CN100532273C - Method for clean production of titanium dioxide by using potassium hydroxide - Google Patents

Method for clean production of titanium dioxide by using potassium hydroxide Download PDF

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CN100532273C
CN100532273C CNB2006101141318A CN200610114131A CN100532273C CN 100532273 C CN100532273 C CN 100532273C CN B2006101141318 A CNB2006101141318 A CN B2006101141318A CN 200610114131 A CN200610114131 A CN 200610114131A CN 100532273 C CN100532273 C CN 100532273C
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solid
titanium
titanium dioxide
intermediate product
obtains
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CN101172649A (en
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王丽娜
齐涛
薛天艳
张懿
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Institute of Process Engineering of CAS
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Abstract

The invention belongs to the preparation of inorganic metallic compound and the processing filed of mineral resource, in particular to a preparation method for preparing titanium dioxide (titanium pigment) through high titanium slag and sodium hydroxide without pollution. The invention is characterized in that the high titanium slag is taken as the raw material; the high titanium slag and the potassium hydroxide having temperature range from 350 DEG C to 550 DEG C are reacted to prepare a medium product; the medium product is then washed through water (or carbonatation), acid solubled, reduced, hydrolyzed and burned to prepare anatase or rutile titanium dioxide. The alkali circulation, the acid circulation and the separation technology of the invention greatly reduce the production energy consumption, simplify the production process, reduce the device investment and increase the technology maneuverability, thereby providing an effective method for the comprehensive use of the titanium resource and the preparation of titanium dioxide (titanium pigment).

Description

Utilize the method for potassium hydroxide clean production of titanium dioxide
Technical field
The invention belongs to the preparation and the Mineral resources manufacture field of inorganic metal compound, be specifically related to a kind of by titanium slag and utilize the method for potassium hydroxide clean production of titanium dioxide (titanium dioxide).
Technical background
Titanium dioxide is commonly called as titanium dioxide, it is a kind of important source material in the chemical industry, nontoxic, be harmless to the health, it is most important white pigment, account for 80% of whole white pigment usage quantitys, it also is the main product of titanium system, 90% of titanium resource all is used for making titanium dioxide in the world, titanium dioxide is widely used in modern industry, agricultural, national defence, scientific and technical numerous areas, with people's lives and national economy close getting in touch is arranged.
The rich titanium material of titanium slag is to use the high quality raw material the most extensive, that turnout is maximum at present, has 41% to use titanium slag to produce in world's titanium dioxide total amount, and rises to 46% to this ratio in 2005 in 1996.In contrast ilmenite in world's titanium dioxide total amount shared ratio will from 1996 30% drop to 2005 25%.Compare with concentrate with ilmenite, titanium slag has the titanium content height, " three wastes " produce (processing) and measure less, help features such as product quality raising.At present external titanium already manufacturers generally adopts with " slag " generation " ore deposit " raw material route, and domestic also progressively popularization uses titanium slag as the main raw material of producing titanium dioxide.
General TiO 2Mass content can vitriolization at 70~85% titanium slag, uses for sulfuric acid process factory as acid-dissolved titanium slag usually.The production technique exploitation of sulfuric acid process early, it is less demanding to the raw materials quality of titanium, generally can use ilmenite or acid-dissolved titanium slag to be raw material, and equipment is simple, technical maturity, anatase titanium dioxide and rutile titanium dioxide can both be made, it is long that but the disadvantage of this technology is technical process, three wastes discharge amount is big, and the supplies consumption height is to such an extent as to the output of sulfate process titanium dioxide has downward trend year by year.
TiO 2The titanium slag solubility in acid of content more than 85% is relatively poor, is used for the production of chloride process titanium dioxide more.The exploitation of chlorination process production technique is later, and good product quality, technical process are lacked, " three wastes " quantity discharged is few, and its shortcoming is the specification of quality height to titanium material, mainly adopts TiO 2Content is greater than 90% natural rutile, artificial rutile etc., have only the company (Du Pont, U.S. connection chemistry, Ke Ermaiji etc.) of a few countries to grasp this technology at present, the technical difficulty of research and development is big, facility investment expense height, and can only produce rutile-type and can not produce anatase titanium dioxide, these shortcomings all have a strong impact on the development and the popularization of chlorination process technology.Therefore, demand developing a kind of clean preparation method that uses titanium slag as raw material production titanium dioxide (titanium white) urgently, with replacement technique difficulty big chlorination process and with serious pollution sulfate process titanium dioxide production technique.
Number of patent application is to use highly basic to obtain metatitanate at 750 ℃~950 ℃ following melting treatment rutile ores in the technical scheme of CN88100410.3, down obtain inorganic strong acid salt solution at comparatively high temps (generally near the acid solution boiling point), under the effect of hydrogen chloride gas, prepare (NH with muriates such as adding ammonium chloride or Repone K behind the iron powder reducing with the inorganic acid reaction 4) 2Ti 2Cl 6Or K 2Ti 2Cl 6Complex salt regulates the pH value with alkali lye at last and make its hydrolysis, and then roasting prepares rutile titanium dioxide.
And the present invention's employing titanium slag lower than rutile ore grade is raw material, (380~500 ℃) react with potassium hydroxide at a lower temperature, reaction product can prepare anatase titanium dioxide or rutile titanium dioxide after sour molten under washing (or carbonating), the lesser temps, hydrolysis, roasting, reaction medium all can obtain recycle, the technological process of production is simple, and must not add other auxiliary material.
Summary of the invention
The objective of the invention is to overcome the characteristics that energy consumption height, environmental pollution are serious and resource utilization is low that in existing titanium white production method, exist, provide a kind of cleaner production novel method, 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 prepared using potassium hydroxide reaction medium directly prepares anatase titanium dioxide or rutile titanium dioxide with the titanium slag.
It is of the present invention that to utilize the method for potassium hydroxide clean production of titanium dioxide be with TiO 2Content is raw material greater than 85% titanium slag, make the potassium hydroxide of itself and 380~500 ℃ preparation intermediate product that reacts, then intermediate product is washed preparation anatase titanium dioxide or rutile titanium dioxide after (or carbonating), acidolysis, reduction, hydrolysis, the calcining.This method may further comprise the steps:
(1) titanium slag is mixed with potassium hydroxide fully, reacted 0.2~3 hour down, obtain solid-state intermediate product at 380 ℃~500 ℃; Wherein the mass ratio of potassium hydroxide and titanium slag is 0.5:1~2:1;
(2) the solid-state intermediate product water that step (1) is obtained washs, filters, and washing process can be common washing, also can carry out the multi-stage countercurrent washing; The wash temperature scope is a normal temperature to 60 ℃, and the solid-liquid mass ratio of solid-state intermediate product and bath water is 1:3~1:100, obtains the solid intermediate product after potassium hydroxide alkali lye and the washing; Potassium hydroxide solution after the washing returns step (1) and is used to decompose titanium slag after evaporation concentration, the intermediate product after the washing continues step (3); Perhaps
The solid-state intermediate product that step (1) is obtained places autoclave, adds certain water gaging and mixes, and the solid-liquid mass ratio of solid-state intermediate product and water is 1:3~1:100; Feeding dividing potential drop then in solution is the CO of 0.2~6MPa 2Gas carries out carbonation reaction, is 20~80 ℃ in temperature and reacts 0.5~10 hour down, and filter, solid intermediate product continues step (3), and filtrate is used the CaO causticization, obtains potassium hydroxide solution, returns step (1) to be used to decompose titanium slag after evaporation concentration;
(3) solid intermediate product that obtains after step (2) washing or the carbonating is dissolved with mineral acid under normal temperature to 60 ℃, the pH of the hierarchy of control is 0.1~0.3, reduces with reductive agent then, obtains titanium liquid; Reductive agent is reduced to ferrous iron with the ferric iron in the product;
Described mineral acid is selected from sulfuric acid or hydrochloric acid etc.
Described reductive agent is selected from metal iron powder, iron filings, iron sheet, metallic zinc, metallic aluminium, S-WAT or Sulfothiorine etc.
(4) the titanium liquid that step (3) is obtained filters, filtrate is hydrolyzed, hydrolysis temperature is controlled at 30~120 ℃, hydrolysis time is 0.5~24 hour, hydrolysate is filtered, obtain the hydrated titanium dioxide solid of white, acid filtrate can return step (3) solid intermediate product that step (2) obtains is carried out acidolysis;
(5) the hydrated titanium dioxide solid that step (4) is obtained was calcined 0.5~10 hour under temperature is 500~1200 ℃, promptly obtained anatase titanium dioxide or rutile titanium dioxide.
The mass content of titanium dioxide is greater than 85% in the described titanium slag.
The present invention proposes in the potassium hydroxide medium clean preparation method of producing titanium dioxide by titanium slag, for the comprehensive utilization of titanium resource and the preparation of titanium dioxide (titanium dioxide) provide a valid approach.The present invention and existing sulfuric acid process, chlorination process and number of patent application are that the technology of CN88100410.3 is compared, and have obvious superiority:
(1) the present invention uses TiO 2Mass content is a raw material greater than 85% titanium slag, with number of patent application is that the technology of CN88100410.3 is compared, avoided using rutile ore of high grade, that ore reserve are few to be raw material, significantly reduced the temperature of reaction of titanium slag and potassium hydroxide, and can carry out the sour molten of intermediate product down at lesser temps (normal temperature~60 ℃), and need not add the muriate auxiliary material, also need not to use the anti-titanium liquid pH value of transferring of alkali lye to impel titanium hydrolysis, simplified technical process greatly, cost is lower.
(2) temperature of reaction of titanium slag of the present invention and potassium hydroxide is 380~500 ℃, technology than chlorination process descends more than 600 ℃, energy consumption reduces greatly, can not only prepare rutile titanium dioxide, also can prepare anatase titanium dioxide, and technical difficulty and facility investment expense significantly reduce, and have improved the operability of technology.
(3) alkali circulation of the present invention, acid circulation and isolation technique greatly reduce production energy consumption, do not add any auxiliary material, and bed drain purge significantly reduces, and no dust waste gas can not cause the pollution of environment.
(4) the titanium transformation efficiency can reach more than 97% in the raw material of the present invention, and the titanium dioxide rate of recovery is greater than 90%, and the purity of titanium dioxide is higher than 97%, and prepared titanium dioxide can be made pigment, coating etc.
Description of drawings
Fig. 1. the XRD figure spectrum of the embodiment of the invention 1 prepared titanium dioxide.
Fig. 2. the XRD figure spectrum of the embodiment of the invention 2 prepared titanium dioxide.
Embodiment
Embodiment 1.
Circulation turns back to the KOH solution of reactor and is ground to 250 purpose titanium slag (TiO 2Mass content is 87.0%) under agitation mix, 450 ℃ of reactions 0.5 hour, wherein, the mass ratio of titanium slag and solid KOH was 1.5:1, obtains solid intermediate product after the reaction, at this moment, the titanium slag rate of decomposition is 100%.Intermediate product is washed with water 2 times, 55 ℃ of wash temperatures, wash the solid-liquid mass ratio is 1:10 at every turn, it is 0.10 that product after the filtration adds sulphuric acid soln regulation system pH value, under 45 ℃ product is all dissolved, add iron powder then, make ferric iron all change ferrous iron into as reductive agent.At last the titanium liquid that obtains is filtered, filtrate was hydrolyzed 8 hours at 80 ℃, and hydrolysate is filtered, and the hydrated titanium dioxide solid that obtains white obtains anatase titanium dioxide 450 ℃ of calcinings 7 hours, and its XRD spectra as shown in Figure 1.The titanium dioxide rate of recovery is 94.2%, the purity 97.7% of titanium dioxide.
Embodiment 2.
Circulation turns back to the KOH solution of reactor and is ground to 300 purpose titanium slag (TiO 2Mass content is 87.0%) under agitation mix, 380 ℃ of reactions 2 hours, wherein, titanium slag and KOH solid mass ratio were 0.6:1, obtain solid intermediate product after the reaction, titanium slag rate of decomposition 98%.To wash with water under the intermediate product normal temperature, washing solid-liquid mass ratio is 1:100, add hydrochloric acid soln in the product that after filtration, obtains, regulation system pH value is 0.15, normal temperature fully dissolves back elimination unreacted titanium slag down, then S-WAT is added in the solution, the reduction ferric iron is a ferrous iron, then the titanium liquid that obtains is filtered, filtrate was hydrolyzed 4 hours at 110 ℃, and hydrolysate is filtered, and the hydrated titanium dioxide solid that obtains white was 950 ℃ of calcinings 8 hours, obtain rutile titanium dioxide, its XRD spectra as shown in Figure 2.The titanium dioxide rate of recovery is 90.9%, the purity 98.3% of titanium dioxide.
Embodiment 3.
Circulation turns back to the KOH solution of reactor and is ground to 200 purpose titanium slag (TiO 2Mass content is 89.5%) under agitation mix, 500 ℃ of reactions 0.5 hour, wherein, titanium slag and KOH solid mass ratio were 1:1, obtain solid intermediate product after the reaction, titanium slag rate of decomposition 100%.Add water and solid intermediate product mixes, intermediate product is carried out carbonation reaction at 50 ℃, in solution, feed CO 2Dividing potential drop is 2MPa, the solid-liquid mass ratio of reaction is 1:100, react and after 4 hours product is filtered, adding hydrochloric acid soln dissolves, regulation system pH value is 0.30, under 60 ℃ product is all dissolved, add iron sheet then as reductive agent, make ferric iron all change ferrous iron into, then this solution was hydrolyzed 15 hours at 40 ℃, hydrolysate is filtered, the hydrated titanium dioxide solid that obtains white was 650 ℃ of calcinings 10 hours, obtain anatase titanium dioxide, hydrolysate obtains rutile titanium dioxide 1000 ℃ of calcinings about 1 hour.The titanium dioxide rate of recovery is 91.5%, the purity 97.3% of titanium dioxide.
Embodiment 4.
Circulation turns back to the KOH solution of reactor and is ground to 300 purpose titanium slag (TiO 2Mass content is 91.9%) under agitation mix, 400 ℃ of reactions 0.5 hour, wherein, titanium slag and KOH solid mass ratio were 1.4:1, obtain solid intermediate product after the reaction, titanium slag rate of decomposition 100%.Intermediate product is carried out the washing of three stage countercurrents at normal temperatures, the washing solid-to-liquid ratio is 1:5, filter, add sulphuric acid soln in the product that after filtration, obtains, regulation system pH value is 0.20, under 35 ℃ product is all dissolved, add metallic zinc then as reductive agent, make ferric iron all change ferrous iron into, then the titanium liquid that obtains is filtered, filtrate was hydrolyzed 0.5 hour at 110 ℃, and hydrolysate is filtered, the hydrated titanium dioxide solid that obtains white obtains rutile titanium dioxide 1000 ℃ of calcinings 2 hours.The titanium dioxide rate of recovery is 91.5%, the purity 97.3% of titanium dioxide.
Embodiment 5.
Circulation turns back to the KOH solution of reactor and is ground to 200 purpose titanium slag (TiO 2Mass content is 85.9%) under agitation mix, 500 ℃ of reactions 20 minutes, wherein, titanium slag and KOH solid mass ratio were 1.8:1, obtain solid intermediate product after the reaction, titanium slag rate of decomposition 100%.With intermediate product at 50 ℃ of washing filterings, washing solid-liquid mass ratio is 1:20, and the product after the filtration adds hydrochloric acid soln, and regulation system pH value is 0.13, under the normal temperature product is all dissolved, add aluminium flake then as reductive agent, make ferric iron all change ferrous iron into, then the titanium liquid that obtains is filtered, filtrate is hydrolyzed half an hour at 120 ℃, hydrolysate is filtered, obtain the hydrated titanium dioxide solid, obtain rutile titanium dioxide 1150 ℃ of calcinings about 0.5 hour.The titanium dioxide rate of recovery is 92.5%, the purity 98.6% of titanium dioxide.

Claims (10)

1. a method of utilizing the potassium hydroxide clean production of titanium dioxide is characterized in that, this method may further comprise the steps:
(1) titanium slag and potassium hydroxide are mixed,, obtain solid-state intermediate product 380 ℃~500 ℃ reactions down; Wherein the mass ratio of potassium hydroxide and titanium slag is 0.5:1~2:1;
(2) the solid-state intermediate product water that step (1) is obtained washs, filters, the solid intermediate product after obtaining potassium hydroxide solution and washing; Perhaps
The solid-state intermediate product that step (1) is obtained places autoclave, adds entry and mixes; Feeding dividing potential drop then in solution is the CO of 0.2~6MPa 2Gas carries out carbonation reaction, and temperature of reaction is 20~80 ℃, filters the solid intermediate product that obtains after carbonating;
(3) solid intermediate product that obtains after step (2) washing or the carbonating is dissolved with mineral acid, the pH of the hierarchy of control is 0.1~0.3, reduces with reductive agent then, obtains titanium liquid;
(4) the titanium liquid that step (3) is obtained filters, and filtrate is hydrolyzed, and hydrolysis temperature is controlled at 30~120 ℃, and hydrolysate is filtered, and obtains the hydrated titanium dioxide solid of white;
(5) the hydrated titanium dioxide solid that step (4) is obtained is 500~1200 ℃ of calcinings down in temperature, promptly obtains anatase titanium dioxide or rutile titanium dioxide.
2. method according to claim 1 is characterized in that: the mass content of titanium dioxide is greater than 85% in the described titanium slag.
3. method according to claim 1 is characterized in that: the described reaction times of step (1) is 0.2~3 hour.
4. method according to claim 1 is characterized in that: the solid-liquid mass ratio of described solid-state intermediate product of step (2) and bath water is 1:3~1:100.
5. method according to claim 1 is characterized in that: in the mixture of solid-state intermediate product of described step (2) and water, the solid-liquid mass ratio of solid-state intermediate product and water is 1:3~1:100.
6. method according to claim 1 is characterized in that: described step (2) the carbonation reaction time is 0.5~10 hour.
7. method according to claim 1 is characterized in that: the potassium hydroxide solution that obtains after step (2) is washed solid-state intermediate product, return step (1) and be used to decompose titanium slag after evaporation concentration.
8. method according to claim 1 is characterized in that: resulting filtrate was used the CaO causticization after step (2) was carried out carbonating to solid-state intermediate product, obtained potassium hydroxide solution, returns step (1) and be used to decompose titanium slag after evaporation concentration.
9. method according to claim 1 is characterized in that: the described time that filtrate is hydrolyzed of step (4) is 0.5~24 hour.
10. method according to claim 1 is characterized in that: the acid filtrate that obtains after step (4) filtrate is hydrolyzed returns step (3) solid intermediate product that step (2) obtains is carried out acidolysis.
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Publication number Priority date Publication date Assignee Title
CN101812588B (en) * 2010-04-19 2011-12-14 中国科学院过程工程研究所 Method for decomposing vanadium slag with solution of potassium hydroxide under normal pressure
CN102757091B (en) * 2011-04-28 2014-07-30 中国科学院过程工程研究所 Method for preparing high-concentration titanic liquid
CN102559958A (en) * 2012-02-20 2012-07-11 武汉科技大学 Method for improving grindability of metallurgical 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
CN107860639B (en) * 2017-09-30 2020-04-28 中国科学院生态环境研究中心 Hydrofluoric acid-free titanium dioxide digestion and separation method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4759916A (en) * 1983-04-11 1988-07-26 The Dow Chemical Company Process for preparing a pigmentary titanium dioxide
CN1034703A (en) * 1988-01-26 1989-08-16 山西大学 The production method of titanium white
CN1151969A (en) * 1996-09-06 1997-06-18 东南大学 Titanium dioxide whisker and its hydrothermal synthesis

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4759916A (en) * 1983-04-11 1988-07-26 The Dow Chemical Company Process for preparing a pigmentary titanium dioxide
CN1034703A (en) * 1988-01-26 1989-08-16 山西大学 The production method of titanium white
CN1151969A (en) * 1996-09-06 1997-06-18 东南大学 Titanium dioxide whisker and its hydrothermal synthesis

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