CN107088423A - 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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- CN107088423A CN107088423A CN201710274642.4A CN201710274642A CN107088423A CN 107088423 A CN107088423 A CN 107088423A CN 201710274642 A CN201710274642 A CN 201710274642A CN 107088423 A CN107088423 A CN 107088423A
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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 14
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 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
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 12
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 claims abstract description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229940107816 ammonium iodide Drugs 0.000 claims abstract description 10
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000010436 fluorite 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 10
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 10
- 239000001103 potassium chloride Substances 0.000 claims abstract description 10
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims abstract description 9
- JQDYLDJOLNKPHG-UHFFFAOYSA-N octadecanoate;trimethylazanium Chemical group CN(C)C.CCCCCCCCCCCCCCCCCC(O)=O JQDYLDJOLNKPHG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 9
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims abstract description 9
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 claims abstract description 8
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- 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 description 8
- 125000003963 dichloro group Chemical group Cl* 0.000 claims abstract description 8
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 8
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 8
- 235000000193 zinc lactate Nutrition 0.000 claims abstract description 8
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 229910021538 borax Inorganic materials 0.000 claims abstract description 7
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 7
- 239000011576 zinc lactate Substances 0.000 claims abstract description 7
- 229940050168 zinc lactate Drugs 0.000 claims abstract description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 6
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940009662 edetate Drugs 0.000 claims abstract description 6
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 229910052773 Promethium Inorganic materials 0.000 claims abstract description 3
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 3
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 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
- -1 by weight Chemical compound 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 125000005594 diketone group Chemical group 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 229940068911 chloride hexahydrate Drugs 0.000 claims description 2
- VOAPTKOANCCNFV-UHFFFAOYSA-N hexahydrate;hydrochloride Chemical compound O.O.O.O.O.O.Cl VOAPTKOANCCNFV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- CHEANNSDVJOIBS-MHZLTWQESA-N (3s)-3-cyclopropyl-3-[3-[[3-(5,5-dimethylcyclopenten-1-yl)-4-(2-fluoro-5-methoxyphenyl)phenyl]methoxy]phenyl]propanoic acid Chemical compound COC1=CC=C(F)C(C=2C(=CC(COC=3C=C(C=CC=3)[C@@H](CC(O)=O)C3CC3)=CC=2)C=2C(CCC=2)(C)C)=C1 CHEANNSDVJOIBS-MHZLTWQESA-N 0.000 claims 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000003610 charcoal Substances 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
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 claims 1
- RLFOVBVRQCNOMD-UHFFFAOYSA-N lutetium;hydrate Chemical compound O.[Lu] RLFOVBVRQCNOMD-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- 238000005660 chlorination reaction Methods 0.000 abstract description 10
- 238000001994 activation Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- WHELTKFSBJNBMQ-UHFFFAOYSA-L dichlororuthenium;2-pyridin-2-ylpyridine;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ru+2].N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 WHELTKFSBJNBMQ-UHFFFAOYSA-L 0.000 abstract description 3
- GDJKGUGXMBNRHL-UHFFFAOYSA-N O.[Lu].C(O)(O)=O Chemical compound O.[Lu].C(O)(O)=O GDJKGUGXMBNRHL-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 229910001868 water Inorganic materials 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
- 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
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 3
- BZSVVCFHMVMYCR-UHFFFAOYSA-N 2-pyridin-2-ylpyridine;ruthenium Chemical compound [Ru].N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 BZSVVCFHMVMYCR-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 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
- 229940048820 edetates Drugs 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 230000004044 response Effects 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
- 238000001179 sorption measurement Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- MITDXNUXOAYFGC-UHFFFAOYSA-N 1-prop-2-ynylbenzimidazole Chemical compound C1=CC=C2N(CC#C)C=NC2=C1 MITDXNUXOAYFGC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 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
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 238000011049 filling Methods 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
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic 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
- ILRLTAZWFOQHRT-UHFFFAOYSA-N potassium;sulfuric acid Chemical compound [K].OS(O)(=O)=O ILRLTAZWFOQHRT-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- PWWGCBMGIAPMHQ-UHFFFAOYSA-N thulium(3+) Chemical compound [Tm+3] PWWGCBMGIAPMHQ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/8953—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 zinc, cadmium or mercury
-
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- 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
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- B01J20/04—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
- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/04—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
- 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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- 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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- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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.Make carrier after lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings with activated carbon, carnallite, montmorillonite, sylvite, fluorite and glauberite, add surfactant diethyl maleate base double（Chlorination dodecyl dimethyl ammonium）Activation process is carried out under ul-trasonic irradiation, then carrier in hydrothermal reaction kettle with composite mineralizer borax and potassium sulfate, the cyclopentadiene promethium of catalytic activity auxiliary agent predecessor three, three (6, 6, 7, 7, 8, 8, 8 seven fluorine 2, 2 dimethyl 3, 5 octene diketone) dysprosium (III), trifluoromethayl sulfonic acid thulium (III), carbonic acid lutetium hydrate, catalytic active center predecessor cobalt edetate, zinc lactate and Tris(2,2'- bipyridyl) ruthenium (II) chloride hexahydrate, the ammino palladium of dichloro four, hydro-thermal reaction is carried out under the effect of emulsifying agent stearic acid trimethylamine groups ethanol ester ammonium iodide, drying is removed after moisture, calcination obtains ozone Heterogeneous oxidation solid catalyst in Muffle furnace.
Description
Technical field
The present invention relates to a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, category environmental protection and chemical catalyst skill
Art field.
Background technology
Ozonation technology using ozone oxidation ability it is strong the characteristics of, can be by many organic pollution oxidation Decompositions, extensively
For wastewater treatment.Catalytic ozonation technology is divided into ozone homogeneous catalytic oxidation and ozone heterogeneous catalytic oxidation, and ozone is equal
Phase catalysis oxidation has that the more difficult separation and recovery of catalyst is reused, ozone utilization rate is low causes water process operating cost higher,
Organic pollutant removal rate is relatively low simultaneously and easily causing secondary pollution of water is limited to its application；Ozone heterogeneous catalysis oxygen
There is change technology catalyst to be easily isolated and recycled and reusable, ozone utilization rate is high, organic pollutant removal rate is higher, drop
Low water process operating cost and receive significant attention its application the advantages of do not result in secondary pollution.Ozone heterogeneous catalysis
It is to reach local organic matter enrichment by catalyst surface absorption organic matter that oxidation of organic compounds, which is decomposed, while ozone molecule absorption exists
The hydroxyl radical free radical that catalyst surface produces high activity under catalyst action decomposes organic matter.Ozone heterogeneous catalytic oxidation
Handle in waste water technology, core technology is the preparation of ozone Heterogeneous oxidation solid catalyst.
Ozone Heterogeneous oxidation solid catalyst is generally made up of carrier, activated centre and auxiliary agent.Due to being polluted in waste water
Species are various, complex chemical composition feature, can produce harmful effect to performance such as absorption, the mithridatism of catalyst.
Prepare that the carrier structure that ozone Heterogeneous oxidation solid catalyst uses is more single at present, adsorptivity is relatively low；Activated centre is universal
Using normal transition metal salt, mithridatism is poor；Preparation method mainly has infusion process, the precipitation method, mixing method and collosol and gel etc.
Method attachment activity center and adjuvant component are easily liquated out in carrier surface, activated centre and adjuvant component, cause catalyst
Easily lose catalytic activity.For exist in current ozone Heterogeneous oxidation solid catalyst preparation method Catalyst Adsorption compared with
Low, mithridatism is poor and easily loses catalytic activity problem, and exploitation is strengthened using multicomponent porous carrier through reaming, surface active
The adsorptivity of catalyst, catalytic activity auxiliary agent predecessor, normal transition Organometallic are made using Rare-earth chemicals
Compound and precious metal chemical complex are made catalytic active center predecessor and prepared with multicomponent porous carrier through hydro-thermal reaction, high temperature sintering
Ozone Heterogeneous oxidation solid catalyst containing multi-element metal has to improve the preparation method of catalyst mithridatism and catalytic activity
There are larger environmental benefit and higher practical value.
The content of the invention
For existing in current ozone Heterogeneous oxidation solid catalyst preparation method, Catalyst Adsorption is relatively low, mithridatism
Poor to lose catalytic activity problem with easy, exploitation strengthens catalyst using multicomponent porous carrier through reaming, surface active
Adsorptivity, catalytic activity auxiliary agent predecessor, normal transition metallo-organic compound and expensive are made using Rare-earth chemicals
Metallic compound is made catalytic active center predecessor and prepared with multicomponent porous carrier through hydro-thermal reaction, high temperature sintering containing polynary gold
The ozone Heterogeneous oxidation solid catalyst of category to improve the preparation method of catalyst mithridatism and catalytic activity, it is characterized in that
Component A can be added in closed reactor and deionized water stirring prepares the aqueous solution, the weight concentration for control component A is 2%~6%,
After the completion of prepared by solution, B component is added under agitation, 35 DEG C~50 DEG C are warming up to, continues stirring reaction 3h~6h, is filtered, instead
Product is answered to obtain reaming modified support after 102 DEG C~106 DEG C dry constant weights；Reaming modified support puts into ultrasound reactor,
The aqueous solution prepared by component C and deionized water is added, the weight concentration of component C is 3%~8%, is uniformly mixed, and control is super
Sound power density is 0.3~0.8W/m3, frequency 20kHz~30kHz, 40 DEG C~55 DEG C, sonic oscillation 2h~5h obtains ultrasound
Surface active carrier mixed liquor；Ultrasonic surface activated carrier mixed liquor is transferred in hydrothermal reaction kettle, add D components and go from
The aqueous solution that sub- water is prepared, the weight concentration of D components is 40%~55%, by weight, D component deionized water solutions:Ultrasonic table
Weight ratio=1 of face activated carrier mixed liquor:（1.5~2）, control 120 DEG C~180 DEG C of temperature, the hydro-thermal reaction time be 8h~
16h, then dries to obtain fine particle；Fine particle is in Muffle furnace, 600 DEG C~950 DEG C, and calcination 3h~8h obtains ozone non-
Homogeneous oxidizing solid catalyst.The component A is made up of lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, by weight, lithium hypochlorite:
Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B component by activated carbon, carnallite, montmorillonite, sylvite, fluorite,
Glauberite is constituted, by weight, activated carbon:Carnallite:Montmorillonite:Sylvite:Fluorite:The weight ratio of glauberite=（5~
15）:（7~17）:（9~19）:（11~21）:（13~23）:（15~25）, by weight, component A:The weight ratio of B component
=1:（10~20）, component C is that diethyl maleate base is double（Chlorination dodecyl dimethyl ammonium）, by weight, component C:Reaming
Weight ratio=1 of modified support:（5~10）, D components are by composite mineralizer borax, potassium sulfate, catalytic activity auxiliary agent predecessor
Three cyclopentadiene promethiums, three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosiums (III), fluoroform
Sulfonic acid thulium (III), carbonic acid lutetium hydrate Rare-earth chemicals, catalytic active center predecessor normal transition metal are organic
Compound cobalt edetate, zinc lactate and precious metal chemical complex Tris(2,2'- bipyridyl) ruthenium (II) chloride hexahydrate, the ammino palladium of dichloro four, emulsification
Agent stearic acid trimethylamine groups ethanol ester ammonium iodide is constituted, by weight, borax:Potassium sulfate:Three cyclopentadiene promethiums:Three (6,6,7,
The fluoro- 2,2- dimethyl -3,5- octenes diketone of 7,8,8,8- seven) dysprosium (III):Trifluoromethayl sulfonic acid thulium (III):Carbonic acid lutetium is hydrated
Thing:Cobalt edetate:Zinc lactate:Tris(2,2'- bipyridyl) ruthenium (II) chloride hexahydrate:The ammino palladium of dichloro four:Stearic acid trimethylamine groups ethanol ester
The weight ratio of ammonium iodide=（4~8）:（6~10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~
18）:（4~7）:（6~9）:（6~20）.Activated carbon, carnallite, montmorillonite, sylvite, fluorite, the glauberite of the B component
Crushed respectively, deionized water washing, which is dried, to be removed after moisture, is carried out -200 mesh ,+400 mesh sieves point through standard screen, is controlled grain
Footpath is the mm of 0.0370mm~0.0750.
What the technical method of the present invention was realized in：Lithium hypochlorite LiClO, double (second can be being added in closed reactor
Acyl acetone) beryllium C10H14BeO4The aqueous solution is prepared with deionized water stirring, it is 0.0370mm~0.0750mm to add particle diameter after screening
Activated carbon, carnallite, montmorillonite, sylvite, fluorite and glauberite porous material carrier, in certain temperature and stirring condition
Under, the small Be of aqueous solution Ionic Radius2+（0.31Å）、Li+（0.60Å）Displace part ion radius in porous material big
Ca2+（0.99Å）、K+（1.33Å）、Ba2+（1.35Å）Plasma, the aperture of porous material carrier becomes big, surface roughness increase,
Filtering, dries the reaming modified support input ultrasound reactor after constant weight, adds diethyl maleate base double（Chlorination 12
Alkyl dimethyl ammonium）C36H72N2 +O4Cl2 -The aqueous solution, when control ultrasonic power density, ultrasonic frequency, temperature and sonic oscillation
Between, under ultrasonic cavitation effect, diethyl maleate base is double（Chlorination dodecyl dimethyl ammonium）C36H72N2 +O4Cl2 -It is easy to
Reaming modified support duct is escaped into from the aqueous solution or reaming modified support surface is attached to, and is beneficial to the mutual of carrier duct
Connection and carrier surface activation, enhance adsorptivity；After the completion of ultrasonic activation, ultrasonic surface activated carrier mixed liquor is transferred to water
In thermal response kettle, with borax Na2B4O7·10H2O, potassium sulfate K2SO4Composite mineralizer, the ring penta of catalytic activity auxiliary agent predecessor three
Diene promethium Pm (C5H5)3, three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosiums (III)
C30H30DyF21O6, trifluoromethayl sulfonic acid thulium (III) C3F9O9S3Tm, carbonic acid lutetium hydrate C3H2Lu2O10Rare earth metal organic compound
Thing, catalytic active center component predecessor normal transition metallo-organic compound cobalt edetate C12H22O14Co, zinc lactate
C6H10O6Zn and Tris(2,2'- bipyridyl) ruthenium (II) chloride hexahydrate (C10H8N2)3Cl2Ru·(H2O)6, the ammino palladium Pd (NH of dichloro four3)4Cl2It is expensive
Metallic compound, in emulsifying agent stearic acid trimethylamine groups ethanol ester ammonium iodide [C17H35COOCH2CH2N(CH3)CH2]+I-Enter under
Water-filling thermal response, mineralizer accelerates diffusion, activates reactant lattice, promotes the progress of solid phase reaction, ultrasonic surface
Activated carrier and Rare-earth chemicals, normal transition metallo-organic compound, precious metal chemical complex Uniform Doped, emulsification
Agent stearic acid trimethylamine groups ethanol ester ammonium iodide make reaction solution formed quasi-stationary emulsion prevent separation of solid and liquid, sedimentation, simultaneously
To the further surface active of porous carrier, by the way that in certain temperature, the hydro-thermal reaction of time, drying obtains the fine powder of Uniform Doped
Grain thing；The fine silt thing of Uniform Doped is in Muffle furnace, through high temperature sintering, and organic matter carbonization therein is further enhanced
The microcellular structure of porous carrier, obtains porous carrier supported rare earth metal oxide, transition metal oxide and noble metal and is formed
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 be in technology of preparing using activated carbon, carnallite, cover de-
Soil, sylvite, fluorite, glauberite porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) beryllium C10H14BeO4
Reaming effect, diethyl maleate base is double（Chlorination dodecyl dimethyl ammonium）C36H72N2 +O4Cl2 -, stearic acid trimethylamine groups
Ethanol ester ammonium iodide [C17H35COOCH2CH2N(CH3)CH2]+I-To being interconnected and surface activation for duct；Pass through hydro-thermal
Reaction makes Rare-earth chemicals, normal transition metallo-organic compound and precious metal chemical complex reach Uniform Doped and attached
In in carrier surface and duct, high temperature sintering makes organic matter carbonization strengthen and form multi-level microcellular structure, many
The carrier loaded rare-earth oxide in hole, transition metal oxide and noble metal formation multi-element metal catalytic active center with it is many
Hole carrier combination is more firm, and the ozone Heterogeneous oxidation solid catalyst of preparation has stronger adsorptivity, multi-element metal
Cooperative effect, the noble metal of particularly doping have stability and high activity, can suppress the liquate of metal catalytic activity component
Go out, 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, 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~+
2.75g activated carbons, 3.75g carnallites, 4.75g montmorillonites, 5.75g sylvites, 6.75g fluorites, the 7.75g of 400 mesh standard sieves
The weight of glauberite, 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 diethyl maleates base double（Chlorination dodecyl dimethyl ammonium）
The aqueous solution of 100ml deionized waters is dissolved in, the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, diethyl maleate
Base is double（Chlorination dodecyl dimethyl ammonium）（3.25g）:Reaming modified support（31g ）=1:9.5；The ultrasonic power density is controlled to be
0.4 W/m3, ultrasonic frequency 21kHz, 41 DEG C of temperature, sonic oscillation 2.2h；After the completion of ultrasonic activation, ultrasound reactor
In ultrasonic surface activated carrier mixed liquor be transferred in 500ml hydrothermal reaction kettles, add by 2.1g boraxs, 3.05g sulfuric acid
Potassium, the cyclopentadiene promethiums of 1.6g tri-, 2.05g tri- (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosium
(III), 2.6g trifluoromethayl sulfonic acids thulium (III), 3.05g carbonic acid lutetiums hydrate, 5.05g cobalt edetates, 6.1g zinc lactates,
2.05g Tris(2,2'- bipyridyl) ruthenium (II) chlorides hexahydrate, the ammino palladium of 3.1g dichloros four, 3.05g stearic acid trimethylamine groups ethanol ester ammonium iodides
The aqueous solution prepared with 50ml deionized waters, the weight concentration of the aqueous solution is 40.3%, the weight of the aqueous solution:Ultrasonic surface
Weight=83.8g of activated carrier mixed liquor:134.25g=1:1.6,125 DEG C of temperature is controlled, the hydro-thermal reaction time is 8.3h, so
Dry to obtain fine silt thing for 105 DEG C afterwards；Fine silt thing is in Muffle furnace, 620 DEG C, calcination 3.2h, after cooling down, can obtain fine powder
Granular ozone Heterogeneous oxidation 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~+
1.45g activated carbons, 1.65g carnallites, 1.85g montmorillonites, 2.05g sylvites, 2.25g fluorites, the 2.45g of 400 mesh standard sieves
The weight of glauberite, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（0.6g）:The weight of porous material（11.7g）=1:19.5, heating
To 48 DEG C, reaming modified support 11.5g is obtained after continuing stirring reaction 5.8h, filtering, 105 DEG C of dry constant weights；In 100ml ultrasounds
In ripple reactor, reaming modified support 11.5g is put into, 2.2g diethyl maleates base is added double（Chlorination dimethyl
Base ammonium）The aqueous solution of 26ml deionized waters is dissolved in, the weight concentration of the aqueous solution is 7.8%, is uniformly mixed, maleic acid two
Ethoxycarbonyl is double（Chlorination dodecyl dimethyl ammonium）（2.2g）:Reaming modified support（11.5g ）=1:5.2；Control ultrasonic power
Density is 0.7 W/m3, ultrasonic frequency 29kHz, 54 DEG C of temperature, sonic oscillation 4.7h；After the completion of ultrasonic activation, ultrasonic wave
Ultrasonic surface activated carrier mixed liquor in reactor is transferred in 100ml hydrothermal reaction kettles, add by 0.78g boraxs,
0.97g potassium sulfates, the cyclopentadiene promethiums of 0.58g tri-, (the fluoro- 2,2- dimethyl -3,5- octenes of 6,6,7,7,8,8,8- seven of 0.67g tri-
Diketone) dysprosium (III), 0.78g trifluoromethayl sulfonic acids thulium (III), 0.87g carbonic acid lutetiums hydrate, 1.48g cobalt edetates, 1.77g
Zinc lactate, 0.68g Tris(2,2'- bipyridyl) ruthenium (II) chlorides hexahydrate, the ammino palladium of 0.87g dichloros four, 1.98g stearic acid trimethylamine groups ethanol
The aqueous solution that ester ammonium iodide 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=1:1.9,175 DEG C of temperature is controlled, the hydro-thermal reaction time is
15.5h, then dries to obtain fine silt thing for 105 DEG C；Fine silt thing is in Muffle furnace, 930 DEG C, calcination 7.5h, can after cooling down
Obtain the ozone Heterogeneous oxidation solid catalyst of fine particle shape.
Comparative example 1:It is double that preparation process is not added with lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, diethyl maleate base（Chlorination ten
Dialkyl dimethyl ammonium）, stearic acid trimethylamine groups ethanol ester ammonium iodide, outside borax and potassium sulfate, whole preparation process, prepare bar
Part is identical with embodiment 1.
The parameter of ozone Heterogeneous oxidation solid catalyst prepared by embodiment 1, embodiment 2 and comparative example 1 is included in table 1.
The embodiment of table 1 and comparative example prepare ozone Heterogeneous oxidation solid catalysis agent parameter
| Project | Average pore size (nm) | Pore volume (cm3/g) | BET is than surface (m2/g) |
| Embodiment 1 | 4.786 | 0.6270 | 746.61 |
| Embodiment 2 | 4.323 | 0.5834 | 624.55 |
| Comparative example 1 | 2.634 | 0.3679 | 438.19 |
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 activated carbon, carnallite, montmorillonite, sylvite, fluorite, glauberite, by weight, activated carbon:Carnallite:Cover de-
Soil:Sylvite: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 that diethyl maleate base is double（Chlorine
Change dodecyl dimethyl ammonium）, by weight, component C:Weight ratio=1 of reaming modified support:（5~10）, D components are by multiple
Close mineralizer borax, potassium sulfate, the cyclopentadiene promethium of catalytic activity auxiliary agent predecessor three, three (6,6,7,7,8,8,8- seven fluoro- 2,2-
Dimethyl -3,5- octenes diketone) dysprosium (III), trifluoromethayl sulfonic acid thulium (III), carbonic acid lutetium hydrate rare earth metal organic compound
Thing, catalytic active center predecessor normal transition metallo-organic compound cobalt edetate, zinc lactate and precious metal chemical complex three
Bipyridyl ruthenic chloride hexahydrate, the ammino palladium of dichloro four, emulsifying agent stearic acid trimethylamine groups ethanol ester ammonium iodide composition, by weight
Meter, borax:Potassium sulfate:Three cyclopentadiene promethiums:Three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosiums
(III):Trifluoromethayl sulfonic acid thulium (III):Carbonic acid lutetium hydrate:Cobalt edetate:Zinc lactate:Tris(2,2'- bipyridyl) ruthenium (II) chloride six is hydrated
Thing:The ammino palladium of dichloro four:, the weight ratio of stearic acid trimethylamine groups ethanol ester ammonium iodide=（4~8）:（6~10）:（3~6）:
（4~7）:（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.
2. B component is made up of activated carbon, carnallite, montmorillonite, sylvite, fluorite, glauberite according to claim 1, living
Property charcoal, carnallite, montmorillonite, sylvite, fluorite, glauberite crushed respectively, deionized water washing, which is dried, to be removed after moisture,
Sieved through standard screen, it is 0.0370mm~0.0750mm to control particle diameter.
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