CN101190800A - Method for preparing rutile-type titanium dioxide by hydrothermal method - Google Patents
Method for preparing rutile-type titanium dioxide by hydrothermal method Download PDFInfo
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- CN101190800A CN101190800A CNA2006101442546A CN200610144254A CN101190800A CN 101190800 A CN101190800 A CN 101190800A CN A2006101442546 A CNA2006101442546 A CN A2006101442546A CN 200610144254 A CN200610144254 A CN 200610144254A CN 101190800 A CN101190800 A CN 101190800A
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Abstract
The invention relates to a new method for preparing rutile titanium oxide. The method adopts anatase titanium oxide as raw material and sodium hydroxide hydrothermal method to prepare the intermediate product of sodium titanate which is then separated from the solution and washed and hydrolyzed to obtain the rutile titanium oxide. The method of the invention adopts simple preparation technique to prepare the rutile TiO2, which spares high temperature calcination in the traditional technique; the conversion rate of titanium in the raw material is of 100 percent and the final product is rutile titanium oxide of 100 percent and the alkali circulation and the acid circulation are realized, which has good economic benefit and environmental benefit. Additionally, the inorganic functional material of sodium titanate obtained from the method is expected to have wide application.
Description
Technical field
The invention belongs to inorganic functional material fabricating technology field, specifically relate under the hydrothermal condition to change the method for rutile titanium dioxide by anatase titanium dioxide into through titanate, this hydrothermal method also can be used for preparing whisker titanate inorganic functional material simultaneously.
Background technology
Titanium dioxide (titanium white) is a kind of white pigment, is widely used in an aspect such as coating, plastics, papermaking, man-made fiber, rubber, printing ink, enamel, metallurgy and catalysis.The pigment performance of rutile type is more good than anatase titanium dioxide.
The production process route of titanium dioxide mainly contains sulfuric acid process and chlorination process.There is long flow path in sulfuric acid process, sulfuric acid, water consumption height, shortcoming such as refuse and by product are many, and be big for environment pollution.Chlorination process but because its equipment, flow process complexity, investment is big, and its production technology is still monopolized by minority major company.Simultaneously, sulfuric acid process is in order to obtain rutile titanium dioxide, and calcining temperature needs at 900-1250 ℃, is subjected to quickening or to stop the influence of factors such as the promotor of crystal conversion or inhibitor simultaneously; Chlorination process directly obtains rutile titanium dioxide, but it needs at 900-1000 ℃ and adds under the condition of nucleator and obtain through oxidizing reaction.
Summary of the invention
The purpose of this invention is to provide that a kind of equipment is simple, the method for technical process weak point, less investment, production rutile titanium dioxide that cost is low.
The objective of the invention is to be achieved through the following technical solutions:
The method of rutile titanium dioxide provided by the invention, be to be raw material with the anatase titanium dioxide, obtain the sodium titanate intermediate with sodium hydroxide reaction under the condition of hydro-thermal, the intermediate sodium titanate is separated again directly prepared rutile titanium dioxide through hydrolysis then, concrete steps are as follows:
1) hydro-thermal reaction: with a certain amount of anatase titanium dioxide and sodium hydroxide solution thorough mixing,, carry out hydro-thermal reaction 0.5-10h under the stirring condition, obtain the hydro-thermal reaction product at 120-280 ℃; Wherein the mass ratio of sodium hydroxide and titanium dioxide is 0.5-5: 1, and the concentration of alkali is 200-1600g/L;
2) separation of intermediate sodium titanate, washing: the reaction product of step 1) obtains to contain the intermediate sodium titanate and the soda-lye of small-amount free alkali through solid-liquid separation, and this soda-lye returns step 1) and is used for hydro-thermal reaction behind dehydration by evaporation; The intermediate sodium titanate that will contain small-amount free alkali water is at normal temperatures washed, is filtered, and is not contained the intermediate sodium titanate and the dilute solution of sodium hydroxide of free alkali, and this dilute solution of sodium hydroxide returns step 1) and is used for hydro-thermal reaction after evaporation concentration;
Described water washing process can be common washing, also can be the multi-stage countercurrent washing; The solid-liquid mass ratio of sodium titanate and bath water is 1: 1-200;
3) the intermediate sodium titanate that hydrolysis: with step 2) obtains is mixed with a certain amount of acid solution, and solid-to-liquid ratio is 1: 5-200, hydrolysis under 50-150 ℃ of condition, hydrolysis time 0.5-48h, hydrolysate is filtered, obtain the titanium dioxide solid and the acid filtrate of white, this acid filtrate reusable edible;
Described acid is hydrochloric acid;
4) product drying: the titanium dioxide that step 3) obtains is dry under 60-120 ℃, promptly obtain rutile titanium dioxide without high-temperature roasting.
The production method of preparing rutile-type titanium dioxide by hydrothermal method provided by the invention (titanium white), comprise that anatase titanium dioxide and sodium hydroxide hydro-thermal reaction obtain converted product, products therefrom is carried out processes such as solid-liquid separation, washing, hydrolysis, can obtain rutile titanium dioxide after the solid phase drying that hydrolysis obtains., to compare with existing production of rutile titanium dioxide technology, the characteristics and the advantage of preparing rutile-type titanium dioxide by hydrothermal method provided by the invention are:
1. shortcomings such as the present invention adopts hydrothermal method to change anatase titanium dioxide into rutile titanium dioxide through the sodium titanate intermediate under cold condition, compares with traditional sulfuric acid process, has avoided sour consumption height, and refuse and by product are many; Compare with chlorination process, temperature of reaction has reduced more than 800 ℃, greatly reduces energy consumption.
2. the pH value that can control the hydrolysis of intermediate sodium titanate is controlled the pattern of products therefrom titanium dioxide, and when pH value during less than certain value, hydrolyzed product titanium dioxide is spherical, and when pH value was worth greater than this, hydrolyzed product was a whisker titanium dioxide.
3. products therefrom can obtain rutile titanium dioxide without roasting after the drying after the hydrolysis of intermediate sodium titanate, has avoided high-temperature roasting, has huge economic benefit.
4. the titanium transformation efficiency can 100% be converted into rutile titanium dioxide in the raw material anatase titanium dioxide, and the purity of rutile titanium dioxide is 100%.
5. the present invention has realized alkali circulation, acid circulation, has greatly reduced raw-material energy consumption, and equipment is simple, easy to operate.
6. method provided by the invention also can make sodium titanate, as the intermediate of serial titanium, and is expected to be used widely.
Description of drawings
Fig. 1. the XRD figure spectrum of the embodiment of the invention 1 prepared titanium dioxide.
Fig. 2. the SEM collection of illustrative plates of the embodiment of the invention 1 prepared titanium dioxide.
Fig. 3. the SEM collection of illustrative plates of the embodiment of the invention 2 prepared titanium dioxide.
Embodiment
Embodiment 1
In reactor, add 400g/L NaOH alkaline solution successively, anatase titanium dioxide, under agitation mix, the mass ratio of NaOH and titanium dioxide is 2.0: 1,160 ℃ of following hydro-thermal reactions 4 hours, obtains the hydro-thermal reaction product, this product is filtered, obtain containing the sodium titanate of free alkali, wash this sodium titanate with water, obtain the sodium titanate product after the filtration; A certain amount of sodium titanate product is mixed with hydrochloric acid soln, regulate PH=0.06, make its whole dissolvings, solid-to-liquid ratio is 1: 200, at last this solution is hydrolyzed under 100 ℃ 2 hours, and hydrolysate is filtered, the white solid that obtains is in 60 ℃ of dryings, obtain rutile titanium dioxide, its XRD spectra as shown in Figure 1, SEM schemes as shown in Figure 2.By XRD spectra as can be known the product that obtains of hydrolysis be rutile titanium dioxide, the titanium dioxide that is obtained under this condition as can be known by SEM figure is spherical.
Embodiment 2
In reactor, add 200g/L NaOH alkaline solution successively, anatase titanium dioxide, under agitation mix, the mass ratio of NaOH and titanium dioxide is 5: 1,260 ℃ of following hydro-thermal reactions 10 hours, obtains the hydro-thermal reaction product, this product is filtered, obtain containing the sodium titanate of free alkali, wash this sodium titanate with water, obtain the sodium titanate product after the filtration; A certain amount of sodium titanate product is mixed with hydrochloric acid soln, regulate PH=0.60, make its whole dissolvings, solid-to-liquid ratio is 1: 100, at last this solution was hydrolyzed under 50 ℃ 10 hours, hydrolysate is filtered, the white solid that obtains is in 120 ℃ of dryings, obtain rutile titanium dioxide, its SEM figure as shown in Figure 3.The titanium dioxide that obtains under this condition as can be known of SEM figure is the whisker shape thus.
Embodiment 3
In reactor, add the 1600g/LNaOH alkaline solution successively, anatase titanium dioxide, under agitation mix, the mass ratio of NaOH and titanium dioxide is 0.5: 1,200 ℃ of following hydro-thermal reactions 2 hours, obtain the hydro-thermal reaction product, this product is filtered, obtain containing the potassium titanate of free alkali, wash this product with water and obtain the sodium titanate product; A certain amount of sodium titanate product is mixed with hydrochloric acid soln, regulate PH=0.20, the sodium titanate solid does not dissolve, solid-to-liquid ratio is 1: 5, at last this mixed solution was hydrolyzed under 150 ℃ 48 hours, hydrolysate is filtered, and the white solid that obtains obtains rutile titanium dioxide in 80 ℃ of dryings.
Claims (4)
1. the method for a preparing rutile-type titanium dioxide by hydrothermal method may further comprise the steps:
1) hydro-thermal reaction: with a certain amount of anatase titanium dioxide and sodium hydroxide solution thorough mixing,, carry out hydro-thermal reaction 0.5-10h under the stirring condition, obtain the hydro-thermal reaction product at 120-280 ℃; Wherein the mass ratio of sodium hydroxide and titanium dioxide is 0.5-5: 1, and concentration sodium hydroxide is 200-1600g/L;
2) separation of intermediate, washing: the reaction product of step 1) obtains to contain the intermediate sodium titanate of small-amount free alkali and the strong solution of alkali through solid-liquid separation, the strong solution of this alkali is returned step 1) be used for hydro-thermal reaction behind dehydration by evaporation; The intermediate sodium titanate that will contain small-amount free alkali water is at normal temperatures washed, is filtered, and obtains the dilute solution of intermediate sodium titanate and alkali, and this dilute solution is returned step 1) and is used for hydro-thermal reaction after evaporation concentration;
3) the intermediate sodium titanate that hydrolysis: with step 2) obtains is mixed with a certain amount of acid solution, 50-150 ℃ of following hydrolysis, hydrolysate is filtered, and obtains white solid and acid filtrate, the acid filtrate recycle;
Described acid is hydrochloric acid;
The solid-to-liquid ratio of described hydrolysis mixed solution is 1: 5-200;
4) product drying: the white solid drying with step 3) obtains obtains rutile titanium dioxide.
2. the method for preparing rutile-type titanium dioxide by hydrothermal method as claimed in claim 1, it is characterized in that: the washing process described step 2) is common washing, or the multi-stage countercurrent washing.
3. the method for preparing rutile-type titanium dioxide by hydrothermal method as claimed in claim 1 is characterized in that, described step 2) in water washing process in, the solid-liquid mass ratio of sodium titanate and bath water is 1: 1-200.
4. the method for preparing rutile-type titanium dioxide by hydrothermal method as claimed in claim 1, it is characterized in that: the drying temperature of described step 4) is 60-120 ℃.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102409179A (en) * | 2011-09-13 | 2012-04-11 | 北京科技大学 | Method for preparing one-dimensional nanostructures of titanium dioxide with melting slag of titanium containing electric furnace |
| CN103708540A (en) * | 2013-12-27 | 2014-04-09 | 攀枝花东方钛业有限公司 | Method for recycling alkali liquor in production process of titanium dioxide |
| CN104843783A (en) * | 2015-05-20 | 2015-08-19 | 山东东佳集团股份有限公司 | Preparation method of amorphous titanium dioxide for lithium titanate |
| CN104961157A (en) * | 2015-07-03 | 2015-10-07 | 燕山大学 | Synthetic method of rutile TiO2 |
| CN106582591A (en) * | 2016-11-17 | 2017-04-26 | 广东工业大学 | Preparation method of quadrangular anatase type TiO2 |
| CN111097543A (en) * | 2018-10-29 | 2020-05-05 | 哈尔滨工业大学 | Preparation method of composite material for enhancing photocatalytic performance of hydrated titanium dioxide by using gold nanorod local surface plasmons |
| CN114072358A (en) * | 2019-05-14 | 2022-02-18 | 帝化株式会社 | Titanium oxide powder and method for producing same |
-
2006
- 2006-11-30 CN CNA2006101442546A patent/CN101190800A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102409179A (en) * | 2011-09-13 | 2012-04-11 | 北京科技大学 | Method for preparing one-dimensional nanostructures of titanium dioxide with melting slag of titanium containing electric furnace |
| CN102409179B (en) * | 2011-09-13 | 2014-02-12 | 北京科技大学 | Method for preparing one-dimensional nanostructures of titanium dioxide with melting slag of titanium containing electric furnace |
| CN103708540A (en) * | 2013-12-27 | 2014-04-09 | 攀枝花东方钛业有限公司 | Method for recycling alkali liquor in production process of titanium dioxide |
| CN103708540B (en) * | 2013-12-27 | 2016-06-01 | 攀枝花东方钛业有限公司 | A kind of method of alkali lye recycle in production process of titanium pigment |
| CN104843783A (en) * | 2015-05-20 | 2015-08-19 | 山东东佳集团股份有限公司 | Preparation method of amorphous titanium dioxide for lithium titanate |
| CN104961157A (en) * | 2015-07-03 | 2015-10-07 | 燕山大学 | Synthetic method of rutile TiO2 |
| CN106582591A (en) * | 2016-11-17 | 2017-04-26 | 广东工业大学 | Preparation method of quadrangular anatase type TiO2 |
| CN111097543A (en) * | 2018-10-29 | 2020-05-05 | 哈尔滨工业大学 | Preparation method of composite material for enhancing photocatalytic performance of hydrated titanium dioxide by using gold nanorod local surface plasmons |
| CN114072358A (en) * | 2019-05-14 | 2022-02-18 | 帝化株式会社 | Titanium oxide powder and method for producing same |
| CN114072358B (en) * | 2019-05-14 | 2023-10-24 | 帝化株式会社 | Titanium oxide powder and method for producing same |
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