CN1320142C - Method for enriching vanadium in vanadium containing steel slag - Google Patents

Abstract

The present invention provides a method for enriching vanadium in steel slag containing vanadium, which belongs to the technical field of the comprehensive utilization of metallurgical slag. The enriching method comprises the following steps: one or multiple kinds of the following additives with 5 to 16 percent of the amount of the slag are added in the steel slag containing the vanadium: SiO2, Al2O3, and mullite (3SiO2.2Al2O3), and melting process is carried out at atmospheric oxygen level or above the atmospheric oxygen level; after cooling and thermal insulation, the steel slag containing the vanadium is taken out and quenched in the air. By the enriching method, over 80 percent of the vanadium in diffused distribution in the steel slag containing the vanadium is diverted to a new phase rich in the vanadium for enriching, and the vanadium is separated by crystallization to obtain a vanadium-rich phase with the grade of the vanadium-rich phase. The present invention is favorable for the separation and the extraction of the vanadium from the steel slag; the enriching method has the advantages of simple process, low cost, high enriching rate of the vanadium, and high economic and social benefits.

Description

The enriching method of vanadium in a kind of v-bearing steel slag

Technical field:

The invention belongs to metallurgical slag comprehensive utilization technique field, be specifically related to the enriching method of vanadium in a kind of v-bearing steel slag.

Background technology:

Explored in the world vanadium resource reserves have 98% symbiosis in vanadium titano-magnetite.China's Panxi Diqu, Anhui Maanshan, v-bearing titanomagnetite smelting iron is being adopted in the Chengde, and part is reduced and enters in the molten iron, and the vanadium major part in steelmaking process that enters in the molten iron changes in the slag, forms vanadiumcontent (with V ₂O ₅Meter) at the v-bearing steel slag of 2-4%.The v-bearing steel slag enormous amount that vanadiumcontent is low not only contains the low and vanadium disperse of vanadium grade and is distributed in a plurality of mineral facies; Contain vanadium phase thing phase composite complexity, therefore directly disseminated grain size is tiny, it is carried out that the technical difficulty of ore dressing, smelting is big, cost is high, and be difficult to big argument and handle.

Utilize v-bearing steel slag to produce vanadium or V at present ₂O ₅Main method two kinds of pyrogenic process-wet process and wet method-firing method process are arranged.Preceding a kind of method is that the slag that will hang down vanadium-containing molten iron direct steelmaking gained returns the blast furnace enrichment again through sintered material, and the high vanadium ferroalloy water of producing blows vanadium and obtains V through converter ₂O ₅The rich vanadium slag that grade is higher, this vanadium-rich slag can be produced V with wet method ₂O ₅This method disadvantage be in the enrichment vanadium also enrichment phosphorus, the phosphorus content that causes high vanadium ferroalloy water and the vanadium slag that blows out thus and smelt the ferro-vanadium that raises; Perhaps will allocate NaCl and Na into after the screening of v-bearing steel slag process, the magnetic separation ₂CO ₃Deng sodium salt.In 750-850 ℃ of oxidizing roasting, the cooling back adopts the carbonating leaching to carry out vanadium extraction in rotary kiln, and the shortcoming of this method is the sodium salt consumption, and energy consumption is higher, and the vanadium recovery rate is low.A kind of method in back is directly to handle v-bearing steel slag with industrial sulphuric acid, forms thick vanadium, soaks with alkali again, obtains ammonium poly-vanadate, carries out roasting with fixed bed or fluidized-bed then; Its shortcoming is that production unit is huge, and floor space is big, and technical process is long, and the vanadium metal rate of recovery is low, and acid, alkali consumption is big, produces a large amount of sour gas during roasting, and environmental pollution is serious, and production efficiency is low, the product cost height.

Summary of the invention:

The present invention is directed to the problem that above-mentioned prior art exists, the enriching method of vanadium in a kind of v-bearing steel slag is provided, be beneficial to separation, the extraction of vanadium from slag.Indication v-bearing steel slag of the present invention is vanadium-bearing hot metal last slag body behind converter smelting, contains that the vanadium grade is lower (to contain 2-4%V ₂O ₅), the vanadium disperse composes the slag be stored in a plurality of mineral facies.

The enriching method of vanadium may further comprise the steps in the v-bearing steel slag that is provided among the present invention:

(1) one or more following additive: SiO of adding quantity of slag 5-16% in v-bearing steel slag ₂, Al ₂O ₃, mullite (3SiO ₂2Al ₂O ₃).

(2), rise to 1500-1550 ℃ with 3-5 ℃/min temperature rise rate and carry out melt processed 30min in the atmosphericoxygen position or be higher than under the condition of atmosphericoxygen position; Rate of cooling with 0.5-5 ℃/min is cooled to 1250-1300 ℃ then, is incubated, and soaking time is at 30-300min.

(3) after insulation finishes, v-bearing steel slag is taken out quenching in air.

Vanadium enrichment in the v-bearing steel slag after above enriching method is handled more than 80% enter a rich vanadium mutually in.The method of calculation of the enrichment of vanadium are as follows in the v-bearing steel slag:

Rich vanadium is the grade of middle vanadium mutually, w (V ₂O ₅%), be with the middle mutually V of rich vanadium ₂O ₅Percentage composition calculate.

The technological principle of this method is as follows:

(1) at atmosphere or be higher than under the condition of atmosphericoxygen position, to v-bearing steel slag melt, modification, slow cooling handle, and makes in the slag multivalence attitude compose the vanadium of depositing, the overwhelming majority is unified to+5 valencys, realizes the unification of valence state, is convenient to it and is easy to be transferred to same slag phase.

(2) add one or more following additive SiO ₂, Al ₂O ₃, mullite (3SiO ₂2Al ₂O ₃), be issued to modification in the high temperature melting condition to v-bearing steel slag, reduced the basicity of v-bearing steel slag $R$ $(=\frac{\mathrm{CaO}\%+\mathrm{MgO}\%+\mathrm{MnO}\%}{{\mathrm{SiO}}_2\%+{\mathrm{Al}}_2{O}_3\%+P_2{O}_5\%}).$ Like this, in the slag overwhelming majority of vanadium with [VO ₄ ^3-] form and [PO ₄ ^3-] solid solution, what form a solid solution contains the vanadium enrichment phase.

(3) add one or more following additive: SiO ₂, Al ₂O ₃, mullite (3SiO ₂2Al ₂O ₃) the v-bearing steel slag fusion and the insulation, it is even to make slag and additive reach composition, cools off then, is incubated, and rich vanadium can be separated out in v-bearing steel slag.

Advantage of the present invention is by adding one or more following additive SiO ₂, Al ₂O ₃, mullite (3SiO ₂2Al ₂O ₃), and at atmosphere or be higher than fusion and cooling curing under the condition of atmosphericoxygen position, with disperse in the slag distribute, the effective isolating vanadium of argument direct economy greatly, be enriched to contain vanadium rich vanadium mutually in, the enrichment of vanadium reaches more than 80%, the rich vanadium grade of middle vanadium mutually reaches 12-20%, obtains the available physical method and carries out the rich vanadium phase that big argument is separated and utilized.This enriching method technology is simple, cost is low, the enrichment height of vanadium, has bigger economic and social benefits.

Embodiment:

Embodiment 1: be the v-bearing steel slag of reality, its component is: 39.2%CaO, 29.4%Fe ₂O ₃, 13.3%SiO ₂, 5.2%Al ₂O ₃, 4.7%MgO, 3.6%V ₂O ₅, 2.5%P ₂O ₅, 0.9%TiO ₂, 1.2%MnO.Add the heavy Al of 16% slag ₂O ₃, under the atmosphericoxygen position,, be cooled to 1250 ℃ of insulation 120min down with 3 ℃/min speed then in 1530 ℃ of fusings 30 minutes, after quenching solidified in the air, slag specimen cutting and abrasive disc were through scanning electron microscope and energy spectrum analysis, the enrichment of vanadium reaches 87.5%, and the rich vanadium grade of middle vanadium mutually is 20%.

Embodiment 2: be the v-bearing steel slag of reality, its component is: 39.2%CaO, 29.4%Fe2O3,13.3%SiO2,5.2%Al2O3,4.7%MgO, 3.6%V2O5,2.5%P2O5,0.9%TiO2,1.2%MnO.Add the heavy SiO2 of 5% slag, under the atmosphericoxygen position, melted 30 minutes in 1530 ℃, be cooled to 1250 ℃ of insulation 120min down with 3 ℃/min speed then, after quenching solidifies in the air, slag specimen cutting and abrasive disc, through scanning electron microscope and energy spectrum analysis, the enrichment of vanadium reaches 86.5%, and the rich vanadium grade of middle vanadium mutually is 12%.

Claims (2)

1, the enriching method of vanadium in a kind of v-bearing steel slag is characterized in that this method may further comprise the steps:

(1) one or more following additive: SiO of adding quantity of slag 5-16% in v-bearing steel slag ₂, Al ₂O ₃, 3SiO ₂2Al ₂O ₃

(2), rise to 1500-1550 ℃ with 3-5 ℃/min temperature rise rate and carry out melt processed 30min in the atmosphericoxygen position or be higher than under the condition of atmosphericoxygen position; Rate of cooling with 0.5-5 ℃/min is cooled to 1250-1300 ℃ then, is incubated, and soaking time is at 30-300min;

(3) after the insulation, v-bearing steel slag is taken out quenching in air.

2, the enriching method of vanadium in a kind of v-bearing steel slag according to claim 1 is characterized in that described v-bearing steel slag is vanadium-bearing hot metal last slag body behind converter smelting.