CN114107773B - 50 ferrovanadium-silicon and preparation method thereof - Google Patents
50 ferrovanadium-silicon and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of metallurgy, and provides 50 ferrovanadium-silicon and a preparation method thereof. The 50V-Si-Fe alloy provided by the invention is an alloy consisting of Si, Fe and V, is an innovative product, can be used as a reinforced alloy additive for ferrous metallurgy, and can also be used as a raw material for producing high-nitrogen ferrovanadium. The method adopts vanadium slag and 75 ferrosilicon as raw materials, obtains vanadium-silicon molten iron through reduction smelting, and leads V in the molten slag to be processed through depletion treatment and reduction treatment on the molten slag 2 O 5 Fully utilizing the vanadium slag, and finally realizing the direct preparation of the 50 vanadium-silicon-iron by adopting the vanadium slag. The preparation method provided by the invention has the advantages of simple steps, easiness in operation, low cost and no generation of waste liquid and waste gas. The method for preparing the 50 ferrosilicon vanadium by using the vanadium slag can simplify the process, reduce the production cost, solve the problem of waste water and waste gas treatment and improve the economic and social benefits.
Description
Technical Field
The invention relates to the technical field of metallurgy, in particular to 50 ferrovanadium-silicon and a preparation method thereof.
Background
The ferrovanadium is an iron alloy, is widely used as an element additive for smelting vanadium-containing alloy steel and alloy cast iron, and can also be used for manufacturing permanent magnets.
At present, the most common ferrovanadium is 50 ferrovanadium or 80 ferrovanadium, the 50 ferrovanadium is generally prepared by using flaky vanadium pentoxide or vanadium trioxide as a raw material by an electric furnace silicon reduction method or an aluminothermic reduction method, and the 80 ferrovanadium is also prepared by using flaky vanadium pentoxide or vanadium trioxide as a raw material by an electric furnace aluminothermic method or an external aluminothermic method. At present, when ferrovanadium is prepared in a factory, vanadium slag is firstly used for preparing vanadium flakes (flaky vanadium pentoxide or vanadium trioxide), and then the ferrovanadium is prepared. When the vanadium slag is used for preparing vanadium tablets, the working procedures of roasting, leaching, purifying, vanadium precipitation, deamination, melting, tablet making and the like are required, the steps are complex, a large amount of wastewater is generated in the working procedures of leaching, purifying, vanadium precipitation and the like, the wastewater is difficult to treat and has serious environmental pollution, and 12.3 tons of vanadium contain 10 percent of V 2 O 5 The vanadium slag can obtain 1 ton of V with the concentration of 98 percent 2 O 5 Flake vanadium, the processing cost is about 2.2 ten thousandYuan per ton of 50 ferrovanadium.
In addition, the existing ferrovanadium alloy is composed of vanadium and iron, and no report is made on ferrovanadium-silicon alloy.
Disclosure of Invention
The invention aims to provide 50 ferrosilicon vanadium and a preparation method thereof. The invention innovatively provides the ferrovanadium-silicon alloy, the 50 ferrovanadium-silicon alloy is prepared by directly utilizing vanadium slag, the preparation process is simple, the cost is low, and the problem of environmental pollution in the process of preparing vanadium flakes by utilizing the vanadium slag is avoided.
In order to achieve the above object, the present invention provides the following technical solutions:
the 50 ferrosilicon vanadium iron comprises the following chemical components in percentage by mass: 48-55% of V, 5-23% of Si, 0-6% of Cr, less than 0.5% of C, less than 0.1% of P, less than 0.05% of S and the balance of Fe.
The invention provides a preparation method of 50 ferrosilicon vanadium iron, which comprises the following steps:
mixing high-grade vanadium slag, 75 ferrosilicon and a slag former for reduction smelting to obtain a molten material, wherein the molten material comprises vanadium-silicon molten iron and molten slag; v in the high-grade vanadium slag 2 O 5 The content of (A) is more than 30 percent;
adding a carbonaceous reducing agent into the molten material to carry out depletion treatment on the molten slag, wherein the molten slag is subjected to depletion treatment to form depleted slag, so that depleted molten material is obtained;
adding aluminum particles into the depleted molten material, reducing the depleted slag, and then discharging slag and vanadium-silicon molten iron;
and (4) casting the discharged ferrovanadium-silicon liquid to obtain a 50 ferrovanadium-silicon block.
Preferably, the reduction smelting is carried out in an electric arc furnace; the capacity of the electric arc furnace is 1800-50000 KVA.
Preferably, the preparation method of the high-grade vanadium slag comprises the following steps:
mixing the low-grade vanadium slag and a carbonaceous reducing agent for melting reduction to obtain molten iron and high-grade vanadium slag; v in the low-grade vanadium slag 2 O 5 The content of (b) is more than 20%.
Preferably, the low-grade vanadium slag is self-made low-grade vanadium slag or outsourcing low-grade vanadium slag; the self-made low-grade vanadium slag is obtained through the following steps:
blowing soda ash into vanadium-containing molten iron for impurity removal treatment, and then slagging off to obtain furnace slag and purified molten iron;
and carrying out oxygen blowing on the purified molten iron to extract vanadium, thereby obtaining the self-made low-grade vanadium slag.
Preferably, the self-made low-grade vanadium slag comprises the following chemical components in percentage by mass: 30-34% of TFe, 20-26% of FeO and V 2 O 5 >25％、Ti<3％、SiO 2 <3％、TiO 2 <3％、CaO<0.8％、MgO<1.2％、Cr 2 O 3 3-4％、P<0.05％、S<0.08 percent; the high-grade vanadium slag prepared from the self-made low-grade vanadium slag comprises the following chemical components in percentage by mass: TFe 11-13% FeO<10％、V 2 O 5 >35％、Ti<3％、SiO 2 <6％、TiO 2 <3％、CaO<0.80％、MgO<1.2％、Cr 2 O 3 3-5％、P<0.05％、S<0.05％；
The outsourcing low-grade vanadium slag comprises the following chemical components in percentage by mass: 30-35% of TFe, 26-30% of FeO and V 2 O 5 20-25.5％、TiO 2 ＜4.5％、SiO 2 <17％、CaO＜2.1％、MgO＜3.2％、Al 2 O 3 ＜1％、Cr 2 O 3 <5.0％、MnO＜4％、P<0.06％、S<0.05 percent; the high-grade vanadium slag prepared from the outsourcing low-grade vanadium slag comprises the following chemical components in percentage by mass: TFe 11-13% FeO<10％、V 2 O 5 >30％、TiO 2 <6％、SiO 2 <21.0％、CaO 0.30-3％、MgO 1.20-3％、Cr 2 O 3 <5.5％、P<0.06％、S<0.10％。
Preferably, V in the lean slag 2 O 5 Less than 8 wt%, FeO less than 1 wt%, Si more than 10 wt% and C less than 0.5 wt% in the molten vanadium-silicon iron after the impoverishment treatment.
Preferably, forReducing the depleted slag to obtain reducing slag, wherein V in the reducing slag 2 O 5 ＜0.35wt％。
Preferably, the discharged molten silicon vanadium iron comprises the following chemical components in percentage by mass: TFe 30-35%, V48-55%, Si 8-23%, Cr 0-6%, C < 0.5%, P < 0.08%, S < 0.05%.
Preferably, the slag discharge is performed to obtain waste slag, and the method further comprises the following steps: and sequentially carrying out impact crushing, jaw crushing, ball milling and magnetic separation on the waste residues, recovering vanadium iron particles, using the residual waste residues for manufacturing cement, and returning the recovered vanadium iron particles to the reduction smelting step for preparing the 50 vanadium silicon iron.
The invention provides 50 ferrosilicon vanadium which comprises the following chemical components in percentage by mass: 48-55% of V, 5-23% of Si, 0-6% of Cr, less than 0.5% of C, less than 0.1% of P, less than 0.05% of S and the balance of Fe. The 50V-Si-Fe provided by the invention is an alloy mainly composed of Si, Fe and V, and is an innovative product, wherein silicon is a beneficial element in steel smelting, the toughness of steel can be improved, the plasticity of the steel can be reduced, and the elasticity and the corrosion resistance of the steel can be improved.
The invention also provides a preparation method of the 50V-Si-Fe in the scheme, the invention takes high-grade vanadium slag and 75 Si-Fe as raw materials, vanadium-silicon molten iron is obtained by reduction smelting, and slag generated in the reduction smelting process is subjected to depletion treatment and reduction treatment, so that V in the slag is subjected to depletion treatment and reduction treatment 2 O 5 Fully utilizing the vanadium slag, and finally realizing the direct preparation of the 50 vanadium-silicon-iron by adopting the vanadium slag. The preparation method provided by the invention has the advantages of simple steps, easy operation and low cost, and the process flow does not have the working procedures of vanadium slag roasting, leaching, purifying, vanadium precipitation, deamination and melting flaking, so that a large amount of waste water is not generated, and the environmental pollution is avoided; the cost for producing the 50 ferrovanadium by adopting the method is lower than the cost for producing the 50 ferrovanadium by adopting the electric furnace silicothermic reduction method by adopting the flake vanadium as the raw material, and the product quality meets the requirements of serving as a reinforced alloy additive for ferrous metallurgy and producing high-nitrogen ferrovanadium raw materials. By usingThe method of the invention prepares the 50 ferrosilicon vanadium by using vanadium slag, can simplify the process, reduce the production cost, solve the problem of waste water and gas treatment, and improve the economic and social benefits.
Detailed Description
The invention provides 50 ferrosilicon vanadium which comprises the following chemical components in percentage by mass: 48-55% of V, 5-23% of Si, 0-6% of Cr, less than 0.5% of C, less than 0.1% of P, less than 0.05% of S and the balance of Fe.
In the invention, the Si is preferably 10-20%, the Cr is preferably 0-2%, the C is preferably less than 0.4%, the P is preferably less than 0.05%, and the S is preferably less than 0.03%.
The 50 ferrovanadium silicon provided by the invention is a new alloy product, and reports of a 50 ferrovanadium silicon product and a preparation method thereof are not seen in the field at present, and the 50 ferrovanadium silicon can be used as a reinforced alloy additive for ferrous metallurgy and can also be used as a raw material for producing high-nitrogen ferrovanadium.
The invention also provides a preparation method of the 50V-Si-Fe in the scheme, which comprises the following steps:
mixing high-grade vanadium slag, 75 ferrosilicon and a slag former, and carrying out reduction smelting and slag formation to obtain a molten material, wherein the molten material comprises vanadium-silicon molten iron and molten slag; v in the high-grade vanadium slag 2 O 5 The content of (A) is more than 30 percent;
adding a carbonaceous reducing agent into the molten material, and enabling the molten slag to form depletion slag to obtain a depletion-treated molten material;
adding aluminum particles into the depleted molten material, reducing the depleted slag, and then discharging slag and vanadium-silicon molten iron;
and (4) casting the discharged ferrovanadium-silicon liquid to obtain a 50 ferrovanadium-silicon block.
In the invention, V in the high-grade vanadium slag 2 O 5 The content of (A) is > 30%, preferably > 35%.
In the invention, the preferable preparation method of the high-grade vanadium slag comprises the following steps:
mixing the low-grade vanadium slag and a carbonaceous reducing agent for melting reduction to obtain molten iron and high-grade vanadium slag; v in the low-grade vanadium slag 2 O 5 The content of (B) is preferably > 20%, more preferably > 25%.
In the present invention, the carbonaceous reducing agent is preferably petroleum coke powder, coke powder or coke particles; the fixed carbon content of the petroleum coke powder is preferably 85 percent, the ash content is preferably less than or equal to 3 percent, the volatile matter content is preferably less than or equal to 10 percent, and the P content is preferably less than 0.05 percent in terms of mass fraction; the fixed carbon content of the coke powder or the coke particles is preferably 83%, the volatile matter content is preferably 1.45%, and the ash content is preferably 15.15%; the mass of the carbonaceous reducing agent is preferably 13% of the mass of the low-grade vanadium slag; in the embodiment of the invention, the coke particles are preferably used in the initial stage of melting reduction, and the coke powder or petroleum coke powder is preferably used in the later stage, so that the recarburization of molten iron can be reduced. According to the method, a carbonaceous reducing agent is used for reducing iron oxide in the vanadium slag to form molten iron, and phosphorus in the vanadium slag enters the molten iron, so that the vanadium slag is purified, the content of iron and phosphorus in the vanadium slag is reduced, and the content of V in the vanadium slag is improved 2 O 5 Grade of (2).
In the invention, the melting reduction is preferably carried out in an electric arc furnace, and the capacity of the electric arc furnace is preferably 1800-50000 KVA. In the embodiment of the invention, the melting reduction is preferably carried out by electrifying by a submerged arc method.
The low-grade vanadium slag is preferably crushed into small blocks with the particle size of less than 10mm, then the small blocks are mixed with the carbonaceous reducing agent, and the obtained mixture is added into the electric arc furnace in batches for melting reduction; during reduction smelting, preferably, a batch of mixture is added firstly, reduction smelting is carried out until FeO in the slag is less than 10%, and then the next batch of mixture is added to continue reduction smelting until all the mixture is melted and reduced completely.
After the smelting reduction is finished, preferably discharging molten iron into a foundry ladle, and then spraying soda powder to the molten iron for removing sulfur and phosphorus, wherein the obtained sulfur and phosphorus slag can be used as a raw material for extracting vanadium by a water method for sale; v in the sulfur phosphorus slag 2 O 5 The content of (B) is preferably 0.06-2%, and the content of P is preferably2-6% is selected, and the content of Na is preferably more than 50%. And recovering molten iron ingots after the sulfur and phosphorus removal, and using the molten iron ingots as a coolant in the oxygen blowing vanadium extraction process.
In the invention, the low-grade vanadium slag is preferably self-made low-grade vanadium slag or outsourcing low-grade vanadium slag; when the low-grade vanadium slag is self-made low-grade vanadium slag, the self-made low-grade vanadium slag comprises the following chemical components in percentage by mass: 30-34% of TFe, 20-26% of FeO and V 2 O 5 >25％、Ti<3％、SiO 2 <3％、TiO 2 <3％、CaO<0.8％、MgO<1.2％、Cr 2 O 3 3-4％、P<0.05％、S<0.08 percent; the high-grade vanadium slag prepared from the self-made low-grade vanadium slag comprises the following chemical components in percentage by mass: TFe 11-13% FeO<10％、V 2 O 5 >35％、Ti<3％、SiO 2 <6％、TiO 2 <3％、CaO<0.80％、MgO<1.2％、Cr 2 O 3 3-5％、P<0.05％、S<0.05％。
In the invention, the self-made low-grade vanadium slag is preferably obtained through the following steps:
blowing soda ash into vanadium-containing molten iron for impurity removal treatment, and then slagging off to obtain furnace slag and purified molten iron;
and carrying out oxygen blowing on the purified molten iron to extract vanadium, thereby obtaining low-grade vanadium slag.
In the invention, the content of vanadium in the vanadium-containing molten iron is preferably 1.35-1.5%; spraying soda ash into molten iron containing vanadium, removing partial impurities such as titanium, silicon, sulfur, phosphorus and the like in the molten iron, allowing the impurities to enter furnace slag, separating the furnace slag from the molten iron by slagging off, and obtaining the residual molten iron as purified molten iron; the invention has no special requirement on the injection amount of the soda ash, and the injection amount of the soda ash is controlled by that P is less than or equal to 0.05 wt% in the purified molten iron. The method has no special requirements on the specific operation method for extracting vanadium by blowing oxygen, and can ensure that the content of P in the molten iron is less than or equal to 0.05 wt%.
In the invention, the low-grade vanadium slag can also be outsourcing low-grade vanadium slag, and the outsourcing low-grade vanadium slag comprises the following chemical components in percentage by mass: TFe 30-35%, FeO 26-30％、V 2 O 5 20-25.5％、TiO 2 ＜4.5％、SiO 2 <17％、CaO＜2.1％、MgO＜3.2％、Al 2 O 3 ＜1％、Cr 2 O 3 <5.0％、MnO＜4％、P<0.06％、S<0.05 percent; the high-grade vanadium slag prepared from the outsourcing low-grade vanadium slag comprises the following chemical components in percentage by mass: TFe 11-13% FeO<10％、V 2 O 5 >30％、TiO 2 <6％、SiO 2 <21.0％、CaO 0.30-3％、MgO1.20-3％、Cr 2 O 3 <5.5％、P<0.06％、S<0.10％。
The method comprises the steps of mixing high-grade vanadium slag, 75 ferrosilicon and a slag former for reduction smelting to obtain a molten material, wherein the chemical components of the molten material comprise vanadium-silicon molten iron and molten slag. In the present invention, the slag former is preferably lime; the content of calcium oxide in the lime is preferably > 85% by mass fraction, and the content of volatile components is preferably<11%, the content of P is preferably<0.05％，SiO 2 Preferably in an amount of<0.6％。
In the present invention, the 75 Si-Fe is preferably FeSi 75 Al 2 -a; the FeSi is calculated by mass fraction 75 Al 2 The composition of-a is preferably: 74-80% of Si and Al<2％，Ca<1％，P<0.05％，S<0.05% and the balance Fe; the granularity of the 75 ferrosilicon is preferably 20-40 mm.
In the invention, the preparation of the 50 ferrosilicon vanadium is preferably carried out in an electric arc furnace, and the capacity of the electric arc furnace is preferably 1800-50000 KVA; in the embodiment of the invention, preferably, after the preparation of the high-grade vanadium slag is finished, according to the content of the vanadium slag required for preparing 50 ferrovanadium, a part of the vanadium slag is left in the electric arc furnace for preparing 50 ferrovanadium, and the rest vanadium slag is poured into a slag pan for standby.
In the invention, the reduction smelting is preferably carried out by electrifying by adopting a submerged arc method; FeO and V in the reduction smelting process 2 O 5 Is reduced to generate ferrovanadium, and carries out slagging and dephosphorizing under the action of a slagging agent (the main component of the slag is 2CaO. SiO) 2 ). The invention preferably performs reduction smelting until the raw materials are dissolved clearly,the slag floats on the surface of the molten iron to form a slag-melting surface.
After reduction smelting, adding a carbonaceous reducing agent into the slag surface, carrying out depletion treatment on the slag, and forming depleted slag from the slag to obtain a depleted material; in the invention, the carbonaceous reducing agent is preferably petroleum coke powder, coke powder or coke particles, more preferably coke powder, and the indexes of the petroleum coke powder, the coke powder or the coke particles are consistent with the scheme, and are not described again; the invention preferably takes a sample to detect the components in the slag and the molten iron after the coke powder is burnt out, and when V is in the slag 2 O 5 When the content is less than 8 wt%, the content of FeO is less than 1 wt%, the content of Si in the molten iron is more than 10 wt%, and the content of C is less than 0.5 wt%, carrying out reduction treatment in the next step; if the components of the slag and the molten iron do not meet the above standard, the depletion treatment is continued until the components of the slag and the molten iron meet the above standard.
After the depletion treatment is finished, the invention preferably adds aluminum particles into the melt after the depletion treatment, reduces the depletion slag, and then carries out slag discharge and molten vanadium-silicon iron discharge. In the invention, the Al content of the aluminum particles is preferably more than 98 wt%, and the particle size of the aluminum particles is preferably 30-50 mm; reducing the depleted slag to obtain reducing slag, wherein V in the reducing slag 2 O 5 Less than 0.35 wt%; the present invention preferably detects the components of the slag and the molten iron during the reduction process, and reduces V into the slag 2 O 5 The content is less than 0.35 wt%, and then slag can be discharged; in the specific embodiment of the present invention, it is preferable to add the aluminum particles in portions until V is included in the slag 2 O 5 The components of (A) meet the requirements; in the embodiment of the invention, 70-100 kg of aluminum particles are preferably added for each 1 ton of 50 ferrovanadium-silicon produced.
After the reduction treatment is finished, the invention discharges the slag and discharges the vanadium-silicon molten iron. In a specific embodiment of the invention, the mass ratio of the vanadium slag, the slag former and the 75-silicon iron is preferably 9-12: 2.7-3.3: 0.5-0.78; in the specific operation, the vanadium slag is preferably reduced and smelted in three batches, during the first reduction smelting, 1/3 vanadium slag, all slag formers and 75 ferrosilicon are added, the reduction smelting, depletion and reduction treatment are carried out according to the method, then slag is discharged, at this time, molten vanadium-silicon iron is not discharged, then the vanadium slag of the second batch (1/3 of the total weight) is added, then the reduction smelting, depletion and reduction treatment are carried out again, slag is discharged again, molten vanadium-silicon iron is not discharged, then the vanadium slag of the third batch (1/3 of the total weight) is added, then the reduction smelting, depletion and reduction treatment are carried out, slag is discharged again, at this time, the molten vanadium-silicon iron is discharged, namely, the vanadium slag is preferably treated in three batches, three batches of slag are discharged, and three batches of molten vanadium-silicon iron are discharged, so that one time of molten vanadium-silicon iron is discharged. In a specific embodiment of the invention, the vanadium slag discharged from the first batch and the second batch are smelted together to improve the utilization rate of V.
In the invention, the finally discharged ferrovanadium-silicon water preferably comprises the following chemical components in percentage by mass: 30-35% of TFe, preferably 33-34%, 48-55% of V, preferably 50-51%, 8-23% of Si, preferably 10-12%, 0-6% of Cr, preferably 3-5%, 0.5% of C, 0.10% of P and 0.05% of S, wherein the molten vanadium-silicon iron can be discharged after meeting the standard, and if the standard is not met, the corresponding metal or ferroalloy is preferably added to adjust the components of the molten vanadium-silicon iron.
After the vanadium-silicon molten iron is obtained, the discharged vanadium-silicon molten iron is cast to obtain a 50 vanadium-silicon iron block. In the embodiment of the invention, the molten vanadium-silicon iron is preferably discharged into a foundry ladle, then the molten vanadium-silicon iron ladle is transported to an iron casting machine by using a crane for casting, and then the cast iron blocks are crushed by using a jaw crusher and then packaged and warehoused.
In the present invention, the slag discharge is performed to obtain a slag, and preferably, the slag discharge further includes: sequentially carrying out impact, jaw crushing, ball milling and magnetic separation on the waste residues, recovering vanadium iron particles, using the residual waste residues for manufacturing cement, and returning the recovered vanadium iron particles to a reduction smelting step for preparing 50 vanadium silicon iron; in the embodiment of the invention, the slag disk is preferably transported to a slag treatment room by a crane for the treatment, and the waste slag left after the vanadium iron particles are recovered is preferably used for manufacturing cement.
The embodiments of the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
50V-Si-Fe was prepared in a 2500KVA electric arc furnace. The used raw materials are vanadium slag (prepared by self), lime, reducing agent coke powder and 75 silicon iron (FeSi) 75 Al 2 -A), the components of each raw material are as follows (all in percentage by mass):
reducing agent petroleum coke powder and coke particles:
the coke powder and coke particle components: 83% of fixed carbon, 1.45% of volatile components and 15.15% of ash;
the petroleum coke powder comprises the following components: fixed carbon 85%, ash content less than or equal to 3%, volatile matter less than or equal to 10%, P less than 0.05%
75 silicon iron component (FeSi) 75 Al 2 -a): 76% of Si, 1.8% of Al1, 0.8% of Ca0, 0.042% of P and 0.02% of S; the particle size is 20-40 mm.
Aluminum particles: al is more than 98 percent, and the granularity is 30-50 mm.
Lime: 85.20% of CaO, 11.70% of volatile matter, 0.047% of P, and SiO 2 0.54％。
The method for producing 50 vanadium-silicon-iron by using vanadium slag as a raw material and adopting an electric furnace silicon reduction method comprises the following steps:
(1) self-made low-grade vanadium slag: blowing soda ash into molten iron containing 1.0-1.35% of vanadium, removing partial impurities of titanium, silicon, sulfur, phosphorus and the like in the molten iron, improving the purity of the molten iron containing vanadium, removing slag, and then carrying out oxygen blowing on the residual molten iron to extract vanadium slag, wherein the obtained vanadium slag comprises the following components in percentage by mass: TFe 31.5%, FeO 20.1%, V 2 O 5 30.7％、TiO 2 2.78％、SiO 2 2.36％、Ti2.85％、CaO 0.25％、MgO1.1％、Cr 2 O 3 3.32％、P0.041％、S<0.062％。
(2) And (2) crushing 12 tons of vanadium slag prepared in the step (1) into small blocks smaller than 10mm, adding 13% of coke powder for mixing, and adding the mixture into an electric arc furnace with the capacity of 2500KVA in 3 batches for melting reduction. After each batch of mixture is added, the mixture is electrified and submerged arc melted and reduced to be molten down, and the mixture is reduced to FeO in 15 minutes<10 percent, removes part of iron and phosphorus in the vanadium slag and improves the V of the vanadium slag 2 O 5 Grade, high yieldAnd (4) grade vanadium slag.
Discharging molten iron (weight of the molten iron is 1200kg, the molten iron contains vanadium: V0.8%) into a ladle, spraying soda ash for further dephosphorization and desulfurization treatment, and removing desulfurized phosphorus slag (V) 2 O 5 0.4 percent of P3.5 percent of Na51.8 percent) is sold as a raw material for extracting vanadium by a water method. Recovering the desulfurized phosphorus molten iron casting block, and reserving the desulfurized phosphorus molten iron casting block as a coolant for adding a vanadium extraction ladle to blow oxygen to extract vanadium slag;
the total amount of high-grade vanadium slag is 12 tons, 1/3 are left in the furnace, 50 vanadium-silicon-iron is smelted in the next step, the rest is poured into a slag pan and evenly divided into two parts, the slag pan is returned to the furnace for smelting in two batches after the subsequent steps, and the high-grade vanadium slag has the following components percentage: TFe 11.4%, FeO 8.41%, V 2 O 5 38.3％、TiO 2 2.6％、SiO 2 4.7％、CaO 0.7％、MgO 1.14％、Cr 2 O 3 4.2％、P 0.035％、S 0.049％。
(3) 3.3 tons lime and 0.78 tons FeSi are added to the electric arc furnace molten bath 75 Al 2 the-A is subjected to submerged arc smelting to reduce FeO and V 2 O 5 Vanadium-silicon-iron is generated and slagging is carried out (the main component of the slag is 2CaO. SiO) 2 ) And (4) desulfurization and phosphorus removal. After the raw materials are dissolved and cleaned, adding coke powder to the surface of the molten slag for dilution, sampling and testing the components of the slag and molten iron after dilution for 15min, and when the carbon powder is used for diluting V in the burnt slag 2 O 5 <8％、FeO<1% of Si in molten iron>When 10 percent, adding 100kg of aluminum particles into the electric arc furnace molten pool, and strongly reducing the aluminum particles to V in slag 2 O 5 <0.35 percent, then discharging the slag into a slag pan; then adding second and third batches of vanadium slag for smelting, wherein the smelting conditions are the same as those of the first batch, and only lime and FeSi are not added 75 Al 2 And A, discharging three batches of furnace burden materials, discharging three times of slag, and discharging one time of ferrovanadium-silicon liquid into a foundry ladle. Testing the components of the vanadium-silicon molten iron: TFe 34.6%, V50.5%, Si 18.3%, Cr 2.9%, C0.3%, P0.08% and S0.04%, and after the requirements of the components are met, 50 vanadium-silicon-iron is discharged to a foundry ladle.
(4) And (3) using a crane to transport the 50V-Si foundry ladle to a pig casting machine ingot, crushing by using a jaw crusher, packaging and warehousing.
(5) And (4) transporting the slag pan in the step (3) to a slag treatment room by adopting a crane, sequentially carrying out drop hammer, jaw crushing, ball milling and magnetic separation on the smelting waste slag to recover ferrovanadium particles, wherein the residual waste slag is used for manufacturing cement, and the ferrovanadium particles are returned to be used for preparing the 50 ferrovanadium in the next furnace.
Example 2
50V-Si-Fe was prepared in a 2500KVA electric arc furnace. The raw materials used are purchased vanadium slag, lime, reducer petroleum coke powder and FeSi 75 Al 2 -a ferrosilicon and aluminium shot, the composition of each raw material being as follows:
outsourcing low-grade vanadium slag components: TFe 32.5%, FeO 28.1%, V 2 O 5 24.5％、TiO 2 4.0％、SiO 2 15.1％、CaO 1.7％、MgO 3.1％、Al 2 O 3 0.83％、Cr 2 O 3 3.6％、MnO 3.1％、P 0.04％、S 0.046％；
Reducing agent petroleum coke powder, coke powder and coke particles:
coke powder and coke particles: 83% of fixed carbon, 1.45% of volatile matter and 15.15% of ash;
the petroleum coke powder comprises the following components: 85% of fixed carbon, less than or equal to 3% of ash, less than or equal to 10% of volatile content and less than 0.05% of P
75 silicon iron component (FeSi) 75 Al 2 -a): 76% of Si, 1.8% of Al1, 0.8% of Ca0, 0.042% of P and 0.02% of S; the particle size is 20-40 mm.
Aluminum particles: al is more than 98%, and the granularity is 30-50 mm.
Lime: 85.20% of CaO, 11.70% of volatile matter, 0.047% of P, and SiO 2 0.54％。
The method for producing 50 vanadium-silicon-iron by using the purchased vanadium slag as a raw material and adopting an electric furnace silicon reduction method comprises the following steps:
(1) will 14 tons of V 2 O 5 Crushing 25.5% of outsourcing vanadium slag into small blocks smaller than 10mm, adding 13% of coke powder, mixing to obtain a mixture, dividing the mixture into 3 batches, and adding the mixture into an electric arc furnace with the capacity of 2500KVA, wherein each batch is 4-5 tons. After the molten iron is reduced and melted down by electrifying submerged arc, the molten iron is discharged into a ladle, desulfurized phosphorus is removed by spraying desulfurized phosphorus powder into the molten iron, and desulfurized phosphorus slag (V) is removed 2 O 5 0.95％、P 4.1％，Na 2 O57.4%) is sold as a raw material for extracting vanadium by a water method. The desulfurized phosphorus molten iron casting block is recycled,keeping the vanadium slag as a coolant added into a vanadium extraction foundry ladle for oxygen blowing extraction;
the obtained high-grade vanadium slag comprises the following components: TFe 11.8%, FeO 8.1%, V 2 O 5 32.7％、TiO 2 4.4％、SiO 2 18.1％、CaO 1.2％、MgO 1.95％、Cr 2 O 3 4.7％、P 0.04％、S 0.07％。
One third of the obtained high-grade vanadium slag is left in the furnace, and two thirds of the high-grade vanadium slag is put into a slag pan to be used as a second batch of furnace charge.
(2) 3.3 tons lime and 0.78 tons FeSi are added into the molten pool of the electric arc furnace 75 Al 2 Submerged arc smelting of-A to reduce FeO and V 2 O 5 Vanadium-silicon-iron is generated and slag (2CaO. SiO. is formed 2 ) And (4) desulfurizing and phosphorus removing. After the raw materials are reduced and melted down, adding coke powder for diluting for 15 minutes until the coke powder is burnt out, sampling and testing the components of the slag and molten iron, and when V is contained in the slag 2 O 5 <8％、FeO<1% of Si in molten iron>When 10 percent, adding 100kg of Al aluminum particles into each batch of furnace charge to strongly reduce V in the slag 2 O 5 <0.35 percent; discharging vanadium slag and putting the vanadium slag into a slag pan; and returning the vanadium slag in the slag pan to the furnace in batches, and smelting the vanadium slag with the second and third batches of high-grade vanadium slag together. After the smelting of the last batch is finished, testing V in the molten iron>And when 50 percent of the total weight is reached, discharging slag into a slag pan. And 3, discharging slag for 3 times in the smelting furnace, and discharging the vanadium-silicon-iron for one time. Testing the content% of the vanadium-silicon molten iron: TFe 33.8%, V50.7%, Si 12.5%, Cr4.1%, C0.4%, P0.06%, S0.04%, and discharging molten vanadium-silicon iron into a foundry ladle.
(3) And (3) after the 50V-Si foundry ladle is transported to a pig casting machine casting block by a crane, crushing by a jaw crusher, packaging and warehousing.
(4) The method comprises the steps of conveying a slag plate to a slag treatment room by using a crane, recovering vanadium iron particles from smelting waste slag through drop hammer, jaw crushing, ball milling and magnetic separation, wherein the residual slag is used for manufacturing cement, and the vanadium iron particles are used for preparing 50 vanadium-silicon-iron in the next furnace.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The preparation method of 50 ferrosilicon vanadium is characterized by comprising the following steps:
mixing high-grade vanadium slag, 75 ferrosilicon and a slag former for reduction smelting to obtain a molten material, wherein the molten material comprises vanadium-silicon molten iron and molten slag; v in the high-grade vanadium slag 2 O 5 The content of (b) is more than 30%;
adding a carbonaceous reducing agent into the molten material to carry out depletion treatment on the molten slag, wherein the molten slag is subjected to depletion treatment to form depleted slag, so as to obtain depleted molten material;
adding aluminum particles into the depleted molten material, reducing the depleted slag, and then discharging slag and vanadium-silicon molten iron;
casting the discharged ferrovanadium-silicon liquid to obtain 50 ferrovanadium-silicon blocks;
the preparation method of the high-grade vanadium slag comprises the following steps: mixing the low-grade vanadium slag and a carbonaceous reducing agent for melting reduction to obtain molten iron and high-grade vanadium slag; v in the low-grade vanadium slag 2 O 5 The content of (A) is more than 20 percent;
the 50V-Si-Fe alloy comprises the following chemical components in percentage by mass: 48-55% of V, 5-23% of Si, 0-6% of Cr, less than 0.5% of C, less than 0.1% of P, less than 0.05% of S and the balance of Fe.
2. The production method according to claim 1, wherein the reduction smelting is performed in an electric arc furnace; the capacity of the electric arc furnace is 1800-50000 KVA.
3. The preparation method according to claim 1, wherein the low-grade vanadium slag is self-made low-grade vanadium slag or outsourcing low-grade vanadium slag; the self-made low-grade vanadium slag is obtained through the following steps:
blowing soda ash into vanadium-containing molten iron for impurity removal treatment, and then slagging off to obtain furnace slag and purified molten iron;
and carrying out oxygen blowing on the purified molten iron to extract vanadium, thereby obtaining the self-made low-grade vanadium slag.
4. The preparation method according to claim 3, characterized in that the self-made low-grade vanadium slag comprises the following chemical components in percentage by mass: 30-34% of TFe, 20-26% of FeO and V 2 O 5 >25％、Ti<3％、SiO 2 <3％、TiO 2 <3％、CaO<0.8％、MgO<1.2％、Cr 2 O 3 3-4％、P<0.05％、S<0.08 percent; the high-grade vanadium slag prepared from the self-made low-grade vanadium slag comprises the following chemical components in percentage by mass: TFe 11-13%, FeO<10％、V 2 O 5 >35％、Ti<3％、SiO 2 <6％、TiO 2 <3％、CaO<0.80％、MgO<1.2％、Cr 2 O 3 3-5％、P<0.05％、S<0.05％；
The outsourcing low-grade vanadium slag comprises the following chemical components in percentage by mass: 30-35% of TFe, 26-30% of FeO, and V 2 O 5 20-25.5％、TiO 2 <4.5％、SiO 2 <17％、CaO<2.1％、MgO<3.2％、Al 2 O 3 <1％、Cr 2 O 3 <5.0％、MnO<4％、P<0.06％、S<0.05 percent; the high-grade vanadium slag prepared from the outsourcing low-grade vanadium slag comprises the following chemical components in percentage by mass: TFe 11-13% FeO<10％、V 2 O 5 >30％、TiO 2 <6％、SiO 2 <21.0％、CaO 0.30-3％、MgO 1.20-3％、Cr 2 O 3 <5.5％、P<0.06％、S<0.10％。
5. The method according to claim 1, wherein V is contained in the lean slag 2 O 5 <8wt％，FeO<1 wt% of Si in the vanadium-silicon molten iron after the depletion treatment>10wt％，C<0.5wt％。
6. The production method according to claim 1, wherein the depleted slag is subjected to reduction treatment to obtain a reducing slag, wherein V in the reducing slag 2 O 5 <0.35wt％。
7. The preparation method according to claim 1, wherein the discharged molten silicon vanadium iron comprises the following chemical components in percentage by mass: TFe 30-35%, V48-55%, Si 8-23%, Cr 0-6%, C < 0.5%, P < 0.08%, S < 0.05%.
8. The method according to claim 1, wherein the slag is discharged to obtain a slag, and the method further comprises the following steps: and sequentially carrying out impact crushing, jaw crushing, ball milling and magnetic separation on the waste residues, recovering vanadium iron particles, using the residual waste residues for manufacturing cement, and returning the recovered vanadium iron particles to the reduction smelting step for preparing the 50 vanadium silicon iron.
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