CN107051538A - The preparation method of ozone Heterogeneous oxidation solid catalyst - Google Patents
The preparation method of ozone Heterogeneous oxidation solid catalyst Download PDFInfo
- Publication number
- CN107051538A CN107051538A CN201710276520.9A CN201710276520A CN107051538A CN 107051538 A CN107051538 A CN 107051538A CN 201710276520 A CN201710276520 A CN 201710276520A CN 107051538 A CN107051538 A CN 107051538A
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- component
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- iii
- acetylacetone
- solid catalyst
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 230000003647 oxidation Effects 0.000 title claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 67
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- -1 diatom is pure Substances 0.000 claims abstract description 17
- 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
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 14
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001864 baryta Inorganic materials 0.000 claims abstract description 11
- 235000019355 sepiolite Nutrition 0.000 claims abstract description 11
- 239000002223 garnet Substances 0.000 claims abstract description 10
- 239000004113 Sepiolite Substances 0.000 claims abstract description 9
- INJRKJPEYSAMPD-UHFFFAOYSA-N aluminum;silicic acid;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O INJRKJPEYSAMPD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052675 erionite Inorganic materials 0.000 claims abstract description 9
- 229910052850 kyanite Inorganic materials 0.000 claims abstract description 9
- 239000010443 kyanite 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
- 229910052624 sepiolite Inorganic materials 0.000 claims abstract description 9
- 235000010339 sodium tetraborate Nutrition 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
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 7
- BYDILAVGJRCJOJ-UHFFFAOYSA-N O.O.[Y+3] Chemical class O.O.[Y+3] BYDILAVGJRCJOJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021538 borax Inorganic materials 0.000 claims abstract description 7
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229960004889 salicylic acid Drugs 0.000 claims abstract description 7
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 7
- HJLLVKXGCPZMAM-UHFFFAOYSA-N N-methyl-N-(nitromethyl)-1-phenylmethanamine Chemical compound CN(Cc1ccccc1)C[N+]([O-])=O HJLLVKXGCPZMAM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 6
- RKKHMLBQJFPHDF-UHFFFAOYSA-N [Os].[K].[K] Chemical compound [Os].[K].[K] RKKHMLBQJFPHDF-UHFFFAOYSA-N 0.000 claims abstract description 6
- BENADMAVJUZZBP-UHFFFAOYSA-N [O-2].C(C)(C)[Sc+2] Chemical compound [O-2].C(C)(C)[Sc+2] BENADMAVJUZZBP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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
- 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
- VSIRWAYMNHKLOS-UHFFFAOYSA-N [V].C(C1=CC=NC=C1)(=O)NN=C(C(=O)O)C Chemical compound [V].C(C1=CC=NC=C1)(=O)NN=C(C(=O)O)C VSIRWAYMNHKLOS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 14
- 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 9
- 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
- 239000010970 precious metal Substances 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- ZGGPNDKKJIWQJU-UHFFFAOYSA-N 2-(pyridine-4-carbonylhydrazinylidene)propanoic acid Chemical compound OC(=O)C(C)=NNC(=O)C1=CC=NC=C1 ZGGPNDKKJIWQJU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 229940102396 methyl bromide Drugs 0.000 claims description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N methyl bromide Substances BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 2
- 125000006502 nitrobenzyl group Chemical group 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 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
- 125000002252 acyl group Chemical group 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 19
- 238000001994 activation Methods 0.000 abstract description 6
- 239000012752 auxiliary agent Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000005416 organic matter Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 150000002910 rare earth metals Chemical class 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- 241000206761 Bacillariophyta Species 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
- 239000002671 adjuvant Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 2
- 125000004005 formimidoyl group Chemical group [H]\N=C(/[H])* 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 125000002524 organometallic group Chemical group 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
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- JTABHYSLUVGCPP-UHFFFAOYSA-N CC(=O)C.C(C)(=O)F Chemical compound CC(=O)C.C(C)(=O)F JTABHYSLUVGCPP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 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
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 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
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 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
- 150000007857 hydrazones Chemical class 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 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
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- GRTBAGCGDOYUBE-UHFFFAOYSA-N yttrium(3+) Chemical compound [Y+3] GRTBAGCGDOYUBE-UHFFFAOYSA-N 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
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
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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 erionite, garnet, diatom is pure, kyanite, sepiolite and baryta fledspar make carrier, carrier is after lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add surfactant dodecyltrimethyl and surface activation process is carried out under ul-trasonic irradiation, then activated carrier in hydrothermal reaction kettle with composite mineralizer borax and potassium sulfate, catalytic activity auxiliary agent predecessor isopropyl scandium oxide (III), three (hexafluoroacetylacetone) yttrium (III) dihydrates, three (3 trifluoroacetyl group D camphors) praseodymiums (III), acetylacetone,2,4-pentanedione samarium, catalytic active center component predecessor titanocenes ring substituted salicylic acid complex, pyruvic acid isonicotinoyl hydrazone vanadium, citric acid nickel, chlordene osmium dipotassium, between emulsifying agent hydro-thermal reaction is carried out under the effect of nitrobenzyl dimethyl amine bromide, drying removes moisture, calcination obtains ozone Heterogeneous oxidation solid catalyst in Muffle furnace.
Description
Technical field
The present invention relates to a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, category environmental protection and chemical catalyst skill
Art field.
Background technology
Ozonation technology using ozone oxidation ability it is strong the characteristics of, can be by many organic pollution oxidation Decompositions, extensively
For wastewater treatment.Catalytic ozonation technology is divided into ozone homogeneous catalytic oxidation and ozone heterogeneous catalytic oxidation, and ozone is equal
Phase catalysis oxidation has that the more difficult separation and recovery of catalyst is reused, ozone utilization rate is low causes water process operating cost higher,
Organic pollutant removal rate is relatively low simultaneously and easily causing secondary pollution of water is limited to its application；Ozone heterogeneous catalysis oxygen
There is change technology catalyst to be easily isolated and recycled and reusable, ozone utilization rate is high, organic pollutant removal rate is higher, drop
Low water process operating cost and receive significant attention its application the advantages of do not result in secondary pollution.Ozone heterogeneous catalysis
It is to reach local organic matter enrichment by catalyst surface absorption organic matter that oxidation of organic compounds, which is decomposed, while ozone molecule absorption exists
The hydroxyl radical free radical that catalyst surface produces high activity under catalyst action decomposes organic matter.Ozone heterogeneous catalytic oxidation
Handle in waste water technology, core technology is the preparation of ozone Heterogeneous oxidation solid catalyst.
Ozone Heterogeneous oxidation solid catalyst is generally made up of carrier, activated centre and auxiliary agent.Due to being polluted in waste water
Species are various, complex chemical composition feature, can produce harmful effect to performance such as absorption, the mithridatism of catalyst.
Prepare that the carrier structure that ozone Heterogeneous oxidation solid catalyst uses is more single at present, adsorptivity is relatively low；Activated centre is universal
Using normal transition metal salt, mithridatism is poor；Preparation method mainly has infusion process, the precipitation method, mixing method and collosol and gel etc.
Method attachment activity center and adjuvant component are easily liquated out in carrier surface, activated centre and adjuvant component, cause catalyst
Easily lose catalytic activity.For exist in current ozone Heterogeneous oxidation solid catalyst preparation method Catalyst Adsorption compared with
Low, mithridatism is poor and easily loses catalytic activity problem, and exploitation is strengthened using multicomponent porous carrier through reaming, surface active
Catalyst Adsorption, makees catalytic activity auxiliary agent predecessor, normal transition Organometallic using Rare-earth 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 erionite, garnet, pure diatom, kyanite, Hai Pao
Stone, baryta fledspar composition, by weight, erionite:Garnet:Diatom is pure:Kyanite:Sepiolite:The weight ratio of baryta fledspar=（5
~15）:（7~17）:（9~19）:（11~21）:（13~23）:（15~25）, by weight, component A:The weight of B component it
Than=1:（10~20）；Component C is dodecyltrimethyl, by weight, component C:The weight of reaming modified support it
Than=1:（5~10）；D components by composite mineralizer borax, potassium sulfate, catalytic activity auxiliary agent predecessor isopropyl scandium oxide (III),
Three (hexafluoroacetylacetone) yttrium (III) dihydrates, three (3- trifluoroacetyl group-D- camphors) praseodymiums (III), acetylacetone,2,4-pentanedione samarium are dilute
Earth metal organic compound, catalytic active center predecessor normal transition metallo-organic compound titanocenes ring substituted salicylic acid is matched somebody with somebody
Nitrobenzyl dimethyl between compound, pyruvic acid isonicotinoyl hydrazone vanadium, citric acid nickel and precious metal chemical complex chlordene osmium dipotassium, emulsifying agent
Amine bromide is constituted, by weight, borax:Potassium sulfate:Isopropyl scandium oxide (III):The water of three (hexafluoroacetylacetone) yttrium (III) two
Compound:Three (3- trifluoroacetyl group-D- camphors) praseodymiums (III):Acetylacetone,2,4-pentanedione samarium:Titanocenes ring substituted salicylic acid complex:Acetone
Sour isonicotinoyl hydrazone vanadium:Citric acid nickel:Chlordene osmium dipotassium:Between nitrobenzyl dimethyl amine bromide weight ratio=（4~8）:（6~
10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6~20）.The B
Erionite, garnet in component, pure diatom, kyanite, sepiolite, baryta fledspar are crushed respectively, and deionized water washing is dry
After dry removing moisture, -200 mesh ,+400 mesh sieves point are carried out through standard screen, it is the mm of 0.0370mm~0.0750 control particle diameter.
What the technical method of the present invention was realized in：Lithium hypochlorite LiClO, double (second can be being added in closed reactor
Acyl acetone) beryllium C10H14BeO4The aqueous solution is prepared with deionized water stirring, it is 0.0370mm~0.0750mm to add particle diameter after screening
Erionite, garnet, pure diatom, kyanite, sepiolite and baryta fledspar porous material carrier, in certain temperature and stirring condition
Under, the small Be of aqueous solution Ionic Radius2+（0.31Å）、Li+（0.60Å）Displace part ion radius in porous material big
Ca2+（0.99Å）、K+（1.33Å）、Ba2+（1.35Å）Plasma, the aperture of porous material carrier becomes big, surface roughness increase,
Filtering, dries the reaming modified support input ultrasound reactor after constant weight, adds dodecyltrimethyl
[C12H25N(CH3)3]+Cl-The aqueous solution, control ultrasonic power density, ultrasonic frequency, temperature and sonic oscillation time, in ultrasound
Under ripple cavitation, dodecyltrimethyl [C12H25N(CH3)3]+Cl-It is easy to escape into reaming modification from the aqueous solution
Carrier duct is attached to reaming modified support surface, is beneficial to being interconnected and carrier surface activation for carrier duct, enhancing
Adsorptivity；After the completion of ultrasonic activation, ultrasonic surface activated carrier mixed liquor is transferred in hydrothermal reaction kettle, with borax
Na2B4O7·10H2O, potassium sulfate K2SO4Composite mineralizer, catalytic activity auxiliary agent isopropyl scandium oxide (III) C9H21O3Sc, three (six
Acetyl fluoride acetone) yttrium (III) dihydrate C15H3F18O6Y·2H2O, three (3- trifluoroacetyl group-D- camphors) praseodymiums (III)
C36H42F9O6Pr, acetylacetone,2,4-pentanedione samarium C15H25O8Sm Rare-earth chemicals, catalytic active center component transition metal is organic
Compound titanocenes ring substituted salicylic acid complex (C10H10)Ti(C7H4O3), pyruvic acid isonicotinoyl hydrazone vanadium [VO2(C9H8N3O5)]
(C5H5N), citric acid nickel C12H10O14Ni3With chlordene osmium dipotassium K2OsCl6Precious metal chemical complex, nitrobenzyl two between emulsifying agent
Methyl bromide amine [C6H4(NO2)CH2N(CH3)2C2H5OH]+Br-The lower progress hydro-thermal reaction of effect, mineralizer acceleration diffusion,
Reactant lattice is activated, the progress of solid phase reaction is promoted, it is ultrasonic surface activated carrier and Rare-earth chemicals, general
Nitrobenzyl dimethyl amine bromide makes reaction between logical transition metal organometallic compound, precious metal chemical complex Uniform Doped, emulsifying agent
Liquid forms quasi-stationary emulsion and prevents separation of solid and liquid, sedimentation, while to the further surface active of porous carrier, by certain
Temperature, the hydro-thermal reaction of time, drying obtain the fine silt thing of Uniform Doped；The fine silt thing of Uniform Doped in Muffle furnace,
Through high temperature sintering, organic matter carbonization therein further enhances the microcellular structure of porous carrier, obtains porous carrier and bears
Carry the ozone Heterogeneous oxidation solid of the catalytic active center of rare-earth oxide, transition metal oxide and noble metal formation
Catalyst, improves the mithridatism and catalytic activity of catalyst.
Relative to art methods, outstanding advantages of the present invention are that erionite, garnet, diatom are used in technology of preparing
Pure, kyanite, sepiolite and baryta fledspar porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) berylliums
C10H14BeO4Reaming effect, dodecyltrimethyl [C12H25N(CH3)3]+Cl-, a nitrobenzyl dimethyl bromination
Amine [C6H4(NO2)CH2N(CH3)2C2H5OH]+Br-To being interconnected and surface activation for duct, organic matter carbonization is strong
The microcellular structure of porous carrier is changed；Rare-earth chemicals, normal transition Organometallic are closed by hydro-thermal reaction
Thing and precious metal chemical complex reach Uniform Doped and are attached in carrier surface and duct that high temperature sintering makes organic matter carbonization
Strengthen and form multi-level microcellular structure, porous carrier supported rare earth metal oxide, transition metal oxide and your gold
The multi-element metal catalytic active center that category is formed is combined more firm with porous carrier, and the ozone Heterogeneous oxidation solid of preparation is urged
Agent has a stronger adsorptivity, the cooperative effect of multi-element metal, stability and high activity that particularly doped precious metal has,
Liquating out for metal catalytic activity component can be suppressed, the mithridatism and catalytic activity of catalyst are improved, with good ring
Border benefit and economic benefit.
Embodiment
Embodiment 1:1.4g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 1.7g, 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 2.2%, 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 2.8g erionites of 400 mesh standard sieves, 3.8g garnets, 4.7g diatoms are pure, 5.8g kyanites, 6.7g sepiolites, 7.8g barium are long
The weight of stone, lithium hypochlorite and double (acetylacetone,2,4-pentanedione) berylliums（3.1g）:The weight of porous material（31.6g）=1:10.2, it is warming up to 36
DEG C, obtain reaming modified support 30g after continuing stirring reaction 3.2h, filtering, 103 DEG C of dry constant weights；In 500ml ultrasonic responses
In device, reaming modified support 30g is put into, the water that 3.3g dodecyltrimethyls are dissolved in 100ml deionized waters is added
Solution, the weight concentration of the aqueous solution is 3.2%, is uniformly mixed, dodecyltrimethyl（3.3g）:Reaming changes
Property carrier（30g ）=1:9.1；It is 0.4W/m to control ultrasonic power density3, ultrasonic frequency 21kHz, 41 DEG C of temperature, ultrasound is shaken
Swing 2.2h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier mixed liquor in ultrasound reactor is transferred to 500ml hydro-thermals
In reactor, add by 2.1g boraxs, 3.1g potassium sulfates, 1.6g isopropyls scandium oxide (III), 2.1g tri- (hexafluoroacetylacetone)
Yttrium (III) dihydrate, 2.6g tri- (3- trifluoroacetyl group-D- camphors) praseodymium (III), 3.1g acetylacetone,2,4-pentanediones samarium, 5.1g titanocenes
Nitro between ring substituted salicylic acid complex, 6.1g pyruvic acid isonicotinoyl hydrazones vanadium, 2g citric acids nickel, 3.1g chlordene osmiums dipotassium, 3.1g
The aqueous solution that benzyl dimethyl amine bromide and 50ml deionized waters are prepared, the weight concentration of the aqueous solution is 40.5%, the aqueous solution
Weight:Weight=84g of ultrasonic surface activated carrier mixed liquor:133.3g=1:1.6,125 DEG C of temperature is controlled, during hydro-thermal reaction
Between be 8.3h, then dry to obtain fine silt thing for 105 DEG C；Fine silt thing is in Muffle furnace, 620 DEG C, calcination 3.2h, cooling down
Afterwards, it 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 erionites of 400 mesh standard sieves, 1.65g garnets, 1.85g diatoms are pure, 2.05g kyanites, 2.25g sepiolites,
The weight of 2.45g baryta fledspars, 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 dodecyltrimethyls is added and is dissolved in
The aqueous solution of 26ml deionized waters, the weight concentration of the aqueous solution is 7.8%, is uniformly mixed, chlorination trimethyl
Ammonium（2.2g）:Many reaming modified supports（11.5g ）=1:5.2；It is 0.7W/m to control ultrasonic power density3, ultrasonic frequency
54 DEG C of 29kHz, temperature, sonic oscillation 4.7h；After the completion of ultrasonic activation, the ultrasonic surface activated carrier in ultrasound reactor
Mixed liquor is transferred in 100ml hydrothermal reaction kettles, is added by 0.78g boraxs, 0.97g potassium sulfates, 0.58g isopropyl scandium oxides
(III), 0.67g tri- (hexafluoroacetylacetone) yttrium (III) dihydrate, 0.78g tri- (3- trifluoroacetyl group-D- camphors) praseodymium
(III), 0.87g acetylacetone,2,4-pentanediones samarium, 1.48g titanocenes ring substituted salicylic acids complex, 1.77g pyruvic acid isonicotinoyl hydrazones vanadium,
Nitrobenzyl dimethyl amine bromide and 10ml deionized waters are prepared between 0.68g citric acids nickel, 0.87g chlordene osmiums dipotassium, 1.98g
The aqueous solution, 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=
21.4g:39.7g=1:1.9,175 DEG C of temperature is controlled, the hydro-thermal reaction time is 15.5h, then dries to obtain fine silt thing for 105 DEG C；
Fine silt thing is in Muffle furnace, 930 DEG C, calcination 7.5h, after cooling down, can obtain the ozone Heterogeneous oxidation of fine particle shape
Solid catalyst.
Comparative example 1:Preparation process be not added with lithium hypochlorite, double (acetylacetone,2,4-pentanedione) berylliums, dodecyltrimethyl,
Outside nitrobenzyl dimethyl amine bromide, borax and potassium sulfate, whole preparation process, preparation condition are identical with embodiment 1.
The parameter of ozone Heterogeneous oxidation solid catalyst prepared by embodiment 1, embodiment 2 and comparative example 1 is included in table 1.
Application Example 1:Ozone Heterogeneous oxidation solid catalyst point prepared by embodiment 1, embodiment 2 and comparative example 1
It is used under the same conditions at the waste water progress ozone Heterogeneous oxidation that Potassium Hydrogen Phthalate, ethylenediamine and fumaric acid are prepared
Reason.Treatment conditions are：Rate of charge=1000L of organic wastewater and catalyst:1g, organic wastewater CODCrValue 965mg/L, ozone
Dosage 60mg/L, processing time 1hr, ozone tail gas KI solution absorption detecting ozone utilization rates.Test data is included in table 2.
The embodiment of table 1 and comparative example prepare ozone Heterogeneous oxidation solid catalysis agent parameter
The ozone Heterogeneous oxidation solid catalyst Application Example of table 2
Claims (2)
1. a kind of preparation method of ozone Heterogeneous oxidation solid catalyst, it is characterized in that A groups can added in closed reactor
Divide and deionized water stirring prepares the aqueous solution, the weight concentration for controlling component A is 2%~6%, after the completion of prepared by solution, in stirring
Lower addition B component, is warming up to 35 DEG C~50 DEG C, continues stirring reaction 3h~6h, and filtering, reaction product is dry at 102 DEG C~106 DEG C
Reaming modified support is obtained after dry constant weight, reaming modified support input ultrasound reactor, addition is matched somebody with somebody by component C and deionized water
The aqueous solution of system, the weight concentration of component C is 3%~8%, is uniformly mixed, and it is 0.3~0.8W/ to control ultrasonic power density
m3, frequency 20kHz~30kHz, 40 DEG C~55 DEG C, sonic oscillation 2h~5h obtains ultrasonic surface activated carrier mixed liquor, transfer
Into hydrothermal reaction kettle, the aqueous solution that D components and deionized water are prepared is added, the weight concentration of D components is 40%~55%, is pressed
Weight meter, D component deionized water solutions:Weight ratio=1 of ultrasonic surface activated carrier mixed liquor:（1.5~2）, control temperature
120 DEG C~180 DEG C, the hydro-thermal reaction time is 8h~16h, then dries to obtain fine silt thing, fine silt thing is in Muffle furnace, 600
DEG C~950 DEG C, calcination 3h~8h obtains ozone Heterogeneous oxidation solid catalyst；The component A is by lithium hypochlorite, double (acetyl
Acetone) beryllium composition, by weight, lithium hypochlorite:Weight ratio=1 of double (acetylacetone,2,4-pentanedione) berylliums:（1~1.6）, B component boiled by hair
Stone, garnet, diatom are pure, kyanite, sepiolite, baryta fledspar composition, by weight, erionite:Garnet:Diatom is pure:Aquamaine
Stone:Sepiolite:The weight ratio of baryta fledspar=（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 dodecyltrimethyl, is pressed
Weight meter, component C:Weight ratio=1 of reaming modified support:（5~10）, D components are urged by composite mineralizer borax, potassium sulfate
Change coagent predecessor isopropyl scandium oxide (III), three (hexafluoroacetylacetone) yttrium (III) dihydrates, three (3- trifluoro second
Acyl group-D- camphors) praseodymium (III), acetylacetone,2,4-pentanedione samarium Rare-earth chemicals, catalytic active center predecessor normal transition gold
Belong to organic compound titanocenes ring substituted salicylic acid complex, pyruvic acid isonicotinoyl hydrazone vanadium, citric acid nickel and precious metal chemical complex
Nitrobenzyl dimethyl amine bromide is constituted between chlordene osmium dipotassium, emulsifying agent, by weight, borax:Potassium sulfate:Isopropyl scandium oxide
(III):Three (hexafluoroacetylacetone) yttrium (III) dihydrates:Three (3- trifluoroacetyl group-D- camphors) praseodymiums (III):Acetylacetone,2,4-pentanedione
Samarium:Titanocenes ring substituted salicylic acid complex:Pyruvic acid isonicotinoyl hydrazone vanadium:Citric acid nickel:Chlordene osmium dipotassium:Between nitrobenzyl two
The weight ratio of methyl bromide amine=（4~8）:（6~10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:（12
~18）:（4~7）:（6~9）:（6~20）.
2. B component is made up of erionite, garnet, pure diatom, kyanite, sepiolite, baryta fledspar according to claim 1,
Erionite, garnet, diatom are pure, kyanite, sepiolite, baryta fledspar are crushed respectively, and deionized water washing, which is dried, removes water
After point, sieved through standard screen, it is 0.0370mm~0.0750mm to control particle diameter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710276520.9A CN107051538A (en) | 2017-04-25 | 2017-04-25 | The preparation method of ozone Heterogeneous oxidation solid catalyst |
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| CN117123209A (en) * | 2023-09-28 | 2023-11-28 | 北京英诺格林科技有限公司 | Catalyst for oxidation treatment of landfill leachate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117123209A (en) * | 2023-09-28 | 2023-11-28 | 北京英诺格林科技有限公司 | Catalyst for oxidation treatment of landfill leachate and preparation method thereof |
| CN117123209B (en) * | 2023-09-28 | 2024-02-06 | 北京英诺格林科技有限公司 | Catalyst for oxidation treatment of landfill leachate and preparation method thereof |
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