CN112520786B - Acid-soluble titanium-rich material and preparation method and application thereof - Google Patents
Acid-soluble titanium-rich material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an acid-soluble titanium-rich material and a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, naturally cooling titanium slag generated after the smelting of the ore smelting electric furnace to 1100-800 ℃; s2, mixing the titanium slag with the temperature of 1100-; s3, after the sodium treatment reaction is ended, sequentially carrying out water washing, magnetic separation and gravity separation on the materials in the iron tank to obtain titanium-containing materials, wherein the magnetic separation is two-stage magnetic separation, the magnetic field intensity of one stage is 0.4T-0.8T, and the magnetic field intensity of the second stage is 1.3T-1.9T; s4, mixing the titanium-containing material obtained in the step S3 with dilute hydrochloric acid for acidification reaction to obtain TiO 2 Precipitating, adding a certain amount of fluorite in the process of acidification reaction, and adding ammonium chloride crystals at the later stage of acidification reaction. The invention solves the problem of the existing titanium-rich material TiO 2 Low grade and low acidolysis rate.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to an acid-soluble titanium-rich material and a preparation method and application thereof.
Background
Titanium-rich material in the broad sense means titanium dioxide (TiO) rich 2 ) The material of (3). The main raw materials used for producing titanium dioxide and titanium sponge are titanium-rich ores, titanium concentrate or titanium slag is generally adopted as the raw material for producing titanium dioxide by a sulfuric acid method, and titanium slag or artificial rutile is generally adopted as the raw material for producing titanium dioxide by a chlorination method and titanium sponge. Titanium-rich ores or slags such as titanium slag and synthetic rutile are generally referred to as titanium-rich materials, and such titanium-rich materials may be generally referred to as titanium-rich materials in a narrow sense. The titanium-rich material used in domestic industrial production is mainly titanium slag.
The mechanical beneficiation method can obtain high-grade titanium concentrate, but the content of calcium and magnesium impurities in the titanium concentrate is high, and the content of calcium and magnesium oxides is generally higher than 6%, so that the product quality is seriously influenced. Calcium in titanium concentrates exists as an impurity mineral or intergrowth, while magnesium exists primarily as a homomorphic substitution. In the acid-soluble titanium slag obtained by smelting the titanium concentrate, the content of calcium and magnesium oxides is usually higher than 9 percent, the production load of titanium white by a sulfuric acid method is increased seriously, and the quality of the titanium white is reduced.
Titanium-containing raw material used in production process of titanium dioxide by sulfuric acid method at home and abroad is existing TiO 2 Titanium concentrate with a content of about 47%, also TiO 2 Titanium slag (acid-soluble titanium slag for short) with the content of 72-76 percent, a mixture of titanium concentrate and titanium slag, and TiO of the acid-soluble titanium slag 2 The content of the titanium dioxide is generally not more than 76%, otherwise, the low-valence titanium generated by the high-temperature over-reduction of the electric furnace is difficult to carry out acidolysis. Titanium-containing raw material used in the production process of titanium dioxide and titanium sponge by chlorination process at home and abroad can only be TiO 2 High titanium slag (titanium chloride slag for short) with the content of more than 90 percent, otherwise, the impurity content in the titanium tetrachloride is too large, so that the product is unqualified, the equipment is blocked and the production is stopped, and simultaneously, a large amount of waste slag is generated. The cost of the artificial rutile is too high, the artificial rutile is produced by a fresh manufacturer, and the products are rarely adopted in the actual production. The hydrochloric acid method titanium white production is not industrialized at present because a suitable titanium-containing raw material is difficult to find.
The production of titanium dioxide by the sulfuric acid method adopts acid-soluble titanium slag as a raw material, is an environment-friendly choice and a development trend, and can greatly reduce the generation of ferrous sulfate and dilute waste sulfuric acid.
The existing acid-soluble titanium slag is usually produced by adopting an electric arc furnace to carry out high-temperature smelting. The raw material is titanium concentrate, and the reducing agent is anthracite or petroleum coke. The process flow comprises the following steps: mixing titanium concentrate and a reducing agent (such as coke) according to a certain proportion, briquetting, adding into a submerged arc furnace, carrying out melting reduction at a high temperature of about 1600-1700 ℃, reducing iron oxide in the titanium concentrate into elemental iron, wherein other metal oxides cannot be reduced, removing iron, and crushing to obtain TiO 2 72-76 percent of acid-soluble titanium slag, and simultaneously, casting molten iron into an iron ingot for steelmaking or cast iron product production.
TiO of the existing acid-soluble titanium slag 2 The grade is not high, the calcium and magnesium content is high, a certain amount of low-valence titanium is contained, the acidolysis rate is limited, so that more than 90% of concentrated sulfuric acid is required to complete acidolysis, the unit cost is high, and the enthusiasm of household slag of titanium white production plants is seriously influenced.
The prior patent (CN103359781A) firstly carries out sodium treatment reaction (titanium concentrate and sodium hydroxide are melted to generate titaniumSodium acid solid phase mixture), then washing, filtering, selecting and acidifying to obtain the titanium-rich material. Although the TiO content in the titanium-rich material is improved compared with the reduction method 2 Grade, but TiO 2 The grade is still not high, and the acidolysis rate is lower.
Thus, how to obtain a TiO 2 The titanium-rich material has higher grade, does not contain low-valent titanium (i.e. has higher acidolysis rate) and has more reasonable cost, and is eagerly expected by titanium dioxide manufacturers by a sulfuric acid process.
Disclosure of Invention
The invention aims to provide a preparation method of an acid-soluble titanium-rich material, which solves the problem of the existing titanium-rich material TiO 2 Low grade and low acidolysis rate.
In addition, the invention also provides the acid-soluble titanium-rich material produced by the preparation method and application thereof.
The invention is realized by the following technical scheme:
the preparation method of the acid-soluble titanium-rich material comprises the following steps:
s1, naturally cooling titanium slag generated after the smelting of the ore smelting electric furnace to 1100-800 ℃;
s2, mixing the titanium slag with the temperature of 1100-800 ℃ and solid caustic soda according to a certain proportion in an iron tank for sodium modification reaction, wherein the reaction time is 20-60min, and at the later stage of the reaction, adding NaCl solution into the iron tank and blowing air into the materials in the iron tank;
s3, after the sodium treatment reaction is ended, sequentially carrying out water washing, magnetic separation and gravity separation on the materials in the iron tank to obtain titanium-containing materials, wherein the magnetic separation is two-section magnetic separation, the magnetic field intensity of one section is 0.4T-0.8T, and the magnetic field intensity of the second section is 1.3T-1.9T;
s4, mixing the titanium-containing material obtained in the step S3 with dilute hydrochloric acid for acidification reaction to obtain TiO 2 Precipitating, adding a certain amount of fluorite in the process of acidification reaction, and adding ammonium chloride crystals at the later stage of acidification reaction;
s5, mixing the TiO obtained in the step S4 2 And (4) filtering, washing and press-filtering the precipitate by a plate-and-frame filter press to obtain the acid-soluble titanium-rich material.
And after the smelting of the ore-smelting electric furnace is finished each time, the titanium slag manufacturer stops the furnace, stops feeding and stops power transmission. Then, titanium slag is taken out from one outlet of the electric furnace, and molten iron is discharged from the other outlet of the electric furnace until all the slag and iron are discharged. The raw materials adopted by the invention are high-temperature molten titanium slag discharged from an electric furnace slag outlet of a manufacturer on site, and the temperature is about 1600 ℃.
The boiling point of NaOH is 1390 ℃ so as to avoid gasifying NaOH, therefore, the temperature of the sodium treatment reaction is required to be lower than 1390 ℃ and lower than 1390 ℃, the high-temperature titanium slag below 1390 ℃ can rapidly melt caustic soda into liquid, as long as the temperature is not lower than 350 ℃ (the melting point of NaOH is 318.4 ℃), NaOH can generate a series of chemical reactions with each component of the titanium slag, but in order to improve the conversion rate of titanium oxide, the temperature is more suitable to be controlled below 1100 ℃ (the melting point of sodium titanate is 1128 ℃, and the product is a solid phase which is beneficial to the forward and reverse reaction, at the moment, the product sodium titanate is a solid phase which is beneficial to improving the conversion rate of the sodium treatment reaction, and when the temperature is lower than 800 ℃, the reaction speed is slower, and longer reaction time is required.
In the later stage of sodium treatment reaction, NaCl solution is added into the iron pot, and air is blown into the materials in the iron pot to form Na solution + Ionic or molten Na + The ions and the rest components of the titanium slag generate a series of chemical reactions (the melting point of NaCl is 801 ℃), one purpose of adding NaCl in the later period is to further sodium-modify the incompletely-reacted components of the titanium slag, and the purpose is to recycle NaCl waste liquid generated in the subsequent process. The purpose of blowing air is to increase the oxygen content in the molten material, accelerate the forward reaction degree, further promote the reaction process of NaOH and NaCl and increase the low-valence titanium oxide Ti 2 O 3 Is converted into Na by sodium 2 TiO 3 Rate of (d) and conversion. If air is not blown, the reaction of the low-price titanium is slow, and the conversion rate is low, so that the production efficiency and the product quality are seriously influenced.
The NaOH reacts specifically as follows:
2NaOH(l)+TiO 2 (s)＝Na 2 TiO 3 (s)+H 2 O(g)
4NaOH(l)+Ti 2 O 3 (s)+1/2O 2 ＝2Na 2 TiO 3 (s)+2H 2 O(g)
na produced 2 TiO 3 (s) is insoluble in water.
SiO 2 、MnO、Al 2 O 3 、V 2 O 5 The oxides react with NaOH to generate Na respectively 2 SiO 3 、Na 2 MnO 4 、NaAlO 2 、NaVO 3 And soluble salts.
2NaOH(l)+SiO 2 (s)＝Na 2 SiO 3 (s)+H 2 O(g)
2NaOH(l)+MnO(s)+O 2 ＝Na 2 MnO 4 (s)+H 2 O(g)
2NaOH(l)+Al 2 O 3 (s)＝2NaAlO 2 (s)+H 2 O(g)
2NaOH(l)+V 2 O 5 (s)＝2NaVO 3 (s)+H 2 O(g)
FeO, Fe, CaO, MgO will not react with NaOH, will be inert, and will remain in the slag as a solid.
The specific reaction of NaCl is as follows:
2NaCl(l)+TiO 2 (s)+H 2 O＝Na 2 TiO 3 (s)+2HCl(g)
4NaCl(l)+Ti 2 O 3 (s)+2H 2 O+1/2O 2 ＝2Na 2 TiO 3 (s)+4HCl(g)
na produced 2 TiO 3 (s) is insoluble in water.
SiO 2 、MnO、Al 2 O 3 、V 2 O 5 Reacting the oxide with NaCl to generate Na respectively 2 SiO 3 、Na 2 MnO 4 、NaAlO 2 、NaVO 3 And soluble salts.
2NaCl(l)+SiO 2 (s)+H 2 O＝Na 2 SiO 3 (s)+2HCl(g)
2NaCl(l)+MnO(s)+H 2 O+O 2 ＝Na 2 MnO 4 (s)+2HCl(g)
2NaCl(l)+Al 2 O 3 (s)+H 2 O＝2NaAlO 2 (s)+2HCl(g)
2NaCl(l)+V 2 O 5 (s)+H 2 O＝2NaVO 3 (s)+2HCl(g)
FeO, Fe, CaO, MgO will not react with NaCl, will be inert and will remain in the slag as a solid.
Stirring is continuously carried out in the reaction process, the time of the melting reaction is controlled to be 20-60min, and the higher the temperature is, the shorter the required reaction time is.
After the sodium treatment reaction is finished, adding water into the iron tank, repeatedly washing the materials with water to remove Na 2 SiO 3 、Na 2 MnO 4 、NaAlO 2 、NaVO 3 Isocratic salts, the remaining solid material comprising the following components: na (Na) 2 TiO 3 FeO, Fe, CaO, MgO, wherein most of the components are Na 2 TiO 3 A small part is FeO and MgO, and the others are very little.
Wherein, Na 2 TiO 3 In the form of hydrated sodium titanate. Na (Na) 2 TiO 3 By washing with water, Na therein + Ions and H in water + Ion exchange reaction of the ions, part of Na + The ions are leached into the liquid phase to form an alkali liquor, leaving a solid phase of hydrated sodium titanate, the reaction equation is as follows:
2Na 2 TiO 3 (s)+2H 2 O(l)＝Na 2 O·2TiO 2 ·H 2 O(s)+2NaOH(l)
the NaOH generated in the process can be returned to the iron tank for recycling.
Then the solid phase is subjected to conventional wet magnetic separation and reselection to remove most FeO and MgO and obtain Na 2 O·2TiO 2 ·H 2 A titaniferous material having an extremely high content of O(s).
Wherein, the magnetic separation is two-section magnetic separation, the magnetic field intensity of one section is 0.4T-0.8T, preferably 0.6T-0.7T, and the magnetic field intensity of the second section is 1.3T-1.9T, preferably 1.4T-1.7T. The solid phase after the sodium treatment reaction contains some simple substance iron powder and a small amount of unreduced Fe besides FeO 2 O 3 The iron oxides are combined with other metal oxides, such as magnetite, titanomagnetite, ferrotite, hematite, calciumThe titanium ore exists in the form of phases. The reason why the weak magnetic separation is adopted at the first stage and the strong magnetic separation is adopted at the second stage is that when strong magnetic minerals such as magnetite, semi-false hematite and the like with strong magnetism are removed, the magnetic blockage of the separation gap of the strong magnetic separator is avoided, the smooth running of the strong magnetic separation is ensured, and meanwhile, a large amount of strong magnetic minerals such as magnetite are abandoned by adopting the weak magnetic separation process, so that the minerals entering the strong magnetic separation are greatly reduced. The magnetic field of the strong magnetic separator is generally more than 1T, and the minimum residual magnetic field is 0.05T, so that the strong magnetic separator can sufficiently absorb magnetite, iron powder and the like. In addition, weakly magnetic iron ores such as hematite ore, including magnetite, semi-pseudohematite ore and the like which are more or less always strongly magnetic, and iron powder obtained by grinding steel balls added in ore grinding are more strongly magnetic. Therefore, even in a strong magnetic dumping zone, it is difficult to completely dump, and magnetic clogging of the ferromagnetic sorting medium is caused. The two-stage magnetic separation with reasonable strength has the advantages of removing iron-containing materials to the maximum extent, ensuring smooth operation of the magnetic separation process, improving the operation efficiency of the magnetic separator and reducing the power consumption.
A small amount of fluorite is added during the acidification reaction to remove SiO which is not yet fully sodium-modified 2 Can obtain the catalyst mainly containing TiO 2 The solid-liquid mixture of (1).
The main reaction of the acidification reaction is as follows:
Na 2 O·2TiO 2 ·H 2 O(s)+2HCl(l)＝2TiO 2 (s)+2NaCl+2H 2 O
the NaCl produced here can be returned to the iron tank for recycling.
The side reaction is as follows:
FeO+2HCl＝FeCl 2 +H 2 O
CaO+2HCl＝CaCl 2 +H 2 O
MgO+2HCl＝MgCl 2 +H 2 O
MgO in the titaniferous material is very soluble in dilute acid, so most of the MgO can be removed. Because the MgO content in the high-calcium magnesium titanium slag is up to more than 6 percent, a small amount of MgO still exists in the titanium-containing material, and in order to remove the MgO more thoroughly, a small amount of ammonium chloride crystals are added into the waste hydrochloric acid at the later stage of the acidification reaction, and the ammonium chloride crystals and the MgO reactThe ammonia gas generated by the reaction is easy to volatilize, and MgO can be removed more completely than dilute hydrochloric acid. NH (NH) 4 The mass fraction of Cl in the hydrochloric acid solution is preferably 0.8% to 1.3%.
Due to SiO in the titanium slag 2 Compared with MnO and Al 2 O 3 、V 2 O 5 Much higher, there will be a small amount of SiO 2 Na cannot be generated 2 SiO 3 Therefore, removal must be managed. Adding a small amount of fluorite (calcium fluoride CaF as main component) into waste hydrochloric acid 2 ) Then, a small amount of hydrofluoric acid is generated, and the reaction equation is as follows:
CaF 2 +2HCl＝CaCl 2 +2HF
hydrofluoric acid can react with silicon dioxide to form gaseous silicon tetrafluoride, the reaction equation being as follows:
SiO 2 (s)+4HF(aq)＝SiF 4 (g)↑+2H 2 O(l)
generated SiF 4 Can continuously react with excessive HF to generate fluosilicic acid, thereby removing solid TiO 2 SiO in(s) 2 The reaction equation is as follows:
SiF 4 (g)+2HF(aq)＝H 2 [SiF 6 ](aq)
then removing soluble NaCl and FeCl by conventional filtration, water washing and pressure filtration of a plate-and-frame filter press 2 、CaCl 2 、MgCl 2 、H 2 After O, the obtained near-solid titanium-rich material mainly contains TiO 2 And also contains small amounts of impurities such as FeO, CaO, MgO, etc.
Compared with the common acid-soluble titanium slag, the acid-soluble titanium-rich material prepared by the method has the advantages that TiO 2 The grade is obviously improved, and the titanium dioxide Ti with low valence is not contained 2 O 3 TiO in acid-soluble titanium-rich material 2 The grade is more than 98 percent, the acidolysis rate of the acid-soluble titanium-rich material is more than 99 percent, and the problem of the existing titanium-rich material TiO is solved 2 Low grade and low acidolysis rate.
Further, in step S1, the titanium slag is placed in a slag pot, and a refractory lining is disposed in the slag pot.
The refractory lining can prevent 1600 ℃ high temperature from softening the tank wall.
Further, in step S2, the reaction time is 30-40 min.
Further, in step S2, the molar amount of the solid caustic soda is TiO in the titanium slag 2 、SiO 2 、MnO、Al 2 O 3 And V 2 O 5 1.8 times of the sum of the molar weight and Ti in the titanium slag 2 O 3 3.6 times the molar weight.
The dosage of the solid caustic soda influences the TiO in the prepared acid-soluble titanium-rich material 2 And (4) grade.
Further, in step S2, the molar amount of the NaCl solution is TiO in the titanium slag 2 、SiO 2 、MnO、Al 2 O 3 And V 2 O 5 0.2 times of the sum of the molar weight and Ti in the titanium slag 2 O 3 0.4 times the sum of the molar amounts, the molar amount of the NaCl solution being calculated as NaCl.
Further, in step S3, the first stage magnetic field strength is 0.6T to 0.7T, and the second stage magnetic field strength is 1.4T to 1.7T.
Further, in step S4, dilute hydrochloric acid is adopted to produce a byproduct of dilute waste hydrochloric acid by a chlorination method, the addition amount of the dilute waste hydrochloric acid is 2.1 times of the molar amount of the titanium-containing material sodium titanate hydrate, and the concentration of the dilute waste hydrochloric acid is 16% -20% by HCl; the addition amount of fluorite is SiO in the titanium slag 2 The molar weight is 0.5 times, the addition amount of ammonium chloride crystals is 0.8-1.3% of the mass fraction of the dilute waste hydrochloric acid, and the mass fraction of the dilute waste hydrochloric acid is calculated by HCl.
The dilute waste hydrochloric acid by-product of the chlorination process is diluted to below 20 percent for use. The reaction time is 40-100 min, preferably 60-70 min, the time is too short, the curing is insufficient, the yield is affected, the time is too long, and the production efficiency is reduced. The concentration (omega) of the dilute hydrochloric acid is 10-20%, preferably 16-20%, and if the concentration is too low, the acidification reaction efficiency is reduced, the reaction time is prolonged, and the conversion rate of titanium is influenced. The concentration of over 20 percent becomes concentrated hydrochloric acid, and the concentrated hydrochloric acid can generate strong volatilization to form smoke and worsen the production environment.
Further, the NaOH solution generated by washing in the step S3 is concentrated and crystallized by using the heat generated by naturally cooling the titanium slag, so as to obtain solid caustic soda crystals; and S4, concentrating and crystallizing the NaCl solution generated by the acidification reaction by using heat generated by natural cooling of the titanium slag to obtain solid NaCl crystals.
Namely, NaOH solution generated by washing is conveyed into a concentration tank through a pipeline, the concentration tank is positioned above a titanium slag tank, the concentration tank is heated by utilizing heat emitted in the high-temperature titanium slag cooling process, water in the NaOH solution is evaporated, the proper temperature is controlled, solid NaOH crystals are formed, and the solid NaOH crystals are returned to the titanium slag iron tank for reuse.
Namely, NaCl solution generated by acidification reaction is conveyed into a concentration tank through a pipeline, the concentration tank is positioned above a titanium slag tank, the concentration tank is heated by utilizing heat emitted in the high-temperature titanium slag cooling process, the proper temperature is controlled, water in the NaCl solution is evaporated, solid NaCl crystals are formed, and the solid NaCl crystals are returned to the titanium slag iron tank for recycling.
An acid-soluble titanium-rich material, wherein TiO in the acid-soluble titanium-rich material 2 The grade is more than 98 percent, and the acidolysis rate of the acid-soluble titanium-rich material is more than 99 percent.
The acid-soluble titanium-rich material is used for producing titanium dioxide by a sulfuric acid method.
When the acid-soluble titanium-rich material is used as a titanium source for titanium dioxide production by a sulfuric acid method, the sulfuric acid consumption of a unit titanium dioxide product is obviously reduced, the acidolysis rate is obviously improved, acidolysis slag is obviously reduced, the impurity source in the titanium dioxide product is obviously reduced, the sulfuric acid with medium concentration can be used as the acidolysis acid, and the discharge of dilute waste sulfuric acid is greatly reduced.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. compared with the common acid-soluble titanium slag, the acid-soluble titanium-rich material prepared by the method of the invention has the advantages that TiO is firstly dissolved 2 The grade is obviously improved, and the titanium dioxide Ti with low valence is not contained 2 O 3 TiO in acid-soluble titanium-rich material 2 The grade is more than 98 percent, and the acidolysis rate of the acid-soluble titanium-rich material is more than 99 percent.
2. When the acid-soluble titanium-rich material prepared by the method is used as a titanium source for titanium white production by a sulfuric acid method, the sulfuric acid consumption of a unit titanium white product is obviously reduced, the acidolysis rate is obviously improved, acidolysis slag is obviously reduced, the impurity source in the titanium white product is obviously reduced, the sulfuric acid with medium concentration can be used as the acid for acidolysis, and the emission of dilute waste sulfuric acid is greatly reduced.
3. The invention effectively utilizes the latent heat of the high-temperature titanium slag of the electric furnace and effectively recycles the dilute waste hydrochloric acid of the chlorination process.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
Example 1:
the preparation method of the acid-soluble titanium-rich material comprises the following steps:
s1, collecting 1kg of high-temperature 1500 ℃ molten acid-soluble titanium slag from a slag outlet of a titanium slag electric furnace in the stable production of a Panzhihua titanium slag factory, placing the titanium slag in a slag tank lined with a high-temperature refractory material, naturally cooling to 1100 ℃ in the slag tank, and placing 777.2g of flake caustic soda in an iron tank with an iron inner surface;
the chemical composition (%) of the titanium slag is shown in Table 1:
TABLE 1
S2, pouring all the titanium slag with the temperature of 1100 ℃ into an iron tank for carrying out sodium treatment reaction, continuously stirring, keeping the reaction for 20min, then adding 126g of NaCl crystals into the iron tank, blowing air into the materials in the iron tank, and continuing the reaction for 15 min;
s3, after the sodium treatment reaction is ended, adding water into the iron tank, repeatedly washing the materials with water until the water washing liquid is neutral, and filtering to obtain a solid mixture; and then carrying out second-stage magnetic separation and gravity separation on the mixture to remove impurities, wherein the first-stage magnetic field intensity is 0.6T, and the second-stage magnetic field intensity is 1.5T. Obtaining a titanium-containing material, and placing the titanium-containing material in a ceramic container;
and (3) conveying the washed NaOH solution into a concentration tank, wherein the concentration tank is positioned above the titanium slag tank, heating the concentration tank by utilizing heat emitted in the high-temperature titanium slag cooling process, evaporating water in the NaOH solution, controlling a proper temperature at a NaOH crystallization point to form solid NaOH crystals, and returning the solid NaOH crystals to the titanium slag iron tank for reuse. The amount used repeatedly was contained in 777.2g of the above flake caustic soda.
S4, adding 2085g of dilute waste hydrochloric acid with the concentration of 18% (omega) by-product of the chlorination process and 9g of fluorite powder (in the form of CaF) into the ceramic container containing the titanium-containing material 2 Metering), keeping normal temperature (10-35 ℃), continuously stirring for 60min, and adding 3.7g of ammonium chloride crystals 20min before the reaction is finished;
and (3) sending the acidified NaCl solution to a concentration tank, wherein the concentration tank is positioned above the titanium slag tank, heating the concentration tank by using heat emitted in the high-temperature titanium slag cooling process, evaporating water in the NaCl solution, controlling proper temperature at a NaCl crystallization point to form solid NaCl crystals, and returning the solid NaCl crystals to the titanium slag iron tank for reuse. The circulated amount was contained in the above 126g of NaCl crystals.
S5, mixing the TiO obtained in the step S4 2 And (4) filtering, washing and press-filtering the precipitate by a plate-and-frame filter press to obtain the acid-soluble titanium-rich material.
The acid-soluble titanium-rich material product prepared in the embodiment is dried and detected to obtain TiO 2 Grade of 98.8%, acidolysis rate of 99.6%, and low-valence Ti 2 O 3 The content is "micro".
TiO 2 The grade measurement method comprises the following steps:
ammonium thiocyanate indicator was obtained by dissolving 24.5g of ammonium thiocyanate in 80mL of hot water, filtering, cooling to room temperature and diluting to 100mL, storing in a closed dark bottle. 30g of ammonium ferric sulfate is weighed into a 1000mL single-scale volumetric flask and dissolved in 300mL of water containing 15mL of sulfuric acid. Potassium permanganate solution was added dropwise until the solution was pink. Dilute to mark with water and shake well. Weighing 190mg-210mg of titanium dioxide standard reference substance dried to constant weight at 105 ℃ and calibrating the solution according to the steps. The titanium dioxide equivalent weight of the solution, T1, was calculated using the formula below and expressed as 2 grams of equivalent TiO per ml:
wherein m1 is the mass of the titanium dioxide standard reference substance in grams (g); omega (TiO2), the titanium dioxide content of a standard reference substance, expressed as a mass fraction; v1 titration consumed volume of standard solution of ferric ammonium sulfate in milliliters (mL).
The method for measuring the acidolysis rate is as follows:
placing acid-soluble titanium-rich material in an acidolysis tank, and adding 10.8mol of sulfuric acid (H) 2 SO 4 Metering), carrying out acidolysis reaction, wherein the concentration of sulfuric acid is 75% (omega), the reaction temperature is 75 ℃, and the reaction time is 30 min.
After the reaction is finished, sequentially measuring the total titanium in the titanium liquid and the total titanium in the titanium-rich material product, and according to a formula: the acidolysis rate was calculated as (total titanium in solution)/(total titanium in mineral powder) × 100, and the obtained acidolysis rate was 99.8%.
Example 2:
the present example is based on example 1, and differs from example 1 in that:
the temperature of the titanium slag during the sodium treatment is 800 ℃.
The acid-soluble titanium-rich material product prepared in the embodiment is dried and then detected, and TiO 2 Grade of 98.3 percent, acidolysis rate of 99.7 percent and low-valent titanium Ti 2 O 3 The content is "micro".
Example 3:
this example is based on example 1, and differs from example 1 in that:
the temperature of the titanium slag during the sodium treatment is 1000 ℃.
The acid-soluble titanium-rich material product prepared in the embodiment is dried and then detected, and TiO 2 Grade of 98.7 percent, acidolysis rate of 99.8 percent and low-valent titanium Ti 2 O 3 The content is "micro".
Example 4:
the present example is based on example 1, and differs from example 1 in that:
the magnetic field intensity of the first section is 0.7T, and the magnetic field intensity of the second section is 1.7T.
For the acid solubility prepared in this exampleDrying the titanium-rich material product and detecting the dried product to obtain TiO 2 Grade of 98.7 percent, acidolysis rate of 99.7 percent and low-valent titanium Ti 2 O 3 The content is "micro".
Example 5:
this example is based on example 1, and differs from example 1 in that:
the magnetic field intensity of the first section is 0.5T, and the magnetic field intensity of the second section is 1.4T.
The acid-soluble titanium-rich material product prepared in the embodiment is dried and detected to obtain TiO 2 Grade of 98.3 percent, acidolysis rate of 99.6 percent and low-valence Ti 2 O 3 The content is "micro".
Example 6:
this example is based on example 1, and differs from example 1 in that:
in step S4, the concentration of the dilute by-product hydrochloric acid produced by the chlorination process used is 16% (ω).
The acid-soluble titanium-rich material product prepared in the embodiment is dried and then detected, and TiO 2 Grade of 98.5 percent, acidolysis rate of 99.5 percent and low-valent titanium Ti 2 O 3 The content is "trace".
Example 7:
this example is based on example 1, and differs from example 1 in that:
in step S4, the concentration of the dilute by-product hydrochloric acid produced by the chlorination process used is 20% (ω).
The acid-soluble titanium-rich material product prepared in the embodiment is dried and then detected, and TiO 2 Grade of 98.9%, acidolysis rate of 99.7%, and low-valence Ti 2 O 3 The content is "micro".
Comparative example 1:
this comparative example is based on example 1 and differs from example 1 in that:
the temperature of the titanium slag during the sodium treatment is 1350 ℃.
The acid-soluble titanium-rich material product prepared by the comparative example is dried and detected, and TiO 2 The grade is 92.1 percent, and the acidolysis rate is 94.2 percent.
In this comparative example, the molten titanium slag temperature was 135 deg.CThe temperature of 0 ℃ is higher than the boiling point of caustic soda, so that the caustic soda is gasified, the caustic soda amount is insufficient, the sodium treatment reaction is insufficient, and the titanium-rich material product TiO is influenced 2 The grade also promotes the increase of the content of low-valence titanium.
Comparative example 2:
this comparative example is based on example 1 and differs from example 1 in that:
the temperature of the titanium slag is 600 ℃ during the sodium treatment reaction.
The acid-soluble titanium-rich material product prepared by the comparative example is dried and detected, and TiO 2 The grade is 95.1 percent, and the acidolysis rate is 96.3 percent.
In the comparative example, the temperature of the molten titanium slag was 600 ℃, the temperature was too low, and TiO was not added for a prolonged period of time 2 The grade and the acidolysis rate are both reduced.
Comparative example 3:
this comparative example is based on example 1 and differs from example 1 in that:
s4, adding 1985g of 16% (omega) chlorination process byproduct dilute waste hydrochloric acid and 9g of fluorite powder (CaF) into the ceramic container containing the titanium-containing material 2 Measured) is kept at normal temperature (10-35 ℃), stirring is continuously carried out for 30min, and 3.7g of ammonium chloride crystals are added 20min before the reaction is finished. Then carrying out conventional filtration, water washing and filter pressing by a plate-and-frame filter press to obtain a titanium-rich material product
The acid-soluble titanium-rich material product prepared by the comparative example is dried and detected, and TiO 2 The grade is 94.5 percent, and the acidolysis rate is 95.2 percent.
In this comparative example, when 1985g of dilute hydrochloric acid, i.e., the ready-to-use amount was insufficient, the concentration was reduced to 16% (ω), and the stirring time was insufficient, TiO was affected 2 And increase the impurity content.
Comparative example 4:
this comparative example is based on example 1 and differs from example 1 in that:
the magnetic field intensity of the first section is 0.3T, and the magnetic field intensity of the second section is 1.1T.
The acid-soluble titanium-rich material product prepared by the comparative example is dried and detected, and TiO 2 The grade is 94.7 percent, and the acidolysis rate is 94.9 percent。
In the comparative example, the strength of the first-stage magnetic field and the second-stage magnetic field is lower than that of the invention, so that weak magnetic separation can not remove strong magnetic minerals, strong magnetic separation can not remove weak magnetic minerals, the content of iron oxide and magnesium oxide is obviously increased, and TiO is seriously influenced 2 And (4) grade.
Comparative example 5:
this comparative example is based on example 1 and differs from example 1 in that:
the magnetic field intensity of the first section is 0.9T, and the magnetic field intensity of the second section is 2.0T.
The acid-soluble titanium-rich material product prepared by the comparative example is dried and detected, and TiO 2 The grade is 95.6 percent, and the acidolysis rate is 95.3 percent.
In the comparative example, the strength of the first-stage magnetic field and the second-stage magnetic field is higher than that of the invention, so that the field intensity is too high during weak magnetic separation to cause weak magnetic minerals to block gaps of the magnetic separator, and the weak magnetic minerals which are adsorbed too much during strong magnetic separation are mixed in an operation area of the magnetic separator, thereby obviously reducing the removal effect of oxides such as iron, magnesium and the like.
Comparative example 6:
this comparative example is based on example 1 and differs from example 1 in that:
magnetic separation is not segmented, and the magnetic field intensity is 1.5T.
The acid-soluble titanium-rich material product prepared by the comparative example is dried and detected, and TiO 2 The grade is 95.4 percent, and the acidolysis rate is 94.8 percent.
In the comparative example, the magnetic separation is not segmented, and the iron-containing material has no two-segment magnetic separation and good removal effect, so that the TiO of the titanium-rich material product 2 The grade is reduced.
Comparative example 7:
this comparative example is based on example 1 and differs from example 1 in that:
in step S2, air is not blown.
The acid-soluble titanium-rich material product prepared by the comparative example is dried and detected, and TiO 2 The grade is 95.3 percent, and the valence of Ti is low 2 O 3 The content of the acid was 1.73%, and the acid hydrolysis rate was 97.9%.
In this comparative exampleWhen NaOH and NaCl are molten and reacted with low-valence titanium, air is not blown in, so that the conversion rate and conversion rate of the low-valence titanium are reduced, and TiO in the titanium-rich material product is caused 2 The grade is reduced, and the content of low-valence titanium is increased.
Comparative example 8:
this comparative example is based on example 1 and differs from example 1 in that:
in step S4, the concentration of the dilute by-product hydrochloric acid produced by the chlorination process used is 14% (ω).
The acid-soluble titanium-rich material product prepared by the comparative example is dried and detected, and TiO 2 The grade is 96.4 percent, and the acidolysis rate is 97.7 percent.
In this comparative example, the concentration of dilute spent hydrochloric acid was lower than in the present invention, and the reaction was not sufficient and the sodium titanate was not completely converted to TiO without changing the acidification time 2 The impurity content increases.
Comparative example 9:
this comparative example is based on example 1 and differs from example 1 in that:
in step S4, the concentration of the dilute by-product hydrochloric acid produced by the chlorination process used is 24% (ω).
The acid-soluble titanium-rich material product prepared by the comparative example is dried and detected, and TiO 2 The grade is 96.3 percent, and the acidolysis rate is 97.8 percent.
In this comparative example, the concentration of dilute spent hydrochloric acid was higher than that of the present invention, causing a large amount of concentrated hydrochloric acid to be volatilized, resulting in insufficient molar amount of effective HCl to participate in the reaction, and incomplete conversion of sodium titanate to TiO 2 The content of impurities increases and the environment is also deteriorated.
Comparative example 10:
this comparative example is based on example 1 and differs from example 1 in that:
in step S4, no fluorite powder is added.
The acid-soluble titanium-rich material product prepared by the comparative example is dried and detected, and TiO 2 The grade is 94.9 percent, and the acidolysis rate is 96.3 percent.
Comparative example 11:
this comparative example is based on example 1 and differs from example 1 in that:
in step S4, no ammonium chloride crystals are added.
The acid-soluble titanium-rich material product prepared by the comparative example is dried and detected, and TiO 2 The grade is 95.1 percent, and the acidolysis rate is 96.1 percent.
Comparative example 12:
this comparative example is based on example 1 and differs from example 1 in that:
in step S4, fluorite powder and ammonium chloride crystals are not added at the same time.
The acid-soluble titanium-rich material product prepared by the comparative example is dried and detected, and TiO 2 The grade was 93.2%, and the acid hydrolysis rate was 94.4%.
Comparative example 13:
1kg of high-temperature 1500 ℃ molten acid-soluble titanium slag is collected on site from a slag outlet of a titanium slag electric furnace in stable production in a steel and titanium smelting plant, placed in a slag tank lined with a high-temperature refractory material and cooled to room temperature for later use. Then 14.3mol of sulfuric acid (as H) are added 2 SO 4 Calculated), acid hydrolysis reaction is carried out, the concentration of sulfuric acid is 92 percent (omega), the reaction temperature is 75 ℃, and the reaction time is 30 min.
After the reaction is finished, sequentially measuring the total titanium in the titanium liquid and the total titanium in the titanium-rich material product, and according to a formula: the acidolysis rate was calculated as (total titanium in solution)/(total titanium in mineral powder) × 100, and the obtained acidolysis rate was 92.8%.
In the comparative example, the acid-soluble titanium slag product produced in a factory was used, and even if concentrated sulfuric acid having a high concentration was used for the acid hydrolysis, the acid hydrolysis rate was not high due to the presence of a large amount of low-valent titanium.
Comparative example 14:
1kg of molten acid-soluble titanium slag with high temperature of 1500 ℃ is collected on site from a slag outlet of a titanium slag electric furnace during stable production in a Panzhi smelting plant, placed in a slag pot lined with a high-temperature refractory material and cooled to room temperature for later use. Then 14.3mol of sulfuric acid (as H) are added 2 SO 4 Metering), carrying out acidolysis reaction, wherein the concentration of sulfuric acid is 75% (omega), the reaction temperature is 75 ℃, and the reaction time is 30 min.
After the reaction is finished, sequentially measuring the total titanium in the titanium liquid and the total titanium in the titanium-rich material product, and according to a formula: the acid hydrolysis ratio was calculated as (total titanium in solution)/(total titanium in ore powder) × 100, and the acid hydrolysis ratio was 79.4%.
This experiment shows that when titanium white is produced using acid-soluble titanium slag products produced in a factory, the acidolysis rate is significantly reduced due to the presence of a large amount of low-valent titanium when acidolysis is performed using sulfuric acid having a concentration equal to that of example 1.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The preparation method of the acid-soluble titanium-rich material is characterized by comprising the following steps:
s1, naturally cooling titanium slag generated after the smelting of the ore smelting electric furnace to 800-1100 ℃;
s2, mixing the titanium slag with the temperature of 800-;
s3, after the sodium treatment reaction is ended, sequentially carrying out water washing, magnetic separation and gravity separation on the materials in the iron tank to obtain titanium-containing materials, wherein the magnetic separation is two-section magnetic separation, the magnetic field intensity of one section is 0.4T-0.8T, and the magnetic field intensity of the second section is 1.3T-1.9T;
s4, mixing the titanium-containing material obtained in the step S3 with dilute hydrochloric acid for acidification reaction to obtain TiO 2 Precipitating, adding a certain amount of fluorite in the process of acidification reaction, and adding ammonium chloride crystals at the later stage of acidification reaction;
s5, mixing the TiO obtained in the step S4 2 Filtering, washing and filter-pressing by a plate-and-frame filter press to obtain an acid-soluble titanium-rich material;
in step S4, dilute saltThe acid adopts a chlorination method to produce a byproduct of dilute waste hydrochloric acid, the addition amount of the dilute waste hydrochloric acid is 2.1 times of the molar amount of the titanium-containing material sodium titanate hydrate, and the concentration of the dilute waste hydrochloric acid is 16-20% in terms of HCl; the addition amount of fluorite is SiO in the titanium slag 2 The molar weight is 0.5 times, the addition amount of ammonium chloride crystals is 0.8-1.3% of the mass fraction of the dilute waste hydrochloric acid, and the mass fraction of the dilute waste hydrochloric acid is calculated by HCl.
2. The method for preparing the acid-soluble titanium-rich material as claimed in claim 1, wherein in step S1, the titanium slag is placed in a slag pot, and a refractory lining is disposed in the slag pot.
3. The method for preparing the acid-soluble titanium-rich material as claimed in claim 1, wherein the reaction time in step S2 is 30-40 min.
4. The method of claim 1, wherein in step S2, the molar amount of the solid caustic soda is TiO in the titanium slag 2 、SiO 2 、MnO、Al 2 O 3 And V 2 O 5 1.8 times of the sum of the molar weight and Ti in the titanium slag 2 O 3 3.6 times the sum of the molar weight.
5. The method of claim 1, wherein in step S2, the molar amount of NaCl solution is TiO in the titanium slag 2 、SiO 2 、MnO、Al 2 O 3 And V 2 O 5 The sum of the molar weight of the titanium slag and the Ti in the titanium slag is 0.2 time 2 O 3 0.4 times of the total molar amount, the molar amount of the NaCl solution being calculated as NaCl.
6. The method of claim 1, wherein in step S3, the first magnetic field strength is 0.6T-0.7T, and the second magnetic field strength is 1.4T-1.7T.
7. The method for preparing the acid-soluble titanium-rich material as claimed in claim 1, wherein the NaOH solution generated by washing in step S3 is concentrated and crystallized by using the heat generated by naturally cooling the titanium slag to obtain solid caustic soda crystals; and S4, concentrating and crystallizing the NaCl solution generated by the acidification reaction by utilizing heat generated by natural cooling of the titanium slag to obtain solid NaCl crystals.
8. The acid-soluble titanium-rich material produced by the method for preparing the acid-soluble titanium-rich material according to any one of claims 1 to 7, wherein TiO in the acid-soluble titanium-rich material 2 The grade is more than 98 percent, and the acidolysis rate of the acid-soluble titanium-rich material is more than 99 percent.
9. The acid-soluble titanium-rich material according to claim 8 is used for producing titanium dioxide by a sulfuric acid method.
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