CN108149015B - Method for extracting valuable components from vanadium-titanium magnetite through oxygen-enriched selective leaching - Google Patents
Method for extracting valuable components from vanadium-titanium magnetite through oxygen-enriched selective leaching Download PDFInfo
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Abstract
A method for extracting valuable components from vanadium titano-magnetite through oxygen-enriched selective leaching is carried out according to the following steps: (1) crushing vanadium titano-magnetite, putting the crushed vanadium titano-magnetite and sodium hydroxide solution into a high-pressure kettle, introducing oxygen, heating, stirring and preserving heat to complete alkaline leaching; (2) filtering and separating the material after alkaline leaching, and washing an alkaline decomposition product to prepare an alkaline decomposition slag material; (3) adding ammonium salt into the alkaline leaching solution, standing for precipitation, and drying and calcining a solid phase to prepare vanadium oxide; (4) adding crystal seeds into the alkaline decomposition slag and a hydrochloric acid autoclave, heating and stirring, and preserving heat to complete acid leaching hydrolysis; (5) filtering and separating, washing and drying the hydrolysate, and calcining to prepare the titanium oxide. The method realizes the cyclic utilization of resources, does not generate industrial wastewater and waste residue, and realizes green production; realizes green circulation, energy conservation and emission reduction.
Description
Technical Field
The invention belongs to the technical field of nonferrous metallurgy, and particularly relates to a method for extracting valuable components from vanadium-titanium magnetite through oxygen-enriched selective leaching.
Background
Vanadium is located in the 4 th period and VB group in the periodic table, has the atomic number of 23 and the atomic weight of 50.9415, and belongs to a high-melting-point element in transition metal elements; vanadium has various oxides, and the oxide of vanadium is mainly V in industry2O2、V2O3、V2O4In particular V2O5The method has the form that the alloy steel containing vanadium is manufactured for the first time in the UK in the 20 th century, and the method firstly breaks through in the application field of vanadium; the vanadium-titanium alloy is then applied to the battery industry as one of the most promising new energy storage systems at present, and meanwhile, the important metal alloy Ti-6A1-4V consisting of vanadium and titanium is widely applied to the fields of military affairs, aviation, superconduction, nuclear reactors and the like; the total content of vanadium in the crust is arranged at the 22 th site of the metal, the content is not small but is very dispersed, and no separate vanadium ore is found so far; the vanadium-titanium magnetite concentrates are mainly symbiotic with some metal ores, rich in vanadium reserves in China and mainly prepared from vanadium-titanium magnetiteAnd carbonaceous shale as a raw material for industrial production.
The titanium content is about 0.61 percent of the earth crust mass, and is a fourth-position structural metal after aluminum, iron and magnesium according to the abundance of elements in the earth crust; the chemical property is active, and the compound is in a natural non-simple substance state, and is widely existed in seawater, soil, rock, animals and plants in the form of oxide, titanate and other compounds; although there are numerous titaniferous minerals, ilmenite, vanadium titano-magnetite and rutile are mainly used in industry at present; the titaniferous minerals in the crust are distributed most widely, the largest reserve is ilmenite which accounts for about 80 percent of the titaniferous resources and is also the main raw material for preparing titanium products; at present, more than 90 percent of titanium ore in the world is used for producing titanium dioxide, about 4 to 5 percent of titanium ore is used for producing metallic titanium, and the rest of ilmenite is used for manufacturing welding electrodes, alloys, carbides, ceramics, glass, chemicals and the like; titanium dioxide is a white inorganic pigment with the chemical name of titanium dioxide, has no toxicity, no harm, optimal opacity and optimal whiteness and brightness, is considered to be the white pigment with the best performance in the world at present, and is widely applied to the industries of coatings, plastics, papermaking, printing ink, chemical fibers, rubber, cosmetics and the like.
Vanadium titano-magnetite is a multi-element symbiotic iron ore mainly containing iron (Fe), vanadium (V) and titanium (Ti) and associated with various valuable elements such as cobalt (Co), nickel (Ni), chromium (Cr), copper (Cu), scandium (Sc), gallium (Ga) and the like, and is generally called vanadium titano-magnetite because Fe and Ti are closely symbiotic and V is present in the titano-magnetite in the form of a homogeneous image. The vanadium titano-magnetite is a main resource for smelting vanadium and titanium at present, and vanadium, iron and titanium in the vanadium titano-magnetite can be recycled. The vanadium-titanium magnetite deposit is widely distributed in China, the reserves are abundant, the reserves and the exploitation amount reside in the third position of iron ore nationwide, the reserves are proved to be 61.9 hundred million tons, and the reserves are proved to be 11.6 percent of the reserves of iron throughout the country. The deposits are mainly distributed in areas of Xichang, Chengde area, Yunyang and Xiangyang.
At present, the main methods for extracting vanadium from vanadium titano-magnetite mainly comprise a pyrogenic method and a wet method, wherein the pyrogenic method is to smelt the vanadium titano-magnetite in a blast furnace or an electric furnace to obtain vanadium-containing pig iron, and then the vanadium-containing pig iron is smeltedOxidizing vanadium in the molten iron into slag by using a selective oxidation method, and further extracting vanadium from the obtained vanadium-containing slag; the wet method is to roast the vanadium titano-magnetite to pretreat, convert the multivalent vanadium element in the vanadium titano-magnetite into the water-soluble salt of the pentavalent vanadium element under the assistance of sodium salt, calcium salt or oxygen, then carry on the water logging or acid leaching to the slag obtained after roasting treatment, the water-soluble salt of vanadium and some impurity metal salt enter the leachate, add ammonium salt after purifying the leachate, or the treatment of calcium salt precipitation method can get the precipitation of vanadate compound, in order to get purer product, need to carry on alkali dissolution and edulcoration to crude vanadic oxide, and carry on the secondary vanadium precipitation of ammonium salt, can get purer ammonium metavanadate, get the vanadium pentoxide of high purity after roasting; the wet process has the characteristic of high total yield; the patent of application No. 201010188625.7 proposes crushing ore or concentrate, adding sodium salt, oxidizing roasting, converting vanadium and chromium into water-soluble sodium vanadate and sodium chromate, soaking in water, and separating vanadium and chromium from the solution to obtain vanadium pentoxide and chromium sesquioxide products; the leached residue can be added into coal powder for pelletizing, and through reduction and magnetic separation, iron and titanium are separated to obtain magnetic iron powder which can be used as raw material for powder metallurgy or steel-making, and contains TiO2More than 50% of non-magnetic products are used as raw materials for extracting titanium; the roasting process of the method consumes a large amount of energy, and the vanadium pentoxide, the iron oxide and the titanium oxide prepared by the method contain more impurities, are primary industrial raw materials and have low added value of products; the patent of application No. 201310183580.8 mentions a method for preparing titanium liquid by wet processing vanadium-titanium magnetite concentrate, mixing the vanadium-titanium magnetite concentrate with hydrochloric acid, leaching to obtain an intermediate slurry, filtering the intermediate slurry to obtain a leaching solution and leaching slag, then washing with water, filtering to obtain washing water and washing slag, and carrying out a molten salt reaction on the washing slag to obtain a molten salt reaction material; washing and filtering the molten salt reaction material to obtain a washing material; pickling the water washing material to obtain slurry, and filtering to obtain a pickling material; carrying out acid dissolution on the acid-washed material by using a sulfuric acid solution to obtain an acid-dissolved material; adding the acid-dissolved material into a sulfuric acid solution for leaching, and filtering to obtain a leaching solution, namely a titanium solution; the method ignores a large amount of vanadium titano-magnetiteIron-containing compounds and a plurality of high value-added metal elements, and the resource utilization rate is low.
Disclosure of Invention
According to the research of the existing vanadium titano-magnetite production process, the invention provides a method for extracting valuable components from vanadium titano-magnetite by oxygen-enriched selective leaching, which takes the vanadium titano-magnetite as a raw material, sodium hydroxide and hydrochloric acid as solvents, and utilizes the strengthening leaching means of mechanical activation, oxygen enrichment, high pressure and the like to carry out high-pressure oxygen-enriched alkaline leaching on the vanadium titano-magnetite,high pressure acid leachingTitanium white is prepared, and high-purity TiO is prepared through subsequent purification and crystal form conversion2(ii) a The valuable vanadium element in the leaching solution is subjected to ammonium salt precipitation recovery and roasting to prepare high-purity vanadium oxide, so that the vanadium element is enriched, the energy consumption is reduced, the acid-base concentration in the leaching process is effectively reduced, the acid-base concentration is recovered to realize the cyclic utilization of resources, the working condition of equipment is improved, and the service life of the equipment is prolonged.
The method of the invention is carried out according to the following steps:
1. crushing the vanadium titano-magnetite to the granularity of less than or equal to 0.125mm to obtain vanadium titano-magnetite powder; putting vanadium-titanium magnetite powder and a sodium hydroxide solution into an autoclave for alkaline leaching, wherein the mass concentration of the sodium hydroxide solution is 20-40%, and the liquid-solid ratio of the sodium hydroxide solution to the vanadium-titanium magnetite powder is (5-15): 1; introducing oxygen into the autoclave for alkaline leaching, heating to 200-300 ℃, and preserving heat for 1-3 hours under the stirring condition to finish alkaline leaching; 2. filtering and separating the material after alkaline leaching to obtain an alkaline decomposition product and an alkaline leaching solution; washing the alkali decomposition product with water until the filtrate is neutral to prepare an alkali decomposition slag material;
3. adding ammonium salt into the alkaline leaching solution according to the VO in the alkaline leaching solution4 3+With NH in ammonium salts4 +The molar ratio of (1: 3), standing until the precipitate is completely separated out, and filtering and separating to obtain a solid phase and a liquid phase; drying the solid phase to remove moisture, and calcining at 850 +/-5 ℃ for 30-60 min to prepare vanadium oxide;
4. placing the alkaline decomposition slag and hydrochloric acid in an autoclave for acid leaching, wherein the mass concentration of the hydrochloric acid is 14-20%, and the liquid-solid ratio of the hydrochloric acid to the alkaline decomposition slag is (4-10): 1; adding seed crystals into an autoclave for acid leaching, so that titanium oxide formed in the hydrolysis process of hydrochloric acid in the alkaline decomposition slag materials can be conveniently formed and grown, then heating to 120-150 ℃, and preserving heat for 1-3 hours under the stirring condition to finish acid leaching hydrolysis;
5. filtering and separating the materials after acid leaching and hydrolysis to obtain a hydrolysate and an acid leaching solution; and (3) washing the hydrolysate with water until the filtrate is neutral, drying to remove water, and finally calcining at 800-900 ℃ for 30-60 min to prepare the titanium oxide.
In the method, the liquid phase obtained in the step 3 is used for removing SiO by using CaO as a precipitator2Recovering calcium silicate by-product as SiO in liquid phase2When the weight percentage is less than or equal to 0.05 percent, the sodium hydroxide solution is used as the sodium hydroxide solution and returned to the step 1 for use.
The seed crystal is titanium dioxide and/or metatitanic acid, and the addition amount of the seed crystal is 0.2-0.5% of the total weight of the alkali decomposition slag charge.
In the method, after the obtained pickle liquor is heated and evaporated, the redundant hydrogen chloride in the pickle liquor is volatilized, and the hydrochloric acid prepared by absorption is concentrated to the weight concentration of 14-20%, and the method is returned to the step 4 for use.
The purity of the vanadium oxide is more than or equal to 95 percent.
The purity of the titanium oxide is more than or equal to 98.5%, and the granularity is 0.1-13 microns.
Separating the residual materials after the pickle liquor is heated and evaporated into single metal salt solution by adopting an extraction method, and electrolyzing the metal salt solution by adopting an electrolytic bath to respectively prepare high-purity hydroxide precipitates; taking Fe as an example, since Fe3+The ion concentration is high, in order to prevent the agglomeration of ferric hydroxide, a small amount of iron oxide red is added before iron removal, mechanical stirring is carried out on the cathode area of the electrolytic cell, the electrolyte and the hydroxide in the cathode area flow directionally, at the moment, the filtering is carried out through a filtering device, solid-liquid separation is realized, and the filtrate is circularly returned to the cathode area to prepare the superfine high-purity iron oxide red; according to the same principle, removing the contained impurity metal ions respectively; the activity of the impurity metal ions contained in the metal salt solution is positioned in H+Then, the leachate contains a large amount of Cl in the electrolytic process-So that hydrogen and chlorine are generated between two stages of the electrolytic cell(ii) a Collecting anode and cathode gases to obtain byproducts hydrogen and chlorine; drying and filtering the electrolysis product to obtain an impurity hydroxide product, or calcining the electrolysis product to obtain a metal oxide product.
The method for directly separating hydroxide precipitate by electrotransformation mainly comprises the following reactions:
and (3) anode reaction: 2Cl--2e＝Cl2↑，
And (3) cathode reaction: 2H++2e＝H2↑，
And (3) total reaction: MeCl2+2H2O＝Me(OH)2+H2+Cl2，
And (3) calcining reaction: me (OH) ═ MeO + H2O↑。
The principle and the beneficial effects of the invention are as follows:
(1) oxygen is introduced in the leaching process, low-valence titanium, iron and vanadium oxides in the vanadium-titanium magnetite are oxidized, a stable magnetite phase is damaged, impurity elements which are dispersed and distributed in the solid solution are combined into a compound which can be dissolved in acid and alkali, and the compound can be separated and removed in the subsequent washing and filtering stage;
(2) the airtightness of the system is ensured in the leaching process, larger air pressure is generated in the kettle along with the introduction of oxygen or the continuous rise of the temperature, the dynamic conditions of the leaching process are optimized to a great extent, the oxidation, impurity precipitation and mineral phase damage of the vanadium titano-magnetite are promoted, and the vanadium titano-magnetite can be used as a means for strengthening leaching, so that the technological conditions such as temperature, pH value, leaching time and the like can be properly reduced in the process of coaction with other leaching technological parameters, and the purposes of environmental protection and energy saving are achieved;
(3) the vanadium titano-magnetite is subjected to alkaline leaching firstly, the surface of slag particles can be damaged to a certain extent, the separation of impurity phases is facilitated, the subsequent acid leaching effect is enhanced, meanwhile, acid-base distribution leaching is adopted, the simple acid leaching is adopted, the impurity removal rate of oxides such as Si, Al and the like is greatly increased, the impurity removal pressure of the subsequent production process is greatly reduced, high-performance materials are easy to prepare, and meanwhile, the oxygen-enriched acid leaching can remove Fe in the leaching solution2+Oxidation can improve the efficiency of the later-stage electric conversion iron precipitation process;
(4) the adopted alkali is sodium hydroxide, and a small amount of ammonium salt can be added into the waste alkali liquor generated in the alkaline leaching process, so that vanadate ions in the waste alkali liquor can be separated out in a precipitation form, and the waste alkali liquor is filtered to be enriched; then adding a small amount of CaO to generate calcium silicate to effectively remove Si impurities, thereby realizing the purposes of enriching vanadium oxides and removing impurities, and simultaneously concentrating the filtered alkali liquor to be continuously used for alkaline leaching of vanadium titano-magnetite so as to realize the recycling of resources; hydrochloric acid is used in the acid leaching process, generated waste acid is heated, water atomization is used for absorbing HCl gas volatilized by heating, and the formed hydrochloric acid solution is concentrated and returned to the leaching process, so that the resource recycling is realized, and industrial wastewater and waste residues are hardly generated to realize green production;
(5) the extraction principle can be utilized to separate and carry out electric conversion on each impurity ion, the prepared metal oxide or hydroxide has high purity, superfine high-purity oxide can be prepared through drying and calcining, meanwhile, valuable byproducts such as hydrogen and chlorine can be generated through electrolysis, and the acid leachate after impurity removal can be recycled to the process flow, so that green circulation, energy conservation and emission reduction are realized.
The specific implementation mode is as follows:
in the embodiment of the invention, CaO is used as a precipitating agent to generate calcium silicate precipitate together with silicate ions in alkali liquor for preparing cement.
The autoclave for alkaline leaching used in the examples of the present invention was a zr yk 1L type stainless steel nickel plating autoclave of zhengwei mechanical equipment ltd.
The autoclave for acid leaching adopted in the embodiment of the invention is a KCFD1-10 type zirconium autoclave of Nicotiana Kogyo Co.
The titanium concentrate crushing equipment in the embodiment of the invention is a pulveresette 5/4 classic line type planetary high-energy ball mill of FRITSCH.
The liquid-solid ratio in the embodiment of the invention is the weight ratio of the volume of a liquid material (sodium hydroxide solution or hydrochloric acid) to a solid material (vanadium-titanium magnetite powder or alkaline decomposition slag), and the unit is L/kg.
In the embodiment of the invention, the stirring speed in alkaline leaching is 500r/min, and the stirring speed in acid leaching hydrolysis is 300 r/min.
The titanium dioxide and the metatitanic acid adopted in the embodiment of the invention are commercially available analytical pure reagents.
In the embodiment of the invention, the residual materials after the pickle liquor is heated and evaporated are separated into single metal salt solution by an extraction method, and the metal salt solution is electrolyzed by an electrolytic bath (the temperature is 20 ℃, the bath voltage is 20V) to respectively prepare high-purity hydroxide precipitates; taking Fe as an example, since Fe3+The ion concentration is high, in order to prevent the agglomeration of ferric hydroxide, a small amount of iron oxide red is added before iron removal, mechanical stirring is carried out on the cathode area of the electrolytic cell, the electrolyte and the hydroxide in the cathode area flow directionally, at the moment, the filtering is carried out through a filtering device, solid-liquid separation is realized, and the filtrate is circularly returned to the cathode area to prepare the superfine high-purity iron oxide red; according to the same principle, removing the contained impurity metal ions respectively; the activity of the impurity metal ions contained in the metal salt solution is positioned in H+Then, the leachate contains a large amount of Cl in the electrolytic process-Therefore, hydrogen and chlorine are generated between two stages of the electrolytic cell; collecting anode and cathode gases to obtain byproducts hydrogen and chlorine; drying and filtering the electrolysis product to obtain an impurity hydroxide product, or calcining the electrolysis product to obtain a metal oxide product with the purity of more than or equal to 95%.
The present invention will be described in further detail with reference to examples.
The vanadium titano-magnetite used in the embodiment of the invention contains TiO according to the weight percentage212.8％，SiO23.83％，CaO 1.16％，MgO 3.22％，TFe 53.7％，MnO 0.24％，Al2O32.86％，V2O50.53％。
Example 1
Crushing the vanadium titano-magnetite to the granularity of less than or equal to 0.125mm to obtain vanadium titano-magnetite powder; putting vanadium-titanium magnetite powder and a sodium hydroxide solution into an autoclave for alkaline leaching, wherein the mass concentration of the sodium hydroxide solution is 20%, and the ratio of the sodium hydroxide solution to the vanadium-titanium magnetite powder is 5:1 in terms of liquid-solid ratio; introducing oxygen into an autoclave for alkaline leaching, heating to 200 ℃, and preserving heat for 3 hours under the stirring condition to finish alkaline leaching; filtering and separating the material after alkaline leaching to obtain an alkaline decomposition product and an alkaline leaching solution; washing the alkali decomposition product with water until the filtrate is neutral to prepare an alkali decomposition slag material;
adding ammonium salt into the alkaline leaching solution according to the VO in the alkaline leaching solution4 3+With NH in ammonium salts4 +The molar ratio of (1: 3), standing until the precipitate is completely separated out, and filtering and separating to obtain a solid phase and a liquid phase; drying the solid phase to remove water, and calcining at 850 +/-5 ℃ for 30min to prepare vanadium oxide with the purity of 96.5%; collecting washing liquor generated after water washing, and adding the washing liquor into alkaline leaching solution; liquid phase uses CaO as a precipitator to remove SiO2When SiO in the liquid phase2When the weight percentage is less than or equal to 0.05 percent, the sodium hydroxide solution is recycled;
placing the alkaline decomposition slag and hydrochloric acid in an autoclave for acid leaching, wherein the weight concentration of the hydrochloric acid is 14%, and the liquid-solid ratio of the hydrochloric acid to the alkaline decomposition slag is 10: 1; seed crystals are added into an autoclave for acid leaching, so that titanium oxide formed in the hydrolysis process of hydrochloric acid by alkali decomposition slag materials is conveniently formed and grown, the temperature is increased to 120 ℃, the temperature is kept for 3 hours under the stirring condition, and the acid leaching hydrolysis is completed; the seed crystal is titanium dioxide, and the addition amount of the seed crystal is 0.5 percent of the total weight of the alkaline decomposition slag charge;
filtering and separating the materials after acid leaching and hydrolysis to obtain a hydrolysate and an acid leaching solution; washing the hydrolysate with water until the filtrate is neutral, drying to remove water, and calcining at 900 deg.C for 30min to obtain titanium oxide; after the pickle liquor is heated and evaporated, the volatilized hydrogen chloride gas is atomized and absorbed by water, and the prepared hydrochloric acid is concentrated to the mass concentration of 14 percent for recycling; the titanium oxide has a purity of 98.5% and contains SiO in mass percent20.31 percent, CaO 0.07 percent, MgO 0.96 percent, TFe 3.6 percent and Mn0.18 percent; the particle size is 0.16-4.29 microns.
Example 2
The method is the same as example 1, except that:
(1) the weight concentration of the sodium hydroxide solution is 30%, and the ratio of the sodium hydroxide solution to the vanadium-titanium magnetite powder is 10: 1; the alkaline leaching temperature is 250 ℃, and the time is 2 hours; (2) calcining for 40min after solid phase drying to prepare vanadium oxide with the purity of 97.2 percent;
(3) the mass concentration of the hydrochloric acid is 18%, and the proportion of the hydrochloric acid to the alkali decomposition slag is 8:1 according to the liquid-solid ratio; the temperature of alkaline leaching hydrolysis is 130 ℃, and the time is 2 hours; the seed crystal is metatitanic acid, and the addition amount is 0.3 percent of the total weight of the alkali decomposition slag charge;
(4) washing and drying the hydrolysate, and calcining at 850 ℃ for 40 min; the hydrochloric acid prepared by absorbing the hydrogen chloride gas is concentrated to the weight concentration of 18 percent; the titanium oxide has a purity of 98.7% and contains SiO in mass percent20.22 percent, CaO 0.07 percent, MgO0.64 percent, TFe 2.1 percent and Mn 0.16 percent; the particle size is 0.5-12 microns.
Example 3
The method is the same as example 1, except that:
(1) the mass concentration of the sodium hydroxide solution is 40%, and the ratio of the sodium hydroxide solution to the vanadium-titanium magnetite powder is 15: 1; the alkaline leaching temperature is 300 ℃, and the time is 1 h; (2) calcining for 60min after solid phase drying to prepare vanadium oxide with the purity of 96.7 percent;
(3) the mass concentration of the hydrochloric acid is 20%, and the ratio of the hydrochloric acid to the alkali decomposition slag is 4: 1; the temperature of alkaline leaching hydrolysis is 150 ℃, and the time is 1 h; the seed crystal is a mixture of titanium dioxide and metatitanic acid with equal mass, and the addition amount is 0.2 percent of the total weight of the alkaline decomposition slag charge;
(4) washing and drying the hydrolysate, and calcining at 800 ℃ for 60 min; hydrochloric acid prepared by absorbing hydrogen chloride gas is concentrated to the mass concentration of 20 percent for recycling; the titanium oxide has a purity of 98.9% and contains SiO in mass percent20.18％，CaO0.07％，MgO 0.32％，TFe 1.5％，Mn<0.05 percent; the particle size is 0.8-13 microns.
Claims (2)
1. A method for extracting valuable components from vanadium titano-magnetite through oxygen-enriched selective leaching is characterized by comprising the following steps:
(1) crushing the vanadium titano-magnetite to the granularity of less than or equal to 0.125mm to obtain vanadium titano-magnetite powder; the vanadium titano-magnetite contains TiO according to weight percentage212.8%，SiO23.83%，CaO 1.16%，MgO 3.22%，TFe 53.7%，MnO 0.24%，Al2O32.86%，V2O50.53 percent; putting vanadium-titanium magnetite powder and sodium hydroxide solution into alkaliThe method comprises the following steps of (1) putting a sodium hydroxide solution into an autoclave for alkaline leaching, wherein the mass concentration of the sodium hydroxide solution is 20 ~ 40%, the liquid-solid ratio of the sodium hydroxide solution to vanadium-titanium magnetite powder is (5 ~ 15):1, introducing oxygen into the autoclave for alkaline leaching, heating to 200 ~ 300 ℃, and keeping the temperature for 1 ~ 3 hours under stirring conditions to complete alkaline leaching, (2) filtering and separating materials after alkaline leaching to obtain an alkaline decomposition product and an alkaline leaching solution, washing the alkaline decomposition product with water until the filtrate is neutral, and preparing an alkaline decomposition slag material;
(3) adding ammonium salt into the alkaline leaching solution according to the VO in the alkaline leaching solution4 3+With NH in ammonium salts4 +The molar ratio of the vanadium oxide to the calcium oxide is 1:3, standing is carried out until the precipitate is completely separated out, filtration and separation are carried out to obtain a solid phase and a liquid phase, the solid phase is dried to remove water, then the solid phase is calcined for 30 ~ 60min at the temperature of 850 +/-5 ℃ to prepare vanadium oxide, the purity of the vanadium oxide is more than or equal to 95 percent, and the liquid phase uses CaO as a precipitator to remove SiO in the liquid phase2Recovering calcium silicate by-product; when SiO in liquid phase2When the mass percent is less than or equal to 0.05 percent, returning to the step (1) for use as a sodium hydroxide solution;
(4) putting the alkaline decomposition slag and hydrochloric acid into an autoclave for acid leaching, wherein the mass concentration of the hydrochloric acid is 14 ~ 20%, and the liquid-solid ratio of the hydrochloric acid to the alkaline decomposition slag is (4 ~ 10):1, adding seed crystals into the autoclave for acid leaching, so that titanium oxide formed in the hydrolysis process of the hydrochloric acid of the alkaline decomposition slag grows up, heating to 120 ~ 150 ℃, keeping the temperature for 1 ~ 3h under the stirring condition, and completing the acid leaching hydrolysis, wherein the seed crystals are titanium dioxide and/or metatitanic acid and the addition amount of the seed crystals is 0.2 ~ 0.5.5% of the total weight of the alkaline decomposition slag;
(5) filtering and separating the materials after acid leaching and hydrolysis to obtain a hydrolysate and an acid leaching solution, washing the hydrolysate with water until the filtrate is neutral, drying to remove water, and finally calcining at 800 ~ 900 ℃ for 30 ~ 60min to prepare titanium oxide, wherein the purity of the titanium oxide is more than or equal to 98.5%, and the granularity of the titanium oxide is 0.1 ~ 13 microns.
2. The method for extracting valuable components from vanadium titano-magnetite by oxygen-enriched selective leaching according to claim 1, characterized in that after the acid leaching solution obtained in step (5) is heated and evaporated, the excess hydrogen chloride is volatilized and absorbed by water atomization to prepare hydrochloric acid which is concentrated to the weight concentration of 14 ~ 20%, and the hydrochloric acid is returned to step (4) for use.
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| CN108300874B (en) * | 2018-01-15 | 2020-09-29 | 东北大学 | Method for selectively leaching and upgrading high-titanium slag |
| CN108149015B (en) * | 2018-01-15 | 2020-01-14 | 东北大学 | Method for extracting valuable components from vanadium-titanium magnetite through oxygen-enriched selective leaching |
| CN109913660A (en) * | 2019-03-18 | 2019-06-21 | 东北大学 | A method of rich vanadium richness iron charge is prepared using v-bearing steel slag |
| CN112430735B (en) * | 2019-08-26 | 2022-04-26 | 中国科学院过程工程研究所 | Treatment method of acid vanadium extraction tailings |
| EP4077751A4 (en) * | 2019-12-19 | 2024-01-24 | Avanti Materials Ltd | Recovery of vanadium from slag materials |
| CN113355511B (en) * | 2021-06-01 | 2022-04-05 | 四川省有色矿冶科技有限公司 | Method for selectively reducing vanadium and titanium content in vanadium-titanium magnetite concentrate through ammonium-ammonia oxidation leaching system |
| CN114480881B (en) * | 2022-01-18 | 2023-12-12 | 龙佰集团股份有限公司 | Method for extracting valuable elements from iron concentrate by wet-fire combined process |
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