CN107159257A - 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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- CN107159257A CN107159257A CN201710277067.3A CN201710277067A CN107159257A CN 107159257 A CN107159257 A CN 107159257A CN 201710277067 A CN201710277067 A CN 201710277067A CN 107159257 A CN107159257 A CN 107159257A
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- solid catalyst
- ozone heterogeneous
- heterogeneous oxidation
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 230000003647 oxidation Effects 0.000 title claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 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
- 239000004575 stone Substances 0.000 claims abstract description 13
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052900 illite Inorganic materials 0.000 claims abstract description 10
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 10
- 239000010456 wollastonite Substances 0.000 claims abstract description 10
- PALNZFJYSCMLBK-UHFFFAOYSA-K magnesium;potassium;trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-].[Cl-].[K+] PALNZFJYSCMLBK-UHFFFAOYSA-K 0.000 claims abstract description 9
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 9
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 9
- KHFLASRWTYBRDK-UHFFFAOYSA-M tributyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](CCCC)(CCCC)CCCC KHFLASRWTYBRDK-UHFFFAOYSA-M 0.000 claims abstract description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 8
- 125000003963 dichloro group Chemical group Cl* 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 8
- 229910052688 Gadolinium 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
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 claims abstract description 7
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 7
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims abstract description 6
- 229930195712 glutamate Natural products 0.000 claims abstract description 6
- DYYFBWLZDJSPGO-UHFFFAOYSA-H holmium(3+);oxalate Chemical class [Ho+3].[Ho+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DYYFBWLZDJSPGO-UHFFFAOYSA-H 0.000 claims abstract description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229960004889 salicylic acid Drugs 0.000 claims abstract description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 5
- BENADMAVJUZZBP-UHFFFAOYSA-N [O-2].C(C)(C)[Sc+2] Chemical compound [O-2].C(C)(C)[Sc+2] BENADMAVJUZZBP-UHFFFAOYSA-N 0.000 claims abstract description 5
- RKKHMLBQJFPHDF-UHFFFAOYSA-N [Os].[K].[K] Chemical compound [Os].[K].[K] RKKHMLBQJFPHDF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 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
- 239000000126 substance Substances 0.000 claims description 12
- -1 holmium oxalate Rare-earth Chemical class 0.000 claims description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 7
- 239000010970 precious metal Substances 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 241000209140 Triticum Species 0.000 claims 1
- 235000021307 Triticum Nutrition 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 235000012054 meals Nutrition 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 238000001994 activation Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 229910052693 Europium Inorganic materials 0.000 abstract description 5
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001649 bromium compounds Chemical class 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
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 2
- 150000002306 glutamic acid derivatives Chemical class 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003870 salicylic acids Chemical class 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
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- SIBSDDUAXJXGHX-UHFFFAOYSA-N CCCCCCCCCCCCBr(C)C Chemical class CCCCCCCCCCCCBr(C)C SIBSDDUAXJXGHX-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical group Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- QBRVEDGYIFXMNT-UHFFFAOYSA-N [K].[K].[Os].[Cl] Chemical compound [K].[K].[Os].[Cl] QBRVEDGYIFXMNT-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 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
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FFJMLWSZNCJCSZ-UHFFFAOYSA-N n-methylmethanamine;hydrobromide Chemical compound Br.CNC FFJMLWSZNCJCSZ-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- RWFHJEVTRVSDNX-UHFFFAOYSA-N phenol;propanoic acid Chemical compound CCC(O)=O.OC1=CC=CC=C1 RWFHJEVTRVSDNX-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 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
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- GYOFRJOMHLYJNZ-UHFFFAOYSA-N tributyl(tetradecyl)azanium Chemical compound CCCCCCCCCCCCCC[N+](CCCC)(CCCC)CCCC GYOFRJOMHLYJNZ-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J23/8946—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/06—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—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 surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Thermal Sciences (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, category environmental protection and technical field of chemical engineering catalysts.With medical stone, wollastonite, activated carbon, carnallite, illite and raphite make carrier, carrier is modified through lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add surfactant myristyl tributyl ammonium chloride and surface activation process is carried out under ul-trasonic irradiation, then activated carrier in hydrothermal reaction kettle with composite mineralizer borax and potassium sulfate, catalytic activity auxiliary agent predecessor isopropyl scandium oxide (III), three (4, 4, (2 thiophene) 1 of 4 trifluoro 1, 3 diacetyl) europium, three (2, 2, 6, 6 tetramethyls 3, 5 heptadione acid) gadolinium, ten water holmium oxalates, catalytic active center component predecessor titanocenes ring substituted salicylic acid complex, cupric glutamate, chlordene osmium dipotassium, the ammino platinum of dichloro two, hydro-thermal reaction is carried out under the effect of emulsifying agent didodecyldimethylammbromide bromide, drying removes 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
Catalyst Adsorption, makees catalytic activity auxiliary agent predecessor, normal transition Organometallic using rare earth organo-metallic compound and closes
Thing and precious metal chemical complex are made catalytic active center predecessor and contained with multicomponent porous carrier through hydro-thermal reaction, high temperature sintering preparation
The ozone Heterogeneous oxidation solid catalyst of multi-element metal has to improve the preparation method of catalyst mithridatism and catalytic activity
Larger environmental benefit and higher practical value.
The content of the invention
For existing in current ozone Heterogeneous oxidation solid catalyst preparation method, Catalyst Adsorption is relatively low, mithridatism
Poor to lose catalytic activity problem with easy, exploitation strengthens catalyst using multicomponent porous carrier through reaming, surface active
Adsorptivity, catalytic activity auxiliary agent predecessor, normal transition metallo-organic compound and expensive are made using rare earth organo-metallic compound
Metallic compound is made catalytic active center predecessor and prepared with multicomponent porous carrier through hydro-thermal reaction, high temperature sintering containing polynary gold
The ozone Heterogeneous oxidation solid catalyst of category to improve the preparation method of catalyst mithridatism and catalytic activity, it is characterized in that
Component A can be added in closed reactor and deionized water stirring prepares the aqueous solution, the weight concentration for control component A is 2%~6%,
After the completion of prepared by solution, B component is added under agitation, 35 DEG C~50 DEG C are warming up to, continues stirring reaction 3h~6h, is filtered, instead
Product is answered to obtain reaming modified support after 102 DEG C~106 DEG C dry constant weights；Reaming modified support puts into ultrasound reactor,
The aqueous solution prepared by component C and deionized water is added, the weight concentration of component C is 3%~8%, is uniformly mixed, and control is super
Sound power density is 0.3~0.8W/m3, frequency 20kHz~30kHz, 40 DEG C~55 DEG C, sonic oscillation 2h~5h obtains ultrasound
Surface active carrier mixed liquor；Ultrasonic surface activated carrier mixed liquor is transferred in hydrothermal reaction kettle, add D components and go from
The aqueous solution that sub- water is prepared, the weight concentration of D components is 40%~55%, by weight, D component deionized water solutions:Ultrasonic table
Weight ratio=1 of face activated carrier mixed liquor:（1.5~2）, control 120 DEG C~180 DEG C of temperature, the hydro-thermal reaction time be 8h~
16h, then dries to obtain fine particle；Fine particle is in Muffle furnace, 600 DEG C~950 DEG C, and calcination 3h~8h obtains ozone non-
Homogeneous oxidizing solid catalyst.The component A is made up of lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, by weight, lithium hypochlorite:
Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B component is by medical stone, wollastonite, activated carbon, carnallite, illite
, raphite composition, by weight, medical stone:Wollastonite:Activated carbon:Carnallite:Illite:The weight of raphite it
Than=（5~15）:（7~17）:（9~19）:（11~21）:（13~23）:（15~25）, by weight, component A:B component
Weight ratio=1:（10~20）, component C is myristyl tributyl ammonium chloride, by weight, component C:Reaming modified support
Weight ratio=1:（5~10）, D components are by composite mineralizer borax, potassium sulfate, catalytic activity auxiliary agent predecessor isopropyl scandium oxide
(III), three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europiums, three (DPM dpm,dipivalomethane acid)
Gadolinium, ten water holmium oxalate Rare-earth chemicals, the cyclopentadienyl of catalytic active center predecessor normal transition metallo-organic compound two
Titanacycle substituted salicylic acid complex, cupric glutamate and precious metal chemical complex chlordene osmium dipotassium, the ammino platinum of dichloro two, emulsifying agent double ten
Dialkyl dimethyl ammonium bromide is constituted, by weight, borax:Potassium sulfate:Isopropyl scandium oxide (III):Three (the fluoro- 1- of 4,4,4- tri-
(2- thiophene) -1,3- diacetyl) europium:Three (DPM dpm,dipivalomethane acid) gadoliniums:Ten water holmium oxalates:Titanocenes ring
Substituted salicylic acid complex:Cupric glutamate:Chlordene osmium dipotassium:The ammino platinum of dichloro two:The weight of didodecyldimethylammbromide bromide
The ratio between amount=（4~8）:（6~10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6
~9）:（6~20）.Medical stone, wollastonite, activated carbon, carnallite, illite, the raphite of B component carry out powder respectively
Broken, deionized water washing, which is dried, to be removed after moisture, and -200 mesh ,+400 mesh sieves point are carried out through standard screen, controls the particle diameter to be
The mm of 0.0370mm~0.0750.
What the technical method of the present invention was realized in：Lithium hypochlorite LiClO, double (second can be being added in closed reactor
Acyl acetone) beryllium C10H14BeO4The aqueous solution is prepared with deionized water stirring, it is 0.0370mm~0.0750mm to add particle diameter after screening
Medical stone, wollastonite, activated carbon, carnallite, illite and raphite porous material carrier, in certain temperature and stirring bar
Under part, the small Be of aqueous solution Ionic Radius2+（0.31Å）、Li+（0.60Å）Displace part ion radius in porous material big
Ca2+（0.99Å）、K+（1.33Å）、Ba2+（1.35Å）Plasma, the aperture of porous material carrier becomes big, surface roughness increasing
Plus, filtering dries the reaming modified support input ultrasound reactor after constant weight, adds myristyl tributyl ammonium chloride
C14H29N+(C4H9)3Cl- The aqueous solution, control ultrasonic power density, ultrasonic frequency, temperature and sonic oscillation time, in ultrasound
Under ripple cavitation, myristyl tributyl ammonium chloride C14H29N+(C4H9)3Cl- It is easy to escape into reaming modification from the aqueous solution
Carrier duct is attached to reaming modified support surface, is beneficial to being interconnected and carrier surface activation for carrier duct, enhancing
Adsorptivity；After the completion of ultrasonic activation, ultrasonic surface activated carrier mixed liquor is transferred in hydrothermal reaction kettle, with borax
Na2B4O7·10H2O, potassium sulfate K2SO4Composite mineralizer, catalytic activity auxiliary agent predecessor isopropyl scandium oxide (III) C9H21O3Sc、
Three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europium C24H18EuF9O6S3, three (2,2,6,6- tetramethyls -3,5- heptan two
Ketone acid) gadolinium C33H57GdO6, ten water holmium oxalate C6Ho2O12Rare-earth chemicals, the common mistake of catalytic active center predecessor
Cross metallo-organic compound titanocenes ring substituted salicylic acid complex (C10H10)Ti(C7H4O3), cupric glutamate C5H7NO4Cu and six
Chlorine osmium dipotassium K2OsCl6, the ammino platinum Pt (NH of dichloro two3)2Cl2Precious metal chemical complex, in the double dodecyl dimethyl bromines of emulsifying agent
Change ammonium [(C12H25)2N(CH3)2]+Br-Effect is lower to carry out hydro-thermal reaction, and mineralizer accelerates diffusion, reactant lattice is lived
Change, promote the progress of solid phase reaction, ultrasonic surface activated carrier and Rare-earth chemicals, normal transition organic metal
Compound, precious metal chemical complex Uniform Doped, it is quasi-stationary that emulsifying agent didodecyldimethylammbromide bromide forms reaction solution
Emulsion prevents separation of solid and liquid, sedimentation, while to the further surface active of porous carrier, passing through the water in certain temperature, time
Thermal response, drying obtains the fine silt thing of Uniform Doped；The fine silt thing of Uniform Doped is in Muffle furnace, through high temperature sintering, its
In organic matter carbonization further enhance the microcellular structure of porous carrier, obtain the oxidation of porous carrier supported rare earth metal
The ozone Heterogeneous oxidation solid catalyst of the catalytic active center of thing, transition metal oxide and noble metal formation, is improved
The mithridatism and catalytic activity of catalyst.
Relative to art methods, outstanding feature of the present invention is that medical stone, wollastonite, activity are used in technology of preparing
Charcoal, carnallite, illite, raphite porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) berylliums
C10H14BeO4Reaming effect, myristyl tributyl ammonium chloride C14H29N+(C4H9)3Cl-, didodecyldimethylammbromide bromide
[(C12H25)2N(CH3)2]+Br- To being interconnected and surface activation for duct；Rare earth organic metal is made by hydro-thermal reaction
Compound, normal transition metallo-organic compound and precious metal chemical complex reach Uniform Doped and are attached to carrier surface and duct
Interior, high temperature sintering makes organic matter carbonization strengthen and form multi-level microcellular structure, porous carrier supported rare earth metal
The multi-element metal catalytic active center of oxide, transition metal oxide and noble metal formation is combined more firm with porous carrier
Gu, the ozone Heterogeneous oxidation solid catalyst of preparation has a stronger adsorptivity, the cooperative effect of multi-element metal, particularly mixes
Stability and high activity that miscellaneous noble metal has, can suppress liquating out for metal catalytic activity component, improve catalyst
Mithridatism and catalytic activity, with good environmental benefit and economic benefit.
Embodiment
Embodiment 1:1.35g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 1.65g, 140ml deionized waters are added to volume for 500ml
Can be uniformly mixed in closed reactor, the weight concentration of the aqueous solution is 2.1%, lithium hypochlorite:Double (acetylacetone,2,4-pentanedione) berylliums
Weight ratio=1:1.2；Add deionized water wash to it is neutral, 103 DEG C dry and remove the mesh of -200 mesh of sieving after moisture~+400
2.75g medical stones, 3.75g wollastonites, 4.75g activated carbons, 5.75g carnallites, 6.75g illites, the 7.75g sodium boron of standard screen
The weight of Xie Shi, 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, the water that 3.25g myristyl tributyl ammonium chlorides are dissolved in 100ml deionized waters is added
Solution, the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, myristyl tributyl ammonium chloride（3.25g）:Reaming
Modified support（31g ）=1:9.5；It is 0.4 W/m to control ultrasonic power density3, ultrasonic frequency 21kHz, 41 DEG C of temperature, ultrasound
Vibrate 2.2h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor is transferred to 500ml water
In thermal response kettle, add by 2.1g boraxs, 3.05g potassium sulfates, 1.6g isopropyls scandium oxide (III), 2.05g tri- (4,4,4- tri-
Fluoro- 1- (2- thiophene) -1,3- diacetyl) europium, 2.6g tri- (DPM dpm,dipivalomethane acid) gadolinium, the water of 3.05g ten
Holmium oxalate, 5.05g titanocenes ring substituted salicylic acids complex, 6.1g cupric glutamates, 2.05g chlordene osmiums dipotassium, 3.1g dichloros two
The aqueous solution that ammino platinum, 3.05g didodecyldimethylammbromide bromides and 50ml deionized waters are prepared, the weight of the aqueous solution
Concentration is 40.3%, the weight of the aqueous solution:Weight=83.8g of ultrasonic surface activated carrier mixed liquor:134.25g =1:1.6,
125 DEG C of temperature is controlled, the hydro-thermal reaction time is 8.3h, then dries to obtain fine silt thing for 105 DEG C；Fine silt thing in Muffle furnace,
620 DEG C, calcination 3.2h after cooling down, can obtain the ozone Heterogeneous oxidation solid catalyst of fine particle shape.
Embodiment 2:0.24g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 0.36g, 10ml deionized waters, being added to volume is
100ml's can be uniformly mixed in closed reactor, and the weight concentration of the aqueous solution is 5.7%, lithium hypochlorite:Double (levulinics
Ketone) beryllium weight ratio=1:1.5；Add deionized water wash to it is neutral, 103 DEG C dry remove -200 mesh of sieving after moisture~+
The 1.45g medical stones of 400 mesh standard sieves, 1.65g wollastonites, 1.85g activated carbons, 2.05g carnallites, 2.25g illites,
The weight of 2.45g raphites, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（0.6g）:The weight of porous material（11.7g）=1:
19.5,48 DEG C are warming up to, reaming modified support 11.5g is obtained after continuing stirring reaction 5.8h, filtering, 105 DEG C of dry constant weights；
In 100ml ultrasound reactors, reaming modified support 11.5g is put into, 2.2g myristyl tributyl ammonium chlorides is added and is dissolved in
The aqueous solution of 26ml deionized waters, the weight concentration of the aqueous solution is 7.8%, is uniformly mixed, myristyl tributyl chlorination
Ammonium（2.2g）:Reaming modified support（11.5g ）=1:5.2；It is 0.7 W/m to control ultrasonic power density3, ultrasonic frequency
54 DEG C of 29kHz, temperature, sonic oscillation 4.7h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier in ultrasound reactor
Mixed liquor is transferred in 100ml hydrothermal reaction kettles, is added by 0.78g boraxs, 0.97g potassium sulfates, 0.58g isopropyl scandium oxides
(III), 0.67g tri- (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europium, (2,2,6,6- tetramethyls -3,5- of 0.78g tri-
Heptadione acid) gadolinium, the water holmium oxalates of 0.87g ten, 1.48g titanocenes ring substituted salicylic acids complex, 1.77g cupric glutamates,
0.68g chlordene osmiums dipotassium, the ammino platinum of 0.87g dichloros two, 1.98g didodecyldimethylammbromide bromides and 10ml deionized waters
The aqueous solution of preparation, the weight concentration of the aqueous solution is 53.3%, the weight of the aqueous solution:Ultrasonic surface activated carrier mixed liquor
Weight=21.43g:39.7g =1:1.9,175 DEG C of temperature is controlled, the hydro-thermal reaction time is 15.5h, is then dried for 105 DEG C
Fine silt thing；Fine silt thing is in Muffle furnace, 930 DEG C, calcination 7.5h, after cooling down, can obtain the ozone of fine particle shape
Heterogeneous oxidation solid catalyst.
Comparative example 1:Preparation process is not added with lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, myristyl tributyl ammonium chloride, double
Outside Dodecydimethylammonium bronides, borax and potassium sulfate, whole preparation process, preparation condition are identical with embodiment 1.
The parameter of ozone Heterogeneous oxidation solid catalyst prepared by embodiment 1, embodiment 2 and comparative example 1 is included in table 1.
Application Example 1:Ozone Heterogeneous oxidation solid catalyst point prepared by embodiment 1, embodiment 2 and comparative example 1
The waste water progress ozone for being used for ethylenediamine, 4,4 '-diaminourea acardite and the preparation of para hydroxybenzene propionic acid under the same conditions is non-
Homogeneous oxidizing processing.Treatment conditions are：Rate of charge=1000L of organic wastewater and catalyst:1g, organic wastewater CODCrValue
976.0mg/L, ozone dosage 80mg/L, processing time 1hr, ozone tail gas KI solution absorption detecting ozone utilization rates.Examination
Test data and be included in table 2.
The embodiment of table 1 and comparative example prepare ozone Heterogeneous oxidation solid catalysis agent parameter
The ozone Heterogeneous oxidation solid catalyst Application Example of table 2
Claims (2)
1. a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, it is characterized in that A groups can added in closed reactor
Divide and deionized water stirring prepares the aqueous solution, the weight concentration for controlling component A is 2%~6%, after the completion of prepared by solution, in stirring
Lower addition B component, is warming up to 35 DEG C~50 DEG C, continues stirring reaction 3h~6h, and filtering, reaction product is dry at 102 DEG C~106 DEG C
Reaming modified support is obtained after dry constant weight, reaming modified support input ultrasound reactor, addition is matched somebody with somebody by component C and deionized water
The aqueous solution of system, the weight concentration of component C is 3%~8%, is uniformly mixed, and it is 0.3~0.8W/ to control ultrasonic power density
m3, frequency 20kHz~30kHz, 40 DEG C~55 DEG C, sonic oscillation 2h~5h obtains ultrasonic surface activated carrier mixed liquor, transfer
Into hydrothermal reaction kettle, the aqueous solution that D components and deionized water are prepared is added, the weight concentration of D components is 40%~55%, is pressed
Weight meter, D component deionized water solutions:Weight ratio=1 of ultrasonic surface activated carrier mixed liquor:（1.5~2）, control temperature
120 DEG C~180 DEG C, the hydro-thermal reaction time is 8h~16h, then dries to obtain fine silt thing, fine silt thing is in Muffle furnace, 600
DEG C~950 DEG C, calcination 3h~8h obtains ozone Heterogeneous oxidation solid catalyst；The component A is by lithium hypochlorite, double (acetyl
Acetone) beryllium composition, by weight, lithium hypochlorite:Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B component is by wheat meal
Stone, wollastonite, activated carbon, carnallite, illite, raphite composition, by weight, medical stone:Wollastonite:Activated carbon:Light
Halogen stone:Illite:The weight ratio of raphite=（5~15）:（7~17）:（9~19）:（11~21）:（13~23）:（15
~25）, by weight, component A:Weight ratio=1 of B component:（10~20）, component C is myristyl tributyl ammonium chloride,
By weight, component C:Weight ratio=1 of reaming modified support:（5~10）, D components by composite mineralizer borax, potassium sulfate,
Catalytic activity auxiliary agent predecessor isopropyl scandium oxide (III), three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europiums, three
(2,2,6,6- tetramethyl -3,5- heptadione acid) gadolinium, ten water holmium oxalate Rare-earth chemicals, catalytic active center forerunner
Thing normal transition metallo-organic compound titanocenes ring substituted salicylic acid complex, cupric glutamate and precious metal chemical complex chlordene osmium
Dipotassium, the ammino platinum of dichloro two, emulsifying agent didodecyldimethylammbromide bromide composition, by weight, borax:Potassium sulfate:Isopropyl
Scandium oxide (III):Three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europiums:Three (2,2,6,6- tetramethyls -3,5- heptan
Two ketone acids) gadolinium:Ten water holmium oxalates:Titanocenes ring substituted salicylic acid complex:Cupric glutamate:Chlordene osmium dipotassium:The ammino of dichloro two
Platinum:The weight ratio of didodecyldimethylammbromide bromide=（4~8）:（6~10）:（3~6）:（4~7）:（5~8）:（6~
9）:（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.
2. B component is by medical stone, wollastonite, activated carbon, carnallite, illite, raphite group according to claim 1
Into medical stone, wollastonite, activated carbon, carnallite, illite, raphite are crushed respectively, and deionized water washing drying is removed
Go after moisture, sieved through standard screen, it is 0.0370mm~0.0750mm to control particle diameter.
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