CN107008379A - The preparation method of ozone Heterogeneous oxidation solid catalyst - Google Patents
The preparation method of ozone Heterogeneous oxidation solid catalyst Download PDFInfo
- Publication number
- CN107008379A CN107008379A CN201710275266.0A CN201710275266A CN107008379A CN 107008379 A CN107008379 A CN 107008379A CN 201710275266 A CN201710275266 A CN 201710275266A CN 107008379 A CN107008379 A CN 107008379A
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- weight
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- double
- solid catalyst
- 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 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 48
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- -1 β hydroxyethyl Chemical group 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims abstract description 14
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 11
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 11
- 229910021532 Calcite Inorganic materials 0.000 claims abstract description 10
- PALNZFJYSCMLBK-UHFFFAOYSA-K magnesium;potassium;trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-].[Cl-].[K+] PALNZFJYSCMLBK-UHFFFAOYSA-K 0.000 claims abstract description 10
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 9
- 239000010459 dolomite Substances 0.000 claims abstract description 9
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 9
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 150000001413 amino acids Chemical class 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- 235000016768 molybdenum Nutrition 0.000 claims abstract description 8
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 8
- 235000005340 Asparagus officinalis Nutrition 0.000 claims abstract description 7
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 7
- 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 7
- 229910021538 borax Inorganic materials 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 7
- 235000000193 zinc lactate Nutrition 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
- 239000012752 auxiliary agent Substances 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
- 229940050168 zinc lactate Drugs 0.000 claims abstract description 6
- 239000011576 zinc lactate Substances 0.000 claims abstract description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052773 Promethium Inorganic materials 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
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 239000011591 potassium Substances 0.000 claims abstract description 5
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 4
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001035 drying Methods 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 19
- 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
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Inorganic materials [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 230000007704 transition Effects 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 241000234427 Asparagus Species 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 125000005594 diketone group Chemical group 0.000 claims description 6
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [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])* 0.000 claims description 2
- KPQDSKZQRXHKHY-UHFFFAOYSA-N gold potassium Chemical compound [K].[Au] KPQDSKZQRXHKHY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 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 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- ZDHDJBQWTWIFLR-UHFFFAOYSA-N dodecyl sulfate;methylazanium Chemical compound [NH3+]C.CCCCCCCCCCCCOS([O-])(=O)=O ZDHDJBQWTWIFLR-UHFFFAOYSA-N 0.000 claims 1
- 239000008103 glucose Substances 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 17
- VMTDNQZNXIFFIZ-UHFFFAOYSA-N CCCCCCCCCCCCOS(OCCC(O)O)(=O)=O.CN Chemical compound CCCCCCCCCCCCOS(OCCC(O)O)(=O)=O.CN VMTDNQZNXIFFIZ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000001994 activation Methods 0.000 abstract description 6
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 abstract description 6
- 229940094989 trimethylsilane Drugs 0.000 abstract description 6
- 229910052692 Dysprosium 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
- 229940063953 ammonium lauryl sulfate Drugs 0.000 abstract description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 2
- 244000003416 Asparagus officinalis Species 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 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
- 239000011737 fluorine Substances 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 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
- 229910001868 water Inorganic materials 0.000 description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 6
- 235000011130 ammonium sulphate Nutrition 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 150000001875 compounds Chemical class 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
- 230000007935 neutral 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
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- MPTMRLYOVAWUMM-UHFFFAOYSA-N C[NH3+].S(=O)(=O)(OCCC(O)O)[O-] Chemical compound C[NH3+].S(=O)(=O)(OCCC(O)O)[O-] MPTMRLYOVAWUMM-UHFFFAOYSA-N 0.000 description 1
- PTGJVXFGOMJCCW-UHFFFAOYSA-J Cl[Au](Cl)(Cl)(Cl)[K] Chemical compound Cl[Au](Cl)(Cl)(Cl)[K] PTGJVXFGOMJCCW-UHFFFAOYSA-J 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 210000000481 breast Anatomy 0.000 description 1
- 239000003610 charcoal 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
- 229940048820 edetates Drugs 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 150000002736 metal compounds Chemical class 0.000 description 1
- NQNOMXXYKHWVKR-UHFFFAOYSA-N methylazanium;sulfate Chemical compound NC.NC.OS(O)(=O)=O NQNOMXXYKHWVKR-UHFFFAOYSA-N 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
- 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
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 239000004575 stone Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J23/8993—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 chromium, molybdenum or tungsten
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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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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, dolomite, calcite, aluminium hydroxide and reddish black masonry carrier are 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, three (6, 6, 7, 7, 8, 8, 8 seven fluorine 2, 2 dimethyl 3, 5 octene diketone) dysprosium (III), three [N, double (trimethyl silane) amine of N] erbium, catalytic active center component predecessor cobalt edetate, zinc lactate, L lucid asparagus amino acid molybdenums and the golden potassium of tetrachloro, hydro-thermal reaction is carried out under the effect of emulsifying agent dodecyl dihydroxypropyl sulfate methyl ammonium, calcination obtains ozone Heterogeneous oxidation solid catalyst in Muffle furnace after drying removing moisture.
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, dolomite, calcite, hydroxide
Aluminium, celestine composition, by weight, activated carbon:Carnallite:Dolomite:Calcite:Aluminium hydroxide:The weight of celestine 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, three (the fluoro- 2,2- diformazans of 6,6,7,7,8,8,8- seven
Base -3,5- octene diketone) dysprosium (III), three [N, N- double (trimethyl silane) amine] erbium Rare-earth chemicals, catalysis lives
Property center predecessor normal transition metallo-organic compound cobalt edetate, zinc lactate, L- lucid asparagus amino acid molybdenums and noble metal
Compound tetrachloro gold potassium, emulsifying agent dodecyl dihydroxypropyl sulfate methyl ammonium composition, by weight, borax:Potassium sulfate:Three
Cyclopentadiene promethium:Three (DPM dpm,dipivalomethane acid) gadoliniums:Three (the fluoro- 2,2- diformazans of 6,6,7,7,8,8,8- seven
Base -3,5- octenes diketone) dysprosium (III):Three [double (trimethyl silane) amine of N, N-] erbiums:Cobalt edetate:Zinc lactate:L- Tianmens
Winter amino acid molybdenum:Tetrachloro gold potassium:The weight ratio of dodecyl dihydroxypropyl sulfate methyl ammonium=（4~8）:（6~10）:（3~
6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.The work of the B component
Property charcoal, carnallite, dolomite, calcite, aluminium hydroxide, celestine crushed respectively, deionized water washing, which is dried, removes water
After point, -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
Activated carbon, carnallite, dolomite, calcite, aluminium hydroxide and celestine porous material carrier, in certain temperature and stirring
Under the conditions of, 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、
Three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosium (III) C30H30DyF21O6, three [N, N- are double
(trimethyl silane) amine] erbium C18H54ErN3Si6Rare-earth chemicals, catalytic active center component predecessor normal transition
Metallo-organic compound cobalt edetate C12H22O14Co, zinc lactate C6H10O6Zn, L- lucid asparagus amino acid molybdenum Mo [OOCCH2CH
(NH2)COO]3(H2O)3With the golden potassium KAuCl of tetrachloro4Precious metal chemical complex, in emulsifying agent dodecyl dihydroxypropyl sulfate methyl ammonium
[C12H25CH2CH(OH)CH(OH)N(CH3)3]+CH3SO4 -Hydro-thermal reaction is carried out under, mineralizer accelerates diffusion, makes reaction
Thing lattice is activated, and promotes the progress of solid phase reaction, ultrasonic surface activated carrier and Rare-earth chemicals, normal transition
Metallo-organic compound, precious metal chemical complex Uniform Doped, emulsifying agent dodecyl dihydroxypropyl sulfate methyl ammonium make reaction solution
Form quasi-stationary emulsion and prevent separation of solid and liquid, sedimentation, while to the further surface active of porous carrier, by a constant temperature
Degree, the hydro-thermal reaction of time, drying obtain the fine silt thing of Uniform Doped；The fine silt thing of Uniform Doped is in Muffle furnace, warp
High temperature sintering, organic matter carbonization therein further enhances the microcellular structure of porous carrier, obtains porous carrier load
The ozone Heterogeneous oxidation solid of the catalytic active center of rare-earth oxide, transition metal oxide and noble metal formation is urged
Agent, improves the mithridatism and catalytic activity of catalyst.
Relative to art methods, outstanding feature of the present invention is that activated carbon, carnallite, white clouds are used in technology of preparing
Stone, calcite, aluminium hydroxide, celestine 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 -, ten
Dialkyl group dihydroxypropyl sulfate methyl ammonium [C12H25CH2CH(OH)CH(OH)N(CH3)3]+CH3SO4 -To duct be interconnected and
Surface activation；Rare-earth chemicals, normal transition metallo-organic compound and noble metal are made by hydro-thermal reaction
Compound reaches Uniform Doped and is attached in carrier surface and duct that high temperature sintering makes organic matter carbonization strengthen and be formed
Multi-level microcellular structure, porous carrier supported rare earth metal oxide, transition metal oxide and noble metal formation it is many
First metal catalytic activity center is combined more firm with porous carrier, and the ozone Heterogeneous oxidation solid catalyst of preparation has more
Strong adsorptivity, the cooperative effect of multi-element metal, the noble metal of particularly doping have stability and high activity, can suppress gold
Liquating out for category catalytic active component, improves the mithridatism and catalytic activity of catalyst, with good environmental benefit and warp
Ji 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 activated carbons, 3.75g carnallites, 4.75g dolomites, 5.75g calcites, 6.75g aluminium hydroxides, the 7.75g of standard screen
The weight of celestine, 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, reaming modified support 31g is obtained after continuing stirring reaction 3.2h, filtering, 103 DEG C of dry constant weights；It is anti-in 500ml ultrasonic waves
Answer in device, put into reaming modified support 31g, add 3.25g beta-hydroxyethyl dimethyl dodecyl base ammonium sulfate and be dissolved in 100ml
The aqueous solution of ionized water, the weight concentration of the aqueous solution is 3.1%, is uniformly mixed, beta-hydroxyethyl dimethyl dodecyl base sulphur
Sour ammonium（3.25g）:Reaming modified support（31g ）=1:9.5；It is 0.4 W/m to control ultrasonic power density3, ultrasonic frequency
41 DEG C of 21kHz, temperature, sonic oscillation 2.2h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier in ultrasound reactor
Mixed liquor is transferred in 500ml hydrothermal reaction kettles, add by 2.1g boraxs, 3.05g potassium sulfates, the cyclopentadiene promethiums of 1.6g tri-,
2.05g tri- (DPM dpm,dipivalomethane acid) gadolinium, 2.6g tri- (the fluoro- 2,2- dimethyl of 6,6,7,7,8,8,8- seven-
3,5- octenes diketone) dysprosium (III), 3.05g tri- [N, N- double (trimethyl silane) amine] erbium, 5.05g cobalt edetates, 6.1g breasts
The golden potassium of sour zinc, 2.05g L- lucid asparagus amino acid molybdenum, 3.1g tetrachloros, 3.05g dodecyl dihydroxypropyl sulfate methyl ammoniums and
The aqueous solution that 50ml deionized waters are prepared, the weight concentration of the aqueous solution is 40.3%, the weight of the aqueous solution:Ultrasonic surface is lived
Change weight=83.8g of carrier mixed liquor:134.25g =1:1.6,125 DEG C of temperature is controlled, the hydro-thermal reaction time is 8.3h, then
105 DEG C dry to obtain fine silt thing；Fine silt thing is in Muffle furnace, 620 DEG C, calcination 3.2h, after cooling down, can obtain fine powder
Granular ozone Heterogeneous oxidation solid catalyst.
Embodiment 2:0.24g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 0.36g, 10ml deionized waters, being added to volume is
100ml's can be uniformly mixed in closed reactor, and the weight concentration of the aqueous solution is 5.7%, lithium hypochlorite:Double (levulinics
Ketone) beryllium weight ratio=1:1.5；Add deionized water wash to it is neutral, 103 DEG C dry remove -200 mesh of sieving after moisture~+
The 1.45g activated carbons of 400 mesh standard sieves, 1.65g carnallites, 1.85g dolomites, 2.05g calcites, 2.25g aluminium hydroxides,
The weight of 2.45g celestines, 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 tri- (6,6,7,7,8,8,
The fluoro- 2,2- dimethyl -3,5- octenes diketone of 8- seven) dysprosium (III), 0.87g tri- [N, N- double (trimethyl silane) amine] erbium, 1.48g
The golden potassium of cobalt edetate, 1.77g zinc lactates, 0.68g L- lucid asparagus amino acid molybdenum, 0.87g tetrachloros, 1.98g dodecyl dihydroxies
The aqueous solution that propyl group sulfate methyl ammonium and 10ml deionized waters are prepared, the weight concentration of the aqueous solution is 53.3%, the aqueous solution
Weight:Weight=21.43g of ultrasonic surface activated carrier mixed liquor:39.7g =1:1.9,175 DEG C of temperature is controlled, hydro-thermal is anti-
It is 15.5h between seasonable, then dries to obtain fine silt thing for 105 DEG C；Fine silt thing is in Muffle furnace, 930 DEG C, calcination 7.5h, cooling
After cooling, the ozone Heterogeneous oxidation solid catalyst of fine particle shape can obtain.
Comparative example 1:Preparation process is not added with lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, Β-hydroxyethyl dimethyl dodecyl
Outside ammonium sulfate, dodecyl dihydroxypropyl sulfate methyl ammonium, borax and potassium sulfate, whole preparation process, preparation condition and implementation
Example 1 is 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 | 4.848 | 0.6323 | 733.93 |
| Embodiment 2 | 4.394 | 0.5905 | 606.38 |
| Comparative example 1 | 2.791 | 0.3836 | 423.62 |
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, dolomite, calcite, aluminium hydroxide, celestine, by weight, activated carbon:Carnallite:
Dolomite:Calcite:Aluminium hydroxide:The weight ratio of celestine=（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 two
Methyl ammonium lauryl sulfate, by weight, component C:Weight ratio=1 of reaming modified support:（5~10）, D components are by multiple
Close mineralizer borax, potassium sulfate, the cyclopentadiene promethium of catalytic activity auxiliary agent predecessor three, three (2,2,6,6- tetramethyl -3,5- heptan two
Ketone acid) gadolinium, three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosiums (III), the three [double (front threes of N, N-
Base silane) amine] erbium Rare-earth chemicals, catalytic active center predecessor normal transition metallo-organic compound glucose
The golden potassium of sour cobalt, zinc lactate, L- lucid asparagus amino acid molybdenums and precious metal chemical complex tetrachloro, emulsifying agent dodecyl dihydroxypropyl sulfuric acid
Ammonium methyl is constituted, by weight, borax:Potassium sulfate:Three cyclopentadiene promethiums:Three (DPM dpm,dipivalomethane acid)
Gadolinium:Three (the fluoro- 2,2- dimethyl -3,5- octenes diketone of 6,6,7,7,8,8,8- seven) dysprosiums (III):Three [double (the trimethyl silicanes of N, N-
Alkane) amine] erbium:Cobalt edetate:Zinc lactate:L- lucid asparagus amino acid molybdenums:Tetrachloro gold potassium:Dodecyl dihydroxypropyl Methylsulfate
The weight ratio of ammonium=（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, dolomite, calcite, aluminium hydroxide, celestine group according to claim 1
Into activated carbon, carnallite, dolomite, calcite, aluminium hydroxide, celestine are crushed respectively, deionized water washing drying
Remove after moisture, sieved through standard screen, it is 0.0370mm~0.0750mm to control particle diameter.
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