CN103950976A - Method for preparing titanium dioxide by utilizing mixed alkali of sodium hydroxide and sodium nitrate - Google Patents
Method for preparing titanium dioxide by utilizing mixed alkali of sodium hydroxide and sodium nitrate Download PDFInfo
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- CN103950976A CN103950976A CN201410136386.9A CN201410136386A CN103950976A CN 103950976 A CN103950976 A CN 103950976A CN 201410136386 A CN201410136386 A CN 201410136386A CN 103950976 A CN103950976 A CN 103950976A
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Abstract
The invention relates to a method for preparing titanium dioxide by utilizing a mixed alkali of sodium hydroxide and sodium nitrate. The method comprises the following steps: 1) mixing uniformly a titanium-enriched material and the mixture of sodium hydroxide and sodium nitrate, carrying out a reaction at the temperature of 300-450 DEG C, and thus obtaining a solid intermediate product; 2) washing the solid intermediate product with water, and filtering to obtain an intermediate product after water washing; 3) dissolving the intermediate product with an inorganic acid, then adding an iron powder, and reducing to obtain a titanium liquid; 4) filtering the titanium liquid, hydrolyzing the filtrate, controlling the hydrolysis temperature at 60-120 DEG C, filtering the hydrolysis product, and thus obtaining white metatitanic acid and an acidic filtrate; and 5) calcining metatitanic acid at the temperature of 500-1200 DEG C, and thus obtaining titanium dioxide. The method can effectively reduce the energy consumption and the cost of a molten salt titanium white technology. While the conversion rate is ensured, the molten salt reaction temperature and the energy consumption of alkali liquid recycling are reduced, the effect is obvious, and the operation is simple and convenient.
Description
Technical field
The invention belongs to preparation and the Mineral resources manufacture field of inorganic metal compound, being specifically related to a kind of is raw material by rich titanium material, sodium hydroxide and SODIUMNITRATE, the method for 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 chemical industry, nontoxic, be harmless to the health, it is most important white pigment, accounts for 80% of whole white pigment usage quantitys, it is also the main product of titanium system, 90% of titanium resource be all used for manufacturing titanium dioxide in the world, titanium dioxide is widely used in modern industry, agricultural, national defence, scientific and technical numerous areas, has close contacting with people's lives and national economy.
At present, the industrial process of titanium dioxide is sulfuric acid process and chlorination process, has that refuse amount is large, strong toxicity, an environmental pollution problem such as heavily.Chinese Academy Of Sciences Process Engineering Research Institute is on the basis of the sub-fused salt chemical industry metallurgical technology of research and development, low-temperature molten salt titanium white clearer production technology has been proposed, this technique be take titanium slag as raw material, take sodium hydroxide or potassium hydroxide fused salt is reaction medium, from beginning of production, eliminate environmental pollution, realize titanium resource and valuable component efficient-clean-comprehensive utilization.The publication number that these two kinds of methods are applied for a patent is CN101172648A and CN101172649A.But the described method temperature of reaction of these two patents is higher, need 500 ℃ and 550 ℃ just can be by titanium slag complete reaction.Adopting in addition titanium slag is raw material, and raw material taste is high, scarcity of resources and very expensive.
Summary of the invention
The object of the invention is in order further to reduce energy consumption and the cost of low-temperature molten salt titanium white technology, adopting comparatively cheap rich titanium material and the lower sodium hydroxide sodium nitrate mixture of fusing point is raw material, has effectively optimized the technique of low-temperature molten salt titanium white technology.
The present invention seeks to be realized by the following technical programs:
The method of utilizing sodium hydroxide and SODIUMNITRATE mixed base to prepare titanium dioxide of the present invention, comprises the following steps:
1) rich titanium material and sodium hydroxide sodium nitrate mixture are mixed, at 300～450 ℃, reaction, obtains solid-state intermediate product; Wherein, the sodium hydroxide in described sodium hydroxide sodium nitrate mixture and the mass ratio of SODIUMNITRATE are 1:2～14:1, and the mass ratio of described sodium hydroxide sodium nitrate mixture and rich titanium material is 1:1～3:1;
2) solid-state intermediate product water step 1) being obtained washs, filters, and obtains the intermediate product after sodium hydroxide SODIUMNITRATE mixing solutions and washing;
3) by step 2) intermediate product that obtains dissolves with mineral acid after washing, and the pH value of the hierarchy of control is 0.1～0.4, then adds iron powder and reduces, and obtains titanium liquid;
4) titanium liquid step 3) being obtained filters, and filtrate is hydrolyzed, and hydrolysis temperature is controlled at 60～120 ℃, and hydrolysate is filtered, and obtains white metatitanic acid and acid filtrate;
5) metatitanic acid step 4) being obtained is calcining at 500～1200 ℃ in temperature, obtains anatase titanium dioxide or rutile titanium dioxide.
According to method of the present invention, in described rich titanium material, the mass content of titanium dioxide is between 70%～85%.
According to method of the present invention, preferably, the reaction times described in step 1) is 0.5～4 hour.
According to method of the present invention, preferably, step 2) described solid-state intermediate product and the solid-liquid mass ratio of bath water are 1:3～1:100.
According to method of the present invention, step 2) to the sodium hydroxide and the SODIUMNITRATE mixing solutions that obtain after solid-state intermediate product washing, through evaporative crystallization with after concentrating, can return to step 1) for decomposing rich titanium material, carry out recycle.
According to method of the present invention, preferably, mineral acid is sulfuric acid described in step 3).The temperature condition that described mineral acid dissolves be use known in this field any sour solubility temperature all can, be preferably 50～65 ℃.
According to method of the present invention, preferably, the time that filtrate is hydrolyzed described in step 4) is 0.5～24 hour.
The method according to this invention, the acid filtrate described in step 4) can return to step 3) for the intermediate product obtaining after washing is carried out to acidolysis, carries out recycle.
According to method of the present invention, preferably, the time that metatitanic acid is calcined described in step 5) is 0.5～10 hour.
The present invention adopts and samples low rich titanium material than titanium slag is raw material, (200 ℃～400 ℃) carry out molten salt react ion with the mixed base of sodium hydroxide and SODIUMNITRATE at a lower temperature, reaction product through washing, acid molten, hydrolysis, calcining after can prepare anatase titanium dioxide or rutile titanium dioxide, Production Flow Chart is simple, reaction medium can evaporate recycling at a lower temperature, and does not need to add other auxiliary material.
The invention has the advantages that, can effectively reduce energy consumption and the cost of fused salt titanium white technology.When guaranteeing transformation efficiency, reduced the energy consumption of molten right temperature of reaction and recycle of alkali liquor, successful, simple to operation.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the rutile titanium dioxide that makes of embodiment 1.
Fig. 2 is the XRD spectra of the anatase titanium dioxide that makes of embodiment 2.
Embodiment
Embodiment 1
By NaOH and NaNO
3according to mass ratio 14:1, grind and mix, the rich titanium material of mixture and 140～200 objects (TiO
2massfraction is 78.6%) under agitation mix, at 450 ℃, react 1.5 hours, wherein, the mass ratio of rich titanium material and mixture is 1:1.5, rich titanium material rate of decomposition is 100%.After reaction, obtain solid intermediate product, wash with water, the solid mass ratio of each washings is 5:1, it is 0.15 that product after filtration adds sulphuric acid soln regulation system pH value, at 50 ℃, product all being dissolved, then add iron powder as reductive agent, is that three-iron is all reduced to ferrous iron.The titanium liquid finally obtaining filters, and filtrate is hydrolyzed 4 hours at 110 ℃, and hydrolysate is filtered, and obtains white metatitanic acid and calcines 4 hours at 950 ℃, obtains rutile titanium dioxide, and its XRD spectra as shown in Figure 1.The titanium dioxide rate of recovery is 94.3%, and titanium dioxide purity is 98.6%.
Embodiment 2
By NaOH and NaNO
3according to mass ratio 1:2, grind and mix, the rich titanium material of mixture and 140～200 objects (TiO
2massfraction is 78.6%) under agitation mix, at 300 ℃, react 4 hours, wherein, the mass ratio of rich titanium material and mixture is 1:3, obtains solid intermediate product after reaction, wash with water, the solid mass ratio of each washings is 100:1, and it is at 0.1,60 ℃, product all to be dissolved that the product after filtration adds sulphuric acid soln regulation system pH value, then adding iron powder as reductive agent, is that three-iron is all reduced to ferrous iron.The titanium liquid finally obtaining filters, and filtrate is hydrolyzed 24 hours at 120 ℃, and hydrolysate is filtered, and obtains white metatitanic acid and calcines 10 hours at 500 ℃, obtains anatase titanium dioxide, and its XRD spectra as shown in Figure 2.The titanium dioxide rate of recovery is 78.8%, and titanium dioxide purity is 97.8%.
Embodiment 3
By NaOH and NaNO
3according to mass ratio 11:4, grind and mix, the rich titanium material of mixture and 140～200 objects (TiO
2massfraction is 70.1%) under agitation mix, at 350 ℃, react 4 hours, wherein, the mass ratio of rich titanium material and mixture is 1:2, obtains solid intermediate product after reaction, wash with water, the solid mass ratio of each washings is 3:1, and it is at 0.3,55 ℃, product all to be dissolved that the product after filtration adds sulphuric acid soln regulation system pH value, then adding iron powder as reductive agent, is that three-iron is all reduced to ferrous iron.The titanium liquid finally obtaining filters, and filtrate is hydrolyzed 0.5 hour at 60 ℃, and hydrolysate is filtered, and obtains white metatitanic acid and calcines 0.5 hour at 1200 ℃, obtains rutile titanium dioxide.The titanium dioxide rate of recovery is 87.6%, and titanium dioxide purity is 97.2%.
Embodiment 4
The mixed base that circulation turns back to reactor adds part NaOH to regulate NaOH and NaNO
3mass ratio be 12:3, the rich titanium material of mixture and 200～250 objects (TiO
2massfraction is 78.6%) under agitation mix, at 400 ℃, react 0.5 hour, wherein, the mass ratio of rich titanium material and mixture is 1:1.5, obtains solid intermediate product after reaction, wash with water, the solid mass ratio of each washings is 5:1, and it is at 0.4,65 ℃, product all to be dissolved that the product after filtration adds sulphuric acid soln regulation system pH value, then adding iron powder as reductive agent, is that three-iron is all reduced to ferrous iron.The titanium liquid finally obtaining filters, and filtrate is hydrolyzed 8 hours at 105 ℃, and hydrolysate is filtered, and obtains white metatitanic acid and calcines 0.5 hour at 700 ℃, obtains anatase titanium dioxide.The titanium dioxide rate of recovery is 93%, and titanium dioxide purity is 98.9%.
Certainly; the present invention can also have various embodiments; in the situation that not deviating from spirit of the present invention and essence thereof; those of ordinary skill in the art can openly make various corresponding changes and distortion according to of the present invention, but these corresponding changes and distortion all should belong to the protection domain of claim of the present invention.
Claims (9)
1. utilize sodium hydroxide and SODIUMNITRATE mixed base to prepare a method for titanium dioxide, comprise the following steps:
1) rich titanium material and sodium hydroxide sodium nitrate mixture are mixed, at 300～450 ℃, reaction, obtains solid-state intermediate product; Wherein, the sodium hydroxide in described sodium hydroxide sodium nitrate mixture and the mass ratio of SODIUMNITRATE are 1:2～14:1, and the mass ratio of described sodium hydroxide sodium nitrate mixture and rich titanium material is 1:1～3:1;
2) solid-state intermediate product water step 1) being obtained washs, filters, and obtains the intermediate product after sodium hydroxide SODIUMNITRATE mixing solutions and washing;
3) by step 2) intermediate product that obtains dissolves with mineral acid after washing, and the pH value of the hierarchy of control is 0.1～0.4, then adds iron powder and reduces, and obtains titanium liquid;
4) titanium liquid step 3) being obtained filters, and filtrate is hydrolyzed, and hydrolysis temperature is controlled at 60～120 ℃, and hydrolysate is filtered, and obtains white metatitanic acid and acid filtrate;
5) metatitanic acid step 4) being obtained is calcining at 500～1200 ℃ in temperature, obtains titanium dioxide.
2. method according to claim 1, is characterized in that, in described rich titanium material, the mass content of titanium dioxide is between 70%～85%.
3. method according to claim 1, is characterized in that, the reaction times described in step 1) is 0.5～4 hour.
4. method according to claim 1, is characterized in that step 2) described solid-state intermediate product and the solid-liquid mass ratio of bath water be 1:3～1:100.
5. according to the method described in claim 1 or 4, it is characterized in that step 2) to the sodium hydroxide and the SODIUMNITRATE mixing solutions that obtain after solid-state intermediate product washing, through evaporative crystallization with after concentrating, return to step 1) for decomposing rich titanium material.
6. method according to claim 1, is characterized in that, mineral acid is sulfuric acid described in step 3).
7. method according to claim 1, is characterized in that, the time that filtrate is hydrolyzed described in step 4) is 0.5～24 hour.
8. according to the method described in claim 1 or 7, it is characterized in that, the acid filtrate described in step 4) returns to step 3) for the intermediate product obtaining after washing is carried out to acidolysis.
9. method according to claim 1, is characterized in that, the time that metatitanic acid is calcined described in step 5) is 0.5～10 hour.
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Cited By (3)
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| CN106929936A (en) * | 2017-02-26 | 2017-07-07 | 浙江峰赫纺织有限公司 | Sun-proof anti-bacterial fibre precursor |
| CN109904439A (en) * | 2017-12-11 | 2019-06-18 | 中信国安盟固利动力科技有限公司 | A kind of low temperature preparation method of novel titanium base material |
| CN111705226A (en) * | 2020-06-22 | 2020-09-25 | 眉山顺应动力电池材料有限公司 | Method for removing impurities from high-titanium slag |
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| CN103265069A (en) * | 2013-05-14 | 2013-08-28 | 中国科学院过程工程研究所 | Method for preparing rutile-type titanium dioxide |
| CN103482695A (en) * | 2012-06-12 | 2014-01-01 | 中国科学院过程工程研究所 | Method for low-temperature production of titanium dioxide by mixed alkali of sodium hydroxide and potassium hydroxide |
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| CN106929936A (en) * | 2017-02-26 | 2017-07-07 | 浙江峰赫纺织有限公司 | Sun-proof anti-bacterial fibre precursor |
| CN109904439A (en) * | 2017-12-11 | 2019-06-18 | 中信国安盟固利动力科技有限公司 | A kind of low temperature preparation method of novel titanium base material |
| CN111705226A (en) * | 2020-06-22 | 2020-09-25 | 眉山顺应动力电池材料有限公司 | Method for removing impurities from high-titanium slag |
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Application publication date: 20140730 |