CN107008414A - The preparation method of ozone Heterogeneous oxidation solid catalyst - Google Patents
The preparation method of ozone Heterogeneous oxidation solid catalyst Download PDFInfo
- Publication number
- CN107008414A CN107008414A CN201710275794.6A CN201710275794A CN107008414A CN 107008414 A CN107008414 A CN 107008414A CN 201710275794 A CN201710275794 A CN 201710275794A CN 107008414 A CN107008414 A CN 107008414A
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- solid catalyst
- lithium
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 24
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 19
- 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 40
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- -1 octadecyl methyl Chemical group 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000019738 Limestone Nutrition 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 12
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 11
- SHXHPUAKLCCLDV-UHFFFAOYSA-N 1,1,1-trifluoropentane-2,4-dione Chemical compound CC(=O)CC(=O)C(F)(F)F SHXHPUAKLCCLDV-UHFFFAOYSA-N 0.000 claims abstract description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229960000892 attapulgite Drugs 0.000 claims abstract description 10
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 10
- 229910052637 diopside Inorganic materials 0.000 claims abstract description 10
- 239000006028 limestone Substances 0.000 claims abstract description 10
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 10
- 239000001103 potassium chloride Substances 0.000 claims abstract description 10
- 239000011017 amazonite Substances 0.000 claims abstract description 9
- UTPOUAZEFGTYAY-UHFFFAOYSA-N azanium;2-chloroacetate Chemical compound [NH4+].[O-]C(=O)CCl UTPOUAZEFGTYAY-UHFFFAOYSA-N 0.000 claims abstract description 9
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 241000723346 Cinnamomum camphora Species 0.000 claims abstract description 8
- 229930008380 camphor Natural products 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 8
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 8
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000002332 ferrous fumarate Nutrition 0.000 claims abstract description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 7
- 230000007704 transition Effects 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021538 borax Inorganic materials 0.000 claims abstract description 6
- 239000011773 ferrous fumarate Substances 0.000 claims abstract description 6
- 229960000225 ferrous fumarate Drugs 0.000 claims abstract description 6
- 229930195712 glutamate Natural products 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
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
- 239000011591 potassium Substances 0.000 claims abstract description 6
- 239000010970 precious metal Substances 0.000 claims abstract description 6
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 6
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 5
- 229910052777 Praseodymium 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
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000007795 chemical reaction product Substances 0.000 claims abstract 2
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 7
- 125000005594 diketone group Chemical group 0.000 claims 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 description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000001914 filtration Methods 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
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- KPQDSKZQRXHKHY-UHFFFAOYSA-N gold potassium Chemical compound [K].[Au] KPQDSKZQRXHKHY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 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
- 239000003054 catalyst Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 7
- 238000001994 activation Methods 0.000 abstract description 6
- 229910052779 Neodymium Inorganic materials 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000003643 water by type Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- 235000021314 Palmitic acid Nutrition 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 229960002887 deanol Drugs 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000008569 process 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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-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
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001816 cooling Methods 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
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 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
- 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
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- IOIFRTZBJMZZFO-UHFFFAOYSA-N dysprosium(3+) Chemical compound [Dy+3] IOIFRTZBJMZZFO-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 230000003179 granulation Effects 0.000 description 1
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- 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
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002943 palmitic acids Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- WCWKKSOQLQEJTE-UHFFFAOYSA-N praseodymium(3+) Chemical compound [Pr+3] WCWKKSOQLQEJTE-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- 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
- B01J23/894—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 rare earths or actinides
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- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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- B01J20/041—Oxides or hydroxides
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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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- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
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Abstract
The present invention relates to a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, category environmental protection and technical field of chemical engineering catalysts.The preparation method is to use attapulgite, diopside, montmorillonite, sylvite, amazonite and lithium lime stone porous material make carrier, carrier is modified through lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add the double hydroxyethyl ammoniums of octadecyl methyl 2 of surfactant chlorination and surface activation process is carried out under ul-trasonic irradiation, then ultrasonic surface activated carrier in hydrothermal reaction kettle with composite mineralizer borax and potassium sulfate, catalytic activity auxiliary agent predecessor three (3 trifluoroacetyl group D camphors) praseodymium (III), 1, 1, 1 trifluoroacetylacetone (TFA) neodymium, three (6, 6, 7, 7, 8, 8, 8 seven fluorine 2, 2 dimethyl 3, 5 octene diketone) dysprosium (III), ten water holmium oxalate Rare-earth chemicals, catalytic active center component predecessor normal transition metallo-organic compound ferrous fumarate, citric acid nickel, cupric glutamate and the golden potassium of precious metal chemical complex tetrachloro, hydro-thermal reaction is carried out under the effect of emulsifying agent palmitic acid dimethylamino-ethanol ester ammonium chloroacetate, reaction product drying is removed after moisture, in Muffle furnace, calcination obtains ozone Heterogeneous oxidation solid catalyst under certain temperature.
Description
Technical field
The present invention relates to a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, category environmental protection and chemical catalyst skill
Art field.
Background technology
Ozonation technology using ozone oxidation ability it is strong the characteristics of, can be by many organic pollution oxidation Decompositions, extensively
For wastewater treatment.Catalytic ozonation technology is divided into ozone homogeneous catalytic oxidation and ozone heterogeneous catalytic oxidation, and ozone is equal
Phase catalysis oxidation has that the more difficult separation and recovery of catalyst is reused, ozone utilization rate is low causes water process operating cost higher,
Organic pollutant removal rate is relatively low simultaneously and easily causing secondary pollution of water is limited to its application；Ozone heterogeneous catalysis oxygen
There is change technology catalyst to be easily isolated and recycled and reusable, ozone utilization rate is high, organic pollutant removal rate is higher, drop
Low water process operating cost and receive significant attention its application the advantages of do not result in secondary pollution.Ozone heterogeneous catalysis
It is to reach local organic matter enrichment by catalyst surface absorption organic matter that oxidation of organic compounds, which is decomposed, while ozone molecule absorption exists
The hydroxyl radical free radical that catalyst surface produces high activity under catalyst action decomposes organic matter.Ozone heterogeneous catalytic oxidation
Handle in waste water technology, core technology is the preparation of ozone Heterogeneous oxidation solid catalyst.
Ozone Heterogeneous oxidation solid catalyst is generally made up of carrier, activated centre and auxiliary agent.Due to being polluted in waste water
Species are various, complex chemical composition feature, can produce harmful effect to performance such as absorption, the mithridatism of catalyst.
Prepare that the carrier structure that ozone Heterogeneous oxidation solid catalyst uses is more single at present, adsorptivity is relatively low；Activated centre is universal
Using normal transition metal salt, mithridatism is poor；Preparation method mainly has infusion process, the precipitation method, mixing method and collosol and gel etc.
Method attachment activity center and adjuvant component are easily liquated out in carrier surface, activated centre and adjuvant component, cause catalyst
Easily lose catalytic activity.For exist in current ozone Heterogeneous oxidation solid catalyst preparation method Catalyst Adsorption compared with
Low, mithridatism is poor and easily loses catalytic activity problem, and exploitation is strengthened using multicomponent porous carrier through reaming, surface active
Catalyst Adsorption, makees catalytic activity auxiliary agent predecessor, normal transition Organometallic using Rare-earth chemicals 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 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 attapulgite, diopside, montmorillonite, sylvite, the Milky Way
Stone, lithium lime stone composition, by weight, attapulgite:Diopside:Montmorillonite:Sylvite:Amazonite:The weight ratio of lithium lime stone=
（5~15）:（7~17）:（9~19）:（11~21）:（13~23）:（15~25）, by weight, component A:The weight of B component
The ratio between=1:（10~20）, component C is the double octadecyl methyl -2- hydroxyethyl ammoniums of chlorination, by weight, component C:Reaming is modified
Weight ratio=1 of carrier:（5~10）, D components are by composite mineralizer borax, the potassium sulfate, (3- of catalytic activity auxiliary agent predecessor three
Trifluoroacetyl group-D- camphors) praseodymium (III), 1,1,1- trifluoroacetylacetone (TFA)s neodymium, three (the fluoro- 2,2- diformazans of 6,6,7,7,8,8,8- seven
Base -3,5- octene diketone) dysprosium (III), ten water holmium oxalate Rare-earth chemicals, catalytic active center predecessor is common
The golden potassium of transition metal organometallic compound ferrous fumarate, citric acid nickel, cupric glutamate and precious metal chemical complex tetrachloro, emulsifying agent palm fibre
Palmitic acid acid dimethylamino-ethanol ester ammonium chloroacetate composition, by weight, borax:Potassium sulfate:Three (3- trifluoroacetyl group-D- camphors) praseodymiums
(III):1,1,1- trifluoroacetylacetone (TFA) neodymiums:Three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosiums
(III) :Ten water holmium oxalates:Ferrous fumarate:Citric acid nickel:Cupric glutamate:Tetrachloro gold potassium:Palmitic acid dimethylamino-ethanol ester
The weight ratio of ammonium chloroacetate=（4~8）:（6~10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~
18）:（4~7）:（6~9）:（6~20）.Attapulgite, diopside, montmorillonite, sylvite, amazonite, the lithium of the B component
Lime stone is crushed respectively, and deionized water washing, which is dried, to be removed after moisture, and -200 mesh ,+400 mesh sieves point, control are carried out through standard screen
Granulation footpath is the mm of 0.0370mm~0.0750.
What the technical method of the present invention was realized in：Lithium hypochlorite LiClO, double (second can be being added in closed reactor
Acyl acetone) beryllium C10H14BeO4The aqueous solution is prepared with deionized water stirring, it is 0.0370mm~0.0750mm to add particle diameter after screening
Attapulgite, diopside, montmorillonite, sylvite, amazonite and lithium lime stone 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 the double octadecyl methyl -2- of chlorination
Hydroxyethyl ammonium [(C18H37)2N(CH2CH2OH)(CH3)]+Cl-The aqueous solution, control ultrasonic power density, ultrasonic frequency, temperature and
The sonic oscillation time, under ultrasonic cavitation effect, double octadecyl methyl -2- the hydroxyethyl ammoniums [(C of chlorination18H37)2N
(CH2CH2OH)(CH3)]+Cl-It is easy to escape into reaming modified support duct from the aqueous solution or is attached to reaming modified support table
Face, is beneficial to being interconnected and carrier surface activation for carrier duct, enhances adsorptivity；After the completion of ultrasonic activation, ultrasonic table
Face activated carrier mixed liquor is transferred in hydrothermal reaction kettle, with borax Na2B4O7·10H2O, potassium sulfate K2SO4Composite mineralizer,
Catalytic activity auxiliary agent predecessor three (3- trifluoroacetyl group-D- camphors) praseodymium (III) C36H42F9O6Pr, 1,1,1- trifluoroacetylacetone (TFA)
Neodymium C15H12F9NdO6, three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosium (III) C6H11O7Tb、
Ten water holmium oxalate C6Ho2O12Rare-earth chemicals, catalytic active center component predecessor normal transition Organometallic
Compound ferrous fumarate C4H2O4Fe, citric acid nickel C12H10O14Ni3, cupric glutamate C5H7NO4The Cu and golden potassium KAuCl of tetrachloro4Your gold
Belong to compound, in emulsifying agent palmitic acid dimethylamino-ethanol ester ammonium chloroacetate C16H33COOCH2CH2N+(CH3)2Cl-CHCOOH makees
Hydro-thermal reaction is carried out under, mineralizer accelerates diffusion, activates reactant lattice, promotes the progress of solid phase reaction, surpasses
Sound surface active carrier is uniformly mixed with Rare-earth chemicals, normal transition metallo-organic compound, precious metal chemical complex
It is miscellaneous, emulsifying agent palmitic acid dimethylamino-ethanol ester ammonium chloroacetate make reaction solution formed quasi-stationary emulsion prevent separation of solid and liquid,
Sedimentation, while to the further surface active of porous carrier, by the way that in certain temperature, the hydro-thermal reaction of time, drying obtains uniform
The fine silt thing of doping；The fine silt thing of Uniform Doped is in Muffle furnace, through high temperature sintering, and organic matter carbonization therein is entered
One step enhances the microcellular structure of porous carrier, obtain porous carrier supported rare earth metal oxide, transition metal oxide and
The ozone Heterogeneous oxidation solid catalyst of the catalytic active center of noble metal formation, improves mithridatism and the catalysis of catalyst
Activity.
Relative to art methods, outstanding feature of the present invention be in technology of preparing using attapulgite, diopside, cover de-
Soil, sylvite, amazonite, lithium lime stone porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) berylliums
C10H14BeO4Reaming effect, double octadecyl methyl -2- the hydroxyethyl ammoniums [(C of chlorination18H37)2N(CH2CH2OH)(CH3)]+Cl-、
Palmitic acid dimethylamino-ethanol ester ammonium chloroacetate C16H33COOCH2CH2N+(CH3)2Cl-The interconnected and surface in CHCOOH ducts
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, stability and high activity that particularly doped precious metal has, 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 attapulgites of 400 mesh standard sieves, 3.75g diopsides, 4.75g montmorillonites, 5.75g sylvites, 6.75g amazonites,
The weight of 7.75g lithium lime stones, 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；It is super in 500ml
In sound wave reactor, reaming modified support 31g is put into, the double octadecyl methyl -2- hydroxyethyl ammoniums of 3.25g chlorinations is added and is dissolved in
The aqueous solution of 100ml deionized waters, the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, the double octadecyl first of chlorination
Base -2- hydroxyethyl ammoniums（3.25g）:Reaming modified support（31g ）=1:9.5；It is 0.4W/m to control ultrasonic power density3, ultrasound
41 DEG C of wave frequency rate 21kHz, temperature, sonic oscillation 2.2h；After the completion of ultrasonic activation, the ultrasonic surface in ultrasound reactor is lived
Change carrier mixed liquor to be transferred in 500ml hydrothermal reaction kettles, add by 2.1g boraxs, 3.05g the potassium sulfates, (3- tri- of 1.6g tri-
Acetyl fluoride base-D- camphors) praseodymium (III), 2.05g1,1,1- trifluoroacetylacetone (TFA)s neodymium, (6,6,7,7,8,8,8- seven is fluoro- by 2.6g tri-
2,2- dimethyl -3,5- octenes diketone) dysprosium (III), the water holmium oxalates of 3.05g ten, 5.05g ferrous fumarates, 6.1g citric acids
The golden potassium of nickel, 2.05g cupric glutamates, 3.1g tetrachloros, 3.05g palmitic acids dimethylamino-ethanol ester ammonium chloroacetate and 50ml deionized waters
The aqueous solution of preparation, the weight concentration of the aqueous solution is 40.3%, the weight of the aqueous solution:Ultrasonic surface activated carrier mixed liquor
Weight=83.8g:134.25g=1:1.6,125 DEG C of temperature is controlled, the hydro-thermal reaction time is 8.3h, then dries carefully for 105 DEG C
Powder material；Fine silt thing is in Muffle furnace, 620 DEG C, calcination 3.2h, and after cooling down, the ozone that can obtain fine particle shape is non-
Homogeneous oxidizing solid catalyst.
Embodiment 2:0.24g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 0.36g, 10ml deionized waters, being added to volume is
100ml's can be uniformly mixed in closed reactor, and the weight concentration of the aqueous solution is 5.7%, lithium hypochlorite:Double (levulinics
Ketone) beryllium weight ratio=1:1.5；Add deionized water wash to it is neutral, 103 DEG C dry remove -200 mesh of sieving after moisture~+
The 1.45g attapulgites of 400 mesh standard sieves, 1.65g diopsides, 1.85g montmorillonites, 2.05g sylvites, 2.25g amazonites,
The weight of 2.45g lithium lime stones, 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, the double octadecyl methyl -2- hydroxyl second of 2.2g chlorinations are added
Base 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, chlorination double 18
Alkyl methyl -2- hydroxyethyl ammoniums（2.2g）:Reaming modified support（11.5g ）=1:5.2；It is 0.7W/ 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,
0.58g tri- (3- trifluoroacetyl group-D- camphors) praseodymium (III), 0.67g1,1,1- trifluoroacetylacetone (TFA)s neodymium, 0.78g tri- (6,6,7,
The fluoro- 2,2- dimethyl -3,5- octenes diketone of 7,8,8,8- seven) dysprosium (III), the water holmium oxalates of 0.87g ten, 1.48g fumaric acid be sub-
The golden potassium of iron, 1.77g citric acids nickel, 0.68g cupric glutamates, 0.87g tetrachloros, 1.98g palmitic acid dimethylamino-ethanol ester monoxones
The aqueous solution that ammonium and 10ml deionized waters are prepared, the weight concentration of the aqueous solution is 53.3%, the weight of the aqueous solution:Ultrasonic table
Weight=21.43g of face 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 fine silt thing is dried to obtain for 105 DEG C；Fine silt thing is in Muffle furnace, 930 DEG C, calcination 7.5h, after cooling down, can obtain thin
The ozone Heterogeneous oxidation solid catalyst of powder particles shape.
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 attapulgite, diopside, montmorillonite, sylvite, amazonite, lithium lime stone, by weight, attapulgite:Diopside:
Montmorillonite:Sylvite:Amazonite:The weight ratio of lithium lime stone=（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 the double octadecyls of chlorination
Methyl -2- hydroxyethyl ammoniums, by weight, component C:Weight ratio=1 of reaming modified support:（5~10）, D components are by grandidierite
Agent borax, potassium sulfate, catalytic activity auxiliary agent predecessor three (3- trifluoroacetyl group-D- camphors) praseodymium (III), 1,1,1- trifluoro second
Acyl acetone neodymium, three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosiums (III), ten water holmium oxalates are dilute
Earth metal organic compound, catalytic active center predecessor normal transition metallo-organic compound ferrous fumarate, citric acid nickel,
Cupric glutamate and the golden potassium of precious metal chemical complex tetrachloro, emulsifying agent palmitic acid dimethylamino-ethanol ester ammonium chloroacetate composition, by weight
Meter, borax:Potassium sulfate:Three (3- trifluoroacetyl group-D- camphors) praseodymiums (III):1,1,1- trifluoroacetylacetone (TFA) neodymiums:Three (6,6,7,
The fluoro- 2,2- dimethyl -3,5- octenes diketone of 7,8,8,8- seven) dysprosium (III):Ten water holmium oxalates:Ferrous fumarate:Citric acid nickel:
Cupric glutamate:Tetrachloro gold potassium: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）.
2. B component is by attapulgite, diopside, montmorillonite, sylvite, amazonite, lithium lime stone group according to claim 1
Into attapulgite, diopside, montmorillonite, sylvite, amazonite, lithium lime stone 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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| CN114100650A (en) * | 2020-08-27 | 2022-03-01 | 万华化学集团股份有限公司 | Ozone-hydrogen peroxide catalytic oxidation catalyst and method for treating biochemical wastewater by using same |
| CN114100650B (en) * | 2020-08-27 | 2023-04-07 | 万华化学集团股份有限公司 | Ozone-hydrogen peroxide catalytic oxidation catalyst and method for treating biochemical wastewater by using same |
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