CN107159248A - 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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- CN107159248A CN107159248A CN201710275852.5A CN201710275852A CN107159248A CN 107159248 A CN107159248 A CN 107159248A CN 201710275852 A CN201710275852 A CN 201710275852A CN 107159248 A CN107159248 A CN 107159248A
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- ozone heterogeneous
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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 15
- 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 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004575 stone Substances 0.000 claims abstract description 13
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000019362 perlite Nutrition 0.000 claims abstract description 12
- UTPOUAZEFGTYAY-UHFFFAOYSA-N azanium;2-chloroacetate Chemical compound [NH4+].[O-]C(=O)CCl UTPOUAZEFGTYAY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010881 fly ash Substances 0.000 claims abstract description 11
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 10
- 229910052656 albite Inorganic materials 0.000 claims abstract description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- 239000010451 perlite Substances 0.000 claims abstract description 10
- 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 9
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 9
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000002253 acid Substances 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
- 235000000193 zinc lactate Nutrition 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 229910021538 borax Inorganic materials 0.000 claims abstract description 7
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940009662 edetate Drugs 0.000 claims abstract description 6
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 6
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 6
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 6
- 229940050168 zinc lactate Drugs 0.000 claims abstract description 6
- 239000011576 zinc lactate Substances 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- AUZRORBINHVFFD-UHFFFAOYSA-N [Rh]N=O Chemical compound [Rh]N=O AUZRORBINHVFFD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 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
- 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 3
- 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
- 239000007864 aqueous solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- -1 (trifluoromethanesulfonimide) ytterbium Rare-earth Chemical class 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 125000005594 diketone group Chemical group 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000010970 precious metal Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- OLGPDUKUFCIQPH-UHFFFAOYSA-N [Na].[Na].[Na].N(=O)[Rh] Chemical compound [Na].[Na].[Na].N(=O)[Rh] OLGPDUKUFCIQPH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 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 description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- 229940070765 laurate Drugs 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-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
- 239000007795 chemical reaction product Substances 0.000 claims 1
- YNSGBSGCDQPURD-UHFFFAOYSA-N dodecanoic acid;n-methylmethanamine Chemical compound CNC.CCCCCCCCCCCC(O)=O YNSGBSGCDQPURD-UHFFFAOYSA-N 0.000 claims 1
- 150000002902 organometallic compounds Chemical class 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- 238000001994 activation Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- CLLQMAZYHOHLEQ-UHFFFAOYSA-N dodecanoate;1-hydroxyethyl(dimethyl)azanium Chemical compound CC(O)[NH+](C)C.CCCCCCCCCCCC([O-])=O CLLQMAZYHOHLEQ-UHFFFAOYSA-N 0.000 abstract description 6
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052692 Dysprosium Inorganic materials 0.000 abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000003245 coal Substances 0.000 abstract 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 5
- 150000002910 rare earth metals Chemical class 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
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- FLNKWZNWHZDGRT-UHFFFAOYSA-N azane;dihydrochloride Chemical compound [NH4+].[NH4+].[Cl-].[Cl-] FLNKWZNWHZDGRT-UHFFFAOYSA-N 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
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229940048820 edetates Drugs 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- ILRLTAZWFOQHRT-UHFFFAOYSA-N potassium;sulfuric acid Chemical compound [K].OS(O)(=O)=O ILRLTAZWFOQHRT-UHFFFAOYSA-N 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- TZIZDKHKROKBAJ-UHFFFAOYSA-N [Rh].[Na].[Na].[Na] Chemical compound [Rh].[Na].[Na].[Na] TZIZDKHKROKBAJ-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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- IOIFRTZBJMZZFO-UHFFFAOYSA-N dysprosium(3+) Chemical compound [Dy+3] IOIFRTZBJMZZFO-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical class CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 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
- 239000010948 rhodium Substances 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
- 241000894007 species Species 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- 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
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
-
- B01J35/60—
-
- 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
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 perlite, albite, kaolin, red metal and stone, flyash and taking coal gangue as carrier are after lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add N octadecyldimethyl N ' thmethylpropyl dichloride ammoniums and activation process is carried out under ul-trasonic irradiation, then carrier in hydrothermal reaction kettle with composite mineralizer borax and potassium sulfate, catalytic activity auxiliary agent predecessor 1, 1, 1 trifluoroacetylacetone (TFA) neodymium, three (2, 2, 6, 6 tetramethyls 3, 5 heptadione acid) gadolinium, three (6, 6, 7, 7, 8, 8, 8 seven fluorine 2, 2 dimethyl 3, 5 octene diketone) dysprosium (III), three (trifluoromethanesulfonimide) ytterbiums, catalytic active center predecessor cobalt edetate, citric acid nickel, zinc lactate and six nitroso rhodium trisodiums, hydro-thermal reaction is carried out under the effect of emulsifying agent laurate dimethylamino-ethanol ester ammonium chloroacetate, drying is removed after moisture, calcination obtains ozone Heterogeneous oxidation solid catalyst in Muffle furnace.
Description
Technical field
The present invention relates to a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, category environmental protection and chemical catalyst skill
Art field.
Background technology
Ozonation technology using ozone oxidation ability it is strong the characteristics of, can be by many organic pollution oxidation Decompositions, extensively
For wastewater treatment.Catalytic ozonation technology is divided into ozone homogeneous catalytic oxidation and ozone heterogeneous catalytic oxidation, and ozone is equal
Phase catalysis oxidation has that the more difficult separation and recovery of catalyst is reused, ozone utilization rate is low causes water process operating cost higher,
Organic pollutant removal rate is relatively low simultaneously and easily causing secondary pollution of water is limited to its application；Ozone heterogeneous catalysis oxygen
There is change technology catalyst to be easily isolated and recycled and reusable, ozone utilization rate is high, organic pollutant removal rate is higher, drop
Low water process operating cost and receive significant attention its application the advantages of do not result in secondary pollution.Ozone heterogeneous catalysis
It is to reach local organic matter enrichment by catalyst surface absorption organic matter that oxidation of organic compounds, which is decomposed, while ozone molecule absorption exists
The hydroxyl radical free radical that catalyst surface produces high activity under catalyst action decomposes organic matter.Ozone heterogeneous catalytic oxidation
Handle in waste water technology, core technology is the preparation of ozone Heterogeneous oxidation solid catalyst.
Ozone Heterogeneous oxidation solid catalyst is generally made up of carrier, activated centre and auxiliary agent.Due to being polluted in waste water
Species are various, complex chemical composition feature, can produce harmful effect to performance such as absorption, the mithridatism of catalyst.
Prepare that the carrier structure that ozone Heterogeneous oxidation solid catalyst uses is more single at present, adsorptivity is relatively low；Activated centre is universal
Using normal transition metal salt, mithridatism is poor；Preparation method mainly has infusion process, the precipitation method, mixing method and collosol and gel etc.
Method attachment activity center and adjuvant component are easily liquated out in carrier surface, activated centre and adjuvant component, cause catalyst
Easily lose catalytic activity.For exist in current ozone Heterogeneous oxidation solid catalyst preparation method Catalyst Adsorption compared with
Low, mithridatism is poor and easily loses catalytic activity problem, and exploitation is strengthened using multicomponent porous carrier through reaming, surface active
The adsorptivity of catalyst, catalytic activity auxiliary agent predecessor, normal transition Organometallic are made using Rare-earth chemicals
Compound and precious metal chemical complex are made catalytic active center predecessor and prepared with multicomponent porous carrier through hydro-thermal reaction, high temperature sintering
Ozone Heterogeneous oxidation solid catalyst containing multi-element metal has to improve the preparation method of catalyst mithridatism and catalytic activity
There are larger environmental benefit and higher practical value.
The content of the invention
For existing in current ozone Heterogeneous oxidation solid catalyst preparation method, Catalyst Adsorption is relatively low, mithridatism
Poor to lose catalytic activity problem with easy, exploitation strengthens catalyst using multicomponent porous carrier through reaming, surface active
Adsorptivity, catalytic activity auxiliary agent predecessor, normal transition metallo-organic compound and expensive are made using Rare-earth chemicals
Metallic compound is made catalytic active center predecessor and prepared with multicomponent porous carrier through hydro-thermal reaction, high temperature sintering containing polynary gold
The ozone Heterogeneous oxidation solid catalyst of category to improve the preparation method of catalyst mithridatism and catalytic activity, it is characterized in that
Component A can be added in closed reactor and deionized water stirring prepares the aqueous solution, the weight concentration for control component A is 2%~6%,
After the completion of prepared by solution, B component is added under agitation, 35 DEG C~50 DEG C are warming up to, continues stirring reaction 3h~6h, is filtered, instead
Product is answered to obtain reaming modified support after 102 DEG C~106 DEG C dry constant weights；Reaming modified support puts into ultrasound reactor,
The aqueous solution prepared by component C and deionized water is added, the weight concentration of component C is 3%~8%, is uniformly mixed, and control is super
Sound power density is 0.3~0.8W/m3, frequency 20kHz~30kHz, 40 DEG C~55 DEG C, sonic oscillation 2h~5h obtains ultrasound
Surface active carrier mixed liquor；Ultrasonic surface activated carrier mixed liquor is transferred in hydrothermal reaction kettle, add D components and go from
The aqueous solution that sub- water is prepared, the weight concentration of D components is 40%~55%, by weight, D component deionized water solutions:Ultrasonic table
Weight ratio=1 of face activated carrier mixed liquor:（1.5~2）, control 120 DEG C~180 DEG C of temperature, the hydro-thermal reaction time be 8h~
16h, then dries to obtain fine particle；Fine particle is in Muffle furnace, 600 DEG C~950 DEG C, and calcination 3h~8h obtains ozone non-
Homogeneous oxidizing solid catalyst.The component A is made up of lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, by weight, lithium hypochlorite:
Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B component is by perlite, albite, kaolin, red metal and stone, fine coal
Ash, gangue composition, by weight, perlite:Albite:Kaolin:Red metal and stone:Flyash:The weight ratio of gangue=（5
~15）:（7~17）:（9~19）:（11~21）:（13~23）:（15~25）, by weight, component A:The weight of B component it
Than=1:（10~20）, component C is N- octadecyldimethyls-N '-trimethyl-propyl dichloride ammonium, by weight, component C:
Weight ratio=1 of reaming modified support:（5~10）, D components are before composite mineralizer borax, potassium sulfate, catalytic activity auxiliary agent
Drive thing 1,1,1- trifluoroacetylacetone (TFA)s neodymium, three (DPM dpm,dipivalomethane acid) gadoliniums, three (6,6,7,7,8,8,8-
Seven fluoro- 2,2- dimethyl -3,5- octenes diketone) dysprosium (III), three (trifluoromethanesulfonimide) ytterbium rare earth metal organic compounds
Thing, catalytic active center predecessor normal transition metallo-organic compound cobalt edetate, citric acid nickel, zinc lactate and noble metal
The nitroso rhodium trisodium of compound six, emulsifying agent laurate dimethylamino-ethanol ester ammonium chloroacetate composition, by weight, borax:Sulphur
Sour potassium:1,1,1- trifluoroacetylacetone (TFA) neodymiums:Three (DPM dpm,dipivalomethane acid) gadoliniums:Three (6,6,7,7,8,8,8-
Seven fluoro- 2,2- dimethyl -3,5- octenes diketone) dysprosium (III):Three (trifluoromethanesulfonimide) ytterbiums:Cobalt edetate:Lemon
Sour nickel:Zinc lactate:Six nitroso rhodium trisodiums:The weight ratio of laurate dimethylamino-ethanol ester ammonium chloroacetate=（4~8）:（6~
10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.The B
Perlite, albite, kaolin, red metal and stone, flyash, the gangue of component are crushed respectively, deionized water washing drying
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, kaolin, red metal and stone, flyash and gangue 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 N- octadecyldimethyls-N '-front three
Base-propyl group dichloride ammonium C18H37N+(CH3)2CH2CH2CH2N+(CH3)3Cl2 - The aqueous solution, control ultrasonic power density, ultrasonic wave
Frequency, temperature and sonic oscillation time, under ultrasonic cavitation effect, N- octadecyldimethyls-N '-trimethyl-propyl two
Ammonium chloride C18H37N+(CH3)2CH2CH2CH2N+(CH3)3Cl2 - It is easy to escape into reaming modified support duct or attached from the aqueous solution
On reaming modified support surface, be beneficial to being interconnected and carrier surface activation for carrier duct, enhance adsorptivity；Ultrasound
After the completion of activation, ultrasonic surface activated carrier mixed liquor is transferred in hydrothermal reaction kettle, with borax Na2B4O7·10H2O, sulfuric acid
Potassium K2SO4Composite mineralizer, the trifluoroacetylacetone (TFA) neodymium C of catalytic activity auxiliary agent predecessor 1,1,1-15H12F9NdO6, three (2,2,6,6-
Tetramethyl -3,5- heptadione acid) gadolinium C33H57GdO6, three (the fluoro- 2,2- dimethyl -3,5- octenes two of 6,6,7,7,8,8,8- seven
Ketone) dysprosium (III) C30H30DyF21O6, three (trifluoromethanesulfonimide) ytterbium [(CF3SO2)2N]3Yb Rare-earth chemicals,
Catalytic active center component predecessor normal transition metallo-organic compound cobalt edetate C12H22O14Co, citric acid nickel C12H10
O14Ni3, zinc lactate C6H10O6Zn and six nitroso rhodium trisodium Na3Rh(NO2)6Precious metal chemical complex, in emulsifying agent laurate diformazan
Aminoethanol ester ammonium chloroacetate C11H23COOCH2CH2N+(CH3)2Cl-CHCOOH effects are lower to carry out hydro-thermal reaction, and mineralizer accelerates
Diffusion, make reactant lattice activate, promote the progress of solid phase reaction, ultrasonic surface activated carrier and rare earth metal are organic
Compound, normal transition metallo-organic compound, precious metal chemical complex Uniform Doped, emulsifying agent laurate dimethylamino-ethanol ester
Ammonium chloroacetate make reaction solution formed quasi-stationary emulsion prevent separation of solid and liquid, sedimentation, while to the further surface of porous carrier
Activation, by the way that in certain temperature, the hydro-thermal reaction of time, drying obtains the fine silt thing of Uniform Doped；The fine powder of Uniform Doped
Grain thing is in Muffle furnace, and through high temperature sintering, organic matter carbonization therein further enhances the microcellular structure of porous carrier,
Obtain the ozone of the catalytic active center of porous carrier supported rare earth metal oxide, transition metal oxide and noble metal formation
Heterogeneous oxidation solid catalyst, improves the mithridatism and catalytic activity of catalyst.
Relative to art methods, outstanding feature of the present invention is that perlite, albite, kaolinite are used in technology of preparing
Native, red metal and stone, flyash, gangue porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) berylliums
C10H14BeO4Reaming effect, N- octadecyldimethyls-N '-trimethyl-propyl dichloride ammonium C18H37N+(CH3)2CH2CH2CH2N+(CH3)3Cl2 -, laurate dimethylamino-ethanol ester ammonium chloroacetate C11H23COOCH2CH2N+(CH3)2Cl-CHCOOH
To being interconnected and surface activation for duct；Rare-earth chemicals, normal transition metal are made by hydro-thermal reaction
Organic compound and precious metal chemical complex reach Uniform Doped and are attached in carrier surface and duct that high temperature sintering makes organic matter
Multi-level microcellular structure, porous carrier supported rare earth metal oxide, transiting metal oxidation are strengthened and formd in carbonization
Thing and the multi-element metal catalytic active center of noble metal formation are combined more firm, the heterogeneous oxygen of ozone of preparation with porous carrier
Changing solid catalyst has stronger adsorptivity, and the cooperative effect of multi-element metal, the noble metal of particularly doping have stability
And high activity, liquating out for metal catalytic activity component can be suppressed, the mithridatism and catalytic activity of catalyst is improved, have
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 kaolin, the red metals and stones of 5.75g, 6.75g flyash, the 7.75g bastard coals of standard screen
The weight of stone, 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, 3.25gN- octadecyldimethyls-N '-trimethyl-propyl dichloride ammonium is added molten
In the aqueous solution of 100ml deionized waters, the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, N- hexadecyldimethylamines
Base-N '-trimethyl-propyl dichloride ammonium（3.25g）:Reaming modified support（31g ）=1:9.5；The ultrasonic power density is controlled to be
0.4 W/m3, ultrasonic frequency 21kHz, 41 DEG C of temperature, sonic oscillation 2.2h；After the completion of ultrasonic activation, ultrasound reactor
In ultrasonic surface activated carrier mixed liquor be transferred in 500ml hydrothermal reaction kettles, add by 2.1g boraxs, 3.05g sulfuric acid
Potassium, 1.6g1,1,1- trifluoroacetylacetone (TFA)s neodymium, 2.05g tri- (DPM dpm,dipivalomethane acid) gadolinium, 2.6g tri- (6,
The fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,7,7,8,8,8- seven) dysprosium (III), 3.05g tri- (trifluoromethanesulfonimide)
Ytterbium, 5.05g cobalt edetates, 6.1g citric acids nickel, 2.05g zinc lactates, the nitroso rhodium trisodiums of 3.1g six, 3.05g laurate two
The aqueous solution that methyl aminoethanol ester ammonium chloroacetate and 50ml deionized waters are prepared, the weight concentration of the aqueous solution is 40.3%, should
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 is in Muffle furnace, 620 DEG C, calcination 3.2h,
After cooling down, the ozone Heterogeneous oxidation solid catalyst of fine particle shape can obtain.
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 kaolin, the red metals and stones of 2.05g, 2.25g flyash,
The weight of 2.45g gangues, 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, 2.2gN- octadecyldimethyls-N '-front three is added
Base-propyl group dichloride ammonium 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, N- octadecyldimethyls-N '-trimethyl-propyl dichloride ammonium（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 is completed
Afterwards, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor is transferred in 100ml hydrothermal reaction kettles, add by
0.78g boraxs, 0.97g potassium sulfates, 0.58g1,1,1- trifluoroacetylacetone (TFA)s neodymium, 0.67g tri- (2,2,6,6- tetramethyls -3,5- heptan
Two ketone acids) gadolinium, 0.78g tri- (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosium (III), 0.87g tri-
(trifluoromethanesulfonimide) ytterbium, 1.48g cobalt edetates, 1.77g citric acids nickel, 0.68g zinc lactates, the nitrosos of 0.87g six
The aqueous solution that rhodium trisodium, 1.98g laurate dimethylamino-ethanol ester ammonium chloroacetate and 10ml deionized waters are prepared, the aqueous solution
Weight concentration is 53.3%, the weight of the aqueous solution:Weight=21.43g of ultrasonic surface activated carrier mixed liquor:39.7g =1:
1.9,175 DEG C of temperature is controlled, the hydro-thermal reaction time is 15.5h, then dries to obtain fine silt thing for 105 DEG C；Fine silt thing is in Muffle
In stove, 930 DEG C, calcination 7.5h after cooling down, can 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, N- octadecyldimethyls-N '-front three
Outside base-propyl group dichloride ammonium, laurate dimethylamino-ethanol ester ammonium chloroacetate, 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 | 4.535 | 0.6047 | 793.27 |
| Embodiment 2 | 4.044 | 0.5557 | 690.01 |
| Comparative example 1 | 2.083 | 0.3087 | 491.41 |
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, kaolin, red metal and stone, flyash, gangue, by weight, perlite:Albite:Kaolinite
Soil:Red metal and stone:Flyash:The weight ratio of gangue=（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 be N- octadecyldimethyls-
N '-trimethyl-propyl dichloride ammonium, by weight, component C:Weight ratio=1 of reaming modified support:（5~10）, D components
By composite mineralizer borax, potassium sulfate, the trifluoroacetylacetone (TFA) neodymium of catalytic activity auxiliary agent predecessor 1,1,1-, three (2,2,6,6- tetra-
Methyl -3,5- heptadione acid) gadolinium, three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosiums (III),
Three (trifluoromethanesulfonimide) ytterbium Rare-earth chemicals, catalytic active center predecessor normal transition Organometallic
Compound cobalt edetate, citric acid nickel, zinc lactate and the nitroso rhodium trisodium of precious metal chemical complex six, emulsifying agent laurate dimethylamine
Base ethanol ester ammonium chloroacetate is constituted, by weight, borax:Potassium sulfate:1,1,1- trifluoroacetylacetone (TFA) neodymiums:Three (2,2,6,6- tetra-
Methyl -3,5- heptadione acid) gadolinium:Three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosiums (III):
Three (trifluoromethanesulfonimide) ytterbiums:Cobalt edetate:Citric acid nickel:Zinc lactate:Six nitroso rhodium trisodiums:Laurate dimethylamine
The weight ratio of base ethanol ester ammonium chloroacetate=（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, kaolin, red metal and stone, flyash, gangue according to claim 1,
Perlite, albite, kaolin, red metal and stone, flyash, gangue 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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