CN107051495A - The preparation method of ozone Heterogeneous oxidation solid catalyst - Google Patents
The preparation method of ozone Heterogeneous oxidation solid catalyst Download PDFInfo
- Publication number
- CN107051495A CN107051495A CN201710275179.5A CN201710275179A CN107051495A CN 107051495 A CN107051495 A CN 107051495A CN 201710275179 A CN201710275179 A CN 201710275179A CN 107051495 A CN107051495 A CN 107051495A
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- weight
- component
- double
- solid catalyst
- potassium
- Prior art date
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 230000003647 oxidation Effects 0.000 title claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 27
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- -1 carbonic acid lutetium hydrate Rare-earth Chemical class 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000019362 perlite Nutrition 0.000 claims abstract description 12
- 150000002148 esters Chemical class 0.000 claims abstract description 11
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims abstract description 10
- 229910052656 albite Inorganic materials 0.000 claims abstract description 10
- 239000010451 perlite Substances 0.000 claims abstract description 10
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 9
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001412 amines Chemical class 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
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 8
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 8
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 8
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 8
- 229910052761 rare earth metal Inorganic materials 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
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 7
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 7
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229940094989 trimethylsilane Drugs 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010970 precious metal Substances 0.000 claims abstract description 6
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims abstract description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 229940009662 edetate Drugs 0.000 claims abstract description 5
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 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
- VAIVGJYVKZVQAA-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;nickel Chemical compound [Ni].OC(=O)CC(O)(C(O)=O)CC(O)=O VAIVGJYVKZVQAA-UHFFFAOYSA-N 0.000 claims abstract description 3
- 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 claims abstract description 3
- 239000007795 chemical reaction product Substances 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000036571 hydration Effects 0.000 claims description 5
- 238000006703 hydration reaction Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- RLFOVBVRQCNOMD-UHFFFAOYSA-N lutetium;hydrate Chemical compound O.[Lu] RLFOVBVRQCNOMD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- SYGKRYHXHZWFMX-UHFFFAOYSA-K [Nd+3].[O-]C(=O)C(F)(F)F.FC(C(=O)CC(C)=O)(F)F.[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F Chemical compound [Nd+3].[O-]C(=O)C(F)(F)F.FC(C(=O)CC(C)=O)(F)F.[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F SYGKRYHXHZWFMX-UHFFFAOYSA-K 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 229960004194 lidocaine Drugs 0.000 claims 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 claims 1
- DVFYDVTUXYPULX-UHFFFAOYSA-N ruthenium hexahydrate Chemical compound O.O.O.O.O.O.[Ru] DVFYDVTUXYPULX-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 16
- 239000011148 porous material Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 238000001994 activation Methods 0.000 abstract description 6
- 229910052779 Neodymium Inorganic materials 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 abstract 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 2
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000004913 activation Effects 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 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
- YPUOTXOJCHHZIY-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;ytterbium(3+) Chemical compound [Yb+3].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YPUOTXOJCHHZIY-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 125000004005 formimidoyl group Chemical group [H]\N=C(/[H])* 0.000 description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 244000131522 Citrus pyriformis Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229940068911 chloride hexahydrate Drugs 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229940048820 edetates Drugs 0.000 description 2
- 239000010433 feldspar Substances 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
- VOAPTKOANCCNFV-UHFFFAOYSA-N hexahydrate;hydrochloride Chemical compound O.O.O.O.O.O.Cl VOAPTKOANCCNFV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 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
- 238000007873 sieving Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 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 description 1
- NAOLWIGVYRIGTP-UHFFFAOYSA-N 1,3,5-trihydroxyanthracene-9,10-dione Chemical compound C1=CC(O)=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1 NAOLWIGVYRIGTP-UHFFFAOYSA-N 0.000 description 1
- MITDXNUXOAYFGC-UHFFFAOYSA-N 1-prop-2-ynylbenzimidazole Chemical compound C1=CC=C2N(CC#C)C=NC2=C1 MITDXNUXOAYFGC-UHFFFAOYSA-N 0.000 description 1
- QNFVGEYXTFRSLK-UHFFFAOYSA-N 2-$l^{1}-sulfanylethanamine Chemical group NCC[S] QNFVGEYXTFRSLK-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- 241000270295 Serpentes Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 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
- 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
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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
- 238000001556 precipitation Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- VWNQJLIVSOOFBX-UHFFFAOYSA-L ruthenium(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Ru]Cl VWNQJLIVSOOFBX-UHFFFAOYSA-L 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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- 238000003746 solid phase reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
- B01J23/8946—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 alkali or alkaline earth metals
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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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- B01J20/02—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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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/615—100-500 m2/g
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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 make carrier with perlite, albite, potassium feldspar, boromagnesite, shepardite and serpentinite porous material, and carrier is modified through lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, adds surfactant 2,6 two（Diethylaminomethyl）4 nonyl phenol Benzene Chloride quaternary ammonium salts carry out surface activation process under ul-trasonic irradiation, then ultrasonic surface activated carrier in hydrothermal reaction kettle with composite mineralizer borax and potassium sulfate, catalytic activity auxiliary agent predecessor 1, 1, 1 trifluoroacetylacetone (TFA) neodymium, three [N, double (trimethyl silane) amine of N] erbium, three (trifluoromethanesulfonimide) ytterbiums, carbonic acid lutetium hydrate Rare-earth chemicals, catalytic active center component predecessor normal transition metallo-organic compound cobalt edetate, citric acid nickel and precious metal chemical complex Tris(2,2'- bipyridyl) ruthenium (II) chloride hexahydrate, tetrachloro two is hydrated iridium, hydro-thermal reaction is carried out under the effect of emulsifying agent etradecyldimethylamine QAE quaternary aminoethyl sulfuric ester, 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
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 is by perlite, albite, potassium feldspar, boromagnesite, water magnesium
Stone, serpentinite composition, by weight, perlite:Albite:Potassium feldspar:Boromagnesite:Shepardite:The weight ratio of serpentinite=
（5~15）:（7~17）:（9~19）:（11~21）:（13~23）:（15~25）, by weight, component A:The weight of B component
The ratio between=1:（10~20）, component C is 2,6- bis-（Diethylaminomethyl）- 4- nonyl phenols-Benzene Chloride quaternary ammonium salt, by weight, C
Component:Weight ratio=1 of reaming modified support:（5~10）, D components help by composite mineralizer borax, potassium sulfate, catalytic activity
Agent predecessor 1,1,1- trifluoroacetylacetone (TFA)s neodymium, three [double (trimethyl silane) amine of N, N-] erbiums, three (trifluoromethanesulfonimides)
Ytterbium, carbonic acid lutetium hydrate Rare-earth chemicals, catalytic active center predecessor normal transition metallo-organic compound Portugal
Grape saccharic acid cobalt, citric acid nickel and precious metal chemical complex Tris(2,2'- bipyridyl) ruthenium (II) chloride hexahydrate, the hydration iridium of tetrachloro two, emulsifying agent 16
Alkyl-dimethyl QAE quaternary aminoethyl sulfuric ester is constituted, by weight, borax:Potassium sulfate:1,1,1- trifluoroacetylacetone (TFA) neodymiums:Three [N, N- are double
(trimethyl silane) amine] erbium:Three (trifluoromethanesulfonimide) ytterbiums:Carbonic acid lutetium hydrate:Cobalt edetate:Citric acid nickel:Three
Bipyridyl ruthenic chloride hexahydrate:Tetrachloro two is hydrated iridium:The weight ratio of etradecyldimethylamine QAE quaternary aminoethyl sulfuric ester=（4~8）:
（6~10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.
Perlite, albite, potassium feldspar, boromagnesite, shepardite, the serpentinite of the B component are crushed respectively, deionized water washing
Dry and remove after moisture, -200 mesh ,+400 mesh sieves point are carried out through standard screen, it is the mm of 0.0370mm~0.0750 control particle diameter.
What the technical method of the present invention was realized in：Lithium hypochlorite LiClO, double (second can be being added in closed reactor
Acyl acetone) beryllium C10H14BeO4The aqueous solution is prepared with deionized water stirring, it is 0.0370mm~0.0750mm to add particle diameter after screening
Perlite, albite, potassium feldspar, boromagnesite, shepardite and serpentinite 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 2,6- bis-（Diethylaminomethyl）- 4- nonyls
Base phenol-Benzene Chloride quaternary ammonium salt Cl-(C2H5)2N+(C6H5C2H5)CH2C6H2(OH)(C9H19)CH2N+(C6H5C2H5)(C2H5)2Cl-Water
Solution, control ultrasonic power density, ultrasonic frequency, temperature and sonic oscillation time, under ultrasonic cavitation effect, 2,6- bis-
（Diethylaminomethyl）- 4- nonyl phenols-Benzene Chloride quaternary ammonium salt Cl-(C2H5)2N+(C6H5C2H5)CH2C6H2(OH)(C9H19)CH2N+
(C6H5C2H5)(C2H5)2Cl- It is easy to escape into reaming modified support duct from the aqueous solution or is attached to reaming modified support table
Face, is beneficial to being interconnected and carrier surface activation for carrier duct, enhances adsorptivity；After the completion of ultrasonic activation, ultrasonic table
Face activated carrier mixed liquor is transferred in hydrothermal reaction kettle, with borax Na2B4O7·10H2O, potassium sulfate K2SO4Composite mineralizer,
Catalytic activity auxiliary agent predecessor 1,1,1- trifluoroacetylacetone (TFA) neodymiums C15H12F9NdO6, three [N, N- double (trimethyl silane) amine] erbiums
C18H54ErN3Si6, three (trifluoromethanesulfonimide) ytterbium [(CF3SO2)2N]3Yb, carbonic acid lutetium hydrate C3H2Lu2O10Rare earth metal
Organic compound, catalytic active center component predecessor normal transition metallo-organic compound cobalt edetate C12H22O14Co, lemon
Lemon acid nickel C12H10O14Ni3With Tris(2,2'- bipyridyl) ruthenium (II) chloride hexahydrate (C10H8N2)3Cl2Ru·(H2O)6, the hydration of tetrachloro two iridium Ir
(H2O)2Cl4Precious metal chemical complex, in emulsifying agent etradecyldimethylamine QAE quaternary aminoethyl sulfuric ester [(C16H33)N(CH3)2C2H5]+
C2H5SO4 -Effect is lower to carry out hydro-thermal reaction, and mineralizer accelerates diffusion, activates reactant lattice, promotes solid phase reaction
Progress, ultrasonic surface activated carrier and Rare-earth chemicals, normal transition metallo-organic compound, noble metal chemical combination
Thing Uniform Doped, emulsifying agent etradecyldimethylamine QAE quaternary aminoethyl sulfuric ester makes reaction solution form quasi-stationary emulsion to prevent solid-liquid point
From, sedimentation, while to the further surface active of porous carrier, by the way that in certain temperature, the hydro-thermal reaction of time, drying is obtained
The fine silt thing of even doping；The fine silt thing of Uniform Doped is in Muffle furnace, through high temperature sintering, organic matter carbonization therein
The microcellular structure of porous carrier is further enhanced, porous carrier supported rare earth metal oxide, transition metal oxide is obtained
With the ozone Heterogeneous oxidation solid catalyst of the catalytic active center of noble metal formation, improve the mithridatism of catalyst and urge
Change activity.
Relative to art methods, outstanding feature of the present invention is long using perlite, albite, potassium in technology of preparing
Stone, boromagnesite, shepardite, serpentinite porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) berylliums
C10H14BeO4Reaming effect, 2,6- bis-（Diethylaminomethyl）- 4- nonyl phenols-Benzene Chloride quaternary ammonium salt Cl-(C2H5)2N+
(C6H5C2H5)CH2C6H2(OH)(C9H19)CH2N+(C6H5C2H5)(C2H5)2Cl-, etradecyldimethylamine QAE quaternary aminoethyl sulfuric ester
[(C16H33)N(CH3)2C2H5]+C2H5SO4 -To being interconnected and surface activation for duct；Rare earth gold is made by hydro-thermal reaction
Category organic compound, normal transition metallo-organic compound and precious metal chemical complex reach Uniform Doped and are attached to carrier surface
In duct, high temperature sintering makes organic matter carbonization strengthen and form multi-level microcellular structure, and porous carrier load is dilute
The multi-element metal catalytic active center of soil metal oxide, transition metal oxide and noble metal formation is combined more with porous carrier
Plus firmly, the ozone Heterogeneous oxidation solid catalyst of preparation has a stronger adsorptivity, the cooperative effect of multi-element metal, especially
It is that the noble metal adulterated has stability and high activity, liquating out for metal catalytic activity component can be suppressed, catalysis is improved
The mithridatism and catalytic activity of agent, with good environmental benefit and economic benefit.
Embodiment
Embodiment 1:1.35g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 1.65g, 140ml deionized waters are added to volume for 500ml
Can be uniformly mixed in closed reactor, the weight concentration of the aqueous solution is 2.1%, lithium hypochlorite:Double (acetylacetone,2,4-pentanedione) berylliums
Weight ratio=1:1.2；Add deionized water wash to it is neutral, 103 DEG C dry and remove the mesh of -200 mesh of sieving after moisture~+400
2.75g perlites, 3.75g albites, 4.75g potassium feldspars, 5.75g boromagnesites, 6.75g shepardites, the 7.75g snakes of standard screen
The weight of rock, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（3g）:The weight of porous material（31.5g）=1:10.5, it is warming up to 36
DEG C, obtain reaming modified support 31g after continuing stirring reaction 3.2h, filtering, 103 DEG C of dry constant weights；In 500ml ultrasonic responses
In device, reaming modified support 31g is put into, 3.25g2,6- bis- is added（Diethylaminomethyl）- 4- nonyl phenols-Benzene Chloride quaternary ammonium
Salt is dissolved in the aqueous solution of 100ml deionized waters, and the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, 2,6- bis-（Diethyl
Amino methyl）- 4- nonyl phenols-Benzene Chloride quaternary ammonium salt（3.25g）:Reaming modified support（31g ）=1:9.5；Control ultrasonic power
Density is 0.4 W/m3, ultrasonic frequency 21kHz, 41 DEG C of temperature, sonic oscillation 2.2h；After the completion of ultrasonic activation, ultrasonic wave
Ultrasonic surface activated carrier mixed liquor in reactor is transferred in 500ml hydrothermal reaction kettles, add by 2.1g boraxs,
3.05g potassium sulfates, 1.6g1,1,1- trifluoroacetylacetone (TFA)s neodymium, 2.05g tri- [double (trimethyl silane) amine of N, N-] erbium, 2.6g tri-
(trifluoromethanesulfonimide) ytterbium, 3.05g carbonic acid lutetiums hydrate, 5.05g cobalt edetates, 6.1g citric acids nickel, 2.05g tri-
Bipyridyl ruthenic chloride hexahydrate, the hydration of 3.1g tetrachloros two iridium, 3.05g etradecyldimethylamine QAE quaternary aminoethyl sulfuric esters and 50ml are gone
The aqueous solution that ionized water is prepared, the weight concentration of the aqueous solution is 40.3%, the weight of the aqueous solution:Ultrasonic surface activated carrier
Weight=83.8g of mixed liquor:134.25g =1:1.6,125 DEG C of temperature is controlled, the hydro-thermal reaction time is 8.3h, then 105 DEG C
Dry to obtain fine silt thing；Fine silt thing is in Muffle furnace, 620 DEG C, calcination 3.2h, after cooling down, can obtain fine particle shape
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~+
The 1.45g perlites of 400 mesh standard sieves, 1.65g albites, 1.85g potassium feldspars, 2.05g boromagnesites, 2.25g shepardites,
The weight of 2.45g serpentinites, 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, 2.2g2,6- bis- is added（Diethylaminomethyl）- 4- nonyls
Base phenol-Benzene Chloride quaternary ammonium salt is dissolved in the aqueous solution of 26ml deionized waters, and the weight concentration of the aqueous solution is 7.8%, and stirring mixing is equal
It is even, 2,6- bis-（Diethylaminomethyl）- 4- nonyl phenols-Benzene Chloride quaternary ammonium salt（2.2g）:Reaming modified support（11.5g ）=1:
5.2；It is 0.7 W/m to control ultrasonic power density3, ultrasonic frequency 29kHz, 54 DEG C of temperature, sonic oscillation 4.7h；Ultrasonic activation
After the completion of, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor is transferred in 100ml hydrothermal reaction kettles, added
By 0.78g boraxs, 0.97g potassium sulfates, 0.58g1,1,1- trifluoroacetylacetone (TFA)s neodymium, 0.67g tri-, [N, N- are double (trimethyl silane)
Amine] erbium, 0.78g tri- (trifluoromethanesulfonimide) ytterbium, 0.87g carbonic acid lutetiums hydrate, 1.48g cobalt edetates, 1.77g lemons
Sour nickel, 0.68g Tris(2,2'- bipyridyl) ruthenium (II) chlorides hexahydrate, the hydration of 0.87g tetrachloros two iridium, 1.98g etradecyldimethylamine QAE quaternary aminoethyl sulphur
The aqueous solution that acid esters and 10ml deionized waters are prepared, the weight concentration of the aqueous solution is 53.3%, the weight of the aqueous solution:Ultrasound
Weight=21.43g of surface active 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:Preparation process is not added with lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, 2,6- bis-（Diethylaminomethyl）-4-
Outside nonyl phenol-Benzene Chloride quaternary ammonium salt, etradecyldimethylamine QAE quaternary aminoethyl sulfuric ester, borax and potassium sulfate, whole preparation process, preparation
Condition 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 | 4.745 | 0.6232 | 753.37 |
| Embodiment 2 | 4.158 | 0.5664 | 662.76 |
| Comparative example 1 | 2.318 | 0.3336 | 468.61 |
Claims (2)
1. a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, it is characterized in that A groups can added in closed reactor
Divide and deionized water stirring prepares the aqueous solution, the weight concentration for controlling component A is 2%~6%, after the completion of prepared by solution, in stirring
Lower addition B component, is warming up to 35 DEG C~50 DEG C, continues stirring reaction 3h~6h, and filtering, reaction product is dry at 102 DEG C~106 DEG C
Reaming modified support is obtained after dry constant weight, reaming modified support input ultrasound reactor, addition is matched somebody with somebody by component C and deionized water
The aqueous solution of system, the weight concentration of component C is 3%~8%, is uniformly mixed, and it is 0.3~0.8W/ to control ultrasonic power density
m3, frequency 20kHz~30kHz, 40 DEG C~55 DEG C, sonic oscillation 2h~5h obtains ultrasonic surface activated carrier mixed liquor, transfer
Into hydrothermal reaction kettle, the aqueous solution that D components and deionized water are prepared is added, the weight concentration of D components is 40%~55%, is pressed
Weight meter, D component deionized water solutions:Weight ratio=1 of ultrasonic surface activated carrier mixed liquor:（1.5~2）, control temperature
120 DEG C~180 DEG C, the hydro-thermal reaction time is 8h~16h, then dries to obtain fine silt thing, fine silt thing is in Muffle furnace, 600
DEG C~950 DEG C, calcination 3h~8h obtains ozone Heterogeneous oxidation solid catalyst；The component A by expanding agent lithium hypochlorite,
Double (acetylacetone,2,4-pentanedione) beryllium compositions, by weight, lithium hypochlorite:Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B groups
Divide and be made up of perlite, albite, potassium feldspar, boromagnesite, shepardite, serpentinite, by weight, perlite:Albite:Potassium is long
Stone:Boromagnesite:Shepardite:The weight ratio of serpentinite=（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 2,6- bis-（Lignocaine first
Base）- 4- nonyl phenols-Benzene Chloride quaternary ammonium salt, by weight, component C:Weight ratio=1 of reaming modified support:（5~10）, D groups
Divide by composite mineralizer borax, potassium sulfate, the trifluoroacetylacetone (TFA) neodymium of catalytic activity auxiliary agent predecessor 1,1,1-, three [N, N- double (three
Methyl-monosilane) amine] erbium, three (trifluoromethanesulfonimide) ytterbiums, carbonic acid lutetium hydrate Rare-earth chemicals, catalytic activity
Center predecessor normal transition metallo-organic compound cobalt edetate, citric acid nickel and precious metal chemical complex terpyridyl chlorination
Ruthenium hexahydrate, the hydration iridium of tetrachloro two, emulsifying agent etradecyldimethylamine QAE quaternary aminoethyl sulfuric ester composition, by weight, borax:Sulfuric acid
Potassium:1,1,1- trifluoroacetylacetone (TFA) neodymiums:Three [double (trimethyl silane) amine of N, N-] erbiums:Three (trifluoromethanesulfonimide) ytterbiums:Carbon
Sour lutetium hydrate:Cobalt edetate:Citric acid nickel:Tris(2,2'- bipyridyl) ruthenium (II) chloride hexahydrate:Tetrachloro two is hydrated iridium:Cetyl two
The weight ratio of first QAE quaternary aminoethyl sulfuric ester=（4~8）:（6~10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:
（12~18）:（4~7）:（6~9）:（6~20）.
2. B component is made up of perlite, albite, potassium feldspar, boromagnesite, shepardite, serpentinite according to claim 1,
Perlite, albite, potassium feldspar, boromagnesite, shepardite, serpentinite 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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