CN107020110A - The preparation method of ozone Heterogeneous oxidation solid catalyst - Google Patents
The preparation method of ozone Heterogeneous oxidation solid catalyst Download PDFInfo
- Publication number
- CN107020110A CN107020110A CN201710274717.9A CN201710274717A CN107020110A CN 107020110 A CN107020110 A CN 107020110A CN 201710274717 A CN201710274717 A CN 201710274717A CN 107020110 A CN107020110 A CN 107020110A
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- weight
- component
- solid catalyst
- ammonium
- ozone heterogeneous
- Prior art date
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 230000003647 oxidation Effects 0.000 title claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 26
- 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 44
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- -1 β hydroxyethyl Chemical group 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 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
- 150000002148 esters Chemical class 0.000 claims abstract description 11
- 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 11
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 10
- UTPOUAZEFGTYAY-UHFFFAOYSA-N azanium;2-chloroacetate Chemical compound [NH4+].[O-]C(=O)CCl UTPOUAZEFGTYAY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 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
- 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
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 8
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000000193 zinc lactate Nutrition 0.000 claims abstract description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 7
- 229910021538 borax Inorganic materials 0.000 claims abstract description 7
- 125000003963 dichloro group Chemical group Cl* 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 7
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 6
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 6
- IXXUIPAFWUIKHO-UHFFFAOYSA-N hexadecanoate;1-hydroxyethyl(dimethyl)azanium Chemical compound CC(O)[NH+](C)C.CCCCCCCCCCCCCCCC([O-])=O IXXUIPAFWUIKHO-UHFFFAOYSA-N 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
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052773 Promethium Inorganic materials 0.000 claims abstract description 5
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 5
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 229940009662 edetate Drugs 0.000 claims abstract description 5
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims abstract description 5
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 230000007704 transition Effects 0.000 claims description 7
- 239000000203 mixture Substances 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
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- 235000021314 Palmitic acid Nutrition 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229960002887 deanol Drugs 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 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
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 2
- 241001614291 Anoplistes Species 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 7
- 238000001994 activation Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 229940063953 ammonium lauryl sulfate Drugs 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 abstract description 2
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 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
- 239000011148 porous material Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000003643 water by type Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 5
- 235000011130 ammonium sulphate Nutrition 0.000 description 5
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- YPUOTXOJCHHZIY-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;ytterbium(3+) Chemical compound [Yb+3].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YPUOTXOJCHHZIY-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229940048820 edetates Drugs 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 238000006385 ozonation reaction Methods 0.000 description 2
- 150000002943 palmitic acids Chemical class 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 241001163600 Bathylaco nigricans Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- ZPLZRFVRRLTMEY-UHFFFAOYSA-N hexadecanoic acid N-methylmethanamine Chemical compound C(CCCCCCCCCCCCCCC)(=O)O.CNC ZPLZRFVRRLTMEY-UHFFFAOYSA-N 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
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- PWWGCBMGIAPMHQ-UHFFFAOYSA-N thulium(3+) Chemical compound [Tm+3] PWWGCBMGIAPMHQ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
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- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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Abstract
The present invention relates to a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, category environmental protection and technical field of chemical engineering catalysts.With activated carbon, carnallite, kaolin, red metal and stone, basalt and astrakanite make carrier after lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add surfactant β hydroxyethyl dimethyls ammonium lauryl sulfate and activation process is carried out under ul-trasonic irradiation, then carrier in hydrothermal reaction kettle with composite mineralizer borax and potassium sulfate, the cyclopentadiene promethium of catalytic activity auxiliary agent predecessor three, three (2, 2, 6, 6 tetramethyls 3, 5 heptadione acid) gadolinium, trifluoromethayl sulfonic acid thulium (III), three (trifluoromethanesulfonimide) ytterbiums, catalytic active center predecessor cobalt edetate, zinc lactate, zirconium carbonate ammonium and the ammino palladium of dichloro four, hydro-thermal reaction is carried out under the effect of emulsifying agent palmitic acid 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 activated carbon, carnallite, kaolin, red metal and stone, the Black Warrior
Rock, astrakanite composition, by weight, activated carbon:Carnallite:Kaolin:Red metal and stone:Basalt:The weight of astrakanite 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 beta-hydroxyethyl dimethyl dodecyl base ammonium sulfate, by weight, component C:Reaming changes
Weight ratio=1 of property carrier:（5~10）, D components are by composite mineralizer borax, potassium sulfate, catalytic activity auxiliary agent predecessor three
Cyclopentadiene promethium, three (DPM dpm,dipivalomethane acid) gadoliniums, trifluoromethayl sulfonic acid thulium (III), three (fluoroforms
Sulfimide) ytterbium Rare-earth chemicals, catalytic active center predecessor normal transition metallo-organic compound glucose
Sour cobalt, zinc lactate, zirconium carbonate ammonium and the ammino palladium of precious metal chemical complex dichloro four, emulsifying agent palmitic acid dimethylamino-ethanol ester chloroethene
Sour ammonium composition, by weight, borax:Potassium sulfate:Three cyclopentadiene promethiums:Three (DPM dpm,dipivalomethane acid)
Gadolinium:Trifluoromethayl sulfonic acid thulium (III):Three (trifluoromethanesulfonimide) ytterbiums:Cobalt edetate:Zinc lactate:Zirconium carbonate ammonium:Dichloro
Four ammino palladiums:The weight ratio of palmitic acid 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）.Activated carbon, the light of the B component
Halogen stone, kaolin, red metal and stone, basalt, astrakanite are crushed respectively, and deionized water washing, which is dried, to be removed after moisture, warp
Standard screen carries out -200 mesh ,+400 mesh sieves point, and 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
Activated carbon, carnallite, kaolin, red metal and stone, basalt and astrakanite 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 beta-hydroxyethyl dimethyl dodecyl base
Ammonium sulfate [C12H25N(CH3)2CH2CH2OH]+CH3SO4 -The aqueous solution, controls ultrasonic power density, ultrasonic frequency, temperature and surpasses
The sound oscillation time, under ultrasonic cavitation effect, beta-hydroxyethyl dimethyl dodecyl base ammonium sulfate [C12H25N(CH3)2CH2CH2OH]+CH3SO4 -It is easy to escape into reaming modified support duct from the aqueous solution or is attached to reaming modified support surface,
It is beneficial to being interconnected and carrier surface activation for carrier duct, enhances adsorptivity；After the completion of ultrasonic activation, ultrasonic surface is lived
Change carrier mixed liquor to be transferred in hydrothermal reaction kettle, with borax Na2B4O7·10H2O, potassium sulfate K2SO4Composite mineralizer, catalysis
The cyclopentadiene promethium Pm (C of coagent predecessor three5H5)3, three (DPM dpm,dipivalomethane acid) gadolinium C33H57GdO6、
Trifluoromethayl sulfonic acid thulium (III) C3F9O9S3Tm, three (trifluoromethanesulfonimide) ytterbium [(CF3SO2)2N]3Yb rare earth metals are organic
Compound, catalytic active center component predecessor normal transition metallo-organic compound cobalt edetate C12H22O14Co, zinc lactate
C6H10O6Zn, zirconium carbonate ammonium (NH4)2·C2H2O8The Zr and ammino palladium Pd (NH of dichloro four3)4Cl2Precious metal chemical complex, in emulsifying agent
Palmitic acid dimethylamino-ethanol ester ammonium chloroacetate C16H33COOCH2CH2N+(CH3)2Cl-CHCOOH carries out hydro-thermal reaction, ore deposit under
Agent accelerates diffusion, activates reactant lattice, promotes the progress of solid phase reaction, ultrasonic surface activated carrier and rare earth
Metallo-organic compound, normal transition metallo-organic compound, precious metal chemical complex Uniform Doped, emulsifying agent palmitic acid dimethylamine
Base ethanol ester ammonium chloroacetate make reaction solution formed quasi-stationary emulsion prevent separation of solid and liquid, sedimentation, while entering to porous carrier
One step surface active, by the way that in certain temperature, the hydro-thermal reaction of time, drying obtains the fine silt thing of Uniform Doped；Uniformly mix
Miscellaneous fine silt thing is in Muffle furnace, through high temperature sintering, and organic matter carbonization therein further enhances porous carrier
Microcellular structure, obtains the catalytic activity of porous carrier supported rare earth metal oxide, transition metal oxide and noble metal formation
The ozone Heterogeneous oxidation solid catalyst at center, improves the mithridatism and catalytic activity of catalyst.
Relative to art methods, outstanding feature of the present invention is that activated carbon, carnallite, kaolinite are used in technology of preparing
Native, red metal and stone, basalt, astrakanite porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) berylliums
C10H14BeO4Reaming effect, beta-hydroxyethyl dimethyl dodecyl base ammonium sulfate [C12H25N(CH3)2CH2CH2OH]+CH3SO4 -, palm fibre
Palmitic acid acid dimethylamino-ethanol ester ammonium chloroacetate C16H33COOCH2CH2N+(CH3)2Cl-CHCOOH is interconnected and surface to duct
Activation；Rare-earth chemicals, normal transition metallo-organic compound and noble metal chemical combination are made by hydro-thermal reaction
Thing reaches Uniform Doped and is attached in carrier surface and duct that high temperature sintering makes organic matter carbonization strengthen and form many
The microcellular structure of level, the polynary gold of porous carrier supported rare earth metal oxide, transition metal oxide and noble metal formation
Category catalytic active center is combined more firm with porous carrier, and the ozone Heterogeneous oxidation solid catalyst of preparation has stronger
Adsorptivity, the cooperative effect of multi-element metal, the noble metal of particularly doping have stability and high activity, can suppress metal and urge
Change liquating out for active component, improve the mithridatism and catalytic activity of catalyst, with good environmental benefit and economic effect
Benefit.
Embodiment
Embodiment 1:1.35g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 1.65g, 140ml deionized waters, being added to volume is
500ml's can be uniformly mixed in closed reactor, and the weight concentration of the aqueous solution is 2.1%, lithium hypochlorite:Double (levulinics
Ketone) beryllium weight ratio=1:1.2；Add deionized water wash to it is neutral, 103 DEG C dry remove -200 mesh of sieving after moisture~+
The 2.75g activated carbons of 400 mesh standard sieves, 3.75g carnallites, 4.75g kaolin, the red metals and stones of 5.75g, 6.75g basalt,
The weight of 7.75g astrakanites, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（3g）:The weight of porous material（31.5g）=1:
10.5,36 DEG C are warming up to, reaming modified support 31g is obtained after continuing stirring reaction 3.2h, filtering, 103 DEG C of dry constant weights；
In 500ml ultrasound reactors, reaming modified support 31g is put into, 3.25g beta-hydroxyethyl dimethyl dodecyl base sulfuric acid is added
Ammonium is dissolved in the aqueous solution of 100ml deionized waters, and the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, beta-hydroxyethyl two
Methyl ammonium lauryl sulfate（3.25g）:Reaming modified support（31g ）=1:9.5；It is 0.4 W/ to control ultrasonic power density
m3, ultrasonic frequency 21kHz, 41 DEG C of temperature, sonic oscillation 2.2h；After the completion of ultrasonic activation, super in ultrasound reactor
Sound surface active carrier mixed liquor is transferred in 500ml hydrothermal reaction kettles, is added by 2.1g boraxs, 3.05g potassium sulfates, 1.6g
Three cyclopentadiene promethiums, 2.05g tri- (DPM dpm,dipivalomethane acid) gadolinium, 2.6g trifluoromethayl sulfonic acids thulium (III),
3.05g tri- (trifluoromethanesulfonimide) ytterbium, 5.05g cobalt edetates, 6.1g zinc lactates, 2.05g zirconium carbonate ammoniums, 3.1g bis-
The aqueous solution that the ammino palladium of chlorine four, 3.05g palmitic acids dimethylamino-ethanol ester ammonium chloroacetate and 50ml deionized waters are prepared, this is water-soluble
The weight concentration of liquid 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 is in horse
Not in stove, 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 activated carbons of 400 mesh standard sieves, 1.65g carnallites, 1.85g kaolin, the red metals and stones of 2.05g, 2.25g basalt,
The weight of 2.45g astrakanites, 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 beta-hydroxyethyl dimethyl dodecyl base sulphur is added
Sour ammonium is dissolved in the aqueous solution of 26ml deionized waters, and the weight concentration of the aqueous solution is 7.8%, is uniformly mixed, beta-hydroxyethyl two
Methyl ammonium lauryl sulfate（2.2g）:Reaming modified support（11.5g ）=1:5.2；It is 0.7 W/ to control ultrasonic power density
m3, ultrasonic frequency 29kHz, 54 DEG C of temperature, sonic oscillation 4.7h；After the completion of ultrasonic activation, super in ultrasound reactor
Sound surface active carrier mixed liquor is transferred in 100ml hydrothermal reaction kettles, add by 0.78g boraxs, 0.97g potassium sulfates,
The cyclopentadiene promethiums of 0.58g tri-, 0.67g tri- (DPM dpm,dipivalomethane acid) gadolinium, 0.78g trifluoromethayl sulfonic acid thuliums
(III), 0.87g tri- (trifluoromethanesulfonimide) ytterbium, 1.48g cobalt edetates, 1.77g zinc lactates, 0.68g zirconium carbonate ammoniums,
It is water-soluble that the ammino palladium of 0.87g dichloros four, 1.98g palmitic acids dimethylamino-ethanol ester ammonium chloroacetate and 10ml deionized waters are prepared
Liquid, the weight concentration of the aqueous solution is 53.3%, the weight of the aqueous solution:The weight of ultrasonic surface activated carrier mixed liquor=
21.43g: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 for 105 DEG C
Thing；Fine silt thing is in Muffle furnace, 930 DEG C, calcination 7.5h, and after cooling down, the ozone that can obtain fine particle shape is heterogeneous
Oxidized solid catalyst.
Comparative example 1:Preparation process is not added with lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, Β-hydroxyethyl dimethyl dodecyl
Outside ammonium sulfate, palmitic acid dimethylamino-ethanol ester ammonium chloroacetate, borax and potassium sulfate, whole preparation process, preparation condition and reality
Apply example 1 identical.
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 | 4.578 | 0.6088 | 786.13 |
| Embodiment 2 | 4.089 | 0.5600 | 679.93 |
| Comparative example 1 | 2.166 | 0.3185 | 483.17 |
Claims (2)
1. a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, it is characterized in that A groups can added in closed reactor
Divide and deionized water stirring prepares the aqueous solution, the weight concentration for controlling component A is 2%~6%, after the completion of prepared by solution, in stirring
Lower addition B component, is warming up to 35 DEG C~50 DEG C, continues stirring reaction 3h~6h, and filtering, reaction product is dry at 102 DEG C~106 DEG C
Reaming modified support is obtained after dry constant weight, reaming modified support input ultrasound reactor, addition is matched somebody with somebody by component C and deionized water
The aqueous solution of system, the weight concentration of component C is 3%~8%, is uniformly mixed, and it is 0.3~0.8W/ to control ultrasonic power density
m3, frequency 20kHz~30kHz, 40 DEG C~55 DEG C, sonic oscillation 2h~5h obtains ultrasonic surface activated carrier mixed liquor, transfer
Into hydrothermal reaction kettle, the aqueous solution that D components and deionized water are prepared is added, the weight concentration of D components is 40%~55%, is pressed
Weight meter, D component deionized water solutions:Weight ratio=1 of ultrasonic surface activated carrier mixed liquor:（1.5~2）, control temperature
120 DEG C~180 DEG C, the hydro-thermal reaction time is 8h~16h, then dries to obtain fine silt thing, fine silt thing is in Muffle furnace, 600
DEG C~950 DEG C, calcination 3h~8h obtains ozone Heterogeneous oxidation solid catalyst；The component A by expanding agent lithium hypochlorite,
Double (acetylacetone,2,4-pentanedione) beryllium compositions, by weight, lithium hypochlorite:Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B groups
Divide and be made up of activated carbon, carnallite, kaolin, red metal and stone, basalt, astrakanite, by weight, activated carbon:Carnallite:It is high
Ridge soil:Red metal and stone:Basalt:The weight ratio of astrakanite=（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 beta-hydroxyethyl dimethyl
Ammonium lauryl sulfate, by weight, component C:Weight ratio=1 of reaming modified support:（5~10）, D components are by grandidierite
Agent borax, potassium sulfate, the cyclopentadiene promethium of catalytic activity auxiliary agent predecessor three, three (2,2,6,6- tetramethyl -3,5- heptadione
Acid) gadolinium, trifluoromethayl sulfonic acid thulium (III), three (trifluoromethanesulfonimide) ytterbium Rare-earth chemicals, in catalytic activity
Heart predecessor normal transition metallo-organic compound cobalt edetate, zinc lactate, zirconium carbonate ammonium and precious metal chemical complex dichloro four
Ammino palladium, emulsifying agent palmitic acid dimethylamino-ethanol ester ammonium chloroacetate composition, by weight, borax:Potassium sulfate:Three rings penta 2
Alkene promethium:Three (DPM dpm,dipivalomethane acid) gadoliniums:Trifluoromethayl sulfonic acid thulium (III):Three (fluoroform sulphonyl Asias
Amine) ytterbium:Cobalt edetate:Zinc lactate:Zirconium carbonate ammonium:The ammino palladium of dichloro four:Palmitic acid dimethylamino-ethanol ester ammonium chloroacetate
Weight ratio=（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 activated carbon, carnallite, kaolin, red metal and stone, basalt, astrakanite group according to claim 1
Into activated carbon, carnallite, kaolin, red metal and stone, basalt, astrakanite 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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