CN100460331C - Process for clean producing titanium dioxide and potassium hexatitanate wiskers by titanium iron ore or high-titanium dreg sub-molten salt - Google Patents
Process for clean producing titanium dioxide and potassium hexatitanate wiskers by titanium iron ore or high-titanium dreg sub-molten salt Download PDFInfo
- Publication number
- CN100460331C CN100460331C CNB200610007297XA CN200610007297A CN100460331C CN 100460331 C CN100460331 C CN 100460331C CN B200610007297X A CNB200610007297X A CN B200610007297XA CN 200610007297 A CN200610007297 A CN 200610007297A CN 100460331 C CN100460331 C CN 100460331C
- Authority
- CN
- China
- Prior art keywords
- titanium
- titanate
- ilmenite
- titanium dioxide
- described step
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The invention relates to a method to produce titanium dioxide and K2Ti6O13 whisker from using ilmenite or high titanium slag as raw material. It includes the following steps: ilmenite or high titanium slag reacting in KOH liquid phase medium, and the weight ratio is 4:1-8:1; gaining the mixture reaction product of alkali liquid, barium titanate and iron enriched slag; taking hydrolysis or acidolysis, burning and purifying to the product to gain purified titanium dioxide and K2Ti6O13 whisker. The reacting temperature is 240-350 degree centigrade and the yield is over 99%. The recycled titanium dioxide could be used as dye, coating, etc; and the K2Ti6O13 whisker could be used as insulating material, refractory material, and friction material.
Description
Technical field
The invention belongs to the field of production of titanate, particularly is the method for raw material clean production of titanium dioxide (titanium dioxide) and crystal whisker of hexa potassium titanate with ilmenite or titanium slag.
Background technology
Titanium powder industry is chemical industry and the metallurgical important foundation primary industry that intersects.At present, nearly 5,000,000 tons of world's titanium dioxide market sales volume, titanium dioxide has become one of three kinds of commodity of sales volume maximum in world's inorganic chemical product as white pigment and filler, is only second to synthetic ammonia and phosphoric acid, is listed as the 3rd.Titanium dioxide is a kind of white pigment, formal name used at school titanium dioxide is as a kind of important inorganic chemical product, because its stable chemical performance, have high refractive index and ideal size-grade distribution, therefore be widely used in the many faster fields of development in recent years speed with its good opacifying power, tinting strength.The consumption nearly 60% of world's titanium dioxide at present is used for coating, and 16% is used for plastics, and 14% is used for papermaking, and 3% is used for printing-ink, and 7% is used for other (comprising rubber, makeup, medicine, enamel and chemical fibre etc.).
Six potassium titanate (K
2Ti
6O
13) whisker has chemical stability, thermostability, premium propertiess such as adiabatic thermotolerance can extensively be used as insulating material, thermal insulation material, friction materials and ion-exchange material etc.
The production method of existing titanium dioxide has sulfuric acid process and chlorination process, though Production By Sulfuric Acid Process titanium dioxide technical maturity, reaction temperature and, a large amount of spent acid solutions that exist sulfuric acid process to produce, shortcoming such as the by product utility value of generation is low; Though and the titanium dioxide titanium recovery rate that chlorination process is produced is higher, its equipment requirements height, temperature of reaction requires harshness to ilmenite raw material about 1000 ℃, and environmental pollution is also relatively more serious.In addition, existing preparation six potassium titanate (K
2Ti
6O
13) method of whisker mainly contains hydrothermal method, sintering process, scorification, flux method, pressed disc method and ion exchange method etc., and be that raw material is prepared with titanium dioxide, therefore its cost is very high, be badly in need of research and development titanium white new cleanproduction process, eliminate its environmental pollution from the source, realize the Sustainable development of titanium white industry.
Summary of the invention
The objective of the invention is to overcome the low shortcoming of resource utilization of the high energy consumption, serious environment pollution and the titanate that in existing titanate production method, exist, provide a kind of cleaner production new technology, to replace existing sulfuric acid process and chlorination process with industrial operation, eco-friendly titanium dioxide; And to provide a kind of be the viable process method that raw material directly prepares potassium titanate crystal whisker with ilmenite or titanium slag.
Method principle of the present invention is based on ilmenite or titanium slag is that raw material with air gas-liquid-solid heterogeneous reaction takes place in 240～350 ℃ inferior fused salt KOH liquid phase medium.Main reaction is:
3FeO·TiO
2(s)+4KOH(l)+3/4O
2(g)＝2K
2O·3TiO
2(s)+3/2Fe
2O
3(s)+2H
2O(g)
Compare with chlorination process with traditional sulfuric acid process, the by product that this method produces is few, increasing substantially titanium recovery rate than under the low reaction temperatures, reaction medium KOH is recyclable to be recycled, rich scum further resource utilization production iron is a product, the environmental pollution degree that has significantly reduced has improved resource utilization, for new way has been opened up in the titanium dioxide cleaner production.
Method by ilmenite or titanium slag sub-molten salt method clean production of titanium dioxide and crystal whisker of hexa potassium titanate of the present invention is: ilmenite or titanium slag decompose in the inferior fused salt liquid phase flow media of KOH, and the potassium titanate coarse-grain separates from leach slurry after hydrolysis, purifying, calcining can get qualified titanium dioxide and crystal whisker of hexa potassium titanate product.This method may further comprise the steps:
(1). ilmenite or titanium slag are reacted in the liquid phase medium of KOH, and temperature of reaction is 240～350 ℃, and the reaction times is 1～6 hour, obtains containing the reaction product mixture of alkali lye, titanate and rich scum; Wherein the weight ratio of KOH and ilmenite or titanium slag is 4:1～8:1;
(2). the reaction product mixture that step (1) is obtained is the mix products that 80～180 ℃ of following washing and filterings obtain KOH alkali lye, titanate and rich scum in temperature, and KOH alkali lye returns step (1) and is used to decompose ilmenite or titanium slag;
(3). the mix products that step (2) is obtained carries out gravity or High-gradient Magnetic separation, obtains titanate and rich scum;
(4). titanate product that step (3) is obtained and water are that 1:10～1:200 packs in the reactor by mass ratio, under stirring condition, raw material is mixed, pH 〉=9.0 with alkali conditioned reaction solution, then reactor is incubated 2～48 hours under 20～100 ℃ condition, reaction product washes solid with water after solid-liquid separation, drying, calcining promptly obtained six potassium titanate (K in 0.5～10 hour under 500～1000 ℃
2Ti
6O
13) whisker; Or
PH≤6.0 with sour conditioned reaction solution are incubated 2～48 hours with reactor then under 20～100 ℃ condition, reaction product washes solid with water after solid-liquid separation, drying, and calcining promptly obtained titanium dioxide product in 0.5～10 hour under 500～1000 ℃.
The acid of described step (4) is mineral acid or sour gas.Described mineral acid is hydrochloric acid, nitric acid, sulfuric acid, carbonic acid etc.; Described sour gas is a carbon dioxide etc.
The alkali of described step (4) is potassium hydroxide or salt of wormwood etc.
The present invention proposes the clean preparation method of in inferior fused salt KOH reaction medium, producing titanium dioxide and crystal whisker of hexa potassium titanate by ilmenite or titanium slag.Produce titanium dioxide with existing sulfuric acid process and chlorination process and compare, have obvious superiority:
(1) temperature of reaction of the present invention is 240～350 ℃, descends about 800 ℃ than chlorination process technology, and energy consumption can reduce by 30%, and the titanium transformation efficiency is near 100%, and titanium recovery rate is more than 99%; Titanium recovery rate improves 10～20% than existing sulfuric acid process; Prepared titanium dioxide can be done pigment, coating etc.; Six prepared potassium titanate (K
2Ti
6O
13) whisker can be used as insulating material, refractory materials, friction materials etc.;
(2) the present invention does not add any auxiliary material, and bed drain purge significantly reduces, and no dust waste gas can not cause the pollution of environment, and the rich scum composition of generation is simple, is easy to comprehensive utilization;
(3) alkali circulation of the present invention greatly reduces production energy consumption with isolation technique, has simplified production process, has reduced the equipment input, has improved the technology operability, has reduced production cost;
(4) reaction conditions gentleness of the present invention, industrial implementation is workable;
Description of drawings
Fig. 1. process flow diagram of the present invention.
Fig. 2. the XRD figure spectrum of the embodiment of the invention 1 prepared titanium dioxide.Preparation condition is: the mass ratio of titanate and deionized water is 1:10, and the pH value of reaction soln is 6.0, calcines 10 hours down at 500 ℃.
Fig. 3. the six potassium titanate (K that the embodiment of the invention 4 is prepared
2Ti
6O
13) XRD figure spectrum.Preparation condition is: the mass ratio of titanate and deionized water is 1:10, and the pH value of reaction soln is 9.0, calcines 10 hours down at 600 ℃.
Specific embodiments
Embodiment 1:
See also attached Fig. 1 and 2.Be warming up to 240 ℃ after the KOH solution that circulation turns back to reactor is deviate from portion water, add 95% particle diameter less than 200 purpose ilmenite or titanium slags, reaction is 6 hours under mixing condition fully, and wherein, the weight ratio of KOH and ilmenite or titanium slag is 4:1; Obtain containing the reaction product mixture of alkali lye, titanate and rich scum; The titanium transformation efficiency is more than 99%.The washing and filtering mix products, washing back temperature is 80 ℃; Titanate carries out High-gradient Magnetic with rich scum mix products to be separated, the titanate that obtains adds the pH=6 of entry and carbonating gas accent solution, be incubated 48 hours down at 20 ℃, separate, wash solid, drying with water, obtain titanium dioxide product in calcining under 500 ℃ after 10 hours, the XRD figure spectrum of the titanium dioxide that obtains as shown in Figure 2.
Embodiment 2:
See also accompanying drawing 1.Be warming up to 280 ℃ after the KOH solution that circulation turns back to reactor is deviate from portion water, add 95% particle diameter less than 200 purpose ilmenite or titanium slags, reaction is 4 hours under mixing condition fully, and wherein, the weight ratio of KOH and ilmenite or titanium slag is 6:1; Obtain containing the reaction product mixture of alkali lye, titanate and rich scum; The titanium transformation efficiency is more than 99%.The washing and filtering mix products, washing back temperature is 140 ℃; Titanate carries out High-gradient Magnetic with rich scum mix products to be separated, the titanate that obtains adds water, transfers the pH=4 of solution with HCl, 60 ℃ of insulations 30 hours down, separates, wash solid, drying with water, obtain titanium dioxide product after 0.5～10 hour in calcining under 500～1000 ℃.
Embodiment 3:
See also accompanying drawing 1.Be warming up to 350 ℃ after the KOH solution that circulation turns back to reactor is deviate from portion water, add 95% particle diameter less than 200 purpose ilmenite or titanium slags, reaction is 2 hours under mixing condition fully, and wherein, the weight ratio of KOH and ilmenite or titanium slag is 8:1; Obtain containing the reaction product mixture of alkali lye, titanate and rich scum; The titanium transformation efficiency is more than 99%.The washing and filtering mix products, washing back temperature is 180 ℃; Titanate carries out High-gradient Magnetic with rich scum mix products to be separated, the titanate that obtains adds entry, transfers the pH=3 of solution with HCl, 100 ℃ of insulations 2 hours down, separates, wash solid, drying with water, obtain titanium dioxide product after 0.5～10 hour in calcining under 500～1000 ℃.
Embodiment 4:
See also accompanying drawing 1.Be warming up to 280 ℃ after the KOH solution that circulation turns back to reactor is deviate from portion water, add 95% particle diameter less than 200 purpose ilmenite or titanium slags, reaction is 4 hours under mixing condition fully, and wherein, the weight ratio of KOH and ilmenite or titanium slag is 8:1; Obtain containing the reaction product mixture of alkali lye, titanate and rich scum; The titanium transformation efficiency is more than 99%.The washing and filtering mix products, washing back temperature is 140 ℃; Titanate carries out High-gradient Magnetic with rich scum mix products to be separated, the titanate that obtains adds entry, transfers the pH=9 of solution with potassium hydroxide, be incubated 6 hours down at 20 ℃, separate, wash solid, drying with water, obtain crystal whisker of hexa potassium titanate in calcining under 600 ℃ after 10 hours, the XRD figure spectrum of six potassium titanates that obtain as shown in Figure 3.
Claims (9)
1. method by ilmenite or titanium slag sub-molten salt method clean production of titanium dioxide and crystal whisker of hexa potassium titanate is characterized in that this method may further comprise the steps:
(1). ilmenite or titanium slag are reacted in the liquid phase medium of KOH, and the weight ratio of KOH and ilmenite or titanium slag is 4:1～8:1, and temperature of reaction is 240～350 ℃, obtains containing the reaction product mixture of alkali lye, titanate and rich scum;
(2). with the reaction product mixture washing and filtering that step (1) obtains, obtaining filtrate is KOH alkali lye, and filter residue is the mix products of titanate and rich scum;
(3). the titanate that step (2) is obtained and the mix products of rich scum separate, and obtain titanate and rich scum respectively;
(4). titanate product that step (3) is obtained and water are packed in the reactor, under stirring condition, raw material is mixed, pH 〉=9.0 with alkali conditioned reaction solution, then reactor is incubated under 20～100 ℃ condition, reaction product washes solid with water after solid-liquid separation, drying, calcining promptly obtains crystal whisker of hexa potassium titanate; Or
PH≤6.0 with sour conditioned reaction solution are incubated reactor then under 20～100 ℃ condition, reaction product washes solid with water after solid-liquid separation, drying, and calcining promptly obtains titanium dioxide product.
2. method according to claim 1 is characterized in that: the reaction times of described step (1) is 1～6 hour.
3. method according to claim 1 is characterized in that: the KOH alkali lye that described step (2) obtains returns step (1) and is used to decompose ilmenite or titanium slag.
4. method according to claim 1 is characterized in that: the washing and filtering temperature of described step (2) is 80～180 ℃.
5. method according to claim 1 is characterized in that: the separation of described step (3) is that gravity separation or High-gradient Magnetic are separated.
6. method according to claim 1 is characterized in that: the mass ratio of described step (4) titanate product and water is 1:10～1:200.
7. method according to claim 1 is characterized in that: described step (4) soaking time is 2～48 hours.
8. method according to claim 1 is characterized in that: described step (4) calcining temperature is 500～1000 ℃, and the time is 0.5～10 hour.
9. method according to claim 1 is characterized in that: the acid of described step (4) is mineral acid or sour gas; Described alkali is potassium hydroxide or salt of wormwood.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610007297XA CN100460331C (en) | 2006-02-17 | 2006-02-17 | Process for clean producing titanium dioxide and potassium hexatitanate wiskers by titanium iron ore or high-titanium dreg sub-molten salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610007297XA CN100460331C (en) | 2006-02-17 | 2006-02-17 | Process for clean producing titanium dioxide and potassium hexatitanate wiskers by titanium iron ore or high-titanium dreg sub-molten salt |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101024512A CN101024512A (en) | 2007-08-29 |
| CN100460331C true CN100460331C (en) | 2009-02-11 |
Family
ID=38743223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200610007297XA Expired - Fee Related CN100460331C (en) | 2006-02-17 | 2006-02-17 | Process for clean producing titanium dioxide and potassium hexatitanate wiskers by titanium iron ore or high-titanium dreg sub-molten salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100460331C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923767A (en) * | 2011-08-12 | 2013-02-13 | 中国科学院过程工程研究所 | Method for producing titanium dioxide from alkali molten salt without intermediate caking |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2008360391A1 (en) * | 2008-08-06 | 2010-02-11 | E. I. Du Pont De Nemours And Company | Processes for producing titanium dioxide |
| CN102925981B (en) * | 2012-11-28 | 2014-12-10 | 北京科技大学 | Method for preparing potassium hexatitanate nano whisker from titanium-containing electric furnace molten slag |
| CN103950976A (en) * | 2014-04-04 | 2014-07-30 | 中国科学院过程工程研究所 | Method for preparing titanium dioxide by utilizing mixed alkali of sodium hydroxide and sodium nitrate |
| CN107304067A (en) * | 2016-04-18 | 2017-10-31 | 云南民族大学 | A kind of phosphoric acid activation heats the method that Combined Treatment high titanium slag prepares synthetic rutile with microwave |
| CN111705226B (en) * | 2020-06-22 | 2022-05-31 | 四川顺应动力电池材料有限公司 | Method for removing impurities from high-titanium slag |
| CN113353977B (en) * | 2021-07-08 | 2024-02-02 | 福建富仕新材料有限责任公司 | Method for preparing titanium dioxide by using ilmenite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202462A (en) * | 1997-06-12 | 1998-12-23 | 中国科学院固体物理研究所 | Fibrous nanometer potasium titanate and its preparing method |
| WO2004113230A1 (en) * | 2003-06-16 | 2004-12-29 | The University Of Leeds | Extraction process for reactive metal oxides |
-
2006
- 2006-02-17 CN CNB200610007297XA patent/CN100460331C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202462A (en) * | 1997-06-12 | 1998-12-23 | 中国科学院固体物理研究所 | Fibrous nanometer potasium titanate and its preparing method |
| WO2004113230A1 (en) * | 2003-06-16 | 2004-12-29 | The University Of Leeds | Extraction process for reactive metal oxides |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102923767A (en) * | 2011-08-12 | 2013-02-13 | 中国科学院过程工程研究所 | Method for producing titanium dioxide from alkali molten salt without intermediate caking |
| CN102923767B (en) * | 2011-08-12 | 2014-04-02 | 中国科学院过程工程研究所 | Method for producing titanium dioxide from alkali molten salt without intermediate caking |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101024512A (en) | 2007-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100460331C (en) | Process for clean producing titanium dioxide and potassium hexatitanate wiskers by titanium iron ore or high-titanium dreg sub-molten salt | |
| CN102010004B (en) | Method for preparing vanadium disulphide nano powder | |
| CN101148779B (en) | Preparation method for potassium titanate crystal whisker | |
| CN102787194B (en) | Method for preparing titanium-rich material by directly reducing molten slag from vanadium-titanium-ferrum concentrate | |
| CN102424394A (en) | Process for preparing water glass from silicon micropowder by using wet method | |
| CN109354029B (en) | Method for preparing mesoporous silicon oxide from fly ash | |
| CN100567167C (en) | A kind of method of producing manganous sulfate by manganese oxide ore | |
| CN101817551B (en) | Method for preparing lithium titanate precursor from titanic iron ore | |
| CN101306819B (en) | Process for abstracting white carbon black from fly ash or slag | |
| CN108557883A (en) | A kind of preparation method of nanmeter antimong trioxide | |
| CN109336123A (en) | A method of using coal ash for manufacturing for soluble glass of high modulus | |
| CN104649279A (en) | Process for preparing white carbon black from pulverized fuel ash as raw material | |
| CN105060326B (en) | The technique that AZS solid wastes prepare sodium metaaluminate | |
| CN103420406B (en) | Method for activating coal gangue and/or coal ash by using red mud | |
| CN104477987B (en) | A kind of clean preparation method of high-purity titanium dioxide | |
| CN101531397A (en) | Clean production method for preparing rutile titanium dioxide from ilmenite | |
| CN202968150U (en) | Device combination for preparing superfine molybdenum trioxide | |
| CN103274460A (en) | Method for preparing rutile phase titanium dioxide sub-microsphere through selective dispergation | |
| CN115057458A (en) | Method for preparing nano alumina from coal gangue | |
| CN111039322A (en) | Preparation method of high-activity zirconia | |
| CN106145187A (en) | A kind of use vanadium titano-magnetite or technique that titanium chats is raw material production titanium dioxide | |
| CN102139882B (en) | Method for co-production preparation of sodium silicate and sodium metasilicate pentahydrate by using oil shale waste residues | |
| CN101525156A (en) | Preparation method for nanometer zinc ferrite | |
| CN110723747B (en) | Method for recovering and preparing high-quality zinc oxide from zinc waste | |
| CN102115207A (en) | Method for producing ferrous carbonate and ammonium sulfate by using waste acid obtained during production of titanium pigment by adopting sulfuric acid process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090211 Termination date: 20210217 |