WO2021175306A1 - 钒铁合金的制备方法 - Google Patents

钒铁合金的制备方法 Download PDF

Info

Publication number
WO2021175306A1
WO2021175306A1 PCT/CN2021/079216 CN2021079216W WO2021175306A1 WO 2021175306 A1 WO2021175306 A1 WO 2021175306A1 CN 2021079216 W CN2021079216 W CN 2021079216W WO 2021175306 A1 WO2021175306 A1 WO 2021175306A1
Authority
WO
WIPO (PCT)
Prior art keywords
vanadium
phase
batch
ferro
smelting
Prior art date
Application number
PCT/CN2021/079216
Other languages
English (en)
French (fr)
Inventor
余彬
景涵
陈海军
师启华
张�林
梁彬
Original Assignee
攀钢集团攀枝花钢铁研究院有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 攀钢集团攀枝花钢铁研究院有限公司 filed Critical 攀钢集团攀枝花钢铁研究院有限公司
Publication of WO2021175306A1 publication Critical patent/WO2021175306A1/zh
Priority to ZA2022/06829A priority Critical patent/ZA202206829B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C35/00—Master alloys for iron or steel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • C22B4/06—Alloys

Definitions

  • the invention belongs to the technical field of metallurgy, and specifically relates to a preparation method of a vanadium-iron alloy.
  • Ferro-vanadium alloy is widely used in vanadium-containing microalloy steels. It has a dual strengthening mechanism of fine-grain strengthening and precipitation strengthening, thereby reducing overheating sensitivity and improving steel strength and wear resistance. It is widely used in construction, aerospace, road and bridge industries.
  • the production of ferrovanadium alloys mainly includes thermal reduction methods such as silicothermal reduction, aluminothermic reduction and carbothermic reduction. Due to the strong reduction activity of aluminum and the large heat generation during the reduction process, thermite reduction is the most widely used.
  • V 2 O 5 is the main vanadium-containing raw material smelted by ferrovanadium production enterprises. With the development of new technologies and new processes, a few domestic and foreign companies have gradually mastered the preparation of vanadium using V 2 O 3 as the raw material by electro-aluminum heating. Ferroalloy method.
  • the world's ferro-vanadium alloy smelting methods can be divided into one-step method, two-step method and multi-phase method.
  • the one-step smelting process is simple, but the vanadium yield is relatively low, and the product quality is controlled by the quality of the raw materials and the accuracy of the batching;
  • the two-step method is mainly through the addition of excess reducing agent to strengthen the reduction of vanadium-containing materials, and then further refine and remove Remove the excess reducing agent in the alloy, so as to reduce the vanadium loss in the slag;
  • the multi-phase method is based on the two-step method, through the operation of phased aluminum allocation, batch feeding and multiple slag tapping operations, to achieve the smelting slag
  • the reduction of vanadium loss and the improvement of smelting efficiency will enhance the stability of the smelting system to a certain extent.
  • ZL201510496769.1 proposes a multi-period thermite with metallic aluminum as a reducing agent, V 2 O 3 and V 2 O 5 mixed vanadium oxide as raw materials, and a large electric furnace with slag tapping and iron tapping functions as the main equipment
  • the preparation method of reduced ferro-vanadium under the premise that the comprehensive aluminum distribution coefficient is ⁇ 1.05, the smelting operation is carried out according to the smelting period using a gradient of aluminum distribution method, which can greatly reduce the vanadium content in the smelting slag in the early stage of smelting, and realize the vanadium loss in the slag and unit
  • the aluminum consumption is reduced, but the thermodynamic conditions of this method need to be improved.
  • the purpose of the present invention is to provide a method for preparing a ferro-vanadium alloy, which is not only beneficial to improve the thermodynamic conditions of the smelting process, but also can greatly reduce the vanadium loss in the slag.
  • the technical scheme of the present invention is: a preparation method of ferro-vanadium alloy, including the following steps:
  • the smelting process is divided into N phases, and the mixtures are configured for each phase.
  • the mixtures of phases 1 to N-1 are divided into two batches for smelting, and the smelting is completed in the N-1 phase.
  • the N-phase mixture is added to the furnace at one time for smelting pre-reduction;
  • the aluminum distribution coefficient of the first batch of mixtures in the period 1 to N-1 is 1.0 to 1.1
  • the aluminum distribution coefficient of the second batch of mixtures in the period 1 to N-1 is 1.0 to 1.4
  • the aluminum distribution coefficient of the mixture in the N period The coefficient is 0.2 ⁇ 1.0
  • the comprehensive aluminum distribution coefficient of the total charge is 1.00 ⁇ 1.08;
  • the molten slag gold is poured into a refining furnace for refining; after the refining is completed, the furnace body is naturally cooled and then the furnace is dismantled, and the slag gold is separated to obtain the alloy.
  • the aluminum distribution coefficients of the first batch and the second batch of the first phase are 1.0 to 1.1 and 1.05 to 1.4, respectively; the first batch and the second batch of the second phase are The aluminum distribution coefficients of the second batch of mixtures are 1.0 to 1.05 and 1.05 to 1.2, respectively.
  • step a the aluminum distribution coefficient of the first batch of mixtures in the period 1 to N-1 ⁇ the aluminum distribution coefficient of the second batch of mixtures in the period N-1.
  • step a satisfies at least one of the following:
  • the weight ratio of the total vanadium-containing materials in phase 1 ⁇ N-1 to the vanadium-containing materials in phase N is 20:2 ⁇ 5 in terms of vanadium content
  • the weight ratio of the first batch of mixture to the second batch of mixture is 1:0.8 to 1.2 based on the vanadium content.
  • step a satisfies at least one of the following:
  • the vanadium-containing material is one or more of vanadium oxide, vanadium-containing dust removal ash or vanadium-containing fine powder;
  • the weight ratio of vanadium oxide in the vanadium-containing material is ⁇ 80%;
  • the vanadium oxide is V 2 O 3 and/or V 2 O 5 ;
  • the mixture is composed of vanadium-containing materials, iron, Al and slagging agent.
  • the total amount of iron added is calculated according to the mass ratio of ferro-vanadium in the alloy products produced, and then evenly distributed to each batch of raw materials in each period
  • the slagging agent is selected from calcium oxide or calcium salt, and its addition amount is 5 to 15% of the weight of vanadium in the vanadium-containing material;
  • N is any integer of 3-5.
  • the criterion for the complete reaction in each phase is that the vanadium content in the slag decreases ⁇ 0.05%/min, and the slag output in each phase is not less than 80% of the total slag volume.
  • step b the pre-reduction time of phase N smelting is 1 to 3 min/ton of alloy, and the refining time is 1 to 3 min/ton of alloy.
  • step b a mixture of reducing agent and flux is pre-installed in the refining furnace; preferably, the reducing agent is aluminum and/or ferrosilicon, and the addition amount is not greater than the single furnace comprehensive reducing agent
  • the theoretical addition amount is 2-8%; the flux is a low melting point oxide or salt containing Ca, K or Na, and the weight ratio of the addition amount to the addition amount of the reducing agent is 0.5-1:1.
  • the present invention redistributes the aluminum allocation coefficient in each phase and period of the smelting process, that is, the aluminum allocation coefficient in each phase of the smelting process is gradually reduced (the aluminum allocation coefficient in the first to N-1 phases is greater than or equal to 1.0, and the aluminum allocation coefficient in the N phase Coefficient ⁇ 1; and during the period from 1 to N-1, the aluminum distribution coefficient of the i period is greater than or equal to the i+1 period), and a gradient increasing method is formed within a single smelting period (the first batch of raw material distribution in the period is (The aluminum coefficient is less than the second batch of aluminum distribution coefficient) to mix aluminum, not only can meet the thermodynamic conditions of excessive aluminum distribution coefficient, but also can further improve the reaction kinetic conditions of each smelting stage, and can greatly reduce vanadium loss in the slag.
  • a method for preparing a ferro-vanadium alloy includes the following steps:
  • the smelting process is divided into N phases, and the mixtures are configured for each phase.
  • the mixtures of phases 1 to N-1 are divided into two batches for smelting, and the smelting is completed in the N-1 phase.
  • the N-phase mixture is added to the furnace at one time for smelting pre-reduction;
  • the aluminum distribution coefficient of the first batch of mixtures in the period 1 to N-1 is 1.0 to 1.1
  • the aluminum distribution coefficient of the second batch of mixtures in the period 1 to N-1 is 1.0 to 1.4
  • the aluminum distribution of the mixture in period N The coefficient is 0.2 ⁇ 1.0
  • the comprehensive aluminum distribution coefficient of the total charge is 1.00 ⁇ 1.08;
  • the molten slag gold is poured into a refining furnace for refining; after the refining is completed, the furnace body is naturally cooled and then the furnace is dismantled, and the slag gold is separated to obtain the alloy.
  • the aluminum allocation method of the method of the present invention is as follows: the aluminum allocation coefficient in each phase of smelting is guaranteed to gradually decrease (the aluminum allocation coefficient in the first to N-1 period is ⁇ 1.0, and the aluminum allocation coefficient in the N period is less than 1; and the aluminum allocation coefficient in the first to N-1 period is less than 1; In terms of the aluminum distribution coefficient of the i-th period ⁇ the i+1 period), a gradual increase is formed in a single smelting period (the aluminum distribution coefficient of the first batch of raw materials in the period is less than the aluminum distribution coefficient of the second batch). With aluminum.
  • i 1 to N-2, and N is an integer.
  • the weight ratio of the total vanadium-containing materials in the period 1 ⁇ N-1 to the vanadium-containing materials in the period N is 20:2 ⁇ 5 based on the vanadium content; in the period 1 ⁇ N-1, the first batch of mixed materials and the second batch of mixed materials
  • the weight ratio is 1:0.8 to 1.2 based on the vanadium content.
  • the mixture of the present invention is composed of vanadium-containing materials, iron, Al and a slag-forming agent.
  • the total amount of iron added is calculated according to the mass ratio of ferro-vanadium in the alloy product produced, and then evenly distributed to each batch of each period In the raw materials;
  • the slagging agent is selected from calcium oxide or calcium salt, and its addition amount is 5-15% of the weight of vanadium in the vanadium-containing material.
  • the criterion for the complete reaction in each phase of the present invention is that the vanadium content in the slag decreases by less than or equal to 0.05%/min, and the slag output in each phase is not less than 80% of the total slag volume.
  • the "theoretical addition amount" of the present invention refers to the theoretical reducing agent (aluminum, ferrosilicon) required per unit of vanadium-containing material and the theoretical iron addition amount corresponding to the required addition when obtaining a certain standard grade of ferro-vanadium alloy.
  • the amount of iron added in the mixture is based on the total input of vanadium-containing materials in a single furnace (vanadium is counted by weight), and the total iron addition of the furnace is calculated according to the mass ratio of the corresponding grade of vanadium-iron alloy, and it is evenly distributed to each period
  • Each batch of raw materials; the addition amount of the slag-forming agent in the mixture is based on the vanadium-containing material (vanadium by weight), and is added in a proportion of 5% to 15%.
  • the "aluminum distribution coefficient" of the present invention is a multiple of the theoretical aluminum consumption.
  • the theoretical aluminum consumption calculation method is as follows:
  • the unit V 2 O 5 /theoretical aluminum consumption of dust removal ash is:
  • the mixture in the following examples also includes the required iron and corresponding slagging agent.
  • the slagging agent is lime; the amount of iron added is based on the total input of vanadium-containing materials in a single furnace (with vanadium as the weight) as the standard.
  • the mass ratio of the ferro-vanadium alloy of the corresponding brand is calculated by calculating the total iron addition amount of the furnace, and it is evenly distributed to each batch of raw materials in each period; the addition amount of slagging agent accounts for 10% of the weight of the vanadium-containing material (in terms of vanadium). %.
  • smelting raw materials are V 2 O 5 , V 2 O 3 and vanadium-containing dust ash (36.2% vanadium mass fraction), and the weight ratio is 2:6:2.
  • the smelting is divided into three phases, the first batch of mixed materials in the first and second phases is 1.0, the second batch of mixed materials in the first and second phases is 1.05, the third phase is 1.0, and the single furnace
  • the comprehensive aluminum distribution coefficient is 1.02.
  • the weight ratio of vanadium-containing materials (based on vanadium content) in the first and second phases is 1:1, and the weight ratio of total vanadium-containing materials in the first and second phases to the weight of vanadium-containing materials in the third phase (based on vanadium content) is 20: 2.
  • the pre-reduction time of the third phase of smelting is 1min/ton of alloy, and then the molten slag gold is poured into the refining furnace for refining operation.
  • the refining furnace is pre-installed with ferrosilicon and CaO.
  • the addition amount of ferrosilicon is the theoretical addition of comprehensive reducing agent.
  • the weight ratio of ferrosilicon to CaO is 1:1, and the refining time is 1 min/ton of alloy. After refining, the furnace body is naturally cooled and then the furnace is dismantled, and the slag gold is separated to obtain the alloy.
  • the vanadium content in the first and second phases is 2.2%
  • the vanadium content in the refining slag is 0.5%
  • the ferro-vanadium yield is 95.3%
  • the unit power consumption is 1100kWh/ton
  • the aluminum content in the alloy is 2.0%.
  • the raw materials for smelting are V 2 O 5 , V 2 O 3 , vanadium-containing dust ash (vanadium mass fraction 36.3%) and vanadium-containing fine powder (vanadium mass fraction 50.5%), and the weight ratio is 2:6:1: 1.
  • the smelting is divided into three phases.
  • the first batch of mixed materials in the first and second phases is 1.0
  • the second batch of mixed materials in the first and second phases is 1.1
  • the third phase is 0.4 in single furnace.
  • the comprehensive aluminum distribution coefficient is 1.05.
  • the weight ratio of vanadium-containing materials (calculated by vanadium content) in the first and second periods is 1:1, and the weight ratio of the total vanadium-containing materials in the first and second periods to the vanadium-containing materials in the third period (calculated by vanadium content) is 20:3.
  • the pre-reduction time of the third phase of smelting is 1min/ton of alloy, and then the molten slag gold is poured into the refining furnace for refining operation.
  • the refining furnace is pre-installed with Al and CaO.
  • the addition amount of Al is the theoretical addition amount of the comprehensive reducing agent. 3wt%, the weight ratio of Al to CaO is 1:1, and the refining time is 1 min/ton of alloy. After refining, the furnace body is naturally cooled and then the furnace is dismantled, and the slag gold is separated to obtain the alloy.
  • the vanadium content in the first and second phases is 1.5%
  • the vanadium content in the refining slag is 0.7%
  • the ferro-vanadium yield is 96.2%
  • the unit power consumption is 1020kWh/ton
  • the aluminum content in the alloy is 1.4%.
  • smelting raw materials are V 2 O 5 , V 2 O 3 and vanadium-containing dust ash (36.3% vanadium mass fraction), and the weight ratio is 2:7:1.
  • the smelting is divided into 4 phases.
  • the aluminum distribution coefficient of the first batch of the first phase is 1.0
  • the second batch of the first phase is 1.3
  • the first batch of the second to the third phase is 1.0
  • the aluminum distribution coefficient of the second batch of mixed materials in phases 2 to 3 is 1.2
  • the aluminum distribution coefficient of the mixed materials in phase 4 is 0.4
  • the comprehensive aluminum distribution coefficient of a single furnace is 1.06.
  • the weight ratio of vanadium-containing materials in the first three phases is 1:1:1, and the weight ratio of the total vanadium-containing materials in the first to third phases to the vanadium-containing materials in the fourth phase (calculated by vanadium content) is 20: 5.
  • the pre-reduction time of the fourth phase of smelting is 2min/ton of alloy, and then the molten slag gold is poured into the refining furnace for refining operation.
  • the refining furnace is pre-installed with Al and CaO.
  • the addition amount of Al is the theoretical addition amount of the comprehensive reducing agent. 2wt%, the weight ratio of Al to CaO is 2:1, and the refining time is 2min/ton of alloy. After refining, the furnace body is naturally cooled and then the furnace is dismantled, and the slag gold is separated to obtain the alloy.
  • the vanadium content in the 1st to 3rd stage slag is 0.7%
  • the vanadium content in the refining slag is 0.8%
  • the ferro-vanadium yield is 97.1%
  • the unit power consumption is 950kWh/ton
  • the aluminum content in the alloy is 1.2%.
  • the raw materials for smelting are V 2 O 5 and V 2 O 3 , and the weight ratio is 5:5.
  • the smelting is divided into four phases.
  • the aluminum distribution coefficient of the first batch of the first phase is 1.1
  • the second batch of the first phase is 1.4
  • the first batch of the second to the third phase is 1.0
  • the aluminum distribution coefficient of the second batch of mixed materials in phases 2 to 3 is 1.2
  • the aluminum distribution coefficient of the mixed materials in phase 4 is 0.2
  • the comprehensive aluminum distribution coefficient of a single furnace is 1.08.
  • the weight ratio of vanadium-containing materials in the first three phases is 1:1:1, and the weight ratio of the total vanadium-containing materials in the first to third phases to the vanadium-containing materials in the fourth phase (calculated by vanadium content) is 20: 5.
  • the pre-reduction time of the fourth phase of smelting is 3min/ton of alloy, and then the molten slag gold is poured into the refining furnace for refining operation. No reducing agent and flux are added to the refining furnace. The refining time is 3min/ton of alloy. After the refining is completed After the furnace body is naturally cooled, the furnace is dismantled, and the slag gold is separated to obtain the alloy.
  • the vanadium content in the 1st to 3rd stage slag is 0.3%
  • the vanadium content in the refining slag is 1.1%
  • the ferro-vanadium yield is 97.7%
  • the unit power consumption is 910kWh/ton
  • the aluminum content in the alloy is 0.8%.
  • the raw materials for smelting are V 2 O 5 , V 2 O 3 and vanadium-containing dust ash (35.7% by mass of vanadium), and the weight ratio is 2:6:2.
  • the smelting is divided into three phases by uniformly distributing aluminum.
  • the aluminum distribution coefficient of each phase is 1.05, and the comprehensive aluminum distribution coefficient is 1.05.
  • the raw materials are put into the furnace twice in each period.
  • the vanadium content in the slag decreases ⁇ 0.05%/min.
  • the average vanadium content in the slags of the first and second phases is 2.5%
  • the vanadium content in the refining slag of the third phase is 1.6%
  • the yield of ferrovanadium is 94.6%
  • the unit power consumption is 1410kWh/ton
  • the aluminum content in the alloy is 1.5%.

Abstract

本发明公开了一种钒铁合金的制备方法，属于冶金技术领域，包括以下步骤：a以含钒物料为原料，将冶炼过程分为N期，按各期分别配置混合料，将1～N-1期混合料分两批次入炉冶炼，在第N-1期冶炼结束出渣后，将第N期混合料一次性加至炉中进行冶炼预还原；其中，1～N-1期第一批混合料的配铝系数为1.0～1.1，1～N-1期第二批混合料的配铝系数为1.0～1.4，第N期混合料的配铝系数为0.2～1.0，总炉料的综合配铝系数为1.00～1.08；b还原结束后，将熔融渣金倾翻至精炼炉中进行精炼；精炼结束后，待炉体自然冷却后拆炉，分离渣金得合金。本发明方法不仅有利于改善冶炼过程的热动力学条件，还能大幅降低渣中钒损。

Description

钒铁合金的制备方法 技术领域
本发明属于冶金技术领域，具体涉及一种钒铁合金的制备方法。
背景技术
钒铁合金被广泛应用于含钒微合金钢中，它具有细晶强化和沉淀强化的双重强化机制，从而降低过热敏感性，提高钢材的强度以及耐磨性。广泛应用于建筑、航空航天、路桥等行业。钒铁合金的生产主要有硅热还原法、铝热还原法及碳热还原法等热还原法。由于铝的还原活性较强，还原过程发热量大，铝热还原应用最为广泛。当前钒铁生产企业冶炼主要含钒原料以V 2O 5为主，随着新技术及新工艺的开发，国内外少数几家企业逐渐掌握了以V 2O 3为原料电铝热法制备钒铁合金的方法。
目前世界上钒铁合金冶炼方法可分为一步法、两步法和多期法。其中，一步法冶炼工艺简单，但钒收率相对偏低，且产品质量受控于原料品质和配料精度；两步法主要通过添加过量还原剂对含钒物料进行强化还原后，进一步通过精炼脱除合金中多余的还原剂，从而达到降低了渣中钒损目的；多期法是在两步法的基础上，通过分期配铝、分批加料和多次出渣的操作，实现冶炼渣中钒损的降低和冶炼效率的提高，并在一定程度上增强冶炼系统的稳定性。
ZL201510496769.1提出一种以金属铝作为还原剂，以V 2O 3和V 2O 5混合钒氧化物为原料，以带有出渣和出铁功能的大型电炉为主体设备的多期铝热还原钒铁制备方法，在综合配铝系数≤1.05的前提下，按照冶炼期次采用梯度递减的配铝方式进行冶炼操作，能够大幅降低冶炼前期渣中钒含量，实现了渣中钒损和单位铝耗的降低，但是该方法的热动力学条件还有待改善。
发明内容
本发明的目的在于提供一种钒铁合金的制备方法，该方法不仅有利于改善冶炼过程的热动力学条件，还能够大幅降低渣中钒损。
本发明的技术方案为：一种钒铁合金的制备方法，包括以下步骤：
a以含钒物料为原料，将冶炼过程分为N期，按各期分别配置混合料，将1～N-1期混合料分两批次入炉冶炼，在第N-1期冶炼结束，出渣后，将第N期混合料一次性加 至炉中进行冶炼预还原；
其中，1～N-1期第一批混合料的配铝系数为1.0～1.1，1～N-1期第二批混合料的配铝系数为1.0～1.4，第N期混合料的配铝系数为0.2～1.0，总炉料的综合配铝系数为1.00～1.08；
b还原结束后，将熔融渣金倾翻至精炼炉中进行精炼；精炼结束后，待炉体自然冷却后拆炉，分离渣金得合金。
其中，上述钒铁合金的制备方法，步骤a中，第1期第一批和第二批混合料的配铝系数分别为1.0～1.1和1.05～1.4；第2～N-1期第一批和第二批混合料的配铝系数分别为1.0～1.05和1.05～1.2。
其中，上述钒铁合金的制备方法，步骤a中，1～N-1期第一批混合料的配铝系数≤1～N-1期第二批混合料的配铝系数。
其中，上述钒铁合金的制备方法，步骤a中，1～N-1期内，第i期配铝系数≥第i+1期配铝系数，i＝1～N-2。
其中，上述钒铁合金的制备方法，步骤a中，第N期混合料的配铝系数为0.2～1.0。
其中，上述钒铁合金的制备方法，步骤a满足以下至少一项：
1～N-1期，第i期含钒物料与第i+1期含钒物料的重量比以含钒量计为1：0.8～1.2，i＝1～N-2；
1～N-1期总含钒物料与第N期含钒物料的重量比以含钒量计为20：2～5；
1～N-1期，第一批混合料与第二批混合料重量比以含钒量计为1：0.8～1.2。
其中，上述钒铁合金的制备方法，步骤a满足以下至少一项：
所述含钒物料为钒氧化物、含钒除尘灰或含钒细粉中的一种以上；
优选的，所述含钒物料中钒氧化物的重量比≥80％；
更优选的，所述钒氧化物为V 2O 3和/或V 2O 5；
所述混合料是由含钒物料、铁、Al和造渣剂组成，其中，铁的总添加量根据生产的合金产品中钒铁质量比计算得到，然后均匀分配到各期次各批次原料中；造渣剂选自钙氧化物或钙盐，其添加量为含钒物料中钒重量的5～15％；
N为3～5中的任一整数。
其中，上述钒铁合金的制备方法，步骤a中，各期反应完全的标准为渣中钒含量降幅≤0.05％/min，各期出渣量不低于总渣量的80％。
其中，上述钒铁合金的制备方法，步骤b中，第N期冶炼预还原时间为1～3min/吨 合金，精炼时间为1～3min/吨合金。
其中，上述钒铁合金的制备方法，步骤b中，精炼炉中预装了还原剂和助熔剂的混合物；优选的，还原剂为铝和/或硅铁，其添加量不大于单炉综合还原剂理论添加量的2～8％；助熔剂为含Ca、K或Na的低熔点氧化物或盐，其添加量与还原剂添加量的重量比为0.5～1：1。
与现有技术相比，本发明的有益效果是：
本发明对冶炼过程各期及期次内配铝系数进行了重新分配，即在保证冶炼各期次配铝系数逐渐降低(第1～N-1期配铝系数≥1.0，第N期配铝系数＜1；且1～N-1期内，第i期配铝系数≥第i+1期)的基础上，在单一冶炼期次内形成梯度递增的方式(期次内第一批原料配铝系数小于第二批配铝系数)进行配铝，不仅能够满足过量配铝系数的热力学条件，同时还能进一步提高各冶炼期次的反应动力学条件，并且能够大幅降低渣中钒损。
具体实施方式
具体的，一种钒铁合金的制备方法，包括以下步骤：
a以含钒物料为原料，将冶炼过程分为N期，按各期分别配置混合料，将1～N-1期混合料分两批次入炉冶炼，在第N-1期冶炼结束，出渣后，将第N期混合料一次性加至炉中进行冶炼预还原；
其中，1～N-1期第一批混合料的配铝系数为1.0～1.1，1～N-1期第二批混合料的配铝系数为1.0～1.4，第N期混合料的配铝系数为0.2～1.0，总炉料的综合配铝系数为1.00～1.08；
b还原结束后，将熔融渣金倾翻至精炼炉中进行精炼；精炼结束后，待炉体自然冷却后拆炉，分离渣金得合金。
本发明方法的配铝方式为：在保证冶炼各期次配铝系数逐渐降低(第1～N-1期配铝系数≥1.0，第N期配铝系数＜1；且1～N-1期内，第i期配铝系数≥第i+1期)的基础上，在单一冶炼期次内形成梯度递增的方式(期次内第一批原料配铝系数小于第二批配铝系数)进行配铝。
本发明中，i＝1～N-2，N为整数，具体为什么数值可以根据实际的冶炼情况确定，一般情况下，N＝3、4、5。
本发明方法中，1～N-1期，第i期含钒物料与第i+1期含钒物料的重量比以含钒量计为1：0.8～1.2，i＝1～N-2；1～N-1期总含钒物料与第N期含钒物料的重量比以含钒量 计为20：2～5；1～N-1期，第一批混合料与第二批混合料重量比以含钒量计为1：0.8～1.2。
本发明的混合料是由含钒物料、铁、Al和造渣剂组成，其中，铁的总添加量根据生产的合金产品中钒铁质量比计算得到，然后均匀分配到各期次各批次原料中；造渣剂选自钙氧化物或钙盐，其添加量为含钒物料中钒重量的5～15％。
本发明各期反应完全的标准为渣中钒含量降幅≤0.05％/min，各期出渣量不低于总渣量的80％。
本发明的“理论添加量”为获得某标准牌号钒铁合金时，单位含钒物料所需的理论还原剂(铝、硅铁)以及对应所需配加的理论铁添加量。
混合料中铁添加量以单炉总投入含钒物料(钒记重量)为标准，并按照相应牌号钒铁合金质量比，通过计算得到该炉次总铁添加量，并将其均匀分配到各期次各批次原料；混合料中造渣剂添加量以含钒物料(钒记重量)为标准，按照5％～15％的比例添加。
本发明的“配铝系数”为理论铝耗量的倍数，当配铝系数为1.0时，理论铝耗量的计算方法如下：
单位V 2O 5/除尘灰理论铝耗量为：
Figure PCTCN2021079216-appb-000001
单位V 2O 3理论铝耗量为：
Figure PCTCN2021079216-appb-000002
其中，x 1为V 2O 5的纯度，％；x 2为V 2O 3的钒质量分数，％。
下面结合实施例对本发明的具体实施方式做进一步的描述，并不因此将本发明限制在所述的实施例范围之中。
以下实施例中混合料除冶炼原料外，还包括所需铁及对应造渣剂，造渣剂为石灰；铁添加量以单炉总投入含钒物料(以钒记重量)为标准，并按照相应牌号钒铁合金质量比，通过计算得到该炉次总铁添加量，并将其均匀分配到各期次各批次原料；造渣剂添加量占含钒物料(以钒记重量)重量的10％。
以下实施例在每期次冶炼前后分别进行加料和出渣操作。
实施例1
冶炼条件：冶炼原料为V 2O 5、V 2O 3和含钒除尘灰(钒质量分数36.2％)，其重量比为2：6：2。分3期冶炼，第1、2期第一批混合料配铝系数为1.0，第1、2期第二批混合料配铝系数为1.05，第3期混合料配铝系数为1.0，单炉综合配铝系数为1.02。第1期与第2期含钒物料重量比(以含钒量计)为1：1，第1、2期总含钒物料与第3期含钒物料重量比(以含钒量计)为20：2。第3期冶炼预还原时间为1min/吨合金，然后 将熔融渣金倾翻至精炼炉中进行精炼操作，精炼炉中预装有硅铁和CaO，硅铁的添加量为综合还原剂理论添加量的6wt％，硅铁与CaO的重量比为1：1，精炼时间为1min/吨合金，精炼结束后待炉体自然冷却后拆炉，分离渣金得合金。
按照上述冶炼条件及操作，第1、2期渣中钒含量为2.2％，精炼炉渣中钒含量为0.5％，钒铁收率为95.3％，单位电耗为1100kWh/吨，合金中铝含量为2.0％。
实施例2
冶炼条件：冶炼原料为V 2O 5、V 2O 3和含钒除尘灰(钒质量分数36.3％)和含钒细粉(钒质量分数50.5％)，其重量比为2：6：1：1。分3期冶炼，第1、2期第一批混合料配铝系数为1.0，第1、2期第二批混合料配铝系数为1.1，第3期混合料配铝系数为0.4，单炉综合配铝系数为1.05。第1期与第2期含钒物料重量比(以含钒量计)为1：1，第1、2期总含钒物料与第3期含钒物料重量比(以含钒量计)为20：3。第3期冶炼预还原时间为1min/吨合金，然后将熔融渣金倾翻至精炼炉中进行精炼操作，精炼炉中预装有Al和CaO，Al的添加量为综合还原剂理论添加量的3wt％，Al与CaO的重量比为1：1，精炼时间为1min/吨合金，精炼结束后待炉体自然冷却后拆炉，分离渣金得合金。
按照上述冶炼条件及操作，第1、2期渣中钒含量为1.5％，精炼炉渣中钒含量为0.7％，钒铁收率为96.2％，单位电耗为1020kWh/吨，合金中铝含量为1.4％。
实施例3
冶炼条件：冶炼原料为V 2O 5、V 2O 3和含钒除尘灰(钒质量分数36.3％)，其重量比为2：7：1。分4期冶炼，第1期第一批混合料配铝系数为1.0，第1期第二批混合料配铝系数为1.3，第2～3期第一批混合料配铝系数为1.0，第2～3期第二批混合料配铝系数为1.2，第4期混合料配铝系数为0.4，单炉综合配铝系数为1.06。前3期含钒物料重量比(以含钒量计)为1：1：1，第1～3期总含钒物料与第4期含钒物料重量比(以含钒量计)为20：5。第4期冶炼预还原时间为2min/吨合金，然后将熔融渣金倾翻至精炼炉中进行精炼操作，精炼炉中预装有Al和CaO，Al的添加量为综合还原剂理论添加量的2wt％，Al与CaO的重量比为2：1，精炼时间为2min/吨合金，精炼结束后待炉体自然冷却后拆炉，分离渣金得合金。
按照上述冶炼条件及操作，第1～3期渣中钒含量为0.7％，精炼炉渣中钒含量为0.8％，钒铁收率为97.1％，单位电耗为950kWh/吨，合金中铝含量为1.2％。
实施例4
冶炼条件：冶炼原料为V 2O 5和V 2O 3，其重量比为5：5。分4期冶炼，第1期第一批混合料配铝系数为1.1，第1期第二批混合料配铝系数为1.4，第2～3期第一批混合料配铝系数为1.0，第2～3期第二批混合料配铝系数为1.2，第4期混合料配铝系数为0.2，单炉综合配铝系数为1.08。前3期含钒物料重量比(以含钒量计)为1：1：1，第1～3期总含钒物料与第4期含钒物料重量比(以含钒量计)为20：5。第4期冶炼预还原时间为3min/吨合金，然后将熔融渣金倾翻至精炼炉中进行精炼操作，精炼炉中不添加还原剂和助熔剂，精炼时间为3min/吨合金，精炼结束后待炉体自然冷却后拆炉，分离渣金得合金。
按照上述冶炼条件及操作，第1～3期渣中钒含量为0.3％，精炼炉渣中钒含量为1.1％，钒铁收率为97.7％，单位电耗为910kWh/吨，合金中铝含量为0.8％。
对比例
冶炼条件：冶炼原料为V 2O 5、V 2O 3和含钒除尘灰(钒质量分数35.7％)，其重量比为2：6：2。采用均匀配铝的方式分三期冶炼，各期配铝系数为1.05，综合配铝系数为1.05。每期原料分两次入炉。
按照上述冶炼条件及操作，反应完全后(渣中钒含量降幅≤0.05％/min)。第1、2期渣中平均钒含量为2.5％，第3期精炼炉渣中钒含量为1.6％，钒铁收率为94.6％，单位电耗为1410kWh/吨，合金中铝含量为1.5％。

Claims (13)

  1. 钒铁合金的制备方法，其特征在于，包括以下步骤：
    a以含钒物料为原料，将冶炼过程分为N期，按各期分别配置混合料，将1～N-1期混合料分两批次入炉冶炼，在第N-1期冶炼结束，出渣后，将第N期混合料一次性加至炉中进行冶炼预还原；
    其中，1～N-1期第一批混合料的配铝系数为1.0～1.1，1～N-1期第二批混合料的配铝系数为1.0～1.4，第N期混合料的配铝系数为0.2～1.0，总炉料的综合配铝系数为1.00～1.08；
    b还原结束后，将熔融渣金倾翻至精炼炉中进行精炼；精炼结束后，待炉体自然冷却后拆炉，分离渣金得合金。
  2. 根据权利要求1所述钒铁合金的制备方法，其特征在于：步骤a中，第1期第一批和第二批混合料的配铝系数分别为1.0～1.1和1.05～1.4；第2～N-1期第一批和第二批混合料的配铝系数分别为1.0～1.05和1.05～1.2。
  3. 根据权利要求1或2所述钒铁合金的制备方法，其特征在于：步骤a中，1～N-1期第一批混合料的配铝系数≤1～N-1期第二批混合料的配铝系数。
  4. 根据权利要求1～3任一项所述钒铁合金的制备方法，其特征在于：步骤a中，1～N-1期内，第i期配铝系数≥第i+1期配铝系数，i＝1～N-2。
  5. 根据权利要求1～4任一项所述钒铁合金的制备方法，其特征在于：步骤a中，第N期混合料的配铝系数为0.2～0.4。
  6. 根据权利要求1～5任一项所述钒铁合金的制备方法，其特征在于：步骤a满足以下至少一项：
    1～N-1期，第i期含钒物料与第i+1期含钒物料的重量比以含钒量计为1：0.8～1.2，i＝1～N-2；
    1～N-1期总含钒物料与第N期含钒物料的重量比以含钒量计为20：2～5；
    1～N-1期，第一批混合料与第二批混合料重量比以含钒量计为1：0.8～1.2。
  7. 根据权利要求1～6任一项所述钒铁合金的制备方法，其特征在于：步骤a满足以下至少一项：
    所述含钒物料为钒氧化物、含钒除尘灰或含钒细粉中的一种以上；
    所述混合料是由含钒物料、铁、Al和造渣剂组成，其中，铁的总添加量根据生产的合金产品中钒铁质量比计算得到，然后均匀分配到各期次各批次原料 中；造渣剂选自钙氧化物或钙盐，其添加量为含钒物料中钒重量的5～15％；
    N为3～5中的任一整数。
  8. 根据权利要求7所述钒铁合金的制备方法，其特征在于：所述含钒物料中钒氧化物的重量比≥80％。
  9. 根据权利要求7或8所述钒铁合金的制备方法，其特征在于：所述钒氧化物为V 2O 3和/或V 2O 5。
  10. 根据权利要求1～9任一项所述钒铁合金的制备方法，其特征在于：步骤a中，各期反应完全的标准为渣中钒含量降幅≤0.05％/min，各期出渣量不低于总渣量的80％。
  11. 根据权利要求1～10任一项所述钒铁合金的制备方法，其特征在于：步骤b中，第N期冶炼预还原时间为1～3min/吨合金，精炼时间为1～3min/吨合金。
  12. 根据权利要求1～11任一项所述钒铁合金的制备方法，其特征在于：步骤b中，精炼炉中预装了还原剂和助熔剂的混合物。
  13. 根据权利要求12所述钒铁合金的制备方法，其特征在于：还原剂为铝和/或硅铁，其添加量不大于单炉综合还原剂理论添加量的2～8％；助熔剂为含Ca、K或Na的低熔点氧化物或盐，其添加量与还原剂添加量的重量比为0.5～1：1。
PCT/CN2021/079216 2020-03-06 2021-03-05 钒铁合金的制备方法 WO2021175306A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
ZA2022/06829A ZA202206829B (en) 2020-03-06 2022-06-20 Preparation method for ferrovanadium alloy

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010152485.1 2020-03-06
CN202010152485.1A CN111254344B (zh) 2020-03-06 2020-03-06 钒铁合金的制备方法

Publications (1)

Publication Number Publication Date
WO2021175306A1 true WO2021175306A1 (zh) 2021-09-10

Family

ID=70947645

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/079216 WO2021175306A1 (zh) 2020-03-06 2021-03-05 钒铁合金的制备方法

Country Status (3)

Country Link
CN (1) CN111254344B (zh)
WO (1) WO2021175306A1 (zh)
ZA (1) ZA202206829B (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113999971A (zh) * 2021-09-24 2022-02-01 攀钢集团攀枝花钢铁研究院有限公司 钒铝合金及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111254344B (zh) * 2020-03-06 2021-03-19 攀钢集团攀枝花钢铁研究院有限公司 钒铁合金的制备方法
CN112981141B (zh) * 2021-02-08 2022-08-05 攀钢集团攀枝花钢铁研究院有限公司 一种四氯化钛精制尾渣制备钒铁合金的方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1235968A1 (ru) * 1984-06-29 1986-06-07 Научно-производственное объединение "Тулачермет" Шихта дл получени феррованади
RU2202646C1 (ru) * 2002-02-15 2003-04-20 Московский государственный вечерний металлургический институт Способ получения лигатуры
CN102206754A (zh) * 2011-04-20 2011-10-05 攀枝花学院 生产钒铁的方法
CN105018828A (zh) * 2015-08-13 2015-11-04 攀钢集团攀枝花钢铁研究院有限公司 一种钒铁合金的制备方法
CN107964599A (zh) * 2017-11-30 2018-04-27 攀钢集团攀枝花钢铁研究院有限公司 能够提高钒收率的钒铁冶炼方法
CN110747359A (zh) * 2019-10-25 2020-02-04 攀钢集团钒钛资源股份有限公司 钒铁的冶炼方法
CN111254344A (zh) * 2020-03-06 2020-06-09 攀钢集团攀枝花钢铁研究院有限公司 钒铁合金的制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO115556B (zh) * 1967-05-31 1968-10-21 Christiania Spigerverk
CN104532105B (zh) * 2015-01-04 2016-05-18 攀钢集团攀枝花钢铁研究院有限公司 倾翻炉电铝热法制备钒铁的方法
CN109825704B (zh) * 2019-04-12 2020-07-21 攀钢集团攀枝花钢铁研究院有限公司 钒铁合金的冶炼方法
CN110042238B (zh) * 2019-04-29 2021-04-27 攀钢集团攀枝花钢铁研究院有限公司 高品质FeV50合金的生产方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU1235968A1 (ru) * 1984-06-29 1986-06-07 Научно-производственное объединение "Тулачермет" Шихта дл получени феррованади
RU2202646C1 (ru) * 2002-02-15 2003-04-20 Московский государственный вечерний металлургический институт Способ получения лигатуры
CN102206754A (zh) * 2011-04-20 2011-10-05 攀枝花学院 生产钒铁的方法
CN105018828A (zh) * 2015-08-13 2015-11-04 攀钢集团攀枝花钢铁研究院有限公司 一种钒铁合金的制备方法
CN107964599A (zh) * 2017-11-30 2018-04-27 攀钢集团攀枝花钢铁研究院有限公司 能够提高钒收率的钒铁冶炼方法
CN110747359A (zh) * 2019-10-25 2020-02-04 攀钢集团钒钛资源股份有限公司 钒铁的冶炼方法
CN111254344A (zh) * 2020-03-06 2020-06-09 攀钢集团攀枝花钢铁研究院有限公司 钒铁合金的制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113999971A (zh) * 2021-09-24 2022-02-01 攀钢集团攀枝花钢铁研究院有限公司 钒铝合金及其制备方法

Also Published As

Publication number Publication date
ZA202206829B (en) 2023-11-29
CN111254344B (zh) 2021-03-19
CN111254344A (zh) 2020-06-09

Similar Documents

Publication Publication Date Title
WO2021175306A1 (zh) 钒铁合金的制备方法
CN102115821B (zh) 冶炼钒铁的方法
CN102703811B (zh) 钛微合金化400MPa级高强度钢筋及其生产方法
CN102094097B (zh) 一种电铝热法冶炼钒铁合金的生产工艺
CN101962727B (zh) 一种制备σ相FeV50的方法
CN109825704B (zh) 钒铁合金的冶炼方法
CN102134657A (zh) 一种钒铝合金制备工艺优化方法
CN103045929A (zh) 电铝热法生产钒铁的方法
CN106086608B (zh) 一种利用碳锰熔渣生产低碳锰硅合金的方法
CN112853190B (zh) 一种高熵铸铁及其制备方法
CN107964599B (zh) 能够提高钒收率的直筒炉钒铁冶炼方法
CN106435223A (zh) 利用倾翻炉电铝热法制备低铝中钒铁的制备方法
CN105112594A (zh) 倾翻炉冶炼钒铁的方法
CN103667690A (zh) 铬钼金属自还原球团及其制备和直接合金化钢液的方法
CN101220413A (zh) 用海绵铁冶炼纯铁的工艺
CN105506271B (zh) 一种氩氧精炼炉还原用铬矿复合球团及其生产方法和应用
CN114277215B (zh) 一种中频感应炉利用高锰废钢冶炼低锰钢的方法
CN113249640B (zh) 一种p91钢中细化夹杂物的冶炼方法
CN103173677B (zh) 低硅碳比、亚共晶、节能型含钒和钛的铸造生铁
CN101864518B (zh) 一种低磷钒铁的生产方法
CN105671420B (zh) 一种炉外精炼法制备的纯净生铁
CN102230115A (zh) 一种用高磷锰矿冶炼锰基含钒的MnAlV合金及其方法
CN104878273A (zh) 采用铁粒与钢屑冶炼钒铁的方法
CN100434539C (zh) 用于钢液脱氧的稀土硅锰铝铁合金及其制备方法
CN111778423B (zh) 钒铁熔渣精炼剂及其制备方法和熔渣脱钒的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21764107

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21764107

Country of ref document: EP

Kind code of ref document: A1