CN101104525B - Method for preparing anatase type bentonite-base porous titanium dioxide nano material - Google Patents
Method for preparing anatase type bentonite-base porous titanium dioxide nano material Download PDFInfo
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- CN101104525B CN101104525B CN200710070703A CN200710070703A CN101104525B CN 101104525 B CN101104525 B CN 101104525B CN 200710070703 A CN200710070703 A CN 200710070703A CN 200710070703 A CN200710070703 A CN 200710070703A CN 101104525 B CN101104525 B CN 101104525B
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- organobentonite
- titanium dioxide
- nano material
- dioxide nano
- titanate
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Abstract
The present invention discloses a preparation method for an anatase type bentonite-based porous TiO2 nanometer material. The preparation method is that the organic bentonite after dehydration and drying or the organic bentonite abandoned after wastewater treatment is added with the mixture of amine and titanate or only added with titanate; then after well mixing and centrifuging, the supernate is abandoned and the solid part left will be removed from surfactant and organic materials through drying and high-temperature calcinations, thus the porous TiO2 nanometer material is obtained. The material prepared by the invention is of large specific surface area, smaller grain size, single particle size and uniform pore distribution, wherein, the aperture ranges between micropore and mesopore and the pores are in high sequence degree. The material is mainly anatase type and is provided with relatively high catalytic activity, which can be applied to the indoor organic pollutant purification field. At the same time, the present invention provides a very good solution to the ultimate disposition of abandoned organobentonite, and makes good use of the abandoned organobentonite after wastewater treatment to achieve the treatment of a waste with another waste. The preparation method is of low energy consumption, simple preparation process, optimal pH control and no need of acid, which is suitable for large-scale engineering applications.
Description
Technical field
The invention belongs to the porous nanometer material technical field, be specifically related to a kind of preparation method of anatase type bentonite-base porous titanium dioxide nano material.Particularly with organobentonite or after handling organic waste water the depleted organobentonite as main body clay starting material and provide cats product to prepare the method for poriferous titanium dioxide nano material.
Background technology
Nanometer titanic oxide material is the research focus of material and catalytic field, shows special advantages aspect the organic pollutant in catalyzed degradation water and in the air.TiO since discovery rayings such as Fujishima in 1972
2Since the redox reaction that the surface take place to continue, scholars started light-catalysed research boom (ZhaoJ, Yang XD.Building and Environment.2003,38,645-654).This technology is through UV-irradiation, just compound oxidations such as many organic pollutants such as chloro thing, aldehydes, ketone, alcohols, aromatic series can be become nontoxic CO at ambient temperature
2And H
2O simultaneously can oxidation other inorganic obnoxious flavour such as CO, NOx etc., effectively sterilization simultaneously.
At present, be used to prepare nano-TiO
2Method have a lot, can be divided into following several usually according to the difference of physical properties: solid phase method, vapor phase process, liquid phase method.Liquid phase method is research at present and uses all a kind of nano-TiO
2The preparation method, sol-gel method, hydrolysis method, the precipitator method, microemulsion method and solvent-thermal method etc. are more typically arranged.Because unique nanometer interlayer space and microvoid structure, laminated clay (as wilkinite) has caused people's attention at catalytic field.People design the angle of catalyzer, regulation and control catalytic performance from molecule and atomic level, and imagination embeds semiconductive particles at the bentonite nano interlayer can demonstrate very high photocatalysis performance.The main preparation method of bentonite base nanometer titanic oxide material is (Stere JP.Clays Clay Miner.1996,34,655-664 so far; Choudary BM, Rani SS, Narender N.Catal.Lett.1993,19,299-307): inorganic ti sources (TiCl
4Or Ti (SO
4)
2Deng) or titanium alkoxide (butyl (tetra) titanate etc.) hydrolysis in organic medium, polycondensation obtain gel; Gel is through ageing, makes after calcining at a certain temperature with wilkinite aqeous suspension reaction gained finished product.These preparation methods carry out in water solution system, and earlier synthetic titanium gel and ageing are consuming time longer; Preparation process need be optimized adjusting pH value, and operating process is wayward; Because titanium source hydrolysis reaction need carry out under the acidic conditions of harshness, very easily causes the corrosion of wilkinite structural damage and equipment.
Wilkinite is to be typical 2: the 1 type layered clay minerals that essential mineral is formed with the montmorillonite, and the organobentonite that forms after tensio-active agent carries out organic modification shows excellent absorption property to organism.The present invention has solved the bentonite problem of complex utilization of having adsorbed organic pollutant simultaneously well, can not only reduce processing cost, and can avoid secondary pollution.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of bentonite base poriferous titanium dioxide nano material.The present invention is intended to simplify synthetic route, reduces operation easier and realizes stably manufactured.
The synthetic method of bentonite base poriferous titanium dioxide nano material is as synthetic main body clay starting material with the organobentonite behind organobentonite or the adsorption treatment organic waste water, promptly obtain the poriferous titanium dioxide nano material after the intermediate roasting of template one-step synthesis gained, concrete preparation process is as follows:
1) with wilkinite and cats product by mass ratio be 1: 0.2～1: 2 in water hybrid reaction make organobentonite, through solid-liquid separation, solid drying 2～48h is to remove ADSORPTION STATE moisture, and is standby;
2) with the organobentonite solid-liquid separation behind the adsorption treatment waste water, solid drying 2～48h is to remove ADSORPTION STATE moisture, and is standby;
3) with step 1) or step 2) dried organobentonite, cosurfactant and titanate ester be by organobentonite: cosurfactant: the mass ratio of titanate ester is to mix in 1: 0.5: 5～1: 2: 200, in 20～90 ℃ of following stirring reaction 2～8h; Or with step 1) or step 2) dried organobentonite, titanate ester be by organobentonite: the mass ratio of titanate ester is to mix in 1: 5～1: 200, in 20～90 ℃ of following stirring reaction 2～8h;
4) with above-mentioned product solid-liquid separation, solid need not washing, obtains intermediate after 20～150 ℃ of dryings;
5) under air atmosphere, intermediate is warming up to 500～700 ℃ with 2～5 ℃/min speed, and roasting 2～10h is to remove tensio-active agent and organic substance.
Organobentonite is that quaternary ammonium salt cationic surfactant and wilkinite react the organic clay that obtains in the aforesaid method.Cosurfactant is a neutral amine, and neutral amine is amino dodecane, normal hexyl Amine or stearylamine.Titanate ester is metatitanic acid methyl esters, titanium ethanolate, metatitanic acid n-propyl, isopropyl titanate or butyl (tetra) titanate.Drying mode for dry, oven dry, vacuum drying one or more.
Compare with existing method, advantage of the present invention is:
1) the present invention carries out in anhydrous system, need not synthesized gel rubber and ageing, and without optimal control pH value, raw material types is few, and synthetic route is simple, and easy handling is economized consumption during the method joint;
2) the used organobentonite of present method can be a depleted organobentonite after the wastewater treatment, has saved the bentonite synthesis technique, has avoided discarded bentonite secondary pollution simultaneously, uses promoting the mass-producing of organobentonite in wastewater treatment;
3) the anatase type bentonite-base porous titanium dioxide nano material specific surface area (111.73～241.25m of present method preparation
2/ g) and pore volume (0.2011～0.2956cm
3/ g) big, particle diameter single (9.7～20.6nm), even aperture distribution (3.634～8.352nm).
Description of drawings
Fig. 1 is the XRD figure spectrum of present embodiment 1 prepared bentonite base poriferous titanium dioxide nano material;
Fig. 2 is the N of present embodiment 1 prepared bentonite base poriferous titanium dioxide nano material
2Adsorption-desorption thermoisopleth collection of illustrative plates;
Fig. 3 is the UV-Vis collection of illustrative plates of present embodiment 1 prepared bentonite base poriferous titanium dioxide nano material.
Embodiment
The invention will be further elaborated below by example:
Embodiment 1
The cetyl trimethylammonium bromide aqueous solution of getting 100g wilkinite and 1000mL 0.1084mol/L prepares organobentonite.With the organobentonite behind the vacuum-drying 12h at room temperature, press organobentonite: butyl (tetra) titanate (mass ratio)=mix at 1: 5, in 50 ℃ of following stirring reaction 4h; Encloses container prevents that with the tinfoil parcel butyl (tetra) titanate decomposes under the illumination.Solid-liquid separation, solid part dries under 20 ℃, under air atmosphere, is warming up to 550 ℃ with 3 ℃/min speed at last, roasting 6h, the organic pollutant of removal tensio-active agent and absorption is promptly.
The sample test explanation: product is mainly anatase titanium dioxide, and particle diameter is 12.2nm (Fig. 1); The product specific surface area is 241.25m
2/ g (multiple spot BET method), pore volume is 0.2391cm
3/ g, mean pore size is 3.964nm (Fig. 2); Product has very strong ultraviolet effect (Fig. 3).
Embodiment 2
The cetyl trimethylammonium bromide aqueous solution of getting 100g wilkinite and 500mL 0.1084mol/L prepares organobentonite.Organobentonite behind the vacuum-drying 48h at first is used for the waste water that adsorption treatment contains the p-NP of 2000mg/L, organobentonite is 122mg/g to the loading capacity of p-NP, solid-liquid separation, after having adsorbed the organobentonite drying of p-NP, press organobentonite: isopropyl titanate (mass ratio)=mix at 1: 22, in 20 ℃ of following stirring reaction 8h; Encloses container prevents that with the tinfoil parcel isopropyl titanate decomposes under the illumination.Solid-liquid separation, solid part under air atmosphere, is warming up to 550 ℃ with 2 ℃/min speed at last in 80 ℃ of oven dry down, and roasting 6h removes tensio-active agent and adsorbed organic matter matter promptly.
The sample test explanation: product is mainly anatase titanium dioxide, and particle diameter is 14.4nm; The product specific surface area is 227.78m
2/ g (multiple spot BET method), pore volume is 0.2526cm
3/ g, mean pore size is 4.472nm; Product has very strong ultraviolet effect.
Embodiment 3
The cetyl trimethylammonium bromide aqueous solution of getting 100g wilkinite and 1000mL 0.1084mol/L prepares organobentonite.With the organobentonite behind the vacuum-drying 2h and cosurfactant by organobentonite: amino dodecane=1: 0.5 (mass ratio) mixes, in 50 ℃ of following stirring reaction 30min; At room temperature, press organobentonite: butyl (tetra) titanate (mass ratio)=mix at 1: 5, in 20 ℃ of following stirring reaction 8h; Encloses container prevents that with the tinfoil parcel butyl (tetra) titanate decomposes under the illumination.Solid-liquid separation, solid part under air atmosphere, is warming up to 700 ℃ with 3 ℃/min speed at last in 100 ℃ of oven dry down, roasting 2h, the organic pollutant of removal tensio-active agent and absorption is promptly.
The sample test explanation: product is mainly anatase titanium dioxide, and particle diameter is 9.7nm; The product specific surface area is 169.94m
2/ g (multiple spot BET method), pore volume is 0.2956cm
3/ g, mean pore size is 7.082nm; Product has very strong ultraviolet effect.
The cetyl trimethylammonium bromide aqueous solution of getting 20g wilkinite and 1000mL 0.1084mol/L prepares organobentonite.With the organobentonite behind the vacuum-drying 24h and cosurfactant by organobentonite: normal hexyl Amine=1: 1 (mass ratio) mixes, in 50 ℃ of following stirring reaction 30min; At room temperature, by above-mentioned organobentonite: metatitanic acid n-propyl (mass ratio)=mix at 1: 25, in 90 ℃ of following stirring reaction 2h; Encloses container prevents that with the tinfoil parcel metatitanic acid n-propyl decomposes under the illumination.Solid-liquid separation, solid part under air atmosphere, is warming up to 550 ℃ with 5 ℃/min speed at last in 80 ℃ of oven dry down, roasting 6h, the organic pollutant of removal tensio-active agent and absorption is promptly.
The sample test explanation: product is mainly anatase titanium dioxide, and particle diameter is 11.5nm; The product specific surface area is 155.32m
2/ g (multiple spot BET method), pore volume is 0.2544cm
3/ g, mean pore size is 6.628nm; Product has very strong ultraviolet effect.
Embodiment 5
The cetyl trimethylammonium bromide aqueous solution of getting 100g wilkinite and 1000mL 0.1084mol/L prepares organobentonite.Organobentonite behind the vacuum-drying 10h at first is used for the waste water that adsorption treatment contains the p-NP of 2000mg/L, organobentonite is 122mg/g to the loading capacity of p-NP, solid-liquid separation, with adsorbed after the organobentonite drying of p-NP with cosurfactant by organobentonite: amino dodecane=1: 1 (mass ratio) mixes, in 50 ℃ of following stirring reaction 30min; At room temperature, press organobentonite: butyl (tetra) titanate (mass ratio)=mix at 1: 20, in 50 ℃ of following stirring reaction 4h; Encloses container prevents that with the tinfoil parcel butyl (tetra) titanate decomposes under the illumination.Solid-liquid separation, solid part under air atmosphere, is warming up to 550 ℃ with 3 ℃/min speed at last in 80 ℃ of oven dry down, roasting 8h, the organic pollutant of removal tensio-active agent and absorption is promptly.
The sample test explanation: product is mainly anatase titanium dioxide, and particle diameter is 20.6nm; The product specific surface area is 111.73m
2/ g (multiple spot BET method), pore volume is 0.2333cm
3/ g, mean pore size is 8.352nm; Product has very strong ultraviolet effect.
Embodiment 6
The cetyl trimethylammonium bromide aqueous solution of getting 100g wilkinite and 1000mL 0.1084mol/L prepares organobentonite.With the organobentonite behind the vacuum-drying 24h at room temperature, press organobentonite: titanium ethanolate (mass ratio)=mix at 1: 200, in 90 ℃ of following stirring reaction 2h; Encloses container prevents that with the tinfoil parcel titanium ethanolate decomposes under the illumination.Solid-liquid separation, solid part under air atmosphere, is warming up to 550 ℃ with 3 ℃/min speed at last in 120 ℃ of oven dry down, roasting 6h, the organic pollutant of removal tensio-active agent and absorption is promptly.
The sample test explanation: product is mainly anatase titanium dioxide, particle diameter 12.6nm; The product specific surface area is 221.37m
2/ g (multiple spot BET method), pore volume is 0.2011cm
3/ g, mean pore size is 3.634nm; Product has very strong ultraviolet effect.
Embodiment 7
The cetyl trimethylammonium bromide aqueous solution of getting 100g wilkinite and 1000mL 0.1084mol/L prepares organobentonite.With the organobentonite behind the vacuum-drying 24h and cosurfactant by organobentonite: stearylamine=1: 2 (mass ratio) mixes, in 50 ℃ of following stirring reaction 30min; At room temperature, by above-mentioned organobentonite: metatitanic acid methyl esters (mass ratio)=mix at 1: 200, in 50 ℃ of following stirring reaction 4h; Encloses container prevents that with the tinfoil parcel metatitanic acid methyl esters decomposes under the illumination.Solid-liquid separation, solid part under air atmosphere, is warming up to 500 ℃ with 3 ℃/min speed at last in 150 ℃ of oven dry down, roasting 10h, the organic pollutant of removal tensio-active agent and absorption is promptly.
The sample test explanation: product is mainly anatase titanium dioxide, and particle diameter is 11.0nm; The product specific surface area is 141.86m
2/ g (multiple spot BET method), pore volume is 0.2326cm
3/ g, mean pore size is 6.558nm; Product has very strong ultraviolet effect.
Claims (5)
1. the synthetic method of a bentonite base poriferous titanium dioxide nano material, it is characterized in that with the organobentonite behind organobentonite or the adsorption treatment organic waste water as synthetic main body clay starting material, after the intermediate roasting of template one-step synthesis gained, promptly obtain the poriferous titanium dioxide nano material
Concrete preparation process is as follows:
1) with wilkinite and cats product by mass ratio be 1: 0.2～1: 2 in water hybrid reaction make organobentonite, through solid-liquid separation, solid drying 2～48h is to remove ADSORPTION STATE moisture, and is standby;
2) with the organobentonite solid-liquid separation behind the adsorption treatment waste water, solid drying 2～48h is to remove ADSORPTION STATE moisture, and is standby;
3) with step 1) or step 2) dried organobentonite, cosurfactant and titanate ester be by organobentonite: cosurfactant: the mass ratio of titanate ester is to mix in 1: 0.5: 5～1: 2: 200, in 20～90 ℃ of following stirring reaction 2～8h; Or with step 1) or step 2) dried organobentonite, titanate ester be by organobentonite: the mass ratio of titanate ester is to mix in 1: 5～1: 200, in 20～90 ℃ of following stirring reaction 2～8h;
4) with above-mentioned product solid-liquid separation, solid need not washing, obtains intermediate after 20～150 ℃ of dryings;
5) under air atmosphere, intermediate is warming up to 500～700 ℃ with 2～5 ℃/min speed, and roasting 2～10h is to remove tensio-active agent and organic substance.
2. a kind of bentonite base poriferous titanium dioxide nano material synthetic method according to claim 1 is characterized in that said organobentonite is that quaternary ammonium salt cationic surfactant and wilkinite react the organic clay that obtains.
3. a kind of bentonite base poriferous titanium dioxide nano material synthetic method according to claim 1 is characterized in that said cosurfactant is a neutral amine, and neutral amine is amino dodecane, normal hexyl Amine or stearylamine.
4. a kind of bentonite base poriferous titanium dioxide nano material synthetic method according to claim 1 is characterized in that said titanate ester is metatitanic acid methyl esters, titanium ethanolate, metatitanic acid n-propyl, isopropyl titanate or butyl (tetra) titanate.
5. a kind of bentonite base poriferous titanium dioxide nano material synthetic method according to claim 1, it is characterized in that said drying mode for dry, oven dry, vacuum drying one or more.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108940339A (en) * | 2018-07-12 | 2018-12-07 | 浙江正洁环境科技有限公司 | A kind of N-TiO2/ calcium system bentonite composite adsorption catalyst and application |
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| CN102489242B (en) * | 2011-11-30 | 2013-07-24 | 浙江大学 | Method for preparing titanium dioxide by integrating adsorption and photocatalysis |
| CN102897831B (en) * | 2012-10-30 | 2015-01-07 | 东华大学 | Method for preparing oil-soluble anatase type nanometer titanium dioxide particles by using oil-water interface method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341484A (en) * | 2001-08-27 | 2002-03-27 | 陈英旭 | Nanotitanium dioxide column supported bentonite and its preparation method |
| CN1554475A (en) * | 2003-12-19 | 2004-12-15 | 浙江大学 | Process for preparing porous clay isomeric material |
| CN1683073A (en) * | 2005-03-12 | 2005-10-19 | 山西大学 | Process for preparing nano titanium dioxide bentonite composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341484A (en) * | 2001-08-27 | 2002-03-27 | 陈英旭 | Nanotitanium dioxide column supported bentonite and its preparation method |
| CN1554475A (en) * | 2003-12-19 | 2004-12-15 | 浙江大学 | Process for preparing porous clay isomeric material |
| CN1683073A (en) * | 2005-03-12 | 2005-10-19 | 山西大学 | Process for preparing nano titanium dioxide bentonite composite material |
Non-Patent Citations (3)
| Title |
|---|
| B.M.Choudary, S.Shobha Rani, N.Narender.Asymmetric oxidation of sulfides to sulfoxides by chiraltitaniumpillared montmorillonite catalyst.Catalysis Letters19.1993,19299-307. * |
| JP特开2002-224564A 2002.08.13 |
| JP特开2006-346527A 2006.12.28 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108940339A (en) * | 2018-07-12 | 2018-12-07 | 浙江正洁环境科技有限公司 | A kind of N-TiO2/ calcium system bentonite composite adsorption catalyst and application |
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