JPS63100019A - Manufacture of vanadium pentoxide - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to chemical and metallurgical technology, and more particularly to a process for producing vanadium pentoxide useful in the production of vanadium alloys, hardeners, and catalysts.

The basic raw material for producing vanadium pentoxide is vanadium-containing slag, which is obtained in metallurgical engineering when processing titanium magnetite ore containing 0.5-2% by weight of vanadium.

[Conventional technology]

In the Soviet Union, a comprehensive process for the processing of titanium magnetite ore was developed and is being implemented industrially, which consists of a step in which iron and vanadium are simultaneously recovered from the ore by pyrometallurgy. A similar system is used to process titanomagnetite ore in South Africa and China (K, M, Sokolov 7).
Overseas production and consumption
Consumption Abroad) J, Bulletin of the Institution) (Bulle
tin of the In5 position
tsija) J, October 1981 issue, (894),
(See pages 3-15). According to this system, titanium magnetite ore is processed into vanadium iron and further processed into steel and vanadium slag by oxidation with a gaseous oxidizer in a converter.

The vanadium slag obtained is the starting material for the production of vanadium pentoxide.

The method for producing vanadium pentoxide from converter slag consists of the following steps. Pretreatment for power calcining (crushing, crushing, separation, mixing with reactants), oxidative power calcining, solvents (water,
leaching of the power-calcined material with solutions of acids and alkalis), precipitation of vanadium pentoxide from the solution, drying, melting and granulation of the vanadium pentoxide obtained.

Other methods of producing vanadium pentoxide from rosyulite, carnotite, patronite and polymetallic ores, bauxite and apatite are approximately the same in terms of the main steps of this system.

The simplest method of hydrometallurgy for the recovery of vanadium from titanomagnetite has been developed and implemented in Finland (N. P. Lyakishev)
“Vanadium i in iron metallurgy”
n Ferrous Metallurgy) J,
Moscow, Nletallurg
izdat), 1983, page 192).

Due to the small amount of silicon and calcium oxides in the starting ore, 67-67.7 wt.% Fe, 0.58 wt.% Sin□, 2.8 wt.% TiO□, 0.98-,
It becomes possible to obtain an iron-vanadium concentrate containing 12% by weight of V2O3, 0.2% by weight of Can. Vanadium is recovered from this concentrate without going through a pyrometallurgical enrichment step.

In this conventional process, pellets containing soda (2%) are oxidatively roasted and then sodium vanadate is produced, from which after the usual operations (precipitation, washing, drying, melting) 95%
% or more of vanadium pentoxide is obtained. The recovery rate of vanadium is 77.5%. However, this method is only effective if the composition of the starting material meets the requirements of the method.

Titanium magnetite is mostly characterized by high concentrations of calcium oxide and silica, and therefore this technology cannot be used for processing titanomanetite.

For such cases, a method has been developed to produce vanadium pentoxide from vanadium slag in a converter.
This method involves the preparation of a starting vanadium-containing slag for power firing,
Torrefaction of the slag in the presence of reactive additives, leaching of the torrefied material, separation of the resulting vanadium solution from the cake,
It consists of the steps of precipitation of vanadium pentoxide, its drying and melting (see N, P, U Akishev et al., Vanadium in Iron Metallurgy, Metallurgyzdat, 1983, page 31). In this way, 65-8 of vanadium was added to the aqueous solution.
5% is extracted. However, along with vanadium, aluminates, titanates, and silicates also pass into solution to form waterglass, which is hydrolyzed to form colloidal precipitates.

This impairs the filtration of the valve and contaminates the final vanadium pentoxide with oxides of silicon, aluminum, and other elements. The product thus produced is 80-85%
Contains up to 87-88.0% vanadium pentoxide. In this process, it is necessary to keep optimally a number of fundamental parameters characterizing the starting materials and the overall process in order to recover vanadium as vanadium pentoxide with high recovery rates. Therefore, vanadium slag is used during preconditioning for torrefaction (separation into phases, crushing), during torrefaction (reducing sintering capacity), during leaching (increasing the amount of vanadium extracted, filtration capacity of the pulp). (increased), it should have good properties with respect to its chemical and mineralogical composition, grain size, porosity, mechanical strength, density, etc. For this reason,
Proper selection of the starting charge and the composition of the vanadium slag is very important.

[Problems to be solved by the invention]

The present invention relates to a solution to the problems associated with the production of vanadium pentoxide from performer's material, which makes it possible to obtain a vanadium-containing solution of higher purity and improve the quality of the final product.

[Means for solving problems]

The method of the present invention to solve this problem consists of producing a comedian material by mixing vanadium slag and soda with each other, power-calcining the comedian material in an oxidizing atmosphere, and leaching the power-calcined material. Separate the vanadium solution from the cake,
In a method for producing vanadium pentoxide, which comprises the step of precipitating vanadium pentoxide from this solution, the entertainer material contains 10-40% by weight of soda and the following composition: Calcium oxide 3-40% by weight Magnesium oxide 2-15% by weight oxide vanadium
14-30% by weight silicon oxide
12-32% by weight oxides of iron, titanium, chromium, manganese, aluminum, phosphorus, balance Sin□: weight ratio of (CaO+Mg0) 0.75-
It is characterized in that it is produced by mixing 60-90% of vanadium slag with 0.85.

In one embodiment of this method, a performer material containing vanadium slag and soda as described above is charged with 3-15% by weight of the cake obtained from the leaching step of the force-baked material.

The present invention makes it possible to increase the recovery of vanadium from the artist material to the final product by 1-2% and to increase the filtration rate of vanadium-containing aqueous solutions by a factor of 5-10.

The method of the invention will be explained in detail below.

Vanadium slag used in the production of vanadium pentoxide is
It is produced by purging vanadium iron with an oxidizing agent in an oxygen converter using magnesium and/or calcium containing materials as the flux.

Vanadium slag has the following composition.

Calcium oxide 3-40% by weight Magnesium oxide 2-15% by weight Vanadium oxide
14-30% by weight silicon oxide
12-32% by weight of oxides of iron, titanium, chromium, manganese, aluminum, phosphorus; the balance of the above-mentioned oxides within the above-mentioned range;
: Weight ratio of (CaO+MgO) is 0.75-0.85
Choose so that This range of ratios of silicon oxide to the total amount of calcium oxide and magnesium oxide in the slag results in the formation of thermodynamically more stable and durable silicates, which allow the power calcined material to be leached with water. Furthermore, it becomes possible to produce solutions with a low content of silicon, manganese and other elemental impurities. Furthermore, the above 5102: (
The ratio of CaO+MgO) makes it possible to significantly reduce the strong tendency to form suspensions that is characteristic of conventional processes and reduces vanadium recovery.

Vanadium slag with the above composition is crushed and mixed with soda ash in the following proportions.

Soda 10-40% by weight Vanadium slag 60-90% by weight The reason for specifying this ratio of charging material components, namely vanadium slag and soda, is that if the soda content in the charging material is less than 10%, from the power-calcined material This is because the recovery of vanadium into solution is less than 60% and additional recovery steps, such as acid leaching steps, are required, resulting in significant contamination of the final product with impurities such as manganese and phosphorus. If the soda content in the charging material exceeds 40%, it is unsuitable because increasing the content will not increase the vanadium recovery rate or improve the quality of the final product, and on the other hand, the undesirable phenomenon of sintering of the entertainer material will occur. This is because it may cause a decrease in power firing productivity.

The above selection of the content of vanadium oxide in the vanadium slag is because below a content of vanadium oxide of less than 14%, the consumption rate of reactants per ton of final product increases significantly; This is because if it exceeds 30%, the degree of sintering of the entertainer material during force sintering increases and the recovery rate of vanadium decreases.

The charge of the above composition is calcined at a temperature in the range of 700-800<0>C. For example, heat the hard-fired material with water to 70-9
Leaching at a temperature of 0° C. and filtering the resulting bulb. Filtration proceeds at high speed.

It is only when the slag has the above-mentioned composition that the valve can be filtered at high speeds and the solution obtained by filtering the valve can ensure the required purity. That is, the content of oxides is 3-40% by weight of calcium oxide, 2-1% by weight of magnesium oxide.
5% by weight, 14-30% by weight of vanadium oxide, 12-32% by weight of silicon oxide, and the remaining amounts of oxides of iron, titanium, chromium, manganese, aluminum, and phosphorous.

Bulb filtration yields a cake and a vanadium-containing solution. In order to obtain vanadium pentoxide of high purity, the vanadium-containing solution can be treated beforehand with aluminum salts, such as aluminum chloride, aluminum sulfate or alum. Vanadium is precipitated from the solution as ammonium vanadate. The resulting ammonium vanadate precipitate is filtered, washed, dried, calcined in an oxidizing atmosphere and then melted at a temperature of 670-720°C, resulting in vanadium pentoxide.

In order to reduce the vanadium lost with the cake (waste) and increase the overall recovery of vanadium from the slag, the charge containing vanadium slag and soda is supplemented with the 1- 3-15% by weight of cake containing 3% by weight of vanadium pentoxide is introduced.

The above amount of cake additives is defined as 3% of the cake.
Adding less than 15% will not have a substantial effect on increasing the recovery rate of vanadium, and adding more than 15% will reduce the productivity of calcining of the charging material and contaminate the final product. It is.

When the method for producing vanadium pentoxide of the present invention is compared with the conventional method, it has the following advantages.

- Recovery of vanadium from the charge to the final product is 1
-2% increase.

The filtration rate of monovanadium-containing pulp is 1-5 m'
/mI-h to 25-35 m'/m'-hl: Increase.

- the impurity content in the vanadium solution and final product is 2
/3-1/2.

The production cost per ton of vanadium pentoxide has decreased.

The best mode for carrying out the method of the invention is described below.

The charge is prepared by mixing 25-30% by weight of soda ash with 70-75% by weight of vanadium slag containing the following oxides:

Calcium oxide 9-15% by weight Magnesium oxide 4-6% by weight Silicon oxide
12-15% by weight vanadium oxide
14-20% by weight Fe, Mn, Ti, Cr.

Oxide of Al5P The weight ratio of silicon dioxide in the residual vanadium slag to the sum of oxides of Ca and Mg, i.e. 5i02: (CaO+λ1g0
) is in the range of 0.75-0.85. The resulting charge is calcined in air at 740-760°C. The force-calcined material is mixed with water and the solid phase-liquid phase ratio S:L=l:(2-4), 7
Leaching at a temperature of 0-80°C. The bulb thus produced is filtered to separate the residue, a cake containing 1-3% vanadium pentoxide. 25-65g obtained
/f! A solution containing vanadium pentoxide of 80-9
At a temperature of 5 DEG C., it is treated with an ammonium salt, for example ammonium sulfate, at a pH of 2.0-2.5, which pH is maintained during the precipitation by adding a mineral acid, for example sulfuric acid. The ammonium vanadate precipitate formed was filtered, washed with water, dried at a temperature of 100-150°C, and calcined at a temperature of 250-450°C in an oxidizing atmosphere to 670°C.
Melts at a temperature of -720°C.

The final (molten) vanadium pentoxide is V2O595°3
Weight%, V2O4 1.2% by weight, Fe5Si, Mn5
S.

The remainder contains PSCr impurities. V, O3 to aqueous solution
The recovery rate is 91-94%.

To produce vanadium pentoxide of high purity (more than 98,0%), an aluminum salt, for example aluminum alum, is added together with an ammonium salt to the filtrate containing 25-65 g#'nov, os.

In this case silicon and other impurities precipitate and this precipitate is removed by filtration.

Add inorganic acid to the filtrate and adjust ammonium vanadate to pH
After precipitating with 2,0-2,5, the precipitate is calcined,
V2O599.8% by weight, v, o, 0.1% by weight,
A final product containing residual amounts of impurities Fe, Si, MnSSPSCr is obtained.

EXAMPLES In order that the present invention may be better understood, the following specific examples illustrate the production of vanadium pentoxide.

Example 1 10% by weight of soda ash, 3% by weight of calcium oxide, 15% by weight of magnesium oxide, and 15% by weight of silicon oxide.
15% by weight vanadium oxide
28% by weight Fe5Ti, CrSMn.

The charge material is prepared by mixing A1 with 90% by weight of vanadium slag containing the remainder of the oxide of P.

5in2 in vanadium slag: (Can +MgO
) is 0.85. The resulting charge is calcined in air at a temperature of 700°C. Mix the hard-baked ingredients with water,
Leaching is carried out at a solid phase-liquid phase ratio S:L=1:4 and a temperature of 75°C. Filter the resulting bulb. The solid residue (cake) contains 3% by weight of vanadium pentoxide.

The filtered solution contains 64 g/R of vanadium pentoxide, which is precipitated with ammonium sulfate at pH 2.0-2.2 in the form of ammonium vanadate. The ammonium vanadate precipitate was filtered and washed, and 140-15
It is dried at a temperature of 0°C, calcined at a temperature in the range of 300-450°C and melted at a temperature of 680-720°C. The final (molten) product contains 94.0% by weight of VzOs, V2O4
1.0 weight ffi%, Fe, Si, Cr, Mn, S
Contains a residual amount of SP impurities.

Example 2 20% by weight of soda ash, 11% by weight of calcium oxide, 5% by weight of magnesium oxide, and 5% by weight of silicon oxide.
12% by weight vanadium oxide
30% by weight Fe, Ti5Cr, Mn.

The charge material is prepared by mixing with 80% by weight of vanadium slag containing the balance ^f, oxide of P.

Stow in vanadium slag: (CaO+MgO
) is 0.75. The produced charge is calcined in air at 700°C. The force-calcined material is mixed with water to form a solid phase.
Leaching is carried out at a liquid phase ratio S:L=1:4 and a temperature of 80°C. Filter the resulting bulb. The resulting solution contains 69 g/l vanadium pentoxide and the cake contains 3% vanadium pentoxide. The vanadium pentoxide in solution is precipitated with ammonium sulfate at p) 12.4-2.5 in the form of ammonium vanadate. The ammonium vanadate precipitate was filtered off, washed, dried at a temperature of 140-150°C, calcined at a temperature in the range of 320-440°C, and
Melts at temperatures of 80-720°C.

The final (molten) product, i.e. vanadium pentoxide, is V2ns
94.5% by weight, V2O40.9% by weight, Fe5S
The remainder contains impurities of T, Cr, S, and P.

Example 3 40% by weight of soda ash, 40% by weight of calcium oxide, 2% by weight of magnesium oxide, and 2% by weight of silicon oxide.
32% by weight vanadium oxide
The charge is prepared by mixing 14% by weight of Fe5TtSCr with 60% by weight of vanadium slag containing the balance oxide of Mn5 1,P.

5in2 in vanadium slag: (Can +MgO
) is 0.75. The charge is calcined at a temperature of 800°C. Mix the hard-burned material with water, ratio S:L=1:4
．． Leaching at a temperature of 90°C. Filter the resulting bulb. The solid residue (cake) contains 1% vanadium pentoxide.

The filtered solution contains 32.5 g/1 vanadium pentoxide, which is purified with ammonium sulfate by p)I L
.

9-2.1 in the form of ammonium vanadate.

The ammonium vanadate precipitate was filtered and washed, and 15
It is dried at a temperature of 0°C, calcined at a temperature of 380-430°C and melted at a temperature of 680-720°C.

The final (molten) product, i.e. vanadium pentoxide, is V2O5
95.1% by weight, v, o, 0.4% by weight, Fe
, Si.

The remainder contains λin, Cr, s, and P impurities.

Example 4 25% by weight of soda ash, 15% by weight of calcium oxide, 5% by weight of magnesium oxide, and 5% by weight of silicon oxide.
16% by weight vanadium oxide
25 wt% 1”e, Ti5Cr, Mn.

A charge material is prepared by mixing with 75% by weight of vanadium slag containing the balance of oxides of Al1 and P.

S+02 in vanadium slag: (CaO+li
The weight ratio of 1go) is 0.80. 75% charge material
Power bake at a temperature of 0°C. Add force-baked materials to water, S:L=
1: Leaching at a temperature of 3.80°C. Filter the resulting pulp. The solid residue (cake) contains 2.1% vanadium pentoxide and the filtered solution contains 32°5 g/l V
Contains 2O. Vanadium pentoxide is precipitated from the solution with ammonium sulfate at pH 2.0-2.2.

The operations described in Examples 1-3 are then repeated, and the resulting product contains 94.8% by weight of V, O, 8% by weight of V2[140°, and the remainder containing impurities Fe5Si, Mn5CrSS, and P. .

Example 5 To the charge previously described in Example 2, 3% by weight of the cake produced by leaching with water is added. The subsequent operations and parameters of calcining, filtration, precipitation and other operations of the material are similar to those described in Example 2.

The final vanadium pentoxide contains v, o, 94.4% by weight, V2O40,9% by weight, Fe, Si, Mn, C
The remainder contains r, S, and P impurities.

Example 6 To the charge previously described in Example 3, 15% by weight of the cake obtained by leaching with water is added. The subsequent operations and parameters of calcining, filtration, precipitation and other operations of the material are similar to those described in Example 3.

The final vanadium pentoxide is V2O, 95.0% by weight,
v, o, 0.4% by weight, Fe5Si, Mn5Cr
The remainder contains impurities of , S, and P.

Example 7 To the charge previously described in Example 4, 8% by weight of the cake obtained by leaching with water is added. The subsequent operations and parameters of calcining, filtration, precipitation and other operations of the material are similar to Example 4.

The final vanadium pentoxide is V, 0. 94.9% by weight
, v, o40.7% by weight, Fe, Si, Mn5Cr
The remainder contains impurities of , S, and P.

〔Effect of the invention〕

The present invention (1) increases the recovery rate of vanadium from slag to the final product by 1-2%, (2) increases the filtration rate of the vanadium-containing valve to 35 m'/m'·h, and (3) reducing the amount of impurities in the final product, (4)
It becomes possible to reduce the raw material consumption per ton of final product.

Claims (1)

[Claims] 1. Prepare a charge material by mixing vanadium slag and soda, calcin it in an oxidizing atmosphere, leaching the calcined material, and cake the resulting vanadium solution. In preparing vanadium pentoxide by separating it from solution and precipitating the vanadium pentoxide from solution, the charge is composed of 10-40% by weight of soda and the following chemical composition: Calcium oxide 3-40% by weight Magnesium oxide 2-15% by weight Vanadium oxide 14-30% by weight Silicon oxide 12-32% by weight Oxides of Fe, Cr, Mn, Ti, Al, P Balance Weight of silicon dioxide relative to the total amount of calcium oxide and magnesium oxide in the slag A method for producing vanadium pentoxide, characterized in that it is produced by mixing vanadium pentoxide with 60-90% by weight of vanadium slag at a ratio of 0.75-0.85. 2. Process according to claim 1, characterized in that the charge contains 3-15% by weight of the cake obtained in the leaching step of the calcined material.