RU2266343C2 - Method of processing vanadium-containing converter slag - Google Patents

Abstract

FIELD: processing vanadium-containing converter slag.

SUBSTANCE: proposed method includes roasting of slag with reaction additive, leaching-out cinder by soda solution for obtaining vanadate solution and separating vanadium oxide from it. At roasting, waste slag of vanadium process is introduced as reaction additive; waste slag contains hematite and manganese oxide at mole ratio of vanadium to manganese equal to 1:1. Roasting is performed at 800-850°C for 3 h; leaching-out is carried out with soda solution at mole ratio of V₂O₅:Na₂CO₃ equal to 1:1.2-1.8 including filtration of sodium vanadate solution and flushing the sediment with water. Vanadium and sodium are separated from solution thus obtained by electrochemical treatment in membrane system, sorption or neutralization by sulfuric acid followed by sedimentation of polyvanadium acid salts.

EFFECT: increased extraction of vanadium products; reduction of waste water disposal.

1 dwg, 8 tbl, 8 ex

Description

The invention relates to metallurgy, to methods for extracting vanadium from converter vanadium-containing slag.

Converter vanadium-containing slags contain a number of valuable elements - vanadium, manganese, chromium and titanium. Existing converter slag processing technologies provide for the extraction of only one component, vanadium, and this is achieved by introducing reaction additives at the stage of oxidative roasting-soda or limestone, which suppress the interaction of manganese with vanadium. Sodium and calcium reaction additives displace manganese from high-oxygen acid-soluble vanadium compounds into sparingly soluble compounds (Mn ₂ O ₃ , Mn ₂ O ₄ , MnO ₂ ). Subsequent leaching of the cinder in a slightly acidic H ₂ SO ₄ medium does not dissolve these manganese compounds. Thus, the calcium and sodium reaction additives introduced in the calcination step reduce the transition of manganese into the solution, which is lost with the waste slurry.

A known method of extracting vanadium from converter slag, including firing with carbonates or calcium oxides, two-stage leaching with sulfuric acid at pH 2.0-3.0 and a temperature not exceeding 70 ° C, followed by washing the precipitate with a 3% solution of H ₂ SO ₄ and hydrolysis of vanadium from the combined solutions (RF patent No. 2118389, 1995).

After separation of vanadium oxide, the mother or drain solution containing 0.3-0.7 g / l V ₂ O ₅ and 7-8 g / l MnO is subjected to liming (Production of technical vanadium pentoxide and ferrovanadium. Technological instruction TP 127-F-05 -88. Tula, 1988).

When liming, sulfuric acid is neutralized, a poorly settling precipitate is formed, consisting of oxides of manganese, calcium and calcium sulfate (rough manganese concentrate). Wet sediment in the form of pulp is pumped into the sludge field. Thus, the method does not provide for the integrated use of converter slag and rough manganese concentrate is a waste product. Other disadvantages include:

- low extraction of vanadium in the finished product - about 75%;

- low quality of the finished product (92-93% V ₂ O ₅ );

- an additional operation is introduced by washing it with a solution of iron or magnesium sulfate.

There is a method in which converter slag is subjected to oxidative roasting with soda, followed by two-stage leaching of the cinder with water and a solution of sulfuric acid (Technological instruction TI 115-F-10-95. Production of vanadium pentoxide. OJSC "Chusovsky Metallurgical Plant", 1995).

The processing of converter slag by soda technology is characterized by the following disadvantages:

- the mixture, consisting of converter slag and soda, is subjected to dry grinding, which causes pollution of the working rooms with dust of slag and soda;

- powdery "soda" charge, prone to melting and rolling in a kiln, impairs filtration, complicates the technology;

- silicon and chromium pass into the solution;

- low extraction of vanadium in the finished product - about 65%;

- the complex salt composition of wastewater and the inability to use water in a closed water circuit;

- loss of manganese with waste sludge.

Closest to the proposed invention is a method of processing converter vanadium-containing slags, including slag preparation, roasting with the addition of a reaction additive, leaching of the cinder with a soda solution at a temperature of at least 90 ° C for 1-2 hours to obtain a vanadate solution and recovering from it technical vanadium oxide (DE 2324737, class C 22 V 7/04, 01.24.1974). The disadvantages of the method include insufficiently high extraction and quality of vanadium products.

The objective of the invention is to develop a method for the comprehensive utilization of converter slag, providing for a softer conduct of all technological operations, reducing the dustiness of working rooms with harmful substances (soda), reducing the melting and rounding of the charge at the stage of oxidative firing, selective leaching and increasing the filtration rate of vanadium solutions.

The technical result is to increase the extraction and quality of vanadium products, the elimination of discharge water and increase the commercial value of chemical waste for manganese, titanium and chromium.

This is provided in a method for processing converter vanadium-containing slags, including slag preparation, roasting with the addition of a reaction additive, leaching of the cinder with a soda solution at a temperature of at least 90 ° C to obtain a vanadate solution and the isolation of vanadium oxide from it, in which the reaction additive is injected with vanadium production slurry containing hematite and manganese oxide, with a molar ratio of vanadium to manganese equal to 1: 1, a temperature of 800-850 ° C for 3 hours, leaching they are carried out with a soda solution at a molar ratio of V ₂ O ₅ : Na ₂ CO ₃ equal to 1: 1.2-1.8, with filtration of a sodium vanadate solution and washing of the precipitate with water, vanadium and sodium are separated from the resulting solution by electrochemical treatment in a membrane system, sorption or neutralization with sulfuric acid, followed by precipitation of salts of polyvanadic acids.

The invention consists in the following. Elemental and ferrous iron in the converter slag, oxidizing autogenously, emits a significant amount of heat, which leads to local overheating and fusion of the reaction products, an increased content of vanadium oxide of more than 16% increases the amount of low-melting phase, respectively. The thermal reduction of the charge is achieved by introducing iron oxide in the form of α-Fe ₂ О ₃ , which binds wustite (FeO) to magnetite (Fe ₃ О ₄ ) and liberates free one and a half vanadium oxide (V ₂ О ₅ ), the α-phase. The oxidation of magnetite is extended over time and does not cause local overheating. In the R ₂ O ₃ phase, with a further increase in temperature, vanadium is oxidized due to the internal oxidizing agent - Mn ₂ O ₃ - with the formation of a more refractory chemical compound - Mn ₂ V ₂ O ₇ .

At a temperature of 800-850 ° C, magnetite completely passes into hematite α-Fe ₂ O ₃ , which does not interact with vanadium salts. The proposed mode allows you to keep the technological opening at the level of 92-95%. At the first stage, a stable electronic structure (+ V) is formed due to the internal oxidizing agent according to the scheme:

The formation of the octahedral structure of vanadium oxide occurs, and tetrahedral voids are occupied by manganese oxide. The stability of the structure is so high that numerous heating and cooling in air do not cause its change, the oxidation state of vanadium and manganese remains constant, respectively +5 and +2.

At the second stage, an exchange reaction is carried out in an aqueous solution between manganese pyrovanate and soda according to the equation:

The method allows to obtain manganese carbonate in the solid phase, sodium pyrovanate in the aqueous phase, without affecting chromium, silicon, titanium and iron, which remain in an insoluble precipitate. Selective leaching of vanadium from the cinder is carried out with a soda solution at a molar ratio of V ₂ O ₅ : Na ₂ CO ₃ equal to 1: 1.2-1.8, at a temperature not lower than 90 ° C for 1.0-2.0 hours.

Filtration and washing of the precipitate with water makes it possible to transfer about 90% of vanadium into the aqueous phase without affecting manganese, titanium, silicon and chromium (these elements are absent in the solution). Filtration is ideal, the precipitate is crystalline, evenly distributed on the filter.

From an aqueous solution of sodium vanadate pH 8.6-9.5 with a concentration of V ₂ O ₅ equal to 35-45 g / l, vanadium can be distinguished in several ways - by electrochemical treatment in the membrane system, sorption or neutralization with sulfuric acid.

In the process of membrane conversion of sodium vanadate salts, hydrogen ions either protonate vanadium cations or bind to water. In a constant electric field of the anode - cation exchange membrane - cathode system, the following processes occur:

on the anode H ₂ O-2e → 2H ⁺ + 1 / 2O ₂

in the anolyte 10 Na ₃ VO ₄ + 6Н ⁺ → H ₆ V ₁₀ O ₂₈ + 30Na ⁺

on the membrane - transfer of sodium ions to the catholyte

at the cathode - water decomposition with the generation of NaOH

The electrochemical treatment of sodium orthovanadate solutions in the membrane system allows efficient removal of 90% sodium. Replacing reagent acidification with electrochemical sharply reduces the salt background in solutions.

In the process of sorption of sodium ion on Kd-2 cation exchanger in the N-form, the reaction proceeds:

30RH + 10Na ₃ VO ₄ → H ₆ V ₁₀ O ₂₈ + 30RNa + 12H ₂ O

Upon reaching a pH of 2.0, up to 90% sodium is excreted.

The neutralization of the solution of sodium orthovanadate with sulfuric acid proceeds according to the reaction:

10Na ₃ VO ₄ + 15H ₂ SO ₄ ↔H ₆ V ₁₀ O ₂₈ + 15Na ₂ SO ₄ + 12Н ₂ О

to obtain vanadium acid.

The insoluble precipitate after water washing contains manganese carbonate and part of the unopened manganese pyrovanate, it can be used as a reaction additive in the firing stage. In addition, the readiness of this product for the conversion of manganese into solution is high, and it can be argued that this product is highly prepared for the conversion of manganese and part of vanadium into a solution of sulfuric acid. Separation of manganese and vanadium is possible on AMP resin. The sorption motherboard contains 50-60 g / l MnO, which can be used for the production of electrolytic manganese dioxide MnO ₂ -EDM.

The proposed method allows you to:

- improve the environmental situation in the departments of charge preparation and firing;

- to simplify the process of oxidative firing of converter slag with waste slurries of vanadium production containing hematite and manganese oxide, eliminating fusion, pelletizing, dust soda;

- exclude the transition of chromium (+6) and silicon into aqueous solutions;

- increase the filtration rate of soda and acid solutions by an order of magnitude;

- allows you to organize a closed water circulation and to eliminate the discharge of drainage water into the surrounding water basin;

- improve the extraction and quality of vanadium products;

- there is a real opportunity to extract manganese, chromium and titanium from the residues.

Examples of specific implementation of the method

Example No. 1.

Take the initial charge of the mixture, consisting of 100 g of converter vanadium-containing slag composition, wt.%: V ₂ O ₅ - 12, MnO - 10, FeO - 45 and 10 g of dump sludge of vanadium production composition, wt.%: Fe ₂ O ₃ - 45, MnO - 10, V ₂ O ₅ - 1.5, mix and carry out oxidative firing at a temperature of 850 ° C for 3 hours (the molar ratio of vanadium to manganese is 1: 1.25).

The resulting cinder weighing 113 g contains V ₂ O ₅ - 12.15 g, Mn - 11.0 g. Technological opening is 97.1%. The cinder is leached with a soda solution, which is used as a carbonized reverse alkaline solution of electrodialysis, at a temperature of 98 ° C for 1.5 hours to achieve a molar ratio of V ₂ O ₅ : Na ₂ CO ₃ equal to 1: 1.8. Extraction into the solution of vanadium oxide was 11.75 g (96.7%). The hot pulp is filtered, the precipitate is washed with water to a sodium content of 1 g / L in the wash.

The insoluble precipitate contains, wt.%: V ₂ O ₃ - 1.3, MnO - 12, Fe ₂ O ₃ - 43.5, Cr ₂ O ₃ - 7, SiO ₂ - 15, TiO ₂ - 8, Na ₂ O - 0.2 and is the dump slurry of vanadium production.

The vanadium-containing solution is subjected to electrodialysis, the result is a solution with a content of 77.7 g / l V ₂ O ₅ , 5.2 g / l Na and a pH of 5.0. The vanadium-containing solution is heated to boiling and, at pH 1.8, vanadium is precipitated as sodium polyvanadate. Direct recovery of V ₂ O ₅ was 90.8%. The composition of the calcined product is 95.6% V ₂ O ₅ , 4.2% Na ₂ O.

Example No. 2.

An initial charge of the charge is taken, consisting of 100 g of converter vanadium-containing slag and 10 g of slurry of vanadium production of the composition, as in example 1, is mixed and oxidative calcination is carried out at a temperature of 850 ° C for 3 hours (the molar ratio of vanadium to manganese is 1 : 1.15).

The resulting cinder weighing 106.2 g contains V ₂ O ₅ - 12.0 g, Mn - 10.0 g. Technological opening is 97.7%. The cinder is leached with a soda solution, which is used as a carbonized reverse alkaline solution of electrodialysis, at a temperature of 98 ° C for 1.5 hours to achieve a molar ratio of V ₂ O ₅ : Na ₂ CO ₃ equal to 1: 1.8. Extraction into the solution of vanadium oxide was 11.76 g (98.0%). The hot pulp is filtered, the precipitate is washed with water to a sodium content of 1 g / L in the wash.

The insoluble precipitate contains, wt.%: V ₂ O ₅ - 1.2, MnO - 11, Fe ₂ O ₃ - 42.8, Cr ₂ O ₃ - 7.2, SiO ₂ - 15.5, TiO ₂ - 8 , 2, Na ₂ O - 0.1 and is the dump slurry of vanadium production.

The vanadium-containing solution is subjected to electrodialysis, the result is a solution with a content of 78.2 g / l V ₂ O ₅ , 5.6 g / l Na and a pH of 5.3. The vanadium-containing solution is heated to boiling and, at pH 1.8, vanadium is precipitated as sodium polyvanadate. Direct recovery of V ₂ O ₅ was 92.2%. The composition of the product calcined at 550 ° C is 94.8% V ₂ O ₅ , 5.1% Na ₂ O.

Example No. 3.

The cinder from Example 2 is leached with a soda solution, which is used as a carbonized reverse alkaline electrodialysis solution, at a temperature of 98 ° C for 2 hours until a molar ratio of V ₂ O ₅ : Na ₂ CO _{3 of} 1: 1.2 is reached. Extraction into the solution of vanadium oxide was 11.78 g (98.1%).

The vanadium-containing solution is subjected to electrodialysis, the result is a solution with a content of 78.3 g / l V ₂ O ₅ , 5.7 g / l Na and a pH of 5.4. The vanadium-containing solution is heated to boiling and, at pH 1.8, vanadium is precipitated as sodium polyvanadate. Direct recovery of V ₂ O ₅ was 92.0%. The composition of the product calcined at 550 ° C is 95.0% V ₂ O ₅ , 5.0% Na ₂ O.

Example No. 4.

Take the initial charge of the mixture, consisting of 100 g of converter vanadium-containing slag composition, wt.%: V ₂ O ₅ - 10, MnO - 8.0, FeO - 46.5 and 10 g of waste sludge of vanadium production composition, wt.%: Fe ₂ O ₃ - 45, MnO - 5.0, V ₂ O ₅ - 1.5, mix and carry out oxidative firing at a temperature of 850 ° C for 3 hours (the molar ratio of vanadium to manganese is 1: 1.1) .

The resulting cinder weighing 112 g contains V ₂ O ₅ - 10.15 g, Mn - 18.5 g. Technological opening is 97.5%. The cinder is leached with a soda solution, which is used as a carbonized reverse alkaline solution of electrodialysis, at a temperature of 98 ° C for 1.5 hours to achieve a molar ratio of V ₂ O ₅ : Na ₂ CO ₃ equal to 1: 1.8. Extraction into the solution of vanadium oxide was 9.72 g (95.7%).

The vanadium-containing solution is subjected to electrodialysis, the result is a solution with a content of 64.8 g / l V ₂ O ₅ , 4.8 g / l Na and a pH of 4.2. The vanadium-containing solution is heated to boiling and, at pH 1.8, vanadium is precipitated as sodium polyvanadate. Direct recovery of V ₂ O ₅ was 92.5%. The composition of the calcined product is 96.2% V ₂ O ₅ , 3.8% Na ₂ O.

Example No. 5.

The cinder of Example 3 was leached with a soda solution at 98 ° C for 1.5 hours until a molar ratio of V ₂ O ₅ : Na ₂ CO _{3 of} 1: 1.8 was reached. Extraction into the solution of vanadium oxide was 9.72 g (95.7%).

The vanadium-containing solution is neutralized with acid to a pH of 7.0 and precipitated with ammonium salts in the form of polyvanadates of ammonium and sodium. Direct recovery of V ₂ O ₅ was 93.6%. The composition of the calcined product is 98.5% V ₂ O ₅ , 1.5% Na ₂ O.

Example No. 6.

The cinder of Example 3 was leached with a soda solution at 98 ° C for 1.5 hours until a molar ratio of V ₂ O ₅ : Na ₂ CO _{3 of} 1: 1.8 was reached. Extraction into the solution of vanadium oxide was 9.72 g (95.7%).

The vanadium-containing solution is neutralized with an acid to a pH of 2.5 and vanadium is sorbed on an Amp resin to 450 kg of V ₂ O ₅ per 1000 kg of resin. Desorption is carried out with a mixture of NH ₄ OH and NH ₄ NO ₃ . Ammonium metavanadate is precipitated from the desorbate. Direct recovery of V ₂ O ₅ was 92.3%. The composition of the calcined product is 99.9% V ₂ O ₅ , 0.01% Na ₂ O.

Example No. 7.

The initial sample of ground and magnetized converter slag, wt.% V - 10.5, Mn - 7.2, Ca - 1.1, Fe - 31.4 in an amount of 100 g were thoroughly mixed with waste slurry of vanadium production composition, wt.% V is 1.1; Mn 3.4; Ca - 1.1; Fe - 34.2 in the amount of 30; 60; 100.9 g

The effect of hematite-containing sludge on the technological opening of vanadium from converter slag is presented in table 1. From the above data we can conclude: the consumption of hematite-containing wastes at the stage of charge and calcination should be 30-100% of converter slag.

Technological autopsy is the absolute amount of vanadium oxide that passes into the solution from the cinder when it is treated with a 7% sulfuric acid solution at T: W = 1: 100. Technological opening of vanadium from converter slag 92-97%. With a lower consumption of waste sludge than 30%, extraction is reduced, with a greater than 100%, the productivity of the kiln decreases. The proposed technical solution allows the processing of converter slag together with waste slurry of vanadium production with a high yield of vanadium in alkali and acid-soluble forms.

Leaching of vanadium is carried out with a 9-15% soda solution at a ratio of Na ₂ CO ₃ / V ₂ O _{5 of} 1.6-1.5 kg / kg for 90 minutes and a temperature of at least 90 ° C. The research results are presented in the drawing and table 2. Soda leaching allows to achieve a selective transition of vanadium into a solution in the form of sodium orthovanadate, the ionic form of vanadium plays an important role in subsequent coprecipitation operations, therefore, the consumption of soda on vanadium oxide is from 1.6 to 1.8 kg / kg at a concentration of 9-15% Na ₂ CO ₃ is determined by the ratio of T: W = 1: 2.0-3.0. Leaching temperature of at least 90 ° C for 90 minutes Under these conditions, silicon and chromium are not extracted into the solution, and manganese passes into poorly soluble manganese carbonate (Mn ₂ CO ₃ ). From the above data it is seen that in strongly alkaline solutions a mononuclear tetrahedral vanadium ion, VO ₄ ^{3-, is formed} . As the sodium ion is removed through the membrane, vanadium is converted into the dimeric, monomeric form, and then polymeric vanadium acid, which contains a small part of sodium. Table 3 shows the results of the precipitation of vanadium from solutions with different ratios of sodium to vanadium. From table 3 it follows that the neutralization of the solution of Na ₃ VO ₃ sulfuric acid to pH 2.0 with subsequent boiling of the solution allows to obtain a precipitate containing V ₂ O ₅ ~ 85-88% and Na ₂ O - 8-10%, and with a ratio sodium to vanadium is less than 0.2 mol / mol of vanadium V ₂ O ₅ ~ 95-97% and Na ₂ O is 1.5-1.7%.

Example No. 8.

Pilot tests.

Slag produced by OAO ChMZ, coming in decks, is unloaded from the wagons to the site in the slag warehouse, where it is broken by a caper into pieces up to 200 mm in size. In the process of cutting the slag is the magnetization of the material (large potholes) with a magnetic washer. Crushed slag is leveled on the battlefield, and vanadium production slurry in the amount of 20% of the slag mass is evenly scattered on the hot slag.

From the launch site, crushed slag is grabbed to the hopper of the jaw crusher, where the first stage of crushing up to 80 mm is performed. Crushed slag is stored in an intermediate hopper, from where it is fed by a conveyor system and elevator to the ball mill hoppers, then it is dispensed by feeders into ball mills for finer grinding. Grinding bodies are balls ⌀80 mm.

Slag, ground up to 15 mm, is fed through a magnetic separator to a tube mill through a magnetic separator to separate metal inclusions, and here 10% of vanadium sludge sludge is supplied through a batcher. In tube mills, mixing is carried out, averaging with simultaneous grinding to a fraction of 0.15 mm. The chemical composition of the raw materials is shown in table 4.

The crushed mixture with the help of a system of elevators and a conveyor is fed into the furnace hopper, then with a screw feeder - into the kiln. The mixture is fired in a rotary kiln. The temperature in the expanded part of the furnace is 830-850 ° C. The furnace load on the burnt charge during the test period averaged 2500 kg / h. The results of firing converter slag with the addition of 30% sludge are shown in table 5.

An analysis of the charge firing showed that the total opening of vanadium pentoxide during the test period varied from 90.5 to 95.2% (average 93.4%). For leaching, water or a washing solution is pumped into a soda precipitator, heated with hot steam to 70 ° C. With stirring, soda is loaded in an amount of 10-12% Na ₂ CO ₃ in solution. Then, the calcined charge is loaded into the soda solution at a ratio of T: W = 1: 3. The leaching temperature is not lower than 90 ° C, the time is 1.5 hours. After leaching, the pulp is pumped to the suction filter.

During the test period 11 operations were carried out, 36 tons of burnt charge were processed. The research results are presented in table 6. According to the obtained experimental data, we can state that:

- at a leaching temperature of at least 90 ° C for 90 min and a concentration of Na ₂ CO ₃ in the solution of 10-12%, chromium is not extracted into the solution, manganese passes into poorly soluble manganese carbonate (MnCO ₃ ) under these conditions. In this case, sodium orthovanadates are formed in the aqueous phase;

- the chemical composition of single samples of alkaline solutions varies in the following limits:

V ₂ O ₅ = 28.6-42.4 g / l Cr ₂ O ₃ = 0.01-0.08 g / l Fe ₂ O ₃ = 0.003-0.005 g / l MnO = 0.0-0.0044 g / l P = 0.005-0.016 g / l Na ⁺ = -30-40 g / l SiO ₂ = 1.0-1.2 g / l СО ₃ ^2- - = 20,0-21,0 g / l

- the solution after washing the blade contains on average 14.9 g / l V ₂ O ₅ and 3.8% Na ₂ CO ₃ ;

- in the waste sludge the content of V ₂ O ₅ total ranged from 1.39 to 3.26% (average 2.1%).

The precipitation of vanadium pentoxide was carried out by thermohydrolysis with sulfuric acid. The precipitator was pumped:

1.2-2.0 m ^{3 of} water,

250-280 liters of sulfuric acid 93%,

alkaline solution of 5.2-6.0 m ³ .

The solution was mixed with compressed air during injection. Precipitation of vanadium pentoxide was carried out at a pH of 1.7-1.9. The solution was boiled with direct steam for 30 minutes. The vanadium pentoxide pulp was pumped onto a suction filter for filtration and subsequent washes (5-10 washes) to remove sodium and sulfur.

During the deposition process, 11 tons of paste of vanadium pentoxide were obtained. The content of V ₂ O ₅ in the drain waters is from 0.25 to 0.97 g / l (average 0.47 g / l), the acidity is 0.9-1.3% (average 1.0%) H ₂ SO ₄ . The results of the deposition of vanadium pentoxide, are presented in tables 7 and 7a, showed that this method can be obtained paste of vanadium pentoxide with a basic substance content of not less than 90%. Analysis of single samples of vanadium pentoxide during the tests showed that its chemical composition varies in the following ranges:

V ₂ O ₅ = 85.1-95.3%; CaO = 0.2-1.1%; S = 0.6-1.8%; Fe ₂ O ₃ = 0.75-1.2%; MnO <0.17%; TiO ₂ = 0.01-0.04%; Cr ₂ O ₃ <0.1%; SiO ₂ = 0.12-0.9%; Na ⁺ = 4.4-7.4%; P = 0.01-0.02%.

Experimentally established:

- washing paste of vanadium pentoxide is carried out at T: W = 1: 1,

- the number of washes is not less than 7.

In vanadium pentoxide obtained from wash water (experiments No. 10, 11, 12), the content of V ₂ O ₃ was 95%.

Table 1
The effect of hematite-containing blade on technological opening The composition of the charge Firing temperature Component Content Ratio The content in the cinder, wt.% Technological showdown material quantity V ₂ O ₅ MnO CaO FeO g ° C wt.% mol g wt.% mol g wt.% mol g wt.% mol g slag
dump V ₂ O ₅ V ₂ O ₅ total % Slag 100.0 15.50 15.50 10.6 10.6 1.40 1.40 31.70 31.70 Blade 30,0 1,1 0.33 5.10 1,53 1.10 0.33 34,20 25.12 Charge 130.0 850 18.18 15.83 9.60 12,13 1.33 1.73 32.60 56.52 1: 0.3 11.20 12.21 91.8 II Slag 100.0 15.50 15.50 10.60 10.60 1.40 1.40 31.70 31.70 31.40 Blade 60.0 2.48 1.49 6.53 3.91 1,52 0.91 35.60 Charge 160,0 850 10.65 16,99 9.07 14.51 1.45 2,31 39.43 63.10 1: 0.6 9.97 10.35 96.4 III Slag 100.0 15.50 15.50 10.60 10.60 1.40 1.40 31.70 31.70 Blade 100.9 1.96 1.97 6.20 6.24 2.10 2.12 38.70 39.00 Charge 200.9 850 8.69 17.47 8.38 16.84 1.75 3.52 35.00 70.30 1: 1 8.41 8.64 97.4

table 2
The effect of soda consumption on the extraction of vanadium from manganese pyrovanate at T: W = 1: 1.5 and a temperature of 90 ° C for 90 min №№ Soda Cinder Vanadium soda solution The ratio of Na ₂ CO ₃ / V ₂ O ₅ , g / g Volume ml Na ₂ CO ₃ , g Na ₂ CO ₃ , g Weight g V ₂ O ₅ ,% Volume ml V ₂ O ₅ , g / l Extracted. V ₂ O ₅ % Ionic form pH MnO SiO ₂ Cr ₂ About ₃ 1 150 7.5 5,0 100 12.55 200 14.6 23.3 V ₃ O ₉ ^3- 9.5 0.007 0.02 out 0.6 2 150 15.0 10.0 100 12.55 200 39.9 63.6 V ₂ O ₇ ^4- 10.0 0.01 0,03 out 1,2 3 150 22.5 15.0 100 12.55 200 59.9 95.5 VO ₄ ^3- 10.5 0.01 0.05 out 1.8

Table 3
The results of the precipitation of vanadium from solutions with a variable ratio of Na: V at 90 ° C for 1 hour at pH 2.0, obtained by neutralization, electrodialysis and sorption Processing method The ratio mol / mol Na / V pH The content in the mother liquor V ₂ O ₅ , g / l Sediment,% VO ²⁺ : VO ₂ V ₂ O ₅ Na ₂ O Neutralization 3: 1 2.0 0.3 83.5 9.8 ^- Electrodialysis 2: 1 2.0 0.3 90.5 7.2 - 0.2: 1 1.8 0.1 97.8 0.7 - Sorption 2: 1 2.0 0.3 91.3 8.2 - 1: 1 2.0 0.3 95.0 7.4 - 0.2: 1 1.9 0.2 98.0 0.6 - Recovery 0.2: 1 2.0 0.1 98.5 0.3 1:20

Claims (1)

A method of processing converter vanadium-containing slags, including slag preparation, roasting with the addition of a reaction additive, leaching the cinder with a solution of soda at a temperature of at least 90 ° C for 1-2 hours to obtain a vanadate solution and isolating vanadium oxide from it, characterized in that during firing, a vanadium production slurry containing hematite and manganese oxide is introduced as a reaction additive at a molar ratio of vanadium to manganese equal to 1: 1, at a temperature of 800-850 ° C for 3 hours, leaching odyat soda solution at a molar ratio of V ₂ O _5: Na ₂ CO ₃ = 1: 1.2-1.8, with sodium vanadate solution by filtration and washing with water, the precipitate is separated from the resulting solution and sodium vanadium electrochemical treatment in a membrane system, sorption or neutralization with sulfuric acid, followed by precipitation of salts of polyvanadic acids.