CN107020119A - The preparation method of ozone Heterogeneous oxidation solid catalyst - Google Patents
The preparation method of ozone Heterogeneous oxidation solid catalyst Download PDFInfo
- Publication number
- CN107020119A CN107020119A CN201710274883.9A CN201710274883A CN107020119A CN 107020119 A CN107020119 A CN 107020119A CN 201710274883 A CN201710274883 A CN 201710274883A CN 107020119 A CN107020119 A CN 107020119A
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- CN
- China
- Prior art keywords
- weight
- component
- acetylacetone
- solid catalyst
- pentanedione
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 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 14
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 68
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 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
- 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 10
- 239000010443 kyanite Substances 0.000 claims abstract description 10
- 229910052850 kyanite Inorganic materials 0.000 claims abstract description 10
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Inorganic materials [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 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
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 8
- BYDILAVGJRCJOJ-UHFFFAOYSA-N O.O.[Y+3] Chemical compound O.O.[Y+3] BYDILAVGJRCJOJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 7
- 239000010459 dolomite Substances 0.000 claims abstract description 7
- 229910052939 potassium sulfate Inorganic materials 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
- 229910021538 borax Inorganic materials 0.000 claims abstract description 6
- 229930195712 glutamate Natural products 0.000 claims abstract description 6
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 6
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 5
- AUZRORBINHVFFD-UHFFFAOYSA-N [Rh]N=O Chemical compound [Rh]N=O AUZRORBINHVFFD-UHFFFAOYSA-N 0.000 claims abstract description 5
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- 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
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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 5
- 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
- HRHBQGBPZWNGHV-UHFFFAOYSA-N azane;bromomethane Chemical compound N.BrC HRHBQGBPZWNGHV-UHFFFAOYSA-N 0.000 claims abstract description 3
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- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- GZUXJHMPEANEGY-UHFFFAOYSA-N methyl bromide Substances BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring 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
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- 230000010355 oscillation Effects 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- OLGPDUKUFCIQPH-UHFFFAOYSA-N [Na].[Na].[Na].N(=O)[Rh] Chemical compound [Na].[Na].[Na].N(=O)[Rh] OLGPDUKUFCIQPH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
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- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 235000005979 Citrus limon Nutrition 0.000 claims 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 claims 1
- 244000248349 Citrus limon Species 0.000 claims 1
- 244000131522 Citrus pyriformis Species 0.000 claims 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims 1
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- 235000019504 cigarettes Nutrition 0.000 claims 1
- 229910000511 dolomite group Inorganic materials 0.000 claims 1
- 229940107700 pyruvic acid Drugs 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 17
- 238000001994 activation Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 229910052688 Gadolinium Inorganic materials 0.000 abstract description 5
- 125000002091 cationic group Chemical group 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 abstract description 4
- 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 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 abstract 1
- 238000003889 chemical engineering Methods 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
- 238000005516 engineering process Methods 0.000 description 7
- -1 hydroxyl radical free radical Chemical class 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 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
- 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 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
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- 150000002910 rare earth metals Chemical class 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 241000206761 Bacillariophyta Species 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- KYYZUZGHOSDPIX-UHFFFAOYSA-N azane 17-bromo-17-hexadecyltritriacontane Chemical compound N.CCCCCCCCCCCCCCCCC(Br)(CCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCC KYYZUZGHOSDPIX-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000008859 change Effects 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
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000000463 material Substances 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
- 239000012071 phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
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- 239000004575 stone Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
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- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910004835 Na2B4O7 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic 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
- 150000004683 dihydrates Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
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Classifications
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- 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
- B01J23/898—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 vanadium, tantalum, niobium or polonium
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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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.It is pure with diatom, kyanite, aluminium hydroxide, celestine, cubric niter and dolomite make carrier after lithium hypochlorite and double (acetylacetone,2,4-pentanedione) beryllium reamings, add surfactant Cationic surfucant and activation process is carried out under ul-trasonic irradiation, then carrier in hydrothermal reaction kettle with composite mineralizer borax and potassium sulfate, catalytic activity auxiliary agent predecessor three (hexafluoroacetylacetone) yttrium (III) dihydrate, acetylacetone,2,4-pentanedione samarium, three (4, 4, (2 thiophene) 1 of 4 trifluoro 1, 3 diacetyl) europium, three (2, 2, 6, 6 tetramethyls 3, 5 heptadione acid) gadolinium, catalytic active center component predecessor pyruvic acid isonicotinoyl hydrazone vanadium, citric acid nickel, cupric glutamate and six nitroso rhodium trisodiums, in emulsifying agent three（Cetyl）The effect of methyl bromide ammonium is lower to carry out hydro-thermal reaction, and drying is removed after moisture, and 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 diatom is pure, kyanite, aluminium hydroxide, celestine, saliter
Stone, dolomite composition, by weight, diatom is pure:Kyanite:Aluminium hydroxide:Celestine:Cubric niter:Dolomitic weight ratio=
（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 Cationic surfucant, by weight, component C:Reaming modified support
Weight ratio=1:（5~10）, D components are by composite mineralizer borax, potassium sulfate, (the hexafluoro second of catalytic activity auxiliary agent predecessor three
Acyl acetone) yttrium (III) dihydrate, acetylacetone,2,4-pentanedione samarium, three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europiums, three
(2,2,6,6- tetramethyl -3,5- heptadione acid) gadolinium Rare-earth chemicals, catalytic active center predecessor normal transition
Metallo-organic compound pyruvic acid isonicotinoyl hydrazone vanadium, citric acid nickel, cupric glutamate and the nitroso rhodium trisodium of precious metal chemical complex six,
Emulsifying agent three（Cetyl）Methyl bromide ammonium is constituted, by weight, borax:Potassium sulfate:Three (hexafluoroacetylacetone) yttriums (III)
Dihydrate:Acetylacetone,2,4-pentanedione samarium:Three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europiums:Three (2,2,6,6- tetramethyls-
3,5- heptadione acid) gadolinium:Pyruvic acid isonicotinoyl hydrazone vanadium:Citric acid nickel:Cupric glutamate:Six nitroso rhodium trisodiums:Three（Hexadecane
Base）The weight ratio of methyl bromide ammonium=（4~8）:（6~10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:
（12~18）:（4~7）:（6~9）:（6~20）.The diatom of the B component is pure, kyanite, aluminium hydroxide, celestine, saliter
Stone, dolomite are crushed respectively, and deionized water washing, which is dried, to be removed after moisture, and -200 mesh ,+400 mesh sieves are carried out through standard screen
Point, 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
Diatom is pure, kyanite, aluminium hydroxide, celestine, cubric niter and dolomite 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 chlorination dodecyl dimethyl hydroxyl second
Base ammonium [C12H25N(CH3)2CH2CH2OH]+Cl-The aqueous solution, control ultrasonic power density, ultrasonic frequency, temperature and sonic oscillation
Time, under ultrasonic cavitation effect, Cationic surfucant [C12H25N(CH3)2CH2CH2OH]+Cl-Easily
In escaping into reaming modified support duct from the aqueous solution or being attached to reaming modified support surface, it is beneficial to the phase in carrier duct
The activation of intercommunicated and carrier surface, enhances adsorptivity；After the completion of ultrasonic activation, ultrasonic surface activated carrier mixed liquor is transferred to
In hydrothermal reaction kettle, with borax Na2B4O7·10H2O, potassium sulfate K2SO4Composite mineralizer, catalytic activity auxiliary agent predecessor three (six
Acetyl fluoride acetone) yttrium (III) dihydrate C15H3F18O6Y·2H2O, acetylacetone,2,4-pentanedione samarium C15H25O8Sm, three (4,4,4- tri- is fluoro-
1- (2- thiophene) -1,3- diacetyl) europium C24H18EuF9O6S3, three (DPM dpm,dipivalomethane acid) gadoliniums
C33H57GdO6Rare-earth chemicals, catalytic active center component predecessor normal transition metallo-organic compound pyruvic acid
Isonicotinoyl hydrazone vanadium [VO2(C9H8N3O5)] (C5H5N), citric acid nickel C12H22O14Co, cupric glutamate C6H7O4Cu and noble metal chemical combination
The nitroso rhodium trisodium Na of thing six3Rh(NO2)6, in emulsifying agent three（Cetyl）Methyl bromide ammonium [(C16H33)3NCH3]+ Br-Make
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 three（Cetyl）Methyl bromide ammonium make reaction solution formed quasi-stationary emulsion prevent separation of solid and liquid, sedimentation, together
When to the further surface active of porous carrier, by the way that in certain temperature, the hydro-thermal reaction of time, drying obtains the thin of Uniform Doped
Powder material；The fine silt thing of Uniform Doped is in Muffle furnace, through high temperature sintering, and organic matter carbonization therein is further strengthened
The microcellular structure of porous carrier, obtains porous carrier supported rare earth metal oxide, transition metal oxide and noble metal shape
Into catalytic active center ozone Heterogeneous oxidation solid catalyst, improve the mithridatism and catalytic activity of catalyst.
Relative to art methods, outstanding feature of the present invention is using diatom is pure, kyanite, hydroxide in technology of preparing
Aluminium, celestine, cubric niter, dolomite porous material make carrier, due to lithium hypochlorite LiClO and double (acetylacetone,2,4-pentanedione) berylliums
C10H14BeO4Reaming effect, Cationic surfucant [C12H25N(CH3)2CH2CH2OH]+Cl-, three（16
Alkyl）Methyl bromide ammonium [(C16H33)3NCH3]+ Br-The interconnected and surface activation in duct；Made by hydro-thermal reaction dilute
Earth metal organic compound, normal transition metallo-organic compound and precious metal chemical complex reach Uniform Doped and are attached to carrier
In surface and duct, high temperature sintering makes organic matter carbonization strengthen and form multi-level microcellular structure, and porous carrier is born
Carry the multi-element metal catalytic active center and porous carrier knot of rare-earth oxide, transition metal oxide and noble metal formation
Close more firm, the ozone Heterogeneous oxidation solid catalyst of preparation has a stronger adsorptivity, the cooperative effect of multi-element metal,
Stability and high activity that particularly doped precious metal has, can suppress liquating out for metal catalytic activity component, improve
The mithridatism and catalytic activity of catalyst, with good environmental benefit and economic benefit.
Embodiment
Embodiment 1:1.35g lithium hypochlorites, double (acetylacetone,2,4-pentanedione) berylliums of 1.65g, 140ml deionized waters, 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 diatoms of 400 mesh standard sieves are pure, 3.75g kyanites, 4.75g aluminium hydroxides, 5.75g celestines, 6.75g cubric niters,
The weight of 7.75g dolomites, 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, 3.25g Cationic surfucants 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, chlorination dimethyl
Base hydroxyethyl ammonium（3.25g）:Reaming modified support（31g ）=1:9.5；It is 0.4W/m to control ultrasonic power density3, ultrasonic wave frequency
41 DEG C of rate 21kHz, temperature, sonic oscillation 2.2h；After the completion of ultrasonic activation, the ultrasonic surface in ultrasound reactor is activated and carried
Body mixed liquor is transferred in 500ml hydrothermal reaction kettles, is added by 2.1g boraxs, 3.05g potassium sulfates, (the hexafluoro acetyl of 1.6g tri-
Acetone) yttrium (III) dihydrate, 2.05g acetylacetone,2,4-pentanediones samarium, (4,4,4- tri- fluoro- 1- (2- the thiophene) -1,3- fourths two of 2.6g tri-
Ketone) europium, 3.05g tri- (DPM dpm,dipivalomethane acid) gadolinium, 5.05g pyruvic acid isonicotinoyl hydrazones vanadium, 6.1g citric acids
Nickel, 2.05g cupric glutamates, the nitroso rhodium trisodiums of 3.1g six, 3.05g tri-（Cetyl）Methyl bromide ammonium 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 diatoms of 400 mesh standard sieves are pure, 1.65g kyanites, 1.85g aluminium hydroxides, 2.05g celestines, 2.25g cubric niters,
The weight of 2.45g dolomites, 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 chlorination dodecyl dimethyl ethoxys are added
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 dodecyl
Dimethyl hydroxyethyl ammonium（2.2g）:Reaming modified support（11.5g ）=1:5.2；It is 0.7W/m to control ultrasonic power density3, it is super
54 DEG C of frequency of sound wave 29kHz, temperature, sonic oscillation 4.7h；After the completion of ultrasonic activation, the ultrasonic surface in ultrasound reactor
Activated carrier mixed liquor is transferred in 100ml hydrothermal reaction kettles, is added by 0.78g boraxs, 0.97g potassium sulfates, 0.58g tri-
(hexafluoroacetylacetone) yttrium (III) dihydrate, 0.67g acetylacetone,2,4-pentanediones samarium, 0.78g tri- (the fluoro- 1- of 4,4,4- tri- (2- thiophene)-
1,3- diacetyl) europium, 0.87g tri- (DPM dpm,dipivalomethane acid) gadolinium, 1.48g pyruvic acid isonicotinoyl hydrazones vanadium,
1.77g citric acids nickel, 0.68g cupric glutamates, the nitroso rhodium trisodiums of 0.87g six, 1.98g tri-（Cetyl）Methyl bromide ammonium and
The aqueous solution that 10ml deionized waters are prepared, the weight concentration of the aqueous solution is 53.3%, the weight of the aqueous solution:Ultrasonic surface is lived
Change weight=21.43g of carrier mixed liquor:39.7g=1:1.9,175 DEG C of temperature is controlled, the hydro-thermal reaction time is 15.5h, then
105 DEG C dry to obtain fine silt thing；Fine silt thing is in Muffle furnace, 930 DEG C, calcination 7.5h, after cooling down, can obtain fine powder
Granular ozone Heterogeneous oxidation solid catalyst.
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
Point by diatom is pure, kyanite, aluminium hydroxide, celestine, cubric niter and dolomite are constituted, by weight, diatom is pure:Kyanite:
Aluminium hydroxide:Celestine:Cubric niter:Dolomitic weight ratio=（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 chlorination dodecane
Base dimethyl hydroxyethyl ammonium, by weight, component C:Weight ratio=1 of reaming modified support:（5~10）, D components are by being combined
Mineralizer borax, potassium sulfate, catalytic activity auxiliary agent predecessor three (hexafluoroacetylacetone) yttrium (III) dihydrate, acetylacetone,2,4-pentanedione
Samarium, three (4,4,4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europiums, three (DPM dpm,dipivalomethane acid) gadoliniums are dilute
Earth metal organic compound, catalytic active center predecessor normal transition metallo-organic compound pyruvic acid isonicotinoyl hydrazone vanadium, lemon
Lemon acid nickel, cupric glutamate and the nitroso rhodium trisodium of precious metal chemical complex six, emulsifying agent three（Cetyl）Methyl bromide ammonium group
Into, by weight, borax:Potassium sulfate:Three (hexafluoroacetylacetone) yttrium (III) dihydrates:Acetylacetone,2,4-pentanedione samarium:Three (4,4,
4- tri- fluoro- 1- (2- thiophene) -1,3- diacetyl) europium:Three (DPM dpm,dipivalomethane acid) gadoliniums:The different cigarette of pyruvic acid
Acylhydrazone vanadium:Citric acid nickel:Cupric glutamate:Six nitroso rhodium trisodiums:Three（Cetyl）The weight ratio of methyl bromide ammonium=
（4~8）:（6~10）:（3~6）:（4~7）:（5~8）:（6~9）:（10~15）:（12~18）:（4~7）:（6~9）:（6
~20）.
2. according to claim 1 B component by diatom is pure, kyanite, aluminium hydroxide, celestine, cubric niter and dolomite group
Into diatom is pure, kyanite, aluminium hydroxide, celestine, cubric niter and dolomite 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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Application publication date: 20170808 |