CN102039118B - Preparation method of supported nano TiO2 photocatalytic material with diatomite filter aid as carrier - Google Patents

Preparation method of supported nano TiO2 photocatalytic material with diatomite filter aid as carrier Download PDF

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Publication number
CN102039118B
CN102039118B CN2009102352080A CN200910235208A CN102039118B CN 102039118 B CN102039118 B CN 102039118B CN 2009102352080 A CN2009102352080 A CN 2009102352080A CN 200910235208 A CN200910235208 A CN 200910235208A CN 102039118 B CN102039118 B CN 102039118B
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super
cell
value
temperature
tio
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CN2009102352080A
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CN102039118A (en
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郑水林
王利剑
傅振彪
许辉
张晓波
刘杰
吕芳丽
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中国矿业大学(北京)
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Abstract

The invention relates to a preparation method of a supported nano TiO2 photocatalysis material with a diatomite filter aid as a carrier. The preparation method comprises the steps of adding water into the diatomite filter aid, stirring the mixture to prepare slurry and adding acid to regulate pH value; then cooling the slurry, then sequentially adding TiCl4 solution and ammonium sulphate for reaction, heating reaction liquid to a certain temperature, then adding ammonium carbonate solution to regulate the pH value of solution and ageing the reaction liquid for a period of time; and finally filtering, washing, drying and calcining the reaction product, thus obtaining the diatomite filter aid supported nano TiO2 photocatalytic material. The supported nano TiO2 photocatalytic material has excellent photocatalytic performance under ultraviolet light and visible light and has more than 80% of degradation removal rate on formaldehyde in 24 hours under a fluorescent lamp.

Description

With the super-cell is the loaded nano TiO of carrier 2The preparation method of catalysis material

1. technical field

The present invention relates to a kind of is the loaded nano TiO of carrier with the super-cell 2The preparation method of catalysis material belongs to mineral processing and field of photocatalytic material.

2. background technology

Since the seventies in 20th century, nano-TiO 2Be proved to be a kind of catalysis material of efficient, nontoxic, stable performance.But there is two large problems in actual the use.

The one, pure nano-TiO 2Be prone to reunite and be difficult to and reclaim.It is loaded on the suitable carriers material is to research and solve one of its easy main method of reuniting and being difficult to reclaim at present.Research at present be used for loaded with nano TiO 2Carrier material mainly contain active carbon, molecular sieve, zeolite, bentonite, sepiolite, glass, pottery, diatomite etc.Super-cell be a kind of be raw material with diatomite, add flux, through the siliceous powder body material of porous of high-temperature calcination processing; Compare with the diatomite that the chemical purification method is produced, characteristics and raw material processing such as have that porosity height, aperture are big, absorption and strainability are good simply, non-wastewater discharge and loaded nano TiO 2Advantages such as the catalysis material preparation cost is lower.

The 2nd, pure nano-TiO 2Photochemical catalyst natural daylight utilization rate is not high.TiO 2Be a kind of wide bandgap semiconductor, its Detitanium-ore-type TiO 2Energy gap be 3.2eV, (300~400nm) just can be absorbed and utilize, and have greatly limited nano-TiO to have only the short ultraviolet light of wavelength 2The range of application of photochemical catalyst.Therefore, utilizing excited by visible light is research TiO 2An important goal of photochemical catalyst, mixing then is to solve it efficiently to utilize the main path of visible light or natural daylight.The doping way that research is at present adopted mainly contains two kinds: nonmetal doping and metal-doped.Metal ion mixing can be expanded TiO effectively 2Visible light-responded, but the TiO of metal ion mixing 2Heat endurance is relatively poor, and doping metals becomes the electron-hole recombinations center easily, and some doping method needs expensive ion to inject instrument; The TiO of nonmetal doping 2Not only have to respond and show stronger photocatalytic activity preferably, and this photocatalytic activity is that to excite down photolytic activity be not cost to sacrifice UV, can overcomes the defective of metal ion mixing at visible region.And with nano-TiO 2The diverse nonmetallic materials of chemical composition are as preparing carriers loaded nano TiO 2Composite is for nano-TiO 2This photochemical catalyst itself also is a kind of doping way, can improve nano-TiO 2Utilization rate to visible light.

The present invention is directed to present nano-TiO 2The problem that catalysis material exists is a carrier with the super-cell, proposes a kind of super-cell loaded with nano TiO 2The preparation method of catalysis material.This loaded nano titanium dioxide photocatalysis material not only can improve utilization rate and the photocatalysis performance of nano titanium oxide to visible light, and practicality is good.

3. summary of the invention

Super-cell is added the water stirring pulping, add behind the acid for adjusting pH value, add TiCl then successively the slurry cooling 4Solution, ammonium sulfate reacts; Reactant liquor is risen to the pH value ageing certain hour also that adds the sal volatile regulator solution after the uniform temperature; With product filtration, washing, dry and calcining, promptly get super-cell loaded with nano TiO at last 2Catalysis material.

Its processing step is following:

(1) the super-cell slurry preparation adds super-cell the water stirring pulping and adds acid and transfers to certain pH value;

(2) nano-TiO 2Load is lowered the temperature to slurries, treats to add titanium tetrachloride solution successively after temperature is reduced to below 10 ℃ and ammonium sulfate reacts; Then reactant liquor is heated up, the question response liquid temp rises to the pH value and the ageing of back adding sal volatile conditioned reaction liquid more than 20 ℃;

(3) step (2) product is filtered, washed, dry, calcining.

Below be prescription of the present invention and main technique condition:

(1) super-cell slurry preparation

The mass ratio of clear water and super-cell=100: 1~15; Slurry pH value is 1.5~3.0.

(2) nano-TiO 2Load

1. former, auxiliary material quality proportioning is a super-cell: titanium tetrachloride: ammonium sulfate=100: 20~200: 30~180;

2. with pH value to 4~6 of sal volatile conditioned reaction liquid;

3. 20~50 ℃ of ageing temperature; Digestion time 0.5~2.0h.

(3) load product filtration, dry and calcining

100~200 ℃ of baking temperatures; 350~900 ℃ of calcining heats, temperature retention time are 1~6h.

Below by embodiment the present invention is done further elaboration, the restriction of the example that protection scope of the present invention is not subjected to be lifted.

Super-cell loaded with nano TiO with the present invention's preparation 2Catalysis material, on the super-cell particle surface load main crystal formation be the nano-TiO of anatase titanium dioxide 2Particle; TiO 2Grain size is 10~20nm.

Super-cell loaded with nano TiO 2Catalysis material all has excellent photocatalytic performance under ultraviolet light and visible light, the interior photocatalytic degradation rate to rhodamine B solution of 20min reaches more than 90% under the ultraviolet light; Under the fluorescent lamp, the degraded clearance of PARA FORMALDEHYDE PRILLS(91,95) is greater than 80% in the 24h.

4. accompanying drawing content

Accompanying drawing 1 is a process chart of the present invention.

5. the specific embodiment

Embodiment one:

Get super-cell 30kg, add water 1500L, with salt acid for adjusting pH value to 2, dispersed with stirring and being cooled to adds the mass concentration for preparing successively after 5 ℃ be the ammonium sulfate 150L that 50% titanium tetrachloride aqueous solution 62L and concentration are 200g/L; Stirring reaction and be warming up to 30 ℃ after to add ammonium carbonate conditioned reaction liquid pH value be 5.0, ageing 1.0h under 30 ℃ of temperature then; With product filter, after Flash Type drying machine drying in the continous way rotary furnace 620~650 ℃ of temperature controls calcining 4h down, promptly get super-cell loaded with nano TiO 2Catalysis material.

Embodiment two:

Get super-cell 30kg, add water 1800L, with salt acid for adjusting pH value to 2, dispersed with stirring and being cooled to adds the mass concentration for preparing successively after 4 ℃ be the ammonium sulfate 200L that 50% titanium tetrachloride aqueous solution 80L and concentration are 200g/L; Stirring reaction and be warming up to 30 ℃ after to add ammonium carbonate conditioned reaction liquid pH value be 4.5, ageing 1.0h under 30 ℃ of temperature then; With product filter, after Flash Type drying machine drying in the continous way rotary furnace 620~650 ℃ of temperature controls calcining 4h down, promptly get super-cell loaded with nano TiO 2Catalysis material.

Embodiment three:

Get super-cell 60kg, add water 1800L, with salt acid for adjusting pH value to 2, dispersed with stirring and being cooled to adds the mass concentration for preparing successively after 5 ℃ be the ammonium sulfate 300L that 50% titanium tetrachloride aqueous solution 124L and concentration are 200g/L; Stirring reaction and be warming up to 28 ℃ after to add ammonium carbonate conditioned reaction liquid pH value be 5.0, ageing 1.0h under 30 ℃ of temperature then; With product filter, after Flash Type drying machine drying in the continous way rotary furnace 620~650 ℃ of temperature controls calcining 4h down, promptly get super-cell loaded with nano TiO 2Catalysis material.

Table 1 is the testing result of embodiment products obtained therefrom.

The check and analysis result of table 1 embodiment sample

Annotate: it is in the rhodamine B solution of 10mg/L that [1] 0.1g composite sample adds 100mL concentration;

[2] 1m 3Airtight glass box in put into the culture dish that fills 3 μ L formaldehyde and the glass plate that scribbles the 8g composite sample, formaldehyde gas initial concentration 0.7mg/m in the case 3The 30W fluorescent lamp shines continuously.

Claims (5)

1. one kind is the loaded nano TiO of carrier with the super-cell 2The preparation method of catalysis material is characterized in that its step of preparation process is:
(1) the super-cell slurry preparation adds super-cell the water stirring pulping and adds acid and transfers to certain pH value;
(2) nano-TiO 2Load is lowered the temperature to slurries, treats to add titanium tetrachloride solution successively after temperature is reduced to below 10 ℃ and ammonium sulfate reacts; Then reactant liquor is heated up, the question response liquid temp rises to the pH value and the ageing of back adding sal volatile conditioned reaction liquid more than 20 ℃;
(3) step (2) product is filtered, washed, dry, calcining.
2. preparation method according to claim 1 is characterized in that, super-cell is meant with diatomite to be raw material, adds flux, through the siliceous powder body material of porous of high-temperature calcination processing.
3. preparation method according to claim 1 is characterized in that, in the step (1), the mass ratio of clear water and super-cell is 100: 1~15, regulates slurry pH value to 1.5~3.0.
4. preparation method according to claim 1 is characterized in that, in the step (2), former, auxiliary material quality proportioning is a super-cell: titanium tetrachloride: ammonium sulfate=100: 20~200: 30~180; Reaction end pH value is 4~6; 20~50 ℃ of ageing temperature; Digestion time 0.5~2.0h.
5. preparation method according to claim 1 is characterized in that, the process conditions of product calcining are: 350~900 ℃ of calcining heats, temperature retention time 1~6h.
CN2009102352080A 2009-10-16 2009-10-16 Preparation method of supported nano TiO2 photocatalytic material with diatomite filter aid as carrier CN102039118B (en)

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CN102390867A (en) * 2011-07-27 2012-03-28 刘芳 Diatomite purification and impurity removal method for manganese sulfate solution
CN102698785B (en) * 2012-06-21 2015-10-21 中国矿业大学(北京) A kind of tripolite loading nitrogen-doped nanometer TiO 2the preparation method of catalysis material
CN103275543B (en) * 2013-05-02 2014-06-25 洛阳理工学院 Preparation method of aqueous paint for degradation of formaldehyde gas and toluene gas
CN103553485B (en) * 2013-10-12 2014-12-17 中国矿业大学(北京) Preparation method of healthful environment-friendly diatomite wall material powder with temperature adjustment function
WO2016196137A1 (en) * 2015-06-04 2016-12-08 Imerys Filtration Minerals, Inc. Compositions and methods for calcining diatomaceous earth with reduced cristobalite and/or reduced beer soluble iron
CN105148723B (en) * 2015-08-18 2016-08-17 王秀宝 Formaldehyde in air, abnormal flavour material and preparation method thereof in deaeration car based on kieselguhr micropowder
CN105694544B (en) * 2016-01-14 2018-05-22 上海大学 A kind of preparation method of nano titanium dioxide/diatomite wall covering
CN105727921B (en) * 2016-01-30 2019-01-08 中国建筑材料科学研究总院 A kind of nano-TiO2Diatomite composite photocatalytic agent and preparation method thereof
CN106423122A (en) * 2016-08-24 2017-02-22 王秀宝 Photocatalytic material with water washed diatomite as carrier loaded with nano TiO2 and preparation method thereof
CN106345443A (en) * 2016-08-24 2017-01-25 王秀宝 Photocatalysis material with nano TiO2 loaded on kieselguhr white carbon black used as carrier and preparation method of photocatalysis material
CN106492772A (en) * 2016-09-13 2017-03-15 富思特新材料科技发展股份有限公司 A kind of titanium dioxide nanoplate and the preparation method of diatomite composite photocatalytic agent

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