TW202248435A - Ferrosilicon vanadium and/or niobium alloy, production of a ferrosilicon vanadium and/or niobium alloy, and the use thereof - Google Patents

Abstract

The invention relates to a ferrosilicon vanadium and/or niobium (FeSi V and/or Nb) alloy comprising 35 - 75 wt % Si; 3 - 35 wt % V and/or Nb; up to 2 wt % Al; up to 25 wt % Mn; up to 25 wt % Cr; up to 0.15 wt % Ca; up to 0.10 wt % Ti; up to 0.10 wt % C; up to 0.02 wt % Cu; up to 0.05 wt % P; up to 0.02 wt % S; balance Fe and incident impurities. The invention also relates to a method for the production of a FeSi V and/or Nb alloy and the use thereof in steel manufacturing.

Description

Ferrosilicon vanadium and/or niobium alloys, their manufacture and uses

The present invention relates to a ferrosilicon vanadium and/or niobium alloy, a method for manufacturing the ferrosilicon vanadium and/or niobium alloy and the application of the alloy. More particularly, the present invention relates to a ferrosilicon vanadium and/or niobium alloy particularly suitable as an additive in steelmaking.

Vanadium metal and niobium metal are known additives to improve steel quality, such as finer grain size resulting in higher strength, increased hardenability, and higher wear resistance through carbide and nitride or carbonitride precipitation sex. Vanadium is traditionally added to liquid steel in the form of vanadium-iron alloy, the most common being FeV80 (80% vanadium). Niobium is conventionally added to liquid steel in the form of ferroniobium alloys, most commonly FeNb with 60-70 weight percent niobium. Ferro-vanadium alloys, in addition to iron and vanadium, and ferro-niobium alloys, in addition to iron and niobium, usually include small amounts of silicon, aluminum, carbon, sulfur, phosphorus, titanium, chromium, arsenic, copper, and manganese, and some It is an important impurity for steelmaking. Ferro-vanadium and ferro-niobium alloys have rather high melting temperatures and therefore long dissolution times when added to the steel melt, which can result in valuable vanadium and niobium units displacing the steel into the slag, thus reducing the yield (also known as Recovery rate). The conventional methods for producing ferro-vanadium and ferro-niobium alloys are reduction by silicon and reduction by aluminum. In both methods the reduction is carried out in a furnace in which vanadium oxide or niobium oxide is reduced by reaction with silicon or with aluminum. Disadvantages of this production method are the energy consumption of the operating reactions and the relatively low vanadium or niobium yields, since large quantities of vanadium or niobium oxides are turned into slags during processing.

Accordingly, there is a need for an improved vanadium and/or niobium additive for steelmaking. An object of the invention is to alleviate, alleviate or obviate one or more disadvantages of the above-mentioned prior art.

According to the first aspect, a ferrosilicon vanadium and/or niobium (FeSi V and/or Nb) alloy is provided, which comprises 35-75 weight percent of Si, 3-35 weight percent of V and/or Nb, and at most 2 weight percent Al, up to 25% by weight of Mn, up to 25% by weight of Cr, up to 0.15% by weight of Ca, up to 0.10% by weight of Ti, up to 0.10% by weight of C, up to 0.02% by weight of Cu, up to 0.05% by weight of P, at most 0.02% by weight of S, the rest being Fe and incidental impurities.

According to the first specific embodiment of the first aspect, the FeSi V and/or Nb alloy comprises 35-60 weight percent of Si, 16-35 weight percent of V and/or Nb, at most 2 weight percent of Al, at most 25 % by weight of Mn, up to 25% by weight of Cr, up to 0.15% by weight of Ca, up to 0.10% by weight of Ti, up to 0.10% by weight of C, up to 0.02% by weight of Cu, up to 0.05% by weight of P, up to 0.02% by weight Percentage of S, the rest is Fe and incidental impurities.

According to the second specific embodiment of the first aspect, the FeSi V and/or Nb alloy comprises 51-75 weight percent of Si, 3-35 weight percent of V and/or Nb, at most 2 weight percent of Al, at most 25 % by weight of Mn, up to 25% by weight of Cr, up to 0.15% by weight of Ca, up to 0.10% by weight of Ti, up to 0.10% by weight of C, up to 0.02% by weight of Cu, up to 0.05% by weight of P, up to 0.02% by weight Percentage of S, the rest is Fe and incidental impurities.

In one embodiment of the second embodiment of the first aspect, the FeSi V and/or Nb alloy contains 5-25 weight percent of V and/or Nb.

In one embodiment of the second embodiment of the first aspect, the FeSi V and/or Nb includes 60-72 weight percent Si.

The following embodiments are compatible with any first or second embodiments of the first aspect.

According to some embodiments, the FeSi V and/or Nb includes at most 0.5 weight percent Al.

According to some embodiments, the FeSi V and/or Nb includes at most 0.025 weight percent Ti.

According to some embodiments, the FeSi V and/or Nb includes at most 0.3 weight percent Mn.

According to some embodiments, the FeSi V and/or Nb includes 0.3-25 weight percent of Mn.

According to some embodiments, the FeSi V and/or Nb includes at most 0.3 weight percent Cr.

According to some embodiments, the FeSi V and/or Nb includes 0.3-25% by weight of Cr.

According to some embodiments, the melting temperature of the FeSiV and/or Nb alloy is in the range of 1250 to 1650°C.

According to some embodiments, the FeSi V and/or Nb alloy is in the form of particles or agglomerates with a particle size classification between 3-80 mm, or in the form of a core wire, or in the form of a green block.

According to some embodiments, the FeSi V and/or Nb alloy is an additive for steel making.

According to the second aspect, there is provided a method for preparing the ferrosilicon vanadium and/or niobium (FeSiV and/or Nb) alloy according to the first aspect and any specific embodiment of the first aspect, the method comprising: A liquid ferrosilicon alloy is provided in a container; a vanadium oxide-containing raw material and/or a niobium oxide-containing raw material is added to the liquid ferrosilicon alloy; Niobium oxide containing niobium oxide raw material is mixed and reacted, thereby forming a melt and slag of FeSi V and/or Nb alloy; separating the slag from the melt; and the liquid FeSi V and/or Nb alloy Freeze or cast.

According to some embodiments of the method, the liquid ferrosilicon is directly provided from a reduction furnace, wherein the ferrosilicon is produced from raw materials according to known methods.

According to some embodiments of the method, the liquid ferrosilicon is provided by remelting a charge of ferrosilicon.

According to some embodiments of the method, the vanadium oxide-containing feedstock and/or the niobium oxide-containing feedstock is in an amount providing essentially a target amount of the elements vanadium and/or niobium (by weight) in the FeSiV and/or Nb alloy (by weight) added.

According to some specific embodiments of the method, the vanadium oxide-containing raw material is one or more selected from vanadium (II) oxide, vanadium (III) oxide, vanadium (IV) oxide, vanadium (V) oxide, and/or vanadium Vanadium oxide phase of other non-primary oxides.

According to some specific embodiments of the method, the niobium oxide-containing raw material is one or more selected from niobium (II) oxide, niobium (III) oxide, niobium (IV) oxide, niobium (V) oxide, and/or niobium oxide Niobium oxide phase of other non-primary oxides.

According to some embodiments of the method, the vanadium oxide phase is vanadium(V) oxide V ₂ O ₅ and/or vanadium (III) oxide V ₂ O ₃ .

According to some embodiments of the method, the niobium oxide phase is niobium(V) Nb ₂ O ₅ and/or niobium(III) Nb ₂ O ₃ oxide.

According to some embodiments of the method, the vanadium oxide-containing raw material further comprises industrial waste or ore comprising elemental vanadium or vanadium oxide.

According to some embodiments of the method, the niobium oxide-containing feedstock further comprises industrial waste or ore comprising elemental niobium or niobium oxide.

According to some embodiments of the method, the slag modifying compound is added to the liquid ferrosilicon in an amount of 0.5-30 weight percent based on the total amount of the ferrosilicon.

According to some embodiments of the method, the slag modifying compound is at least one of CaO and MgO.

According to some embodiments of the method, the liquid ferrosilicon has the general composition: Si of 45-90 weight percent; Up to 0.5% by weight of C; Al at most 2% by weight; Up to 1.5 weight percent Ca; Up to 0.1 weight percent Ti; Up to 26% by weight of Mn; Up to 26% by weight of Cr; Up to 0.02% by weight of P; Up to 0.005% by weight of S; The rest is Fe and incidental impurities.

According to some specific embodiments of the method, the method further comprises, before, at the same time, or after adding the vanadium oxide-containing raw material and/or niobium oxide-containing raw material, adding aluminum to the total amount of ferrosilicon and vanadium oxide and/or niobium oxide An amount of up to about 10 weight percent is added to the ferrosilicon melt.

According to some embodiments of the method, the liquid ferrosilicon is mixed with the vanadium oxide-containing raw material and/or the niobium oxide-containing raw material, and any added aluminum and/or slag modifying compounds, by mechanical stirring or gas stirring.

According to some embodiments of the method, the slag is separated before or during the casting of the liquid FeSi V and/or Nb alloy.

According to some embodiments of the method, solidified or cast FeSi V and/or Nb alloys are crushed and optionally classified by particle size components.

According to a third aspect, there is provided a use of the FeSi V and/or Nb alloy according to the first aspect and any specific embodiment of the first aspect as an additive in the manufacture of vanadium and/or niobium-containing steel.

According to some specific embodiments of the third aspect, the steel containing vanadium and/or niobium is selected from but not limited to spring steel, tool steel, forged steel, rail steel, reinforced steel, thick plate steel, microalloyed vehicle steel and aircraft steel .

The present invention will be apparent from the detailed description given below. The detailed description and specified examples disclose preferred embodiments of the invention by way of illustration only. Those skilled in the art will understand from the guidance in the detailed description that changes and modifications may be made within the scope of the invention as defined by the appended claims.

It is therefore to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. It should be noted that the indefinite articles one ("a", "an") and ("the", "said") used in the specification and appended claims are intended to indicate that there is one or more of the element, unless the context clearly states otherwise instructed. Furthermore, the words "comprising", "including", "comprising" and similar words do not exclude other elements or steps.

It should be understood that, according to the normal interpretation of this term, the term "incidental impurities" means trace impurity elements present in FeSiV and/or Nb alloys or ferrosilicon alloys.

It should be understood that the term "iron-silicon alloy" (which may also be shown as "ferrosilicon", "FeSi alloy", or simply "FeSi") herein refers to an alloy containing iron, manganese and/or chromium, optionally and above impurity concentrations. Silicon-based alloys are conventionally produced in a submerged arc furnace (SAF) by carbothermal reduction of silica or sand with coke (or any other carbonaceous reducing agent) in the presence of iron or an iron source. Common FeSi formulations on the market are ferrosilicon with 15%, 45%, 65%, 75%, and 90% (by weight) silicon. Ferrosilicon alloys so produced typically contain about 2 weight percent of other elements, primarily aluminum and calcium; however, trace amounts of carbon, titanium, copper, manganese, phosphorus, and sulfur are also common. The ferrosilicon alloy herein may also contain manganese and/or chromium as alloying elements. This alloy may also be indicated as FeSiMn, FeSiCr and FeSiMnCr alloys. All such possible alloys are referred to herein for simplicity as ferrosilicon (or "ferrosilicon", "FeSi alloy", or just "FeSi"), as indicated above.

It should be understood that the term "iron-silicon-vanadium and/or niobium alloy" (which may also be expressed as "FeSi V and/or Nb alloy" or simply "FeSi V and/or Nb") herein refers to containing vanadium or niobium, or containing Ferrosilicon alloy of vanadium and niobium. Besides vanadium and/or niobium, other elements as defined in the first aspect may also be present in the alloy.

It should be understood that the term "up to" when used in the context to indicate an amount of an element means that the element may be present in the range of 0 weight percent up to the indicated weight percent value.

The ferrosilicon vanadium and/or niobium (FeSi V and/or Nb) alloy of the present invention is especially suitable as an additive in steel making for producing steel containing vanadium and/or niobium. According to the first aspect of the present invention, there is provided a FeSiV and/or Nb alloy comprising 35-75% by weight of silicon (Si), 3-35% by weight of vanadium (V) and/or niobium (Nb), at most 2% by weight of aluminum (Al), up to 25% by weight of manganese (Mn), up to 25% by weight of chromium (Cr), up to 0.15% by weight of calcium (Ca), up to 0.10% by weight of titanium (Ti), up to 0.10% by weight of carbon (C), at most 0.02% by weight of copper (Cu), at most 0.05% by weight of phosphorus (P), at most 0.02% by weight of sulfur (S), and the rest being iron (Fe) and incidental impurities.

The FeSi V and/or Nb alloys of the present invention are particularly suitable as additives in steelmaking for several reasons, for example the FeSi V and/or Nb alloys are low in impurities. A low aluminum content in FeSiV and/or Nb alloys is advantageous because aluminum may cause inclusion formation when added to the liquid steel, such as for example Al ₂ O ₃ inclusions. These types of inclusions are detrimental in many types of steel, such as but not limited to spring and rail steels.

In addition, compared with conventional FeV alloys and conventional FeNb alloys, the FeSiV and/or Nb alloys of the present invention have lower melting temperatures and different assimilation pathways in liquid steel. This lower melting temperature and different assimilation pathway lead to a significantly higher dissolution rate in liquid steel compared to FeV and FeNb. When added to liquid steel, lower melting temperatures and higher dissolution rates result in lower energy consumption and result in better distribution of vanadium and/or niobium in the melt.

Furthermore, the higher dissolution rate means that the ferrosilicon vanadium and/or niobium additive alloys can be added later in the steelmaking process, which can lead to less oxidation of the vanadium and/or niobium in the steel melt. Additionally, the higher dissolution rate of the alloy prevents the added clumps from resurfacing. Resurfacing at high temperatures causes contact between the alloy and the atmosphere or slag, and reduces the yield of alloying elements into the steel melt. Compared to FeV and/or FeNb, which are endothermic and consume a lot of heat when added to the steel, FeSiV and/or Nb require less superheat to melt and dissolve into the steel. Another advantage is the option to save up to 2 addition steps in the alloying process using FeSiV and/or Nb alloys. It can reduce the time required for the steelmaking process and the required equipment in the steel yard, such as storage tanks/hoppers for various alloys. When microalloys such as FeV and/or FeNb are manually handled due to the high cost per kg, this labor can be saved by using the lower cost per kg FeSiV and/or Nb alloys.

Silicon is a common additive in steelmaking. Silicon is an alloying element in steel known to increase strength, wear resistance, elasticity, and pot scale resistance. In addition, Si reduces electrical conductivity and magnetostriction in steel. Si is also used as a processing additive in steel making, such as an oxygen scavenger and a slag reducing agent, which is often added as a silicon-iron alloy. Silicon protection in FeSi V and/or Nb can be especially relevant to semi-clean steels such as HSLA rebar or SBQ wrought steel grades to increase V and/or Nb yields. Additionally, silicon protection reduces vacuum degassing labor for certain steel grades. The lower V and/or Nb content in combination with the oxidation protection of silicon compared to FeV and/or FeNb alloys allows less complicated transport and packing than the prior art. Essentially, FeSi V and/or Nb can be processed in the same way as FeSi. The amount of Si in the FeSiV and/or Nb alloy of the present invention is between 35 and 75 weight percent. In a specific embodiment, the amount of Si is at least 40 weight percent, at least 45 weight percent, at least 47 weight percent, or at least 51 weight percent, such as at least 55 weight percent or at least 58 weight percent. In a specific embodiment, the amount of Si is at most 72 weight percent, such as at most 70 weight percent, or at most 68 weight percent, or at most 60 weight percent.

The FeSi V and/or Nb alloy of the present invention contains V and/or Nb at 3 to 35 weight percent. It means that if only V is present, it can be present in the range of 3 to 35 weight percent. If only Nb is present, it may be present in the range of 3 to 35 weight percent. If both V and Nb are present, the total amount of V and Nb in the alloy is in the range of 3 to 35 weight percent. If both V and Nb are present, they are present in any ratio of V to Nb within the ranges shown. Vanadium and niobium form stable nitrides and/or carbides and/or carbonitrides, resulting in a significant increase in steel strength. Steels containing vanadium and/or niobium are such as, but not limited to, spring steels, tool steels, forged steels, rail steels, steel reinforcement steels, plate steels, microalloyed automotive steels, and aircraft steels. Depending on the desired amount of vanadium and/or niobium that should be added in different steel applications, the vanadium and/or niobium content in FeSi V and/or Nb alloys can range from 5 to 30 weight percent in some embodiments . In some embodiments, the vanadium and/or niobium content in the FeSi V and/or Nb alloy may be at least 5 wt%, or at least 9 wt%, or at least 10 wt%, such as at least 16 wt%. In some embodiments, the vanadium and/or niobium content in the FeSi V and/or Nb alloy may be at most 25 wt%, or at most 20 wt%, or at most 15 wt%, or at most 10 wt%.

The range of V and/or Nb in the FeSi V alloy relative to Si can be determined by the amount of Si in the starting silicon-iron alloy of the FeSi V and/or Nb alloy produced by it. Alloys start with higher V and/or Nb relative to Si ranges.

In some specific embodiments, the FeSi V and/or Nb alloy may comprise 35-60 weight percent of Si and 16-35 weight percent of V and/or Nb, such as 16-30 weight percent of V and/or Nb, Or V and/or Nb such as 16-25% by weight, and other elements as defined above according to the first aspect (Al at most 2% by weight, Mn at most 25% by weight, Cr at most 25% by weight, Cr at most 0.15% by weight of Ca, at most 0.10% by weight of Ti, at most 0.10% by weight of C, at most 0.02% by weight of Cu, at most 0.05% by weight of P, at most 0.02% by weight of S, and the rest are Fe and incidental impurities).

In other specific embodiments, the FeSi V and/or Nb alloy may comprise 51 to 75 weight percent Si, such as 55-75 weight percent Si, or 58-72 weight percent Si, or 60-72 weight percent Si. Si; and 3-35 weight percent of V and/or Nb, such as 5 to 30 weight percent of V and/or Nb, such as 5-25 weight percent of V and/or Nb, or 9-25 weight percent of V and /or Nb, or 10-20 weight percent of V and/or Nb, and other elements as defined above in accordance with the first aspect (at most 2 weight percent of Al, at most 25 weight percent of Mn, at most 25 weight percent of Cr, Ca at most 0.15% by weight, Ti at most 0.10% by weight, C at most 0.10% by weight, Cu at most 0.02% by weight, P at most 0.05% by weight, S at most 0.02% by weight, and the rest being Fe and incidental impurities ).

It should be appreciated that several ranges of V and/or Nb relative to Si may be practiced in the alloy compositions defined above.

The following disclosures about the amounts of other elements Al, Mn, Cr, Ca, Ti, C, Cu, P, S, the rest being Fe and incidental impurities are applicable to each of the above-mentioned specific embodiments, unless otherwise stated.

The FeSiV and/or Nb alloy comprises at most 2 weight percent Al, or at most 1 weight percent Al, at most 0.5 weight percent Al, for example 0.001 to 0.4 weight percent Al, or 0.01 to 0.35 weight percent Al, or Up to 0.2 weight percent Al. _In steels such as spring steels and rail steels, Al causes harmful inclusions such as, for example, _Al2O3 inclusions. Therefore, the content of Al in the FeSiV and/or Nb alloy is preferably kept low. In the manufacture of FeSiV and/or Nb, Al in liquid ferrosilicon will react with oxygen added in vanadium oxide and/or niobium oxide, resulting in a low concentration of Al. In the alloys of the present invention, the Al content can be very low in some embodiments, for example at most only 0.04 weight percent.

The FeSiV and/or Nb alloy contains at most 25 weight percent Mn. Manganese is generally an impurity in the manufacture of ferrosilicon-based alloys, and the FeSiV and/or Nb alloys of the present invention may contain up to 0.3 weight percent Mn, typically in the range of 0.02-0.3 weight percent Mn. Mn can be present in the starting ferrosilicon alloy as an alloying element when it is required as an alloying element in the steel. Therefore, the FeSi V and/or Nb alloy of the present invention may contain manganese in the range of 0.3-25 weight percent. Other suitable Mn ranges are 0.5-20 wt%, or 1-15 wt%, 2-12 wt%, or 3-10 wt%.

The FeSiV and/or Nb alloy contains up to 25 weight percent Cr. Chromium may exist as an impurity in the manufacture of ferrosilicon-based alloys, and the FeSiV and/or Nb alloys of the present invention may contain up to 0.3 weight percent Cr, typically in the range of 0.02-0.3 weight percent Cr. Cr can be present in the starting ferrosilicon alloy as an alloying element when it is required as an alloying element in the steel. Therefore, the FeSiV and/or Nb alloy of the present invention may contain chromium in the range of 0.3 to 25 weight percent. Other possible Cr ranges are 0.5-20 wt%, or 1-15 wt%, 2-12 wt%, or 3-10 wt%.

The FeSiV and/or Nb alloy contains at most 0.15 wt % Ca, eg 0.01 to 0.15 wt %. Calcium is also a common element in ferrosilicon so produced. During FeSi V and/or Nb fabrication, some of the Ca in the liquid ferrosilicon reacts with the added oxygen of vanadium oxide and/or niobium oxide and results in Ca concentrations of up to about 0.15 weight percent.

The FeSiV and/or Nb alloy contains Ti at most 0.10 wt%, eg 0.003 to 0.10 wt%. Titanium is usually present in the starting ferrosilicon alloys in low amounts. Titanium can also come from vanadium oxide and/or niobium oxide raw materials added during the manufacture of FeSi V and/or Nb alloys. Titanium is detrimental in some steel grades because it can form hard carbides and nitrides which lead to brittleness and low fatigue stress. Therefore, the content of Ti in the FeSiV and/or Nb alloy is preferably as low as possible, such as less than 0.025% by weight.

The FeSiV and/or Nb alloy may contain trace amounts of C, Cu, P, and S. This element can usually be present in small amounts in the ferrosilicon so produced, or added via vanadium oxide feedstock and/or niobium oxide feedstock and/or slag modifying compounds added during FeSiV and/or Nb alloy fabrication. The indicated amounts of this element are generally not hazardous to steelmaking. The FeSi V and/or Nb alloy may contain up to 0.10 weight percent C, for example 0.003 to 0.10 weight percent C. The FeSi V and/or Nb alloy may comprise up to 0.02 wt % Cu, eg 0.001 to 0.02 wt % Cu, or 0.001 to 0.01 wt %. The FeSi V and/or Nb alloy may contain up to 0.05 weight percent P, eg, 0.001 to 0.05 weight percent P. The FeSi V and/or Nb alloy may contain up to 0.02 weight percent S, such as 0.001 to 0.02 weight percent S.

According to any of the above embodiments, the FeSi V and/or Nb alloy is advantageously in the form of lumps. As used herein, the term "agglomerate" means particles or flakes of FeSi V and/or Nb alloy (eg, crushed FeSi V and/or Nb alloy particles). FeSi V and/or Nb alloy agglomerates can be produced in different particle sizes. Grain size classifications commonly used in steelmaking are from about 3 millimeters to about 80 millimeters. The term size fractionation refers to the size of the holes in the screen through which the agglomerates pass. It should be appreciated that smaller or larger sized FeSi V and/or Nb agglomerates are feasible depending on the application. Thus, the particle size fractionation may be from about 3 mm, such as from 5 mm, such as from about 10 mm, such as from about 20 mm, up to about 80 mm, or up to about 50 mm, or up to about 30 mm, or up to about 20 mm. mm, or at most about 10 mm. Since FeSi V and/or Nb agglomerates are less tough than FeV and/or FeNb, they can be crushed in conventional FeSi crushers to give the option of conveniently manufacturing different particle size fractions. According to any of the above embodiments, the FeSi V and/or Nb alloy may also be in the form of a core wire or a green block.

According to any of the foregoing embodiments, the FeSi V and/or Nb alloy has a melting temperature in the range of about 1250 to about 1650°C. The relatively low melting temperature and assimilation path of the inventive FeSi V and/or Nb alloy in the steel melt has the effect that the FeSi V and/or Nb added to the steel melt dissolves rapidly. Tests carried out by the inventors of the present case have shown, for example, that FeSi V agglomerates according to the invention with a particle size fraction of about 25 mm melt within about 20 seconds, compared to FeV agglomerates which melt after only about 60 seconds.

The method for preparing FeSi V and/or Nb alloys according to any of the above embodiments comprises: providing a liquid ferrosilicon in a container; adding a vanadium oxide-containing raw material and/or a niobium oxide-containing raw material to the liquid ferrosilicon; Liquid ferrosilicon alloy, mixed with vanadium oxide obtained from the vanadium oxide-containing raw material and/or niobium oxide obtained from the niobium oxide-containing raw material, thereby forming FeSi V and/or Nb alloy melts and slags; The slag is separated from the melt of FeSiV and/or Nb alloy; and the liquid FeSiV and/or Nb alloy is solidified or cast.

The reaction between liquid ferrosilicon and vanadium oxide and/or niobium oxide is fast and allows high production rates. The FeSi V and/or Nb alloy can be carried out, for example, in a ladle or in a similar vessel, such as a crucible or melting pot, including any kind of furnace. Since the liquid FeSi in the ladle occurs in any ferrosilicon manufacturing process, it does not need to be heated by supplying external energy, such as using a furnace, so it is superior to the prior art to obtain vanadium and/or ferro-niobium alloys, and can be economically and Ecological savings. The energy released from the exothermic reaction would have additional economic benefits for FeSi fabrication. The aluminum and calcium normally present in ferrosilicon alloys (as produced) are consumed during the reaction with vanadium oxide and/or niobium oxide and result in FeSi V and/or Nb alloys with very low aluminum and calcium content. In addition, compared with the conventional method of manufacturing ferro-vanadium alloy FeV and/or ferro-niobium alloy FeNb, the method of manufacturing FeSi V and/or Nb alloy of the present invention also results in the addition of vanadium oxide and/or niobium oxide (such as five Vanadium oxide and/or niobium pentoxide) for high V and/or Nb yields. Therefore, compared with the conventional production of FeV and FeNb, the method of the present invention is compact, cost-effective, and more environmentally friendly.

The following detailed description of the method of making FeSi V and/or Nb alloys applies to any of the aforementioned embodiments of FeSi V and/or Nb alloys of the present invention.

The liquid ferrosilicon alloy can be provided directly from a reduction furnace, generally a submerged arc furnace (SAF), wherein the ferrosilicon alloy is manufactured according to a known method. Alternatively, the liquid ferrosilicon may be provided by remelting a charge of ferrosilicon, which may be refined, or by combining the so produced ferrosilicon with solidified ferrosilicon brought into a liquid state by any suitable heating means. The combination is provided for remelting.

The method of preparing FeSiV and/or Nb alloys can be carried out in ladles, or in any container suitable for holding liquid ferrosilicon, such as crucibles or melting pots, including any kind of furnace. The temperature of the ferrosilicon melt before adding the vanadium oxide-containing raw material and/or the niobium oxide-containing raw material desirably ranges from about 1400 to about 1700°C.

According to this method, vanadium oxide-containing raw materials (such as V ₂ O ₅ ) and/or niobium oxide-containing raw materials (such as Nb ₂ O ₅ ) are added to liquid ferrosilicon. The vanadium oxide-containing feedstock and/or niobium oxide-containing feedstock may be added in an amount (by weight) to provide essentially the targeted amount of the elements vanadium and/or niobium (by weight) in the FeSiV and/or Nb alloy. The method of adding the vanadium oxide-containing material and/or the niobium oxide-containing material can be carried out in any convenient manner which ensures contact between the vanadium oxide and/or niobium oxide and the liquid ferrosilicon.

The vanadium oxide-containing raw material can be one or more vanadium oxide phases, such as vanadium oxide (II), vanadium oxide (III), vanadium oxide (IV), vanadium oxide (V), and/or other non-main oxides of vanadium . The vanadium oxide is preferably vanadium (V) oxide (V ₂ O ₅ ) and/or vanadium (III) oxide (V ₂ O ₃ ). The vanadium oxide-containing raw material may also include industrial waste or ore containing elemental vanadium or vanadium oxide.

The niobium oxide-containing raw material can be one or more niobium oxide phases, such as niobium(II) oxide, niobium(III) oxide, niobium(IV) oxide, niobium(V) oxide, and/or other non-main oxides of niobium . The niobium oxide is preferably niobium (V) oxide (Nb ₂ O ₅ ) and/or niobium (III) oxide (Nb ₂ O ₃ ). The niobium oxide-containing raw material may also include industrial waste or ores containing elemental niobium or niobium oxide.

The reduction reaction of vanadium oxide and/or niobium oxide results in the formation of oxide compounds, usually shown as slag. Slag modifying compounds may be added to the ferrosilicon melt to modify the slag formed during the reaction. The slag modifying compound may be CaO and/or MgO, and may be added in an amount of about 0.5-30 weight percent of the final alloy based on the total amount of the initial ferrosilicon alloy. The required amount is based on the added amount of vanadium oxide and/or niobium oxide. The slag modifying compound may be added before or during the addition of the vanadium oxide-containing feedstock and/or the niobium oxide-containing feedstock. The slag composition is modified in such a way as to obtain a low viscosity and low melting slag, allowing good slag/metal contact during the reduction reaction. Additionally, it can be modified for good metal/slag separation prior to casting. Both the slag produced and added during the reaction float on the melt so that any scrap formed during the reaction and the slag compounds formed accumulate in the slag layer floating on top of the melt.

The general composition of the starting ferrosilicon alloys for the manufacture of FeSiV and/or Nb alloys should be 45-90 wt% Si, at most 0.5 wt% C, at most 2 wt% Al, at most 1.5 wt% Ca, at most 0.1% by weight of Ti, at most 26% by weight of Mn, at most 26% by weight of Cr, at most 0.02% by weight of P, at most 0.005% by weight of S, and the rest are Fe and incidental impurities;

Examples of the composition of the starting ferrosilicon are: 45-90% by weight Si, up to 0.5% by weight of C, up to 2% by weight of Al, up to 1.5% by weight of Ca, up to 0.1% by weight of Ti, up to 0.5% by weight Mn at most, Cr at most 0.5% by weight, P at most 0.02% by weight, S at most 0.005% by weight, and the rest are Fe and incidental impurities; 45-90 wt% Si, up to 0.5 wt% C, up to 2 wt% Al, up to 1.5 wt% Ca, up to 0.1 wt% Ti, 0.5-26 wt% Mn, up to 0.5 wt% Cr , up to 0.02% by weight of P, up to 0.005% by weight of S, and the rest is Fe and incidental impurities; Si at 45-90% by weight, C at most 0.5% by weight, Al at most 2% by weight, Ca at most 1.5% by weight, Ti at most 0.1% by weight, Mn at most 0.5% by weight, Cr at 0.5-26% by weight , up to 0.02% by weight of P, up to 0.005% by weight of S, and the rest is Fe and incidental impurities; 45-90% by weight of Si, at most 0.5% by weight of C, at most 2% by weight of Al, at most 1.5% by weight of Ca, at most 0.1% by weight of Ti, 0.5-26% by weight of Mn, 0.5-26% by weight of Cr, up to 0.02 weight percent of P, up to 0.005 weight percent of S, and the rest is Fe and incidental impurities.

According to some embodiments of the method, the amount of Si in the initial ferrosilicon alloy is 70-80% by weight.

The ferrosilicon so produced contains a small amount of Al derived from the raw material, typically in an amount of up to 1.5 weight percent. The starting ferrosilicon alloy of the present invention may contain up to 2 weight percent Al, for example 0.01-2 weight percent. When vanadium oxide-containing raw materials and/or niobium oxide-containing raw materials are added to liquid ferrosilicon, metal Al present in the liquid ferrosilicon reacts with oxygen of vanadium oxide and/or niobium oxide to reduce vanadium and/or niobium, And generate pure V and/or Nb and heat, while oxidized Al will accumulate in the slag. Si in liquid ferrosilicon also reacts with the oxygen of vanadium oxide and/or niobium oxide to reduce vanadium oxide and/or niobium oxide to element V and/or Nb, and the oxidized Si will also accumulate in the slag phase. In this mixture, Si is less reactive than Al; therefore, essentially most of the Al present in the ferrosilicon alloy will react with the oxygen of vanadium oxide and/or niobium oxide, and in the produced FeSi V and/or Nb alloy A very low amount of aluminum is formed in the Calcium is also a common element in ferrosilicon alloys, typically in amounts of up to about 1.5 weight percent. Ca present in liquid ferrosilicon also reacts with the oxygen of vanadium oxide and/or niobium oxide to generate pure V and/or Nb and heat, which generates low amounts of Ca in the fabricated FeSi V and/or Nb alloy.

Additional aluminum may be added to the liquid ferrosilicon to increase the amount of Al available in the melt for reduction of vanadium oxide and/or niobium oxide. When the amount of silicon in the FeSiV and/or Nb alloy is kept in a relatively high range to produce FeSiV and/or Nb alloys with a high amount of vanadium and/or niobium, such as from the amount of V and/or Nb being 20 wt. % of FeSi V and/or Nb (FeSi V and/or Nb 20), up to FeSi V and/or Nb 25, or up to FeSi V and/or Nb 30, even up to FeSi V and/or Nb 35, which is particularly appropriate . If additional aluminum is added to the ferrosilicon melt, this addition can be done before, during or after, preferably during or after, the addition of the vanadium oxide-containing raw material and/or the niobium oxide-containing raw material. Aluminum may be added in an amount of at most about 10 weight percent, or at most about 5 weight percent, or at most about 1 weight percent, based on the total amount of ferrosilicon and vanadium oxide and/or niobium oxide.

The liquid ferrosilicon is preferably stirred during the addition of the vanadium oxide-containing raw material and/or the niobium oxide-containing raw material and any added aluminum and/or slag modifying compounds, and during the reduction reaction, to ensure that the V oxide and/or Nb oxide is in contact with the metal. The melt is conveniently stirred by mechanical stirring and/or gas stirring means well known in the art.

Slag can be separated before or during liquid FeSi V and/or Nb alloy casting. After the reaction is completed, the slag is separated from the FeSiV and/or Nb melt to produce purified FeSiV and/or Nb with very low levels of aluminum and calcium. FeSi V and/or Nb alloys can be cast or solidified according to methods well known in the art. Solidified or cast metals can be crushed and classified into particle size components for different applications.

The FeSi V and/or Nb alloy of the present invention can be used as an additive in steel making, especially as an additive for making vanadium-containing and/or niobium-containing steel. The vanadium and/or niobium-containing steel may be selected from but not limited to spring steel, tool steel, forged steel, rail steel, reinforced steel, thick plate steel, microalloyed vehicle steel and aircraft steel.

Surprisingly, it has now been found that FeSiV and FeSiNb have higher vanadium and niobium yields than the individual iron alloys (FeV and FeNb). It is particularly advantageous because both vanadium and niobium are rare alloys and are relatively expensive. Furthermore, it has now surprisingly been found that FeSiV and FeSiNb alloys dissolve faster than prior art alloys (FeV and FeNb). This quickly incorporates the alloying elements into the steel and prevents V and/or Nb from being further oxidized or embedded in the slag.

A method of manufacturing steel (such as spring steel, tool steel, forged steel, rail steel, steel reinforcement steel, thick plate steel, microalloyed vehicle steel and aircraft steel) comprising adding a FeSi V and/or Nb alloy comprising 35-75 Silicon (Si) by weight percent, vanadium (V) and/or niobium (Nb) 3-35 percent by weight, aluminum (Al) up to 2 percent by weight, manganese (Mn) up to 25 percent by weight, up to 25 percent by weight Chromium (Cr), up to 0.15% by weight of calcium (Ca), up to 0.10% by weight of titanium (Ti), up to 0.10% by weight of carbon (C), up to 0.02% by weight of copper (Cu), up to 0.05% by weight Phosphorus (P), sulfur (S) up to 0.02% by weight, and the rest iron (Fe) and incidental impurities. The steel making method includes adding FeSi V and/or Nb alloys of any of the above embodiments. Examples Example 1. Manufacture of FeSiV alloy

Five experiments for producing FeSiV alloys of the present invention were prepared. Table 1 below shows the raw material amounts of FeSi75 and _V2O5 used for the ₅ FeSiV test fabrications. In addition, the amount of lime (CaO) in the modified slag and the total Al in the system are displayed. The temperature (T) was set above the melting point of the _FeSiV alloy before adding _V2O5 . The liquid ferrosilicon is stirred during the addition of V ₂ O ₅ , lime and any aluminum. The manufactured compositions are shown in the right part of the table. During tapping, the purity of the produced FeSiV alloy is important to separate slag and metal. Table 1: Amounts and temperatures of FeSi, vanadium oxide, lime, and aluminum. Analysis of the composition of the fabricated FeSiV alloy. Add to analyze test FeSi (kg) V ₂ O ₅ (kg) Lime (kg) Added Al* (kg) T (℃) Si (wt%) V (wt%) Fe (wt%) Al (wt%) 1 10.0 1.84 1.00 0.01 1565 67.1 9.4 22.8 0.020 2 7.94 1.46 0.80 0.11 1588 68.5 10.0 21.6 0.035 3 10.0 3.78 2.00 0.28 1585 58.7 19.2 21.4 0.024 4 10.0 1.83 1.00 0.06 1620 67.0 9.7 22.8 0.015 5 8.80 5.30 2.80 0.19 1630 49.7 29.5 17.8 0.29 *Added Al includes Al derived from FeSi and Al added separately.

Analysis has shown that each resulting FeSiV alloy produced by the method of the present invention has a rather low amount of aluminum. Therefore, the FeSiV alloy is very suitable as an additive in steelmaking where the amount of aluminum should be kept low.

Starting from a FeSi alloy containing Mn and Cr as alloying elements with a Mn or Cr content of 5 weight percent, 14 weight percent, or 25 weight percent, a FeSi V and/or Nb alloy containing Mn and/or Cr results. The case of the FeSiV alloy having the composition shown in Table 2 below was calculated. Table 2: FeSiMn/FeSiCr, vanadium oxide, lime, and the amount of alloy composition generated by adding V ₂ O ₅ to FeSiMn or FeSiCr Add to Alloy produced FeSiCr/FeSiMn alloy lime V ₂ O ₅ Si wt% Fe wt% Mnwt% Cr wt% kg kg kg kg Si wt% V wt% Fe wt% Mnwt% Cr wt% 70 25 5 0 9.7 1 1.8 10 60.9 10 twenty four 4.8 0.0 70 25 5 0 9.4 2 3.6 10 51.9 20 twenty three 4.7 0.0 69 26 0 5 9.7 1 1.8 10 60.9 10 twenty four 0.0 4.8 69 26 0 5 9.4 2 3.6 10 51.9 20 twenty three 0.0 4.7 62 twenty four 14 0 9.7 1 1.8 10 53.2 10 twenty three 13.6 0.0 62 twenty four 14 0 9.4 2 3.6 10 44.4 20 twenty three 13.1 0.0 59 27 0 14 9.7 1 1.8 10 53.2 10 twenty three 0.0 13.6 59 27 0 14 9.4 2 3.6 10 44.4 20 twenty three 0.0 13.1 52 twenty three 25 0 9.7 1 1.8 10 43.5 10 twenty two 24.2 0.0 52 twenty three 25 0 9.4 2 3.6 10 35.0 20 twenty two 23.4 0.0 46 29 0 25 9.7 1 1.8 10 43.5 10 twenty two 0.0 24.2 46 29 0 25 9.4 2 3.6 10 35.0 20 twenty two 0.0 23.4

A further experiment was prepared to manufacture the FeSiV alloy of the present invention using FeSiMn or FeSiCr as raw material. Table 3 below shows the raw material amounts of FeSiMn or FeSiCr used in the test manufacture of 2 kinds of FeSiV. In addition, the amount of lime (CaO) in the modified slag and the total Al in the system are displayed. _The liquid alloy is stirred during the addition of _V2O5 , lime and any aluminum. The manufactured compositions are shown in the right part of Table 3. Table 3: Amounts of FeSiMn/FeSiCr, lime, aluminum, V ₂ O ₅ . Analysis of the fabricated alloy composition. Add to analyze FeSiCr/FeSiMn alloy lime V ₂ O ₅ al Si wt% Fe wt% Mnwt% Cr wt% kg kg kg kg T (℃) Si wt% V wt% Fe wt% Mnwt% Cr wt% 63 twenty one 14 9.7 1.0 1.8 0.1 1600 56 10 19 13 60 twenty four 15 9.7 1.0 1.8 0.1 1650 53 10 twenty three 15 Example 2. Manufacture of FeSiNb alloy

Three tests for producing FeSiNb alloys of the present invention were prepared. Table ₄ below shows the raw material amounts of FeSi75 and _Nb2O5 used for the 3 FeSiNb test fabrications. In addition, the amount of lime (CaO) in the modified slag and the total Al in the system are displayed. The temperature (T) was set above the melting point of the _FeSiNb alloy before the addition of _Nb2O5 . _The liquid ferrosilicon is stirred during the addition of _Nb2O5 , lime and any aluminum. The manufactured compositions are shown in the right part of Table 4. During tapping, the purity of the produced FeSiNb alloy is important to separate slag and metal. Table 4: Amounts and temperatures of FeSi, niobium oxide, lime, and aluminum. Analysis of the fabricated FeSiNb alloy composition. Add to analyze test FeSi (kg) Nb ₂ O ₅ (kg) Lime (kg) Al (kg) T (℃) Si (wt%) Nb (wt%) Fe (wt%) Al (wt%) 1 9 1.4 0.6 0.2 1550 70 9 twenty one 0.25 2 9 3.1 1.2 0.5 1550 58 19 twenty two 0.29 3 9 5.1 2.0 0.8 1650 47 32 twenty one 0.35 Example 3. Comparison of dissolution behavior of FeSiV relative to FeV80

In order to demonstrate that the dissolution behavior of FeSiV according to the invention is faster than that of a commercially available alloy as an example, FeSiV10 (FeSiV with about 10% V) and FeSiV20 (FeSiV with about 20% The dissolution behavior of FeSiV) alloy of V is compared with that of FeV80. The dissolution time can be measured by different techniques known from the literature. Examples are attaching load cells to ferroalloys and measuring weight loss [Argyropoulus, 1983], or taking samples of steel melts at regular intervals and analyzing elemental content [Gourtsoyannis et al., 1984].

Figure 1 is a graph showing the dissolution times of FeSiV10 alloys and FeSiV20 alloys according to the present invention in low alloy steel melts at a temperature of about 1600°C, compared to standard commercially available FeV80 alloys. The graph shows dissolution time versus FeSiV10 and FeSiV20 and FeV80 agglomerates of different size fractions. Figure 1 shows that the dissolution time measured for a size of 25 mm and FeV80 is more than 3 times longer than that of FeSiV10. Compared to FeSiV10 and FeSiV20 alloys, the dissolution time of FeV80 becomes significantly longer as the size of the agglomerates added to the steel melt increases. Faster dissolution times shorten steelmaking process times, thereby saving costs and increasing flexibility over state-of-the-art solutions. Embodiment 4. The yield test of FeSiV10 relative to FeV80

To demonstrate the productivity behavior and utility of the alloys of the invention for the manufacture of steel, tests of FeSiV10 versus FeV80 were performed. Six steel melts of identical composition were produced in a 100 kg electric arc furnace at 1600°C. The steel is deoxidized with aluminum and alloyed with essential alloying elements other than silicon and vanadium. Use case 1 alloying of 3 melts: addition of FeSi75 and FeV80, and use case 2 alloying of 3 melts: addition of FeSiV10.

Steel melt samples were taken before and after alloying and analyzed by ICP (Inductively Coupled Plasma) method. Additionally, solute oxygen, total oxygen, pre-alloyed samples, and ladle samples were analyzed to detect any possible irregularities. Yields were calculated using the vanadium and silicon added to the melt compared to the vanadium and silicon analyzed in the ICP analysis. The results are shown in Table 5 below. Table 5: Average yields from six steelmaking tests of 54SiCrV6 steel average yield alloy vanadium silicon FeSi75+FeV80 90.4% 92.2% FeSiV10 93.9% 92.8% to improve +3.5% +0.6%

It can be seen from Table 5 that the average vanadium yield of FeSiV10 is 3.5% higher than that of FeV80. Average silicon yields are similar.

This test proves that the present invention not only efficiently obtains various alloying elements from oxides, but also improves the steelmaking process due to the higher yield of each alloy. Example 5. Manufacture of an alloy comprising vanadium and niobium

Combination alloys of vanadium and niobium made of oxides as described in Table 6 can be produced using the present invention. The alloy can be fabricated in a single or two-step process. The difference is that in a two-step process, for example FeSiV is first produced from oxides with desired Al and lime additions. The slag was then removed, and Nb was added as oxide to the liquid FeSiV with the desired Al and lime additions. The dross can then be modified to aid in dross removal prior to casting. Alloys can be fabricated in the same manner as above by starting with FeSiNb and adding V as an oxide to liquid FeSiNb. Table 6: Amounts of FeSi, vanadium oxide, niobium oxide, lime, aluminum, and resulting alloy components. Add to Generate alloy FeSi (kg) V ₂ O ₅ (kg) Nb ₂ O ₅ (kg) Lime (kg) Al (kg) Si (wt%) Fe (wt%) V (wt%) Nb (wt%) kg 9.4 0.9 0.7 0.7 0.2 66 twenty four 5 5 10 9.2 1.8 0.7 1.1 0.3 62 twenty three 10 5 10 9.1 0.9 1.4 0.9 0.3 62 twenty three 5 10 10 8.9 1.8 1.4 1.4 0.4 58 twenty two 10 10 10 8.7 2.7 1.4 1.8 0.4 53 twenty two 15 10 10 8.5 1.8 2.1 1.6 0.5 54 twenty one 10 15 10 9.0 2.7 0.7 1.6 0.3 57 twenty three 15 5 10 8.7 0.9 2.1 1.1 0.4 58 twenty two 5 15 10 8.3 2.7 2.1 2.0 0.6 49 twenty one 15 15 10 8.5 3.6 1.4 2.2 0.5 49 twenty one 20 10 10 8.1 1.8 2.9 1.8 0.6 50 20 10 20 10 7.7 3.6 2.9 2.7 0.8 41 19 20 20 10 Example 6. Manufacture of FeSiVNb alloy

Experiments were prepared for the manufacture of FeSiVNb alloys of the present invention. Table 7 below shows the raw material amounts of FeSi75, V ₂ O ₅ and Nb ₂ O ₅ used in the test fabrication of FeSiVNb. In addition, the amount of lime (CaO) in the modified slag and the total Al in the system are displayed. The temperature (T) was set above the melting point of the FeSiVNb alloy before any oxide was added. _The liquid ferrosilicon was stirred during the addition of _V2O5 , _Nb2O5 , _lime , and any aluminum. The manufactured compositions are shown in the right part of Table 7. During tapping, the purity of the produced FeSiVNb alloy is important to separate slag and metal. Table 7: Amounts and temperatures of FeSi, vanadium oxide, niobium oxide, lime, and aluminum. Analysis of the fabricated FeSiVNb alloy composition. Add to analyze FeSi (kg) V ₂ O ₅ (kg) N ₂ O ₅ (kg) Lime (kg) Al (kg) T (℃) Si (wt%) V (wt%) Nb (wt%) Fe (wt%) Al (wt%) 9.0 1.93 1.51 1.68 0.44 1700 57 8.8 10.6 twenty three 0.1

Those skilled in the art recognize that the present invention is not limited to the above preferred specific embodiments. Those skilled in the art further recognize that modifications and changes are possible within the scope of the appended claims. In addition, those skilled in the art can understand and make changes to the disclosed specific embodiments by studying the present disclosure and the appended claims when implementing the claimed invention.

none

FIG. 1 is a graph showing the comparison of the dissolution time of FeSiV10 alloy and FeSiV20 alloy according to one embodiment of the present invention, and the standard FeV80 alloy in a steel melt.

Claims (30)

A ferrosilicon vanadium and/or niobium (FeSiV and/or Nb) alloy comprising: 35 to 75 weight percent Si; 3 to 35 weight percent of V and/or Nb; Al at most 2% by weight; Up to 25% by weight of Mn; Up to 25% by weight of Cr; Up to 0.15% by weight of Ca; Up to 0.10 weight percent Ti; Up to 0.10% by weight C; Up to 0.02 weight percent Cu; Up to 0.05% by weight of P; Up to 0.02% by weight of S; The rest is Fe and incidental impurities. FeSi V and/or Nb alloy such as claim 1, which comprises 35 to 60 weight percent of Si, 16 to 35 weight percent of V and/or Nb, at most 2 weight percent of Al, at most 25 weight percent of Mn, at most 25% by weight of Cr, at most 0.15% by weight of Ca, at most 0.10% by weight of Ti, at most 0.10% by weight of C, at most 0.02% by weight of Cu, at most 0.05% by weight of P, at most 0.02% by weight of S, and the rest are Fe and incidental impurities. Such as the FeSiV and/or Nb alloy of claim 1, which comprises 51 to 75 weight percent of Si, 3 to 35 weight percent of V and/or Nb, at most 2 weight percent of Al, at most 25 weight percent of Mn, at most 25% by weight of Cr, at most 0.15% by weight of Ca, at most 0.10% by weight of Ti, at most 0.10% by weight of C, at most 0.02% by weight of Cu, at most 0.05% by weight of P, at most 0.02% by weight of S, and the rest are Fe and incidental impurities. The FeSi V and/or Nb alloy according to claim 1 or 3, which contains 5 to 25 weight percent of V and/or Nb. The FeSiV and/or Nb alloy as claimed in claim 1, 3 or 4, comprising 60 to 72 weight percent Si. The FeSiV and/or Nb alloy according to any one of claims 1 to 3, comprising at most 0.5% by weight of Al. The FeSiV and/or Nb alloy according to any one of claims 1 to 3, which contains Ti at most 0.025 wt%. The FeSiV and/or Nb alloy according to any one of claims 1 to 3, comprising at most 0.3 weight percent of Mn. The FeSiV and/or Nb alloy according to any one of claims 1 to 3, comprising 0.3 to 25 weight percent of Mn. The FeSiV and/or Nb alloy according to any one of claims 1 to 3, which contains Cr at most 0.3% by weight. The FeSiV and/or Nb alloy according to any one of claims 1 to 3, comprising 0.3 to 25 weight percent Cr. The FeSiV and/or Nb alloy according to any one of claims 1 to 3, wherein the melting temperature of the FeSiV and/or Nb alloy is in the range of 1250 to 1650°C. The FeSiV and/or Nb alloy according to any one of Claims 1 to 3, wherein the FeSiV and/or Nb alloy is in the form of particles or agglomerates with a particle size classification of 3 mm to 80 mm, or in the form of a core wire , or in the form of embryo blocks. The FeSiV and/or Nb alloy according to any one of Claims 1 to 3, wherein the FeSiV and/or Nb alloy is an additive for steelmaking. A method of manufacturing ferrosilicon vanadium and/or niobium (FeSiV and/or Nb) alloys as claimed in any one of claims 1 to 14, the method comprising: - provision of liquid ferrosilicon in containers; - adding vanadium oxide-containing raw materials and/or niobium oxide-containing raw materials to the liquid ferrosilicon; - mixing and reacting the liquid ferrosilicon alloy with vanadium oxide from the vanadium oxide-containing raw material and/or niobium oxide from the niobium oxide-containing raw material, thereby forming a melt and slag of FeSi V and/or Nb alloy ; - separating the slag from the melt; and - Solidification or casting of the liquid FeSi V and/or Nb alloy. The method of claim 15, wherein the liquid ferrosilicon alloy is directly provided from a reduction furnace, wherein the ferrosilicon is produced from raw materials according to a known method. The method according to claim 15, wherein the liquid ferrosilicon is provided by remelting the loaded ferrosilicon. The method according to any one of claims 15 to 17, wherein the vanadium oxide-containing raw material and/or the niobium oxide-containing raw material are used to essentially provide a target amount of elemental vanadium and/or niobium in the FeSiV and/or Nb alloy (by weight) amount (by weight) added. The method according to any one of claims 15 to 17, wherein the vanadium oxide-containing raw material is one or more selected from vanadium oxide (II), vanadium oxide (III), vanadium oxide (IV), vanadium oxide (V), And/or the vanadium oxide phase of other non-main oxides of vanadium, and/or the niobium oxide-containing raw material is one or more selected from niobium (II) oxide, niobium (III) oxide, niobium (IV) oxide, niobium oxide (V), and/or the niobium oxide phase of other non-primary oxides of niobium. The method according to claim 19, wherein the vanadium oxide phase is vanadium oxide (V) V ₂ O ₅ and/or vanadium oxide (III) V ₂ O ₃ , and/or the niobium oxide phase is niobium oxide (V) Nb ₂ O ₅ and/or niobium(III) oxide Nb ₂ O ₃ . The method of claim 19, wherein the vanadium oxide-containing raw material further comprises industrial waste or ore containing elemental vanadium or vanadium oxide, and/or the niobium oxide-containing raw material further comprises industrial waste or ore comprising elemental niobium or niobium oxide . The method according to any one of claims 15 to 17, further comprising adding a slag modifying compound to the liquid ferrosilicon in an amount of 0.5 to 30 weight percent based on the total amount of the ferrosilicon. The method of claim 22, wherein the slag modifying compound is at least one of CaO and MgO. The method according to any one of claims 15 to 17, wherein the liquid ferrosilicon has a general composition: 45 to 90 weight percent Si; Up to 0.5% by weight of C; Al at most 2% by weight; Up to 1.5 weight percent Ca; Up to 0.1 weight percent Ti; Up to 26% by weight of Mn; Up to 26% by weight of Cr; Up to 0.02% by weight of P; Up to 0.005% by weight of S; The rest is Fe and incidental impurities. The method according to any one of claims 15 to 17, further comprising, before, at the same time, or after adding the vanadium oxide-containing raw material and/or the niobium oxide-containing raw material, combining aluminum with ferrosilicon and vanadium oxide and/or The total amount of niobium oxide is added to the ferrosilicon melt in an amount of up to 10 weight percent. The method according to any one of claims 15 to 17, which comprises the liquid ferrosilicon alloy with the vanadium oxide-containing raw material and/or the niobium oxide-containing raw material, and any added aluminum and/or slag modification compound, by mechanical Stir or gas stir to mix. The method according to any one of claims 15 to 17, wherein the molten slag is separated before or during casting of the liquid FeSiV and/or Nb alloy. The method according to any one of claims 15 to 17, further comprising crushing the solidified or cast FeSiV and/or Nb alloy and optionally classifying by particle size components. A use of FeSi V and/or Nb alloy according to any one of claims 1 to 14, which is used as an additive in the manufacture of vanadium and/or niobium-containing steel. Such as the use of claim 29, wherein the steel containing vanadium and/or niobium is selected from spring steel, tool steel, forged steel, rail steel, reinforced steel, thick plate steel, microalloyed vehicle steel and aircraft steel.

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