CN1557721A - Method for preparing rutile type calcination crystal seed - Google Patents
Method for preparing rutile type calcination crystal seed Download PDFInfo
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- CN1557721A CN1557721A CNA2004100217679A CN200410021767A CN1557721A CN 1557721 A CN1557721 A CN 1557721A CN A2004100217679 A CNA2004100217679 A CN A2004100217679A CN 200410021767 A CN200410021767 A CN 200410021767A CN 1557721 A CN1557721 A CN 1557721A
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- rutile type
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- type calcining
- calcining seeds
- metatitanic acid
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Abstract
The rutile type calcining crystal seed preparation process includes the following steps: boiling metatitanic acid and concentrated sulfuric acid for reaction to prepare titanium sulfate solution; cooling, diluting and adding alkali solution to neutralize and obtain titanic acid; filtering, washing, pulping, adding concentration hydrochloric acid and heating to reaction, and rapid cooling to rutile type calcining crystal seed. The rystal seed has high rutile content over 99 %. In the process, the salt treatment has no zinc salt and other auxiliary promoter are used. The crystal seed may be used in obtaining rutile type TiO2 powder with particle size of several nanometer and oil absorption lower than 19 %.
Description
Technical field
The present invention relates to a kind of preparation method of rutile in high activity type calcining seeds.
Background technology
Rutile type calcining seeds is widely used in making TiO in the Production By Sulfuric Acid Process rutile pigment titanium white process
2Rutilization promotor also can be used for producing rutile type nano TiO
2Function powder material.The preparation method of existing rutile type calcining seeds normally mixes metatitanic acid with sodium hydroxide by a certain percentage, boil again and generate positive sodium titanate about two hours, form positive metatitanic acid after the positive sodium titanate hydrolysis, obtain rutile type calcining seeds with a certain amount of hydrochloric acid reaction again.But use that this method prepares that the rutilization rate active low, crystal seed of rutile type calcining seeds is low, first product oil number height, also owing to handle at salt and to add zinc salt or its oxide compound often as secondary accelerator, make the TiO of anatase structures
2Change into rutile-type structure up hill and dale, and the introducing of zinc increases the median size of titanium white particulate.
Summary of the invention
Technical problem to be solved by this invention provides the preparation method of a kind of rutilization rate height, the first product oil number is low, median size is little rutile type calcining seeds.
The technical scheme that technical solution problem of the present invention is adopted is: the preparation method of rutile type calcining seeds may further comprise the steps: 1) metatitanic acid and the vitriol oil are boiled reaction and make titanium sulfate liquid; 2) cooling back dilution adds the alkali lye neutralization and makes positive metatitanic acid; 3) after filtration, after washing and the making beating, add chilling after concentrated hydrochloric acid and the reacting by heating, obtain rutile type calcining seeds.
The concentration of above-mentioned metatitanic acid is 200g/l-340g/l.Cooling temperature is 40 ℃-45 ℃.Deionized water is adopted in dilution, contains TiO in the titanium sulfate liquid of dilution back
2At 100g/l-280g/l.Alkali lye is sodium hydroxide solution or solution of ammonium hydroxide.Neutral temperature is 45 ℃-70 ℃.When the pH value of positive metatitanic acid during, stop dripping alkali liquid at 6.0-7.5.The Heating temperature of positive metatitanic acid and hydrochloric acid is 80 ℃-110 ℃, and be 30min-90min heat-up time.The temperature of chilling is 60 ℃-70 ℃.
The invention has the beneficial effects as follows: the rutilization rate of the inventive method gained crystal seed is not less than 99%, rutilization rate height.In addition since the inventive method when salt is handled without zinc salt and other secondary accelerator, the rutile TiO that makes with this crystal seed
2The particle diameter of powder is several nanometers, and median size is little.The rutile TiO that makes with this crystal seed
2The oil number of first product powder is not more than 19g/100g.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1:
Metatitanic acid is pulled an oar into 250g/l (with TiO
2Meter), gets in the beaker that 400ml pours 1000ml into, add vitriol oil 245ml while stirring, boil the titanium sulfate clear liquid that no suspended substance is made in reaction under the normal pressure.After being cooled to 40 ℃-45 ℃, add the deionized water dilution of 540ml while stirring.Get this titanium liquid of 200ml and pour in the beaker of 1000ml, stir the NaOH solution of slow dropping 10% down and make positive metatitanic acid, the control neutral temperature when the pH value of slurries is 7.0-7.5, stops dripping alkali liquid at 50 ℃-65 ℃.Filter then and do not have SO with deionized water wash to washing lotion
4 -2Till (splash into 10% barium chloride solution no white precipitate gets final product in the washing lotion).Then filter cake is pulled an oar into 100g/l (with TiO
2Meter), add concentrated hydrochloric acid, wherein TiO
2: HCl=1: 0.50 (mass ratio), in the time of 85 ℃-110 ℃, behind the constant temperature stirring reaction 45min, add 40ml deionized water chilling immediately, slowly be cooled to room temperature then, make rutile in high activity type calcining seeds.The TiO of this crystal seed
2Rutilization rate 〉=99%, median size are 5nm-8nm.
Embodiment 2:
Metatitanic acid is pulled an oar into 280g/l, get in the beaker that 357ml pours 1000ml into, add vitriol oil 272ml while stirring, boil the titanium sulfate clear liquid that no suspended substance is made in reaction under the normal pressure.After when being cooled to 40 ℃-45 ℃, add the deionized water dilution of 400ml while stirring.Get 300ml concentration and be 15% NaOH solution and pour in the beaker of 1000ml, stir and slowly drip this titanium liquid down and make positive metatitanic acid, the control neutral temperature when the pH value of slurries is 7.0-7.5, stops to drip titanium liquid at 50 ℃-60 ℃.Filter then and do not have SO with deionized water wash to washing lotion
4 -2Till.Filter cake is pulled an oar into 120g/l, add concentrated hydrochloric acid, wherein TiO
2: HCl=1: 0.55, in the time of 85 ℃-110 ℃, behind the constant temperature stirring reaction 40min, add 100ml deionized water chilling immediately, slowly be cooled to room temperature then, make rutile in high activity type calcining seeds.The TiO of this crystal seed
2Rutilization rate 〉=99%, median size are 6nm-7nm.
Embodiment 3:
Metatitanic acid is pulled an oar into 320g/l, get in the beaker that 313ml pours 1000ml into, add vitriol oil 255ml while stirring, boil the titanium sulfate clear liquid that no suspended substance is made in reaction under the normal pressure.After being cooled to 40 ℃-45 ℃, add the deionized water dilution of 450ml while stirring.Get this titanium liquid of 200ml and pour in the beaker of 1000ml, stir down the slowly NH of dropping 20%
4OH solution is made positive metatitanic acid, and the control neutral temperature when the pH value of slurries is 7.0-7.5, stops dripping alkali liquid at 45 ℃-65 ℃.Filter then and do not have SO with deionized water wash to washing lotion
4 -2Till.Filter cake is pulled an oar into 140g/l, add concentrated hydrochloric acid, wherein TiO
2: HCl=1: 0.45, in the time of 85 ℃-110 ℃, behind the constant temperature stirring reaction 50min, add 60ml deionized water chilling immediately, slowly be cooled to room temperature then, make rutile in high activity type calcining seeds.The TiO of this crystal seed
2Rutilization rate 〉=99%, median size are 5nm-10nm.
Claims (10)
1, the preparation method of rutile type calcining seeds may further comprise the steps: 1) metatitanic acid and the vitriol oil are boiled reaction and make titanium sulfate liquid; 2) cooling back dilution adds the alkali lye neutralization and makes positive metatitanic acid; 3) after filtration, after washing and the making beating, add chilling after concentrated hydrochloric acid and the reacting by heating, obtain rutile type calcining seeds.
2, according to the preparation method of the described rutile type calcining seeds of claim 1, it is characterized in that: the concentration of described metatitanic acid is 200g/l-340g/l.
3, according to the preparation method of the described rutile type calcining seeds of claim 1, it is characterized in that:
Described cooling temperature is 40 ℃-45 ℃.
4, according to the preparation method of the described rutile type calcining seeds of claim 1, it is characterized in that:
Deionized water is adopted in described dilution, contains TiO in the titanium sulfate liquid of dilution back
2At 100g/l-280g/l.
5, according to the preparation method of the described rutile type calcining seeds of claim 1, it is characterized in that:
Described alkali lye is sodium hydroxide solution or solution of ammonium hydroxide.
6, according to the preparation method of the described rutile type calcining seeds of claim 1, it is characterized in that:
Described neutral temperature is 45 ℃-70 ℃.
7, according to the preparation method of the described rutile type calcining seeds of claim 1, it is characterized in that:
When the pH value of described positive metatitanic acid during, stop dripping alkali liquid at 6.0-7.5.
8, according to the preparation method of the described rutile type calcining seeds of claim 1, it is characterized in that:
The Heating temperature of described positive metatitanic acid and hydrochloric acid is 80 ℃-110 ℃.
9, according to the preparation method of the described rutile type calcining seeds of claim 1, it is characterized in that:
Described positive metatitanic acid and hydrochloric acid heat-up time are 30min-90min.
10, according to the preparation method of the described rutile type calcining seeds of claim 1, it is characterized in that:
The temperature of described chilling is 60 ℃-70 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410021767 CN1238258C (en) | 2004-02-05 | 2004-02-05 | Method for preparing rutile type calcination crystal seed |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410021767 CN1238258C (en) | 2004-02-05 | 2004-02-05 | Method for preparing rutile type calcination crystal seed |
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| CN1557721A true CN1557721A (en) | 2004-12-29 |
| CN1238258C CN1238258C (en) | 2006-01-25 |
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| CN 200410021767 Expired - Fee Related CN1238258C (en) | 2004-02-05 | 2004-02-05 | Method for preparing rutile type calcination crystal seed |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102390865A (en) * | 2011-08-11 | 2012-03-28 | 四川龙蟒钛业股份有限公司 | Method for preparing high-activity double-effect seed crystals from metatitanic acid |
| CN106698504A (en) * | 2016-11-24 | 2017-05-24 | 攀枝花市钛都化工有限公司 | Salt treatment method for rutile titanium dioxide and treated titanium dioxide initial product |
| CN106745234A (en) * | 2016-11-24 | 2017-05-31 | 攀枝花市钛都化工有限公司 | The preparation method of rutile type titanium white |
| CN106745233A (en) * | 2016-11-24 | 2017-05-31 | 攀枝花市钛都化工有限公司 | For the preparation method of the calcining seeds of rutile titanium white powder production |
| CN106745213A (en) * | 2017-01-10 | 2017-05-31 | 四川龙蟒钛业股份有限公司 | The preparation method of trivalent tiron |
| CN106966428A (en) * | 2017-03-30 | 2017-07-21 | 四川龙蟒钛业股份有限公司 | The method that calcining seeds are prepared using alkali soluble filtrate |
| CN107162046A (en) * | 2017-06-30 | 2017-09-15 | 安徽金星钛白（集团）有限公司 | A kind of preparation method of inexpensive rutile type titanium white |
| CN112875750A (en) * | 2021-03-16 | 2021-06-01 | 广东惠云钛业股份有限公司 | Preparation method and application of rutile titanium dioxide calcination seed crystal |
-
2004
- 2004-02-05 CN CN 200410021767 patent/CN1238258C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102390865A (en) * | 2011-08-11 | 2012-03-28 | 四川龙蟒钛业股份有限公司 | Method for preparing high-activity double-effect seed crystals from metatitanic acid |
| CN102390865B (en) * | 2011-08-11 | 2013-07-31 | 四川龙蟒钛业股份有限公司 | Method for preparing high-activity double-effect seed crystals from metatitanic acid |
| CN106698504A (en) * | 2016-11-24 | 2017-05-24 | 攀枝花市钛都化工有限公司 | Salt treatment method for rutile titanium dioxide and treated titanium dioxide initial product |
| CN106745234A (en) * | 2016-11-24 | 2017-05-31 | 攀枝花市钛都化工有限公司 | The preparation method of rutile type titanium white |
| CN106745233A (en) * | 2016-11-24 | 2017-05-31 | 攀枝花市钛都化工有限公司 | For the preparation method of the calcining seeds of rutile titanium white powder production |
| CN106745213A (en) * | 2017-01-10 | 2017-05-31 | 四川龙蟒钛业股份有限公司 | The preparation method of trivalent tiron |
| CN106966428A (en) * | 2017-03-30 | 2017-07-21 | 四川龙蟒钛业股份有限公司 | The method that calcining seeds are prepared using alkali soluble filtrate |
| CN107162046A (en) * | 2017-06-30 | 2017-09-15 | 安徽金星钛白（集团）有限公司 | A kind of preparation method of inexpensive rutile type titanium white |
| CN112875750A (en) * | 2021-03-16 | 2021-06-01 | 广东惠云钛业股份有限公司 | Preparation method and application of rutile titanium dioxide calcination seed crystal |
| CN112875750B (en) * | 2021-03-16 | 2021-09-21 | 广东惠云钛业股份有限公司 | Preparation method and application of rutile titanium dioxide calcination seed crystal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1238258C (en) | 2006-01-25 |
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