CN114716162A - Method for removing magnesium and calcium from acid-soluble titanium slag - Google Patents
Method for removing magnesium and calcium from acid-soluble titanium slag Download PDFInfo
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- CN114716162A CN114716162A CN202210374634.8A CN202210374634A CN114716162A CN 114716162 A CN114716162 A CN 114716162A CN 202210374634 A CN202210374634 A CN 202210374634A CN 114716162 A CN114716162 A CN 114716162A
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000010936 titanium Substances 0.000 title claims abstract description 70
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 69
- 239000002893 slag Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000011575 calcium Substances 0.000 title claims abstract description 14
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 14
- 239000011777 magnesium Substances 0.000 title claims abstract description 14
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000002386 leaching Methods 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 22
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012065 filter cake Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 235000010215 titanium dioxide Nutrition 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 4
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 239000000292 calcium oxide Substances 0.000 claims description 12
- 239000000395 magnesium oxide Substances 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 229910021538 borax Inorganic materials 0.000 claims description 10
- 239000004328 sodium tetraborate Substances 0.000 claims description 10
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000498 cooling water Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 15
- 239000006104 solid solution Substances 0.000 abstract description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 11
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000002671 adjuvant Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a method for removing magnesium and calcium from acid-soluble titanium slag, belonging to the technical field of acid-soluble titanium slag; the method comprises the following steps: s1, mixing the acid-soluble titanium slag and the auxiliary agent, roasting and crushing; the using amount of the auxiliary agent is 5-25 wt% of that of the acid-soluble titanium slag; s2, performing pressure acid leaching on the mixture obtained in the step S1, an acid solution and water, wherein the mass ratio of the mixture to the acid solution to the water is 1:1-2.5: 2-5; and S3, carrying out suction filtration on the slurry obtained in the step S2, and carrying out liquid-solid separation to obtain a filter cake used for titanium white chloride or titanium sponge raw materials. The main impurity elements in the acid-soluble titanium slag are distributed in the form of solid solution, and the low-melting-point specific auxiliary agent is added into the titanium slag, so that the impurities which are difficult to be dissolved by acid can generate a new phase which is easy to be dissolved by acid to the maximum extent by matching with a proper raw material ratio at a medium-low temperature roasting temperature, thereby removing the impurities in the acid leaching process, effectively reducing the content of calcium and magnesium in the acid-soluble titanium slag, and improving the grade of the acid-soluble titanium slag.
Description
Technical Field
The invention relates to the technical field of acid-soluble titanium slag, in particular to a method for removing magnesium and calcium from acid-soluble titanium slag.
Background
Two mainstream methods for producing titanium dioxide in the world are a sulfuric acid method and a chlorination method, wherein the sulfuric acid method is widely applied to various countries in the world due to the universality of the sulfuric acid method on titanium ore raw materials since the world comes out, but the sulfuric acid method is inferior to the chlorination method in terms of environmental protection and product quality, and the chlorination method has the advantages of short flow, low acid consumption and energy consumption, less discharge of three wastes and the like.
With the rapid development of titanium white by chlorination process and titanium brocade industry, the demand of acid-soluble titanium slag is increased year by year, and the market prospect is very wide. The acid-soluble titanium slag is obtained by smelting reducing agents such as titanium concentrate, petroleum coke and the like in an electric furnace to remove Fe and Ti, selectively enriching Ti elements into slag, and then separating slag iron. The acid-soluble titanium slag has high content of Ca and Mg elements, and the phase of the acid-soluble titanium slag mainly consists of a titanium black solid solution and silicate minerals, and can not be directly used as a titanium white chloride raw material.
The method for improving the grade of the titanium slag (CN110482603A) applies a vacuum melting method, requires to control the vacuum degree to be-5-20 Pa and the smelting temperature to be 1400 ℃ and 1550 ℃, and has the advantages of harsh conditions, high equipment requirement, higher smelting temperature and high energy consumption.
In a method (CN101812595A) for producing artificial rutile from titanium slag, the taste of the titanium slag is improved through an alkali roasting-water washing-hydrochloric acid leaching process, after the titanium slag is mixed and roasted with alkali, a large amount of water is required to be added to wash the roasted titanium slag to be neutral, a large amount of waste water is generated, and titanium loss is caused when the hydrochloric acid solution is used for leaching and impurity removal.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for removing magnesium and calcium from acid-soluble titanium slag, which can solve the defects in the prior art, can convert the existing forms of magnesium and calcium in the biotite into structures which are easy to dissolve in acid at a lower roasting temperature, and can greatly reduce the loss of titanium because the titanium is converted into rutile titanium dioxide in the roasting process.
In order to solve the technical problems, the invention provides the following technical scheme:
the method for removing magnesium and calcium from acid-soluble titanium slag comprises the following steps:
s1, mixing the acid-soluble titanium slag and the auxiliary agent, roasting and crushing;
the using amount of the auxiliary agent is 5-25 wt% of that of the acid-soluble titanium slag; the auxiliary agent is at least one of diboron trioxide, boric acid and borax; the roasting conditions comprise: the roasting temperature is 750-;
s2, carrying out pressure acid leaching on the mixture obtained in the step S1, an acid solution and water, wherein the mass ratio of the mixture to the acid solution to the water is 1:1-2.5: 2-5; wherein the acid concentration of the acid in the acid solution is 10-30 wt% in the acid solution and water;
the conditions of the pressure acid leaching comprise: the acid leaching temperature is 160-200 ℃, the acid leaching time is 1-4h, the pressure is 0.4-0.6MPa, and the stirring speed is 400-500 r/min;
and S3, carrying out suction filtration on the slurry obtained in the step S2 for liquid-solid separation, washing and drying the obtained filter cake for titanium white chloride or titanium sponge raw materials, and optionally, carrying out pressure acid leaching on the obtained filtrate to obtain a part of water for recycling.
In some embodiments, the sum of the contents of CaO and MgO in the acid-soluble titanium slag is 6.50 wt% or more.
In some embodiments, the pulverization results in a mixture having a particle size of 300 to 800 mesh.
More preferably, the pulverization is carried out so that the particle size of the mixture is 400 to 600 meshes.
In some embodiments, the amount of the auxiliary agent is 5-25 wt% of the amount of the acid-soluble titanium slag.
In some embodiments, the adjuvant is diboron trioxide and/or borax.
In some embodiments, the conditions of the firing include: the roasting temperature is 750-950 ℃, and the roasting time is 1-3 h.
In some embodiments, the acid is at least one of sulfuric acid, hydrochloric acid, and nitric acid.
In some embodiments, the process of pressure acid leaching comprises:
adding the mixture, the acid solution and water into a pressurized reaction kettle, covering and screwing the mixture, tightly sealing the mixture, starting a stirring and stirring shaft to cool water, and starting a heating sleeve to heat the mixture to perform pressurized acid leaching; after the pressure acid leaching is finished, the heating sleeve is closed to heat, then the cooling water of the inner sleeve of the kettle is opened, when the temperature in the kettle is reduced to 50-80 ℃, the emptying pipe is opened to empty, and finally the kettle cover of the reaction kettle is opened to pour out the slurry.
In some embodiments, the method further comprises: and (4) after the filtrate is circulated for a plurality of times, removing impurities and concentrating, and then recovering the auxiliary agent.
More preferably, the impurity removing agent used for removing the impurities is ammonium carbonate or ammonia water.
The technical scheme of the invention has the following beneficial effects:
the main impurity elements in the acid-soluble titanium slag are distributed in the titanium black in the form of solid solution, and the low-melting-point specific auxiliary agent is added into the titanium slag at the medium-low temperature roasting temperature and in combination with the proper raw material ratio, so that the impurities which are difficult to be dissolved by acid can generate a new phase which is easy to be dissolved by acid to the maximum extent, thereby removing the impurities in the acid leaching process, effectively reducing the content of calcium and magnesium in the acid-soluble titanium slag and improving the grade of the acid-soluble titanium slag. The melting point of the selected auxiliary agent is low, the roasting phase inversion temperature is reduced, the process operation is simple, and the equipment investment is low.
The method has simple operation, less equipment investment and easy realization of industrialization; not only can reduce energy consumption, but also can recycle the roasting auxiliary agent.
According to the invention, nitric acid is preferably used as the acid for pressure acid leaching, and compared with other acids, the acid does not cause the loss of titanium in acid-soluble titanium slag, the impurity removal effect is obvious, and waste acid can be recycled.
Drawings
FIG. 1 is a flow chart of a specific process of the present invention.
Detailed Description
The invention provides a method for removing magnesium and calcium from acid-soluble titanium slag, which comprises the following steps:
s1, mixing the acid-soluble titanium slag and the auxiliary agent, roasting and crushing;
the using amount of the auxiliary agent is 5-25 wt% of that of the acid-soluble titanium slag; the auxiliary agent is at least one of diboron trioxide, boric acid and borax; the roasting conditions comprise: the roasting temperature is 750-1050 ℃, and the roasting time is 1-3 h;
s2, performing pressure acid leaching on the mixture obtained in the step S1, an acid solution and water, wherein the mass ratio of the mixture to the acid solution to the water is 1:1-2.5: 2-5; wherein the acid concentration of the acid in the acid solution is 10-30 wt% in the acid solution and water;
the pressure acid leaching conditions comprise: the acid leaching temperature is 160-200 ℃, the acid leaching time is 1-4h, the pressure is 0.4-0.6MPa, and the stirring speed is 400-500 r/min;
and S3, carrying out suction filtration on the slurry obtained in the step S2, carrying out liquid-solid separation, washing and drying the obtained filter cake for titanium white chloride or titanium sponge raw materials, and optionally, carrying out pressure acid leaching on the obtained filtrate to obtain a part of water for recycling.
The steps of the invention are mutually cooperated, so that the content of calcium and magnesium in the acid-soluble titanium slag can be effectively reduced, and the grade of the acid-soluble titanium slag is improved.
In some embodiments, the sum of the contents of CaO and MgO in the acid-soluble titanium slag is 6.50 wt% or more. After the acid-soluble titanium slag is treated by the method, the sum of CaO and MgO contents in the acid-soluble titanium slag can meet the standards of titanium white chloride and titanium sponge raw materials.
In a specific embodiment, the acid-soluble titanium slag used contains TiO269.88% of the total weight of the steel, 3.17% of CaO and 4.16% of MgO.
In some embodiments, the pulverizing is such that the particle size of the mixture is 300 to 800 mesh.
More preferably, the pulverization is carried out so that the particle size of the mixture is 400 to 600 meshes.
In some embodiments, the amount of the auxiliary agent is 5-25 wt% of the amount of the acid-soluble titanium slag. The optimal scheme is more beneficial to generating a new phase which is easy to dissolve by acid to the maximum extent during roasting, thereby being efficiently removed.
In some embodiments, the adjuvant is diboron trioxide and/or borax. The optimal scheme is more beneficial to generating a new phase which is easy to dissolve by acid to the maximum extent during roasting, thereby being efficiently removed.
In some embodiments, the conditions of the firing include: the roasting temperature is 750-950 ℃, and the roasting time is 1-3 h. The optimal scheme can enable calcium and magnesium to generate a new phase which is easy to dissolve by acid to the maximum extent at a low temperature in proper roasting, so that the new phase can be efficiently removed.
In some embodiments, the acid is at least one of sulfuric acid, hydrochloric acid, and nitric acid.
In some embodiments, the process of pressure acid leaching comprises:
adding the mixture, the acid solution and water into a pressurized reaction kettle, covering and screwing the mixture, tightly sealing the mixture, starting a stirring and stirring shaft to cool water, and starting a heating sleeve to heat the mixture to perform pressurized acid leaching; after the pressure acid leaching is finished, the heating sleeve is closed to heat, then the cooling water of the inner sleeve of the kettle is opened, when the temperature in the kettle is reduced to 50-80 ℃, the emptying pipe is opened to empty, and finally the kettle cover of the reaction kettle is opened to pour out the slurry.
In some embodiments, the method further comprises: and (4) after the filtrate is circulated for a plurality of times, removing impurities and concentrating, and then recovering the auxiliary agent.
More preferably, the impurity removing agent used for removing the impurities is ammonium carbonate or ammonia water.
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments. TiO in acid-soluble titanium slag in the following examples269.88% in content, 3.17% in content of CaO and 4.16% in content of MgO. The nitric acid used in the following examples was a 60 wt% strength industrial nitric acid solution.
Example 1
As shown in figure 1, 120g of acid-soluble titanium slag and 12g of borax are uniformly mixed, then are subjected to heat preservation at 800 ℃ for 2 hours, and then are cooled, crushed and sieved, and the particle size is 400-600 meshes, and the mixture is used for pressure acid leaching;
100g of the obtained mixture, 100g of nitric acid and 200g of water are respectively added into a 2L pressurized reaction kettle, a cover is added, the kettle is tightly screwed and sealed, a stirring bearing is sequentially opened to cool water, stir and heat a heating sleeve for heating, the temperature is slowly raised from room temperature, the reaction is carried out for 2 hours, the reaction temperature is 160 ℃, the pressure is 0.4MPa, the rotating speed is 500r/min, a coil pipe in the reaction kettle is opened to cool water after the reaction is finished, when the temperature in the kettle is reduced to 60-80 ℃, a drain opening is opened to empty, slurry is sequentially poured out for solid-liquid separation, a filter cake is washed with water, dried, ground and sieved, and then is analyzed and detected, and the content of calcium oxide and magnesium oxide in filter residues is 1.40%.
Example 2
Uniformly mixing 120g of acid-soluble titanium slag and 15g of borax, preserving heat for 2 hours at 850 ℃, cooling, crushing and screening for pressure acid leaching;
100g of the roasted acid-soluble titanium slag, 120g of nitric acid and 200g of water are respectively added into a 2L pressurized reaction kettle, a cover is added, the kettle is tightly screwed and sealed, a stirring bearing is sequentially opened to cool water, stir and a heating sleeve are sequentially heated, the temperature is slowly increased from room temperature, the reaction is carried out for 2 hours, the reaction temperature is 180 ℃, the pressure is 0.6MPa, the rotating speed is 500r/min, coil pipe cooling water in the reaction kettle is opened after the reaction is finished, when the temperature in the kettle is reduced to 60-80 ℃, a drain hole is opened to drain, slurry is sequentially poured out to carry out solid-liquid separation, a filter cake is washed with water, dried, ground and sieved, and then is analyzed and detected, and the content of calcium oxide and magnesium oxide in filter residues is 1.23%.
Example 3
Uniformly mixing 120g of acid-soluble titanium slag and 10g of boric acid, preserving heat for 3 hours at 750 ℃, cooling, crushing and screening for pressure acid leaching;
100g of the roasted acid-soluble titanium slag, 100g of nitric acid and 250g of water are respectively added into a 2L pressurized reaction kettle, a cover is added, the kettle is tightly screwed and sealed, a stirring bearing is sequentially opened to cool water, stir and a heating sleeve are sequentially heated, the temperature is slowly increased from room temperature, the reaction is carried out for 1.5 hours, the reaction temperature is 180 ℃, the pressure is 0.6MPa, the rotating speed is 500r/min, coil pipe cooling water in the reaction kettle is opened after the reaction is finished, when the temperature in the kettle is reduced to 60-80 ℃, a drain opening is opened to drain, slurry is sequentially poured out to carry out solid-liquid separation, a filter cake is washed with water, dried, ground and sieved, and then is analyzed and detected, and the content of calcium oxide and magnesium oxide in the filter cake is 0.98%.
Example 4
Uniformly mixing 120g of acid-soluble titanium slag and 20g of borax, preserving heat at 900 ℃ for 1 hour, cooling, crushing and screening for pressure acid leaching;
100g of the roasted acid-soluble titanium slag, 150g of nitric acid and 300g of water are respectively added into a 2L pressurized reaction kettle, a cover is added, the kettle is tightly screwed and sealed, a stirring bearing is sequentially opened to cool water, stir and a heating sleeve are sequentially heated, the temperature is slowly increased from room temperature, the reaction is carried out for 2 hours, the reaction temperature is 160 ℃, the pressure is 0.4MPa, the rotating speed is 500r/min, coil pipe cooling water in the reaction kettle is opened after the reaction is finished, when the temperature in the kettle is reduced to 60-80 ℃, a drain opening is opened to drain, slurry is sequentially poured out to carry out solid-liquid separation, a filter cake is washed with water, dried, ground and sieved, and then is analyzed and detected, and the content of calcium oxide and magnesium oxide in filter residues is 0.87%.
Example 5
Uniformly mixing 120g of acid-soluble titanium slag and 15g of boron trioxide, preserving the heat at 850 ℃ for 1.5 hours, cooling, crushing and sieving the mixture, and using the mixture for pressure acid leaching;
100g of the roasted acid-soluble titanium slag, 100g of nitric acid and 200g of water are respectively added into a 2L pressurized reaction kettle, a cover is added, the kettle is tightly screwed and sealed, a stirring bearing is sequentially opened to cool water, stir and a heating sleeve are sequentially heated, the temperature is slowly increased from room temperature, the reaction is carried out for 2 hours, the reaction temperature is 160 ℃, the pressure is 0.4MPa, the rotating speed is 500r/min, coil pipe cooling water in the reaction kettle is opened after the reaction is finished, when the temperature in the kettle is reduced to 60-80 ℃, a drain hole is opened to drain, slurry is sequentially poured out to carry out solid-liquid separation, a filter cake is washed with water, dried, ground and sieved, and then is analyzed and detected, and the content of calcium oxide and magnesium oxide in filter residues is 0.78%.
Example 6
Uniformly mixing 120g of acid-soluble titanium slag and 25g of borax, preserving heat at 950 ℃ for 1 hour, cooling, crushing and screening for pressure acid leaching;
100g of the roasted acid-soluble titanium slag, 150g of nitric acid and 200g of water are respectively added into a 2L pressurized reaction kettle, a cover is added, the kettle is tightly screwed and sealed, a stirring bearing is sequentially opened to cool water, stir and a heating sleeve are sequentially heated, the temperature is slowly increased from room temperature, the reaction is carried out for 2 hours, the reaction temperature is 180 ℃, the pressure is 0.6MPa, the rotating speed is 500r/min, coil pipe cooling water in the reaction kettle is opened after the reaction is finished, when the temperature in the kettle is reduced to 60-80 ℃, a drain opening is opened to drain, slurry is sequentially poured out to carry out solid-liquid separation, a filter cake is washed with water, dried, ground and sieved, and then is analyzed and detected, and the content of calcium oxide and magnesium oxide in filter residues is 0.65%.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The method for removing magnesium and calcium from acid-soluble titanium slag is characterized by comprising the following steps:
s1, mixing the acid-soluble titanium slag and the auxiliary agent, roasting and crushing;
the using amount of the auxiliary agent is 5-25 wt% of that of the acid-soluble titanium slag; the auxiliary agent is at least one of diboron trioxide, boric acid and borax; the roasting conditions comprise: the roasting temperature is 750-;
s2, performing pressure acid leaching on the mixture obtained in the step S1, an acid solution and water, wherein the mass ratio of the mixture to the acid solution to the water is 1:1-2.5: 2-5; wherein the acid concentration of the acid in the acid solution is 10-30 wt% in the acid solution and water;
the conditions of the pressure acid leaching comprise: the acid leaching temperature is 160-200 ℃, the acid leaching time is 1-4h, the pressure is 0.4-0.6MPa, and the stirring speed is 400-500 r/min;
and S3, carrying out suction filtration on the slurry obtained in the step S2, carrying out liquid-solid separation, washing and drying the obtained filter cake for titanium white chloride or titanium sponge raw materials, and optionally, carrying out pressure acid leaching on the obtained filtrate to obtain a part of water for recycling.
2. The method according to claim 1, characterized in that the sum of the contents of CaO and MgO in the acid-soluble titanium slag is 6.50 wt% or more.
3. The method according to claim 1, wherein the pulverization is carried out so that the particle size of the mixture is 300 to 800 mesh.
4. The method according to claim 3, wherein the pulverization is carried out so that the particle size of the mixture is 400 to 600 mesh.
5. The method according to claim 1, characterized in that the amount of the auxiliary agent is 5-25% of the amount of the acid-soluble titanium slag, and the auxiliary agent is boron trioxide and/or borax.
6. The method of claim 1, wherein the firing conditions include: the roasting temperature is 750-950 ℃, and the roasting time is 1-3 h.
7. The method of claim 1, wherein the acid in S2 is at least one of sulfuric acid, hydrochloric acid, and nitric acid.
8. The method according to claim 1, wherein the pressure acid leaching process in S2 comprises:
adding the mixture, the acid solution and water into a pressurized reaction kettle, covering and screwing the mixture, tightly sealing the mixture, starting a stirring and stirring shaft to cool water, and starting a heating sleeve to heat the mixture to perform pressurized acid leaching; after the pressure acid leaching is finished, the heating sleeve is closed to heat, then the cooling water of the inner sleeve of the kettle is opened, when the temperature in the kettle is reduced to 50-80 ℃, the emptying pipe is opened to empty, and finally the kettle cover of the reaction kettle is opened to pour out the slurry.
9. The method of claim 1, further comprising: and (4) after the filtrate is circulated for a plurality of times, removing impurities and concentrating, and then recovering the auxiliary agent.
10. The method according to claim 9, wherein the impurity removing agent used for impurity removal is ammonium carbonate or ammonia water.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1549915A1 (en) * | 1988-06-21 | 1990-03-15 | Ленинградский Государственный Научно-Исследовательский И Проектный Институт Основной Химической Промышленности | Method of purifying wet-process phosphoric acid from fluorine |
| CN103882241A (en) * | 2014-04-17 | 2014-06-25 | 攀枝花学院 | Method for preparing titanium-rich material from titanium-containing blast furnace slags by virtue of fusion treatment of boric acid |
| CN106048256A (en) * | 2016-06-30 | 2016-10-26 | 重庆大学 | Method for removing calcium and magnesium impurities in titanium slag by using modified additive |
| CN110396610A (en) * | 2019-07-29 | 2019-11-01 | 中国科学院过程工程研究所 | A kind of method of the processing of ammonium salt pressurized pyrolysis titanium mineral and metal silicate mineral |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1549915A1 (en) * | 1988-06-21 | 1990-03-15 | Ленинградский Государственный Научно-Исследовательский И Проектный Институт Основной Химической Промышленности | Method of purifying wet-process phosphoric acid from fluorine |
| CN103882241A (en) * | 2014-04-17 | 2014-06-25 | 攀枝花学院 | Method for preparing titanium-rich material from titanium-containing blast furnace slags by virtue of fusion treatment of boric acid |
| CN106048256A (en) * | 2016-06-30 | 2016-10-26 | 重庆大学 | Method for removing calcium and magnesium impurities in titanium slag by using modified additive |
| CN110396610A (en) * | 2019-07-29 | 2019-11-01 | 中国科学院过程工程研究所 | A kind of method of the processing of ammonium salt pressurized pyrolysis titanium mineral and metal silicate mineral |
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