Procedure for processing vanadium containing raw material
SUBSTANCE: procedure consists in preparation of water pulp from raw material, in introduction of sulphuric acid and anionite into it for leaching and in extraction of vanadium from pulp by sorption. Upon sorption saturated anionite is withdrawn and washed; vanadium is de-sorbed from anionite and regenerated anionite is introduced to the stage of leaching and sorption. Also, water vanadium pulp is prepared from vanadium containing raw material. As such there is used oxidised slag or slime at pH 11.5-7.5. Sulphuric acid is introduced into prepared water pulp at S:L=1:2 to pH 4.5-4.0. Vanadium is extracted from pulp by counter-flow sorption at pH 4.5-1.8 with following saturated ionite washing at drainage. Value of pH in pulp is maintained at 4.5-4.0 at withdrawal of saturated anionite, while at introduction of regenerated anionite - 2.0-1.8.
EFFECT: raised extraction of vanadium, elimination of upset of sparingly soluble forms of vanadium at moment of leaching, facilitation of completeness of sorbent saturation and minimal concentration of impurities on it, reduced consumption of sulphuric acid, reduced number of operations in process flow sheet.
2 cl, 4 tbl, 2 ex
The invention relates to the processing of hard vanadium-containing raw materials, namely product pyrometallurgical enrichment of vanadium-containing Converter slag and sludge Ferroalloy production and can be used in the manufacture of pure salts of vanadium.
There is a method by which the vanadium BOF slag is subjected to grinding, magnetic separation of metallocene, mixing with soda, oxidative calcination at high temperatures (750-850°C) with subsequent two-stage leaching of vanadium from the oxidized slag water and sulfuric acid solution, the allocation of vanadium compounds from the combined aqueous solution by boiling with live steam (Technological instruction TI 115-f-10-95. Production of vanadium pentoxide. JSC Chusovoy metallurgical plant, 1995).
Recycling of BOF slag on soda technology has the following disadvantages:
low extraction of vanadium in final products, about 65%;
- low quality of the finished product (85-90% V2About5);
- complex salt composition of the wastewater and the impossibility of using them in a closed circulation.
There is a method comprising grinding the BOF slag magnetic separation of metallocene, mixing with the reaction agent such as limestone, oxidative roasting the mixture at t is mperature 750-850°C until complete burnout of elemental iron and translation of vanadium in the highest oxidation state, grinding cinder with the production of oxidized vanadium water slurry with subsequent two-stage weak acid leaching at pH 3,01-3.6 and temperature 71-85°C, filtering and processing of cake 3,5% H2SO4on the filter to extract the insoluble forms of vanadium and released from the combined aqueous solution by boiling with live steam (RF patent No. 2041278, publ. 1995.08.09). The disadvantages of this method include:
- loss of vanadium on stage pH leaching due to coprecipitation;
low extraction from slag at 75% and the low quality of the finished product and, as a consequence, high vanadium content (more than 3.0% V2O5in atalina sludge;
- high consumption of sulfuric acid is more than 1.5 t/t V2O5a considerable part of which is unnecessarily lost on the site neutralization of waste water with lime milk;
is a time - consuming filtering operation in special vehicles (FPAKM);
- high energy consumption by Tervasaari manganese Vanadate (8 tonnes of steam per 1 t V2O5);
- the complexity of the technological scheme associated with the separation of vanadium and manganese;
- loss of vanadium with the drain water.
The closest in technical essence is a method of extracting uranium, molybdenum, vanadium from ores (RF patent No. 2211253, publ. 2003.08.27). The method includes ore crushing, grinding the leaching of valuable components of mineral acid and subsequent sorption extraction of dissolved uranium, molybdenum and vanadium from the pulp. Before leaching the crushed ore in the form of an aqueous slurry oxidized by treatment with anion exchange resin in Oh form at pH 8.5 and 11.6, the redox potential of from 50 to 150 mV at a temperature of 30-80°C., and the leaching and sorption extraction of lead by adding oxidized slurry with sulfuric acid to a pH of 1.5 to 3.5, and the anion exchange resin.
However, this method does not allow to oxidize the compound of vanadium (spinels) and elemental iron in hard BOF slag anion exchange resin in Oh form at pH 8.5-11.6 and ORP from 50 to 150 mV. Elemental iron and its compounds in oxidation States (+2) at the stage acid leach into solution and prevent the extraction of vanadium. In the known method the oxidation of components of the raw material in the pulp is carried out at pH 8.5-11.6 and redox potential of from 50 to 150 mV and t° 30-80°C anion exchange resin in Oh-form, and the leaching and sorption extraction are added to the oxidized slurry with sulfuric acid to a pH of 1.5 to 3.5, and the ion exchanger. Oxidation of BOF slag and sludge Ferroalloy production in these conditions is impossible, and at the stage of pulp leaching and sorption inevitably translates into solution a large amount of iron, which leads to the precipitation of sparingly soluble salts of vanadium at pH most effective process of dissolution and sorption. An important moment in technology and the desire of vanadium from Converter slag and sludge is burning dispersed and Pallas's willow iron and translation VOSTOCHNOGO iron (FeO) in hematite (Fe 2About3), membrane not easily soluble in dilute sulfuric acid. However, the firing of slag and sludge from the complete oxidation of iron to hematite is not achieved, and in the process of acid leaching has a border pH of 1.8-2.0, after which the transition of iron in the solution increases sharply.
The analysis described above analogs and prototypes revealed that none of them achieved high recovery while reducing reagent consumption, energy consumption and reduction of technological operations.
The technical result of the invention is to improve the extraction of vanadium, eliminating the landing insoluble forms of vanadium in the time of leaching, ensure full saturation of the sorbent and the minimum concentration therein of impurities, reduction of the consumption of sulfuric acid and reducing operations of the technological scheme, namely the filtering operation.
The technical result is achieved in the method of processing vanadium-containing raw materials, including the preparation of the raw water of the pulp, the introduction of its sulfuric acid and anion leaching and extraction of vanadium sorption from the pulp, the output is saturated anion exchange resin, washing, desorption of vanadium from the anion to the stage of leaching and sorption, water, vanadium pulp is prepared from a vanadium-containing raw material, which is used as the oxidized was going or slurry at a pH of 11.5 and 7.5, the introduction of sulfuric acid in the prepared pulp is carried out at T:W=1:2 and to pH 4.5 to 4.0, and the extraction of vanadium from the pulp are countercurrent sorption at pH 4.5-1.8 with subsequent washing of saturated anion exchange resin on the drainage, the output is saturated anion exchange resin is carried out at pH 4.5 to 4.0, and typing regenerated anion-exchange support pH 2.0 and 1.8.
In addition, leaching of saturated anion exchange resin is carried out at the content of 350-650 kg V2O5per ton of resin with 1%sulfuric acid solution and the desorption of lead nitrate ammonium 150-200 g/l at pH 7.5-8.5 in-phase mode and pH 4.5-5.5 in liquid phase mode.
In the tail of the column, the pH is maintained at the expense of acid anion and a sulfuric acid, and the intermediate columns with sulfuric acid. The residence time of the pulp and resin in each column is 1-2 hours. The anion exchange resin from the head of the column is unloaded only after saturation 350-650 kg V2O5per ton of resin. Pulp tail of the column is filtered, the mother liquor sorption is used at the stage of deposition of manganese in the form of high-purity concentrate of manganese (VKM).
How should the current level of technology, the processes of leaching and sorption of vanadium from aqueous slurries of oxidized slag or sludge depend on the pH of the acidic environment. The increase of pH leads to an increase in the saturation of the anion, and the decrease in pH to increase leaching is Anadia and iron in the solution of the oxidized slag or sludge. Simultaneously with the increase of iron concentration in the solution increases the formation of insoluble salts of vanadium. To eliminate this undesirable process requires combining operations leaching and sorption, sorption of vanadium should be ahead of the leaching of impurities. This effect is achieved if the system slag or sludge - solution - anion moves from neutral to acidic. Under these conditions, the vanadium concentration in the equilibrium solution will always be minimal, and the increase in the concentration of iron in acidic solution will not be as unfavorable. Currently in the acid processing methods involved vanadium BOF slags with higher, compared with the previously processed slag, the content of manganese compounds. A significant part of the sulfuric acid is consumed at the opening of the manganese - and iron-containing compounds, the intensity and completeness of disclosure of the components depends on many factors, the main of which is pH - processing of the pulp.
In the proposed method, the opening of the useful component and removing the resin, roaming the backflow of water to the pulp, leading to the conditions under which the iron has not yet translated into a solution pH of 1.8-2.0, and vanadium with a fully transformed into a liquid phase and focuses on the sorbent. Preparation of vanadium waters of the second slurry from the oxidized slag or sludge are from a pH of 11.5-7.5 to pH 4.5 to 4.0 processing sour proryvnym solution or sulfuric acid, and countercurrent sorption and leaching of vanadium at pH 4.5 and 1.8. Conclusion saturated anion exchange resin from the pulp is carried out at pH 4.5 to 4.0, enter regenerated anion exchanger on the sorption is carried out at pH 2.0 and 1.8. Ion-exchange extraction of vanadium on the anion exchange resin reduces the concentration of the useful component in the liquid phase and leads to additional translation of the useful component of the oxidized slag or sludge in the solution.
The operation of preparing a water slurry of appropriate conduct on site grinding and thickening to pH 4.5 to 4.0, and acid treatment in sorption columns at pH 4.5 and 1.8. Most preferred in the proposed method is conducting sorption at high pH in the head, in the course of the slurry, the apparatus to achieve the maximum saturation of the sorbent vanadium and subsequent decrease in pH to the tail unit, which allows for sufficient completeness opening of the useful component and eliminates the possibility of precipitation of sparingly soluble salts of vanadium, and the pulp after the tail of the filter apparatus. The acidic liquor containing manganese, send to install ozonation for the selection of chemical manganese dioxide (CMU), and the sludge on the filter was washed with 3%sulfuric acid solution, in circulation, and use as directed. Regulation of pH sorption in predetermined optimal range cascade columns can is provided as the supply of sulphuric acid, and entering into the slurry of acid regenerated anion exchanger that is determined by the intensity of treatment of the anion in the system of sorption-desorption - recharge. The combination of processes of leaching and sorption is carried out in apparatus of anionite processing, where each device is constantly given pH.
Thus, in the proposed method, the most important and controllable parameters are the pH of the slurry to stabilize compounds of vanadium in the solution, and maintaining the required pH in the head and tail in the course of the slurry apparatus ionite processing, the first of them determines the saturation of the anion exchanger, and a second weight for vanadium recovery from sludge or slag and the total flow rate of the reagent.
The method is as follows.
The process of preparing a water slurry are on crushed slag or sludge particle size of 0.1 mm 100% at T:W=1:1.5 and a pH of 11.5-7.5 and treatment with acid to T:W=1:2 and pH 4.5 to 4.0. The initial pH of the oxidized vanadium water slurry depend on the content in the feedstock, the reaction agent coming on stage oxidation firing. Anionite the treatment is carried out by highly basic anion exchanger in countercurrent multistage scheme, the residence time of the pulp and of the anion at each stage is 1-2 hours, the content of the sorbent support 5-15% of the volume of the pulp. Protiviti the Noah multistage sorption leaching of vanadium with the introduction of regenerated anion exchange resin, output saturated anion exchange resin is carried out in the range of pH of 1.8 to 4.5. The separation of the anion exchange resin is carried out on the drainage grids with flushing from the pulp saturated anion exchange resin at a content of 350-650 kg V2O5at the last stage of a 1%solution of sulfuric acid. Desorption of vanadium with saturated anion exchange resin regeneration) provide a solution of NH4NO3150-200 g/l at pH 7.5-8.5 in the solid phase, and at pH 4.5-5.5 in liquid-phase mode, the first volumes of the eluate containing (NH4)2SO4used on a node reload, the output of the eluates is 4.0-5.0 volume on the volume of anion exchange resin, optionally recharge spend 1% solution of H2SO4volume the volume of the anion exchange resin with subsequent supply of regenerated anion exchange resin on the sorption of vanadium.
Taken oxidized slag 100 g with a content of 13% V2O5, rasulpur in water at T:W=1:2 and pH 8.5, and then oxidized in the aqueous slurry is introduced sulfuric acid to a pH of 4.5 to 4.0 and downloaded in its sulfate form the anion exchanger Ambersep 920 by volume 10% by volume of the slurry. After that, at intervals of 1 hour reduced the pH of the pulp to 4.0; 3,5; 3,0; 2,5; 1,8 under stirring. The anion exchange resin from the head of the column were washed from the pulp to drain the grid and went on desorption of vanadium, and the pulp from the tail of the column with pH 1.8 was filtered and washed with water. The mother liquor contained 0.05 g/l V2O5and 0.2 g/is Fe, insoluble sludge - sludge 76 g contained 1.6% of V2O5. The extraction of vanadium amounted to 90.0%. After desorption contents V2O5- 98,5%.
Taken slurry of 100 g with a content of 3.0% V2About5, rasulpur in water at T:W=1:2 and a pH of 9.5, and then oxidized in the aqueous slurry is introduced sulfuric acid to a pH of 4.5 to 4.0 and downloaded in its sulfate form the anion exchanger Ambersep 920 volume at the rate of 7% on the amount of pulp. After that, at intervals of 1 hour reduced the pH of the pulp to 4.0; 3,5; 3,0; 2,5; 1,8 under stirring. The anion exchange resin from the head of the column were washed from the pulp to drain the grid and went on desorption of vanadium, and the pulp from the tail of the column with pH 1.8 was filtered and washed with water. The mother liquor contained 0.03 g/l V2O5and 0.1 g/l Fe, insoluble sludge - sludge 85 g contained 1,15% V2O5. The extraction of vanadium was 71.0 per cent. After desorption contents V2O5- 98,0%. The data obtained (see table 1, 2) show that the extraction of vanadium on the proposed method has a higher degree (up to 80% of the sludge and up to 90% of the slag) in comparison with the known method. At the same time the proposed method allows to reduce the consumption of sulfuric acid to 750 kg/t V2O5. Justification the boundary of the parameter values of the proposed method are presented in the drawing and tables 2, 3. The drawing shows the dependence of the iron content of the solution from the pH of the processing of slag or sludge. The obtained curve shows that at pH 2.0 to 1.8 degree of transfer of iron in the solution is minimal, at lower pH the acid treatment to 1.8 most of the iron remains in the solid, a further decrease in pH leads to his transition into the liquid phase of the pulp, which, in turn, causes the recovery of vanadium, which is not adsorbed on the anion exchange resin. Accordingly, the graphical dependence shows that the minimum boundary value of the pH of the processing of slag or sludge is 1.8, which is also supported by the values obtained when modeling scheme countercurrent multi-stage acid-anionite processing of the pulp. The data presented in table 2 show that the extraction of vanadium from the oxidized slurry confirms the good results within the specified limits of pH. From the data of table 3 area boundary values pH o saturated anion exchange resin is determined within the range pH 4.5 to 4.0, the content of iron and manganese sorbent, respectively, does not exceed 0.1 and 10.0 kg/ton of resin, the saturation of its vanadium respectively 350-650 kg/so raising the pH to 5.0, as well as the reduction at this stage to 1.0, leads to the decrease of the concentration of vanadium on the sorbent and in the latter case, the increase of iron content on the anion exchange resin.
Thus, it is shown that the area of the process of adsorption of vanadium, cos EDINOGO by leaching it from the solid phase, is in the range of pH values of 4.5 and 1.8, its lower boundary is determined by the minimum pH value of 1.8, when the reduction begins intensive transition of iron in solution, respectively, increased consumption of sulfuric acid and an increase in the concentration of sulfate ions in the solution, the upper bound of the optimal saturation of the sorbent with the lowest amount of iron on it, above pH 4.5, the concentration of vanadium on the anion exchange resin is reduced. Process for preparation of oxidized vanadium pulp without the presence of the anion region defined pH in the range of 4.5 to 4.0, the upper boundary value leads to a decrease in sorption due to the formation rezorbiruetsa supramolecular compounds of vanadium, a minimum pH value of the leaching is included in the above field of extreme high sorptive extraction. The range of values of pH of the pulp at the conclusion of the saturated sorbent and the input of regenerated anion exchange resin, enter the pH of the combined process 4,5-1,8, their values accordingly be 4.5 to 4.0 and 2.0 to 1.8. Saturated sorbent is washed with a 1%solution of sulfuric acid for leaching productive solution and removal of impurities of iron and manganese. Increase or decrease in acidity leads to the leaching of vanadium from the anion exchange resin. To keep the structure of the anion desorption is conducted NH4NO3within 150-200 g/l Bottom is th limit is determined by the inefficiency of the desorption of vanadium with saturated anion exchange resin, and the upper - saving consumption of reagents. Desorption in solid-phase and liquid-phase mode ends crystallization of metavanadate ammonium, during thermal decomposition which is obtained pure vanadium oxide (>99% V2O5). Liquid-phase desorption yields a more pure vanadium oxide. The results of solid-phase and liquid-phase desorption of vanadium from the results presented in table 4, which shows a high degree of desorption 98,7% and high quality metavanadate ammonium due to the selectivity of the sorption process.
The results of the leaching of vanadium from an aqueous slurry of slag, combined with countercurrent adsorption on the anion exchange resin in the range of pH 4.5 to 1.8.
Conditions of the experiments: T:W=1:2, time - 60 min, temperature = 60°C, the anion - 15% vol.
|Columns||Slag 16,8% V2O5in the solution of 11.3 g/l V2O5||Removing the V2O5%||The consumption of H2SO4kg/t V2O5|
|№ p/p||Description||pH||the contents of the V 2O5|
|the solution, g/l||sludge, %||the anion exchange resin, mg/g|
The results of the leaching of vanadium from an aqueous pulp slurry, combined with countercurrent adsorption on the anion exchange resin in the range of pH 4.5 to 1.8.
Conditions of the experiments: T:W=1:2, time - 60 min, temperature = 60°C, the anion - 5-10% vol.
|Columns||Sludge 3,4% V2O5in a solution of 4.0 g/l V2O5||Removing the V2O5%||The consumption of H2SO4kg/t V2O5|
|№ p/p||Description||pH||Contents V2O5|
|the solution, g/l||sludge, %||the anion exchange resin, mg/g|
|The dependence of the saturation of the sorbent vanadium, iron and manganese from acidic pH-anionite processing|
|the pH of the acid-anionite processing||5,0||4,5||4,0||3,5||3,0||2,5||2,0||1,5||1,0|
|Contents V2About5on the sorbent, kg/t||480||520||600||650||580||500||350||160||30|
|The Fe content in the sorbent, kg/t||less than 0.1||less than 0.1||less than 0.1||0,1||0,1||0,1||0,1||1,5||the 10.1|
|The content of IGOs on the sorbent, kg/t||1,0||2,1||5,2||7,1||8,0||9,0||10,5||13,2||14,1|
|The results of solid-phase and liquid-phase desorption with anion-exchange|
|Type desorption||Saturated anion exchange resin||Desorbed||The pulp of metavanadate ammonium|
|The mother liquor||The ammonium metavanadate|
|Volume ml||V2O5g/kg dry. anion-exchange||V2O5g||Volume, ml||V2O5, g/l||%||PH||Volume ml||V2O , g/l||pH||Weight MVA, g||The content of V2O5%||Output %|
|Solid-phase||100||350||of 17.5||200||82,0||93,5||7,5||200||1,05||8,2||23,23||75,5||of 99.1|
|Liquid-phase||100||350||of 17.5||1000||15,8||90,0||4,5||1000||1,50||23,10||77,2||of 98.2|
1. A method of processing vanadium-containing raw materials, including the preparation of the raw water of the pulp, the introduction of its sulfuric acid and anion leaching and extraction of vanadium sorption from the pulp, the output is saturated anion exchange resin, washing, desorption of vanadium from the anion exchanger and the input of regenerated anion exchange resin to the stage of leaching and sorption, characterized in that the aqueous vanadium pulp is prepared from a vanadium-containing raw material, which is used as the oxidized slag or sludge at a pH of 11.5-7.5, the introduction of sulfuric acid in the prepared aqueous slurry is carried out at T:W=1:2 and to pH 4.5 to 4.0, and removing vanadium from the pulp are countercurrent sorption at pH 4.5-1.8 with subsequent washing of saturated ion exchange on the drainage, the output is saturated anion exchange resin is carried out at pH 4.5 to 4.0, and typing regenerated anion exchanger support the claim in the pulp pH of 2.0 and 1.8.
2. The method according to claim 1, characterized in that the washing of the saturated anion exchange resin is carried out at the content of the anion exchange resin 350-650 kg V2O5per ton of resin with 1%sulfuric acid solution and the desorption of lead nitrate ammonium 150-200 g/l at pH 7.5-8.5 in-phase mode or at pH 4.5-5.5 in liquid phase mode.
SUBSTANCE: method includes formation of charge consisting of concentrate and sodium carbonate by means of intergrinding of components and reduction of charge components at presence of taken with excess carbonaceous reducing material at temperature 850-1300°C. Additionally batch material reduction is implemented up to providing of content of metallic iron in the range of particles dimensions 10-300 mcm not less than 80%. Received partly reduced conservative mass, consisting of metalise phase containing main part of iron and vanadium and oxide phase, containing main part of titanium and vanadium, it is grinned up to size not more than 300 mcm. Then it is implemented leaching of vanadium from reaction mass and leaching residue is separated from vanadate solution. After separation residue of leaching is subject to gravitational separation in water flow with separation of metalised and oxide phases. Metalised and oxide phases are separately subject to wet magnetic separation for receiving of metallic iron and titanium oxide concentrate. Additionally wet magnetic separation is implemented in the range of field intensity 20-300 E.
EFFECT: increasing of extraction of iron and titanium oxide.
7 cl, 4 dwg, 6 ex
SUBSTANCE: invention relates to technology of rare metals, particularly to method of processing of vanadium-bearing raw material: vanadium ores, vanadium-bearing slag of metallurgical manufacturing, treated vanadium catalysts and, particularly to complex treatment of Karatau quartzites by hydrometallurgy method. Method of processing of vanadium-bearing raw material includes acid leaching, sorption by resin of vanadium, uranium and phosphorus from solutions of leaching up to saturation of resin by vanadium, desorption of vanadium from resin and receiving of vanadium oxide. Additionally it is implemented double-circuit saturation of resin by vanadium: originally up to 200-250 g/kg by means of sorption from leaching solutions. Then it is complete saturate up to 450-650 g/kg by treatment b solutions of vanadic acid containing not less than 15 g/l of vanadium oxide, with simultaneous extraction of uranium and phosphorus into mother solution. Desorption of vanadium from resin saturated by vanadium up to 450-650 g/kg is implemented by method of solid-phase or liquid-phase desorption. In the capacity of vanadic acid there are used strippings of liquid-phase desorption or solutions prepared from vanadate of ammonium.
EFFECT: upgraded division grade of vanadium from uranium and phosphorus and upgraded efficiency of process.
2 cl, 2 ex
SUBSTANCE: invention relates to technology of rare metals, particularly to method of processing of vanadium-bearing raw material: vanadium ores, vanadium-bearing slag of metallurgical manufacturing, treated vanadium catalysts, fuel-oil residues by hydrometallurgical methods and, particularly to complex treatment of Karatau quartzites by percolation leaching methods. Method of processing of vanadium-bearing raw material includes two-stage heap leaching of vanadium, sorption of vanadium from efficient solutions, complete consolidation of circulating manifold of sorption of sulfuric acid and its feeding to leaching. Before leaching raw material is laid into heap with simultaneous blending with vitriol oil with consumption not less than 30 kg/t and is leached at the first stage by circulating manifolds of sorption with water concentration 3.5-4.5 l/m2hour and cycles number not less than 3. Complete consolidation of circulating manifolds by sulfuric acid is implemented up to its content 8.0-8.5% and fed to heap at the second stage of leaching.
EFFECT: increasing of extraction ratio of vanadium into solution, providing of steady-state load on sorption limit and reduction of cost price of final product.
SUBSTANCE: invention relates to methods of vanadium sedimentation from water solutions and can be used in hydrometallurgy of rare refractory metals, particularly receiving of vanadium oxide (V+5) of high purity. Method of vanadium extraction from sodium-bearing solutions includes electrodialysis of solution for membrane withdrawal of sodium cation from solution and sedimentation of ammonium pol-vanadate. Electrodialysis is implemented at circulation of solution through working chamber of electrodialysis apparatus and at achievement of pH 6.5-7.5 circulating solution is treated by ammonia water or ammonia. Treatment is implemented up to molar ratio Na:V<0.1.
EFFECT: providing of intensification of sedimentation process of vanadium, improvement of finished product and elimination of discharge of industrial flows.
1 dwg, 4 ex
SUBSTANCE: final tailings are leached with circulating concentrated hydrochloric acid at boiling temperature of hydrochloric pulp of 103-109°C thereby producing gaseous mixture of water vapours, hydrogen chloride and hydrochloric acid solution containing titanium, vanadium, iron, chromium, manganese and cake. Produced cake is washed and dried; so final product is obtained in form of concentrate of silicon oxide. The following compositions of metals are extracted by selective sedimentation out of obtained hydrochloric acid solution in three stages: titanium hydroxide, hydrated vanadium pentaoxide, mixture of iron and chromium oxides and basic manganese carbonate. Vapour-gas mixture of water and hydrogen chloride formed in each stage of metal composition extraction is condensed producing circulating hydrochloric acid. The acid is used for washing sediments of metal compounds and for leaching of source final tailings.
EFFECT: selective and waste-free extraction of compounds of titanium, vanadium, iron, chromium and manganese out of final tailings and producing commodity products in form of concentrates of titanium dioxide, vanadium pentaoxide, and mixture of iron, chromium and manganese oxides performed in closed process circuit.
1 dwg, 3 tbl
SUBSTANCE: invention relates to the method and device of preparation slag-soda charge containing vanadium for oxidising roasting. The method involves crushing the slag, magnetic separation, breaking, mixing it with chemical additives for the follow-up roasting. Before roasting the resulting mixture is granulated, and the slag is crushed in several steps classifying the slag into size groups. The first step is preparatory when the slag is crushed into pieces of 200 mm maximum. The second step is when the slag is crushed into pieces of 80 mm maximum, and the slag is classified into the following fractions: +80 mm, 10-80 mm and - 10 mm. During the third step the resulting fraction of 10-80 mm is crushed on the rotary crusher in the closed cycle with the vibration onesieve sizing screen with the sieve cells of 10×10 mm. Then the fraction of 10 mm is mixed with the early obtained fraction of 10 mm and processed in two steps. Step 1 does centrifugal crushing and seperation to achieve pieces of 0.15 mm that go through the centrifugal crushing and air centrifugal separation in Step 2. The slag with 0.06-0.15 mm pieces is supplied to the dosing and mixing unit to determine the content of vanadium pentoxide in the slag depending on which the required amount of chemical additives and soda is supplied to be mixed with the slag.
EFFECT: reduced loss of vanadium in the course of preparing the charge, reduced content of the metallic inclusions, increased total extraction of vanadium, increased output of vanadium products, better environment.
7 cl, 1 dwg
SUBSTANCE: invention relates to metallurgy, namely to a method of recovery of vanadium from titanium-vanadium slag obtained at the time of processing titanium-vanadium concentrates using methods of obtaining iron. The method involves breakage of slag, oxidising roasting with conversion of vanadium into a soluble form, cooling of the roasted slag and leaching it to extract vanadium in the solution. The slag is roasted at a temperature of 1050-1150°C during 15-45 min. If the slag contains more than 8% of CaO, roasting requires no additives. If the slag contains less than 8% of CaO, roasting requires CaCO3 in the amount of 5-15% of the slag weight. After cooling the roasted slag is leached with sulfuric acid at pH - 2.5-3.0 during 10-20 min.
EFFECT: increased amount of extracted vanadium from titanium-vanadium slag reaching 85-97%, as well as improved technical and economic performance of the process as a whole.
3 cl, 1 tbl, 1 ex
SUBSTANCE: invention can be implemented for extraction, purification and concentration of vanadium, for example at processing re-circulated mother solutions of production V2O5 and acid solutions of leaching ashes after black oil burning. The method of extracting vanadium from weak-acid mediums consists in extracting with nitrogen containing extracting agent, in the capacity of which N-(2-hydroxy-5-nonylbenzyl)-ββ-dihydroxyethylamine (NBEA) is used in organic diluter. After extraction re-extraction of vanadium is performed with ammonia solution.
EFFECT: upgraded degree of vanadium extracting from weak-acid solutions.
1 tbl, 5 ex
SUBSTANCE: invention refers to method of producing high-quality vanadium pentoxide from hydrated deposited industrial vanadium pentoxide. Method includes as follows. Deposit is filtered, washed with water with following reagent processing by calcium-containing salt solutions to recover it from manganese. Reagent processing is enabled in ratio 3.0-8.5 g Ca2 + per 1 g MnO. Produced is supplied to reagent processing of new portions of hydrated deposited industrial vanadium pentoxide in the same Ca2 + to MnO ratio. As manganese is accumulated in solution, it is regenerated with adding calcium hydroxide suspension, containing CaO, or slaked lime of consumption 1.0-1.45 g CaO per 1 g MnO in stirring. After that manganese concentrate is isolated. Liquid phase is delivered back to reagent processing of new portions of hydrated deposited industrial vanadium pentoxide.
EFFECT: production of the second end product - manganese concentrate, cost saving of production and enhanced ecology.
1 dwg, 4 tbl, 6 ex
SUBSTANCE: invention concerns hydrometallurgy. Particularly it concerns method of vanadium extraction. Method includes leaching of vanadium-bearing material by water solution of soda with receiving of alkaline vanadium solution. Received solution is mixed with monohydric alcohol and implemented aliquation of formed mixture for two phases: upper - soda-alcohol, which is subject to regeneration, and bottom - in the form of sodium vanadate solution, where it is concentrated vanadium. Then phase separation is implemented. From bottom phase it is precipitaled vanadium by means of addition to it and mixing with ammonium salt of ammonium carbonate, taken in 1-3-fold amount with respect to stoichiometric quantity, necessary for formation of ammonium vanadate. Ammonium vanadate is dried and burnt for receiving of vanadium pentoxide.
EFFECT: simplification of process and receiving from lye vanadium pentoxide of higher-purity.
3 tbl, 1 ex
SUBSTANCE: procedure consists in refining solution of ammonia paratangstate with sulphate of ammonia from molybdenum impurity. Further, refining is carried out with ion exchange on anionite AM-n and with thermal decomposition of ammonia paratangstate at temperature 600-800°C till production of tungsten trioxide. Tungsten trioxide is refined with zone sublimation at temperature 900-950°C in a continuous flow of oxygen. Further, trioxide of tungsten is heterogeneous reduced with hydrogen at temperature 700-750°C till production of powder of tungsten. Powder is compressed to tungsten rod which is subjected to electronic vacuum zone re-crystallisation till production of tungsten crystal. Tungsten crystals are melt in electron vacuum in a flat crystalliser with melt of flat ingot of tungsten on each side at total depth not less, than twice. A tungsten rod is treated with chlorine prior to zone re-crystallisation at rate of chlorine supply 100 ml/min and temperature 300°C during 1 hour.
EFFECT: raised purity of tungsten designed for thin film metallisation by magnetron target sputtering and improved electro-physical parametres of applied thin layers.
SUBSTANCE: procedure consists in purification of solution of ammonia paramolybdate form impurities by ion exchange in neutral and sub-alkali mediums on hydrated oxide of tin and on sub-basic anionite AN-106. Further, ammonia paramolybdate is thermally decomposed at temperature 600-800°C to production of molybdenum oxide and is refined by zone sublimation at temperature 750-800°C in continuous flow of oxygen. Molybdenum oxide is heterogeneous reduced with hydrogen at temperature 700-750°C till production of powder of molybdenum. Powder is compressed to a rod which is subjected to electronic vacuum zone re-crystallisation till production of high purity molybdenum crystal. Molybdenum crystals are melt in electron vacuum in a flat crystalliser with melt of flat ingot of high purity molybdenum on each side at total depth not less, than twice. A molybdenum rod is treated with chlorine prior to zone re-crystallisation at rate of chlorine supply 100 ml/min and temperature 300°C during 1 hour.
EFFECT: great rise of molybdenum purity.
SUBSTANCE: invention refers to application of mono-disperse macro-porous chelate ion-exchange resins for sorption of metals from pulp in hydro-metallurgical processes, particularly, in so called processes "resin-in-pulp". Mono-disperse macro-porous chelate ion-exchanging resin has average diametre of granules within the range from 0.35 to 1.5 mm. Sorbed metals correspond to mercury, iron, titanium, chromium, tin, cobalt, nickel, copper, zinc, lead, cadmium, manganese, uranium, bismuth, vanadium, such elements of platinum group as ruthenium, osmium, iridium, rhodium, palladium, platinum and also such valuable metals, as gold and silver. Here is also disclosed the procedure for production of mono-disperse macro-porous chelate resin containing picoline-amine groups.
EFFECT: increased output of extracted metals and more efficient sorption of metals.
9 cl, 1 tbl, 5 ex
SUBSTANCE: method for extracting nickel from nickel-containing production solutions of sulphuric underground or heap leaching involves nickel sorption on cation-exchange resin of chelate type with functional group bis(2-piridyl methyl)amino. After sorption the nickel desorption and strippant treatment is performed. Prior to strippant treatment, ferric iron is removed from it by sorption on anion-exchange resin in in the shape of at pH=1.6-2.4.
EFFECT: reducing the number of ferric iron prior to treatment of nickel-containing solutions in order to improve nickel extraction.
1 dwg, 3 tbl
SUBSTANCE: procedure for extraction of nickel from solutions and purification from impurities: Cr3+, Fe3+, Al3+, Cu2+, Zn2+, Co2+, Fe2+, Mn2+, Ca2+, Mg2+ consists in bringing pH of solutions to values 4.0-6.5, in sorption of nickel at pH=4.0-6.5 from solutions or pulps on sub-acid cationites, in desorption of nickel from saturated cationites with solution of sulphuric or hydrochloric acid with production of solution of nickel strippant. Before desorption saturated cationite is treated with solution of nickel purified from impurities, also with portion of solution of strippant with concentration of nickel higher, than its concentration in source solution or pulp coming to sorption at a value of pH less, than pH of solution or pulp in the process of sorption. Ratio of CNI:ΣCimpurity in solution of strippant changes from 7:1 to 500:1.
EFFECT: more deep purification of solution of nickel strippant from impurities.
SUBSTANCE: invention refers to extraction of niobium (V) from water fluorine-containing solution with the use of sorbents and can be used in non-ferrous and ferrous metallurgy, as well as for cleaning of industrial and domestic sewage systems. Method involves sorption by contact of solution and anionite. At that, sorption is performed at pH=1-4 with AM-2b anionite pre-treated with acid or water, and containing the following exchange groups: -CH2-N(CH3)2, -CH2-N(CH3)3.
EFFECT: providing optimum conditions for quick and effective extraction method of niobium (V) anions from fluoride-containing water solution.
4 dwg, 2 tbl, 3 ex
SUBSTANCE: procedure for extraction of molybdenum (VI) from solutions of cations of heavy metals consists in sorption of molybdenum (VI) at value of pH of solution less, than value of pH of hydrolytic sedimentation of cations of heavy metals. As sorbent at sorption there is used activated bone coal.
EFFECT: raised efficiency of procedure.
2 tbl, 2 dwg, 2 ex
SUBSTANCE: procedure for extraction of tungsten (VI) from solutions of cations of heavy metals consists in sorption of tungsten (VI) at value of pH of solution less, than value of pH of hydrolytic sedimentation of cations of heavy metals. As sorbent at sorption there is used activated bone coal.
EFFECT: efficient procedure for selective extraction of ions of tungsten from water solution of cations of heavy metals.
2 dwg, 2 tbl, 2 ex
SUBSTANCE: procedure consists in desorption of copper with cyanic solutions containing cyanic sodium (NaCN). Also, desorption is carried out with cyanic solutions containing ammonium carbonate (NH4)2CO3 at ratio NaCN/(NH4)2CO3=1-3:50 at temperature as high, as 60°C.
EFFECT: increased extraction of copper into eluate at reduced consumption of cyanide; replacement of eluate composition with more efficient one and reduced expenditures for neutralisation of reagent.
2 cl, 1 dwg, 1 tbl, 6 ex
SUBSTANCE: procedure for extraction of gold from gold containing copper ore consists in cyanic sodium (NaCN) cyanic leaching with circulating solutions, in filtration and sorption of gold from solutions. Also, leaching is performed with circulating solutions upon sorption without additional replenishment with NaCN with addition of 5-10 g/l of ammonium carbonate into solutions. Circulating solutions are replenished with NaCN to concentration not less, than 0.5 g/l before sorption.
EFFECT: reduced consumption of cyanide and production of qualitative commodity product.
2 cl, 2 dwg, 1 tbl, 1 ex
SUBSTANCE: procedure for extraction of metals from silicate nickel ore consists in preparation of silicate nickel ore by crushing and classification, in silicon leaching from ore with cultural medium of silicate bacteria and in successive extraction nickel from cake. Silicate minerals of ore are bio-degraded at leaching silicon with cultural medium of silicate bacteria; bio-degradation is performed at pH as high, as 4, without mixing and with replacement of cultural medium. Nickel is extracted from cake of bio-degradation by leaching with utilisation of solution of bio-degradation upon silicon has been extracted from it and by adding sulphuric acid to concentration 50÷450 g/l. Further, metal is extracted from leaching solution of cake bio-degradation.
EFFECT: increased extraction of nickel from silicate ore, raised rate and efficiency of silicate nickel ore leaching.
7 cl, 2 ex