CN107008399A - 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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- CN107008399A CN107008399A CN201710275652.XA CN201710275652A CN107008399A CN 107008399 A CN107008399 A CN 107008399A CN 201710275652 A CN201710275652 A CN 201710275652A CN 107008399 A CN107008399 A CN 107008399A
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- solid catalyst
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 230000003647 oxidation Effects 0.000 title claims abstract description 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 16
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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
- 229910052656 albite 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
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 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
- 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
- 241000723346 Cinnamomum camphora Species 0.000 claims abstract description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 8
- 229930008380 camphor Natural products 0.000 claims abstract description 8
- 239000010451 perlite Substances 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 239000011591 potassium Substances 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
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 6
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims abstract description 6
- 229910021538 borax Inorganic materials 0.000 claims abstract description 6
- ITZXULOAYIAYNU-UHFFFAOYSA-N cerium(4+) Chemical compound [Ce+4] ITZXULOAYIAYNU-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
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 6
- 239000004328 sodium tetraborate 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
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 5
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims abstract description 4
- KZXFBCUXEQXICP-UHFFFAOYSA-N [W].C=1(O)C(O)=CC=CC1.C(CN)N Chemical compound [W].C=1(O)C(O)=CC=CC1.C(CN)N KZXFBCUXEQXICP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 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 18
- 239000000126 substance Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- -1 ytterbium Rare-earth Chemical class 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 230000007704 transition Effects 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 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
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000010970 precious metal Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 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
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- ZQSSRUAWBFTSKE-UHFFFAOYSA-N benzene-1,2-diol;tungsten Chemical compound [W].OC1=CC=CC=C1O ZQSSRUAWBFTSKE-UHFFFAOYSA-N 0.000 claims description 2
- KPQDSKZQRXHKHY-UHFFFAOYSA-N gold potassium Chemical compound [K].[Au] KPQDSKZQRXHKHY-UHFFFAOYSA-N 0.000 claims description 2
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 229910052769 Ytterbium Inorganic materials 0.000 claims 1
- LHBIPBNRUPCJPN-UHFFFAOYSA-N [SH2]=N.CF Chemical compound [SH2]=N.CF LHBIPBNRUPCJPN-UHFFFAOYSA-N 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- BOLCLFSSFZOGPX-UHFFFAOYSA-N N.[Cl-].C(CCCCCCCCCCC)[NH+](C)C Chemical class N.[Cl-].C(CCCCCCCCCCC)[NH+](C)C BOLCLFSSFZOGPX-UHFFFAOYSA-N 0.000 abstract description 9
- 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
- HRLJRVRWYAHDFN-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC.CN Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC.CN HRLJRVRWYAHDFN-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
- 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
- 239000011148 porous material Substances 0.000 description 6
- 150000002910 rare earth metals Chemical class 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 235000018977 lysine Nutrition 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- ONRPGGOGHKMHDT-UHFFFAOYSA-N benzene-1,2-diol;ethane-1,2-diamine Chemical class NCCN.OC1=CC=CC=C1O ONRPGGOGHKMHDT-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YPUOTXOJCHHZIY-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;ytterbium(3+) Chemical compound [Yb+3].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YPUOTXOJCHHZIY-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 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
- 238000006385 ozonation reaction Methods 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000254158 Lampyridae Species 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N anhydrous methyl chloride Natural products ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 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
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 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
- 238000001802 infusion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- WCWKKSOQLQEJTE-UHFFFAOYSA-N praseodymium(3+) Chemical compound [Pr+3] WCWKKSOQLQEJTE-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
- B01J23/8993—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 chromium, molybdenum or tungsten
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- B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
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- B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
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Abstract
The present invention relates to a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, category environmental protection and technical field of chemical engineering catalysts.With gamma-alumina, barite, perlite, albite, fluorite and glauberite carrier are after lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add the double dodecyldimethylamine ammonium chlorides of surfactant and activation process is carried out under ul-trasonic irradiation, then carrier in hydrothermal reaction kettle with composite mineralizer borax and potassium sulfate, catalytic activity auxiliary agent predecessor four (2, 2, 6, 6 tetramethyls 3, 5 heptadione acid) cerium (IV), three (3 trifluoroacetyl group D camphors) praseodymiums (III), three (6, 6, 7, 7, 8, 8, 8 seven fluorine 2, 2 dimethyl 3, 5 octene diketone) dysprosium (III), three (trifluoromethanesulfonimide) ytterbiums, catalytic active center component predecessor lysine manganese, cupric glutamate, ethylenediamine pyrocatechol tungsten complex and the golden potassium of tetrachloro, hydro-thermal reaction is carried out under the effect of emulsifying agent hexatriacontane 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 gama-alumina, barite, perlite, albite, firefly
Stone, glauberite composition, by weight, gama-alumina:Barite:Perlite:Albite: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 double dodecyldimethylamine ammonium chlorides, by weight, component C:The weight of reaming modified support
The ratio between amount=1:（5~10）, D components are by composite mineralizer borax, potassium sulfate, catalytic activity auxiliary agent predecessor four (2,2,6,6- tetra-
Methyl -3,5- heptadione acid) cerium (IV), three (3- trifluoroacetyl group-D- camphors) praseodymiums (III), three (6,6,7,7,8,8,8- seven
Fluoro- 2,2- dimethyl -3,5- octene diketone) dysprosium (III), three (trifluoromethanesulfonimide) ytterbium Rare-earth chemicals,
Catalytic active center predecessor normal transition metallo-organic compound lysine manganese, cupric glutamate, ethylenediamine pyrocatechol tungsten are matched somebody with somebody
Compound and the golden potassium of precious metal chemical complex tetrachloro, three-cetylmethylammonium chloride of emulsifying agent composition, by weight, borax:Sulfuric acid
Potassium:Four (DPM dpm,dipivalomethane acid) ceriums (IV):Three (3- trifluoroacetyl group-D- camphors) praseodymiums (III):Three (6,
The fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,7,7,8,8,8- seven) dysprosium (III):Three (trifluoromethanesulfonimide) ytterbiums:Rely ammonia
Sour manganese:Cupric glutamate:Ethylenediamine pyrocatechol tungsten complex:Tetrachloro gold potassium:The weight ratio of three-cetylmethylammonium 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, albite, fluorite, glauberite in the B component are crushed respectively,
Deionized water washing, which is dried, to be removed after moisture, and -200 mesh ,+400 mesh sieves point are carried out through standard screen, control particle diameter be 0.0370mm~
0.0750 mm。
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, 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 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 (6,6,7,7,
The fluoro- 2,2- dimethyl -3,5- octenes diketone of 8,8,8- seven) dysprosium (III) C30H30DyF21O6, three (trifluoromethanesulfonimide) ytterbiums
[(CF3SO2)2N]3Yb Rare-earth chemicals, catalytic active center component predecessor normal transition metallo-organic compound
Lysine manganese C12H26N4O4, cupric glutamate C5H7NO4Cu, ethylenediamine pyrocatechol tungsten complex (NH2CH2CH2NH3)2[W(VI)O2
(OC6H4O)2] and the golden potassium KAuCl of precious metal chemical complex tetrachloro4, in three-cetylmethylammonium chloride of emulsifying agent [(C16H33)3NCH3]+Cl-Effect is lower to carry out hydro-thermal reaction, and mineralizer accelerates diffusion, activates reactant lattice, promotes solid phase anti-
The progress answered, ultrasonic surface activated carrier and Rare-earth chemicals, normal transition metallo-organic compound, noble metal
Compound Uniform Doped, three-cetylmethylammonium chloride of emulsifying agent makes reaction solution form quasi-stationary emulsion to prevent solid-liquid point
From, sedimentation, while to the further surface active of porous mineral carrier, by certain temperature, the hydro-thermal reaction of time, drying
To the fine silt thing of Uniform Doped；The fine silt thing of Uniform Doped is in Muffle furnace, through high temperature sintering, and organic matter therein is complete
Carbonization further enhances the microcellular structure of porous carrier, obtains porous carrier supported rare earth metal oxide, oxo transition metal
The ozone Heterogeneous oxidation solid catalyst of compound and the catalytic active center of noble metal formation, improves the mithridatism of catalyst
And catalytic activity.
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, fluorite, glauberite 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-Three-cetyl methyl chloride
Change ammonium [(C16H33)3NCH3]+Cl-To being interconnected and surface activation for duct；Make rare earth metal organic by hydro-thermal reaction
Compound, normal transition metallo-organic compound and precious metal chemical complex reach Uniform Doped and are attached to carrier surface and duct
Interior, high temperature sintering makes organic matter carbonization strengthen and form multi-level microcellular structure, porous carrier supported rare earth metal
The multi-element metal catalytic active center of oxide, transition metal oxide and noble metal formation is combined more firm with porous carrier
Gu, the ozone Heterogeneous oxidation solid catalyst of preparation has a stronger adsorptivity, the cooperative effect of multi-element metal, particularly mixes
Stability and high activity that miscellaneous noble metal has, can suppress liquating out for metal catalytic activity component, improve catalyst
Mithridatism and catalytic activity, 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 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, 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), (6,6,7,7,8,8,8- seven of 2.6g tri-
Fluoro- 2,2- dimethyl -3,5- octenes diketone) dysprosium (III), 3.05g tri- (trifluoromethanesulfonimide) ytterbium, 5.05g lysines
The golden potassium of manganese, 6.1g cupric glutamates, 2.05g ethylenediamine pyrocatechols tungsten complex, 3.1g tetrachloros, 3.05g tri--cetyl methyl
The aqueous solution that ammonium chloride and 50ml deionized waters are prepared, the weight concentration of the aqueous solution is 40.3%, the weight of the aqueous solution:It is super
Weight=83.8g of sound surface active carrier mixed liquor:134.25g=1:1.6,125 DEG C of temperature is controlled, the hydro-thermal reaction time is
8.3h, then dries to obtain fine silt thing for 105 DEG C；Fine silt thing is in Muffle furnace, 620 DEG C, calcination 3.2h, can after cooling down
Obtain the ozone Heterogeneous oxidation solid catalyst of fine particle shape.
Embodiment 2:0.24g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 0.36g, 10ml deionized waters, being added to volume is
100ml's can be uniformly mixed in closed reactor, and the weight concentration of the aqueous solution is 5.7%, lithium hypochlorite:Double (levulinics
Ketone) beryllium weight ratio=1:1.5；Add deionized water wash to it is neutral, 103 DEG C dry remove -200 mesh of sieving after moisture~+
The 1.45g gama-aluminas of 400 mesh standard sieves, 1.65g barites, 1.85g perlites, 2.05g albites, 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, 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 tri- (6,6,7,
The fluoro- 2,2- dimethyl -3,5- octenes diketone of 7,8,8,8- seven) dysprosium (III), 0.87g tri- (trifluoromethanesulfonimide) ytterbium,
The golden potassium of 1.48g lysines manganese, 1.77g cupric glutamates, 0.68g ethylenediamine pyrocatechols tungsten complex, 0.87g tetrachloros, 1.98g
The aqueous solution that three-cetylmethylammonium chloride and 10ml deionized waters are prepared, the weight concentration of the aqueous solution is 53.3%, should
The weight of the aqueous solution:Weight=21.43g of ultrasonic surface activated carrier mixed liquor:39.7g=1:1.9, control 175 DEG C of temperature, water
The thermal response 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, the ozone Heterogeneous oxidation solid catalyst of fine particle shape can obtain.
Comparative example 1:Preparation process be not added with lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, double dodecyldimethylamine ammonium chlorides,
Outside three-cetylmethylammonium chloride, 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, fluorite, glauberite composition, by weight, gama-alumina:Barite:Pearl
Rock:Albite: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 double dodecyldimethylamine base chlorine
Change ammonium, by weight, component C:Weight ratio=1 of reaming modified support:（5~10）, D components are by composite mineralizer borax, sulphur
Sour potassium, catalytic activity auxiliary agent predecessor four (2,2,6,6- tetramethyl -3,5- heptadione acid) cerium (IV), three (3- trifluoroacetyl groups -
D- camphors) praseodymium (III), three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosiums (III), three (three
Fluoromethane sulfimide) ytterbium Rare-earth chemicals, catalytic active center predecessor normal transition metallo-organic compound
The golden potassium of lysine manganese, cupric glutamate, ethylenediamine pyrocatechol tungsten complex and precious metal chemical complex tetrachloro, emulsifying agent three-ten six
Alkyl methyl ammonium chloride is constituted, by weight, borax:Potassium sulfate:Four (DPM dpm,dipivalomethane acid) ceriums
(IV):Three (3- trifluoroacetyl group-D- camphors) praseodymiums (III):Three (the fluoro- 2,2- dimethyl -3,5- of 6,6,7,7,8,8,8- seven are pungent
Alkene diketone) dysprosium (III):Three (trifluoromethanesulfonimide) ytterbiums:Lysine manganese:Cupric glutamate:Ethylenediamine pyrocatechol tungsten is matched somebody with somebody
Compound:Tetrachloro gold potassium:The weight ratio of three-cetylmethylammonium chloride=（4~8）:（6~10）:（3~6）:（4~7）:
（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.
2. B component is by gama-alumina, barite, perlite, albite, fluorite, glauberite group according to claim 1
Into gama-alumina, barite, perlite, albite, 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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