高炉冶炼钒钛磁铁矿钒还原机理研究
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摘要
钒是一种重要的金属,在钢铁、化工、能源等领域有广泛的应用。自然界中钒钛磁铁矿是最重要的钒的寄生矿床之一,我国攀西地区有丰富的钒钛磁铁矿。目前攀钢从钒钛磁铁矿中提钒主要为火法提钒,即通过高炉冶炼使钒氧化物得到还原,进入铁水,再通过转炉氧化吹炼得到富钒渣。
攀钢高炉冶炼钒钛磁铁精矿的特点是难选、难烧、难炼,入炉料中钛、铝含量高,在冶炼过程中严重影响高炉炉况的顺行。近年来,随着炉料结构的优化,高炉入炉料中钒钛矿比例逐渐降低,增加了普通矿的比例,炉料中TiO2量逐渐降低,高炉冶炼钒钛磁铁矿技术经济指标得到了改善。随着入炉料中钒钛矿配比的降低,炉料中钒的含量有所降低,但钒的回收率却有所提高；如何在提高入炉料中钒含量的同时,改善高炉内钒氧化物还原的热力学条件,促进钒氧化物的还原,进而提高钒的回收率,是一个亟待解决的问题,需要进一步开展研究。
本文通过模拟固态炉料中钒氧化物在高炉块状带、软熔滴落带中的还原反应,实验研究了温度、炉料中钒钛矿配比、粒度及装料制度对钒氧化物还原的影响规律；通过热力学分析了铁水中钒的活度及影响因素,并进行了计算；模拟高炉炉缸渣铁间钒的还原反应,计算了渣系组分及反应温度对钒平衡分配比及铁水中钒含量的影响规律并进行了实验研究；主要得到以下结果：
①固态炉料中钒主要以钒铁尖晶石的形式存在,热力学计算表明固态炉料中铁氧化物的充分还原及高温将极大改善钒氧化物还原的热力学条件；
②实验研究表明在块状带区,温度高于850℃、粒度保持在5—10mm及钒钛矿配比为70—75%时,炉料还原性较好,有利于钒氧化物的还原；炉料还原度为85—90%时,铁中开始出现钒；铁中钒含量随还原度的增加而增加,当还原度达到90%后,铁中钒含量增加加快；
③在软熔滴落区,随炉料预还原度的增加,铁中钒含量逐渐升高；矿焦混装率为50%时,铁中钒含量达最大0.36%；混装率达到75%后,铁中钒含量降低明显,要使钒还原得到加强,矿焦混装率应维持在50%左右；随钒钛矿配比的增加,铁中钒含量呈下降趋势,钒钛矿配比为60%时,铁中钒含量可达到0.29%,钒钛矿配比增加到77%时,铁中钒含量仅为0.16%；
④热力学计算表明铁水中Si、V均能提高fv,P、S、C能够降低fv；铁中钒的活度系数随温度升高而降低；
⑤标准状态下钒氧化物将先于硅、钛氧化物与碳发生还原反应；热力学计算及实验表明升温有利于钒的还原；炉渣碱度的增加有利于钒氧化物的还原；随渣中V2O3含量的增加,铁中钒含量增加；随渣中TiO2含量的增加,钒分配比降低,铁中钒含量降低；铁水中硅含量的增加有利于钒的还原,且变化较为明显。
Vanadium is a very important metal, which are widely used in iron and steel, chemical industry and the energy fields. In nature the V-Ti-magetite is the important parasitic deposits of vanadium, in the west of Pangangzhihua there are abundant V-Ti-magetite. In present, extracting the vanadium from the V-Ti-magetite in Pangzhihua Ltd is pyrogenic process, which is extracting vanadium from V-Ti-magetite into hot metal in BF and oxidizing vanadium to vanadium oxide into slag in converter.
The characteristic of V-Ti-magetite is hard agglomeration, hard smelting and hard ore dressing, there are a mass of aluminum and titanium in burden and that will deteriorate the furnace condition. In recent years, with the optimization of burden structure, the ratio of V-Ti-magetite in burden have been cut down and the ratio of common ore have been raised at the same time, so the content of Titanium dioxide lessened and the technical economical index have been improved markedly in the process of smelting V-Ti-magetite in BF. With the decreasing of ratio of V-Ti-magetite, the content of vanadium in burden decreased, but the recovery of vanadium improved. How increase the content of vanadium in burden simultaneously improve the thermodynamics conditions of reduction of vanadium oxides and the recovery ratio of vanadium is a burning question and it need further research.
In this work, the tests, which simulated an actual blast furnace under certain conditions, have been carried out to look for the effect of temperature, the ratio of V-Ti-magetite in burden, granularity and the charging method on the reduction of vanadium oxides; the activity of vanadium in hot metal and influencing factor have been analyzed by the thermodynamic calculations; the effect of temperature, the content of vanadium in hot metal and component of slag on the distribution ratio of vanadium between slag and hot metal in hearth have been calculated and made experimental research.
The research results indicate that:
①The mode of occurrence of V in burden is vanadium-iron spinel, thermodynamic calculations have shown that the high temperature and the sufficient reduction of iron oxides can improve the thermodynamic condition of the reduction of vanadium oxide.
②In lumpy zone, when the temperature is higher than 850℃, the particle size of ore lies between 5mm and 10mm and the ratio of V-Ti-magnetite lies between 70% and 75%, the ore has a good reduction, under these conditions vanadium oxide can be reduced, too. When the reduced degree of iron oxides is between 85% and 90%, the reduction of vanadium would happen, and when the reduction degree exceeded 90%, the content of vanadium in iron would increase gradually.
③In soft dripping with molten, the content of vanadium in iron increased with the increasing of reduction degree and the ratio of coke in ore, decrease with the increasing of the ratio of V-Ti-magetite. When the ratio of coke in ore reached 50%, the content of vanadium in iron can reached 0.36%, but when the ratio of coke exceeded 75%, the content of vanadium began to decrease. When the ratio of V-Ti-magetite is 60%, the content of vanadium is 0.29%, but when the ratio of V-Ti-magetite is 77%, the content of vanadium is only 0.16%;
④The thermodynamic calculations have shown that the content of Si, V in hot metal can increase the activity of V, but the content of P, S, C in hot metal can decrease the activity of V; and the activity of V decreased with the increasing of temperature;
⑤Under the standard condition the reduction of vanadium oxides will priority react to the reduction of silicon oxides and titanium oxides; the thermodynamic calculations and the results of experiment have showen that the high temperature, high basicity, high silicon content in hot metla can be benefited to the reduction of vanadium, increase the content of vanadium sesquioxide and titanium dioxide can shorten the distribution of vanadium, but with the increasing of content of vanadium sesquioxide, the content of vanadium in iron increased and with the increasing of content of titanium dioxide, the content of vanadium in iron decreased.
攀钢高炉冶炼钒钛磁铁精矿的特点是难选、难烧、难炼,入炉料中钛、铝含量高,在冶炼过程中严重影响高炉炉况的顺行。近年来,随着炉料结构的优化,高炉入炉料中钒钛矿比例逐渐降低,增加了普通矿的比例,炉料中TiO2量逐渐降低,高炉冶炼钒钛磁铁矿技术经济指标得到了改善。随着入炉料中钒钛矿配比的降低,炉料中钒的含量有所降低,但钒的回收率却有所提高；如何在提高入炉料中钒含量的同时,改善高炉内钒氧化物还原的热力学条件,促进钒氧化物的还原,进而提高钒的回收率,是一个亟待解决的问题,需要进一步开展研究。
本文通过模拟固态炉料中钒氧化物在高炉块状带、软熔滴落带中的还原反应,实验研究了温度、炉料中钒钛矿配比、粒度及装料制度对钒氧化物还原的影响规律；通过热力学分析了铁水中钒的活度及影响因素,并进行了计算；模拟高炉炉缸渣铁间钒的还原反应,计算了渣系组分及反应温度对钒平衡分配比及铁水中钒含量的影响规律并进行了实验研究；主要得到以下结果：
①固态炉料中钒主要以钒铁尖晶石的形式存在,热力学计算表明固态炉料中铁氧化物的充分还原及高温将极大改善钒氧化物还原的热力学条件；
②实验研究表明在块状带区,温度高于850℃、粒度保持在5—10mm及钒钛矿配比为70—75%时,炉料还原性较好,有利于钒氧化物的还原；炉料还原度为85—90%时,铁中开始出现钒；铁中钒含量随还原度的增加而增加,当还原度达到90%后,铁中钒含量增加加快；
③在软熔滴落区,随炉料预还原度的增加,铁中钒含量逐渐升高；矿焦混装率为50%时,铁中钒含量达最大0.36%；混装率达到75%后,铁中钒含量降低明显,要使钒还原得到加强,矿焦混装率应维持在50%左右；随钒钛矿配比的增加,铁中钒含量呈下降趋势,钒钛矿配比为60%时,铁中钒含量可达到0.29%,钒钛矿配比增加到77%时,铁中钒含量仅为0.16%；
④热力学计算表明铁水中Si、V均能提高fv,P、S、C能够降低fv；铁中钒的活度系数随温度升高而降低；
⑤标准状态下钒氧化物将先于硅、钛氧化物与碳发生还原反应；热力学计算及实验表明升温有利于钒的还原；炉渣碱度的增加有利于钒氧化物的还原；随渣中V2O3含量的增加,铁中钒含量增加；随渣中TiO2含量的增加,钒分配比降低,铁中钒含量降低；铁水中硅含量的增加有利于钒的还原,且变化较为明显。
Vanadium is a very important metal, which are widely used in iron and steel, chemical industry and the energy fields. In nature the V-Ti-magetite is the important parasitic deposits of vanadium, in the west of Pangangzhihua there are abundant V-Ti-magetite. In present, extracting the vanadium from the V-Ti-magetite in Pangzhihua Ltd is pyrogenic process, which is extracting vanadium from V-Ti-magetite into hot metal in BF and oxidizing vanadium to vanadium oxide into slag in converter.
The characteristic of V-Ti-magetite is hard agglomeration, hard smelting and hard ore dressing, there are a mass of aluminum and titanium in burden and that will deteriorate the furnace condition. In recent years, with the optimization of burden structure, the ratio of V-Ti-magetite in burden have been cut down and the ratio of common ore have been raised at the same time, so the content of Titanium dioxide lessened and the technical economical index have been improved markedly in the process of smelting V-Ti-magetite in BF. With the decreasing of ratio of V-Ti-magetite, the content of vanadium in burden decreased, but the recovery of vanadium improved. How increase the content of vanadium in burden simultaneously improve the thermodynamics conditions of reduction of vanadium oxides and the recovery ratio of vanadium is a burning question and it need further research.
In this work, the tests, which simulated an actual blast furnace under certain conditions, have been carried out to look for the effect of temperature, the ratio of V-Ti-magetite in burden, granularity and the charging method on the reduction of vanadium oxides; the activity of vanadium in hot metal and influencing factor have been analyzed by the thermodynamic calculations; the effect of temperature, the content of vanadium in hot metal and component of slag on the distribution ratio of vanadium between slag and hot metal in hearth have been calculated and made experimental research.
The research results indicate that:
①The mode of occurrence of V in burden is vanadium-iron spinel, thermodynamic calculations have shown that the high temperature and the sufficient reduction of iron oxides can improve the thermodynamic condition of the reduction of vanadium oxide.
②In lumpy zone, when the temperature is higher than 850℃, the particle size of ore lies between 5mm and 10mm and the ratio of V-Ti-magnetite lies between 70% and 75%, the ore has a good reduction, under these conditions vanadium oxide can be reduced, too. When the reduced degree of iron oxides is between 85% and 90%, the reduction of vanadium would happen, and when the reduction degree exceeded 90%, the content of vanadium in iron would increase gradually.
③In soft dripping with molten, the content of vanadium in iron increased with the increasing of reduction degree and the ratio of coke in ore, decrease with the increasing of the ratio of V-Ti-magetite. When the ratio of coke in ore reached 50%, the content of vanadium in iron can reached 0.36%, but when the ratio of coke exceeded 75%, the content of vanadium began to decrease. When the ratio of V-Ti-magetite is 60%, the content of vanadium is 0.29%, but when the ratio of V-Ti-magetite is 77%, the content of vanadium is only 0.16%;
④The thermodynamic calculations have shown that the content of Si, V in hot metal can increase the activity of V, but the content of P, S, C in hot metal can decrease the activity of V; and the activity of V decreased with the increasing of temperature;
⑤Under the standard condition the reduction of vanadium oxides will priority react to the reduction of silicon oxides and titanium oxides; the thermodynamic calculations and the results of experiment have showen that the high temperature, high basicity, high silicon content in hot metla can be benefited to the reduction of vanadium, increase the content of vanadium sesquioxide and titanium dioxide can shorten the distribution of vanadium, but with the increasing of content of vanadium sesquioxide, the content of vanadium in iron increased and with the increasing of content of titanium dioxide, the content of vanadium in iron decreased.
引文
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