CN114671460B - Method for removing impurities from industrial meta-titanic acid in sulfuric acid method titanium dioxide short-process technology - Google Patents
Method for removing impurities from industrial meta-titanic acid in sulfuric acid method titanium dioxide short-process technology 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 110
- 238000000034 method Methods 0.000 title claims abstract description 102
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 53
- 239000012535 impurity Substances 0.000 title claims abstract description 40
- 238000005516 engineering process Methods 0.000 title abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000004537 pulping Methods 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 239000008139 complexing agent Substances 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 57
- 239000002253 acid Substances 0.000 claims description 51
- 239000002002 slurry Substances 0.000 claims description 33
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 23
- 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 19
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims 1
- 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
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 238000001354 calcination Methods 0.000 description 15
- 229910052742 iron Inorganic materials 0.000 description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000007865 diluting Methods 0.000 description 5
- 238000001723 curing Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000000706 filtrate 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
- 239000006185 dispersion Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 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
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 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
- 239000003973 paint Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 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
Abstract
The invention relates to a method for removing impurities from industrial meta-titanic acid in a sulfuric acid method titanium dioxide short-process, belonging to the field of high-purity titanium dioxide preparation. The method for removing the impurities of the industrial meta-titanic acid in the sulfuric acid method titanium dioxide short-process technology comprises the following steps: a, pulping and dispersing; b adding a complexing agent; c, adding a dispersing agent; e, purifying and washing. The method removes impurity ions through complex, dispersing and hydro-thermal treatment comprehensive means, has simple process, low cost and remarkable impurity removal effect, and the content of titanium dioxide after the purified meta-titanic 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 meta-titanic acid in a sulfuric acid method titanium dioxide short-process, belonging to the field of high-purity titanium dioxide preparation.
Background
Titanium dioxide (commonly known as titanium dioxide) has stable physical and chemical properties and high refractive index, is the best white pigment, and 90% of titanium resources are used for manufacturing titanium dioxide, and nearly 60% of titanium dioxide is used in the field of paint. High purity TiO 2 Due to the semiconductor property, and the dielectric constant and the resistivity are relatively highHigh, widely applied to PTC thermistors, semiconductor capacitors and SrTiO 3 Electronic fields such as basic piezoresistors; high purity TiO 2 The titanium alloy can 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 demands in recent years. The existing preparation methods of the high-purity titanium dioxide mainly comprise 4 types: the titanium alkoxide hydrolysis method, the titanium tetrachloride direct hydrolysis method, the chlorination method and the sulfuric acid method have 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, so that the purity of the product is reduced. The meta-titanic acid prepared by hydrolyzing unconcentrated titanium liquid contains a large amount of impurities, the impurities are removed in a washing way in industrial production, the impurities are not completely removed, the impurity removing effect is limited, and the high-purity TiO is difficult to meet 2 Is required for purity.
CN110357153a discloses a method for preparing high-purity titanium dioxide by industrial metatitanic acid water heating, which comprises the following steps: dispersing industrial meta-titanic acid in water, filtering, and washing until no ferrous ions exist in the washing liquid; adding water again to obtain slurry, wherein the concentration of the slurry is 100-300g/L based on the mass of titanium dioxide; carrying out hydrothermal crystallization on the slurry at 110-180 ℃ for 24-48h; after the completion, cooling to 60-80 ℃, filtering, washing until no ferrous ions exist in the washing liquid, and obtaining a metatitanic acid filter cake; calcining, heating to 840-900 deg.C at 10-15 deg.C/min, maintaining for 60-300min, cooling to room temperature, pulverizing, and grinding to obtain high purity titanium dioxide. The invention relates to a method for preparing titanium dioxide by using industrial meta-titanic acid, and the purity is more than 99.8%.
CN109850941a discloses a method for preparing high-purity titanium dioxide by hydrolyzing industrial titanium sulfate solution, which belongs to the technical field of chemical industry. The method for preparing high-purity titanium dioxide by hydrolyzing industrial titanium sulfate solution comprises the following steps: freezing out ferrous sulfate crystals from titanium sulfate liquid, and filtering to obtain filtrate A; taking 1 volume of filtrate A and 0.20-1.00 volume of filtrate A, respectively preheating to 90-98 ℃; adding the filtrate A into water under stirring, heating again to maintain a micro-boiling state for 20-40 min, stopping heating, stirring and curing for 20-40 min; heating again to keep the micro-boiling state for 120-240 min, cooling to 60-70 ℃, filtering while the mixture is hot, and washing the filtered solid to obtain purified meta-titanic acid; and (3) heating the purified meta-titanic acid to 750-850 ℃ at a heating rate of 10-15 ℃/min, preserving heat for 100-150 min, and cooling to obtain the high-purity titanium dioxide. The invention directly prepares high-purity titanium dioxide with purity more than or equal to 99.9 percent by industrial raw material titanium sulfate, and has simple process and low cost.
CN106365200a discloses a method for preparing high-purity ultrafine titanium dioxide from industrial meta-titanic acid. The method comprises the following steps: a. pulping and dispersing: washing and bleaching the hydrolyzed metatitanic acid, diluting and pulping by adding water, performing ultrasonic dispersion to obtain slurry, and adding a dispersing agent into the slurry to perform dispersion to obtain metatitanic acid slurry; b. curing: curing the metatitanic acid slurry, cooling to 60-70 ℃, filtering, and washing until no ferrous ions exist, thus obtaining a purified metatitanic acid filter cake; c. calcining: adding water into the meta-titanic acid filter cake, performing ultrasonic dispersion, calcining, cooling to room temperature, crushing and grinding to obtain the meta-titanic acid filter cake. The invention directly prepares the high-purity superfine titanium dioxide by utilizing the occurrence form of impurity ions in the hydrolyzed meta-titanic acid particles and the composition and structural characteristics of the meta-titanic acid, through dispersion, washing, curing, calcining and the like, can increase new types of titanium dioxide and realize the functionalization of product application, and has wide application prospect.
However, the prior art is directed to industrial metatitanic acid of conventional sulfuric acid process titanium dioxide process. The problem of industrial meta-titanic acid impurity removal in short-flow processes cannot be solved. The short process refers to the traditional sulfuric acid process titanium white process, a titanium liquid concentration section (i.e. concentration process) is eliminated, and low-concentration industrial titanium liquid is directly used for hydrolysis to prepare the metatitanic acid. Compared with the metatitanic acid obtained by hydrolyzing the concentrated titanium liquid, the grain size of the metatitanic acid obtained by the short flow process of the titanium white by the sulfuric acid method is smaller, and the primary aggregation particles are smaller, so that the specific surface area is larger, the adsorption of impurity ions and the like is about stronger, and the impurity ions are generally more difficult to remove.
Disclosure of Invention
The invention aims to provide a method for removing impurities from industrial metatitanic acid in a short-flow process of titanium dioxide by a sulfuric acid method.
In order to achieve the purpose of the invention, the method for removing the impurities of the industrial meta-titanic acid in the sulfuric acid method titanium dioxide short-process technology comprises the following steps:
and a, pulping and dispersing: adding water into industrial metatitanic acid obtained by hydrolysis in a short-flow process of titanium dioxide by sulfuric acid method, pulping and dispersing to obtain metatitanic acid slurry, wherein the metatitanic acid is prepared from TiO 2 The mass is M, and the concentration meter of M in the metatitanic acid slurry is controlled to be 50-95 g/L;
b adding a complexing agent: uniformly mixing the meta-titanic 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 3.0-6.0wt% 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% 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 hours;
e, purifying and washing: after the hydrothermal reaction is finished, cooling to 60-80 ℃, filtering, washing with water until no ferrous ions exist, and obtaining the purified meta-titanic acid.
The purified meta-titanic acid mainly contains free water, bound water and a small amount of sulfate radical, and can be removed only by calcining, so that the high-purity titanium dioxide can be obtained by calcining. 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 preparing high-purity titanium dioxide, and in principle, free water and bound water can be removed when the calcination is carried out at 400 ℃ for about 1 hour; the sulfate radical can be basically removed after the temperature is kept at 800 ℃ for 120 minutes.
In a specific embodiment, the mass ratio of sulfosalicylic acid to citric acid in the step b is 0.5-2.0.
In a specific embodiment, the mass ratio of sulfosalicylic acid to 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 4.5wt% to 5.0wt% M.
In a specific embodiment, the mixing in step b is carried out by stirring, and dispersing for 5-20 minutes, preferably for 10-15 minutes after mixing.
The dispersion of the invention can be carried out by dispersing the metatitanic acid in an ultrasonic dispersion and stirring mode, and the metatitanic acid particles are maintained in a suspension state in a liquid phase.
The stirring is carried out by dispersing the metatitanic acid slurry well, and keeping the metatitanic acid particles in a suspension state in a liquid phase.
In one embodiment, the sodium dodecyl sulfate in step c has a mass of 0.10wt% to 0.14wt% M.
In a specific embodiment, the mixing in step c is carried out by stirring, and dispersing for 5-15 minutes, preferably for 10-12 minutes after mixing.
In a specific embodiment, the temperature of the hydrothermal reaction in step d is 140-160 ℃.
In one embodiment, the time of the hydrothermal reaction in step d is preferably 8 to 24 hours.
In a specific embodiment, the water temperature of the wash in step e is 50 to 80 ℃, preferably 65 ℃.
The beneficial effects are that:
the method removes impurity ions through complex, dispersing and hydro-thermal treatment comprehensive means, has simple process, low cost and remarkable impurity removal effect, and the content of titanium dioxide after the purified meta-titanic acid is calcined is more than or equal to 99.8 percent. The titanium dioxide obtained by removing impurities and calcining the meta-titanic acid can be used in the application fields of electronic grade titanium white and the like.
Detailed Description
In order to achieve the purpose of the invention, the method for removing the impurities of the industrial meta-titanic acid in the sulfuric acid method titanium dioxide short-process technology comprises the following steps:
and a, pulping and dispersing: adding water into industrial metatitanic acid obtained by hydrolysis in a short-flow process of titanium dioxide by sulfuric acid method, pulping and dispersing to obtain metatitanic acid slurry, wherein the metatitanic acid is prepared from TiO 2 The mass is M, and the concentration meter of M in the metatitanic acid slurry is controlled to be 50-95 g/L;
b adding a complexing agent: uniformly mixing the meta-titanic 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 3.0-6.0wt% 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% 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 hours;
e, purifying and washing: after the hydrothermal reaction is finished, cooling to 60-80 ℃, filtering, washing with water until no ferrous ions exist, and obtaining the purified meta-titanic acid.
In a specific embodiment, the mass ratio of sulfosalicylic acid to citric acid in the step b is 0.5-2.0.
In a specific embodiment, the mass ratio of sulfosalicylic acid to 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 4.5wt% to 5.0wt% M.
In a specific embodiment, the mixing in step b is carried out by stirring, and dispersing for 5-20 minutes, preferably for 10-15 minutes after mixing.
In one embodiment, the sodium dodecyl sulfate in step c has a mass of 0.10wt% to 0.14wt% M.
In a specific embodiment, the mixing in step c is carried out by stirring, and dispersing for 5-15 minutes, preferably for 10-12 minutes after mixing.
In a specific embodiment, the temperature of the hydrothermal reaction in step d is 140-160 ℃.
In one embodiment, the time of the hydrothermal reaction in step d is preferably 8 to 24 hours.
In a specific embodiment, the water temperature of the wash in step e is 50 to 80 ℃, preferably 65 ℃.
The following describes the invention in more detail with reference to examples, which are not intended to limit the invention thereto.
Comparative example 1
The industrial meta-titanic acid prepared by the short-flow process used in examples 1-4 was calcined (all comparative examples of the present invention and calcination conditions of examples were the same, and specifically, 2-stage heating was employed: the first stage room temperature was raised to 420 ℃, the temperature was raised for 30 minutes, the heat was kept for 60 minutes, the temperature was raised to 420 ℃ to 850 ℃, the temperature was raised for 80 minutes, and the heat was kept for 150 minutes.) to obtain a product having a titanium dioxide content of 98.21% and an impurity iron content of 0.137%.
Example 1
Diluting industrial metatitanic acid hydrolyzed by short-process technology with water, pulping and dispersing, controlling the slurry concentration at 60g/L, and adding TiO according to the ratio to the metatitanic acid slurry 2 Sulfosalicylic acid and citric acid with the mass ratio of 5.0 percent and 1.0 percent are stirred and mixed uniformly and then are redispersed for 10 minutes, and then TiO is added into the metatitanic acid slurry 2 0.12% of sodium dodecyl sulfonate by mass, stirring and uniformly mixing, re-dispersing for 12 minutes, transferring the obtained metatitanic acid slurry into a hydrothermal kettle for hydrothermal reaction at 140 ℃ for 12 hours, cooling to 60 ℃ after the hydrothermal reaction is finished, filtering, and washing with water at 60 ℃ until no ferrous ions exist, thereby obtaining the purified metatitanic acid.
The content of titanium dioxide after calcination is 99.81%, the content of impurity iron is reduced from 0.137% to 0.062%, and the iron removal rate is 54.7%.
Example 2
Diluting industrial metatitanic acid hydrolyzed by short-process technology with water, pulping and dispersing, controlling the slurry concentration at 70g/L, and adding TiO into the metatitanic acid slurry 2 Sulfosalicylic acid and citric acid with the mass ratio of 6.0 percent and 1.5 are stirred and mixed uniformly and then are dispersed for 11 minutes, and then TiO is added into the metatitanic acid slurry 2 0.15% of sodium dodecyl sulfonate by mass, stirring and uniformly mixing, re-dispersing for 11 minutes, transferring the obtained metatitanic acid slurry into a hydrothermal kettle for hydrothermal reaction, wherein the hydrothermal reaction temperature is 150 ℃, the hydrothermal reaction time is 14 hours, and the hydrothermal reaction is finishedAnd cooling to 65 ℃, filtering, washing with water at 65 ℃ until no ferrous ions exist, and obtaining the purified meta-titanic acid.
The content of titanium dioxide after calcination is 99.87%, the content of impurity iron is reduced from 0.137% to 0.051%, and the iron removal rate is 62.8%.
Example 3
Diluting industrial metatitanic acid hydrolyzed by short-process technology with water, pulping and dispersing, controlling the slurry concentration at 80g/L, and adding TiO into the metatitanic acid slurry 2 Sulfosalicylic acid and citric acid with mass ratio of 5.0% of 1.0, stirring and mixing uniformly, re-dispersing for 11 minutes, and then adding TiO into the metatitanic acid slurry 2 Stirring and mixing 0.14% of sodium dodecyl sulfate by mass, re-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, and washing with water at 70 ℃ until no ferrous ions exist, thereby obtaining the purified metatitanic acid.
The obtained calcined titanium dioxide content is 99.94%, the impurity iron content is reduced from 0.137% to 0.044%, and the iron removal rate is 67.9%.
Example 4
Diluting industrial metatitanic acid hydrolyzed by short-process technology with water, pulping and dispersing, controlling the slurry concentration at 75g/L, and adding TiO into the metatitanic acid slurry 2 Sulfosalicylic acid and citric acid with the mass ratio of 4.5 percent of 1.2 are stirred and mixed uniformly and then are dispersed for 13 minutes, and then TiO is added into the metatitanic acid slurry 2 0.12% of sodium dodecyl sulfonate by mass, stirring and uniformly mixing, re-dispersing for 11 minutes, transferring the obtained metatitanic acid slurry into a hydrothermal kettle for hydrothermal reaction, wherein the hydrothermal reaction temperature is 150 ℃, the hydrothermal reaction time is 16 hours, cooling to 70 ℃ after the hydrothermal reaction is finished, filtering, and washing with water at 65 ℃ until no ferrous ions exist, thus obtaining the purified metatitanic acid.
The content of titanium dioxide after calcination is 99.91%, the content of impurity iron is reduced from 0.137% to 0.046%, and the iron removal rate is 66.4%.
Claims (13)
1. The method for removing the impurities of the industrial metatitanic acid in the sulfuric acid process titanium dioxide short process is characterized by comprising the following steps of:
and a, pulping and dispersing: adding water into industrial metatitanic acid obtained by hydrolysis in a short-flow process of titanium dioxide by sulfuric acid method, pulping and dispersing to obtain metatitanic acid slurry, wherein the metatitanic acid is prepared from TiO 2 The mass is M, and the M concentration meter in the metatitanic acid slurry is controlled to be 50-95 g/L;
b adding a complexing agent: uniformly mixing the meta-titanic 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 3.0-6.0wt% 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% 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 hours;
e, purifying and washing: after the hydrothermal reaction is finished, cooling to 60-80 ℃, filtering, washing with water until no ferrous ions exist, and obtaining the purified meta-titanic acid.
2. The method for removing impurities from industrial meta-titanic acid in a short flow process of titanium dioxide by a sulfuric acid method 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 meta-titanic acid in a short-flow process of titanium dioxide by a sulfuric acid method 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 meta-titanic acid in a short flow process of titanium dioxide by a sulfuric acid method according to claim 1 or 2, wherein the total mass of sulfosalicylic acid and citric acid in the step b is 4.5-5.0wt% M.
5. The method for removing impurities from industrial meta-titanic acid in a short flow process of titanium dioxide by a sulfuric acid method according to claim 1 or 2, wherein the mixing in the step b is carried out by stirring, and the mixture is redispersed for 5-20 minutes.
6. The method for removing impurities from industrial metatitanic acid in a short flow process of titanium dioxide by a sulfuric acid method according to claim 5, wherein the step b is carried out after the uniform mixing, and the mixture is redispersed for 10 to 15 minutes.
7. The method for removing impurities from industrial meta-titanic acid in a short flow process of titanium dioxide by a sulfuric acid method according to claim 1 or 2, wherein the mass of sodium dodecyl sulfate in the step c is 0.10-0.14wt% M.
8. The method for removing impurities from industrial meta-titanic acid in a short flow process of titanium dioxide by a sulfuric acid method according to claim 1 or 2, wherein in the step c, stirring is adopted for uniformly mixing, and then the materials are redispersed for 5-15 minutes.
9. The method for removing impurities from industrial metatitanic acid in a short flow process of titanium dioxide by a sulfuric acid method according to claim 8, wherein the step c is characterized by re-dispersing for 10-12 minutes after uniformly mixing.
10. The method for removing impurities from industrial metatitanic acid in a short-flow process of titanium dioxide by sulfuric acid method according to claim 1 or 2, wherein the temperature of the hydrothermal reaction in the step d is 140-160 ℃.
11. The method for removing impurities from industrial meta-titanic acid in a short-flow process of titanium dioxide by sulfuric acid method according to claim 1 or 2, wherein the hydrothermal reaction time in the step d is 8-24 h.
12. The method for removing impurities from industrial meta-titanic acid in a short flow process of titanium dioxide by sulfuric acid method according to claim 1 or 2, wherein the water temperature for washing in the step e is 50-80 ℃.
13. The method for removing impurities from industrial metatitanic acid in a short-flow process of titanium dioxide by sulfuric acid method according to claim 12, wherein the water temperature for washing in the step e is 65 ℃.
Priority Applications (1)
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