CN85103475A - Preparation of rutile type pigment titanium white by high activity crystal - Google Patents
Preparation of rutile type pigment titanium white by high activity crystal Download PDFInfo
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- CN85103475A CN85103475A CN85103475.6A CN85103475A CN85103475A CN 85103475 A CN85103475 A CN 85103475A CN 85103475 A CN85103475 A CN 85103475A CN 85103475 A CN85103475 A CN 85103475A
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Abstract
The present invention uses in the weak ammonia and industrial titanium sulfate solution under strictness control preparation condition situation, has made in the highly active ammonia and crystal seed, and this crystal seed not only has activity to the hydrolysis stage of titanium liquid, and to TiO
2The calcination stage of hydrate has activity, has the anatase titanium dioxide crystal is converted into rutile-type crystalline rutilization characteristic.This crystal seed is added titanium liquid, realized the ordinary-pressure hydrolysis of high density titanium liquid.Hydrolysate is handled through the salt of appropriate prescription, adds the crystal seed burning phase transformation, grinds classification, and coating is handled, and has made the rutile pigment titanium dioxide.The titanium hydrolysis rate reaches 95%, and it is 99% that the anatase titanium dioxide crystal is converted into rutile-type crystalline phase transformation transformation efficiency.
Description
The invention belongs to the category of Titanium White Production By Sulfuric Acid Process, is to utilize high-activity crystal seed, carries out the thermal hydrolysis of titanium liquid under normal pressure, to make the rutile pigment titanium dioxide.As a kind of white pigment of performance the best, titanium dioxide is industrial having a wide range of applications such as paint, papermaking, leather, synthon, plastics.
The technology of existing Titanium White Production By Sulfuric Acid Process, the external method of automatic growing crystal species that extensively adopts is (as the U.S. Pat 4,098 of promulgation on July 4th, 1978, the US4 of promulgation on June 9th, 869 and 1979,133,864), domestic then many with in the sodium hydroxide and crystal seed method.The former defective is that the crystal seed preparation condition is difficult to control, be difficult to obtain even particle size distribution, the regular crystal seed of shape, and the operation of titanium liquid thermal hydrolysis is comparatively loaded down with trivial details, is difficult to obtain the good titanium dioxide of pigment performance once Shen not slightly.The latter's defective is: sodium hydroxide is highly basic, when neutralizing acid titanium liquid with it, and the sharp thermal distortion of regional area generation pH value, the crystal seed of generation is big and inhomogeneous, thereby activity is lower, can't be at hydrolysis high density titanium liquid under the normal pressure to make the pigment-level titanium dioxide.For specific pigment, Chan Pin De Teeth grain size, particularly size distribution situation are the important factors that influences pigment performance.Small particle size distribution is even more more for product cut size in certain limit, and its tinting strength is just high more.， Teeth grain diameter is controlled in the scope of 0.20～0.25 μ ideal for the rutile pigment titanium dioxide.Reach this kind size distribution, (concentration must be greater than 220 gram TiO for the thermal hydrolysis of necessary realization high density titanium liquid
2/ liter).Experiment shows that the sodium hydroxide crystal seed can't finish this task.To guarantee 95% above percent hydrolysis during ordinary-pressure hydrolysis, this crystal seed can hydrolysis titanium liquid maximum concentration be no more than 160 grams per liters.During the high density titanium hydrolysis, its percent hydrolysis has only about 70%.In order to address this problem, more domestic producers have adopted the way of pressurized hydrolysis.Like this, equipment complexity not only, operational difficulty, initial cost is big.And fundamentally do not solve quality problems.Also should be mentioned that:, and do not have activity calcining the phase transformation stage no matter be all only there is activity in the titanium hydrolysis stage with crystal seed in automatic growing crystal species or the sodium hydroxide.All have to make in addition rutile type calcining seeds in order to produce the rutile pigment titanium dioxide.
The objective of the invention is to develop a kind of high-activity crystal seed, can be at hydrolysis high density titanium liquid under the normal pressure, to make the pigment-level titanium dioxide.This crystal seed both had activity to the titanium hydrolysis stage, again there was activity in the calcining phase transformation stage, promptly had the characteristic of rutilization.
In view of the foregoing, we have carried out the screening operation of new crystal seed.Grasp in strictness under the situation of preparation condition through effort in 2 years, use in the weak ammonia and industrial titanium sulfate solution, made in the highly active ammonia and crystal seed.This crystal seed is added titanium liquid, realized the ordinary-pressure hydrolysis of high density titanium liquid, handle through the salt of appropriate prescription, the calcining phase transformation is ground classification, operations such as coating processing.Made rutile pigment level titanium dioxide.The titanium hydrolysis rate reaches 95%, and the phase transformation transformation efficiency that the anatase titanium dioxide crystal is converted into the golden red N-type waferN reaches 99%, and relevant colleague thinks that this achievement occupies first place at home.
The preparation technology of high-activity crystal seed: hydrolysis is a most important operation in the titanium white production, and the crystal seed preparation then is the key link of hydrolyzing process.Naturally the nucleus of Xing Chenging can not possess satisfactory good character, must prepare crystal seed under the particular solution condition, it is added in the titanium liquid goes, and has both accelerated hydrolysis reaction speed, has improved percent hydrolysis, and the particle diameter to hydrolysis prods has played Accommodation again.The activity of crystal seed and type have a significant impact the percent hydrolysis and the pigment performance of product.
The principle process of ammonia crystal seed preparation is as follows:
The alkali neutralization reaction was a thermopositive reaction when crystal seed prepared, and made titanium liquid generation hydrolysis for fear of neutral temperature is too high, must the control neutral temperature about 40 ℃.Should in titanium liquid, add ammoniacal liquor while stirring, all can reduce activity of crystal seed with the time in too high temperature and the prolongation.In and terminal point should be strict controlled in PH=3～3.5 scopes, gained titanic Acid precipitation is maximum with this understanding, and does not have Fe(OH)
2Interference.The ammoniacal liquor add-on is very few, PH＞3 o'clock, and then the titanic Acid precipitation is incomplete, and the ammoniacal liquor add-on is too much, PH＞3.5 o'clock, crystal seed can be subjected to the hydroxide iron pollution.The washing of titanic Acid precipitation and shelf-time can not be oversize, otherwise can influence sour molten because of ageing.Ammonium sulfate in the precipitation must be with deionized water flush away as far as possible, otherwise the gained crystal seed does not have TiO
2The character of hydrate rutilization, and percent hydrolysis reduction, tinting strength will descend, and product is yellow.Must control HCl: TiO during titanic Acid precipitation peptization well
2=0.35～0.45(mol ratio).The hydrochloric acid add-on is very few, and positive metatitanic acid is peptization fully, crosses and not only wastes reagent at most, and can produce the gelling phenomenon.In the ammoniacal liquor and the positive metatitanic acid of titanium liquid gained be amorphous compound, the chemically reactive height has by acid dissociable dissolution in the titanium liquid or changes the danger of its structure, therefore, must make its micritization through overcuring, to obtain being insoluble to the crystal seed of diluted acid.Curing temperature is 60～65 ℃, during the hold-time 3～4 hours.With crystal seed three tangible advantages are arranged in the ammonia: (1) this crystal seed both had activity to hydrolysis stage, again to TiO
2The hydrate calcination stage has activity, has the characteristic that the anatase titanium dioxide crystal is converted into rutile-type crystalline rutilization, so, can adopt at hydrolysis stage, also can adopt at calcination stage.(2) activity cycle of this crystal seed is longer, places still to have activity in about one month.(3) with this crystal seed hydrolysis high density titanium liquid, products obtained therefrom has good pigment performance.
The hydrolysis process condition: the factor that influences titanium liquid thermal hydrolysis is a lot, as the composition of titanium liquid, and crystal seed add-on, hydrolysis temperature, hydrolysis time, free acid concentration of titanium solution or the like.This research has been carried out a series of tests to the various factors that influences hydrolysis, has found top condition basically: the titanium liquid that the acidolysis ilmenite obtains, need to make through clean earlier, and operations such as vacuum concentration, freezing deironing, making supplies water separates the original titanium liquid of usefulness.TiO in the titanium liquid
2Concentration be 200～220 grams per liters, F=2.0～2.2, iron titanium ratio are between 0.3～0.5, and effective acid is 380～480 grams per liters, hydrolysis temperature is 103～105 ℃, hydrolysis time is 2～2.5 hours, and the metatitanic acid precipitation that hydrolysis goes out is through washing, and the salt of appropriate prescription is handled, add crystal seed calcination phase transformation, grind classification, coating is handled, and makes rutile-type face material titanium dioxide at last.It is 99% that the titanium hydrolysis rate reaches 95% rutile transformation efficiency.
For relevant technologies of the present invention is described better, now be exemplified below:
Example 1: get 100 milliliters of industrial titanium sulfate solutions and (wherein contain TiO
2196 grams per liters) put into 500 milliliters of Burn cups, add 100 ml deionized water.Slow Slow is heated to 30 ℃, drips 10% weak ammonia while stirring, and its reactional equation is:
Control neutral temperature be lower than 40 ℃, in and terminal point be PH=3.5.The positive metatitanic acid that obtains spends deionised water, and flush away is ammonium sulfate wherein, and the washing terminal point is with 10% BaCl
2Check.Obtain precipitating 18.2 grams.Then the titanic Acid precipitation of cleaning is distributed in the mixed solution of 120 ml waters and 3 milliliters of concentrated hydrochloric acids, gained suspension is cooled to room temperature 65 ℃ of following constant temperature slakings 3 hours, promptly gets the high-activity crystal seed that is insoluble to diluted acid, and its concentration is 64.4 grams per liter (TiO
2Meter)
Example 2: in 500 milliliters of three mouthfuls of Burn bottles that doubtful device of returned cold and electric mixer are housed, add 200 milliliters of industrial titanium sulfate solutions.It consists of TiO
2220 grams per liters, Ti
2O
33 grams per liters, effective acid 450 grams per liters, Fe
++80 grams per liters.Slow Slow is warming up to 70 ℃.Add the made crystal seed (TiO in the crystal seed of 10 milliliters of examples 1
2Account for TiO in the titanium liquid
2About 1.5%).Heating while stirring is until boiling.Solution bleaches after hydrolysis half an hour, and the sampling and measuring percent hydrolysis is about 60%, measures once every half an hour later on, and after 2.5 hours, percent hydrolysis reaches 95.4%, stops heating, pours out suspension, be chilled to room temperature after, with deionized water wash gained metatitanic acid precipitation.Handle through the salt of appropriate prescription then, add 1% crystal seed and forge Burn phase transformation 2 hours under 850 ℃, grind classification, coating is handled and is made rutile-type face material titanium dioxide.Its rutile transformation efficiency is 99%.
Claims (6)
1, the present invention is a high-activity crystal seed, and ordinary-pressure hydrolysis prepares the rutile pigment titanium dioxide.The preparation technology of crystal seed is: under strict controlled temperature condition, use in the weak ammonia and industrial titanium sulfate solution, terminal point is about PH=3.5.Gained titanic acid solution is used the dilute hydrochloric acid peptization then with deionized water flush away ammonium sulfate, and slaking makes in the highly active ammonia and crystal seed.
Crystal seed with 1.0～2.2% adds industrial titanium sulfate solution, boiling hydrolysis 2.5 hours, and gained metatitanic acid precipitation is handled through the salt of washing, appropriate prescription, adds the crystal seed burning phase transformation, grinds classification, and coating is handled, and makes the rutile pigment titanium dioxide.The titanium hydrolysis rate reaches 95%, and rutile-type crystal transformation efficiency is 99%.
2, according to described in the claim 1, used weak ammonia concentration was 10% when crystal seed prepared, and neutral temperature is 40 ℃.
3, according to described in the claim 1, positive metatitanic acid must be controlled HCl: TiO during with the dilute hydrochloric acid peptization well
2=0.35～0.45(mol ratio).
4, according to described in the claim 1, the crystal seed curing temperature is that 60～65 ℃ of soaking times are 3～4 hours.
5, according to described in the claim 1, the processing condition of titanium liquid thermal hydrolysis are: TiO in the titanium liquid
2Concentration be 200～220 grams per liters, F=2.0～2.2, iron titanium ratio is between 0.3～0.5, effective acid content is 380～480 grams per liters, the crystal seed add-on is that 1.0～2.2%(is with TiO
2Be benchmark), hydrolysis temperature is 103～105 ℃, hydrolysis time is 2～2.5 hours.
6, according to described in the claim 1, the add-on of calcining phase transformation stage crystal seed is about 1%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85103475A CN1008356B (en) | 1985-04-30 | 1985-04-30 | Preparation of rutile type pigment titanium white by high activity crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85103475A CN1008356B (en) | 1985-04-30 | 1985-04-30 | Preparation of rutile type pigment titanium white by high activity crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85103475A true CN85103475A (en) | 1986-10-29 |
| CN1008356B CN1008356B (en) | 1990-06-13 |
Family
ID=4793216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85103475A Expired CN1008356B (en) | 1985-04-30 | 1985-04-30 | Preparation of rutile type pigment titanium white by high activity crystal |
Country Status (1)
| Country | Link |
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| CN (1) | CN1008356B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067967C (en) * | 1998-09-11 | 2001-07-04 | 清华大学 | Superfine titanium white surface cladding tech. and reactor thereof |
| CN101705035B (en) * | 2009-11-11 | 2011-09-21 | 江苏镇钛化工有限公司 | Method for preparing predispersed rutile type titanium pigment paste |
| CN102558918A (en) * | 2010-12-07 | 2012-07-11 | 河南佰利联化学股份有限公司 | Production method for preparing titanium dioxide by seed crystal |
| CN105883913A (en) * | 2014-09-18 | 2016-08-24 | 攀枝花新中钛钒钛技术研发有限公司 | Method for external seed normal pressure introduced hydrolysis of high-concentration titaniferous solution |
| CN107857298A (en) * | 2017-11-30 | 2018-03-30 | 河北麦森钛白粉有限公司 | A kind of preparation method of sulfuric acid titanium hydrolysis high-activity crystal seed |
| CN110028100A (en) * | 2019-05-21 | 2019-07-19 | 四川大学 | The preparation method of the method for Production By Sulfuric Acid Process rutile titanium white and double-effect seed crystal used |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102012379B (en) * | 2010-10-19 | 2013-05-15 | 攀钢集团钢铁钒钛股份有限公司 | Method for characterizing activity of titanium tetrachloride hydrolytic seed crystal |
-
1985
- 1985-04-30 CN CN85103475A patent/CN1008356B/en not_active Expired
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067967C (en) * | 1998-09-11 | 2001-07-04 | 清华大学 | Superfine titanium white surface cladding tech. and reactor thereof |
| CN101705035B (en) * | 2009-11-11 | 2011-09-21 | 江苏镇钛化工有限公司 | Method for preparing predispersed rutile type titanium pigment paste |
| CN102558918A (en) * | 2010-12-07 | 2012-07-11 | 河南佰利联化学股份有限公司 | Production method for preparing titanium dioxide by seed crystal |
| CN102558918B (en) * | 2010-12-07 | 2014-05-07 | 河南佰利联化学股份有限公司 | Production method for preparing titanium dioxide by seed crystal |
| CN105883913A (en) * | 2014-09-18 | 2016-08-24 | 攀枝花新中钛钒钛技术研发有限公司 | Method for external seed normal pressure introduced hydrolysis of high-concentration titaniferous solution |
| CN107857298A (en) * | 2017-11-30 | 2018-03-30 | 河北麦森钛白粉有限公司 | A kind of preparation method of sulfuric acid titanium hydrolysis high-activity crystal seed |
| CN110028100A (en) * | 2019-05-21 | 2019-07-19 | 四川大学 | The preparation method of the method for Production By Sulfuric Acid Process rutile titanium white and double-effect seed crystal used |
| CN110028100B (en) * | 2019-05-21 | 2021-11-12 | 四川大学 | Method for producing rutile titanium white by sulfuric acid process and preparation method of used double-effect seed crystal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1008356B (en) | 1990-06-13 |
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