CN101172648A - Method for clean production of titanium dioxide by using sodium hydroxide - Google Patents
Method for clean production of titanium dioxide by using sodium hydroxide Download PDFInfo
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- CN101172648A CN101172648A CNA2006101141303A CN200610114130A CN101172648A CN 101172648 A CN101172648 A CN 101172648A CN A2006101141303 A CNA2006101141303 A CN A2006101141303A CN 200610114130 A CN200610114130 A CN 200610114130A CN 101172648 A CN101172648 A CN 101172648A
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- titanium dioxide
- intermediate product
- sodium hydroxide
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 131
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 title claims abstract description 103
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000010936 titanium Substances 0.000 claims abstract description 69
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 67
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000002893 slag Substances 0.000 claims abstract description 47
- 239000002253 acid Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000002829 reductive effect Effects 0.000 claims abstract description 11
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 5
- 239000011707 mineral Substances 0.000 claims abstract description 5
- 239000013067 intermediate product Substances 0.000 claims description 36
- 239000007787 solid Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000000413 hydrolysate Substances 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 10
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 2
- 239000001038 titanium pigment Substances 0.000 abstract 2
- 229910000765 intermetallic Inorganic materials 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 235000010215 titanium dioxide Nutrition 0.000 description 45
- 230000008569 process Effects 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 229910010413 TiO 2 Inorganic materials 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 3
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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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 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 sodium hydroxide having temperature range from 350 DEG C to 550DEG 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 titanium resource and the preparation of titanium dioxide(titanium pigment).
Description
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 sodium hydroxide clean production of titanium dioxide (titanium dioxide).
Background technology
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 be 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 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.This invention complex steps, and add various auxiliary materials, production cost is higher.
And the present invention's employing titanium slag lower than rutile ore grade is raw material, (350～550 ℃) react with sodium 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, the technological process of production is simple, the equal reusable edible of reaction medium, 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 method, to replace existing sulfuric acid process and chlorination process with industrial operation, eco-friendly clean production of titanium dioxide; And to provide a kind of be the viable process method that prepared using sodium 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 sodium hydroxide clean production of titanium dioxide be with TiO
2Content is raw material greater than 85% titanium slag, make the sodium hydroxide of itself and 350～550 ℃ preparation intermediate product that reacts, then intermediate product is washed that (or carbonating), acid are molten, preparation anatase titanium dioxide or rutile titanium dioxide after the reduction, hydrolysis, calcining.This method may further comprise the steps:
(1) titanium slag and sodium hydroxide are mixed, reacted 0.2～5 hour down, obtain solid-state intermediate product at 350 ℃～550 ℃; Wherein the mass ratio of sodium hydroxide and titanium slag is 0.8: 1～3: 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 multi-stage countercurrent washing, and the wash temperature scope is a normal temperature to 60 ℃; The solid-liquid mass ratio of solid-state intermediate product and bath water is 1: 3～1: 100, the solid intermediate product after obtaining sodium hydroxide solution and washing; Sodium hydroxide solution after the washing returns step (1) and is used to decompose titanium slag after evaporation concentration, the solid 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 sodium 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 0.1～0.4, 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 solid intermediate product that step (3) obtains step (2), and to carry out acid molten;
(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 sodium hydroxide medium the 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 sodium hydroxide, and can carry out the sour molten of intermediate product down at lesser temps (normal temperature to 60 ℃), and need not add the muriate auxiliary material, need not use the anti-titanium liquid pH value of transferring of alkali lye to impel titanium hydrolysis yet, simplified technical process greatly, cost is lower.Rutile titanium dioxide can not only be prepared, also anatase titanium dioxide can be prepared.
(2) temperature of reaction of titanium slag of the present invention and sodium hydroxide is 350～550 ℃, descends more than 500 ℃ than the technology of chlorination process, and energy consumption reduces greatly, and technical difficulty and facility investment expense significantly reduce, and has 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 96% 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 titanium dioxide that the embodiment of the invention 1 is prepared.
Fig. 2. the XRD figure spectrum of the titanium dioxide that the embodiment of the invention 2 is prepared.
Embodiment
Embodiment 1.
Circulation turns back to the NaOH solution of reactor and is ground to 250 purpose titanium slag (TiO
2Mass content is 87.0%) under agitation mix, 500 ℃ of reactions 0.5 hour, wherein, the mass ratio of NaOH and titanium slag was 1: 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: 20 at every turn, it is 0.12 that the product after the filtration adds sulphuric acid soln adjusting pH value, normal temperature all adds iron powder as reductive agent after the dissolving down, makes ferric iron all change ferrous iron into.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 650 ℃ of calcinings 7 hours, and its XRD spectra as shown in Figure 1.The titanium dioxide rate of recovery is 92.9%, the purity 98.1% of titanium dioxide.
Embodiment 2.
Circulation turns back to the NaOH solution of reactor and is ground to 300 purpose titanium slag (TiO
2Mass content is 91.0%) under agitation mix, 450 ℃ of reactions 5 hours, wherein, titanium slag and NaOH solid mass ratio were 2: 1, obtain solid intermediate product after the reaction, titanium slag rate of decomposition 99%.With the washing down of intermediate product water normal temperature, washing solid-liquid mass ratio is 1: 100, adding hydrochloric acid soln adjusting pH value in the product that obtains after filtration is 0.25,60 ℃ fully dissolve 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 ℃, hydrolysate is filtered, the hydrated titanium dioxide solid that obtains white obtains rutile titanium dioxide 950 ℃ of calcinings 8 hours, and its XRD spectra as shown in Figure 2.The titanium dioxide rate of recovery is 94.2%, the purity 97.5% of titanium dioxide.
Embodiment 3.
Circulation turns back to the NaOH solution of reactor and is ground to 200 purpose titanium slag (TiO
2Mass content is 90.5%) under agitation mix, 350 ℃ of reactions 2 hours, wherein, titanium slag and NaOH solid mass ratio were 3: 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: 50, react and after 6 hours product is filtered, adding sulphuric acid soln dissolves, regulating the pH value is 0.25, product adds iron sheet as reductive agent after the dissolving down at 35 ℃, make ferric iron all change ferrous iron into, then the titanium liquid that obtains is filtered, filtrate was hydrolyzed 15 hours at 40 ℃, and hydrolysate is filtered, the hydrated titanium dioxide solid that obtains white was 600 ℃ of calcinings 10 hours, obtain anatase titanium dioxide two titanium dioxide, hydrolysate obtains rutile titanium dioxide 1000 ℃ of calcinings about 1 hour.The titanium dioxide rate of recovery is 90.6%, the purity 97.2% of titanium dioxide.
Embodiment 4.
Circulation turns back to the NaOH solution of reactor and is ground to 300 purpose titanium slag (TiO
2Mass content is 86.5%) under agitation mix, 500 ℃ of reactions 5 hours, wherein, titanium slag and NaOH solid mass ratio were 2.5: 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, adding hydrochloric acid soln adjusting pH value in the product that obtains after filtration is 0.11, and product all dissolves back adding metallic zinc as reductive agent under the normal temperature, 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 93.8%, the purity 97.8% of titanium dioxide.
Embodiment 5.
Circulation turns back to the NaOH solution of reactor and is ground to 200 purpose titanium slag (TiO
2Mass content is 92.3%) under agitation mix, 550 ℃ of reactions 15 minutes, wherein, titanium slag and NaOH solid mass ratio were 3: 1, obtain solid intermediate product after the reaction, titanium slag rate of decomposition 100%.With intermediate product at 60 ℃ of washing and filterings, washing solid-liquid mass ratio is 1: 20, product after the filtration adds sulphuric acid soln, and regulating the pH value is that 0.29,45 ℃ of following product all dissolves back adding aluminium flake 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 ℃, and hydrolysate is filtered, obtain the hydrated titanium dioxide solid 1150 ℃ of calcinings about 0.5 hour, obtain rutile titanium dioxide.The titanium dioxide rate of recovery is about 92%, the purity 97.5% of titanium dioxide.
Claims (10)
1. a method of utilizing the sodium hydroxide clean production of titanium dioxide is characterized in that, this method may further comprise the steps:
(1) titanium slag and sodium hydroxide are mixed,, obtain solid-state intermediate product 350 ℃～550 ℃ reactions down; Wherein the mass ratio of sodium hydroxide and titanium slag is 0.8: 1～3: 1;
(2) the solid-state intermediate product water that step (1) is obtained washs, filters, the solid intermediate product after obtaining sodium 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 0.1～0.4, 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 0.2～5 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 sodium 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 sodium 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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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102534236A (en) * | 2012-02-20 | 2012-07-04 | 武汉科技大学 | Method for recovering valuable metal from metallurgical slag materials |
| CN102757091A (en) * | 2011-04-28 | 2012-10-31 | 中国科学院过程工程研究所 | Method for preparing high-concentration titanic liquid |
| CN102774884A (en) * | 2012-07-09 | 2012-11-14 | 中国科学院过程工程研究所 | Method for comprehensive utilization of sulfate process titanium dioxide black mud |
| 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 |
| 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 |
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| US4759916A (en) * | 1983-04-11 | 1988-07-26 | The Dow Chemical Company | Process for preparing a pigmentary titanium dioxide |
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