CN102039117A - Method for preparing loaded nano TiO2 composite material by using precipitated white carbon black as carrier - Google Patents
Method for preparing loaded nano TiO2 composite material by using precipitated white carbon black as carrier Download PDFInfo
- Publication number
- CN102039117A CN102039117A CN200910093640.0A CN200910093640A CN102039117A CN 102039117 A CN102039117 A CN 102039117A CN 200910093640 A CN200910093640 A CN 200910093640A CN 102039117 A CN102039117 A CN 102039117A
- Authority
- CN
- China
- Prior art keywords
- precipitated silica
- value
- tio
- nano
- solution
- 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.)
- Granted
Links
Images
Abstract
The invention relates to a method for preparing a loaded nano TiO2 composite material by using precipitated white carbon black as a carrier. The method comprises the following steps of: adding water into the precipitated white carbon black to prepare slurry with stirring, adding acid to adjust the pH value, then cooling the slurry, and adding TiCl4 solution and ammonium sulfate solution in turn for reaction; heating the reaction solution to a certain temperature, adding ammonium carbonate solution to adjust the pH value of the solution, and then ageing the solution for certain time; and finally, filtering, washing, drying and calcining the reaction product to obtain the precipitated white carbon black loaded nano TiO2 composite material. The composite material has excellent photocatalysis performance under ultraviolet light and visible light, and the degradation and removal rate of formaldehyde is more than 80 percent in 24 hours under a fluorescent lamp.
Description
1. technical field
The present invention relates to a kind of is the loaded nano TiO of carrier with the precipitated silica
2The preparation method of composite belongs to inorganic chemical industry 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
2Easily reunite and be difficult to and reclaim.It is loaded on the suitable carriers material is to research and solve it at present easily to reunite and one of the main method that is difficult to reclaim.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.Precipitated silica be a kind of be the amorphous silica powder body material of main material production with waterglass, having characteristics such as specific area is big, porosity is high, the aperture is little, chemical stability is good, is a kind of nano TiO 2 carrying body material with performance advantage and cost comparative advantages.
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 precipitated silica, proposes a kind of white carbon loaded with nano TiO
2The preparation method of composite.This loading nano-titania composite not only can improve utilization rate and the photocatalysis performance of nanometer titanic oxide material to visible light, and practicality is good.
3. summary of the invention
Precipitated silica 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 precipitated silica loaded with nano TiO at last
2Material.
Its processing step is as follows:
(1) the precipitated silica slurry preparation adds precipitated silica 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) precipitated silica slurry preparation
The mass ratio of clear water and precipitated silica=100: 1～10; Slurry pH value is 1.5～3.0.
(2) nano-TiO
2Load
1. former, auxiliary material mass ratio is a precipitated silica: titanium tetrachloride: ammonium sulfate=100: 20～200: 30～180;
2. use 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 further elaborated, protection scope of the present invention is not limited by the cases cited.
Precipitated silica loaded with nano TiO with the present invention's preparation
2Composite, on the precipitated silica particles surface load main crystal formation be the nano-TiO of anatase titanium dioxide
2Particle; TiO
2Grain size is 10～20nm.
Precipitated silica loaded with nano TiO
2Composite 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 precipitated silica 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 precipitated silica loaded with nano TiO
2Material.
Embodiment two:
Get precipitated silica 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 precipitated silica loaded with nano TiO
2Material.
Embodiment three:
Get precipitated silica 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 1 24L 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 precipitated silica loaded with nano TiO
2Material.
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 (4)
1. one kind is the loaded nano TiO of carrier with the precipitated silica
2The preparation method of composite is characterized in that its step of preparation process is:
(1) the precipitated silica slurry preparation adds precipitated silica the clear water stirring pulping and adds acid and transfers to certain pH value;
(2) nano-TiO
2Load is lowered the temperature to the described slurries of step (1), 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. precipitated silica slurry preparation according to claim 1, the mass ratio that it is characterized in that clear water and precipitated silica is 100: 1～10; Slurry pH value is 1.5～3.0.
3. described nano-TiO according to claim 1
2Load is characterized in that: former, auxiliary material mass ratio is a precipitated silica: titanium tetrachloride: ammonium sulfate=100: 20～200: 30～180; Reaction end pH value is 4～6; 20～50 ℃ of ageing temperature; Time 0.5～2.0h.
4. precipitated silica loaded with nano TiO according to claim 1
2The preparation method of composite is characterized in that describedly with product calcining, and its process conditions are: 350～900 ℃ of calcining heats, temperature retention time 1～6h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910093640.0A CN102039117B (en) | 2009-10-15 | 2009-10-15 | Method for preparing loaded nano TiO2 composite material by using precipitated white carbon black as carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910093640.0A CN102039117B (en) | 2009-10-15 | 2009-10-15 | Method for preparing loaded nano TiO2 composite material by using precipitated white carbon black as carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102039117A true CN102039117A (en) | 2011-05-04 |
| CN102039117B CN102039117B (en) | 2012-08-08 |
Family
ID=43905853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910093640.0A Expired - Fee Related CN102039117B (en) | 2009-10-15 | 2009-10-15 | Method for preparing loaded nano TiO2 composite material by using precipitated white carbon black as carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102039117B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105214734A (en) * | 2014-06-09 | 2016-01-06 | 中国石油化工股份有限公司 | The preparation method of illite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals |
| CN105435850A (en) * | 2014-06-09 | 2016-03-30 | 中国石油化工股份有限公司 | Illite mesoporous composite material, supported catalyst and preparation method and application thereof and preparation method of cyclohexanone glyceryl ketal |
| CN105435853A (en) * | 2014-06-09 | 2016-03-30 | 中国石油化工股份有限公司 | Illite mesoporous composite material, supported catalyst and preparation method and application thereof and preparation method of cyclohexanone glyceryl ketal |
| CN105460973A (en) * | 2015-11-30 | 2016-04-06 | 洛阳绿仁环保设备有限公司 | Method for preparing white carbon black/TiO2 composite material from potassium feldspar |
| CN106237983A (en) * | 2016-09-08 | 2016-12-21 | 洛阳理工学院 | A kind of organic waste water treatment agent 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 |
| 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 |
| CN106699061A (en) * | 2016-12-26 | 2017-05-24 | 长沙洛迪环保科技有限公司 | Diatom ooze capable of being scrubbed |
| CN106925255A (en) * | 2017-04-12 | 2017-07-07 | 龙岩紫荆创新研究院 | A kind of photochemical catalyst of room temperature catalytic decomposition formaldehyde and preparation method thereof |
| CN109621932A (en) * | 2018-10-22 | 2019-04-16 | 昆明理工大学 | White carbon black-titanic oxide composite photochemical catalyst antibacterial agent preparation method |
| CN110038616A (en) * | 2019-04-23 | 2019-07-23 | 襄阳先创环保科技有限公司 | A kind of municipal sewage treatment agent |
| CN111334102A (en) * | 2020-01-19 | 2020-06-26 | 广西正花涂料有限公司 | Moisture-proof and mildew-proof dry powder coating |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3981919B2 (en) * | 2002-08-30 | 2007-09-26 | セイコーエプソン株式会社 | Toner and image forming apparatus using the same |
| CN1288213C (en) * | 2004-12-07 | 2006-12-06 | 中国科学院山西煤炭化学研究所 | Method for preparing silicon oxide/titanium dioxide composite oxide ultraviolet screening agent |
| CN100365207C (en) * | 2006-02-17 | 2008-01-30 | 上海东升新材料有限公司 | Composite titania material and its prepn and application |
| CN101195086A (en) * | 2006-12-06 | 2008-06-11 | 中国矿业大学(北京) | Method for producing tripolite loading nano-TIO2 material capable of being used for water and air purification |
-
2009
- 2009-10-15 CN CN200910093640.0A patent/CN102039117B/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105435850B (en) * | 2014-06-09 | 2017-09-29 | 中国石油化工股份有限公司 | The preparation method of illite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals |
| CN105435850A (en) * | 2014-06-09 | 2016-03-30 | 中国石油化工股份有限公司 | Illite mesoporous composite material, supported catalyst and preparation method and application thereof and preparation method of cyclohexanone glyceryl ketal |
| CN105435853A (en) * | 2014-06-09 | 2016-03-30 | 中国石油化工股份有限公司 | Illite mesoporous composite material, supported catalyst and preparation method and application thereof and preparation method of cyclohexanone glyceryl ketal |
| CN105214734A (en) * | 2014-06-09 | 2016-01-06 | 中国石油化工股份有限公司 | The preparation method of illite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals |
| CN105214734B (en) * | 2014-06-09 | 2017-11-07 | 中国石油化工股份有限公司 | The preparation method of illite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals |
| CN105435853B (en) * | 2014-06-09 | 2017-09-29 | 中国石油化工股份有限公司 | The preparation method of illite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals |
| CN105460973A (en) * | 2015-11-30 | 2016-04-06 | 洛阳绿仁环保设备有限公司 | Method for preparing white carbon black/TiO2 composite material from potassium feldspar |
| 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 |
| 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 |
| CN106237983B (en) * | 2016-09-08 | 2018-11-23 | 洛阳理工学院 | A kind of organic waste water treatment agent and preparation method thereof |
| CN106237983A (en) * | 2016-09-08 | 2016-12-21 | 洛阳理工学院 | A kind of organic waste water treatment agent and preparation method thereof |
| CN106699061A (en) * | 2016-12-26 | 2017-05-24 | 长沙洛迪环保科技有限公司 | Diatom ooze capable of being scrubbed |
| CN106925255A (en) * | 2017-04-12 | 2017-07-07 | 龙岩紫荆创新研究院 | A kind of photochemical catalyst of room temperature catalytic decomposition formaldehyde and preparation method thereof |
| CN109621932A (en) * | 2018-10-22 | 2019-04-16 | 昆明理工大学 | White carbon black-titanic oxide composite photochemical catalyst antibacterial agent preparation method |
| CN110038616A (en) * | 2019-04-23 | 2019-07-23 | 襄阳先创环保科技有限公司 | A kind of municipal sewage treatment agent |
| CN111334102A (en) * | 2020-01-19 | 2020-06-26 | 广西正花涂料有限公司 | Moisture-proof and mildew-proof dry powder coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102039117B (en) | 2012-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102039117B (en) | Method for preparing loaded nano TiO2 composite material by using precipitated white carbon black as carrier | |
| CN102039118B (en) | Preparation method of supported nano TiO2 photocatalytic material with diatomite filter aid as carrier | |
| Aghdam et al. | Precipitation dispersion of various ratios of BiOI/BiOCl nanocomposite over g-C3N4 for promoted visible light nanophotocatalyst used in removal of acid orange 7 from water | |
| CN102698785B (en) | A kind of tripolite loading nitrogen-doped nanometer TiO 2the preparation method of catalysis material | |
| CN101927177B (en) | Preparation method of nitrogen-doped attapulgite load nano TiO2 visible light photocatalyst | |
| WO2018205539A1 (en) | Three-dimensional lignin porous carbon/zinc oxide composite material, preparation thereof and use thereof in field of photocatalysis | |
| CN106582771B (en) | A kind of preparation method of the magnetic photocatalyst of wide spectrum response | |
| CN104801328B (en) | Method for preparing TiO2/g-C3N4 composite photocatalyst at low temperature | |
| CN107098381B (en) | The preparation method of the zinc titanate catalysis material of special appearance | |
| CN105944711B (en) | A kind of visible light-responded BiVO4/TiO2/ graphene Three-element composite photocatalyst and preparation method thereof | |
| CN109012721A (en) | A kind of preparation method of silver orthophosphate/graphite phase carbon nitride composite photo-catalyst | |
| CN102335616A (en) | Synthesis method of novel visible-light photocatalyst indium sulfide | |
| CN109550500A (en) | It is a kind of can Magnetic Isolation graphene-based zinc-iron mixing bimetallic oxide photochemical catalyst preparation method and applications | |
| CN115283015B (en) | Organometallic framework composite photocatalyst BiVO 4 @NH 2 Preparation method of MIL-125 (Ti) | |
| Zhang et al. | Preparation of graphitic carbon nitride with nitrogen-defects and its photocatalytic performance in the degradation of organic pollutants under visible light | |
| CN106362768B (en) | A kind of honeycomb ceramic plate loads TiO2The preparation technology of the immobilized photochemical catalysts of-NCP | |
| Shariatzadeh et al. | Nanostructured α-Fe2O3: Solvothermal synthesis, characterization, and effect of synthesis parameters on structural properties | |
| Mohamed et al. | Preparation and photocatalytic activity of mixed phase anatase/rutile TiO2 nanoparticles for phenol degradation | |
| CN102698759A (en) | Preparation method of expanded perlite loaded nanometer TiO2 compound photocatalysis material | |
| Sedneva et al. | TiO 2-and Nb 2 O 5-based photocatalytic composites | |
| KR102393117B1 (en) | Manufacturing method of n-doped titanium dioxide nanotubes/graphitic carbon nitride composites for photocatalyst | |
| CN102199369A (en) | Preparation method of tourmaline/nano TiO2 composite functional material | |
| CN106311240B (en) | A kind of preparation method of spherical shape hierarchical organization cobalt titanate-titanium dioxide composite nano material | |
| Xu et al. | Erbium and nitrogen co-doped SrTiO3 with highly visible light photocatalytic activity and stability by solvothermal synthesis | |
| CN102198394B (en) | Method for preparing opoka loaded nanometer TiO2 composite powder material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20110504 Assignee: Linjiang City Baojian nano composite Mstar Technology Ltd. Assignor: LUOYANG INSTITUTE OF SCIENCE AND TECHNOLOGY|CHINA University OF MINING AND TECHNOLOGY BEIJING Contract record no.: 2016220000002 Denomination of invention: Preparation method of supported nano TiO[sub]2[/sub] composite material using precipitated white carbon as carrier Granted publication date: 20120808 License type: Exclusive License Record date: 20160203 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120808 Termination date: 20211015 |