CN101190802B - Clean method for preparing rutile-type titanium dioxide from high-titanium slag by hydrothermal method - Google Patents
Clean method for preparing rutile-type titanium dioxide from high-titanium slag by hydrothermal method Download PDFInfo
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- CN101190802B CN101190802B CN2006101440517A CN200610144051A CN101190802B CN 101190802 B CN101190802 B CN 101190802B CN 2006101440517 A CN2006101440517 A CN 2006101440517A CN 200610144051 A CN200610144051 A CN 200610144051A CN 101190802 B CN101190802 B CN 101190802B
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- titanium slag
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- sodium titanate
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Abstract
The invention relates to a clean production method by high titanium slag hydrothermal method to prepare rutile titanium oxide. The method adopts high titanium slag as raw material and sodium hydroxide hydrothermal method to prepare the intermediate product of sodium titanate which is then separated from the solution and washed and hydrolyzed to obtain the rutile titanium oxide. The method of the invention adopts simple preparation technique to prepare the rutile TiO2, which spares high temperature calcination in the traditional technique; the conversion rate of titanium in the high titanium slag is of over 99.0 percent and the alkali circulation and the acid circulation are realized, which has good economic benefit and environmental benefit. Additionally, the sodium titanate which can be taken as the intermediate product for preparing titanium series obtained from the method is expected to have wide application.
Description
Technical field
The invention belongs to Mineral resources processing and utilization and inorganic functional material fabricating technology field, specifically relate to the clean preparation method of titanium slag preparing rutile-type titanium dioxide by hydrothermal method.
Background technology
Titanium dioxide is commonly called as titanium white, it is a kind of white inorganic pigment, have nontoxic, best opacity, best whiteness and luminance brightness, be considered to the best a kind of white pigment of performance in the world, be widely used in industry such as coating, plastics, papermaking, printing-ink, chemical fibre, rubber, makeup.
The titanium dioxide industrialized preparing process mainly contains two kinds: sulfuric acid process and chlorination process.Sulfuric acid process is that the titanium-iron powder and the vitriol oil are carried out acidolysis reaction generation titanyl sulfate, generates metatitanic acid through hydrolysis, promptly obtains the titanium dioxide product through calcining, pulverizing again, and in order to obtain rutile titanium dioxide, calcining temperature needs at 900-1250 ℃.Its shortcoming is a long flow path, can only be based on periodical operation, and the wet method operation, sulfuric acid, water consumption height, refuse and by product are many, and be big for environment pollution.Chlorination process be with rutile or titanium slag powder with carry out high-temp chlorination after coke mixes and produce titanium tetrachloride, through high temperature oxidation, more after filtration, washing, dry, pulverize and obtain the titanium dioxide product.Its shortcoming is that investment is big, the equipment complexity, and high temperature resistant, corrosion-resistant to the material requirements height, device is difficult to maintenance, and the research and development difficulty is big.
Summary of the invention
The objective of the invention is to overcome existing titanium white industrial manufacture process energy consumption height, seriously polluted, defectives such as investment is big, equipment complexity, a kind of energy consumption is low, the clean preparation method of titanium slag preparing rutile-type titanium dioxide by hydrothermal method with good economic benefits and environmental benefit thereby provide.
The objective of the invention is to be achieved through the following technical solutions:
The clean preparation method of titanium slag preparing rutile-type titanium dioxide by hydrothermal method provided by the invention, be to be raw material with the titanium slag, utilize the sodium hydroxide hydrothermal method to make the sodium titanate intermediate, then intermediate is separated again and directly prepared rutile titanium dioxide through hydrolysis, this method may further comprise the steps:
1) with titanium slag and sodium hydroxide solution thorough mixing, at 180-280 ℃, carry out hydro-thermal reaction 0.5-10h under the stirring condition, obtain the hydro-thermal reaction product; Wherein the mass ratio of sodium hydroxide and titanium slag is 0.5-5:1, and concentration sodium hydroxide is 200-500g/L;
2) reaction product of step 1) obtains intermediate sodium titanate crude product and soda-lye through solid-liquid separation, this soda-lye is returned step 1) be used for hydro-thermal reaction decomposition titanium slag behind dehydration by evaporation;
3) with step 2) the intermediate sodium titanate crude product that obtains at normal temperatures water wash, filter, the intermediate sodium titanate and the dilute solution of sodium hydroxide that are not contained free alkali, this dilute solution of sodium hydroxide return step 1) and are used for hydro-thermal reaction decomposition titanium slag after evaporation concentration;
Described water washing process can be common washing, also multi-stage countercurrent washing; The solid-liquid mass ratio of intermediate sodium titanate crude product and bath water is 1: 1-200;
4) the intermediate sodium titanate that step 3) is obtained is filtered and is obtained titaniferous solution after carrying out acidolysis and reduction under 20-80 ℃;
Described acid is mineral acids such as sulfuric acid, hydrochloric acid or nitric acid;
Described reductive agent is metal iron powder, iron filings, metallic zinc, S-WAT or Sulfothiorine;
Intermediate sodium titanate during described acidolysis is 1 with the solid-to-liquid ratio of acid: 50-200;
5) titaniferous solution that step 4) is obtained or sodium titanate mixed solution are at the 50-150 ℃ of 0.5-48h that is hydrolyzed, hydrolysate is filtered, obtain the titanium dioxide solid and the acid filtrate of white, acid filtrate returns step 4) and is used for acidolysis or preparation sodium titanate mixed solution;
6) titanium dioxide that step 5) is obtained is dry under 60-120 ℃, promptly obtains rutile titanium dioxide without high-temperature roasting.
The clean preparation method of titanium slag preparing rutile-type titanium dioxide by hydrothermal method provided by the invention (titanium white), comprise that titanium slag and sodium hydroxide hydro-thermal reaction obtain converted product, products therefrom is carried out processes such as solid-liquid separation, washing, reduction, hydrolysis, can obtain rutile titanium dioxide after the solid phase drying that hydrolysis obtains.Compare with existing titanium white industrial production technology, the advantage of titanium slag cleaning transforming method provided by the invention is:
1. the present invention uses the sodium hydroxide hydrothermal method to handle titanium slag and since adopted raw material---titanium slag is a kind of TiO of containing
2Higher rich titanium material is compared with concentrate with ilmenite, has titanium content height, " three wastes " and produces (processings) and measure less, help features such as product quality raising.Adopt the fine fodder of this " with slag for the ore deposit ", can alleviate environmental protection pressure, and comprehensively improve economic benefit.
2. shortcomings such as compare with traditional sulfuric acid process, the present invention has avoided the consumption height of water, and refuse and by product are many have huge environmental benefit;
3. compare with chlorination process, the temperature of reaction of hydrothermal method of the present invention is 180-280 ℃, has reduced more than 800 ℃ than the temperature of reaction of chlorination process, has huge economic benefit.
4. the titanium transformation efficiency can reach more than 99.0% in the raw material, the titanium dioxide rate of recovery is greater than 90%, the purity of titanium dioxide is greater than 95%, and prepared titanium dioxide has been avoided the high-temperature roasting of product in the traditional technology, can directly obtain rutile titanium dioxide without high-temperature roasting, energy consumption reduces greatly.
5. the present invention has realized alkali circulation, acid circulation, has greatly reduced raw-material energy consumption, has improved the technology operability, has reduced production cost.
6. method provided by the invention also can make sodium titanate, as the intermediate of the serial titanium of preparation, and is expected to be used widely.
Description of drawings
Fig. 1 is the XRD figure spectrum of the prepared titanium dioxide of embodiment 1;
Fig. 2 is the SEM collection of illustrative plates of the prepared titanium dioxide of embodiment 1.
Embodiment
Embodiment 1
The 500g/L NaOH alkaline solution of reactor is returned in circulation, adds 200 purpose titanium slags and under agitation mixes, and the mass ratio of NaOH and titanium slag is 0.5:1,180 ℃ of hydro-thermal reactions 0.5 hour, obtains the hydro-thermal reaction product, and the titanium slag transformation efficiency is 100%.Reaction product is filtered, obtain containing the strong solution of the crude product and the sodium hydroxide of sodium titanate, this soda-lye can be used for above-mentioned steps and carries out hydro-thermal reaction behind dehydration by evaporation;
The crude product of the water washing sodium titanate of returning with circulation 2 times, wash the solid-liquid mass ratio is 1:40 at every turn, and the sodium titanate product that obtains after the filtration adds the sulphuric acid soln that circulation is returned, and makes its whole dissolvings, and solid-to-liquid ratio is 1:200, adds S-WAT to this solution then.At last this solution was hydrolyzed 0.5 hour at 50 ℃, hydrolysate is filtered, the white solid that obtains obtains rutile titanium dioxide in 60 ℃ of dryings, its XRD spectra as shown in Figure 1, SEM schemes as shown in Figure 2.By XRD figure as can be known the product that obtains of hydrolysis be rutile titanium dioxide, scheming as can be seen by SEM, product is spherical.
Embodiment 2
The 200g/L NaOH alkaline solution of reactor is returned in circulation, adds 300 purpose titanium slags and under agitation mixes, and the mass ratio of NaOH and titanium slag is 5:1,280 ℃ of hydro-thermal reactions 10 hours, obtains the hydro-thermal reaction product, and the titanium slag transformation efficiency is 99.0%.Reaction product is filtered, obtain containing the strong solution of the crude product and the sodium hydroxide of sodium titanate, this soda-lye can be used for above-mentioned steps and carries out hydro-thermal reaction behind dehydration by evaporation;
The crude product of the water washing sodium titanate of returning with circulation 2 times, wash the solid-liquid mass ratio is 1:10 at every turn, and the sodium titanate product that obtains after the filtration adds the hydrochloric acid soln that circulation is returned, and solid-to-liquid ratio is 1:50, adds iron filings then in this mixed solution.At last this mixed solution was hydrolyzed 48 hours at 150 ℃, hydrolysate is filtered, the white solid that obtains obtains rutile titanium dioxide in 100 ℃ of dryings.
Embodiment 3.
The 320g/L NaOH alkaline solution of reactor is returned in circulation, adds 250 purpose titanium slags and under agitation mixes, and the mass ratio of NaOH and titanium slag is 3.8:1,240 ℃ of hydro-thermal reactions 4 hours, obtains the hydro-thermal reaction product, and the titanium slag transformation efficiency is 99.4%.Reaction product is filtered, obtain containing the strong solution of the crude product and the sodium hydroxide of sodium titanate, this soda-lye can be used for above-mentioned steps and carries out hydro-thermal reaction behind dehydration by evaporation;
The crude product of the water washing sodium titanate of returning with circulation 2 times, wash the solid-liquid mass ratio is 1:20 at every turn, and the sodium titanate product that obtains after the filtration adds the salpeter solution that circulation is returned, and solid-to-liquid ratio is 1:100, adds Sulfothiorine then in this mixed solution.At last this mixed solution was hydrolyzed 24 hours at 150 ℃, hydrolysate is filtered, the white solid that obtains obtains rutile titanium dioxide in 120 ℃ of dryings.
Claims (4)
1. the clean preparation method of a titanium slag preparing rutile-type titanium dioxide by hydrothermal method may further comprise the steps:
1) with titanium slag and sodium hydroxide solution thorough mixing, at 180-280 ℃, carry out hydro-thermal reaction 0.5-10h under the stirring condition, obtain the hydro-thermal reaction product; Wherein the mass ratio of sodium hydroxide and titanium slag is 0.5-5: 1, and concentration sodium hydroxide is 200-500g/L;
2) reaction product of step 1) obtains intermediate sodium titanate crude product and soda-lye through solid-liquid separation, this soda-lye is returned step 1) be used for hydro-thermal reaction decomposition titanium slag behind dehydration by evaporation;
3) with step 2) the intermediate sodium titanate crude product that obtains at normal temperatures water wash, filter, the intermediate sodium titanate and the dilute solution of sodium hydroxide that are not contained free alkali, this dilute solution of sodium hydroxide return step 1) and are used for hydro-thermal reaction decomposition titanium slag after evaporation concentration;
4) the intermediate sodium titanate that step 3) is obtained is filtered and is obtained titaniferous solution after carrying out acidolysis and reduction under 20-80 ℃;
The acid that described acidolysis is adopted is sulfuric acid, hydrochloric acid or nitric acid;
The reductive agent that described reduction is adopted is metal iron powder, iron filings, metallic zinc, S-WAT or Sulfothiorine;
Intermediate sodium titanate during described acidolysis is 1 with the solid-to-liquid ratio of acid: 50-200;
5) the titaniferous solution that step 4) is obtained filters hydrolysate at the 50-150 ℃ of 0.5-48h that is hydrolyzed, and obtains the titanium dioxide solid and the acid filtrate of white, and acid filtrate returns step 4) and is used for acidolysis;
6) the titanium dioxide drying that step 5) is obtained obtains rutile titanium dioxide.
2. the clean preparation method of titanium slag preparing rutile-type titanium dioxide by hydrothermal method as claimed in claim 1 is characterized in that: the water washing process of described step 3) is common washing, or the multi-stage countercurrent washing.
3. the clean preparation method of titanium slag preparing rutile-type titanium dioxide by hydrothermal method as claimed in claim 1 is characterized in that: in the water washing process of described step 3), the solid-liquid mass ratio of intermediate sodium titanate crude product and bath water is 1: 1-200.
4. the clean preparation method of titanium slag preparing rutile-type titanium dioxide by hydrothermal method as claimed in claim 1 is characterized in that: the drying temperature of described step 6) is 60-120 ℃.
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| CN101812595A (en) * | 2010-05-06 | 2010-08-25 | 北京矿冶研究总院 | Method for producing artificial rutile from titanium slag |
| CN101898791B (en) * | 2010-06-25 | 2012-10-03 | 四川龙蟒钛业股份有限公司 | Method for preparing rutile titanium dioxide from new process titanium slag |
| CN101994012B (en) * | 2010-12-07 | 2012-08-29 | 东北大学 | Method for producing titanium dioxide by using titanium-containing blast furnace slag |
| CN102409179B (en) * | 2011-09-13 | 2014-02-12 | 北京科技大学 | Method for preparing one-dimensional nanostructures of titanium dioxide with melting slag of titanium containing electric furnace |
| CN102616836B (en) * | 2012-03-31 | 2014-07-02 | 攀枝花东方钛业有限公司 | Preparation method of trivalent titanium solution |
| CN104843777B (en) * | 2015-04-17 | 2016-12-07 | 北京矿冶研究总院 | Method for preparing rutile titanium dioxide from titanium slag |
| CN105967231A (en) * | 2016-06-22 | 2016-09-28 | 中国神华能源股份有限公司 | Method for extracting TiO2 from white clay |
| CN106542504A (en) * | 2016-10-26 | 2017-03-29 | 四川省高能钛坦环保科技有限公司 | A kind of hydrolysis method for extracting titanium dioxide |
| CN109482198B (en) * | 2018-11-28 | 2021-10-08 | 西南石油大学 | Method for preparing photocatalyst nano material from vanadium-titanium industrial waste residues and product |
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