CN107051506A - 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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- CN107051506A CN107051506A CN201710275623.3A CN201710275623A CN107051506A CN 107051506 A CN107051506 A CN 107051506A CN 201710275623 A CN201710275623 A CN 201710275623A CN 107051506 A CN107051506 A CN 107051506A
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- solid catalyst
- glauberite
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 24
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 raphite Chemical compound 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims abstract description 13
- GYZGFUUDAQXRBT-UHFFFAOYSA-J calcium;disodium;disulfate Chemical compound [Na+].[Na+].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GYZGFUUDAQXRBT-UHFFFAOYSA-J 0.000 claims abstract description 12
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052637 diopside Inorganic materials 0.000 claims abstract description 10
- 229960000892 attapulgite Drugs 0.000 claims abstract description 9
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000010436 fluorite Substances 0.000 claims abstract description 9
- 229910052900 illite Inorganic materials 0.000 claims abstract description 9
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 9
- 241000723346 Cinnamomum camphora Species 0.000 claims abstract description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229930008380 camphor Natural products 0.000 claims abstract description 8
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000002332 ferrous fumarate Nutrition 0.000 claims abstract description 8
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 7
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 7
- VMTDNQZNXIFFIZ-UHFFFAOYSA-N CCCCCCCCCCCCOS(OCCC(O)O)(=O)=O.CN Chemical compound CCCCCCCCCCCCOS(OCCC(O)O)(=O)=O.CN VMTDNQZNXIFFIZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 6
- AUZRORBINHVFFD-UHFFFAOYSA-N [Rh]N=O Chemical compound [Rh]N=O AUZRORBINHVFFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021538 borax Inorganic materials 0.000 claims abstract description 6
- 229960000225 ferrous fumarate Drugs 0.000 claims abstract description 6
- 239000011773 ferrous fumarate Substances 0.000 claims abstract description 6
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 6
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 6
- 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 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 5
- 229910052693 Europium Inorganic materials 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
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 4
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 9
- 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
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 230000007704 transition Effects 0.000 claims description 7
- 239000010970 precious metal Substances 0.000 claims description 6
- 150000002910 rare earth metals Chemical class 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000005594 diketone group Chemical group 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000000243 solution Substances 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- OLGPDUKUFCIQPH-UHFFFAOYSA-N [Na].[Na].[Na].N(=O)[Rh] Chemical compound [Na].[Na].[Na].N(=O)[Rh] OLGPDUKUFCIQPH-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
- 235000005979 Citrus limon Nutrition 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
- 244000248349 Citrus limon Species 0.000 claims 1
- 244000131522 Citrus pyriformis Species 0.000 claims 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- ILRLTAZWFOQHRT-UHFFFAOYSA-N potassium;sulfuric acid Chemical compound [K].OS(O)(=O)=O ILRLTAZWFOQHRT-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 238000001994 activation Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 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 abstract description 3
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 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
- 239000011148 porous material Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
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- 239000002671 adjuvant Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 238000003763 carbonization Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 241000254158 Lampyridae Species 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- 229910052773 Promethium 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- IOIFRTZBJMZZFO-UHFFFAOYSA-N dysprosium(3+) Chemical compound [Dy+3] IOIFRTZBJMZZFO-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
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- WCWKKSOQLQEJTE-UHFFFAOYSA-N praseodymium(3+) Chemical compound [Pr+3] WCWKKSOQLQEJTE-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 239000010948 rhodium Substances 0.000 description 1
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- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- 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.With attapulgite, diopside, illite, raphite, fluorite and glauberite make carrier after lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add surfactant tri-n-octyl methyl ammonium chloride and surface activation process is carried out under ul-trasonic irradiation, then carrier in hydrothermal reaction kettle with composite mineralizer borax and potassium sulfate, catalytic activity auxiliary agent predecessor three (3 trifluoroacetyl group D camphors) praseodymium (III), three cyclopentadiene promethiums, three (4, 4, (2 thiophene) 1 of 4 trifluoro 1, 3 diacetyl) europium, three (6, 6, 7, 7, 8, 8, 8 seven fluorine 2, 2 dimethyl 3, 5 octene diketone) dysprosium (III), catalytic active center predecessor ferrous fumarate, citric acid nickel, zirconium carbonate ammonium and six nitroso rhodium trisodiums, hydro-thermal reaction is carried out under the effect of emulsifying agent dodecyl dihydroxypropyl sulfate methyl ammonium, calcination obtains ozone Heterogeneous oxidation solid catalyst in Muffle furnace after drying removing moisture.
Description
Technical field
The present invention relates to a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, category environmental protection and chemical catalyst skill
Art field.
Background technology
Ozonation technology using ozone oxidation ability it is strong the characteristics of, can be by many organic pollution oxidation Decompositions, extensively
For wastewater treatment.Catalytic ozonation technology is divided into ozone homogeneous catalytic oxidation and ozone heterogeneous catalytic oxidation, and ozone is equal
Phase catalysis oxidation has that the more difficult separation and recovery of catalyst is reused, ozone utilization rate is low causes water process operating cost higher,
Organic pollutant removal rate is relatively low simultaneously and easily causing secondary pollution of water is limited to its application；Ozone heterogeneous catalysis oxygen
There is change technology catalyst to be easily isolated and recycled and reusable, ozone utilization rate is high, organic pollutant removal rate is higher, drop
Low water process operating cost and receive significant attention its application the advantages of do not result in secondary pollution.Ozone heterogeneous catalysis
It is to reach local organic matter enrichment by catalyst surface absorption organic matter that oxidation of organic compounds, which is decomposed, while ozone molecule absorption exists
The hydroxyl radical free radical that catalyst surface produces high activity under catalyst action decomposes organic matter.Ozone heterogeneous catalytic oxidation
Handle in waste water technology, core technology is the preparation of ozone Heterogeneous oxidation solid catalyst.
Ozone Heterogeneous oxidation solid catalyst is generally made up of carrier, activated centre and auxiliary agent.Due to being polluted in waste water
Species are various, complex chemical composition feature, can produce harmful effect to performance such as absorption, the mithridatism of catalyst.
Prepare that the carrier structure that ozone Heterogeneous oxidation solid catalyst uses is more single at present, adsorptivity is relatively low；Activated centre is universal
Using normal transition metal salt, mithridatism is poor；Preparation method mainly has infusion process, the precipitation method, mixing method and collosol and gel etc.
Method attachment activity center and adjuvant component are easily liquated out in carrier surface, activated centre and adjuvant component, cause catalyst
Easily lose catalytic activity.For exist in current ozone Heterogeneous oxidation solid catalyst preparation method Catalyst Adsorption compared with
Low, mithridatism is poor and easily loses catalytic activity problem, and exploitation is strengthened using multicomponent porous carrier through reaming, surface active
Catalyst Adsorption, makees catalytic activity auxiliary agent predecessor, normal transition Organometallic using Rare-earth 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 attapulgite, diopside, illite, raphite, firefly
Stone, glauberite composition, by weight, attapulgite:Diopside:Illite:Raphite:Fluorite:The weight ratio of glauberite=
（5~15）:（7~17）:（9~19）:（11~21）:（13~23）:（15~25）, by weight, component A:The weight of B component
The ratio between=1:（10~20）, component C is tri-n-octyl methyl ammonium chloride, by weight, component C:The weight ratio of reaming modified support
=1:（5~10）, D components are by composite mineralizer borax, the potassium sulfate, (3- trifluoroacetyl groups-D- of catalytic activity auxiliary agent predecessor three
Camphor) praseodymium (III), three cyclopentadiene promethiums, three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europiums, three (6,6,7,7,
8,8,8- seven fluoro- 2,2- dimethyl -3,5- octene diketone) dysprosium (III) Rare-earth chemicals, catalytic active center forerunner
Thing normal transition metallo-organic compound ferrous fumarate, citric acid nickel, zirconium carbonate ammonium and the nitroso rhodium of precious metal chemical complex six
Trisodium, emulsifying agent dodecyl dihydroxypropyl sulfate methyl ammonium composition, by weight, borax:Potassium sulfate:Three (3- trifluoroacetyls
Base-D- camphors) praseodymium (III):Three cyclopentadiene promethiums:Three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europiums:Three (6,6,
The fluoro- 2,2- dimethyl -3,5- octenes diketone of 7,7,8,8,8- seven) dysprosium (III):Ferrous fumarate:Citric acid nickel:Zirconium carbonate ammonium:
Six nitroso rhodium trisodiums:The weight ratio of dodecyl dihydroxypropyl sulfate methyl ammonium=（4~8）:（6~10）:（3~6）:（4
~7）:（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.The concave convex rod of the B component
Soil, diopside, illite, raphite, fluorite, glauberite are crushed respectively, and deionized water washing, which is dried, to be removed after moisture,
- 200 mesh ,+400 mesh sieves point are carried out through standard screen, it is the mm of 0.0370mm~0.0750 control particle diameter.
What the technical method of the present invention was realized in：Lithium hypochlorite LiClO, double (second can be being added in closed reactor
Acyl acetone) beryllium C10H14BeO4The aqueous solution is prepared with deionized water stirring, it is 0.0370mm~0.0750mm to add particle diameter after screening
Attapulgite, diopside, illite, raphite, fluorite and glauberite porous material carrier, in certain temperature and stirring bar
Under part, the small Be of aqueous solution Ionic Radius2+（0.31Å）、Li+（0.60Å）Displace part ion radius in porous material big
Ca2+（0.99Å）、K+（1.33Å）、Ba2+（1.35Å）Plasma, the aperture of porous material carrier becomes big, surface roughness increasing
Plus, filtering dries the reaming modified support input ultrasound reactor after constant weight, adds tri-n-octyl methyl ammonium chloride
[(C8H17)3NCH3]+Cl-The aqueous solution, control ultrasonic power density, ultrasonic frequency, temperature and sonic oscillation time, in ultrasound
Under ripple cavitation, tri-n-octyl methyl ammonium chloride [(C8H17)3NCH3]+Cl-It is easy to escape into reaming modified support from the aqueous solution
Duct is attached to reaming modified support surface, is beneficial to being interconnected and carrier surface activation for carrier duct, enhances suction
Attached property；After the completion of ultrasonic activation, ultrasonic surface activated carrier mixed liquor is transferred in hydrothermal reaction kettle, with borax Na2B4O7·
10H2O, potassium sulfate K2SO4Composite mineralizer, catalytic activity auxiliary agent predecessor three (3- trifluoroacetyl group-D- camphors) praseodymium (III)
C36H42F9O6Pr, three cyclopentadiene promethium Pm (C5H5)3, three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europiums
C24H18EuF9O6S3, three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosium (III) C30H30DyF21O6
Rare-earth chemicals, catalytic active center component predecessor normal transition metallo-organic compound ferrous fumarate
C4H2O4Fe, citric acid nickel C12H10O14Ni3, zirconium carbonate ammonium (NH4)2·C2H2O8Zr and six nitroso rhodium trisodium Na3Rh(NO2)6It is expensive
Metallic compound, in emulsifying agent dodecyl dihydroxypropyl sulfate methyl ammonium [C12H25CH2CH(OH)CH(OH)N(CH3)3]+
CH3SO4 -Effect is lower to carry out hydro-thermal reaction, and mineralizer accelerates diffusion, activates reactant lattice, promotes solid phase reaction
Carry out, ultrasonic surface activated carrier and Rare-earth chemicals, normal transition metallo-organic compound, precious metal chemical complex
Uniform Doped, emulsifying agent dodecyl dihydroxypropyl sulfate methyl ammonium makes reaction solution form quasi-stationary emulsion to prevent solid-liquid point
From, sedimentation, while to the further surface active of porous 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 feature of the present invention is that attapulgite, diopside, Erie are used in technology of preparing
Stone, raphite, fluorite, glauberite porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) berylliums
C10H14BeO4Reaming effect, tri-n-octyl methyl ammonium chloride [(C8H17)3NCH3]+Cl-, dodecyl dihydroxypropyl Methylsulfate
Ammonium [C12H25CH2CH(OH)CH(OH)N(CH3)3]+CH3SO4 -The interconnected and surface activation in duct；Pass through hydro-thermal reaction
Rare-earth chemicals, normal transition metallo-organic compound and precious metal chemical complex is set to reach Uniform Doped and be attached to
In carrier surface and duct, high temperature sintering makes organic matter carbonization strengthen and form multi-level microcellular structure, porous load
The multi-element metal catalytic active center of body supported rare earth metal oxide, transition metal oxide and noble metal formation is carried with porous
Body combination is more firm, and the ozone Heterogeneous oxidation solid catalyst of preparation has stronger adsorptivity, the collaboration of multi-element metal
Effect, stability and high activity that particularly doped precious metal has, can suppress liquating out for metal catalytic activity component, carry
The mithridatism and catalytic activity of high catalyst, 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 attapulgites of 400 mesh standard sieves, 3.75g diopsides, 4.75g illites, 5.75g raphites, 6.75g fluorites,
The weight of 7.75g glauberite, 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, 3.25g tri-n-octyl methyl ammonium chlorides is added and is dissolved in 100ml deionized waters
The aqueous solution, the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, tri-n-octyl methyl ammonium chloride（3.25g）:Reaming changes
Property carrier（31g ）=1:9.5；It is 0.4W/m to control ultrasonic power density3, ultrasonic frequency 21kHz, 41 DEG C of temperature, ultrasound is shaken
Swing 2.2h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor is transferred to 500ml hydro-thermals
In reactor, add by 2.1g boraxs, 3.05g potassium sulfates, 1.6g tri- (3- trifluoroacetyl group-D- camphors) praseodymium (III),
The cyclopentadiene promethiums of 2.05g tri-, 2.6g tri- (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europium, 3.05g tri- (6,6,7,7,
The fluoro- 2,2- dimethyl -3,5- octenes diketone of 8,8,8- seven) dysprosium (III), 5.05g ferrous fumarates, 6.1g citric acids nickel, 2.05g
Zirconium carbonate ammonium, the nitroso rhodium trisodiums of 3.1g six, 3.05g dodecyl dihydroxypropyl sulfate methyl ammoniums 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 attapulgites of 400 mesh standard sieves, 1.65g diopsides, 1.85g illites, 2.05g raphites, 2.25g fluorites,
The weight of 2.45g glauberite, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（0.6g）:The weight of porous material（11.7g）=1:
19.5,48 DEG C are warming up to, reaming modified support 11.5g is obtained after continuing stirring reaction 5.8h, filtering, 105 DEG C of dry constant weights；
In 100ml ultrasound reactors, reaming modified support 11.5g is put into, 2.2g tri-n-octyl methyl ammonium chlorides is added and is dissolved in 26ml
The aqueous solution of deionized water, the weight concentration of the aqueous solution is 7.8%, is uniformly mixed, tri-n-octyl methyl ammonium chloride
（2.2g）:Reaming modified support（11.5g ）=1:5.2；It is 0.7W/m to control ultrasonic power density3, ultrasonic frequency 29kHz,
54 DEG C of temperature, sonic oscillation 4.7h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor
It is transferred in 100ml hydrothermal reaction kettles, adds by 0.78g boraxs, 0.97g the potassium sulfates, (3- trifluoroacetyl groups-D- of 0.58g tri-
Camphor) praseodymium (III), the cyclopentadiene promethiums of 0.67g tri-, 0.78g tri- (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europium,
0.87g tri- (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosium (III), 1.48g ferrous fumarates,
1.77g citric acids nickel, 0.68g zirconium carbonate ammoniums, the nitroso rhodium trisodiums of 0.87g six, 1.98g dodecyl dihydroxypropyl Methylsulfates
The aqueous solution that ammonium and 10ml deionized waters are prepared, the weight concentration of the aqueous solution is 53.3%, the weight of the aqueous solution:Ultrasonic table
Weight=21.43g of face 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 fine silt thing is dried to obtain for 105 DEG C；Fine silt thing is in Muffle furnace, 930 DEG C, calcination 7.5h, after cooling down, can obtain thin
The ozone Heterogeneous oxidation solid catalyst of powder particles shape.
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 attapulgite, diopside, illite, raphite, fluorite, glauberite, by weight, attapulgite:Diopside:
Illite:Raphite:Fluorite:The weight ratio of glauberite=（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 tricaprylmethyl chlorination
Ammonium, by weight, component C:Weight ratio=1 of reaming modified support:（5~10）, D components are by composite mineralizer borax, sulfuric acid
Potassium, catalytic activity auxiliary agent predecessor three (3- trifluoroacetyl group-D- camphors) praseodymium (III), three cyclopentadiene promethiums, three (4,4,4- tri-
Fluoro- 1- (2- thiophene) -1,3- diacetyl) europium, three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosiums
(III) Rare-earth chemicals, catalytic active center predecessor normal transition metallo-organic compound ferrous fumarate, lemon
Lemon acid nickel, zirconium carbonate ammonium and the nitroso rhodium trisodium of precious metal chemical complex six, emulsifying agent dodecyl dihydroxypropyl sulfate methyl ammonium
Composition, by weight, borax:Potassium sulfate:Three (3- trifluoroacetyl group-D- camphors) praseodymiums (III):Three cyclopentadiene promethiums:Three (4,4,
4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europium:Three (the fluoro- 2,2- dimethyl -3,5- octenes two of 6,6,7,7,8,8,8- seven
Ketone) dysprosium (III):Ferrous fumarate:Citric acid nickel:Zirconium carbonate ammonium:Six nitroso rhodium trisodiums:Dodecyl dihydroxypropyl sulfuric acid first
The weight ratio of ester ammonium=（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 attapulgite, diopside, illite, raphite, fluorite, glauberite group according to claim 1
Into attapulgite, diopside, illite, raphite, fluorite, glauberite are crushed respectively, and deionized water washing drying is removed
Go after moisture, sieved through standard screen, it is 0.0370mm~0.0750mm to control particle diameter.
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Application publication date: 20170818 |