CN1506311A - Prepn process of nano level rutile-type titania powder - Google Patents
Prepn process of nano level rutile-type titania powder Download PDFInfo
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- CN1506311A CN1506311A CNA021555133A CN02155513A CN1506311A CN 1506311 A CN1506311 A CN 1506311A CN A021555133 A CNA021555133 A CN A021555133A CN 02155513 A CN02155513 A CN 02155513A CN 1506311 A CN1506311 A CN 1506311A
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Abstract
The present invention is the preparation process of nano level rutile-type titania powder. The preparation process includes the concentrated sulfuric acid treatment of the metatitanic acid material to form titanyl sulfate solution with certain F value, sodium carbonate neutralization to obtain precipitate, water washing of the precipitate, hydrochloric acid peptization, ammonia water gelification, filtering, washing, drying, calcination, airflow crushing and other steps. The present invention has the advantages of cheap material, simple technological process, and less water gas and waste water exhaust. The spherical titania powder product produced with common apparatus and at normal temperature and normal pressure has rutile content higher than 99 %, average particle size of 20-40 nm and stable quality.
Description
Technical field
The invention belongs to the titanium dioxide powder preparing technical field, specially referring to a kind of is raw material with the metatitanic acid, prepares the method for nanometre-grade titanic-schorl type titanium dioxide powder.
Background technology
With metatitanic acid is the generally existing both at home and abroad report of method of feedstock production nm-class rutile titanium dioxide powder, as: 1, English Patent 2205088A points out, hydrated titanium dioxide is handled with NaOH, uses the salt acid treatment subsequently, can obtain needle-like titanium dioxide.2, Japanese patent laid-open 7-187677 points out, titanium compound and alkali reaction are made the titanium dioxide suspension liquid, in the presence of reductive agent, carries out heat treated and can obtain rutile type nano titanic oxide.3, Chinese patent publication number 1146976 is pointed out, to be raw material with the metatitanic acid can make rutile type nano titanic oxide through washing purifying, dispersion and emulsion, thermal treatment, and (calcining temperature is 700～800 ℃, and median size is 80～100nm).4, Chinese patent publication number 1192992 is pointed out, is raw material with the metatitanic acid, and urea is the precipitation from homogeneous solution agent, and it is the Nano titanium dioxide of 45nm that the synthetic throw out was got median size in 2.5～3.5 hours 950～1000 ℃ of calcinings.5, Chinese patent publication number 1217297 is pointed out, is raw material with the metatitanic acid, and yellow soda ash is precipitation agent, zinc sulfate is made compound modifying agent, adopts zinc carbonate to coat positive metatitanic acid, and carries out predissolve, 800～900 ℃ of calcinings 2 hours, can get the nm-class rutile titanium dioxide powder at last.
Above-mentioned Patent document data all is feedstock production nano rutile-type titanium dioxide powder with the metatitanic acid, but there are the following problems: above-mentioned (1), (2) method, when handling metatitanic acid with highly basic, can make the depolymerization of cohesion titanium dioxide, but technological process is wayward, usually depolymerization is incomplete, and the molten material of highly basic is strict to production unit in scale production, is difficult for suitability for industrialized production; Above-mentioned (3), (4) method, too high in calcining temperature, and need to add compound modifying agent, cause average particle size thick partially: 80～100nm, and the rutile transformation efficiency is not high; Above-mentioned (5) method complex technical process, predissolve, and need molten 97% the coating zinc oxide powder that goes, and use 800 ℃ of roastings again, wayward, the industrial-scale production difficulty.
For solving above-mentioned existing problems, purpose of the present invention aims to provide the simple and normal temperature and pressure reaction of a kind of technological process, does not introduce compound modifying agent, and can realize that low temperature (450～550 ℃) calcining transformation prepares the method for nm-class rutile titanium dioxide powder.
The preparation method of nanometre-grade titanic-schorl type titanium dioxide powder of the present invention is, is raw material with the metatitanic acid, uses earlier dense H
2SO
4Metatitanic acid is dissolved as the titanyl sulfate of certain F value, uses sodium carbonate solution neutralisation of sulphuric acid oxygen titanium solution then, obtain Ti (OH)
4Precipitation, throw out eliminates sodium salt through abundant washing, uses the concentrated hydrochloric acid peptization again, regulates pH value with ammoniacal liquor, after filtration, washing, drying, calcining and disintegrating process make the nanometre-grade titanic-schorl type titanium dioxide powder.
Technical process is as follows: 1 metatitanic acid → 2 acid is molten → and 3 yellow soda ash neutralization → 4 filtration washings → 5 hydrochloric acid peptizations → 6 filtration washings → 7 dryings → 8 calcining → 9 comminution by gas stream → 10 products
Further be, the selected metatitanic acid of the present invention is that sulfate process titanium dioxide is produced the pilot process product, and its impurity is few, and iron level is generally less than 50ppm.
Further be, the present invention is with the concentrated sulfuric acid dissolution metatitanic acid and control its F value less than 4, so that the control reaction can intuitively be reacted the depolymerization effect again, is better than handling metatitanic acid with NaOH.
Further be, to be 7～8 to make Ti (OH) up to the pH value with sodium carbonate solution neutralisation of sulphuric acid oxygen titanium solution
4
Further be, at yellow soda ash neutralisation of sulphuric acid oxygen titanium solution or Ti (OH)
4Throw out washs to neutrality after using the hydrochloric acid peptization, removes Na
+And SO
4 2-, usable concentration is 10% BaCl
2The check washing effect.Refilter, and 120 ℃ of dryings 2 hours.
Further be, adopt the concentrated hydrochloric acid peptization, control peptization conditions: peptization F value 0.45～0.60,80～90 ℃ of peptization temperature, peptization time 30～50 minutes.
Further be, the present invention does not add any crystal type promoting reagent, has realized low temperature calcination transition, and promptly calcining temperature is 450～550 ℃, calcination time＜5 hour.
The key technical indexes of the red schorl type titanium oxide nano powder of the present invention's preparation sees Table 1.
Table 1 red schorl type titanium oxide nano powder the key technical indexes
| Crystal formation | Purity | Outward appearance | Particle diameter | Specific surface | ??PH | Surface properties |
| Rutile | ??＞98％ | Little Huang | ??20～40nm | ??64m 2/g | ??6～8 | Wetting ability |
The advantage that the present invention gives prominence to is:
1, the main raw material metatitanic acid is cheap and easy to get, nontoxic nothing corrosion.
2, technological process is simple and easy to control, and conversion unit uses the construction equipment that routinizes, and is convenient to industrially scalable production.
3, in the prior art, the general method that adopts is to add organic dispersion agent, add compound modifying agent, and calcine preparation gold redrock nano-titanium dioxide powder down 700～1000 ℃ of comparatively high tempss, TiO 2 particles is partially sintered, produce hard aggregation, problem such as coarse particle is on the high side, and application performance is bad.And the present invention does not add any dispersion agent, does not add compound modifying agent, and realizes low temperature (450～550 ℃) calcining transformation, rutile transformation efficiency＞99%.
4, waste gas, the waste water that produces in the technological process of the present invention is few.
Embodiment
Below in conjunction with embodiment the technical scheme of invention is further described.
Embodiment 1
Take by weighing metatitanic acid 1300g, add vitriol oil 900ml, dissolving back titanyl sulfate F value is 3.57.With the sodium carbonate solution neutralization, control pH value about 7.The filtration washing precipitation is removed a large amount of sodium salts and sulfate ion, gained precipitation concentrated hydrochloric acid peptization, and control F value is 0.5,85 ℃ of temperature, 35 minutes time, adding the ammoniacal liquor adjust pH is 7.Again after filtration, washing, drying, the control calcining temperature calcine 4.5 hours less than 550 ℃, best comminution by gas stream obtains the nm-class rutile titanium dioxide powder.
Quality index: rutile transformation efficiency＞99%, average particle size 30～50nm.
Embodiment 2
Take by weighing the 143Kg metatitanic acid in reactor, add the 99456ml analytical pure vitriol oil, steam-heated cal(l)andria also is stirred to moltenly entirely, obtains titanyl sulfate solution, and dissolving back titanyl sulfate F value is 3.80.With the industrial anhydrous sodium carbonate wiring solution-forming of 250Kg, and the Plate Filtration removal of impurities, under agitation with the slow neutralisation of sulphuric acid oxygen of sodium carbonate solution titanium solution, and make that the pH value is 7.Filter, wash and repeatedly remove sodium salt, filter cake is pulled an oar in reactor, adds peptization in the reactor, 85 ℃ of control reaction temperature, 35 minutes reaction times with dense HCl 58L.Again after filtration, washing, drying, use pushed bat kiln calcining 4.5 hours, 500 ℃ of control top temperatures are after comminution by gas stream obtains nm-class rutile titanium dioxide powder 50Kg.
Quality index: rutile transformation efficiency＞99%, average particle size 36nm.
Claims (5)
1, the nanometre-grade titanic-schorl type titanium dioxide powder preparation method is characterized in that, is raw material with the metatitanic acid, uses earlier dense H
2SO
4Metatitanic acid is dissolved as the titanyl sulfate of certain F value, uses sodium carbonate solution neutralisation of sulphuric acid oxygen titanium solution then, obtain Ti (OH)
4Precipitation, throw out eliminates sodium salt through abundant washing, uses the concentrated hydrochloric acid peptization again, regulates p H value with ammoniacal liquor, after filtration, washing, drying, calcining and disintegrating process make the nanometre-grade titanic-schorl type titanium dioxide powder.
2, nanometre-grade titanic-schorl type titanium dioxide powder preparation method as claimed in claim 1 is characterized in that, will control the vitriol oil consumption when acid of described metatitanic acid is molten, makes F value＜4 of titanyl sulfate.
3, nanometre-grade titanic-schorl type titanium dioxide powder preparation method as claimed in claim 1 is characterized in that, during with sodium carbonate solution neutralisation of sulphuric acid oxygen titanium solution, the pH value of solution must be controlled to be 7～8.
4, nanometre-grade titanic-schorl type titanium dioxide powder preparation method as claimed in claim 1 is characterized in that, eliminates the Ti (OH) of sodium salt through water Xian
4Controlled variable is when precipitating with the hydrochloric acid peptization: the peptization temperature is 80～90 ℃, and the F value is 0.45～0.6, and peptization time is 30～50 minutes.
5, nanometre-grade titanic-schorl type titanium dioxide powder preparation method as claimed in claim 1 is characterized in that, the control calcining temperature is 450～550 ℃ during calcining, calcination time＜5 hour.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA021555133A CN1506311A (en) | 2002-12-09 | 2002-12-09 | Prepn process of nano level rutile-type titania powder |
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|---|---|---|---|
| CNA021555133A CN1506311A (en) | 2002-12-09 | 2002-12-09 | Prepn process of nano level rutile-type titania powder |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330578C (en) * | 2005-10-25 | 2007-08-08 | 郴州市金贵有色金属有限公司 | Method of preparing nano-titanium dioxide precusor |
| CN100369818C (en) * | 2005-06-09 | 2008-02-20 | 江苏大学 | Process for preparing rutile-type nano TiO2 by meta titanic acid |
| CN100445209C (en) * | 2005-07-28 | 2008-12-24 | 同济大学 | Preparation method of new type nano-titanium dioxide powder |
| CN106698508A (en) * | 2017-01-10 | 2017-05-24 | 四川龙蟒钛业股份有限公司 | Production method of titanium dioxide base material |
| WO2018001175A1 (en) * | 2016-06-27 | 2018-01-04 | 中国科学院金属研究所 | Preparation method for high visible light absorption titanium dioxide nanoparticle |
| CN108070315A (en) * | 2017-11-28 | 2018-05-25 | 马鞍山蓝科再制造技术有限公司 | A kind of high-temp.-resisting fire-proof composite nano paint |
| CN111484075A (en) * | 2020-04-22 | 2020-08-04 | 龙佰四川钛业有限公司 | Method for efficiently recycling hydrolysis scale |
| CN111604042A (en) * | 2020-04-10 | 2020-09-01 | 安徽迪诺环保新材料科技有限公司 | Rutile crystal form denitration catalyst carrier and preparation method thereof |
-
2002
- 2002-12-09 CN CNA021555133A patent/CN1506311A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100369818C (en) * | 2005-06-09 | 2008-02-20 | 江苏大学 | Process for preparing rutile-type nano TiO2 by meta titanic acid |
| CN100445209C (en) * | 2005-07-28 | 2008-12-24 | 同济大学 | Preparation method of new type nano-titanium dioxide powder |
| CN1330578C (en) * | 2005-10-25 | 2007-08-08 | 郴州市金贵有色金属有限公司 | Method of preparing nano-titanium dioxide precusor |
| WO2018001175A1 (en) * | 2016-06-27 | 2018-01-04 | 中国科学院金属研究所 | Preparation method for high visible light absorption titanium dioxide nanoparticle |
| CN106698508A (en) * | 2017-01-10 | 2017-05-24 | 四川龙蟒钛业股份有限公司 | Production method of titanium dioxide base material |
| CN108070315A (en) * | 2017-11-28 | 2018-05-25 | 马鞍山蓝科再制造技术有限公司 | A kind of high-temp.-resisting fire-proof composite nano paint |
| CN111604042A (en) * | 2020-04-10 | 2020-09-01 | 安徽迪诺环保新材料科技有限公司 | Rutile crystal form denitration catalyst carrier and preparation method thereof |
| CN111484075A (en) * | 2020-04-22 | 2020-08-04 | 龙佰四川钛业有限公司 | Method for efficiently recycling hydrolysis scale |
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