CN100366584C - Preparation method of TiO2 photocatalyst for loading on ceramic surface - Google Patents
Preparation method of TiO2 photocatalyst for loading on ceramic surface Download PDFInfo
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- CN100366584C CN100366584C CNB2005100408933A CN200510040893A CN100366584C CN 100366584 C CN100366584 C CN 100366584C CN B2005100408933 A CNB2005100408933 A CN B2005100408933A CN 200510040893 A CN200510040893 A CN 200510040893A CN 100366584 C CN100366584 C CN 100366584C
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- photocatalyst
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- 239000000919 ceramic Substances 0.000 title claims abstract description 44
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 18
- 238000011068 loading method Methods 0.000 title abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 15
- 238000003980 solgel method Methods 0.000 claims abstract description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 56
- 238000010792 warming Methods 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052572 stoneware Inorganic materials 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000012876 carrier material Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000006303 photolysis reaction Methods 0.000 abstract description 16
- 238000012360 testing method Methods 0.000 abstract description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- -1 propyl titanate Chemical compound 0.000 abstract description 6
- 239000000969 carrier Substances 0.000 abstract 5
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 36
- 238000000034 method Methods 0.000 description 28
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 239000002689 soil Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003610 charcoal Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000003905 agrochemical Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- TWFZGCMQGLPBSX-UHFFFAOYSA-N carbendazim Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- JNPZQRQPIHJYNM-UHFFFAOYSA-N carbendazim Chemical compound C1=C[CH]C2=NC(NC(=O)OC)=NC2=C1 JNPZQRQPIHJYNM-UHFFFAOYSA-N 0.000 description 1
- 239000006013 carbendazim Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011284 combination treatment Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000003351 photoxidation Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011032 tourmaline Substances 0.000 description 1
- 229940070527 tourmaline Drugs 0.000 description 1
- 229910052613 tourmaline Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
The present invention relates to a preparation method for TiO2 photocatalysts loading on a ceramic surface. Materials of compact ceramic carriers are loaded by TiO2 collosol, and a sol-gel method is adopted to load, the TiO2 collosol is prepared through butyl titanate or propyl titanate dissolving into acid, alcohol and water, finished ceramic carriers which are washed and baked are dipped into the TiO2 collosol for 2 to 40 min, and then the finished ceramic carriers are dried; the carriers loading the collosol are baked in a furnace, the temperature is raised to 80 to 250 DEG C from the room temperature to be maintained for 10 to 80 min, then the temperature is raised to 250 to 400 DEG C to be maintained for 20 to 80 min, the temperature is further raised to 450 to 550 DEG C to be maintained for 40 to 90 min, and then the carriers are cooled to the room temperature. After TiO2 films experience six months and 26 photolysis tests, the photolysis rate constant of phenol is only reduced by about 10%, and the stable catalytic activity is displayed.
Description
One, technical field
The present invention relates to TiO
2Photocatalyst is in the preparation method of area load.
Two, background technology
Photocatalytic oxidation be based on photocatalyst in aqueous systems because of light action produces the very strong active oxygen of oxidation capacity (as hydroxyl radical free radical etc.), can make various types of oxidation of organic compounds, eventual degradation Cheng Shui, CO
2And inorganics.The effect of organic compound (as dyestuff, agricultural chemicals etc.) that molecule is contained heterocycle or unsaturated link(age) is better, is the very potential method of a kind of waste water control, drink water purifying.Semi-conductor TiO
2Be most typical photocatalyst, have that chemical property is stable, nontoxicity, inexpensive, reaction conditions is gentle, advantages such as non-secondary pollution.But powdered form TiO
2The difficult recovery in addition, has only wavelength just can make its produce katalysis less than the UV-light of 387nm, the drawbacks limit that these are fatal its application in waste water treatment.The personage has done many explorations for this reason both at home and abroad, and one of measure is with TiO
2Be fixed on the carrier.The carrier of having reported has metal, glass, pottery and textile fibres etc., but the carrier loaded back TiO that has
2Easily come off, the carrier cracky that has is difficult in industrial application.
CN1587085 cartridge type photo catalysis reactor and water treatment method thereof, comprise tank, ultraviolet lamp, rotating cylinder, described tank is provided with water-in and water outlet, the two ends of described rotating cylinder are connected with support by the back up pad that is provided with bearing, described rotating cylinder is horizontally set in the described tank, buncher carries out transmission by the gear interlock on timing belt and the rotating cylinder outer wall, scribble TiO2 photocatalyst thin layer on the inwall of described rotating cylinder, described ultraviolet lamp is arranged on the tapping of the one or both sides of described tank, the present invention is that the main part with reactor is designed to drum-type, supported catalyst TiO#-[2 on rotating cylinder] film changes the distribution of handling waste water and catalyzer by the rotating speed of regulating rotating cylinder, increased catalyzer, contact surface between reactant and the light source.
The preparation method of CN1515352 loading type light catalytic purifying net piece, adopt gac as sorbent material, efficient composite catalyst is as photocatalyst, tourmalinite is as subsidiary material, with gac, composite photo-catalyst and tourmaline powder carry out the effectively compound multifunctional efficient photocatalyst for preparing by the physical mechanical blending means, adopt water-based latex as tackiness agent then, the multifunctional efficient photocatalyst is mixed with the water-base cement emulsion, disperse, make stable suspension slurry, adopt spraying or dipping process that the catalyst cupport carrier is evenly covered catalyst coat at last, obtain loading type light catalytic purifying net piece.
The glass microballon of a CN1490079 high absorbability photocatalysis performance is by forming by generated in-situ nano active charcoal with through the TiO2 photocatalysis thin film of silver or zinc or copper burning modification of hollow glass micropearl carrier and top layer load.Photocatalyst film possesses the excellent properties of nano active charcoal and composite photo-catalyst.Its main preparation technology adds pasted starch in dehydrated alcohol; photocatalyst presoma butyl (tetra) titanate; diethanolamine and polyoxyethylene glycol; Silver Nitrate or cupric nitrate or zinc nitrate stir and make colloidal sol, and dipping is through the hollow glass micropearl of cleaning oven dry; then in shielding gas; after 300～650 ℃ of following carbonization-activation, cellular in the formation of glass microballon surface, the photocatalyst film of nano active charcoal and nano composite photo-catalyst structure.
The material and the preparation of the inorganic heatproof carrier surface of CN1491743 load gradient composite performance photocatalysis thin film, it is a kind of method at glass or ceramic monolith surface preparation composite photocatalyst thin-film, the film of preparation possesses the variation of gradient composition, gradient performance changes and honeycomb structure, and hydrophilicity is arranged.Film is 3～10 layers, with the colloidal sol of different ingredients repeatedly load form.Colloidal sol is mixed by dehydrated alcohol, butyl (tetra) titanate and diethanolamine, polyoxyethylene glycol, tetraethyl silicate, pasted starch, Zulkovsky starch, Silver Nitrate or cupric nitrate or zinc nitrate and forms.Through washed glass or ceramic monolith surface impregnation or after applying described colloidal sol,, form the gradient composite photocatalyst thin-film of high absorbability nano active charcoal and hydrophilicity through high temperature carbonization, activation treatment.
The method of the photocatalyst film of above-mentioned nano active charcoal and nano composite photo-catalyst structure and glass or ceramic monolith surface preparation composite photocatalyst thin-film is arranged and need be controlled the whether assurance nanometer of film, still must improving of the method for high temperature carbonization, activation treatment could form practical photocatalyst film like this.
Pottery is a kind of dense form pottery later, that development is very fast of developing, and has the blank sintering densification, and porosity and water-intake rate are low, can be processed into the advantages such as container of different shapes and size.Especially its high mechanical strength, anti-vibration, breakage resistant luer, characteristics cheaply, more giving it becomes a kind of ideal solid support material.Close report but still find no so far both at home and abroad.
The experience of the photochemical degradation work of organic pollutants such as dyestuff, agricultural chemicals, weedicide, tensio-active agent, oil and goods is engaged in utilization of the present invention for many years always.Problem according to state natural sciences funds such as " the free radical mechanism of action of water surrounding PetroChina Company Limited. hydrocarbon photochemical degradation " born and multinomial equipment development and utilisation technology." phenol pause reaction depth photoxidation wastewater treatment preparation " obtained and " light helps the method for Fenton's reaction, flocculation and microbiological deterioration combination treatment waste water ".
Three, summary of the invention
The present invention seeks to: a kind of TiO is provided
2Photocatalyst is in the preparation method of ceramic surface load, especially at the dense form pottery---and stoneware is solid support material load TiO
2Photocatalyst.Obtain a kind of high mechanical strength, anti-vibration, breakage resistant luer, solid support material cheaply; Formation has the nano TiO 2 photocatalyst film of efficient catalytic effect, guarantees the arrangement of TiO2 nanometer, and method is controlled easily, and film quality guarantees to some extent.And thoroughly solve TiO
2Loss in water treatment problem.
The object of the invention also is to provide a kind of Fe of mixing
+ 3TiO
2Photocatalyst makes absorption spectrum " blue shift ", improves catalytic effect.
The object of the present invention is achieved like this: TiO
2Photocatalyst is in the preparation method of ceramic surface load, in that the dense form pottery---ceramic carrier material is with TiO
2The colloidal sol load, adopt the sol-gel method load: the finished product ceramic monolith of will clean, drying is dipped in TiO
22-40min in the colloidal sol dries; In stove the roasting load carrier of colloidal sol, rise to 80-250 ℃ from room temperature, keep 10-80min; Be warming up to 250-400 ℃ then, keep 20-80min; Be warming up to 450-550 ℃ again, keep 40-90min; Cool to room temperature with the furnace.Can butyl (tetra) titanate or titanium propanolate be raw material, described acid is hydrochloric acid, oxalic acid, Glacial acetic acid or methacrylic acid; Described alcohol is ethanol, n-propyl alcohol, Virahol, propyl carbinol; The mol ratio 1 of butyl (tetra) titanate and acid, alcohol, water, diethanolamine: 6-10: 8-20: 2-6: 1 mixes, and obtains even, transparent TiO
2Colloidal sol.
At above-mentioned TiO
2In the colloidal sol, with the ratio adding Fe (NO of mol ratio 0.002-0.006
3)
39H
2O obtains mixing Fe
+ 3Colloidal sol.At described TiO
2Colloidal sol or mix Fe
+ 3Colloidal sol load and roasting 2 to 6 times.
TiO of the present invention
2Colloidal sol is conventional colloidal sol: be main raw material with butyl (tetra) titanate (or propyl ester) generally, auxiliary material is for acid, pure, water and can prolong the diethanolamine in colloidal sol life-span and be prepared.Adopt L
16(4
5) orthogonal test, 5 factors of design are respectively that kind (hydrochloric acid, oxalic acid, Glacial acetic acid, methacrylic acid), the acid of acid is measured, the consumption of kind (ethanol, n-propyl alcohol, Virahol, propyl carbinol), pure consumption and the water of alcohol; Each factor has designed 4 levels.According to experimental result and statistical study, the best preparation scheme that obtains colloidal sol be with butyl (tetra) titanate, Glacial acetic acid, propyl carbinol, water, diethanolamine by its mol ratio 1: 8: 10: mix at 3: 1, obtain even, transparent TiO
2Colloidal sol, recording its viscosity is 4.93 * 10
3PaS.Simultaneously, other gets a and preparation TiO
2The reagent that colloidal sol is identical, 0.003 adds Fe (NO in molar ratio
3)
39H
2O obtains mixing Fe
+ 3Colloidal sol.
Above load and roasting process are repeated 2-6 time.
Characteristics of the present invention are: provide TiO
2Being carried on ceramic of compact effectively---the preparation method of ceramic surface obtains a kind of high mechanical strength, anti-vibration, breakage resistant luer, carrier cheaply; Formation has the nano-TiO of efficient catalytic effect
2Photocatalyst film guarantees TiO
2Nanometer is arranged, and method is controlled easily, and film quality guarantees to some extent.With thorough solution TiO
2Loss in water treatment.By to TiO
2In mix Fe
+ 3, cause absorption spectrum " blue shift ", promote photoelectricity to transform, thereby reduce cost for wastewater treatment.The present invention can provide reliable basis for the application of photocatalysis oxidation technique.Prepared metatitanic acid colloidal sol (TiO respectively
2Precursor) and ceramic monolith; Implemented TiO with sol-gel method and temperature-programmed calcination method
2Load at ceramic surface; Adopt weighting method to draw TiO
2Charge capacity be 0.21mg/cm
2Adopt X diffraction approach (XRD) to measure and calculate, obtain the powder TiO of preparation under the similarity condition
2Crystal formation is Detitanium-ore-type completely, TiO
2Median size be 15nm; The thickness that adopts scanning electron microscope method (SEM) to record loaded film is 350～400nm, TiO in the film
2Particle diameter is 15～20nm, and marshalling; The main component that adopts electron spectroscopy for chemical analysis (XPS) to record loaded film is TiO
2By the photodissociation test of phenol under static conditions, show TiO
2Film Pyrogentisinic Acid's photodissociation rate constant improves 40%; By the photodissociation test of derosal agricultural chemicals waste water under dynamic condition, also show TiO
2Film improves 7.2% to this COD removal; The present invention also in the ceramic surface load mix Fe
+ 3TiO
2Film, this kind film can make phenol photodissociation rate constant compare TiO
2Film improves 42.5%, adopts inductively coupled plasma direct-reading spectrometer (ICP) to measure, and obtains the powder TiO of preparation under the similarity condition
2Contain Fe
+ 3Amount is 0.044%; TiO
2Film experienced 6 months, after 26 photodissociation tests, the photodissociation rate constant of phenol only reduces about 10%, has shown more stable catalytic activity.The surface of film of the present invention has the good adsorption performance.
Four, description of drawings
Fig. 1 for load of the present invention TiO
2The surperficial SEM figure of ceramic stoneware
Fig. 2 for load of the present invention TiO
2The transverse section SEM figure of ceramic stoneware
Five, embodiment
The preparation of ceramic monolith: can use general pottery, guarantee that especially goods have high mechanical strength, anti-vibration, breakage resistant luer, the ceramic formula of solid support material cheaply, generally based on kaolin.Better fill a prescription following (intensity height, cost is low simultaneously):
The mixing raw material of preparation stoneware pottery is planetesimal soil, Jinjiang soil, East Lake mud, Shunchang soil, small stream mouth soil, Ningguo's soil, quartz, kieselguhr, Langxi soil, light good fortune soil, Suzhou soil etc., and the percentage composition of various compositions is: SiO
2Be 62.63, Fe
2O
3Be 0.77, Ae
2O
3Be 26.34, CaO is 0.47, and MgO is 0.14, K
2O is 1.30, Na
2O is 0.71, and the igloss amount is 7.64.Ceramic monolith is divided into two kinds of tubulose, sheets: ceramic pipe range 400mm, internal diameter 100mm, wall thickness 20mm; Ceramic plate is shaped as 90mm * 45mm * 3mm. manufacture craft following (conventional ceramic process): preparation base substrate pug, slip casing by pressure, making moulded pottery not yet put in a kiln to bake, drying, biscuiting, correction of the flank shape, glazing, airing, glaze firing obtain finished product.
The biscuiting of base substrate adopts programmed temperature method to carry out in chamber type electric resistance furnace: 1. the speed with 1.4 ℃/min rises to 300 ℃ from room temperature, keeps 30min; 2. the speed with 2.6 ℃/min is warming up to 924 ℃, and keeps 120min; 3. cool to room temperature with the furnace.
Base substrate after the burning needs the last layer transparent, and the representative formula of glaze is per-cent (weight): feldspar is 49, and calcite is 12, and Suzhou stone is 7, and burning high mountain range is 14, and barium carbonate is 14, and zinc oxide is 4.The glaze firing technique of glazing base substrate still adopts programmed temperature method to carry out in chamber type electric resistance furnace: 1. the speed with 10.3 ℃/min rises to 980 ℃ from room temperature, keeps 60min; 2. the speed with 3.7 ℃/min is warming up to 1200 ℃, and keeps 60min; 3. cool to room temperature with the furnace.
Finished product detection result is: the shrinking percentage of vitrified pipe is 8.26%, and water-intake rate is 3.76%; The shrinking percentage of ceramic plate is 8.07%, and water-intake rate is 3.93%.
TiO
2The colloidal sol preparation
With the butyl (tetra) titanate is main raw material, and auxiliary material is acid, alcohol, water and the diethanolamine that can prolong the colloidal sol life-span.Adopt L
16(4
5) orthogonal test, 5 factors of design are respectively that kind (hydrochloric acid, oxalic acid, Glacial acetic acid, methacrylic acid), the acid of acid is measured, the consumption of kind (ethanol, n-propyl alcohol, Virahol, propyl carbinol), pure consumption and the water of alcohol; Each factor has designed 4 levels.According to test-results and statistical study, the best preparation scheme that obtains colloidal sol be with butyl (tetra) titanate, Glacial acetic acid, propyl carbinol, water, diethanolamine by its mol ratio 1: 8: 10: mix at 3: 1, obtain even, transparent pure TiO
2Colloidal sol, its viscosity are 4.93 * 10
3PaS, the ageing a few days is stand-by.Simultaneously, other gets a and the pure TiO of preparation
2The reagent that colloidal sol is identical, 0.003 adds Fe (NO in molar ratio
3)
39H
2O obtains mixing Fe
+ 3Colloidal sol.
Titanium propanolate is that raw material can obtain equifinality, and the amount of titanium is more less slightly.
TiO
2Colloidal sol is load on pottery:
Adopt the sol-gel method load: the finished product ceramic monolith that (1) will be cleaned, dry (tubulose or sheet) is dipped in TiO
25min in the colloidal sol lifts with the 5cm/min linear velocity then, dries.(2) in chamber type electric resistance furnace the roasting load carrier of colloidal sol, temperature programming is: 1. the speed with 5 ℃/min rises to 100 ℃ from room temperature, keeps 30min; 2. the speed with 5 ℃/min is warming up to 200 ℃, keeps 30min; 3. the speed with 5 ℃/min is warming up to 300 ℃, keeps 30min; 4. the speed with 5 ℃/min is warming up to 400 ℃, keeps 30min; 5. the speed with 5 ℃/min is warming up to 500 ℃, keeps 60min; 6. cool to room temperature with the furnace.Above process is repeated 4 times, make it to experience 4 loads and roasting.
The invention provides TiO
2Be carried on the ceramic surface technology effectively, with thorough solution TiO
2Loss in water treatment.Pass through to TiO simultaneously
2In mix Fe
+ 3, cause absorption spectrum " blue shift ", promote photoelectricity to transform, thereby reduce cost for wastewater treatment.The present invention can provide reliable basis for the application of photocatalysis oxidation technique.
Can make the required pure TiO of generation on the carrier with this method
2Film or contain Fe
+ 3TiO
2Film.
TiO
2The physicochemical property test of film
(1) adopt weighting method to draw the TiO of ceramic surface after 4 loads
2Amount is for only being 0.21mg/cm
2, the film difficult drop-off of this low charge capacity, smooth with carrier surface, smooth, fine and close relevant.
(2) adopt the SEM method to measure the configuration of surface and the thickness of film, the results are shown in accompanying drawing 1 and accompanying drawing 2.Fig. 1 for load TiO
2Ceramic surface SEM figure, TiO as can be seen
2Particle alignment is neat, TiO
2Particle diameter is about 15～20nm.Fig. 2 for load TiO
2The transverse section SEM figure of pottery, the TiO on demonstration top layer
2About 350～the 400nm of film thickness, and thickness is even.
(3) adopt xrd method to powdered form TiO
2Mensuration and Myers method of calculation show the TiO of preparation
2Crystal formation is Detitanium-ore-type completely.Calculate the about 15nm of its median size according to the Scherrer formula, basic identical with the measurement result of SEM method.Show powdered form TiO
2With TiO in the load layer
2Particle diameter identical, be nano level.
(4) adopt the ICP method to measure, similarity condition is the powder TiO of preparation down
2Middle Fe
+ 3Content is 0.044%.
(5) XPS method analysis revealed, bound energy be 458 and each power spectrum of 531eV in the photoelectron peak of Ti2P and OlS has all significantly appearred, the top layer film that ceramic load is described is mainly by TiO
2Form, this result with ICP is consistent.
(6) TiO
2The photocatalytic activity of film is by the degradation of phenol aqueous solution and the checking of derosal agricultural chemicals waste water liquid.Phenol solution photodissociation test of (being first valve state) under static conditions shows TiO
2Film Pyrogentisinic Acid's photodissociation rate constant can improve 40%.Carbendazim wastewater photodissociation test of (being flow state) under dynamic condition also shows TiO
2Film can improve 7.2% to the clearance of this waste water COD.All demonstrate TiO
2The photocatalytic activity of film.
(7) the static photodissociation test card of phenol solution is bright, mixes Fe
+ 3TiO
2Film makes the photodissociation rate constant of phenol than pure TiO
2Film improves 42.5%.
(8) photodissociation of phenol test also shows TiO
2Film experienced 6 months, after 26 photodissociation tests, the photodissociation rate constant of phenol only reduces about 10%, has shown more stable catalytic activity.
Claims (7)
1.TiO
2Photocatalyst is characterized in that at the dense form ceramic carrier material with TiO in the preparation method of ceramic surface load
2The colloidal sol load, and adopt the sol-gel method load; TiO
2Colloidal sol is dissolved in acid, alcohol, the water with butyl (tetra) titanate or titanium propanolate and is prepared from; The finished product ceramic monolith of cleaning, dry is dipped in TiO
22-40min in the colloidal sol dries; In stove the roasting load carrier of colloidal sol, rise to 80-250 ℃ from room temperature, keep 10-80min; Be warming up to 250-400 ℃ then, keep 20-80min; Be warming up to 450-550 ℃ again, keep 40-90min; Cool to room temperature with the furnace.
2. by the described TiO of claim 1
2Photocatalyst is characterized in that TiO in the preparation method of ceramic surface load
2Colloidal sol butyl (tetra) titanate or titanium propanolate are raw material, and described acid is hydrochloric acid, oxalic acid, Glacial acetic acid or methacrylic acid; Described alcohol is ethanol, n-propyl alcohol, Virahol or propyl carbinol; The mol ratio 1 of butyl (tetra) titanate or titanium propanolate and acid, alcohol, water and the diethanolamine that adds in addition: 6-10: 8-20: 2-6: 1 mixes, and obtains even, transparent TiO
2Colloidal sol.
3. by the described TiO of claim 2
2Photocatalyst is characterized in that at TiO in the preparation method of ceramic surface load
2Mol ratio 0.002-0.006 adds Fe (NO in the colloidal sol
3)
39H
2O obtains mixing Fe
+ 3Colloidal sol.
4. by the described TiO of claim 3
2Photocatalyst is characterized in that at described TiO in the preparation method of ceramic surface load
2Colloidal sol or mix Fe
+ 3Colloidal sol load and roasting 2 to 6 times.
5. by the described TiO of claim 1
2Photocatalyst is characterized in that in the preparation method of ceramic surface load with the finished product ceramic monolith of cleaning, dry be tubulose or sheet.
6. by the described TiO of claim 1
2Photocatalyst is characterized in that in the preparation method of ceramic surface load ceramic monolith is dipped in TiO
2In the colloidal sol, lift, dry with the 5cm/min linear velocity; In chamber type electric resistance furnace the roasting load carrier of colloidal sol, temperature programming is: 1. the speed with 5 ℃/min rises to 100 ℃ from room temperature, keeps 30min; 2. the speed with 5 ℃/min is warming up to 200 ℃, keeps 30min; 3. the speed with 5 ℃/min is warming up to 300 ℃, keeps 30min; 4. the speed with 5 ℃/min is warming up to 400 ℃, keeps 30min; 5. the speed with 5 ℃/min is warming up to 500 ℃, keeps 60min; 6. cool to room temperature with the furnace.
7. by the described TiO of claim 1
2Photocatalyst is characterized in that in the preparation method of ceramic surface load described ceramic carrier material is a dense form stoneware pottery.
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| CN101972639B (en) * | 2010-09-30 | 2012-05-30 | 中国石油大学(华东) | Method for preparing high-activity titanium dioxide photocatalyst by using segmental calcination method |
| CN102180705B (en) * | 2011-02-28 | 2013-04-10 | 武汉大方机电有限公司 | Preparation method for titanium dioxide thin layer loaded on surface of inorganic ceramic matrix |
| CN102728339B (en) * | 2012-06-21 | 2014-06-25 | 华北电力大学 | Porous inorganic ceramic membrane-graphene-TiO2 photocatalyst composite material and its preparation method |
| CN105384464B (en) * | 2015-11-10 | 2018-01-02 | 河海大学 | A kind of preparation method and device of bottom photocatalysis Porous permeable bricks |
| CN107973599A (en) * | 2016-10-21 | 2018-05-01 | 江苏今道投资发展有限公司 | Titanium deoxid film preparation method based on sol-gal process |
| CN106587630B (en) * | 2016-12-26 | 2019-01-22 | 陕西科技大学 | A kind of preparation method with photo-catalysis function zirconic acid yttrium ceramic microcrystalline milkiness glaze |
| CN111635260A (en) * | 2020-06-04 | 2020-09-08 | 朱叶华 | Preparation method of ceramic material for photocatalysis |
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| CN1220185A (en) * | 1997-12-18 | 1999-06-23 | 中国科学院光电技术研究所 | Titanium dioxide optical catalyst and its preparing method |
| CN1490079A (en) * | 2003-09-01 | 2004-04-21 | 武汉理工大学 | High-adsorbability glass beads with photocatalysis function |
| CN1491743A (en) * | 2003-09-10 | 2004-04-28 | 武汉理工大学 | Composite material of inorganic temperature-resistant carrier and loaded gradient photocatalytic film and its preparation |
| CN1515352A (en) * | 2003-08-28 | 2004-07-28 | 上海交通大学 | Preparation method of load type photocatalytic purification net block |
| CN1587085A (en) * | 2004-09-09 | 2005-03-02 | 天津理工大学 | Rotary tubular photo-catalytic reactor and its water treating method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1220185A (en) * | 1997-12-18 | 1999-06-23 | 中国科学院光电技术研究所 | Titanium dioxide optical catalyst and its preparing method |
| CN1515352A (en) * | 2003-08-28 | 2004-07-28 | 上海交通大学 | Preparation method of load type photocatalytic purification net block |
| CN1490079A (en) * | 2003-09-01 | 2004-04-21 | 武汉理工大学 | High-adsorbability glass beads with photocatalysis function |
| CN1491743A (en) * | 2003-09-10 | 2004-04-28 | 武汉理工大学 | Composite material of inorganic temperature-resistant carrier and loaded gradient photocatalytic film and its preparation |
| CN1587085A (en) * | 2004-09-09 | 2005-03-02 | 天津理工大学 | Rotary tubular photo-catalytic reactor and its water treating method |
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