CN107814411B - Preparation method of trivalent titanium solution - Google Patents
Preparation method of trivalent titanium solution Download PDFInfo
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- CN107814411B CN107814411B CN201711209889.4A CN201711209889A CN107814411B CN 107814411 B CN107814411 B CN 107814411B CN 201711209889 A CN201711209889 A CN 201711209889A CN 107814411 B CN107814411 B CN 107814411B
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- C01G23/008—Titanium- and titanyl sulfate
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Abstract
the invention relates to a titanium dioxide production process, and particularly discloses a preparation method of a trivalent titanium solution, which comprises the following steps: A. in a pressure vesselWashing metatitanic acid slurry (according to TiO)2Calculated) with concentrated sulfuric acid (in terms of H)2SO4calculated) is 1: 1.8-5; B. measuring the concentration of the sulfuric acid solution; C. pressurizing the interior of the pressure container according to the measured concentration, so that the boiling point of the sulfuric acid solution in the pressure container is not lower than 140 ℃; D. heating and boiling for at least 30 min; E. stopping heating, relieving pressure, cooling, adding water to adjust the concentration, adding aluminum powder to reduce tetravalent titanium in the solution into trivalent titanium, and obtaining the trivalent titanium solution. The invention has the advantages that: solves the problems of stacking and pollution of the titanium gypsum, and can obviously reduce the production cost of the trivalent titanium solution.
Description
Technical Field
the invention relates to a titanium dioxide production process, in particular to a sulfuric acid method titanium dioxide production process.
background
Titanium dioxide is an important inorganic chemical raw material, is non-toxic and harmless to health, is the most important white pigment, accounts for 80 percent of the using amount of all the white pigments, and is widely applied to the industries of coatings, plastics, papermaking, printing ink, chemical fibers, rubber, cosmetics, food and the like. At present, the total production amount of titanium dioxide in China reaches 180 million tons, the production process of the titanium dioxide mainly comprises a sulfuric acid method and a chlorination method, and the production process in China mainly comprises the sulfuric acid method. The typical production process flow can be summarized as follows:
(1) Carrying out acidolysis reaction on the titanium concentrate or the acid-soluble titanium slag and sulfuric acid to obtain a titanyl sulfate solution;
(2) Hydrolyzing titanyl sulfate solution to obtain coarse metatitanic acid slurry;
(3) washing and salting the coarse metatitanic acid slurry to obtain pretreated metatitanic acid;
(4) The pretreated metatitanic acid is sent into a rotary kiln to be calcined to produce TiO2and (5) producing the product.
The process for washing the coarse metatitanic acid slurry comprises the following specific steps:
(1) Primary water washing: carrying out solid-liquid separation on the crude metatitanic acid slurry to obtain a primary filter cake; washing the primary filter cake with water to remove iron ions in the primary filter cake to obtain a washed metatitanic acid cake; adding water into the metatitanic acid washing cake for pulping to obtain metatitanic acid washing slurry;
(2) Bleaching and reducing: adding a bleaching agent and a reducing agent into the metatitanic acid washing slurry for bleaching, and adding calcined crystal seeds to obtain bleached slurry;
(3) And (3) secondary water washing: carrying out solid-liquid separation on the bleaching slurry to obtain a secondary filter cake; washing the secondary filter cake with water to further remove iron ions in the secondary filter cake to obtain a secondary metatitanic acid washing cake; adding water into the secondary metatitanic acid washing cake for pulping to obtain secondary metatitanic acid washing slurry.
In the production process of titanium dioxide by a sulfuric acid method, iron impurities in metatitanic acid after primary washing are gradually oxidized along with the prolonging of washing time and the reduction of acidity, exist in a solid high-iron form, cannot be removed through washing, and are converted into Fe/TiO2The ratio of (A) to (B) is about 500 to 1000 ppm. After trace iron in metatitanic acid is calcined at high temperature, red ferric oxide is generated and mixed into rutile crystal lattices to cause crystal lattice deformation and generate crystal lattice defects, and chromophoric active points are formed, so that the whiteness and the achromatism of a product are reduced, the optical properties of titanium dioxide are influenced, and the rutile titanium dioxide is yellow. Therefore, when the rutile titanium dioxide is produced, the metatitanic acid washed once must be bleached and reduced, and then impurity iron mixed in the metatitanic acid is removed through secondary washing. The current general method is to bleach with sulfuric acid, then reduce with trivalent titanium reagent, and after twice water washing, Fe/TiO can be made2the content is reduced to 0-30 ppm, and the whiteness of the obtained finished titanium dioxide is obviously improved.
The trivalent titanium reagent for reduction is generally called trivalent titanium solution, and the production method is that the trivalent titanium reagent is prepared by adopting metatitanic acid slurry after being washed by water for one time: adding metatitanic acid washing slurry and concentrated sulfuric acid (98 acids are usually used) into a trivalent titanium preparation tank, heating for acid dissolution, then cooling, adding metered desalted water for adjusting the concentration, and then reducing tetravalent titanium in the system into trivalent titanium by using aluminum powder to obtain a trivalent titanium solution. The production practice shows that tons of trivalent titanium solution (in TiO) are produced2calculated) about 5 to 10 tons of 98 acid is added.
The obtained trivalent titanium solution is used for a bleaching reduction process, enters a secondary washing process along with the process, and after secondary washing, the generated wastewater enters a sewage system for treatment and then is discharged. Generally, lime is adopted to neutralize discharged wastewater, a neutralization product is mainly titanium gypsum, about 0.04 ton of lime is consumed for producing one ton of titanium dioxide, 0.2 ton of titanium gypsum is produced, the economic value of the byproduct titanium gypsum is very low, and a large amount of site is occupied for stockpiling, which is a big problem puzzling many enterprises producing titanium dioxide by a sulfuric acid method.
Disclosure of Invention
The invention provides a preparation method of a trivalent titanium solution, aiming at solving the problems of land occupation and pollution of titanium gypsum.
the technical scheme adopted by the invention is as follows: the preparation method of the trivalent titanium solution comprises the following steps:
A. Injecting a metatitanic acid washing slurry and a metered concentrated sulfuric acid into a pressure container, and uniformly mixing to obtain a mixture, wherein the liquid phase of the mixture is a sulfuric acid solution; the metatitanic acid slurry (TiO) is washed2Calculated) with concentrated sulfuric acid (in terms of H)2SO4In terms of) is 1: 1.8-5;
B. Measuring and recording the concentration of the sulfuric acid solution;
C. then closing the pressure container, and pressurizing the interior of the pressure container according to the measured concentration of the sulfuric acid solution, wherein the pressurization standard is that the boiling point of the sulfuric acid solution in the pressure container is not lower than 140 ℃;
D. heating a reaction system in the pressure container to boil, and keeping boiling for at least 30min to obtain an acid soluble solution;
E. Stopping heating, relieving pressure, cooling, adding metered water into the acid soluble solution to adjust the concentration, and then adding metered aluminum powder to reduce tetravalent titanium in the solution into trivalent titanium, thus obtaining the trivalent titanium solution.
The inventors found that in actual production, the amount of concentrated sulfuric acid added as a raw material is related to the concentration of metatitanic acid-washed slurry (i.e., titanium concentration) per unit yield of the trivalent titanium solution. The inventors propose that in current production practice, an excess of sulphuric acid may be added, mainly because the acid dissolution of the metatitanic acid slurry needs to reach a higher temperature, which we have experimentally measured is at least 140 ℃. The boiling point of the reaction system is increased along with the increase of the concentration of sulfuric acid in the system, so that only when the concentration of the sulfuric acid in the system reaches a certain concentration, the boiling point of the solution can reach the suitable acid dissolution temperature of the metatitanic acid washing slurry, and the metatitanic acid washing slurry can be fully dissolved, therefore, the lower the concentration of the metatitanic acid washing slurry is, the more sulfuric acid needs to be added. The inventors hereby believe that the amount of sulphuric acid added during the preparation of the trivalent titanium solution may be higher than actually required at present.
The inventor researches that, the main component of the metatitanic acid washing slurry is a polymer of titanium dioxide and contains partial bound water, concentrated sulfuric acid is commonly used for dissolving metatitanic acid, the essence of which is that metatitanic acid is converted into titanyl sulfate or exists in the form of titanyl sulfate in the solution, and according to the premise, if metatitanic acid is completely converted into titanyl sulfate, concentrated sulfuric acid (according to H) is required2SO4calculated as TiO) should be a metatitanic acid slurry2Meter) 1.2 times the mass; if the metatitanic acid is completely converted into titanium sulfate, concentrated sulfuric acid (as H) is required2SO4calculated as TiO) should be a metatitanic acid slurry2Calculated) 2.4 times the mass. However, titanyl sulfate in solution is substantially a dihydroxy complex of titanium in an aqueous solution, which is easily hydrolyzed in solution to form titanium precipitate, and therefore, in order to prevent the hydrolysis of the material, titanium in the acid-soluble solution should be present as much as possible in the form of titanium sulfate. I.e. concentrated sulfuric acid (as H) which is theoretically required2SO4Calculated as TiO) should be a metatitanic acid slurry2calculated) 2.4 times the mass.
Furthermore, we have found that the presence of a small amount of a dihydroxy complex of titanium in an acid solution is not unacceptable because the precipitation reaction of titanyl sulfate occurs at a certain acidity, temperature and time, and that intermolecular dehydration occurs very easily to form a precipitation reaction because the external electrons of tetravalent titanium ions are practically all lost after orbital hybridization to form a complex containing two hydroxyl groups (coordinated by lone electrons) and four-membered water on the D2SP3 orbital. Therefore, in the subsequent process, the aluminum powder can be reduced into trivalent titanium through the addition of the aluminum powder, and the fact that the position of electrons on the coordination orbit of titanium ions is occupied reduces the number of hydroxyl groups which are matched as ions, so that the stability of the ions is changed (the number of hydroxyl groups which can be dehydrated among molecules is reduced), the titanium precipitate formed among the molecules is difficult, and the trivalent titanium solution can be stably prepared even under the condition that the acidity is not very high and the titanium sulfate cannot be completely formed. Accordingly, experimental studies have been conducted to demonstrate that the method of the present invention is applied to concentrated sulfuric acid (according toH2SO4calculated as TiO) to a low-mass metatitanic acid slurry2calculated) 1.8 times of the mass, the trivalent titanium solution can still be stably prepared.
however, since the addition amount of concentrated sulfuric acid is greatly reduced in the present invention, which results in a great reduction in the concentration of sulfuric acid in the solution, the boiling point of the solution cannot reach the temperature required for acid dissolution, and for this reason, we propose that the reaction system can be placed in a pressure vessel for pressure reaction. The purpose of increasing the boiling point of the solution is achieved by increasing the reaction pressure. From the above analysis it will be appreciated that the pressure of the pressure vessel should be adjusted according to the concentration of the sulphuric acid solution therein, the lower the sulphuric acid solution concentration the higher the pressure required.
In experiments we have also shown that it is possible to add a slurry of at least one metatitanic acid (in terms of TiO) by mass to a pressure vessel2calculated by H) 1.8 times of concentrated sulfuric acid2SO4Meter) and the concentration of the sulfuric acid solution before reaction is measured to achieve the aim of promoting the acid dissolution of the metatitanic acid washing slurry by controlling the pressure. When concentrated sulfuric acid (as H)2SO4Calculated) is added in excess of the amount of metatitanic acid slurry (in terms of TiO)2Calculated) 5 times of the mass, the preparation of the trivalent titanium reagent is carried out by adopting a conventional method only by controlling the concentration of the metatitanic acid-washing slurry and the concentration of sulfuric acid.
The corresponding boiling points of the sulfuric acid solutions of different concentrations at different pressures can be determined by routine experimentation in the art, and the following table provides part of the experimental data provided by the applicant:
For example, when washing metatitanic acid slurry (according to TiO)2calculated) with concentrated sulfuric acid (in terms of H)2SO4Calculated) is added according to the proportion of 1:1.8, and the concentration of the metatitanic acid slurry is calculated according to TiO2The mass concentration of the sulfuric acid solution in the step A is measured to be about 10% when the concentration is 300g/L and the concentrated sulfuric acid is 98%, and the boiling point of the sulfuric acid solution can be ensured to be over 140 ℃ when the internal pressure of the pressure container is 0.35 MPa.
After bleaching and water washing, the trivalent titanium solution enters a sewage system in the forms of tetravalent titanium, residual trivalent titanium, free sulfuric acid and the like.
the invention has the beneficial effects that: the method can reduce the addition of concentrated sulfuric acid in the process of preparing the trivalent titanium solution to the maximum extent, so that in the subsequent process, the trivalent titanium solution enters a secondary washing procedure, and the free sulfuric acid generated after the secondary washing procedure is greatly reduced, so that the lime consumption for neutralizing wastewater is also greatly reduced, the generated titanium gypsum is correspondingly greatly reduced, the problems of stacking and pollution of the titanium gypsum are solved, and the production cost of the trivalent titanium solution can be obviously reduced.
Detailed Description
The present invention will be further described with reference to the following examples.
The first embodiment is as follows:
The trivalent titanium solution a was prepared as follows:
(1) Taking metatitanic acid slurry (TiO)2300g/l) and 98 acid are injected into a pressure container and uniformly mixed to obtain a mixture, and the liquid phase of the mixture is a sulfuric acid solution; the metatitanic acid slurry (TiO) is washed2Calculated) with 98 acids (in terms of H)2SO4Meter) is 1: 1.8;
(2) measuring the mass concentration of the sulfuric acid solution to be 9.9%;
(3) Then the pressure vessel is closed, and the pressure inside the pressure vessel is controlled to be 0.35Mpa by pressurization;
(4) Heating a reaction system in the pressure container to boil, and keeping boiling for 30min to obtain an acid soluble solution;
(5) Stopping heating, relieving pressure, cooling to 70 deg.C, adding water into the acid solution, and adjusting concentration to TiO2And (3) adding aluminum powder (the mass ratio of the aluminum powder to the total titanium dioxide is 0.11) to reduce the tetravalent titanium in the solution into trivalent titanium, thus obtaining a trivalent titanium solution A.
(6) The trivalent titanium concentration and the clarity of the trivalent titanium solution A are detected, and the results are shown in Table 1.
Example two:
The trivalent titanium solution B was prepared as follows:
(1) Taking metatitanic acid slurry (TiO)2300g/l) and 98 acid are injected into a pressure container and uniformly mixed to obtain a mixture, and the liquid phase of the mixture is a sulfuric acid solution; the metatitanic acid slurry (TiO) is washed2calculated) with 98 acids (in terms of H)2SO4Meter) is 1: 2.4;
(2) Measuring the mass concentration of the sulfuric acid solution to be 12.3 percent;
(3) Then the pressure vessel is closed, and the pressure inside the pressure vessel is controlled to be 0.32Mpa by pressurization;
(4) Heating a reaction system in the pressure container to boil, and keeping boiling for 40min to obtain an acid soluble solution;
(5) Stopping heating, relieving pressure, cooling to 70 deg.C, adding water into the acid solution, and adjusting concentration to TiO2and (3) adding aluminum powder (the mass ratio of the aluminum powder to the total titanium dioxide is 0.11) to reduce the tetravalent titanium in the solution into trivalent titanium, thus obtaining a trivalent titanium solution B.
(6) The trivalent titanium concentration and the clarity of the trivalent titanium solution B were measured, and the results are shown in Table 1.
Example three:
The trivalent titanium solution C was prepared as follows:
(1) Taking metatitanic acid slurry (TiO)2300g/l) and concentrated sulfuric acid with the mass concentration of 93% are injected into a pressure container and uniformly mixed to obtain a mixture, and the liquid phase of the mixture is a sulfuric acid solution; the metatitanic acid slurry (TiO) is washed2Calculated) with concentrated sulfuric acid (in terms of H)2SO4Meter) is 1: 4.8;
(2) Measuring the mass concentration of the sulfuric acid solution to be 47.2%;
(3) Then the pressure vessel is closed, and the pressure inside the pressure vessel is controlled to be 0.20Mpa by pressurization;
(4) heating a reaction system in the pressure container to boil, and keeping boiling for 40min to obtain an acid soluble solution;
(5) stopping heating, relieving pressure, cooling to 70 deg.C, adding water into the acid solution, and adjusting concentration to TiO2And (3) adding aluminum powder (the mass ratio of the aluminum powder to the total titanium dioxide is 0.11) to reduce the tetravalent titanium in the solution into trivalent titanium, thus obtaining a trivalent titanium solution C.
(6) The trivalent titanium concentration and clarity of the trivalent titanium solution C were measured and the results are shown in Table 1.
Example four:
The trivalent titanium solution D was prepared as follows:
(1) taking metatitanic acid slurry (TiO)2300g/l) and 98 acid are injected into a trivalent titanium preparation tank and uniformly mixed to obtain a mixture, and the metatitanic acid slurry is washed (according to TiO)2Calculated) with 98 acids (in terms of H)2SO4Meter) is 1: 5;
(2) Heating to boil, and keeping boiling for 30min to obtain acid soluble solution;
(3) Stopping heating, cooling to 70 deg.C, adding water into the above acid solution, and adjusting concentration to TiO2And (3) adding aluminum powder (the mass ratio of the aluminum powder to the total titanium dioxide is 0.11) to reduce the tetravalent titanium in the solution into trivalent titanium, thus obtaining a trivalent titanium solution D.
(4) The trivalent titanium concentration and the clarity of the trivalent titanium solution D were measured, and the results are shown in Table 1.
table 1: table of results of trivalent titanium solution testing
| clarity of the product | Concentration of trivalent titanium | Ton of sulfuric acid consumption | |
| trivalent titanium solution A | Clarification | 90.3g/l | 1.8t |
| Titanium (III) solution B | clarification | 90.3g/l | 2.4t |
| Trivalent titanium solution C | Clarification | 90.4g/l | 4.8t |
| Trivalent titanium solution D | Clarification | 90.3g/l | 5.0t |
Claims (6)
1. the preparation method of the trivalent titanium solution comprises the following steps:
A. Injecting a metatitanic acid washing slurry and a metered concentrated sulfuric acid into a pressure container, and uniformly mixing to obtain a mixture, wherein the liquid phase of the mixture is a sulfuric acid solution; the metatitanic acid slurry is TiO2metering concentrated sulfuric acid according to H2SO4The mass ratio is 1: 1.8-5;
B. Measuring and recording the concentration of the sulfuric acid solution;
C. then closing the pressure container, and pressurizing the interior of the pressure container according to the measured concentration of the sulfuric acid solution, wherein the pressurization standard is that the boiling point of the sulfuric acid solution in the pressure container is not lower than 140 ℃;
D. Heating a reaction system in the pressure container to boil, and keeping boiling for at least 30min to obtain an acid soluble solution;
E. Stopping heating, relieving pressure, cooling, adding metered water into the acid soluble solution to adjust the concentration, and then adding metered aluminum powder to reduce tetravalent titanium in the solution into trivalent titanium, thus obtaining the trivalent titanium solution.
2. the method for producing a trivalent titanium solution according to claim 1, characterized in that: in the step A, the metatitanic acid slurry is mixed with TiO2Metering concentrated sulfuric acid according to H2SO4the mass ratio is 1: 1.8-2.4.
3. The method for producing a trivalent titanium solution according to claim 1, characterized in that: in the step A, the metatitanic acid slurry is mixed with TiO2Metering concentrated sulfuric acid according to H2SO4The mass ratio is 1: 2.4-5.
4. The method for producing a trivalent titanium solution according to claim 1, characterized in that: in the step A, the metatitanic acid slurry is mixed with TiO2Metering concentrated sulfuric acid according to H2SO4the mass ratio is 1: 1.8.
5. The method for producing a trivalent titanium solution according to claim 1, characterized in that: in the step A, the metatitanic acid slurry is mixed with TiO2Metering concentrated sulfuric acid according to H2SO4The mass ratio is 1: 2.4.
6. The method of producing a trivalent titanium solution according to claim 4, characterized in that: the concentration of the metatitanic acid slurry washed in the step A is TiO2The concentration is 300g/L, the concentrated sulfuric acid is 98 acid, and the internal pressure of the pressure container is 0.35 MPa.
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| CN111392767A (en) * | 2020-04-22 | 2020-07-10 | 龙佰四川钛业有限公司 | Method for preparing trivalent titanium by hydrolyzing scale |
| CN115367788B (en) * | 2022-07-11 | 2023-11-21 | 云南国钛金属股份有限公司 | Method for preparing trivalent titanium aqueous solution at low cost |
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| DE4129308C2 (en) * | 1991-09-03 | 1994-07-07 | Metallgesellschaft Ag | Process for the preparation of a titanium (III) sulfate solution and its use |
| CN102616836A (en) * | 2012-03-31 | 2012-08-01 | 攀枝花东方钛业有限公司 | Preparation method of trivalent titanium solution |
| CN103708538A (en) * | 2013-12-20 | 2014-04-09 | 攀枝花东方钛业有限公司 | Preparation method of titanous solution |
| CN103723765A (en) * | 2014-01-20 | 2014-04-16 | 韶关学院 | Method for preparing titanium dioxide through sulfuric acid method |
| CN106745213A (en) * | 2017-01-10 | 2017-05-31 | 四川龙蟒钛业股份有限公司 | The preparation method of trivalent tiron |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4129308C2 (en) * | 1991-09-03 | 1994-07-07 | Metallgesellschaft Ag | Process for the preparation of a titanium (III) sulfate solution and its use |
| CN102616836A (en) * | 2012-03-31 | 2012-08-01 | 攀枝花东方钛业有限公司 | Preparation method of trivalent titanium solution |
| CN103708538A (en) * | 2013-12-20 | 2014-04-09 | 攀枝花东方钛业有限公司 | Preparation method of titanous solution |
| CN103723765A (en) * | 2014-01-20 | 2014-04-16 | 韶关学院 | Method for preparing titanium dioxide through sulfuric acid method |
| CN106745213A (en) * | 2017-01-10 | 2017-05-31 | 四川龙蟒钛业股份有限公司 | The preparation method of trivalent tiron |
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