WO2020228750A1 - Method for producing calcium-containing vanadium slag by adding lime to converter molten iron and leaching method therefor - Google Patents

Method for producing calcium-containing vanadium slag by adding lime to converter molten iron and leaching method therefor Download PDF

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Publication number
WO2020228750A1
WO2020228750A1 PCT/CN2020/090081 CN2020090081W WO2020228750A1 WO 2020228750 A1 WO2020228750 A1 WO 2020228750A1 CN 2020090081 W CN2020090081 W CN 2020090081W WO 2020228750 A1 WO2020228750 A1 WO 2020228750A1
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Prior art keywords
blowing
oxygen
molten iron
vanadium slag
slag
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PCT/CN2020/090081
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French (fr)
Chinese (zh)
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陈炼
周海龙
刁江
戈文荪
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成都先进金属材料产业技术研究院有限公司
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Publication of WO2020228750A1 publication Critical patent/WO2020228750A1/en
Priority to ZA2021/10287A priority Critical patent/ZA202110287B/en

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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/28—Manufacture of steel in the converter
    • C21C5/30—Regulating or controlling the blowing
    • C21C5/35—Blowing from above and through the bath
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/28—Manufacture of steel in the converter
    • C21C5/36—Processes yielding slags of special composition
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention belongs to the technical field of vanadium metallurgy, and specifically relates to a method for producing calcium-containing vanadium slag by adding lime to molten iron in a converter and a method for leaching the same.
  • Vanadium (V) is a transition metal element, its chemical properties are relatively stable at room temperature and more active at high temperatures. Vanadium is widely used in steel, chemical, aviation and other fields due to its excellent strength, hardness and anti-fatigue effect. About 84% of vanadium is used in steel as an alloying element to dissolve into steel to form VC and VN, refine grains, inhibit the development of bainite and pearlite, increase martensite strength, and improve the hardness, strength, toughness and toughness of steel. Anti-wear performance.
  • Vanadium used in non-ferrous alloys is mainly structural materials represented by V-Al alloys, such as excellent high-temperature aerospace structural materials Ti-6Al-4V, Ti-8Al-1V-Mo and Ti-6Al-6V-2Sn alloys.
  • the vanadium products used in the chemical industry mainly include V 2 O 5 , NH 4 VO 3 , V 2 O 3 , VOCl 3 and VCl 4, etc., which are used as catalysts, colorants, and electrode materials for large-capacity batteries.
  • Vanadium resources are very dispersed in nature, mainly associated with sulfovanadium, lead-vanadium, vanadium marble, uranium vanadate, vanadium-titanium magnetite and other minerals. Due to the large differences in the types of vanadium raw materials, mineral characteristics, and vanadium content, there are various techniques and methods for extracting vanadium from vanadium-containing materials, mainly including pyrometallurgical smelting, wet leaching and combined pyro-wet extraction.
  • Pyro smelting usually uses vanadium-titanium magnetite as the main raw material to obtain vanadium-containing molten iron through a blast furnace or other iron-making process, and then blow oxygen into the converter to oxidize and enrich the vanadium in the metal into the slag, and obtain vanadium slag or The vanadium-containing steel slag is subsequently extracted by roasting-leaching or direct leaching.
  • Wet leaching is more suitable for waste products such as waste catalysts, fly ash and petroleum ash, and a small amount of it is used in stone coal, vanadium-titanium magnetite and other raw ores, but because vanadium is mainly in the form of insoluble trivalent vanadium ,
  • the recovery rate of direct leaching is lower than that of pyrometallurgy and pyrometallurgical-wet combined extraction process.
  • Fire-wet combined extraction usually requires the roasting of vanadium in an oxidizing atmosphere to convert it into high-priced compounds to facilitate leaching.
  • the traditional fire-wet combined extraction process includes sodium salt roasting-water leaching, blank roasting-acid leaching (alkali leaching). ), low-salt roasting-cyclic leaching and calcium salt roasting-acid leaching (alkali leaching), etc.
  • CN102086487A discloses an energy-saving and emission-reducing vanadium slag processing method, which includes the following steps: firstly, placing a high-temperature liquid vanadium slag above 1200°C separated from molten iron in a slag tank; then, placing it in a slag tank according to the vanadium slag grade Add sodium compound, and then supply oxygen to the slag tank with a water-cooled supersonic or subsonic oxygen lance, creating a strong oxidizing atmosphere, and at the same time it can play a stirring role, prompting the rapid generation of water-soluble sodium vanadate in the vanadium slag to ensure oxygen supply
  • the amount of oxygen is greater than the amount of oxygen required for all the components in the slag to oxidize to the highest valence oxide.
  • the FeO/TFe in the slag should be used as an indicator of the degree of oxidation.
  • the V 2 O 5 generated in the vanadium slag reacts with the added sodium compound Water-soluble sodium vanadate is generated, and finally, the obtained slag containing water-soluble sodium vanadate is processed to obtain V 2 O 5 , wherein the dissolution rate of vanadium is 90-94%.
  • the above method adds a large amount of sodium compounds: the molar ratio of Na 2 O to V 2 O 5 in the sodium compound is 1 to 10, and the molar ratio of Na 2 O to V 2 O 5 in the examples is 2.3 to 3.
  • the technical problem to be solved by the present invention is that the prior art molten iron has many procedures for producing vanadium-containing leaching solution, the vanadium oxidation rate of vanadium extraction by the converter is low, and the energy consumption is high.
  • the present invention first provides a converter molten iron and lime to produce calcium-containing vanadium slag, which includes the following steps:
  • step A in the method for producing calcium-vanadium-containing slag by adding lime to molten iron from a converter, in step A, the amount of the coolant is 15-35 kg/tFe.
  • step A in the method for producing calcium-vanadium-containing slag by adding lime to molten iron from a converter, in step A, the time for adding the coolant is within 3 minutes before the start of oxygen blowing.
  • step A in the method for producing calcium-vanadium-containing slag by adding lime to molten iron from a converter, in step A, the added amount of lime is 3 to 4 kg/tFe.
  • step A the time for adding the lime is within 2 minutes after adding the coolant.
  • step A the position of the oxygen lance is controlled in a "high-low-high" mode, that is, 0.5 Use 1.7-2.0m high gun position for ⁇ 1.5min, use 1.6-1.8m low gun position in mid-term, and use 1.7-2.0m high gun position for 1.0-1.5min before the end of blowing.
  • step A during blowing, the oxygen supply intensity of top blowing oxygen is controlled at 2.0-3.0m 3 /(min ⁇ tFe), and oxygen blowing The time is controlled at 5 to 6.5min, and the oxygen pressure is controlled at 0.7 to 0.9MPa.
  • step A the flow rate of bottom blowing nitrogen in the top blowing oxygen stage is controlled at 0.1-0.5 m 3 /(min ⁇ tFe).
  • the flow rate of bottom blowing oxygen is 0.25-0.75 m 3 /(min ⁇ tFe).
  • step B the addition amount of CaF 2 is 0.5-1.0 kg/tFe.
  • the bottom oxygen blowing time is 2 to 3 minutes.
  • the present invention also leaches it, including the following steps:
  • the invention combines calcification roasting and converter vanadium extraction, which can reduce the number of procedures for producing vanadium-containing leaching liquid from molten iron, and at the same time, vanadium slag does not need to be cooled and then roasted, reducing energy consumption; high-pressure oxygen is used in the converter to blow and stir the vanadium slag The effect is greatly improved, so that the mixing of CaO in the slag is more uniform, which is more conducive to the calcification treatment effect of the vanadium slag; then the self-heating of the vanadium slag is effectively used to oxidize the V 2 O 3 in the vanadium slag to V 2 O 5 and reduce the vanadium slag
  • the method for producing calcium-vanadium-containing slag by adding lime to molten iron in a converter includes the following steps:
  • step A of the present invention 15-35kg/tFe coolant is added within 3 minutes before the start of oxygen blowing.
  • the coolant can use materials with more iron oxides commonly used in the field, such as high-grade iron ore, hematite A mixture of one or more of ore, iron red, iron oxide scale, etc.
  • the mass ratio of CaO//V 2 O 5 in the calcium-containing vanadium slag can be controlled at 0.55 ⁇ 0.65.
  • the lime and vanadium slag can be combined during the conversion period. Uniform mixing is conducive to the generation of calcium vanadate in the subsequent oxidation process of vanadium slag, and is most conducive to the extraction of vanadium from vanadium slag; and the melting point of vanadium slag is reduced after lime is added, the effect of slag-iron separation is good, and the iron content in the slag Less, the process oxygen utilization rate of vanadium oxide slag is higher.
  • step A of the present invention during blowing, the oxygen lance position of the oxygen lance is controlled in the "high-low-high” mode, that is, the high lance position of 1.7-2.0m is adopted for 0.5-1.5min in the early stage of blowing, and the high-lance position of 1.6-1.8 is adopted in the middle stage.
  • m low lance position use 1.7 ⁇ 2.0m high lance position for 1.0 ⁇ 1.5min before the end of blowing; at the same time control the oxygen supply intensity of top blowing oxygen to 2.0 ⁇ 3.0m 3 /(min ⁇ tFe), and the oxygen blowing time is 5 ⁇ 6.5min, the oxygen pressure is 0.7 ⁇ 0.9MPa, and the flow rate of bottom blowing nitrogen is controlled at 0.1 ⁇ 0.5m 3 /(min ⁇ tFe) during the top blowing oxygen stage.
  • the vanadium slag is blown with high-pressure oxygen in the converter, and the stirring effect is greatly improved, so that the CaO in the slag is more uniformly mixed, and it is more conducive to obtain vanadium slag from the vanadium oxide element in the molten iron and the subsequent vanadium slag calcification treatment effect.
  • step A the mass ratio of CaO//V 2 O 5 in the calcium-containing vanadium slag is controlled by adding lime, while the blowing parameters are adjusted to promote the reaction of vanadium and oxygen in the molten iron and increase the vanadium oxidation rate.
  • step A After blowing in step A, pour the semi-steel into the semi-steel tank, leave the vanadium slag in the converter, blow oxygen into the vanadium slag by bottom blowing, and control the bottom blowing oxygen flow to 0.25 ⁇ 0.75m 3 /( min ⁇ tFe), using the heat of the high-temperature vanadium slag to promote the reaction of V 2 O 3 and oxygen in the vanadium slag to produce V 2 O 5 , the mass of CaO//V 2 O 5 in the slag is 0.55 ⁇ 0.65, and it can be formed with CaO to the greatest extent Calcium vanadate further improves the leaching rate of vanadium.
  • 0.5-1.0kg/tFe calcium fluoride is added after the bottom blowing oxygen is started in the present invention to adjust the vanadium slag slag state and lower the melting point of the vanadium slag, so that the metal iron content in the vanadium slag is reduced , Promote the separation of slag and iron, improve the fluidity of vanadium slag, improve the conditions for the formation of calcium vanadate, and make the oxygen utilization rate higher during the second blow of vanadium oxide slag; the amount of calcium fluoride should not be too large, otherwise it is easy Cause erosion of the furnace lining.
  • step B of the present invention the self-heating of the vanadium slag is used, and the bottom blowing oxygen time is 2 to 3 minutes, so that V 2 O 3 in the vanadium slag can be oxidized to V 2 O 5 , and the production efficiency is improved.
  • the present invention also provides a method for leaching calcium-vanadium-containing slag, which further includes the following steps:
  • the leaching step can be completed by conventional operations in the field, and the following specific steps can be used: pour the calcium-containing vanadium slag into the vanadium slag tank and cover it for cooling. The cooling time is controlled within 36-72h. After cooling, the vanadium slag is crushed and magnetized. Select and ball mill into 120 mesh fine powder. After mixing the fine powder and water at a weight ratio of 1:2, use a 1:1 sulfuric acid solution for leaching. The pH value is controlled between 2.8 and 3.2. The leaching process is mixed with mechanical stirring ( The rotating speed of the stirring paddle is 300 ⁇ 400r/min) and heating to maintain the temperature at 50 ⁇ 2°C. After 1h, vacuum filtration is carried out, and the obtained filtrate is the leachate.
  • the initial molten iron temperature is generally 1190-1360°C, and the temperature during the blowing process does not exceed 1400°C.
  • Oxygen lance blowing oxygen is used for blowing.
  • the lance position is controlled by the "high-low-high” mode, that is, the 1.9m high lance position is used for 1 minute in the early stage of blowing, and the 1.6m low lance position is used in the mid-term.
  • Use a 1.7m high gun position 1.0 min before the end of blowing; control the flow rate of bottom blowing nitrogen at 0.5m 3 /(min ⁇ tFe) in the top blowing oxygen stage; control the oxygen supply intensity of top blowing oxygen at 2.0m 3 / during blowing (min ⁇ tFe), the oxygen blowing time is controlled at 5min, and the oxygen pressure is controlled at 0.7MPa;
  • the calcium-vanadium slag is crushed, magnetically separated, and ball milled into 120 mesh fine powder. After the fine powder is mixed with water in a weight ratio of 1:2, it is leached with a 1:1 sulfuric acid solution, and the pH value is controlled at 2.8-3.2. During the leaching process, the mixture is mechanically stirred (stirring blade rotation speed 300-400r/min) and heated to maintain a temperature of 50 ⁇ 2°C. After 1 hour, vacuum filtration is performed, and the resulting filtrate is the leachate.
  • the vanadium oxidation rate of the whole process is 91.03%, and the vanadium leaching rate is 84.36%.
  • Oxygen lance is used to blow oxygen for blowing.
  • the lance position is controlled by the "high-low-high” mode, that is, the 2.0m high lance position is used for 1.5min in the early stage of blowing, and the 1.8m low lance position is used in the mid-term.
  • 1.0min before the end of blowing adopt a 1.9m high gun position; the flow of bottom blowing nitrogen in the top blowing oxygen stage is controlled at 0.45m 3 /(min ⁇ tFe); during blowing, the oxygen supply intensity of top blowing oxygen is controlled at 3.0m 3 /(min ⁇ tFe), the oxygen blowing time is controlled at 5.5min, and the oxygen pressure is controlled at 0.9MPa;
  • the calcium-vanadium slag is crushed, magnetically separated, and ball milled into 120 mesh fine powder. After the fine powder is mixed with water in a weight ratio of 1:2, it is leached with a 1:1 sulfuric acid solution, and the pH value is controlled at 2.8-3.2. During the leaching process, the mixture is mechanically stirred (stirring blade rotation speed 300-400r/min) and heated to maintain a temperature of 50 ⁇ 2°C. After 1 hour, vacuum filtration is performed, and the resulting filtrate is the leachate.
  • the vanadium oxidation rate of the whole process is 90.63%, and the vanadium leaching rate is 85.07%.

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Abstract

A method for producing calcium-containing vanadium slag by adding lime to converter molten iron and a leaching method therefor, comprising: adding molten iron into a converter, adding a coolant and lime, and performing blowing using top-blowing oxygen and bottom-blowing nitrogen; when the blowing is finished, leaving vanadium slag in the converter, changing the bottom-blowing gas into oxygen, and adding CaF2, so as to prepare calcium-containing vanadium slag; and acid-leaching the calcium-containing vanadium slag to obtain a leaching solution.

Description

转炉铁水加石灰生产含钙钒渣及其浸出的方法Method for producing calcium and vanadium slag by adding lime to molten iron in converter and its leaching method 技术领域Technical field
本发明属于钒冶金技术领域，具体涉及一种转炉铁水加石灰生产含钙钒渣及其浸出的方法。The invention belongs to the technical field of vanadium metallurgy, and specifically relates to a method for producing calcium-containing vanadium slag by adding lime to molten iron in a converter and a method for leaching the same.
背景技术Background technique
钒(V)是一种过渡族金属元素，其在常温下化学性质较稳定，高温下较活泼。钒因其具有优良的强度、硬度及抗疲劳效应，被广泛应用于钢铁、化工、航空等领域。大约84％的钒用于钢铁作为合金元素溶解到钢中形成VC和VN，细化晶粒，抑制贝氏体和珠光体的发育增加马氏体强度，从而提高钢的硬度、强度、韧性和抗磨损性能。钒用于有色合金主要是以V-Al系合金为代表的结构材料，如优良的高温航空结构材料Ti-6Al-4V、Ti-8Al-1V-Mo和Ti-6Al-6V-2Sn等合金。用于化工领域的钒产品主要有V 2O 5、NH 4VO 3、V 2O 3、VOCl 3及VCl 4等，用作催化剂、着色剂、大容量电池用的电极材料。 Vanadium (V) is a transition metal element, its chemical properties are relatively stable at room temperature and more active at high temperatures. Vanadium is widely used in steel, chemical, aviation and other fields due to its excellent strength, hardness and anti-fatigue effect. About 84% of vanadium is used in steel as an alloying element to dissolve into steel to form VC and VN, refine grains, inhibit the development of bainite and pearlite, increase martensite strength, and improve the hardness, strength, toughness and toughness of steel. Anti-wear performance. Vanadium used in non-ferrous alloys is mainly structural materials represented by V-Al alloys, such as excellent high-temperature aerospace structural materials Ti-6Al-4V, Ti-8Al-1V-Mo and Ti-6Al-6V-2Sn alloys. The vanadium products used in the chemical industry mainly include V 2 O 5 , NH 4 VO 3 , V 2 O 3 , VOCl 3 and VCl 4, etc., which are used as catalysts, colorants, and electrode materials for large-capacity batteries.
钒资源在自然界分布很分散，主要伴生于硫钒矿、铅钒矿、钒云石、钒酸钾铀矿以及钒钛磁铁矿等矿物中。因钒原料种类、矿物特征及其中钒含量差异较大，从含钒物料中提取钒的工艺和方法也多种多样，主要有火法冶炼、湿法浸出和火法-湿法联合提取工艺。火法冶炼通常以钒钛磁铁矿为主要原料，通过高炉或其它炼铁流程得到含钒铁水，再在转炉中吹入氧气使金属中的钒氧化富集到渣中，得到的钒渣或含钒钢渣经过焙烧-浸出或直接浸出的方式进行后续提取。湿法浸出比较适用于废催化剂、飞灰和石油灰渣等废产品，也有少量应用于石煤中、钒钛磁铁矿等原矿，但由于其中钒都主要以难溶的三价钒形式存在，直接浸出较火法冶炼和火法-湿法联合提取工艺回收率更低。火法-湿法联合提取通常需要将钒在氧化气氛下焙烧转化成高价化合物以利于浸出，传统的火法-湿法联合提取工艺有钠盐焙烧-水浸、空白焙烧-酸浸(碱浸)、少盐焙烧-循环浸出以及钙盐焙烧-酸浸(碱浸)等。Vanadium resources are very dispersed in nature, mainly associated with sulfovanadium, lead-vanadium, vanadium marble, uranium vanadate, vanadium-titanium magnetite and other minerals. Due to the large differences in the types of vanadium raw materials, mineral characteristics, and vanadium content, there are various techniques and methods for extracting vanadium from vanadium-containing materials, mainly including pyrometallurgical smelting, wet leaching and combined pyro-wet extraction. Pyro smelting usually uses vanadium-titanium magnetite as the main raw material to obtain vanadium-containing molten iron through a blast furnace or other iron-making process, and then blow oxygen into the converter to oxidize and enrich the vanadium in the metal into the slag, and obtain vanadium slag or The vanadium-containing steel slag is subsequently extracted by roasting-leaching or direct leaching. Wet leaching is more suitable for waste products such as waste catalysts, fly ash and petroleum ash, and a small amount of it is used in stone coal, vanadium-titanium magnetite and other raw ores, but because vanadium is mainly in the form of insoluble trivalent vanadium , The recovery rate of direct leaching is lower than that of pyrometallurgy and pyrometallurgical-wet combined extraction process. Fire-wet combined extraction usually requires the roasting of vanadium in an oxidizing atmosphere to convert it into high-priced compounds to facilitate leaching. The traditional fire-wet combined extraction process includes sodium salt roasting-water leaching, blank roasting-acid leaching (alkali leaching). ), low-salt roasting-cyclic leaching and calcium salt roasting-acid leaching (alkali leaching), etc.
CN102086487A公开了一种节能减排的钒渣处理方法，包括以下步骤：首先，将与铁水分离后的1200℃以上的高温液态钒渣置于渣罐中；然后，根据钒渣品位向渣罐中加入钠化合物，然后用水冷超音速或亚音速氧枪向渣罐中供氧，造成强氧化性气氛，同时能起到搅拌作用，促使钒渣中快速生成水溶性钒酸钠，为保证供氧量大于渣中各组分全 部氧化成最高价氧化物所需的氧量，需以渣中的FeO/TFe作为检验氧化程度的指标，钒渣中生成的V 2O 5与加入的钠化合物反应生成水溶性钒酸钠，最后，把得到的含有水溶性钒酸钠的渣子，处理得到V 2O 5，其中，钒的溶出率为90～94％。但是上述方法加入了大量的钠化合物：钠化合物中的Na 2O与V 2O 5的摩尔比为1～10，实施例中Na 2O与V 2O 5的摩尔比为2.3～3，这是因为钠化合物在高温下容易分解气化，在高温下加入钠化合物会导致钠化合物的损耗较大；同时上述方法的原料只能使用转炉提钒生产的钒渣，生产路线长，成本高。 CN102086487A discloses an energy-saving and emission-reducing vanadium slag processing method, which includes the following steps: firstly, placing a high-temperature liquid vanadium slag above 1200°C separated from molten iron in a slag tank; then, placing it in a slag tank according to the vanadium slag grade Add sodium compound, and then supply oxygen to the slag tank with a water-cooled supersonic or subsonic oxygen lance, creating a strong oxidizing atmosphere, and at the same time it can play a stirring role, prompting the rapid generation of water-soluble sodium vanadate in the vanadium slag to ensure oxygen supply The amount of oxygen is greater than the amount of oxygen required for all the components in the slag to oxidize to the highest valence oxide. The FeO/TFe in the slag should be used as an indicator of the degree of oxidation. The V 2 O 5 generated in the vanadium slag reacts with the added sodium compound Water-soluble sodium vanadate is generated, and finally, the obtained slag containing water-soluble sodium vanadate is processed to obtain V 2 O 5 , wherein the dissolution rate of vanadium is 90-94%. However, the above method adds a large amount of sodium compounds: the molar ratio of Na 2 O to V 2 O 5 in the sodium compound is 1 to 10, and the molar ratio of Na 2 O to V 2 O 5 in the examples is 2.3 to 3. This is because sodium compounds are easy to decompose and gasify at high temperatures, and adding sodium compounds at high temperatures will result in greater loss of sodium compounds; at the same time, the raw materials of the above method can only use vanadium slag produced by vanadium extraction from a converter, and the production route is long and the cost is high.
发明内容Summary of the invention
本发明所要解决的技术问题是现有技术铁水生产含钒浸出液的工序繁多、转炉提钒的钒氧化率低、能耗大等。The technical problem to be solved by the present invention is that the prior art molten iron has many procedures for producing vanadium-containing leaching solution, the vanadium oxidation rate of vanadium extraction by the converter is low, and the energy consumption is high.
本发明为解决上述技术问题，首先提供了一种转炉铁水加石灰生产含钙钒渣，其包括以下步骤：In order to solve the above technical problems, the present invention first provides a converter molten iron and lime to produce calcium-containing vanadium slag, which includes the following steps:
A、铁水兑入转炉后，加入冷却剂和石灰，采用顶吹氧气底吹氮气进行吹炼；A. After the molten iron is poured into the converter, add coolant and lime, and use top-blowing oxygen and bottom-blowing nitrogen for blowing;
B、吹炼结束后，将半钢倒入半钢罐内、钒渣留于转炉内，转炉回复到吹炼位后，将底吹气体切换为氧气，并加入CaF 2，吹氧结束，得含钙钒渣。 B. After blowing, pour the semi-steel into the semi-steel tank and leave the vanadium slag in the converter. After the converter returns to the blowing position, switch the bottom blowing gas to oxygen and add CaF 2 , and the oxygen blowing is complete. Containing calcium vanadium slag.
其中，上述所述的转炉铁水加石灰生产含钙钒渣的方法中，步骤A中，所述冷却剂的用量为15～35kg/tFe。Wherein, in the method for producing calcium-vanadium-containing slag by adding lime to molten iron from a converter, in step A, the amount of the coolant is 15-35 kg/tFe.
其中，上述所述的转炉铁水加石灰生产含钙钒渣的方法中，步骤A中，所述冷却剂的加入时间为吹氧开始前3min内。Wherein, in the method for producing calcium-vanadium-containing slag by adding lime to molten iron from a converter, in step A, the time for adding the coolant is within 3 minutes before the start of oxygen blowing.
其中，上述所述的转炉铁水加石灰生产含钙钒渣的方法中，步骤A中，所述石灰的加入量为3～4kg/tFe。Wherein, in the method for producing calcium-vanadium-containing slag by adding lime to molten iron from a converter, in step A, the added amount of lime is 3 to 4 kg/tFe.
其中，上述所述的转炉铁水加石灰生产含钙钒渣的方法中，步骤A中，所述石灰的加入时间为加入冷却剂后2min内。Wherein, in the above-mentioned method for adding lime to molten iron in a converter to produce calcium-vanadium-containing slag, in step A, the time for adding the lime is within 2 minutes after adding the coolant.
其中，上述所述的转炉铁水加石灰生产含钙钒渣的方法中，步骤A中，吹炼时，氧枪吹氧枪位采用“高-低-高”模式进行控制，即吹炼前期0.5～1.5min采用1.7～2.0m高枪位，中期采用1.6～1.8m低枪位，吹炼结束前1.0～1.5min采用1.7～2.0m高枪位。Wherein, in the above-mentioned method for producing calcium-vanadium-containing slag by adding lime to molten iron from a converter, in step A, during the blowing process, the position of the oxygen lance is controlled in a "high-low-high" mode, that is, 0.5 Use 1.7-2.0m high gun position for ~1.5min, use 1.6-1.8m low gun position in mid-term, and use 1.7-2.0m high gun position for 1.0-1.5min before the end of blowing.
其中，上述所述的转炉铁水加石灰生产含钙钒渣的方法中，步骤A中，吹炼时，顶吹氧气的供氧强度控制在2.0～3.0m 3/(min·tFe)，吹氧时间控制在5～6.5min，氧气压力控制在0.7～0.9MPa。 Wherein, in the above-mentioned method for producing calcium-containing vanadium slag by adding lime to molten iron from a converter, in step A, during blowing, the oxygen supply intensity of top blowing oxygen is controlled at 2.0-3.0m 3 /(min·tFe), and oxygen blowing The time is controlled at 5 to 6.5min, and the oxygen pressure is controlled at 0.7 to 0.9MPa.
其中，上述所述的转炉铁水加石灰生产含钙钒渣的方法中，步骤A中，顶吹氧气 阶段底吹氮气流量控制在0.1～0.5m 3/(min·tFe)。 Wherein, in the above-mentioned method for producing calcium-vanadium-containing slag by adding lime to molten iron in a converter, in step A, the flow rate of bottom blowing nitrogen in the top blowing oxygen stage is controlled at 0.1-0.5 m 3 /(min·tFe).
其中，上述所述的转炉铁水加石灰生产含钙钒渣的方法中，步骤B中，底吹氧气流量为0.25～0.75m 3/(min·tFe)。 Wherein, in the above-mentioned method for producing calcium-vanadium-containing slag by adding lime to molten iron from a converter, in step B, the flow rate of bottom blowing oxygen is 0.25-0.75 m 3 /(min·tFe).
其中，上述所述的转炉铁水加石灰生产含钙钒渣的方法中，步骤B中，CaF 2的加入量为0.5～1.0kg/tFe。 Wherein, in the above-mentioned method for producing calcium-vanadium-containing slag by adding lime to molten iron from a converter, in step B, the addition amount of CaF 2 is 0.5-1.0 kg/tFe.
其中，上述所述的转炉铁水加石灰生产含钙钒渣的方法中，步骤B中，底吹氧气时间为2～3min。Wherein, in the above-mentioned method for producing calcium-vanadium-containing slag by adding lime to molten iron from a converter, in step B, the bottom oxygen blowing time is 2 to 3 minutes.
在利用上述方法制备得到含钙钒渣后，本发明还对其进行了浸出，包括以下步骤：After the calcium-containing vanadium slag is prepared by the above method, the present invention also leaches it, including the following steps:
C、含钙钒渣经冷却、破碎、磁选、球磨、酸浸和分离，得浸出液。C. After cooling, crushing, magnetic separation, ball milling, acid leaching and separation of calcium-containing vanadium slag, the leachate is obtained.
本发明的有益效果：The beneficial effects of the present invention:
本发明将钙化焙烧和转炉提钒结合，能够减少铁水生产含钒浸出液的工序数量，同时钒渣无需冷却后再焙烧，减少了能源消耗；在转炉内利用高压氧气对钒渣进行吹炼，搅拌效果大大提高，使得渣中CaO混合的更加均匀，更有利于钒渣钙化处理效果；然后有效利用钒渣的自热，使钒渣中V 2O 3被氧化成V 2O 5，减少钒渣冷却后再进行焙烧带来的热量消耗；通过铁水吹炼和渣吹炼的结合，控制CaO//V 2O 5质量比及吹炼参数，提高了钒的氧化率；处理后的钒渣冷却、磁选后可直接进行水浸，能提高钒的浸出率，有利于资源的利用及提钒生产成本降低。 The invention combines calcification roasting and converter vanadium extraction, which can reduce the number of procedures for producing vanadium-containing leaching liquid from molten iron, and at the same time, vanadium slag does not need to be cooled and then roasted, reducing energy consumption; high-pressure oxygen is used in the converter to blow and stir the vanadium slag The effect is greatly improved, so that the mixing of CaO in the slag is more uniform, which is more conducive to the calcification treatment effect of the vanadium slag; then the self-heating of the vanadium slag is effectively used to oxidize the V 2 O 3 in the vanadium slag to V 2 O 5 and reduce the vanadium slag The heat consumption caused by roasting after cooling; the combination of hot metal blowing and slag blowing, controlling the CaO//V 2 O 5 mass ratio and blowing parameters, and improving the oxidation rate of vanadium; cooling the treated vanadium slag , Water leaching can be carried out directly after magnetic separation, which can increase the leaching rate of vanadium, which is beneficial to the utilization of resources and the reduction of production cost of vanadium extraction.
具体实施方式Detailed ways
具体的，转炉铁水加石灰生产含钙钒渣的方法，其包括以下步骤：Specifically, the method for producing calcium-vanadium-containing slag by adding lime to molten iron in a converter includes the following steps:
A、铁水兑入转炉后，加入冷却剂和石灰，采用顶吹氧气底吹氮气进行吹炼；A. After the molten iron is poured into the converter, add coolant and lime, and use top-blowing oxygen and bottom-blowing nitrogen for blowing;
B、吹炼结束后，将半钢倒入半钢罐内、钒渣留于转炉内，转炉回复到吹炼位后，将底吹气体切换为氧气，并加入CaF 2，吹氧结束，得含钙钒渣。 B. After blowing, pour the semi-steel into the semi-steel tank and leave the vanadium slag in the converter. After the converter returns to the blowing position, switch the bottom blowing gas to oxygen and add CaF 2 , and the oxygen blowing is complete. Containing calcium vanadium slag.
本发明步骤A中，在吹氧开始前3min内加入15～35kg/tFe的冷却剂，冷却剂可采用本领域内常用的含铁氧化物较多的材料，如：高品位铁矿、赤铁矿、铁红、氧化铁皮等其中一种或几种的混合物。In step A of the present invention, 15-35kg/tFe coolant is added within 3 minutes before the start of oxygen blowing. The coolant can use materials with more iron oxides commonly used in the field, such as high-grade iron ore, hematite A mixture of one or more of ore, iron red, iron oxide scale, etc.
加入冷却剂后2min内，再加入3～4kg/tFe的石灰，此时可将含钙钒渣中CaO//V 2O 5质量比控制在0.55～0.65，在吹炼期将石灰与钒渣进行均匀混合，有利于后续对钒渣的氧化过程中生成钒酸钙，最有利于钒渣中钒的提取；且加入石灰后钒渣的熔点降低，渣铁分离效果好，渣中含铁量少，氧化钒渣的过程氧气利用率更高。 Within 2 minutes after adding the coolant, add 3~4kg/tFe lime. At this time, the mass ratio of CaO//V 2 O 5 in the calcium-containing vanadium slag can be controlled at 0.55~0.65. The lime and vanadium slag can be combined during the conversion period. Uniform mixing is conducive to the generation of calcium vanadate in the subsequent oxidation process of vanadium slag, and is most conducive to the extraction of vanadium from vanadium slag; and the melting point of vanadium slag is reduced after lime is added, the effect of slag-iron separation is good, and the iron content in the slag Less, the process oxygen utilization rate of vanadium oxide slag is higher.
本发明步骤A中，吹炼时，氧枪吹氧枪位采用“高-低-高”模式进行控制，即吹 炼前期0.5～1.5min采用1.7～2.0m高枪位，中期采用1.6～1.8m低枪位，吹炼结束前1.0～1.5min采用1.7～2.0m高枪位；同时控制顶吹氧气的供氧强度为2.0～3.0m 3/(min·tFe)，吹氧时间为5～6.5min，氧气压力为0.7～0.9MPa，顶吹氧气阶段底吹氮气流量控制在0.1～0.5m 3/(min·tFe)。在转炉内利用高压氧气对钒渣进行吹炼，搅拌效果大大提高，使得渣中CaO混合的更加均匀，更有利于从铁水中氧化钒元素得到钒渣和后续钒渣钙化处理效果。 In step A of the present invention, during blowing, the oxygen lance position of the oxygen lance is controlled in the "high-low-high" mode, that is, the high lance position of 1.7-2.0m is adopted for 0.5-1.5min in the early stage of blowing, and the high-lance position of 1.6-1.8 is adopted in the middle stage. m low lance position, use 1.7～2.0m high lance position for 1.0～1.5min before the end of blowing; at the same time control the oxygen supply intensity of top blowing oxygen to 2.0～3.0m 3 /(min·tFe), and the oxygen blowing time is 5～ 6.5min, the oxygen pressure is 0.7～0.9MPa, and the flow rate of bottom blowing nitrogen is controlled at 0.1～0.5m 3 /(min·tFe) during the top blowing oxygen stage. The vanadium slag is blown with high-pressure oxygen in the converter, and the stirring effect is greatly improved, so that the CaO in the slag is more uniformly mixed, and it is more conducive to obtain vanadium slag from the vanadium oxide element in the molten iron and the subsequent vanadium slag calcification treatment effect.
步骤A中，通过加入石灰控制含钙钒渣中CaO//V 2O 5质量比，同时调整吹炼参数，促进铁水中钒与氧气反应，提高钒氧化率。 In step A, the mass ratio of CaO//V 2 O 5 in the calcium-containing vanadium slag is controlled by adding lime, while the blowing parameters are adjusted to promote the reaction of vanadium and oxygen in the molten iron and increase the vanadium oxidation rate.
步骤A中吹炼结束后，将半钢倒入半钢罐内、钒渣留于转炉内，通过底吹方式向钒渣中吹氧气，并控制底吹氧气流量为0.25～0.75m 3/(min·tFe)，利用高温钒渣的热量，促进钒渣中V 2O 3与氧气反应生成V 2O 5，渣中CaO//V 2O 5质量为0.55～0.65，进而最大程度与CaO生成钒酸钙，进一步提高钒的浸出率。 After blowing in step A, pour the semi-steel into the semi-steel tank, leave the vanadium slag in the converter, blow oxygen into the vanadium slag by bottom blowing, and control the bottom blowing oxygen flow to 0.25～0.75m 3 /( min·tFe), using the heat of the high-temperature vanadium slag to promote the reaction of V 2 O 3 and oxygen in the vanadium slag to produce V 2 O 5 , the mass of CaO//V 2 O 5 in the slag is 0.55～0.65, and it can be formed with CaO to the greatest extent Calcium vanadate further improves the leaching rate of vanadium.
为避免钒渣流动性较差，本发明在底吹氧气开始后加入0.5～1.0kg/tFe氟化钙，以调整钒渣渣态和降低钒渣的熔点，使得钒渣中的金属铁含量降低，促进渣铁分离，实现钒渣流动性的改善，提高钒酸钙形成的条件，使后续第二次吹氧氧化钒渣时氧气的利用率更高；氟化钙用量不宜过大，否则易造成炉衬侵蚀。In order to avoid poor fluidity of vanadium slag, 0.5-1.0kg/tFe calcium fluoride is added after the bottom blowing oxygen is started in the present invention to adjust the vanadium slag slag state and lower the melting point of the vanadium slag, so that the metal iron content in the vanadium slag is reduced , Promote the separation of slag and iron, improve the fluidity of vanadium slag, improve the conditions for the formation of calcium vanadate, and make the oxygen utilization rate higher during the second blow of vanadium oxide slag; the amount of calcium fluoride should not be too large, otherwise it is easy Cause erosion of the furnace lining.
本发明步骤B中，利用钒渣的自热，底吹氧气时间为2～3min，即可使钒渣中V 2O 3被氧化成V 2O 5，提高了生产效率。 In step B of the present invention, the self-heating of the vanadium slag is used, and the bottom blowing oxygen time is 2 to 3 minutes, so that V 2 O 3 in the vanadium slag can be oxidized to V 2 O 5 , and the production efficiency is improved.
在上述所述的转炉铁水加石灰生产含钙钒渣的方法基础上，本发明还提供了一种含钙钒渣的浸出方法，其还包括以下步骤：Based on the above-mentioned method for producing calcium-vanadium-containing slag by adding lime to molten iron in a converter, the present invention also provides a method for leaching calcium-vanadium-containing slag, which further includes the following steps:
C、含钙钒渣经冷却、破碎、磁选、球磨、酸浸和分离，得浸出液。C. After cooling, crushing, magnetic separation, ball milling, acid leaching and separation of calcium-containing vanadium slag, the leachate is obtained.
浸出步骤可采用本领域内常规操作完成，可采用如下具体步骤：将含钙钒渣倒入钒渣罐内后加盖冷却，冷却时间控制在36～72h，冷却结束后将钒渣破碎、磁选、球磨成120目细粉，细粉与水按重量比1：2混合后，采用1：1的硫酸溶液进行浸出，pH值控制在2.8～3.2之间，浸出过程混合液采用机械搅拌(搅拌桨转速300～400r/min)并加热保持温度50±2℃，1h后进行真空抽滤，所得滤液为浸出液。The leaching step can be completed by conventional operations in the field, and the following specific steps can be used: pour the calcium-containing vanadium slag into the vanadium slag tank and cover it for cooling. The cooling time is controlled within 36-72h. After cooling, the vanadium slag is crushed and magnetized. Select and ball mill into 120 mesh fine powder. After mixing the fine powder and water at a weight ratio of 1:2, use a 1:1 sulfuric acid solution for leaching. The pH value is controlled between 2.8 and 3.2. The leaching process is mixed with mechanical stirring ( The rotating speed of the stirring paddle is 300～400r/min) and heating to maintain the temperature at 50±2℃. After 1h, vacuum filtration is carried out, and the obtained filtrate is the leachate.
本发明中，初始铁水温度一般为1190～1360℃，吹炼过程温度不超过1400℃。In the present invention, the initial molten iron temperature is generally 1190-1360°C, and the temperature during the blowing process does not exceed 1400°C.
下面通过实施例对本发明作进一步详细说明，但并不因此将本发明保护范围限制在所述的实施例范围之中。Hereinafter, the present invention will be further described in detail through examples, but the protection scope of the present invention is not limited to the scope of the described examples.
实施例1Example 1
A、铁水兑入转炉后，吹氧开始前3min内加入20kg/tFe的冷却剂，加入冷却剂后2min内加入石灰4kg/tFe，将钒渣中CaO/V 2O 5质量比控制在0.65； A. After the molten iron is poured into the converter, add 20kg/tFe coolant within 3 minutes before oxygen blowing, and 4kg/tFe lime within 2 minutes after adding coolant, and control the CaO/V 2 O 5 mass ratio in vanadium slag to 0.65;
B、采用氧枪吹氧进行吹炼，氧枪吹氧时枪位采用“高-低-高”模式进行控制，即吹炼前期1min采用1.9m高枪位，中期采用1.6m低枪位，吹炼结束前1.0min采用1.7m高枪位；顶吹氧气阶段底吹氮气流量控制在0.5m 3/(min·tFe)；吹炼时，顶吹氧气的供氧强度控制在2.0m 3/(min·tFe)，吹氧时间控制在5min，氧气压力控制在0.7MPa； B. Oxygen lance blowing oxygen is used for blowing. When blowing oxygen, the lance position is controlled by the "high-low-high" mode, that is, the 1.9m high lance position is used for 1 minute in the early stage of blowing, and the 1.6m low lance position is used in the mid-term. Use a 1.7m high gun position 1.0 min before the end of blowing; control the flow rate of bottom blowing nitrogen at 0.5m 3 /(min·tFe) in the top blowing oxygen stage; control the oxygen supply intensity of top blowing oxygen at 2.0m 3 / during blowing (min·tFe), the oxygen blowing time is controlled at 5min, and the oxygen pressure is controlled at 0.7MPa;
C、氧气吹炼结束后，将半钢倒入半钢罐内、钒渣留于转炉内，转炉回复到吹炼位后，将底吹气体切换为氧气，控制底吹氧气流量为0.75m 3/(min·tFe)，底吹氧开始后加入CaF 20.5kg/tFe，吹气时间2min；钒渣吹氧结束后，冷却64h得含钙钒渣； C. After the oxygen blowing is finished, pour the semi-steel into the semi-steel tank and leave the vanadium slag in the converter. After the converter returns to the blowing position, switch the bottom blowing gas to oxygen, and control the bottom blowing oxygen flow to 0.75m 3 /(min·tFe), CaF 2 0.5kg/tFe is added after the bottom blowing oxygen starts, and the blowing time is 2min; after the vanadium slag blowing oxygen is finished, it is cooled for 64h to obtain calcium-containing vanadium slag;
D、将含钙钒渣破碎、磁选、球磨成120目细粉，细粉与水按重量比1：2混合后，采用1：1的硫酸溶液进行浸出，pH值控制在2.8～3.2之间，浸出过程混合液采用机械搅拌(搅拌桨转速300～400r/min)并加热保持温度50±2℃，1h后进行真空抽滤，所得滤液为浸出液。D. The calcium-vanadium slag is crushed, magnetically separated, and ball milled into 120 mesh fine powder. After the fine powder is mixed with water in a weight ratio of 1:2, it is leached with a 1:1 sulfuric acid solution, and the pH value is controlled at 2.8-3.2. During the leaching process, the mixture is mechanically stirred (stirring blade rotation speed 300-400r/min) and heated to maintain a temperature of 50±2°C. After 1 hour, vacuum filtration is performed, and the resulting filtrate is the leachate.
全流程的钒氧化率为91.03％，钒浸出率为84.36％。The vanadium oxidation rate of the whole process is 91.03%, and the vanadium leaching rate is 84.36%.
实施例2Example 2
A、铁水兑入转炉后，吹氧开始前3min内加入19kg/tFe的冷却剂，加入冷却剂后2min内加入石灰3kg/tFe，将钒渣中CaO/V 2O 5质量比控制在0.55； A. After the molten iron is added to the converter, add 19kg/tFe coolant within 3 minutes before the oxygen blowing, and 3kg/tFe lime within 2 minutes after adding the coolant, and control the CaO/V 2 O 5 mass ratio in the vanadium slag to 0.55;
B、采用氧枪吹氧进行吹炼，氧枪吹氧时枪位采用“高-低-高”模式进行控制，即吹炼前期1.5min采用2.0m高枪位，中期采用1.8m低枪位，吹炼结束前1.0min采用1.9m高枪位；顶吹氧气阶段底吹氮气流量控制在0.45m 3/(min·tFe)；吹炼时，顶吹氧气的供氧强度控制在3.0m 3/(min·tFe)，吹氧时间控制在5.5min，氧气压力控制在0.9MPa； B. Oxygen lance is used to blow oxygen for blowing. When blowing oxygen, the lance position is controlled by the "high-low-high" mode, that is, the 2.0m high lance position is used for 1.5min in the early stage of blowing, and the 1.8m low lance position is used in the mid-term. , 1.0min before the end of blowing, adopt a 1.9m high gun position; the flow of bottom blowing nitrogen in the top blowing oxygen stage is controlled at 0.45m 3 /(min·tFe); during blowing, the oxygen supply intensity of top blowing oxygen is controlled at 3.0m 3 /(min·tFe), the oxygen blowing time is controlled at 5.5min, and the oxygen pressure is controlled at 0.9MPa;
C、氧气吹炼结束后，将半钢倒入半钢罐内、钒渣留于转炉内，转炉回复到吹炼位后，将底吹气体切换为氧气，控制底吹氧气流量为0.5m 3/(min·tFe)，底吹氧开始后加入CaF 21.0kg/tFe，吹气时间2min；钒渣吹氧结束后，冷却72h得含钙钒渣； C. After the oxygen blowing is completed, pour the semi-steel into the semi-steel tank and leave the vanadium slag in the converter. After the converter returns to the blowing position, switch the bottom blowing gas to oxygen and control the bottom blowing oxygen flow rate to 0.5m 3 /(min·tFe), CaF 2 1.0kg/tFe is added after the bottom blowing oxygen starts, and the blowing time is 2min; after the vanadium slag blowing oxygen is finished, cooling for 72h to obtain calcium-containing vanadium slag;
D、将含钙钒渣破碎、磁选、球磨成120目细粉，细粉与水按重量比1：2混合后，采用1：1的硫酸溶液进行浸出，pH值控制在2.8～3.2之间，浸出过程混合液采用机械搅拌(搅拌桨转速300～400r/min)并加热保持温度50±2℃，1h后进行真空抽滤，所得滤液为浸出液。D. The calcium-vanadium slag is crushed, magnetically separated, and ball milled into 120 mesh fine powder. After the fine powder is mixed with water in a weight ratio of 1:2, it is leached with a 1:1 sulfuric acid solution, and the pH value is controlled at 2.8-3.2. During the leaching process, the mixture is mechanically stirred (stirring blade rotation speed 300-400r/min) and heated to maintain a temperature of 50±2°C. After 1 hour, vacuum filtration is performed, and the resulting filtrate is the leachate.
全流程的钒氧化率为90.63％，钒浸出率为85.07％。The vanadium oxidation rate of the whole process is 90.63%, and the vanadium leaching rate is 85.07%.

Claims (10)

  1. 转炉铁水加石灰生产含钙钒渣的方法，其特征在于：包括以下步骤：The method for producing calcium-containing vanadium slag by adding lime to molten iron in a converter is characterized in that it comprises the following steps:
    A、铁水兑入转炉后，加入冷却剂和石灰，采用顶吹氧气底吹氮气进行吹炼；A. After the molten iron is poured into the converter, add coolant and lime, and use top-blowing oxygen and bottom-blowing nitrogen for blowing;
    B、吹炼结束后，将半钢倒入半钢罐内、钒渣留于转炉内，转炉回复到吹炼位后，将底吹气体切换为氧气，并加入CaF 2，吹氧结束，得含钙钒渣。 B. After blowing, pour the semi-steel into the semi-steel tank and leave the vanadium slag in the converter. After the converter returns to the blowing position, switch the bottom blowing gas to oxygen and add CaF 2 , and the oxygen blowing is complete. Containing calcium vanadium slag.
  2. 根据权利要求1所述的转炉铁水加石灰生产含钙钒渣的方法，其特征在于：步骤A中，所述冷却剂的用量为15～35kg/tFe；所述冷却剂的加入时间为吹氧开始前3min内。The method for producing calcium-containing vanadium slag by adding lime to molten iron in a converter according to claim 1, characterized in that: in step A, the amount of the coolant is 15-35kg/tFe; the adding time of the coolant is oxygen blowing Within 3min before starting.
  3. 根据权利要求1所述的转炉铁水加石灰生产含钙钒渣的方法，其特征在于：步骤A中，所述石灰的加入量为3～4kg/tFe；所述石灰的加入时间为加入冷却剂后2min内。The method for producing calcium-vanadium-containing slag by adding lime to molten iron in a converter according to claim 1, characterized in that: in step A, the addition amount of the lime is 3 to 4 kg/tFe; the addition time of the lime is the addition of a coolant Within 2min.
  4. 根据权利要求1所述的转炉铁水加石灰生产含钙钒渣的方法，其特征在于：步骤A中，吹炼时，氧枪吹氧枪位采用“高-低-高”模式进行控制，即吹炼前期0.5～1.5min采用1.7～2.0m高枪位，中期采用1.6～1.8m低枪位，吹炼结束前1.0～1.5min采用1.7～2.0m高枪位。The method for producing calcium-containing vanadium slag by adding lime to molten iron in a converter according to claim 1, characterized in that: in step A, during blowing, the position of the oxygen lance is controlled in a "high-low-high" mode, namely 1.7-2.0m high gun position is used for 0.5～1.5min in the early stage of blowing, 1.6～1.8m low gun position is adopted in the middle stage, and 1.7～2.0m high gun position is adopted 1.0～1.5min before the end of blowing.
  5. 根据权利要求1所述的转炉铁水加石灰生产含钙钒渣的方法，其特征在于：步骤A中，吹炼时，顶吹氧气的供氧强度控制在2.0～3.0m 3/(min·tFe)，吹氧时间控制在5～6.5min，氧气压力控制在0.7～0.9MPa。 The method for producing calcium-containing vanadium slag by adding lime to molten iron in a converter according to claim 1, characterized in that: in step A, during the blowing, the oxygen supply intensity of the top blowing oxygen is controlled at 2.0～3.0m 3 /(min·tFe ), the oxygen blowing time is controlled at 5～6.5min, and the oxygen pressure is controlled at 0.7～0.9MPa.
  6. 根据权利要求1所述的转炉铁水加石灰生产含钙钒渣的方法，其特征在于：步骤A中，顶吹氧气阶段底吹氮气流量控制在0.1～0.5m 3/(min·tFe)。 The method for producing calcium-containing vanadium slag by adding lime to molten iron in a converter according to claim 1, characterized in that: in step A, the flow of bottom blowing nitrogen in the top blowing oxygen stage is controlled at 0.1-0.5 m 3 /(min·tFe).
  7. 根据权利要求1所述的转炉铁水加石灰生产含钙钒渣的方法，其特征在于：步骤B中，底吹氧气流量为0.25～0.75m 3/(min·tFe)。 The method for producing calcium-containing vanadium slag by adding lime to molten iron in a converter according to claim 1, characterized in that: in step B, the flow rate of bottom blowing oxygen is 0.25-0.75 m 3 /(min·tFe).
  8. 根据权利要求1所述的转炉铁水加石灰生产含钙钒渣的方法，其特征在于：步骤B中，CaF 2的加入量为0.5～1.0kg/tFe。 The method for producing calcium-containing vanadium slag by adding lime to molten iron in a converter according to claim 1, characterized in that: in step B, the added amount of CaF 2 is 0.5-1.0 kg/tFe.
  9. 根据权利要求1所述的转炉铁水加石灰生产含钙钒渣的方法，其特征在于：步骤B中，底吹氧气时间为2～3min。The method for producing calcium-containing vanadium slag by adding lime to molten iron in a converter according to claim 1, characterized in that: in step B, the bottom blowing oxygen time is 2 to 3 minutes.
  10. 转炉铁水加石灰生产含钙钒渣及其浸出的方法，其特征在于：在权利要求1～9任一项的基础上，还包括以下步骤：The method for producing calcium-containing vanadium slag by adding lime to the converter molten iron and its leaching method is characterized in that: on the basis of any one of claims 1-9, the method further comprises the following steps:
    C、含钙钒渣经冷却、破碎、磁选、球磨、酸浸和分离，得浸出液。C. After cooling, crushing, magnetic separation, ball milling, acid leaching and separation of calcium-containing vanadium slag, the leachate is obtained.
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CN110079643A (en) * 2019-05-16 2019-08-02 成都先进金属材料产业技术研究院有限公司 Using the method for lime treatment vanadium-bearing hot metal vanadium extraction
CN110106305A (en) * 2019-05-16 2019-08-09 成都先进金属材料产业技术研究院有限公司 The method that calcium system handles vanadium-bearing hot metal production calcic vanadium slag and directly leaches vanadium extraction

Cited By (2)

* Cited by examiner, † Cited by third party
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CN113549769A (en) * 2021-07-30 2021-10-26 攀枝花钢城集团有限公司 Method for enriching vanadium in vanadium-containing steel slag
CN113549769B (en) * 2021-07-30 2022-09-27 攀枝花钢城集团有限公司 Method for enriching vanadium in vanadium-containing steel slag

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