMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
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- 150000003624 transition metals Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 claims 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims 1
- 150000002902 organometallic compounds Chemical class 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
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- 229910052779 Neodymium Inorganic materials 0.000 abstract description 3
- WHELTKFSBJNBMQ-UHFFFAOYSA-L dichlororuthenium;2-pyridin-2-ylpyridine;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ru+2].N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 WHELTKFSBJNBMQ-UHFFFAOYSA-L 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 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
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- 235000021355 Stearic acid Nutrition 0.000 description 4
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
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- 150000001875 compounds Chemical class 0.000 description 3
- 125000004005 formimidoyl group Chemical group [H]\N=C(/[H])* 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
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- 229910000510 noble metal Inorganic materials 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
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- 239000007787 solid Substances 0.000 description 3
- BZSVVCFHMVMYCR-UHFFFAOYSA-N 2-pyridin-2-ylpyridine;ruthenium Chemical compound [Ru].N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 BZSVVCFHMVMYCR-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
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- NAPFHXCBNVVCGD-UHFFFAOYSA-N carbonic acid;lutetium Chemical compound [Lu].OC(O)=O NAPFHXCBNVVCGD-UHFFFAOYSA-N 0.000 description 2
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- MITDXNUXOAYFGC-UHFFFAOYSA-N 1-prop-2-ynylbenzimidazole Chemical compound C1=CC=C2N(CC#C)C=NC2=C1 MITDXNUXOAYFGC-UHFFFAOYSA-N 0.000 description 1
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- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- GDJKGUGXMBNRHL-UHFFFAOYSA-N O.[Lu].C(O)(O)=O Chemical compound O.[Lu].C(O)(O)=O GDJKGUGXMBNRHL-UHFFFAOYSA-N 0.000 description 1
- SYGKRYHXHZWFMX-UHFFFAOYSA-K [Nd+3].[O-]C(=O)C(F)(F)F.FC(C(=O)CC(C)=O)(F)F.[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F Chemical compound [Nd+3].[O-]C(=O)C(F)(F)F.FC(C(=O)CC(C)=O)(F)F.[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F SYGKRYHXHZWFMX-UHFFFAOYSA-K 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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- 230000002079 cooperative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- IOIFRTZBJMZZFO-UHFFFAOYSA-N dysprosium(3+) Chemical compound [Dy+3] IOIFRTZBJMZZFO-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
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- 238000006703 hydration reaction Methods 0.000 description 1
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- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
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- DTMHTVJOHYTUHE-UHFFFAOYSA-N thiocyanogen Chemical compound N#CSSC#N DTMHTVJOHYTUHE-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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
- B01J23/894—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 rare earths or actinides
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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 perlite, albite, bentonite, polyhalite, talcum and sal soda stone porous material make carrier, carrier is modified through lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add surfactant nonyl phenolic group bi-quaternary ammonium salt 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 1, 1, 1 trifluoroacetylacetone (TFA) neodymium, three (6, 6, 7, 7, 8, 8, 8 seven fluorine 2, 2 dimethyl 3, 5 octene diketone) dysprosium (III), ten water holmium oxalates, carbonic acid lutetium hydrate Rare-earth chemicals, catalytic active center component predecessor normal transition metallo-organic compound cobalt edetate, citric acid nickel and the thiocyanato of precious metal chemical complex two silver（I）Sour potassium, Tris(2,2'- bipyridyl) ruthenium (II) chloride hexahydrate, carry out hydro-thermal reaction under the effect of emulsifying agent stearic acid trimethylamine groups ethanol ester ammonium iodide, and reaction product drying is removed after moisture, and 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
The adsorptivity of catalyst, catalytic activity auxiliary agent predecessor, normal transition Organometallic are made using Rare-earth chemicals
Compound and precious metal chemical complex are made catalytic active center predecessor and prepared with multicomponent porous carrier through hydro-thermal reaction, high temperature sintering
Ozone Heterogeneous oxidation solid catalyst containing multi-element metal has to improve the preparation method of catalyst mithridatism and catalytic activity
There are larger environmental benefit and higher practical value.
The content of the invention
For existing in current ozone Heterogeneous oxidation solid catalyst preparation method, Catalyst Adsorption is relatively low, mithridatism
Poor to lose catalytic activity problem with easy, exploitation strengthens catalyst using multicomponent porous carrier through reaming, surface active
Adsorptivity, catalytic activity auxiliary agent predecessor, normal transition metallo-organic compound and expensive are made using Rare-earth chemicals
Metallic compound is made catalytic active center predecessor and prepared with multicomponent porous carrier through hydro-thermal reaction, high temperature sintering containing polynary gold
The ozone Heterogeneous oxidation solid catalyst of category to improve the preparation method of catalyst mithridatism and catalytic activity, it is characterized in that
Component A can be added in closed reactor and deionized water stirring prepares the aqueous solution, the weight concentration for control component A is 2%~6%,
After the completion of prepared by solution, B component is added under agitation, 35 DEG C~50 DEG C are warming up to, continues stirring reaction 3h~6h, is filtered, instead
Product is answered to obtain reaming modified support after 102 DEG C~106 DEG C dry constant weights；Reaming modified support puts into ultrasound reactor,
The aqueous solution prepared by component C and deionized water is added, the weight concentration of component C is 3%~8%, is uniformly mixed, and control is super
Sound power density is 0.3~0.8W/m3, frequency 20kHz~30kHz, 40 DEG C~55 DEG C, sonic oscillation 2h~5h obtains ultrasound
Surface active carrier mixed liquor；Ultrasonic surface activated carrier mixed liquor is transferred in hydrothermal reaction kettle, add D components and go from
The aqueous solution that sub- water is prepared, the weight concentration of D components is 40%~55%, by weight, D component deionized water solutions:Ultrasonic table
Weight ratio=1 of face activated carrier mixed liquor:（1.5~2）, control 120 DEG C~180 DEG C of temperature, the hydro-thermal reaction time be 8h~
16h, then dries to obtain fine particle；Fine particle is in Muffle furnace, 600 DEG C~950 DEG C, and calcination 3h~8h obtains ozone non-
Homogeneous oxidizing solid catalyst.The component A is made up of lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, by weight, lithium hypochlorite:
Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B component by perlite, albite, bentonite, polyhalite, talcum,
Sal soda stone is constituted, by weight, perlite:Albite:Bentonite:Polyhalite:Talcum:The weight ratio of sal soda stone=（5~
15）:（7~17）:（9~19）:（11~21）:（13~23）:（15~25）, by weight, component A:The weight ratio of B component
=1:（10~20）, component C is nonyl phenolic group bi-quaternary ammonium salt, by weight, component C:Weight ratio=1 of reaming modified support:
（5~10）, D components by composite mineralizer borax, potassium sulfate, the trifluoroacetylacetone (TFA) neodymium of catalytic activity auxiliary agent predecessor 1,1,1-,
Three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosiums (III), ten water holmium oxalates, the hydration of carbonic acid lutetium
Thing Rare-earth chemicals, catalytic active center predecessor normal transition metallo-organic compound cobalt edetate, lemon
The sour thiocyanato of nickel and precious metal chemical complex two silver（I）Sour potassium, Tris(2,2'- bipyridyl) ruthenium (II) chloride hexahydrate, emulsifying agent stearic acid three
Methyl aminoethanol ester ammonium iodide is constituted, by weight, borax:Potassium sulfate:1,1,1- trifluoroacetylacetone (TFA) neodymiums:Three (6,6,7,7,
The fluoro- 2,2- dimethyl -3,5- octenes diketone of 8,8,8- seven) dysprosium (III):Ten water holmium oxalates:Carbonic acid lutetium hydrate:Gluconic acid
Cobalt:Citric acid nickel:Two thiocyanatos silver（I）Sour potassium:Tris(2,2'- bipyridyl) ruthenium (II) chloride hexahydrate:Stearic acid trimethylamine groups ethanol ester
The weight ratio of ammonium iodide=（4~8）:（6~10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~
18）:（4~7）:（6~9）:（6~20）.Perlite, albite, bentonite, polyhalite, talcum, the sal soda stone of the B component
Crushed respectively, deionized water washing, which is dried, to be removed after moisture, is carried out -200 mesh ,+400 mesh sieves point through standard screen, is controlled grain
Footpath is the mm of 0.0370mm~0.0750.
What the technical method of the present invention was realized in：Lithium hypochlorite LiClO, double (second can be being added in closed reactor
Acyl acetone) beryllium C10H14BeO4The aqueous solution is prepared with deionized water stirring, it is 0.0370mm~0.0750mm to add particle diameter after screening
Perlite, albite, bentonite, polyhalite, talcum and sal soda stone porous material carrier, in certain temperature and stirring condition
Under, the small Be of aqueous solution Ionic Radius2+（0.31Å）、Li+（0.60Å）Displace part ion radius in porous material big
Ca2+（0.99Å）、K+（1.33Å）、Ba2+（1.35Å）Plasma, the aperture of porous material carrier becomes big, surface roughness increase,
Filtering, dries the reaming modified support input ultrasound reactor after constant weight, adds nonyl phenolic group bi-quaternary ammonium salt [(C2H5)2NCH2C6H2(OH)(C6H19)CH2N(C2H5)3]2 +Br2 -The aqueous solution, controls ultrasonic power density, ultrasonic frequency, temperature and surpasses
The sound oscillation time, under ultrasonic cavitation effect, nonyl phenolic group bi-quaternary ammonium salt [(C2H5)2NCH2C6H2(OH)(C6H19)CH2N
(C2H5)3]2 +Br2 - It is easy to escape into reaming modified support duct from the aqueous solution or is attached to reaming modified support surface, it is beneficial
In being interconnected and carrier surface activation for carrier duct, adsorptivity is enhanced；After the completion of ultrasonic activation, ultrasonic surface activation is carried
Body mixed liquor is transferred in hydrothermal reaction kettle, with borax Na2B4O7·10H2O, potassium sulfate K2SO4Composite mineralizer, catalytic activity
Auxiliary agent predecessor 1,1,1- trifluoroacetylacetone (TFA) neodymiums C15H12F9NdO6, three (fluoro- 2,2- dimethyl -3 of 6,6,7,7,8,8,8- seven,
5- octenes diketone) dysprosium (III) C30H30DyF21O6, ten water holmium oxalate C6Ho2O12, carbonic acid lutetium hydrate C3H2Lu2O10Rare earth gold
Belong to organic compound, catalytic active center component predecessor normal transition metallo-organic compound cobalt edetate C12H22O14Co、
Citric acid nickel C12H10O14Ni3With two thiocyanatos silver（I）Sour potassium K [Ag (SCN)2], Tris(2,2'- bipyridyl) ruthenium (II) chloride hexahydrate
(C10H8N2)3Cl2Ru·(H2O)6Precious metal chemical complex, in emulsifying agent stearic acid trimethylamine groups ethanol ester ammonium iodide
[C17H35COOCH2CH2N(CH3)CH2]+I-Effect is lower to carry out hydro-thermal reaction, and mineralizer accelerates diffusion, makes reactant lattice
Activation, promotes the progress of solid phase reaction, ultrasonic surface activated carrier has with Rare-earth chemicals, normal transition metal
Machine compound, precious metal chemical complex Uniform Doped, emulsifying agent stearic acid trimethylamine groups ethanol ester ammonium iodide make reaction solution form standard
The emulsion of stable state prevents separation of solid and liquid, sedimentation, while to the further surface active of porous carrier, by certain temperature, when
Between hydro-thermal reaction, drying obtains the fine silt thing of Uniform Doped；The fine silt thing of Uniform Doped burns in Muffle furnace through high temperature
Burn, organic matter carbonization therein further enhances the microcellular structure of porous carrier, obtain porous carrier supported rare earth gold
Belong to the ozone Heterogeneous oxidation solid catalyst of the catalytic active center of oxide, transition metal oxide and noble metal formation,
Improve the mithridatism and catalytic activity of catalyst.
Relative to art methods, outstanding feature of the present invention is that perlite, albite, swelling are used in technology of preparing
Soil, polyhalite, talcum, sal soda stone porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) beryllium C10H14BeO4
Reaming effect, nonyl phenolic group bi-quaternary ammonium salt [(C2H5)2NCH2C6H2(OH)(C6H19)CH2N(C2H5)3]2 +Br2 -, stearic acid front three
Aminoethanol ester ammonium iodide [C17H35COOCH2CH2N(CH3)CH2]+I-To being interconnected and surface activation for duct；Pass through
Hydro-thermal reaction makes Rare-earth chemicals, normal transition metallo-organic compound and precious metal chemical complex reach Uniform Doped
And be attached in carrier surface and duct, high temperature sintering makes organic matter carbonization strengthen and form multi-level micropore knot
In structure, the multi-element metal catalytic activity of porous carrier supported rare earth metal oxide, transition metal oxide and noble metal formation
The heart is combined more firm with porous carrier, and the ozone Heterogeneous oxidation solid catalyst of preparation has stronger adsorptivity, polynary
The cooperative effect of metal, the noble metal of particularly doping have stability and high activity, can suppress metal catalytic activity component
Liquate 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 are added to volume for 500ml
Can be uniformly mixed in closed reactor, the weight concentration of the aqueous solution is 2.1%, lithium hypochlorite:Double (acetylacetone,2,4-pentanedione) berylliums
Weight ratio=1:1.2；Add deionized water wash to it is neutral, 103 DEG C dry and remove the mesh of -200 mesh of sieving after moisture~+400
2.75g perlites, 3.75g albites, 4.75g bentonites, 5.75g polyhalites, 6.75g talcums, the 7.75g sal soda of standard screen
The weight of stone, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（3g）:The weight of porous material（31.5g）=1:10.5, it is warming up to 36
DEG C, obtain reaming modified support 31g after continuing stirring reaction 3.2h, filtering, 103 DEG C of dry constant weights；In 500ml ultrasonic responses
In device, reaming modified support 31g is put into, 3.25g nonyl phenolic group bi-quaternary ammonium salts is added and is dissolved in the water-soluble of 100ml deionized waters
Liquid, the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, nonyl phenolic group bi-quaternary ammonium salt（3.25g）:Reaming modified support
（31g ）=1:9.5；It is 0.4 W/m to control ultrasonic power density3, ultrasonic frequency 21kHz, 41 DEG C of temperature, sonic oscillation
2.2h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor is transferred to 500ml hydro-thermals anti-
Answer in kettle, add by 2.1g boraxs, 3.05g potassium sulfates, 1.6g1,1,1- trifluoroacetylacetone (TFA) neodymium, 2.05g tri- (6,6,7,7,
The fluoro- 2,2- dimethyl -3,5- octenes diketone of 8,8,8- seven) dysprosium (III), the water holmium oxalates of 2.6g ten, 3.05g carbonic acid lutetiums hydrate,
5.05g cobalt edetates, 6.1g citric acids nickel, the thiocyanatos of 2.05g bis- silver（I）Sour potassium, 3.1g Tris(2,2'- bipyridyl) ruthenium (II) chlorides six
The aqueous solution that hydrate, 3.05g stearic acid trimethylamine groups ethanol ester ammonium iodides and 50ml deionized waters are prepared, the aqueous solution
Weight concentration 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
Interior, 620 DEG C, calcination 3.2h after cooling down, can obtain the ozone Heterogeneous oxidation solid catalyst of fine particle shape.
Embodiment 2:0.24g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 0.36g, 10ml deionized waters, being added to volume is
100ml's can be uniformly mixed in closed reactor, and the weight concentration of the aqueous solution is 5.7%, lithium hypochlorite:Double (levulinics
Ketone) beryllium weight ratio=1:1.5；Add deionized water wash to it is neutral, 103 DEG C dry remove -200 mesh of sieving after moisture~+
1.45g perlites, 1.65g albites, 1.85g bentonites, 2.05g polyhalites, 2.25g talcums, the 2.45g of 400 mesh standard sieves
The weight of sal soda stone, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（0.6g）:The weight of porous material（11.7g）=1:19.5, heating
To 48 DEG C, reaming modified support 11.5g is obtained after continuing stirring reaction 5.8h, filtering, 105 DEG C of dry constant weights；In 100ml ultrasounds
In ripple reactor, reaming modified support 11.5g is put into, 2.2g nonyl phenolic group bi-quaternary ammonium salts is added and is dissolved in 26ml deionized waters
The aqueous solution, the weight concentration of the aqueous solution is 7.8%, is uniformly mixed, nonyl phenolic group bi-quaternary ammonium salt（2.2g）:Reaming is modified
Carrier（11.5g ）=1:5.2；It is 0.7 W/m to control ultrasonic power density3, ultrasonic frequency 29kHz, 54 DEG C of temperature, ultrasound is shaken
Swing 4.7h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor is transferred to 100ml hydro-thermals
In reactor, add by 0.78g boraxs, 0.97g potassium sulfates, 0.58g1,1,1- trifluoroacetylacetone (TFA) neodymium, 0.67g tri- (6,6,
The fluoro- 2,2- dimethyl -3,5- octenes diketone of 7,7,8,8,8- seven) dysprosium (III), the water holmium oxalates of 0.78g ten, 0.87g carbonic acid lutetium water
Compound, 1.48g cobalt edetates, 1.77g citric acids nickel, the thiocyanatos of 0.68g bis- silver（I）Sour potassium, 0.87g terpyridyls
The aqueous solution that ruthenic chloride hexahydrate, 1.98g stearic acid trimethylamine groups ethanol ester ammonium iodides and 10ml deionized waters are prepared, the water
The weight concentration of solution is 53.3%, the weight of the aqueous solution:Weight=21.43g of ultrasonic surface activated carrier mixed liquor:
39.7g =1:1.9,175 DEG C of temperature is controlled, the hydro-thermal reaction time is 15.5h, then dries to obtain fine silt thing for 105 DEG C；Fine silt
Thing is in Muffle furnace, 930 DEG C, calcination 7.5h, after cooling down, and the ozone Heterogeneous oxidation solid that can obtain fine particle shape is urged
Agent.
Comparative example 1:Preparation process is not added with lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, nonyl phenolic group bi-quaternary ammonium salt, stearic acid
Outside trimethylamine groups ethanol ester ammonium iodide, 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
| Project | Average pore size (nm) | Pore volume (cm3/g) | BET is than surface (m2/g) |
| Embodiment 1 | 4.625 | 0.6127 | 776.17 |
| Embodiment 2 | 4.023 | 0.5529 | 694.71 |
| Comparative example 1 | 2.048 | 0.3051 | 494.56 |
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 by expanding agent lithium hypochlorite,
Double (acetylacetone,2,4-pentanedione) beryllium compositions, by weight, lithium hypochlorite:Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B groups
Divide and be made up of perlite, albite, bentonite, polyhalite, talcum, sal soda stone, by weight, perlite:Albite:Swelling
Soil:Polyhalite:Talcum:The weight ratio of sal soda 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 nonyl phenolic group bi-quaternary ammonium salt, is pressed
Weight meter, component C:Weight ratio=1 of reaming modified support:（5~10）, D components are urged by composite mineralizer borax, potassium sulfate
Change coagent predecessor 1,1,1- trifluoroacetylacetone (TFA)s neodymiums, three (the fluoro- 2,2- dimethyl -3,5- of 6,6,7,7,8,8,8- seven are pungent
Alkene diketone) dysprosium (III), ten water holmium oxalates, carbonic acid lutetium hydrate Rare-earth chemicals, catalytic active center predecessor is general
Logical transition metal organometallic compound cobalt edetate, citric acid nickel and the thiocyanato of precious metal chemical complex two silver（I）Sour potassium, three
Bipyridyl ruthenic chloride hexahydrate, emulsifying agent stearic acid trimethylamine groups ethanol ester ammonium iodide composition, by weight, borax:Sulfuric acid
Potassium:1,1,1- trifluoroacetylacetone (TFA) neodymiums:Three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosiums
(III):Ten water holmium oxalates:Carbonic acid lutetium hydrate:Cobalt edetate:Citric acid nickel:Two thiocyanatos silver（I）Sour potassium:Three
Pyridine ruthenic chloride hexahydrate:The weight ratio of stearic acid trimethylamine groups ethanol ester ammonium iodide=（4~8）:（6~10）:（3~
6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.
2. B component is made up of perlite, albite, bentonite, polyhalite, talcum, sal soda stone according to claim 1, precious
Zhu Yan, albite, bentonite, polyhalite, talcum, sal soda stone are crushed respectively, and deionized water washing, which is dried, to be removed after moisture,
Sieved through standard screen, it is 0.0370mm~0.0750mm to control particle diameter.
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