CN1034703A - The production method of titanium white - Google Patents
The production method of titanium white Download PDFInfo
- Publication number
- CN1034703A CN1034703A CN 88100410 CN88100410A CN1034703A CN 1034703 A CN1034703 A CN 1034703A CN 88100410 CN88100410 CN 88100410 CN 88100410 A CN88100410 A CN 88100410A CN 1034703 A CN1034703 A CN 1034703A
- Authority
- CN
- China
- Prior art keywords
- titanium
- add
- titanium dioxide
- leaching liquid
- production
- 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.)
- Withdrawn
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A kind of method of production of titanium dioxide is to be raw material with the rutile ore after ilmenite or the highly basic melting treatment, obtains containing the inorganic strong acid salt solution of titanium oxide ion with the inorganic acid reaction, adds NH in this solution
4Cl or KCl generate corresponding complex salt (NH
4)
2TiCl
6Or K
2TiCl
6, complex salt hydrolysis gained metatitanic acid, under 850 ℃-1050 ℃, calcine the Rutile type Titanium Dioxide product.This method technology, equipment are simple, less investment, and cost is low, and the products obtained therefrom whiteness is good, and opacifying power is big, and is stable, is suitable for making high grade paint, plastics, paint, catalyzer etc., has vast potential for future development.
Description
The present invention relates to method of production of titanium dioxide, be specifically related to the method for wet production titanium dioxide.
Titanium white-titanium dioxide is a kind of white pigment, is widely used in all respects such as coating, printing ink, plastics, papermaking, rubber, enamel, metallurgy and catalyzer, is in great demand.At home, particularly high-quality titanium white (rutile-type) does not satisfy needs far away.
At present, the production method of Chang Yong titanium white has chlorination process and sulfuric acid process.Chlorination process comprises steps such as chlorination, distillation, vapor phase hydrolysis or plasma high-temperature oxidation, and not only equipment, flow process complexity, investment are big, and also have the chlorine pollution problem.Japanese Patent (J7904899) discloses the technology of Production By Sulfuric Acid Process titanium white.This method is that ilmenite is contained titanyl sulfate (TiOSO with what sulfuric acid decomposed that the back generated
4) resultant of reaction isolate FeSO
47H
2Behind the O, get a part of non-concentrated solution and make crystal seed, be added in the titaniferous stoste, 100 ℃ of following heating hydrolysis 1.5 hours, cold filtration; Add crystal seed in the mother liquor again, about 6 hours of heating hydrolysis filters and obtains the metatitanic acid filter cake, and calcination gets the anatase titanium dioxide product, this method does not have suitable purification separation process, contain many impurity in the gained filter cake, not only influence the color and luster of titanium white product, and the obstruction anatase titanium dioxide transforms to rutile-type in calcination process, so poor product quality, instability is easily decomposed, and does not adapt to the needs of each side.
The object of the present invention is to provide that a kind of equipment is simple, the method for technical process weak point, less investment, production high-quality rutile type that cost is low.
Method of production of titanium dioxide provided by the present invention may further comprise the steps:
1. the material porphyrize that will contain metatitanate adds stoichiometric at least inorganic acid, carries out sour decomposition reaction 0.5-1.5 hour under room temperature to 130 ℃, be chilled to room temperature, thin up soaked under 60-65 ℃ about 2-3 hour, be chilled to 0 ℃-room temperature, filter, obtain containing titanium oxide ion (TiO
2) the leaching liquid of inorganic strong acid salt, representational reaction formula is:
M represents Fe, K or Na, X=1 or 2,
2. the pre-treatment of above-mentioned leaching liquid and hydrolysis,
3. the mixture after the said hydrolyzed obtains the metatitanic acid filter cake after filtration,
4. metatitanic acid filter cake oven dry, porphyrize were calcined 2-6 hour down at 850-1050 ℃, sieve,
It is characterized in that described pre-treatment and the hydrolysis that contains the leaching liquid of titanium oxide ion carry out according to the following steps:
A) add a small amount of iron filings in the titanium oxide ion leaching liquid in above-mentioned containing, stir, be light brown, filter until solution,
B) add any muriate (MCl) in stoichiometric at least ammonium chloride, Repone K, rubidium chloride or the cesium chloride in the titanium oxide ion leaching liquid in above-mentioned containing after reduction is handled, feed hydrogen chloride gas, generate complex salt M
2TiCl
6Precipitation is filtered, the metal ion in the flush away filter cake, and reaction formula is:
C) add the ionized water dilution in the complex salt after above-mentioned purification, under agitation heated and boiled constantly drips alkali aqueous solution, and is complete until hydrolysis.
The material that contains metatitanate involved in the present invention can be that the mineral that contain metatitanate for example contain FeTiO
3Ilmenite, also can be titaniferous ore for example contain titanium dioxide rutile ore respectively with stoichiometric at least flux Na
2NO
3Or NaOH, K
2CO
3Or KOH 750-950 ℃ down mix calcination and obtain contain meta-titanium perborate or Potassium titanate material, can also be other titaniferous material, adopt similar approach to change into and contain meta-titanium perborate or Potassium titanate material.Reaction formula is:
For for example waste iron filing, titaniferous materials such as titanium slag can also directly dissolve with nitre, sulfuric acid mixture, by method of the present invention, make rutile titanium white through complex salt-hydrolysis again.
It can be sulfuric acid, nitric acid or hydrochloric acid that the present invention is used for the inorganic acid that hydrolysis contains the metatitanate material, sulfuric acid boiling point height, and not volatile, therefore low price, preferably selects sulfuric acid for use.The add-on of acid decide according to decomposition reaction, and the suitably excessive metatitanic acid hydrochloric acid that helps decomposes fully, when being raw material with the rutile ore, excessive acid can in metatitanate in the excessive basic flux that may exist.The temperature of acid decomposition reaction is difference with the difference of the titaniferous material and the acid of selecting for use.With the rutile ore through flux mixing calcination processing is raw material, and its temperature of reaction should be controlled at a little less than sour boiling point, when being raw material with the ilmenite, adopts sulfuric acid, need be preheated near sour boiling point.
Acid decomposition reaction resultant is a mashed prod, and the salt that contains titanium oxide ion that thin up leaching reaction is generated makes it to separate with the throw out of mineral residue or generation after filtration, and the 2-5 water doubly that adds sour decomposition product usually dilutes.Leaching temperature needs strict control, is lower than 60 ℃ of leachings not exclusively, and is higher than 65 ℃, the titanium oxide ion facile hydrolysis.With the ilmenite is raw material, and leaching liquid should be reduced to lower temperature, is beneficial to separate out FeSO
47H
2O can adopt cryosel to be cooled to 0-5 ℃ usually.
Usually the V, the Cr ionic impurity that contain high price in the resulting as stated above leaching liquid that contains titanium oxide ion, adding iron filings can be reduced to low price V, the Cr ion that is very easily water-washed away with V, the Cr of wherein high valence state, can improve the whiteness of finished product titanium white.
The leaching liquid that contains titanium oxide ion of the present invention can be selected NH for use
4Cl, KCl, RbCl or NH
4Any recommends to select for use KCl or NH as complexing agent among the Cl
4Cl preferably selects ammonium chloride for use.NH
4Cl is not only inexpensive, and in last handling process, ammonium ion is easy to be removed.
For guaranteeing the whiteness of titanium white product of the present invention, need the Fe that may exist in the abundant flush away complex salt filter cake
2+, Fe
3+, Vo
2+, Cr
3+, washing methods is a prior art, can adopt for example Sodium hexametaphosphate 99, EDTA solution etc., the present invention adopts H
2SO
4, H
3PO
4And go plasma water to wash.
Complex salt after the purification need add gained complex salt 15-25 deionized water doubly usually and dilute, and the reaction that is hydrolyzed in the presence of alkali then can be selected NaOH, KOH or ammonia soln for use, to promote hydrolysis complete, preferably selects ammonia soln for use.
The present invention will be described further by following examples:
Embodiment 1
The about 200 purpose Shanxi Dai County rutile ores of 20 grams (are contained TiO approximately
285%) and 30 the gram calcined soda for industry mix, 900 ℃ of following calcinations 40 minutes, Na
2TiO
3Loose frit 36 grams.With the frit porphyrize, add 100ml 98% industrial H
2SO
4, fully stir into yellow mashed prod, after keeping one hour under 120 ℃, be chilled to room temperature, add water 400ml dilution, leached 2.5 hours down at 62 ℃, be chilled to room temperature, filter, get titanyl sulfate (TiOSO
4) solution.
At above-mentioned TiOSO
4Add a small amount of iron filings to solution in the solution and be light brown, filter, the elimination iron filings add the industrial KCL of 80 grams, feed hydrogenchloride 100ml in 10 minutes, filter, and successively use 30ml1: 8H
2SO
4, 1: 9H
3PO
4Wash three times, do not have Fe with the deionized water wash precipitation until effluent liquid again
3+, Fe
2+Till (with KCNS, K
3Fe(CN)
6Check obtains white complex salt K
2TiCl
6Filter cake.
Add 500 ml deionized water in above-mentioned filter cake, stir, the limit heating edge drips 1: 1 ammonia soln and boiled 1 hour to PH=3-4 is little, is chilled to room temperature, filters and obtains the metatitanic acid filter cake, is washed till (checking with sodium tetraphenylborate) till the no K with deionized water.
With the oven dry of above-mentioned metatitanic acid filter cake, porphyrize, 900 ℃ of calcinings 6 hours down, white titanium dioxide 17.6 restrained 320 mesh sieves and got the finished product titanium dioxide, product index sees Table 1,2 and accompanying drawing.
The TiOSO after iron filings are handled that is obtaining by embodiment 1 same steps as
4Add 57 gram NH in the solution
4Cl feeds 100 milliliters of hydrogen chloride gas in 10 minutes, placed 8 hours, filters, and below handles to such an extent that titanium dioxide 17.2 gram product indexs see Table 1 by the method steps of embodiment 1, and 2(schemes summary).
Embodiment 3
In the about 200 purpose ilmenite powders of 20 grams, add and be preheating to 120 ℃ 98% industrial H
2SO
4, reacting 25 minutes, thin up to proportion is 1.52, leaching is four hours under 62 ℃ of conditions, bathes with cryosel and is chilled to 0 ℃, filters, and gets TiOSO
4Solution.
At above-mentioned TiOSO
4Add a small amount of iron filings to solution in the solution and be light brown, filter, the elimination iron filings, add to add the industrial KCl of 37.6 grams, feed 50 milliliters in hydrogenchloride in 10 minutes, below press the method steps processing of embodiment 1 after, calcined 4 hours down at 1000 ℃, get the titanium dioxide of 7 gram whites, product index sees Table 1, and 2(schemes slightly)
Embodiment 4
Pressing the resulting TiOSO after iron filings are handled of embodiment 3 same steps as
4Add the industrial NH of 27 grams in the solution
4Cl fed 50 milliliters of hydrogen chloride gas in ten minutes, placed 8 hours, filter, below by the method steps of embodiment 3 handle the white titanium dioxide of 6.8 grams, product index sees Table 1,2 figure summary)
Accompanying drawing is the X-diffractogram of embodiment 1 product titanium white.
Accompanying drawing and table 1 data provide by Chinese Academy of Sciences's Shanxi coalification.By accompanying drawing and table 1 data as can be known, the titanium white of producing by the inventive method is rutile-type.
Table 2 is mass analysis index synopsis of different titanium whites.Japanese R820 type titanium white data are seen " chemical goods " (Shanghai industrial chemicals purchasing and supply station) in the table, and China merchant does not formulate the rutile type standard.
The opacifying power of product titanium white of the present invention, oil number are to be analyzed by " ministerial standard " pigment analysis method by dye processing plant, Taiyuan central laboratory; The whiteness of titanium white shows blancometer mensuration by the used BOJ-D type numeral of Shanxi applied chemistry; Fe
2O
3Content is that University Of Shanxi's analysis bank gets with Atomic Emission Spectral Analysis.
By table 2 as seen, all reach by the main performance index of the product titanium white of the inventive method gained or be better than Japanese R820 rutile type.
Titanium white production method provided by the present invention, technological process, equipment are simple, cost is low, and by to the reduction processing of the leaching liquid that contains titanium oxide ion, complexing, the washing, purifying of complex compound (complex salt), the washing, purifying of hydrolysis product, the metatitanic acid filter cake is fully separated with objectionable impurities, thus the inclined to one side titanium product of gained not only color and luster is good but also quality index all meets or exceeds country-level standard. The product scope of application is wide, and use value is high, and economic benefit improves greatly.
This law not only can be used for transforming the old technology of ilmenite-Production By Sulfuric Acid Process titanium white, make it to obtain the high-quality titanium white, increase economic efficiency, and opened up a kind of rutile ore take high titanium content and be the new way of raw material production high-quality titanium white, for the rutile ore resource of exploitation China's abundant, it is significant to satisfy the growing needs to the high-quality titanium white.
Claims (4)
1, a kind of production method of titanium white may further comprise the steps:
1) will contain the material porphyrize of metatitanate, add stoichiometric at least inorganic acid, ℃ carried out sour decomposition reaction 0.5-1.5 hour in room temperature to 130, be chilled to room temperature, thin up leached about 2-3 hour down at 60-65 ℃, was chilled to 0 ℃-room temperature, filtration obtains containing the leaching liquid of the inorganic strong acid salt of titanium oxide ion
2) pre-treatment of above-mentioned leaching liquid and hydrolysis,
3) mixture after the said hydrolyzed obtains the metatitanic acid filter cake after filtration,
4) metatitanic acid filter cake oven dry, porphyrize 850-1050 ℃ of calcining 2-6 hour down, sieve, and it is characterized in that described pre-treatment and the hydrolysis that contains the titanium oxide ion leaching liquid carry out according to the following steps:
A) add a small amount of iron filings in the titanium oxide ion leaching liquid in above-mentioned containing, stir, be light brown, filter until solution,
B) add stoichiometry NH at least in the titanium oxide ion leaching liquid in above-mentioned containing after reduction is handled
4Cl, KCl, R
6Any muriate among Cl or the CsCl feeds hydrogen chloride gas, generates complex salt M
2TiCl
6Precipitation is filtered, the metal ion in the flush away filter cake,
C) add the deionized water dilution in the complex salt after above-mentioned purification, under agitation heated and boiled constantly drips alkali aqueous solution, and is complete until hydrolysis.
2, method of production of titanium dioxide as claimed in claim 1 is characterized in that the described material that contains metatitanate is to contain metatitanic acid iron (FeTiO
3) titanium iron ore.
3, method of production of titanium dioxide as claimed in claim 1 is characterized in that the described material that contains metatitanate is rutile and flux Na
2CO
3Or NaOH, K
2CO
3Or KOH mixes calcination and containing sodium titanate or containing the Potassium titanate material of obtaining down at 750-900 ℃.
4, method of production of titanium dioxide as claimed in claim 1 is characterized in that described muriate is Repone K or ammonium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88100410 CN1009079B (en) | 1988-01-26 | 1988-01-26 | Method of production of titanium dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88100410 CN1009079B (en) | 1988-01-26 | 1988-01-26 | Method of production of titanium dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1034703A true CN1034703A (en) | 1989-08-16 |
| CN1009079B CN1009079B (en) | 1990-08-08 |
Family
ID=4831329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88100410 Expired CN1009079B (en) | 1988-01-26 | 1988-01-26 | Method of production of titanium dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1009079B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100532273C (en) * | 2006-10-30 | 2009-08-26 | 中国科学院过程工程研究所 | Method for clean production of titanium dioxide by using potassium hydroxide |
| CN102557128A (en) * | 2010-12-07 | 2012-07-11 | 河南佰利联化学股份有限公司 | Novel production process of titanium dioxide powder |
| CN102557127A (en) * | 2010-12-07 | 2012-07-11 | 河南佰利联化学股份有限公司 | Method for reducing leaching titanium solution by utilizing trivalent titanium |
| CN102815746A (en) * | 2012-09-17 | 2012-12-12 | 安徽迪诺环保新材料科技有限公司 | Production method of titanium dioxide for denitrifying catalyst |
| CN103232063A (en) * | 2013-04-18 | 2013-08-07 | 中国科学院过程工程研究所 | Method for preparing alpha-sodium metatitanate by sodium hydroxide molten salt process |
| CN103241770A (en) * | 2013-05-22 | 2013-08-14 | 河南佰利联化学股份有限公司 | Meta titanate treatment method |
| CN103553123A (en) * | 2013-10-18 | 2014-02-05 | 中国有色集团（广西）平桂飞碟股份有限公司 | Bleaching method of metatitanic acid in titanium dioxide production by sulfuric acid method |
| CN106186056A (en) * | 2016-06-30 | 2016-12-07 | 广西金茂钛业有限公司 | A kind of produce the method for the continuous acidolysis of ilmenite in titanium dioxide technique |
| CN115744971A (en) * | 2022-09-28 | 2023-03-07 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing metatitanic acid powder |
-
1988
- 1988-01-26 CN CN 88100410 patent/CN1009079B/en not_active Expired
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100532273C (en) * | 2006-10-30 | 2009-08-26 | 中国科学院过程工程研究所 | Method for clean production of titanium dioxide by using potassium hydroxide |
| CN102557128B (en) * | 2010-12-07 | 2014-05-07 | 河南佰利联化学股份有限公司 | Novel production process of titanium dioxide powder |
| CN102557128A (en) * | 2010-12-07 | 2012-07-11 | 河南佰利联化学股份有限公司 | Novel production process of titanium dioxide powder |
| CN102557127A (en) * | 2010-12-07 | 2012-07-11 | 河南佰利联化学股份有限公司 | Method for reducing leaching titanium solution by utilizing trivalent titanium |
| CN102557127B (en) * | 2010-12-07 | 2014-06-25 | 河南佰利联化学股份有限公司 | Method for reducing leaching titanium solution by utilizing trivalent titanium |
| CN102815746A (en) * | 2012-09-17 | 2012-12-12 | 安徽迪诺环保新材料科技有限公司 | Production method of titanium dioxide for denitrifying catalyst |
| CN102815746B (en) * | 2012-09-17 | 2014-03-12 | 安徽迪诺环保新材料科技有限公司 | Production method of titanium dioxide for denitrifying catalyst |
| CN103232063A (en) * | 2013-04-18 | 2013-08-07 | 中国科学院过程工程研究所 | Method for preparing alpha-sodium metatitanate by sodium hydroxide molten salt process |
| CN103232063B (en) * | 2013-04-18 | 2017-03-22 | 中国科学院过程工程研究所 | Method for preparing alpha-sodium metatitanate by sodium hydroxide molten salt process |
| CN103241770A (en) * | 2013-05-22 | 2013-08-14 | 河南佰利联化学股份有限公司 | Meta titanate treatment method |
| CN103553123A (en) * | 2013-10-18 | 2014-02-05 | 中国有色集团（广西）平桂飞碟股份有限公司 | Bleaching method of metatitanic acid in titanium dioxide production by sulfuric acid method |
| CN103553123B (en) * | 2013-10-18 | 2015-09-30 | 中国有色集团（广西）平桂飞碟股份有限公司 | The bleaching method of metatitanic acid in a kind of Titanium White Production By Sulfuric Acid Process |
| CN106186056A (en) * | 2016-06-30 | 2016-12-07 | 广西金茂钛业有限公司 | A kind of produce the method for the continuous acidolysis of ilmenite in titanium dioxide technique |
| CN115744971A (en) * | 2022-09-28 | 2023-03-07 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing metatitanic acid powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1009079B (en) | 1990-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Middlemas et al. | A new method for production of titanium dioxide pigment | |
| US4923682A (en) | Preparation of pure titanium dioxide with anatase crystal structure from titanium oxychloride solution | |
| CN110589884B (en) | Method for recycling waste and side-product titanium oxychloride | |
| US3071439A (en) | Method for the preparation of titanium hydrate | |
| DE2343344A1 (en) | METHOD FOR MANUFACTURING TITANIUM DIOXY DIGMENT | |
| EP0186370A2 (en) | Titanium dioxide pigment production from ilmenite | |
| CN1034703A (en) | The production method of titanium white | |
| CN111453768A (en) | Rutile metatitanic acid, titanium white and preparation method thereof | |
| CN109110807A (en) | A kind of method of coproduction synthetic rutile and sulfuric acid method titanium pigment | |
| CN104477987B (en) | A kind of clean preparation method of high-purity titanium dioxide | |
| US6090354A (en) | Process for the production of titanium oxide | |
| CN1020273C (en) | Method for producing barium carbonate | |
| CN104609472A (en) | Method for producing vanadium pentoxide from titanium tetrachloride refinement vanadium-removal slurry | |
| EP1194378B1 (en) | Processing aqueous titanium solutions to titanium dioxide pigment | |
| CN107475520A (en) | The separating technology of iron aluminium in a kind of red mud | |
| AU633652B2 (en) | A process for the production of tio2 pigments | |
| CN1030308C (en) | Process for preparation of titanate | |
| CN1095809C (en) | Treatment of solution containing iron salts | |
| US3660078A (en) | Process for the preparation of titanium dioxide concentrates | |
| CN1013358B (en) | Production of ammonium tungstate from fine tungsten mud | |
| DE2405271C3 (en) | Process for the extraction of titanium dioxide from ilmenite ore | |
| DE19841774A1 (en) | Preparation of high purity tantalum oxide of optical quality | |
| CN1038323C (en) | Method for preparing titanium dioxide of rutile type pigment | |
| CN107964591A (en) | A kind of method of simultaneous removing iron and vanadium in acid solution from trivalent chromium | |
| Wang et al. | Separation of Fe3+ during hydrolysis of TiO2+ by addition of EDTA |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |