CN114671460A - Method for removing impurities from industrial metatitanic acid in sulfuric acid method titanium dioxide short-flow process - Google Patents
Method for removing impurities from industrial metatitanic acid in sulfuric acid method titanium dioxide short-flow process Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 89
- 239000002253 acid Substances 0.000 title claims abstract description 86
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 49
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000012535 impurity Substances 0.000 title claims abstract description 42
- 238000005406 washing Methods 0.000 claims abstract description 23
- 238000004537 pulping Methods 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 75
- 239000002002 slurry Substances 0.000 claims description 32
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 10
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 238000001354 calcination Methods 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 239000010936 titanium Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 238000001723 curing Methods 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910000348 titanium sulfate Inorganic materials 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- NMJKIRUDPFBRHW-UHFFFAOYSA-N titanium Chemical compound [Ti].[Ti] NMJKIRUDPFBRHW-UHFFFAOYSA-N 0.000 description 1
- -1 titanium alkoxide Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a method for removing impurities from industrial metatitanic acid in a sulfuric acid method titanium dioxide short-flow process, belonging to the field of preparation of high-purity titanium dioxide. The method for removing impurities from industrial metatitanic acid in the sulfuric acid method titanium dioxide short-process technology comprises the following steps: a, pulping and dispersing; b, adding a coordination agent; c, adding a dispersing agent; e, purifying and washing. The method removes impurity ions by complex, dispersion and hydrothermal treatment, has simple process, low cost and obvious impurity removal effect, and the content of titanium dioxide after the purified metatitanic acid is calcined is more than or equal to 99.8 percent.
Description
Technical Field
The invention relates to a method for removing impurities from industrial metatitanic acid in a short-flow process of sulfate-process titanium dioxide, belonging to the field of preparation of high-purity titanium dioxide.
Background
Titanium dioxide (commonly known as titanium dioxide) is stable in physical and chemical properties, high in refractive index and the best white pigment, 90% of titanium resources are used for manufacturing titanium dioxide, and nearly 60% of titanium resources are used in the field of coatings. High purity TiO2Because of its semiconductor performance, high dielectric constant and resistivity, it is widely used in PTC thermistor, semiconductor capacitor, SrTiO3The electronic field such as piezoresistors; high purity TiO2The titanium-titanium alloy can also be used in the cosmetic industry, can also be used as a raw material for preparing titanium and titanium alloy, has great effect on the fields of aerospace, military, electronic materials and the like, and has rapidly increased market demand in recent years. The existing preparation methods of high-purity titanium dioxide mainly comprise 4 methods: titanium alkoxide hydrolysis, titanium tetrachloride direct hydrolysis, chlorination and sulfuric acid, wherein the sulfuric acid has the advantages of simple and mature process, easily available raw materials, low production cost, simple equipment and the like, but impurities are easily introduced in the preparation process to reduce the purity of the product. The metatitanic acid prepared by hydrolyzing the unconcentrated titanium solution contains a large amount of impurities, and the industrial production adopts a washing mode to remove the impurities, so that the impurity removal is not complete enough, the impurity removal effect is limited, and the condition that high-purity TiO is difficult to meet is met2The purity requirement of (2).
CN110357153A discloses a method for preparing high-purity titanium dioxide by using industrial metatitanic acid hydrothermal method, which comprises the following steps: adding water to industrial metatitanic acid for dispersing, filtering and washing until no ferrous ion exists in washing liquid; adding water again for dispersion to obtain slurry, wherein the concentration of the slurry is 100-300g/L in terms of the mass of the titanium dioxide; carrying out hydrothermal crystallization on the slurry at the temperature of 110-180 ℃ for 24-48 h; after the reaction is finished, cooling to 60-80 ℃, filtering, and washing until the washing liquid has no ferrous ions, so as to obtain a metatitanic acid filter cake; then calcining, heating the temperature from room temperature to 840-900 ℃ at the heating rate of 10-15 ℃/min, preserving the temperature for 60-300min, then cooling to room temperature, crushing and grinding to obtain the high-purity titanium dioxide. The purity of the method for preparing titanium dioxide by using industrial metatitanic acid is more than 99.8 percent.
CN109850941A discloses a method for preparing high-purity titanium dioxide by hydrolyzing industrial titanium sulfate solution, belonging to the technical field of chemical industry. The method for preparing high-purity titanium dioxide by hydrolyzing the industrial titanium sulfate solution comprises the following steps: freezing the titanium sulfate solution to separate out ferrous sulfate crystals, and filtering to obtain filtrate A; taking 1 volume of filtrate A and 0.20-1.00 volume of water to respectively preheat to 90-98 ℃; adding the filtrate A into water under the condition of stirring, heating to maintain a slightly boiling state for 20-40 min, and stopping heating and stirring for curing for 20-40 min; heating and keeping a micro-boiling state for 120-240 min, cooling to 60-70 ℃, filtering while hot, and washing the solid obtained by filtering to obtain purified metatitanic acid; and raising the temperature of the purified metatitanic acid to 750-850 ℃ at the heating rate of 10-15 ℃/min, preserving the temperature for 100-150 min, and cooling to obtain the high-purity titanium dioxide. The invention directly prepares the high-purity titanium dioxide with the purity more than or equal to 99.9 percent by using the industrial raw material titanium sulfate, and has simple process and low cost.
CN106365200A discloses a method for preparing high-purity superfine titanium dioxide by using industrial metatitanic acid. The method comprises the following steps: a. pulping and dispersing: washing and bleaching hydrolyzed metatitanic acid, adding water for dilution and pulping, and performing ultrasonic dispersion to obtain slurry, and adding a dispersing agent into the slurry for dispersion to obtain metatitanic acid slurry; b. curing: curing the metatitanic acid slurry, then cooling to 60-70 ℃, filtering, and washing until no ferrous ion exists, so as to obtain a purified metatitanic acid filter cake; c. and (3) calcining: adding water into the metatitanic acid filter cake, performing ultrasonic dispersion, calcining, cooling to room temperature, crushing, and grinding to obtain the metatitanic acid filter cake. The invention utilizes the occurrence form of impurity ions in hydrolyzed metatitanic acid particles and the composition and structural characteristics of metatitanic acid, directly prepares high-purity superfine titanium dioxide by dispersion, washing, curing, calcination and the like, can increase new varieties of titanium dioxide and realize the functionalization of product application, and has wide application prospect.
However, the above prior arts are all industrial metatitanic acid aiming at the conventional sulfate process of titanium dioxide. The problem of impurity removal of industrial metatitanic acid in a short-flow process cannot be solved. The short-flow process is to eliminate the titanium liquid concentration section (i.e. concentration procedure) and directly use the low-concentration industrial titanium liquid to hydrolyze to prepare metatitanic acid aiming at the traditional sulfuric acid method titanium dioxide process. Compared with metatitanic acid obtained by hydrolyzing concentrated titanium liquid, metatitanic acid obtained by a sulfuric acid method titanium white short-process has smaller grain size and smaller primary aggregated particles, so that the specific surface area is larger, the adsorption to impurity ions and the like is enhanced, and the impurity ions are more difficult to remove on the whole.
Disclosure of Invention
The invention aims to provide a method for removing impurities from industrial metatitanic acid in a short-flow process of titanium white by a sulfuric acid method.
In order to achieve the aim of the invention, the method for removing impurities from the industrial metatitanic acid in the sulfuric acid method titanium dioxide short-flow process comprises the following steps:
a, pulping and dispersing: adding water into industrial metatitanic acid obtained by hydrolysis in a short-flow process of titanium dioxide by a sulfuric acid method, pulping and dispersing to obtain metatitanic acid slurry, wherein the metatitanic acid is TiO2The mass is M, and the concentration of M in the metatitanic acid slurry is controlled to be 50-95 g/L;
b, adding a coordination agent: uniformly mixing the metatitanic acid slurry with sulfosalicylic acid and citric acid to obtain a solution 1, wherein the total mass of the sulfosalicylic acid and the citric acid is 3.0-6.0 wt% M;
c, adding a dispersing agent: uniformly mixing the solution 1 with sodium dodecyl sulfate to obtain a solution 2, wherein the mass of the sodium dodecyl sulfate is 0.10-0.20 wt% of M;
d, hydrothermal crystallization: carrying out a hydrothermal reaction on the solution 2, wherein the temperature of the hydrothermal reaction is 110-180 ℃, and the time of the hydrothermal reaction is 4-48 h;
e, purification and washing: and after the hydrothermal reaction is finished, cooling to 60-80 ℃, filtering, and washing with water until no ferrous ion exists to obtain the purified metatitanic acid.
The metatitanic acid after impurity removal and purification mainly contains free water, bound water and a small amount of sulfate radical, and can be removed only by calcination, and high-purity titanium dioxide can be obtained by calcination. While other metal ions not previously removed are not removed during the calcination process.
The calcination process can be a conventional calcination method in the industries of titanium white and high-purity titanium dioxide, and in principle, free water and bound water can be removed by keeping the calcination at 400 ℃ for about 1 hour; the sulfate radical can be removed basically by keeping the temperature at 800 ℃ for 120 minutes.
In a specific embodiment, the mass ratio of the sulfosalicylic acid to the citric acid in the step b is 0.5-2.0.
In a specific embodiment, the mass ratio of the sulfosalicylic acid to the citric acid in the step b is 1.0-1.5.
In a specific embodiment, the total mass of sulfosalicylic acid and citric acid in step b is 4.5 wt% to 5.0 wt% M.
In a specific embodiment, the step b is uniformly mixed by stirring, and then is dispersed for 5 to 20 minutes, preferably 10 to 15 minutes.
The dispersion of the invention can be realized by dispersing metatitanic acid in an ultrasonic dispersion and stirring manner and maintaining metatitanic acid particles in a suspension state in a liquid phase.
Stirring needs to disperse the metatitanic acid slurry well and maintain the metatitanic acid particles in a suspension state in a liquid phase.
In a specific embodiment, the mass of the sodium dodecyl sulfate in the step c is 0.10 wt% to 0.14 wt% of M.
In a specific embodiment, the step c is to mix uniformly by stirring, and then disperse for 5 to 15 minutes, preferably for 10 to 12 minutes.
In a specific embodiment, the temperature of the hydrothermal reaction in the step d is 140-160 ℃.
In a specific embodiment, the time of the hydrothermal reaction in the step d is preferably 8-24 hours.
In a specific embodiment, the temperature of the washing water in the step e is 50-80 ℃, and preferably 65 ℃.
Has the advantages that:
the method removes impurity ions by complex, dispersion and hydrothermal treatment, has simple process, low cost and obvious impurity removal effect, and the content of titanium dioxide after the purified metatitanic acid is calcined is more than or equal to 99.8 percent. The titanium dioxide obtained by removing impurities and calcining metatitanic acid can be used in the application fields of electronic grade titanium white and the like.
Detailed Description
In order to achieve the aim of the invention, the method for removing impurities from the industrial metatitanic acid in the sulfuric acid method titanium dioxide short-flow process comprises the following steps:
a, pulping and dispersing: adding water into industrial metatitanic acid obtained by hydrolysis in a short-flow process of titanium dioxide by a sulfuric acid method, pulping and dispersing to obtain metatitanic acid slurry, wherein the metatitanic acid is TiO2The mass is M, and the concentration of M in the metatitanic acid slurry is controlled to be 50-95 g/L;
b, adding a complexing agent: uniformly mixing the metatitanic acid slurry with sulfosalicylic acid and citric acid to obtain a solution 1, wherein the total mass of the sulfosalicylic acid and the citric acid is 3.0-6.0 wt% M;
c, adding a dispersing agent: uniformly mixing the solution 1 with sodium dodecyl sulfate to obtain a solution 2, wherein the mass of the sodium dodecyl sulfate is 0.10-0.20 wt% of M;
d, hydrothermal crystallization: carrying out a hydrothermal reaction on the solution 2, wherein the temperature of the hydrothermal reaction is 110-180 ℃, and the time of the hydrothermal reaction is 4-48 h;
e, purification and washing: and after the hydrothermal reaction is finished, cooling to 60-80 ℃, filtering, and washing with water until no ferrous ion exists to obtain the purified metatitanic acid.
In a specific embodiment, the mass ratio of the sulfosalicylic acid to the citric acid in the step b is 0.5-2.0.
In a specific embodiment, the mass ratio of the sulfosalicylic acid to the citric acid in the step b is 1.0-1.5.
In a specific embodiment, the total mass of sulfosalicylic acid and citric acid in step b is 4.5 wt% to 5.0 wt% M.
In a specific embodiment, the step b is uniformly mixed by stirring, and then is dispersed for 5 to 20 minutes, preferably 10 to 15 minutes.
In a specific embodiment, the mass of the sodium dodecyl sulfate in the step c is 0.10 wt% to 0.14 wt% of M.
In a specific embodiment, the step c is to mix uniformly by stirring, and then disperse the mixture for 5 to 15 minutes, preferably 10 to 12 minutes.
In a specific embodiment, the temperature of the hydrothermal reaction in the step d is 140-160 ℃.
In a specific embodiment, the time of the hydrothermal reaction in the step d is preferably 8-24 hours.
In a specific embodiment, the temperature of the washing water in the step e is 50-80 ℃, and preferably 65 ℃.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Comparative example 1
The industrial metatitanic acid prepared by the short-flow process used in examples 1-4 was calcined (all comparative examples and examples of the present invention have the same calcination conditions, specifically, the titanium dioxide content of the product was 98.21% and the impurity iron content was 0.137% after 2-stage heating of the first stage chamber temperature to 420 ℃, 30 minutes, 60 minutes, 420 ℃ to 850 ℃, 80 minutes, 150 minutes).
Example 1
Adding water into industrial metatitanic acid hydrolyzed by a short-flow process for dilution, pulping and dispersion, controlling the concentration of slurry to be 60g/L, and then adding TiO into metatitanic acid slurry25.0 mass percent of sulfosalicylic acid and citric acid, the mass ratio of the sulfosalicylic acid to the citric acid is 1.0, the sulfosalicylic acid and the citric acid are evenly stirred and then dispersed for 10 minutes, and then TiO is added into metatitanic acid slurry2And (2) stirring and uniformly mixing 0.12% of sodium dodecyl sulfate by mass, then dispersing for 12 minutes, transferring the obtained metatitanic acid slurry into a hydrothermal kettle for hydrothermal reaction at the temperature of 140 ℃ for 12 hours, cooling to 60 ℃ after the hydrothermal reaction is finished, filtering, washing with 60 ℃ water until no ferrous ions exist, and obtaining the metatitanic acid after impurity removal and purification.
The content of the obtained calcined titanium dioxide is 99.81 percent, the content of impurity iron is reduced from 0.137 percent to 0.062 percent, and the iron removal rate is 54.7 percent.
Example 2
Diluting, pulping and dispersing the industrial metatitanic acid hydrolyzed by the short-flow process by adding water, and preparing the slurryThe concentration is controlled to be 70g/L, and TiO is added into metatitanic acid slurry26.0 mass percent of sulfosalicylic acid and citric acid with the mass ratio of 1.5, stirring and uniformly mixing, then dispersing for 11 minutes, and then adding TiO into metatitanic acid slurry2And (2) stirring and uniformly mixing 0.15% of sodium dodecyl sulfate by mass, then dispersing for 11 minutes, transferring the obtained metatitanic acid slurry into a hydrothermal kettle for hydrothermal reaction at the temperature of 150 ℃ for 14 hours, cooling to 65 ℃ after the hydrothermal reaction is finished, filtering, washing with 65 ℃ water until no ferrous ions exist, and obtaining the metatitanic acid after impurity removal and purification.
The content of the titanium dioxide after calcination is 99.87 percent, the content of impurity iron is reduced from 0.137 percent to 0.051 percent, and the iron removal rate is 62.8 percent.
Example 3
Adding water into industrial metatitanic acid hydrolyzed by a short-flow process for dilution, pulping and dispersion, controlling the concentration of the slurry to be 80g/L, and then adding TiO into metatitanic acid slurry25.0 mass percent of sulfosalicylic acid and citric acid, the mass ratio of the sulfosalicylic acid to the citric acid is 1.0, the sulfosalicylic acid and the citric acid are evenly stirred and then dispersed for 11 minutes, and TiO is added into metatitanic acid slurry2And (2) stirring and uniformly mixing 0.14% of sodium dodecyl sulfate by mass, then dispersing for 12 minutes, transferring the obtained metatitanic acid slurry into a hydrothermal kettle for hydrothermal reaction at 160 ℃ for 16 hours, cooling to 70 ℃ after the hydrothermal reaction is finished, filtering, washing with 70 ℃ water until no ferrous ions exist, and obtaining the metatitanic acid after impurity removal and purification.
The content of the obtained calcined titanium dioxide is 99.94 percent, the content of impurity iron is reduced from 0.137 percent to 0.044 percent, and the iron removal rate is 67.9 percent.
Example 4
Adding water into industrial metatitanic acid hydrolyzed by a short-flow process for dilution, pulping and dispersion, controlling the concentration of slurry to be 75g/L, and then adding TiO into metatitanic acid slurry24.5 percent of sulfosalicylic acid and citric acid by mass, the mass ratio of the sulfosalicylic acid to the citric acid is 1.2, the sulfosalicylic acid and the citric acid are evenly stirred and then dispersed for 13 minutes, and then TiO is added into the metatitanic acid slurry20.12 percent of sodium dodecyl sulfate by mass is stirredUniformly mixing, then dispersing for 11 minutes, then transferring the obtained metatitanic acid slurry into a hydrothermal kettle for hydrothermal reaction at the temperature of 150 ℃ for 16 hours, cooling to 70 ℃ after the hydrothermal reaction is finished, filtering, washing with 65 ℃ water until no ferrous ions exist, and obtaining the metatitanic acid after impurity removal and purification.
The content of the obtained calcined titanium dioxide is 99.91 percent, the content of impurity iron is reduced from 0.137 percent to 0.046 percent, and the iron removal rate is 66.4 percent.
Claims (10)
1. The method for removing impurities from industrial metatitanic acid in the sulfuric acid method titanium dioxide short-flow process is characterized by comprising the following steps of:
a, pulping and dispersing: adding water into industrial metatitanic acid obtained by hydrolysis in a short-flow process of titanium dioxide by a sulfuric acid method, pulping and dispersing to obtain metatitanic acid slurry, wherein the metatitanic acid is TiO2The mass is M, and the concentration of M in the metatitanic acid slurry is controlled to be 50-95 g/L;
b, adding a complexing agent: uniformly mixing the metatitanic acid slurry with sulfosalicylic acid and citric acid to obtain a solution 1, wherein the total mass of the sulfosalicylic acid and the citric acid is 3.0-6.0 wt% M;
c, adding a dispersing agent: uniformly mixing the solution 1 with sodium dodecyl sulfate to obtain a solution 2, wherein the mass of the sodium dodecyl sulfate is 0.10-0.20 wt% of M;
d, hydrothermal crystallization: carrying out a hydrothermal reaction on the solution 2, wherein the temperature of the hydrothermal reaction is 110-180 ℃, and the time of the hydrothermal reaction is 4-48 h;
e, purification and washing: and after the hydrothermal reaction is finished, cooling to 60-80 ℃, filtering, and washing with water until no ferrous ion exists to obtain the purified metatitanic acid.
2. The method for removing impurities from industrial metatitanic acid in the sulfuric acid process titanium dioxide short-flow process according to claim 1, wherein the mass ratio of sulfosalicylic acid to citric acid in the step b is 0.5-2.0.
3. The method for removing impurities from industrial metatitanic acid in the sulfuric acid process titanium dioxide short-flow process according to claim 1 or 2, wherein the mass ratio of sulfosalicylic acid to citric acid in the step b is 1.0-1.5.
4. The method for removing impurities from industrial metatitanic acid in the sulfuric acid process titanium dioxide short-flow process according to claim 1 or 2, wherein the total mass of the sulfosalicylic acid and the citric acid in the step b is 4.5-5.0 wt% M.
5. The method for removing impurities from industrial metatitanic acid in the sulfuric acid process titanium dioxide short-flow process according to claim 1 or 2, wherein the mixing in the step b is performed by stirring, and the mixture is re-dispersed for 5-20 minutes, preferably 10-15 minutes.
6. The method for removing impurities from industrial metatitanic acid in the sulfuric acid process titanium dioxide short-flow process according to claim 1 or 2, wherein the mass of the sodium dodecyl sulfate in the step c is 0.10-0.14 wt% M.
7. The method for removing impurities from industrial metatitanic acid in the sulfuric acid process titanium dioxide short-flow process according to claim 1 or 2, wherein the step c is to mix uniformly by stirring, and disperse the uniformly mixed solution for 5 to 15 minutes, preferably 10 to 12 minutes.
8. The method for removing impurities from industrial metatitanic acid in the sulfuric acid process titanium dioxide short-process technology according to claim 1 or 2, wherein the temperature of the hydrothermal reaction in the step d is 140-160 ℃.
9. The method for removing impurities from industrial metatitanic acid in the short-flow process of titanium dioxide by a sulfuric acid process according to claim 1 or 2, wherein the time of the hydrothermal reaction in the step d is preferably 8-24 hours.
10. The method for removing impurities from industrial metatitanic acid in the short-flow process of titanium dioxide by a sulfuric acid process according to claim 1 or 2, wherein the temperature of the washing water in the step e is 50-80 ℃, preferably 65 ℃.
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