CN111004930A - Process for refining vanadium from low-grade vanadium waste slag - Google Patents

Process for refining vanadium from low-grade vanadium waste slag Download PDF

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Publication number
CN111004930A
CN111004930A CN201911410473.8A CN201911410473A CN111004930A CN 111004930 A CN111004930 A CN 111004930A CN 201911410473 A CN201911410473 A CN 201911410473A CN 111004930 A CN111004930 A CN 111004930A
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vanadium
low
grade
silica
waste residue
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Chinese (zh)
Inventor
羊泰宇
周泽宇
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Sichuan Runcheng Zhiyuan Technology Co., Ltd
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Yongping Yongtai Industrial Waste Co Ltd
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Priority to CN201911410473.8A priority Critical patent/CN111004930A/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00Obtaining refractory metals
    • C22B34/20Obtaining niobium, tantalum or vanadium
    • C22B34/22Obtaining vanadium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00General methods of reducing to metals
    • C22B5/02Dry methods smelting of sulfides or formation of mattes
    • C22B5/04Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00General methods of reducing to metals
    • C22B5/02Dry methods smelting of sulfides or formation of mattes
    • C22B5/10Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001Dry processes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04Working-up slag
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Abstract

The invention discloses a process for extracting vanadium from low-grade vanadium waste slag, which comprises the steps of placing the low-grade vanadium waste slag and ingredients in a submerged arc furnace for melting, wherein the melting temperature is 1600-1650 ℃, and the ingredients comprise semi-coke, silica and industrial silicon. According to the invention, a certain amount of silica and industrial silicon are added into the low-grade vanadium waste residue for producing the silicon-vanadium alloy by smelting reduction of the low-grade vanadium waste residue, vanadium in the low-grade vanadium waste residue is extracted in the form of the silicon-vanadium alloy, and the recovery of vanadium in the low-grade vanadium waste residue is realized through the mutual synergistic effect of the blue silica and the industrial silicon, wherein the recovery rate of vanadium is about 80-85%.

Description

Process for refining vanadium from low-grade vanadium waste slag
Technical Field
The invention relates to the technical field of vanadium-containing waste residue treatment, in particular to a process for refining vanadium from low-grade vanadium waste residue.
Background
The vanadium-containing waste residue is industrial waste residue, contains recyclable components and has high recycling value. Silicon-vanadium alloy, tailings, ferrovanadium and high-purity pig iron can be produced by refining vanadium-containing waste residues.
The low-grade vanadium slag is vanadium-containing waste slag generated in converter steelmaking, is high-calcium slag, does not separate slag iron, and has high alkalinity and no arcing. The low-grade vanadium waste residue comprises the following components in percentage by weight:
vanadium pentoxide (V)2O5) 1.8-3.5%, iron oxide (FeO) 17-23%, calcium oxide (CaO) 37%, BSilicon oxide (SiO)2) 13-14%, magnesium oxide (MgO) 10%, aluminium oxide (Al)2O3) 3%, phosphorus (P) 0.5%, and the balance other impurities.
At present, no relevant technology for refining vanadium from low-grade vanadium waste residues exists, the significance of researching the refining of vanadium from low-grade vanadium waste residues is important, the treatment of the low-grade vanadium waste residues can realize the recycling of wastes, can avoid environmental pollution, has huge economic benefits and commercial prospects, and also conforms to the sustainable development strategy.
Disclosure of Invention
The invention aims to provide a process for refining vanadium from low-grade vanadium waste residues, which is characterized in that semi-coke, silica and industrial silicon are added into the low-grade vanadium waste residues to refine vanadium, so that the recovery of vanadium in the low-grade vanadium waste residues is realized, and the recovery rate of vanadium is about 80-85%.
The invention is realized by the following technical scheme:
a process for extracting vanadium from low-grade vanadium waste slag comprises the steps of placing the low-grade vanadium waste slag and ingredients into a submerged arc furnace for melting, wherein the melting temperature is 1600-1650 ℃, and the ingredients comprise semi-coke, silica and industrial silicon.
Because the low-grade vanadium waste residue has the characteristics of high calcium, no iron slag and high alkalinity without arcing, no related technology for extracting vanadium from the low-grade vanadium waste residue exists at present, but the low-grade vanadium waste residue contains recyclable components and has high recycling value. The extraction of vanadium from low-grade vanadium waste residue has great significance in researching the extraction of vanadium from waste residue containing vanadium, which can produce silicon-vanadium alloy, tailings, ferrovanadium and high-purity pig iron.
The semi-coke, the silica and the industrial silicon are all commercial products.
In the using process, after a certain amount of semi-coke, silica and industrial silicon are added into the low-grade vanadium waste slag, the mixture is uniformly mixed and put into a submerged arc furnace for refining treatment, an electrode rod is arranged in the submerged arc furnace in a matching way and is inserted into the low-grade vanadium waste slag, silicon-vanadium alloy molten iron and tailings are generated after the low-grade vanadium waste slag is melted at high temperature, raw molten iron is discharged from an outlet at the lower part of the submerged arc furnace, and the tailings are led out of the submerged arc furnace from a slag discharge port at the upper part.
The semi-coke has the effects of reducing vanadium pentoxide in the low-grade vanadium waste residue into a simple substance, reducing the alkalinity of furnace slag (the low-grade vanadium waste residue) by the silica, improving the fluidity of the furnace slag, being a heat release process, and being beneficial to the full melting and reduction of the low-grade vanadium waste residue, so that vanadium is fully reduced, industrial silicon has a strong vanadium reduction effect, and the simple substance silicon is formed for producing silicon-vanadium alloy and is extracted into the low-grade vanadium waste residue in the form of the silicon-vanadium alloy.
According to the invention, a certain amount of semi-coke, silica and industrial silicon are added into the low-grade vanadium waste residue for producing the silicon vanadium alloy by melting reduction of the low-grade vanadium waste residue, vanadium in the low-grade vanadium waste residue is extracted in the form of the silicon vanadium alloy, the recovery effect of the vanadium is outstanding through the mutual synergistic effect of the semi-coke, the silica and the industrial silicon, and the recovery rate of the vanadium is about 80-85%.
Further, by weight, 80-100Kg of semi-coke, 100-150Kg of silica and 100-150Kg of industrial silicon are added to each ton of low-grade vanadium waste slag.
Through experiments, the applicant finds that the addition of the semi-coke, the silica and the industrial silicon according to the proportion not only can realize high recovery rate of vanadium, but also is beneficial to saving the semi-coke, the silica and the industrial silicon.
Furthermore, 90Kg of semi-coke, 150Kg of silica and 150Kg of industrial silicon are added to each ton of low-grade vanadium waste residue by weight.
Further, the low-grade vanadium waste residue comprises the following components in percentage by weight:
V2O51.8-3.5%,FeO17-23%,CaO 37%,SiO213-14%,MgO 10%,Al2O33%, P0.5%, and the balance of other impurities.
Further, the low-grade vanadium waste residue and the ingredients are fully and uniformly mixed and then put into a submerged arc furnace for melting.
The operation is favorable for ensuring that the ingredients are uniformly dispersed in the low-grade vanadium waste slag and is favorable for melting and refining vanadium.
Further, the specific steps of fully mixing the low-grade vanadium waste residue and the ingredients are as follows:
1) respectively crushing and sieving the semi-coke, the silica and the industrial silicon;
2) stirring and mixing the pulverized and sieved semi-coke, silica and industrial silicon uniformly;
3) and adding the mixed semi-coke, silica and industrial silicon into the low-grade vanadium waste residue, and stirring and mixing uniformly again.
The operation is beneficial to fully and uniformly mixing the low-grade vanadium waste residue and the ingredients.
Further, the sieve is 20-100 meshes.
Semi-coke, silica and industrial silicon with smaller particles are beneficial to being uniformly distributed in the low-grade vanadium waste slag, and the recovery efficiency is beneficial to being improved.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the invention, a certain amount of semi-coke, silica and industrial silicon are added into the low-grade vanadium waste residue for producing the silicon vanadium alloy by melting reduction of the low-grade vanadium waste residue, vanadium in the low-grade vanadium waste residue is extracted in the form of the silicon vanadium alloy, and the recovery of vanadium in the low-grade vanadium waste residue is realized through the mutual synergistic effect of the semi-coke, the silica and the industrial silicon, wherein the recovery rate of the vanadium is about 80-85%.
2. The semi-coke, the silica and the industrial silicon are all sold in the market, and the raw materials are easy to obtain and low in price, so that the cost for extracting vanadium from low-grade vanadium waste residues is low, and the industrial popularization is easy.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
Example 1:
a method for extracting vanadium from low-grade vanadium waste residue for a submerged arc furnace comprises the steps of crushing semi-coke, silica and industrial silicon respectively, and sieving by a 50-mesh sieve; stirring and mixing the pulverized and sieved semi-coke, silica and industrial silicon uniformly; adding the mixed semi-coke, silica and industrial silicon into low-grade vanadium waste residues, uniformly mixing, and then putting into a submerged arc furnace for melting, wherein the melting temperature is 1600 ℃, and the ingredients are added with 80 percent of semi-coke, 150 percent of silica and 150 percent of industrial silicon by weight in each ton of low-grade vanadium waste residues, and the low-grade vanadium waste residues comprise the following components in percentage by weight:
V2O53.5%,FeO 22%,CaO 37%,SiO213%,MgO 10%,Al2O33%, P0.5%, and the balance of other impurities.
According to the embodiment, the ingredients are added into the low-grade vanadium slag to refine vanadium (3.5 tons of low-grade vanadium slag are used in the refining process), the content of vanadium in the molten iron discharged from the lower outlet of the submerged arc furnace is about 5.76%, and the recovery rate of vanadium is about 84%.
Calculated according to the following formula:
v in molten iron2O5The recovery rate of vanadium is 0.56 percent of the weight of the grade vanadium waste residue, and the recovery rate of vanadium is vanadium/(V) in molten iron2O5Content 0.56% by weight of the low-grade vanadium slag), wherein V is in the medium vanadium of molten iron and V is in the low-grade vanadium slag2O5The content can be obtained by testing.
For example: in this example, the content of vanadium in the molten iron is about 5.76%, the weight of the low-grade vanadium slag is 3.5 tons, and V in the low-grade vanadium slag2O5The content was 3.5%, and the recovery rate of vanadium was 5.76/(3.5 × 0.56) ═ 84%.
Example 2:
a method for extracting vanadium from low-grade vanadium waste residue for a submerged arc furnace comprises the steps of crushing semi-coke, silica and industrial silicon respectively, and sieving by a 50-mesh sieve; stirring and mixing the pulverized and sieved semi-coke, silica and industrial silicon uniformly; adding the mixed semi-coke, silica and industrial silicon into the low-grade vanadium waste residue, uniformly mixing, and then putting into a submerged arc furnace for melting, wherein the melting temperature is 1650 ℃, and 100Kg of semi-coke, 100Kg of silica and 100Kg of industrial silicon are added into each ton of low-grade vanadium waste residue according to the weight of the ingredients; the low-grade vanadium waste residue comprises the following components in percentage by weight:
V2O51.8%,FeO23%,CaO 37%,SiO214%,MgO 10%,Al2O33%0.5% of P, and the balance of other impurities.
According to the embodiment, the ingredients are added into the low-grade vanadium waste residue to refine vanadium (3.5 tons of low-grade vanadium waste residue are used in the refining process), the content of vanadium in the molten iron discharged from the lower outlet of the submerged arc furnace is about 2.92%, and the recovery rate of vanadium is about 83%.
Example 3:
a method for extracting vanadium from low-grade vanadium waste residue for a submerged arc furnace comprises the steps of respectively crushing semi-coke, silica and industrial silicon by a 20-mesh sieving treatment; stirring and mixing the pulverized and sieved semi-coke, silica and industrial silicon uniformly; adding the mixed semi-coke, silica and industrial silicon into the low-grade vanadium waste residue, uniformly mixing, and then putting into a submerged arc furnace for melting, wherein the melting temperature is 1650 ℃, and the ingredients are added with 90Kg of semi-coke, 150Kg of silica and 150Kg of industrial silicon in each ton of low-grade vanadium waste residue by weight; the low-grade vanadium waste residue comprises the following components in percentage by weight:
V2O53.0%,FeO23%,CaO 37%,SiO213%,MgO 10%,Al2O33%, P0.5%, and the balance of other impurities.
According to the embodiment, the ingredients are added into the low-grade vanadium waste residue to refine vanadium (3.5 tons of low-grade vanadium waste residue are used in the refining process), the content of vanadium in the molten iron discharged from the lower outlet of the submerged arc furnace is about 5.0%, and the recovery rate of vanadium is about 85%.
Example 4:
a method for extracting vanadium from low-grade vanadium waste residue for a submerged arc furnace comprises the steps of crushing semi-coke, silica and industrial silicon respectively, and sieving by a 40-mesh sieve; stirring and mixing the pulverized and sieved semi-coke, silica and industrial silicon uniformly; adding the mixed semi-coke, silica and industrial silicon into the low-grade vanadium waste residue, uniformly mixing, and then putting into a submerged arc furnace for melting, wherein the melting temperature is 1650 ℃, and the ingredients are added with 80Kg of semi-coke, 100Kg of silica and 100Kg of industrial silicon in each ton of low-grade vanadium waste residue by weight; the low-grade vanadium waste residue comprises the following components in percentage by weight:
V2O52.5%,FeO 22%,CaO 37%,SiO214%,MgO 10%,Al2O33%, P0.5%, and the balance of other impurities.
According to the embodiment, the ingredients are added into the low-grade vanadium slag to refine vanadium (3.5 tons of low-grade vanadium slag are used in the refining process), the content of vanadium in the molten iron discharged from the lower outlet of the submerged arc furnace is about 4.12%, and the recovery rate of vanadium is about 82%.
Example 5:
a method for extracting vanadium from low-grade vanadium waste residue for a submerged arc furnace comprises the steps of respectively crushing semi-coke, silica and industrial silicon by 30-mesh sieving; stirring and mixing the pulverized and sieved semi-coke, silica and industrial silicon uniformly; adding the mixed semi-coke, silica and industrial silicon into the low-grade vanadium waste residue, uniformly mixing, and then putting into a submerged arc furnace for melting, wherein the melting temperature is 1650 ℃, and 100Kg of semi-coke, 150Kg of silica and 150Kg of industrial silicon are added into each ton of low-grade vanadium waste residue by weight of the ingredients; the low-grade vanadium waste residue comprises the following components in percentage by weight:
V2O53.0%,FeO 22%,CaO 37%,SiO214%,MgO 10%,Al2O33%, P0.5%, and the balance of other impurities.
According to the embodiment, the ingredients are added into the low-grade vanadium slag to refine vanadium (3.5 tons of low-grade vanadium slag are used in the refining process), the content of vanadium in the molten iron discharged from the lower outlet of the submerged arc furnace is about 5.11%, and the recovery rate of vanadium is about 86%.
Comparative example 1:
this comparative example is based on example 5, differing from the examples in that: 60Kg of semi-coke, 80 silica and 80 industrial silicon are added into each ton of low-grade vanadium waste residue.
According to the proportion, the ingredients are added into the low-grade vanadium waste residue to refine vanadium (3.5 tons of low-grade vanadium waste residue are used in the refining process), the content of vanadium in the molten iron discharged from the lower outlet of the submerged arc furnace is about 4.0 percent, and the recovery rate of vanadium is about 68 percent.
Comparative example 2:
this comparative example is based on example 5, differing from the examples in that: 60 blue carbon, 180Kg silica and 180Kg industrial silicon are added to each ton of low grade vanadium waste slag.
According to the proportion, the ingredients are added into the low-grade vanadium waste residue to refine vanadium (3.5 tons of low-grade vanadium waste residue is used in the refining process), the content of vanadium in the molten iron discharged from the lower outlet of the submerged arc furnace is about 4.7 percent, and the recovery rate of vanadium is about 80 percent.
Comparative example 3:
this comparative example is based on example 5, differing from the examples in that: 60Kg of semi-coke, 150Kg of silica and 150Kg of industrial silicon are added to each ton of low grade vanadium waste slag.
According to the proportion, the ingredients are added into the low-grade vanadium waste residue to refine vanadium (3.5 tons of low-grade vanadium waste residue is used in the refining process), the content of vanadium in the molten iron discharged from the lower outlet of the submerged arc furnace is about 4.6 percent, and the recovery rate of vanadium is about 78 percent.
Comparative example 4:
this comparative example is based on example 5, differing from the examples in that: 120Kg of semi-coke, 80Kg of silica and 80Kg of industrial silicon are added to each ton of low grade vanadium waste slag.
According to the proportion, the ingredients are added into the low-grade vanadium waste residue to refine vanadium (3.5 tons of low-grade vanadium waste residue is used in the refining process), the content of vanadium in the molten iron discharged from the lower outlet of the submerged arc furnace is about 4.21 percent, and the recovery rate of vanadium is about 70 percent.
Comparative example 5:
this comparative example is based on example 5, differing from the examples in that: 120Kg of semi-coke, 100Kg of silica and 100Kg of industrial silicon are added to each ton of low grade vanadium waste slag.
According to the proportion, the ingredients are added into the low-grade vanadium waste residue to refine vanadium (3.5 tons of low-grade vanadium waste residue are used in the refining process), the content of vanadium in the molten iron discharged from the lower outlet of the submerged arc furnace is about 4.23 percent, and the recovery rate of vanadium is about 72 percent.
Comparative example 6:
this comparative example is based on example 5, differing from the examples in that: 120Kg of semi-coke, 180Kg of silica and 180Kg of industrial silicon are added to each ton of low grade vanadium waste residue.
According to the proportion, the materials are added into the low-grade vanadium waste residue to refine vanadium (3.5 tons of low-grade vanadium waste residue is used in the refining process), the content of vanadium in the molten iron discharged from the lower outlet of the submerged arc furnace is about 5.12 percent, and the recovery rate of vanadium is about 87 percent.
The low-grade vanadium waste residue refining process comprises the following steps:
adding semi-coke, silica and industrial silicon into the low-grade vanadium waste slag according to a proportion, uniformly mixing, putting into a submerged arc furnace for refining treatment, wherein the refining temperature is 1600-.
In conclusion, the semi-coke, the silica and the industrial silicon are added into the low-grade vanadium waste residue according to the proportion to produce the silicon-vanadium alloy, and the recovery rate of vanadium is about 80-85 percent. When the addition amounts of the semi-coke, the silica and the industrial silicon are less, the recovery rate of the vanadium is obviously reduced, when the addition amounts of the semi-coke, the silica and the industrial silicon are more, the recovery rate of the vanadium is not obviously increased, and the addition amounts of the semi-coke, the silica and the industrial silicon are set within the range of the invention to be the optimal scheme by comprehensively considering the recovery rate and the economic cost of the vanadium.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (7)

1. A process for extracting vanadium from low-grade vanadium waste slag is characterized in that the low-grade vanadium waste slag and ingredients are placed in a submerged arc furnace to be melted, the melting temperature is 1600-1650 ℃, and the ingredients comprise semi-coke, silica and industrial silicon.
2. The process for extracting vanadium from low-grade vanadium waste residue as claimed in claim 1, wherein 80-100Kg of semi-coke, 150Kg of silica in 100-150Kg of silica and 150Kg of industrial silicon in 100-150Kg of industrial silicon are added per ton of low-grade vanadium waste residue by weight.
3. The process for extracting vanadium from low-grade vanadium waste residue according to claim 2, wherein 90Kg of semi-coke, 150Kg of silica and 150Kg of industrial silicon are added in each ton of low-grade vanadium waste residue by weight.
4. The process for refining vanadium from low-grade vanadium waste residues according to claim 2 or 3, wherein the low-grade vanadium waste residues comprise the following components in percentage by weight:
V2O51.8-3.5%,FeO 17-23%,CaO 37%,SiO213-14%,MgO 10%,Al2O33%, P0.5%, and the balance of other impurities.
5. The process for extracting vanadium from low-grade vanadium waste residues according to claim 1, wherein the low-grade vanadium waste residues and the ingredients are fully and uniformly mixed and then are put into a submerged arc furnace for melting.
6. The process for extracting vanadium from low-grade vanadium waste residues according to claim 5, wherein the specific steps of fully mixing the low-grade vanadium waste residues with the ingredients are as follows:
1) respectively crushing and sieving the semi-coke, the silica and the industrial silicon;
2) stirring and mixing the pulverized and sieved semi-coke, silica and industrial silicon uniformly;
3) and adding the mixed semi-coke, silica and industrial silicon into the low-grade vanadium waste residue, and stirring and mixing uniformly again.
7. The process for extracting vanadium from low-grade vanadium waste residue according to claim 6, wherein the screening is performed by using 20-50 meshes.
CN201911410473.8A 2019-12-31 2019-12-31 Process for refining vanadium from low-grade vanadium waste slag Pending CN111004930A (en)

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