CN107008452A - The preparation method of ozone Heterogeneous oxidation solid catalyst - Google Patents
The preparation method of ozone Heterogeneous oxidation solid catalyst Download PDFInfo
- Publication number
- CN107008452A CN107008452A CN201710277070.5A CN201710277070A CN107008452A CN 107008452 A CN107008452 A CN 107008452A CN 201710277070 A CN201710277070 A CN 201710277070A CN 107008452 A CN107008452 A CN 107008452A
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- China
- Prior art keywords
- component
- weight
- solid catalyst
- acetylacetone
- double
- Prior art date
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Links
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 230000003647 oxidation Effects 0.000 title claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 74
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004575 stone Substances 0.000 claims abstract description 13
- 125000003963 dichloro group Chemical group Cl* 0.000 claims abstract description 12
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- -1 carbonic acid lutetium hydrate Rare-earth Chemical class 0.000 claims abstract description 10
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 10
- 239000010456 wollastonite Substances 0.000 claims abstract description 10
- PALNZFJYSCMLBK-UHFFFAOYSA-K magnesium;potassium;trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-].[Cl-].[K+] PALNZFJYSCMLBK-UHFFFAOYSA-K 0.000 claims abstract description 9
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 9
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 9
- KHFLASRWTYBRDK-UHFFFAOYSA-M tributyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](CCCC)(CCCC)CCCC KHFLASRWTYBRDK-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 8
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000007704 transition Effects 0.000 claims abstract description 8
- 229910021538 borax Inorganic materials 0.000 claims abstract description 7
- 239000010970 precious metal Substances 0.000 claims abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 7
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 7
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims abstract description 6
- 229930195712 glutamate Natural products 0.000 claims abstract description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229960004889 salicylic acid Drugs 0.000 claims abstract description 6
- BENADMAVJUZZBP-UHFFFAOYSA-N [O-2].C(C)(C)[Sc+2] Chemical compound [O-2].C(C)(C)[Sc+2] BENADMAVJUZZBP-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
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract 5
- 239000001103 potassium chloride Substances 0.000 claims abstract 5
- 235000011164 potassium chloride Nutrition 0.000 claims abstract 5
- 229910052741 iridium Inorganic materials 0.000 claims abstract 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract 3
- 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 2
- 239000007795 chemical reaction product Substances 0.000 claims abstract 2
- 239000007864 aqueous solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 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
- 238000002604 ultrasonography Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims 2
- 238000006703 hydration reaction Methods 0.000 claims 2
- 241001614291 Anoplistes Species 0.000 claims 1
- 240000000203 Salix gracilistyla Species 0.000 claims 1
- 241000209140 Triticum Species 0.000 claims 1
- 235000021307 Triticum Nutrition 0.000 claims 1
- 229910052769 Ytterbium Inorganic materials 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- NAPFHXCBNVVCGD-UHFFFAOYSA-N carbonic acid;lutetium Chemical compound [Lu].OC(O)=O NAPFHXCBNVVCGD-UHFFFAOYSA-N 0.000 claims 1
- GOJQGSSHWWZKMA-UHFFFAOYSA-N decyl(dimethyl)-lambda3-chlorane Chemical compound C(CCCCCCCCC)Cl(C)C GOJQGSSHWWZKMA-UHFFFAOYSA-N 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 235000012054 meals Nutrition 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 239000011148 porous material Substances 0.000 abstract description 7
- 238000001994 activation Methods 0.000 abstract description 6
- 239000012752 auxiliary agent Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 6
- 239000002367 phosphate rock Substances 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 229910052775 Thulium Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 125000002704 decyl group Chemical group [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])* 0.000 description 3
- SELQTGHBKXPMSR-UHFFFAOYSA-M decyl-hexadecyl-dimethylazanium bromide Chemical compound [Br-].C(CCCCCCCCC)[N+](C)(C)CCCCCCCCCCCCCCCC SELQTGHBKXPMSR-UHFFFAOYSA-M 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- KSHUVRDBEMSQGS-UHFFFAOYSA-N C(CCCCCCCCC)C(C1=CC=CC=C1)[N+](C)(C)CCCCCCCCCCCCCCCC Chemical compound C(CCCCCCCCC)C(C1=CC=CC=C1)[N+](C)(C)CCCCCCCCCCCCCCCC KSHUVRDBEMSQGS-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 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
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- 150000002306 glutamic acid derivatives Chemical class 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- VHDPPDRSCMVFAV-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH+](C)C VHDPPDRSCMVFAV-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 1
- NPBDWXMKLFBNIW-UHFFFAOYSA-N 3-[4-[(2-chloro-4-nitrophenyl)diazenyl]-n-ethylanilino]propanenitrile Chemical compound C1=CC(N(CCC#N)CC)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1Cl NPBDWXMKLFBNIW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- RLFOVBVRQCNOMD-UHFFFAOYSA-N lutetium;hydrate Chemical compound O.[Lu] RLFOVBVRQCNOMD-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001421 myristyl 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])[H] 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
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
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- 230000003746 surface roughness Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- PWWGCBMGIAPMHQ-UHFFFAOYSA-N thulium(3+) Chemical compound [Tm+3] PWWGCBMGIAPMHQ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- GYOFRJOMHLYJNZ-UHFFFAOYSA-N tributyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](CCCC)(CCCC)CCCC GYOFRJOMHLYJNZ-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/894—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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- 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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- B01J20/048—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 phosphorus, e.g. phosphates, apatites, hydroxyapatites
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- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
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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 medical stone, wollastonite, activated carbon, carnallite, montmorillonite and sylvite porous material make carrier, carrier is modified through lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add surfactant myristyl tributyl ammonium chloride 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 isopropyl scandium oxide (III), acetylacetone,2,4-pentanedione samarium, three (trifluoromethanesulfonimide) ytterbiums, carbonic acid lutetium hydrate Rare-earth chemicals, catalytic active center component predecessor normal transition metallo-organic compound titanocenes ring substituted salicylic acid complex, cupric glutamate and the ammino palladium of precious metal chemical complex dichloro four, tetrachloro two is hydrated iridium, hydro-thermal reaction is carried out under the effect of emulsifying agent double-track suspended self-propelled conveyor, reaction product drying is removed after moisture, in Muffle furnace, calcination obtains ozone Heterogeneous oxidation solid catalyst under certain temperature.
Description
Technical field
The present invention relates to a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, category environmental protection and chemical catalyst skill
Art field.
Background technology
Ozonation technology using ozone oxidation ability it is strong the characteristics of, can be by many organic pollution oxidation Decompositions, extensively
For wastewater treatment.Catalytic ozonation technology is divided into ozone homogeneous catalytic oxidation and ozone heterogeneous catalytic oxidation, and ozone is equal
Phase catalysis oxidation has that the more difficult separation and recovery of catalyst is reused, ozone utilization rate is low causes water process operating cost higher,
Organic pollutant removal rate is relatively low simultaneously and easily causing secondary pollution of water is limited to its application;Ozone heterogeneous catalysis oxygen
There is change technology catalyst to be easily isolated and recycled and reusable, ozone utilization rate is high, organic pollutant removal rate is higher, drop
Low water process operating cost and receive significant attention its application the advantages of do not result in secondary pollution.Ozone heterogeneous catalysis
It is to reach local organic matter enrichment by catalyst surface absorption organic matter that oxidation of organic compounds, which is decomposed, while ozone molecule absorption exists
The hydroxyl radical free radical that catalyst surface produces high activity under catalyst action decomposes organic matter.Ozone heterogeneous catalytic oxidation
Handle in waste water technology, core technology is the preparation of ozone Heterogeneous oxidation solid catalyst.
Ozone Heterogeneous oxidation solid catalyst is generally made up of carrier, activated centre and auxiliary agent.Due to being polluted in waste water
Species are various, complex chemical composition feature, can produce harmful effect to performance such as absorption, the mithridatism of catalyst.
Prepare that the carrier structure that ozone Heterogeneous oxidation solid catalyst uses is more single at present, adsorptivity is relatively low;Activated centre is universal
Using normal transition metal salt, mithridatism is poor;Preparation method mainly has infusion process, the precipitation method, mixing method and collosol and gel etc.
Method attachment activity center and adjuvant component are easily liquated out in carrier surface, activated centre and adjuvant component, cause catalyst
Easily lose catalytic activity.For exist in current ozone Heterogeneous oxidation solid catalyst preparation method Catalyst Adsorption compared with
Low, mithridatism is poor and easily loses catalytic activity problem, and exploitation is strengthened using multicomponent porous carrier through reaming, surface active
Catalyst Adsorption, makees catalytic activity auxiliary agent predecessor, normal transition Organometallic using rare earth organo-metallic compound 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 organo-metallic compound
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 medical stone, wollastonite, activated carbon, carnallite, inclined hydrogen-oxygen
Change aluminium, phosphorite composition, by weight, medical stone:Wollastonite:Activated carbon:Carnallite:Inclined aluminium hydroxide:Phosphorite
Weight ratio=(5~15):(7~17):(9~19):(11~21):(13~23):(15~25), by weight, component A:B
Weight ratio=1 of component:(10~20), component C is myristyl tributyl ammonium chloride, by weight, component C:Reaming is modified
Weight ratio=1 of carrier:(5~10), D components are by composite mineralizer borax, potassium sulfate, catalytic activity auxiliary agent predecessor isopropyl
Scandium oxide (III), acetylacetone,2,4-pentanedione samarium, trifluoromethayl sulfonic acid thulium (III), carbonic acid lutetium hydrate Rare-earth chemicals, are urged
Activated centre predecessor normal transition metallo-organic compound titanocenes ring substituted salicylic acid complex, cupric glutamate and your gold changed
Belong to the ammino palladium of compound dichloro four, the ammino platinum of dichloro two, emulsifying agent decyl cetyl dimethyl ammonium bromide is constituted, by weight
Meter, borax:Potassium sulfate:Isopropyl scandium oxide (III):Acetylacetone,2,4-pentanedione samarium:Trifluoromethayl sulfonic acid thulium (III):Carbonic acid lutetium hydrate:
Titanocenes ring substituted salicylic acid complex:Cupric glutamate:The ammino palladium of dichloro four:The ammino platinum of dichloro two:Decyl etradecyldimethylamine
The weight ratio of base ammonium bromide=(4~8):(6~10):(3~6):(4~7):(5~8):(6~9):(10~15):(12~
18):(4~7):(6~9):(6~20).Medical stone, wollastonite, activated carbon, carnallite, inclined aluminium hydroxide, the phosphorus block of B component
Rock is crushed respectively, and deionized water washing, which is dried, to be removed after moisture, and -200 mesh ,+400 mesh sieves point, control are carried out through standard screen
Particle diameter 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
Medical stone, wollastonite, activated carbon, carnallite, inclined aluminium hydroxide and phosphorite porous material carrier, in certain temperature and stirring
Under the conditions of, the small Be of aqueous solution Ionic Radius2+(0.31Å)、Li+(0.60Å)Displace part ion radius in porous material
Big Ca2+(0.99Å)、K+(1.33Å)、Ba2+(1.35Å)Plasma, the aperture of porous material carrier becomes big, surface roughness increasing
Plus, filtering dries the reaming modified support input ultrasound reactor after constant weight, adds myristyl tributyl ammonium chloride
C14H29N+(C4H9)3Cl- The aqueous solution, control ultrasonic power density, ultrasonic frequency, temperature and sonic oscillation time, in ultrasound
Under ripple cavitation, myristyl tributyl ammonium chloride C14H29N+(C4H9)3Cl- It is easy to escape into reaming modification from the aqueous solution
Carrier duct is attached to reaming modified support surface, is beneficial to being interconnected and carrier surface activation for carrier duct, enhancing
Adsorptivity;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 isopropyl scandium oxide (III) C9H21O3Sc、
Acetylacetone,2,4-pentanedione samarium C15H25O8Sm, trifluoromethayl sulfonic acid thulium (III) C3F9O9S3Tm, carbonic acid lutetium hydrate C3H2Lu2O10Rare earth metal
Organic compound, catalytic active center predecessor normal transition metallo-organic compound titanocenes ring substituted salicylic acid complex
(C10H10)Ti(C7H4O3), cupric glutamate C5H7NO4The Cu and ammino palladium Pd (NH of dichloro four3)4Cl2, the ammino platinum K of dichloro two2OsCl6
Precious metal chemical complex, in emulsifying agent decyl cetyl dimethyl ammonium bromide [(C16H33) (C10H21)N(CH3)2]+ Br-Effect
Lower carry out hydro-thermal reaction, mineralizer accelerates diffusion, activates reactant lattice, promotes the progress of solid phase reaction, ultrasound
Surface active carrier and Rare-earth chemicals, normal transition organo-metallic compound, precious metal chemical complex Uniform Doped,
Emulsifying agent decyl cetyl dimethyl ammonium bromide make reaction solution formed quasi-stationary emulsion prevent separation of solid and liquid, sedimentation, together
When to the further surface active of porous carrier, by the way that in certain temperature, the hydro-thermal reaction of time, drying obtains the thin of Uniform Doped
Powder material;The fine silt thing of Uniform Doped is in Muffle furnace, through high temperature sintering, and organic matter carbonization therein is further strengthened
The microcellular structure of porous carrier, obtains porous carrier supported rare earth metal oxide, transition metal oxide and noble metal shape
Into catalytic active center ozone Heterogeneous oxidation solid catalyst, improve the mithridatism and catalytic activity of catalyst.
Relative to art methods, outstanding feature of the present invention is that medical stone, wollastonite, activity are used in technology of preparing
Charcoal, carnallite, inclined aluminium hydroxide, phosphorite porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) berylliums
C10H14BeO4Reaming effect, myristyl tributyl ammonium chloride C14H29N+(C4H9)3Cl-, decyl hexadecyldimethyl benzyl ammonium bromination
Ammonium [(C16H33) (C10H21)N(CH3)2]+ Br- To being interconnected and surface activation for duct;Made by hydro-thermal reaction dilute
Native organo-metallic compound, normal transition metallo-organic compound and precious metal chemical complex reach Uniform Doped and are attached to carrier
In surface and duct, high temperature sintering makes organic matter carbonization strengthen and form multi-level microcellular structure, and porous carrier is born
Carry the multi-element metal catalytic active center and porous carrier knot of rare-earth oxide, transition metal oxide and noble metal formation
Close more firm, the ozone Heterogeneous oxidation solid catalyst of preparation has a stronger adsorptivity, the cooperative effect of multi-element metal,
Stability and high activity that particularly doped precious metal has, can suppress liquating out for metal catalytic activity component, improve
The mithridatism and catalytic activity of 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 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 medical stones, 3.75g wollastonites, 4.75g activated carbons, 5.75g carnallites, the inclined aluminium hydroxides of 6.75g, the 7.75g of standard screen
The weight of phosphorite, 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, reaming modified support 31g is obtained after continuing stirring reaction 3.2h, filtering, 103 DEG C of dry constant weights;It is anti-in 500ml ultrasonic waves
Answer in device, put into reaming modified support 31g, add 3.25g myristyl tributyl ammonium chlorides and be dissolved in 100ml deionized waters
The aqueous solution, the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, myristyl tributyl ammonium chloride(3.25g):Expand
Hole 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, surpass
Sound oscillation 2.2h;After the completion of ultrasonic activation, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor is transferred to 500ml
In hydrothermal reaction kettle, add by 2.1g boraxs, 3.05g potassium sulfates, 1.6g isopropyls scandium oxide (III), 2.05g acetylacetone,2,4-pentanediones
Samarium, 2.6g trifluoromethayl sulfonic acids thulium (III), 3.05g carbonic acid lutetiums hydrate, 5.05g titanocenes ring substituted salicylic acids complex,
6.1g cupric glutamates, the ammino palladium of 2.05g dichloros four, the ammino platinum of 3.1g dichloros two, 3.05g decyl hexadecyldimethyl benzyl ammonium brominations
The aqueous solution that ammonium and 50ml deionized waters are prepared, the weight concentration of the aqueous solution is 40.3%, the weight of the aqueous solution:Ultrasonic table
Weight=83.8g of face 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 fine silt thing is dried to obtain for 105 DEG C;Fine silt thing is in Muffle furnace, 620 DEG C, calcination 3.2h, after cooling down, can obtain thin
The ozone Heterogeneous oxidation solid catalyst of powder particles 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 medical stones of 400 mesh standard sieves, 1.65g wollastonites, 1.85g activated carbons, 2.05g carnallites, the inclined aluminium hydroxides of 2.25g,
The weight of 2.45g phosphorites, 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 myristyl tributyl ammonium chlorides is added and is dissolved in
The aqueous solution of 26ml deionized waters, the weight concentration of the aqueous solution is 7.8%, is uniformly mixed, myristyl tributyl chlorination
Ammonium(2.2g):Reaming modified support(11.5g )=1:5.2;It is 0.7 W/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 isopropyl scandium oxides
(III), 0.67g acetylacetone,2,4-pentanediones samarium, 0.78g trifluoromethayl sulfonic acids thulium (III), 0.87g carbonic acid lutetiums hydrate, 1.48g titanocenes
Ring substituted salicylic acid complex, 1.77g cupric glutamates, the ammino palladium of 0.68g dichloros four, the ammino platinum of 0.87g dichloros two, the 1.98g last of the ten Heavenly stems
The aqueous solution that base cetyl dimethyl ammonium bromide and 10ml deionized waters are prepared, the weight concentration of the aqueous solution is 53.3%,
The weight of the aqueous solution:Weight=21.43g of ultrasonic surface activated carrier mixed liquor:39.7g =1:1.9, control temperature 175
DEG C, the hydro-thermal reaction time is 15.5h, then dries to obtain fine silt thing for 105 DEG C;Fine silt thing is in Muffle furnace, 930 DEG C, calcination
After 7.5h, cooling down, the ozone Heterogeneous oxidation solid catalyst of fine particle shape can obtain.
Comparative example 1:Preparation process is not added with lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, myristyl tributyl ammonium chloride, the last of the ten Heavenly stems
Outside base cetyl dimethyl ammonium bromide, 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.
Application Example 1:Ozone Heterogeneous oxidation solid catalyst point prepared by embodiment 1, embodiment 2 and comparative example 1
The waste water progress ozone for being used for ethylenediamine, 4,4 '-diaminourea acardite and the preparation of disperse red 50 under the same conditions is heterogeneous
Oxidation processes.Treatment conditions are:Rate of charge=1000L of organic wastewater and catalyst:1g, organic wastewater CODCrValue
850.8mg/L, ozone dosage 80mg/L, processing time 1hr, ozone tail gas KI solution absorption detecting ozone utilization rates.Examination
Test data and be included in table 2.
The embodiment of table 1 and comparative example prepare ozone Heterogeneous oxidation solid catalysis agent parameter
The ozone Heterogeneous oxidation solid catalyst Application Example of table 2
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 is by wheat meal
Stone, wollastonite, activated carbon, carnallite, montmorillonite, sylvite composition, by weight, medical stone:Wollastonite:Activated carbon:Light halogen
Stone:Montmorillonite:The weight ratio of sylvite=(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 myristyl tributyl ammonium chloride, 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 isopropyl scandium oxide (III), acetylacetone,2,4-pentanedione samarium, three (trifluoromethanesulfonimide) ytterbiums, the hydration of carbonic acid lutetium
Thing Rare-earth chemicals, catalytic active center predecessor normal transition metallo-organic compound titanocenes ring substitution bigcatkin willow
Sour complex, cupric glutamate and the ammino palladium of precious metal chemical complex dichloro four, the hydration iridium of tetrachloro two, the double decyl dimethyl chlorine of emulsifying agent
Change ammonium composition, by weight, borax:Potassium sulfate:Isopropyl scandium oxide (III):Acetylacetone,2,4-pentanedione samarium:Three (fluoroform sulphonyl Asias
Amine) ytterbium:Carbonic acid lutetium hydrate:Titanocenes ring substituted salicylic acid complex:Cupric glutamate:The ammino palladium of dichloro four:Tetrachloro two is hydrated
Iridium:The weight ratio of double-track suspended self-propelled conveyor=(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 medical stone, wollastonite, activated carbon, carnallite, montmorillonite, sylvite according to claim 1,
Medical stone, wollastonite, activated carbon, carnallite, montmorillonite, sylvite are crushed respectively, and deionized water washing, which is dried, removes water
After point, sieved through standard screen, it is 0.0370mm~0.0750mm to control particle diameter.
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