钒钛磁铁矿综合利用新流程及其比较研究
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摘要
我国的钒钛磁铁矿资源十分丰富,但由于资源的特殊性,目前已工业化的高炉-转炉法传统流程仅能提取其中的铁和钒,大量的钛资源进入高炉渣无法回收利用,且该方法存在流程长、能耗高、投资大、环境污染严重等问题,因此,开展钒钛磁铁矿综合利用新流程研究,将资源优势转化为经济优势,对于促进我国国民经济持续健康发展具有重要意义。
本文在热力学研究的基础上,以我国内蒙小红山钒钛磁铁矿资源为对象,对选矿所得钒钛磁铁精矿产品在研究其固态还原行为及其强化技术的基础上,采用还原-磨选法和预还原-电炉法对钒钛磁铁精矿综合回收铁、钒、钛进行了系统研究,并从工艺流程及主要设备、生产规模与产品方案、建厂投资与成本、环保与能耗等方面对还原-磨选法和预还原-电炉法新流程进行了比较分析,取得以下结论：
(1)钒钛磁铁精矿碳热还原反应热力学研究发现,钒钛磁铁精矿中铁氧化物还原的热力学趋势最大,其次为钒氧化物,钛氧化物还原的热力学趋势最小。在有液态铁存在时会大大改善钒氧化物还原的热力学条件,当有杂质组分MgO、CaO存在时,将会进一步降低钛氧化物还原的热力学趋势。
(2)研究钒钛磁铁精矿固态还原行为发现,钒钛磁铁精矿属较难还原矿物,当铁氧化物金属化率提高到80%左右时,提高还原温度和延长还原时间,钒钛磁铁精矿还原产品金属化率增加的较为缓慢。预氧化处理有利于促进钒钛磁铁精矿的后续还原,但不利于铁晶粒的生长,其作用机理是破坏了钒钛磁铁精矿颗粒结构,提高了反应比表面积。添加剂硼砂具有较好促进钒钛磁铁精矿的还原和铁晶粒生长作用,其作用机理是强化了钒钛磁铁精矿中钛铁晶石和钛铁矿的还原过程。
(3)研究了基于煤基回转窑还原工艺的钒钛磁铁精矿还原-磨选法新流程。研究结果表明,通过添加硼砂强化钒钛磁铁精矿还原过程,能显著改善还原-磨选过程的铁与钒钛分离效果。钒钛磁铁精矿配加硼砂和F粘结剂经润磨处理后造球,所得生球经干燥、预热后在适宜的还原磨选条件下,可获得TFe90.06%、回收率96.53%的直接还原铁精粉,非磁性物(富钒钛料)V205含量为1.64%,Ti02含量为28.4%的富钒钛料。富钒钛料适于采取酸浸提钒的技术路线,在适宜的条件下,钒的浸出率可达到70.18%,获得了纯度大于98%的V205产品。
(4)研究了基于煤基回转窑预还原工艺的钒钛磁铁精矿预还原-电炉法新流程。研究结果表明,预还原-电炉法流程的预还原产品适宜的金属化率为70%左右。钒钛磁铁精矿预还原采用预氧化强化还原技术,电炉冶炼通过调整碱度和MgO含量进行适量造渣的方法,在适宜的球团预还原制度、电炉冶炼渣型制度及操作参数下,获得了钒品位0.253%、钒回收率85.36%的含钒生铁,以及Ti02为35.97%的含钛炉渣。
(5)还原-磨选法新流程具有耗电量小,还原过程中钒钛走向易控制等特点,适于电力资源缺乏、资源处理量要求小的地区等采用。预还原-电炉法新流程具有生产规模大、效率高、耗电量大等特点,适于电力资源丰富、资源处理量要求大的地区等采用。从生产规模、生产效率、污染源控制方面来看,采用预还原-电炉法新流程处理钒钛磁铁精矿更有优势。
本文系统研究了钒钛磁铁精矿碳热还原反应的热力学,查明了实现钒钛磁铁精矿中铁、钒及钛氧化物选择性还原的热力学条件,通过研究钒钛磁铁精矿固态还原行为、电炉冶炼渣型制度,开发钒钛磁铁精矿固态还原强化技术和电炉冶炼过程钒钛走向控制技术,优化了钒钛磁铁精矿还原-磨选法和预还原-电炉法综合利用新流程,为钒钛磁铁矿资源综合利用新流程工业化应用提供技术基础和决策依据。
Vanadium-titanium magnetite is abundant in our country, which has been widely utilized by using the process of blast furnace-converter smelting. This traditional process is capable of extracting iron and vanadium, while cannot recycle titanium due to its entering into the blast-furnace slag. Moreover, due to the lots of serious problems of the traditional method, such as long process, high energy consumption, huge investment and environmental pollution, it is imperative to explore a new process to research the comprehensive utilization of vanadium-titanium magnetite. The research is of significance not only for the transformation of resource advantage to economic advantage, but also for the sustained rapid and sound development of our national economy.
In this paper, we have done with the vanadium-titanium magnetite of China's Inner Mongolia Xiaohongshan on the basis of thermodynamics. Besides the study of its solid-state reduction behavior and improving measures, the methods, reduction-grinding and pre-reduction-electric furnace, have been systematic researched about the comprehensive recovery of iron, vanadium, titanium. Given other aspects of the two methods as well, the process and the main equipments, production scale and product solutions, plant investments and costs, environment and energy, we reached the main conclusions as follows:
(1) From thermodynamics study of the carbothermic reduction reaction of vanadium-titanium magnetite concentrate, it was found that the thermodynamic tendencies of iron oxide reduction, vanadium oxide reduction, titanium oxide reduction were in turn decreased. In the presence of a liquid iron, the thermodynamic conditions of vanadium oxide reduction will be greatly improved. While the thermodynamic tendency of titanium oxide reduction will further reduce when there exist impurities components such as MgO, CaO.
(2) We found that vanadium-titanium magnetite concentrate is hard for reduction when studied its solid-state reduction behavior. When the metallization rate of iron oxide was80%, the metallization rate of reduction products was increased more slowly even by increasing the reduction temperature and time. Pre-oxidation can promote the subsequent reduction while go against the growth of iron grains, due to its mechanism that the structures of iron particles are destroyed and the surface area of action is increased in pre-oxidation. Borax is a good additive to promote the reduction of vanadium-titanium magnetite concentrate and the growth of iron grains with its mechanism that the reductions of ulvite and ilmenite in vanadium-titanium magnetite concentrate were strengthened.
(3) The new process of treatment of vanadium-titanium magnetite concentrate, reduction-grinding based on coal-based rotary kiln, was studied. Borax can efficiently improve the separation of iron and vanadium-titanium in the reduction-grinding and separation process. After a series of processes, damp milling the raw materials with borax and F binder as additives, pelletizing, drying and preheating the green balls, and grinding under the suitable conditions, we got the iron powders in which TFe was90.06%and recovery rate was96.53%, and the non-magnetic materials (vanadium-titanium-rich materials) in which V2O5content was1.64%, TiO2content was28.4%. It is conducive to choose vanadium acid extraction technology to utilize vanadium-titanium-rich materials, in which the leaching rate of vanadium reached70.18%and the purity of V2O5product was more than98%under proper conditions.
(4) As the study of another new process of vanadium-titanium magnetite concentrate, the pre-reduction-electric furnace process based on coal-based rotary kiln, we found that the suitable metallization rate of the pre-reduction products was70%in the process. Pre-oxidation was used to enhance the pre-reduction process, and adjusting the alkalinity and MgO content were used to moderate slag in the electric furnace. Under the appropriate conditions of pre-reduction and slag type in smelting furnace, we gained the pig iron in which vanadium grade was0.253%and the vanadium recovery was85.36%, and titanium slag in which TiO2content was35.97%.
(5) It is suitable for areas that are lack of power resources and have small amounts of vanadium-titanium magnetite to deal with to choose reduction-grinding, which has many benefits, including small power consumption, easy controlling of vanadium and titanium in the reduction. Taking advantages of pre-reduction-electric furnace, production of large-scale, high efficiency, heavy power consumption, we recommended this process is suitable for the areas that are rich in electric power resource and have large amounts of vanadium-titanium magnetite to deal with. Pre-reduction-electric furnace weighs more than other processes in dealing with vanadium-titanium magnetite, when the production scale, production efficiency and pollution control are taken into account.
The thermodynamics of the carbothermic reduction of vanadium-titanium magnetite concentrate was systematically researched in this paper, and we identified the thermodynamic conditions to realize the selective reductions of iron oxide, vanadium oxide and titanium oxide. By studying the solid-state reduction behavior and slag type in electric furnace, we developed the technologies to enhance the solid-state reduction of vanadium-titanium magnetite concentrate and control the vanadium and titanium in the smelting of electric furnace, optimizing the new comprehensive utilization processes, reduction-grinding and pre-reduction-electric furnace, leading train of novel thoughts to select and develop new processes to utilize vanadium-titanium magnetite.
本文在热力学研究的基础上,以我国内蒙小红山钒钛磁铁矿资源为对象,对选矿所得钒钛磁铁精矿产品在研究其固态还原行为及其强化技术的基础上,采用还原-磨选法和预还原-电炉法对钒钛磁铁精矿综合回收铁、钒、钛进行了系统研究,并从工艺流程及主要设备、生产规模与产品方案、建厂投资与成本、环保与能耗等方面对还原-磨选法和预还原-电炉法新流程进行了比较分析,取得以下结论：
(1)钒钛磁铁精矿碳热还原反应热力学研究发现,钒钛磁铁精矿中铁氧化物还原的热力学趋势最大,其次为钒氧化物,钛氧化物还原的热力学趋势最小。在有液态铁存在时会大大改善钒氧化物还原的热力学条件,当有杂质组分MgO、CaO存在时,将会进一步降低钛氧化物还原的热力学趋势。
(2)研究钒钛磁铁精矿固态还原行为发现,钒钛磁铁精矿属较难还原矿物,当铁氧化物金属化率提高到80%左右时,提高还原温度和延长还原时间,钒钛磁铁精矿还原产品金属化率增加的较为缓慢。预氧化处理有利于促进钒钛磁铁精矿的后续还原,但不利于铁晶粒的生长,其作用机理是破坏了钒钛磁铁精矿颗粒结构,提高了反应比表面积。添加剂硼砂具有较好促进钒钛磁铁精矿的还原和铁晶粒生长作用,其作用机理是强化了钒钛磁铁精矿中钛铁晶石和钛铁矿的还原过程。
(3)研究了基于煤基回转窑还原工艺的钒钛磁铁精矿还原-磨选法新流程。研究结果表明,通过添加硼砂强化钒钛磁铁精矿还原过程,能显著改善还原-磨选过程的铁与钒钛分离效果。钒钛磁铁精矿配加硼砂和F粘结剂经润磨处理后造球,所得生球经干燥、预热后在适宜的还原磨选条件下,可获得TFe90.06%、回收率96.53%的直接还原铁精粉,非磁性物(富钒钛料)V205含量为1.64%,Ti02含量为28.4%的富钒钛料。富钒钛料适于采取酸浸提钒的技术路线,在适宜的条件下,钒的浸出率可达到70.18%,获得了纯度大于98%的V205产品。
(4)研究了基于煤基回转窑预还原工艺的钒钛磁铁精矿预还原-电炉法新流程。研究结果表明,预还原-电炉法流程的预还原产品适宜的金属化率为70%左右。钒钛磁铁精矿预还原采用预氧化强化还原技术,电炉冶炼通过调整碱度和MgO含量进行适量造渣的方法,在适宜的球团预还原制度、电炉冶炼渣型制度及操作参数下,获得了钒品位0.253%、钒回收率85.36%的含钒生铁,以及Ti02为35.97%的含钛炉渣。
(5)还原-磨选法新流程具有耗电量小,还原过程中钒钛走向易控制等特点,适于电力资源缺乏、资源处理量要求小的地区等采用。预还原-电炉法新流程具有生产规模大、效率高、耗电量大等特点,适于电力资源丰富、资源处理量要求大的地区等采用。从生产规模、生产效率、污染源控制方面来看,采用预还原-电炉法新流程处理钒钛磁铁精矿更有优势。
本文系统研究了钒钛磁铁精矿碳热还原反应的热力学,查明了实现钒钛磁铁精矿中铁、钒及钛氧化物选择性还原的热力学条件,通过研究钒钛磁铁精矿固态还原行为、电炉冶炼渣型制度,开发钒钛磁铁精矿固态还原强化技术和电炉冶炼过程钒钛走向控制技术,优化了钒钛磁铁精矿还原-磨选法和预还原-电炉法综合利用新流程,为钒钛磁铁矿资源综合利用新流程工业化应用提供技术基础和决策依据。
Vanadium-titanium magnetite is abundant in our country, which has been widely utilized by using the process of blast furnace-converter smelting. This traditional process is capable of extracting iron and vanadium, while cannot recycle titanium due to its entering into the blast-furnace slag. Moreover, due to the lots of serious problems of the traditional method, such as long process, high energy consumption, huge investment and environmental pollution, it is imperative to explore a new process to research the comprehensive utilization of vanadium-titanium magnetite. The research is of significance not only for the transformation of resource advantage to economic advantage, but also for the sustained rapid and sound development of our national economy.
In this paper, we have done with the vanadium-titanium magnetite of China's Inner Mongolia Xiaohongshan on the basis of thermodynamics. Besides the study of its solid-state reduction behavior and improving measures, the methods, reduction-grinding and pre-reduction-electric furnace, have been systematic researched about the comprehensive recovery of iron, vanadium, titanium. Given other aspects of the two methods as well, the process and the main equipments, production scale and product solutions, plant investments and costs, environment and energy, we reached the main conclusions as follows:
(1) From thermodynamics study of the carbothermic reduction reaction of vanadium-titanium magnetite concentrate, it was found that the thermodynamic tendencies of iron oxide reduction, vanadium oxide reduction, titanium oxide reduction were in turn decreased. In the presence of a liquid iron, the thermodynamic conditions of vanadium oxide reduction will be greatly improved. While the thermodynamic tendency of titanium oxide reduction will further reduce when there exist impurities components such as MgO, CaO.
(2) We found that vanadium-titanium magnetite concentrate is hard for reduction when studied its solid-state reduction behavior. When the metallization rate of iron oxide was80%, the metallization rate of reduction products was increased more slowly even by increasing the reduction temperature and time. Pre-oxidation can promote the subsequent reduction while go against the growth of iron grains, due to its mechanism that the structures of iron particles are destroyed and the surface area of action is increased in pre-oxidation. Borax is a good additive to promote the reduction of vanadium-titanium magnetite concentrate and the growth of iron grains with its mechanism that the reductions of ulvite and ilmenite in vanadium-titanium magnetite concentrate were strengthened.
(3) The new process of treatment of vanadium-titanium magnetite concentrate, reduction-grinding based on coal-based rotary kiln, was studied. Borax can efficiently improve the separation of iron and vanadium-titanium in the reduction-grinding and separation process. After a series of processes, damp milling the raw materials with borax and F binder as additives, pelletizing, drying and preheating the green balls, and grinding under the suitable conditions, we got the iron powders in which TFe was90.06%and recovery rate was96.53%, and the non-magnetic materials (vanadium-titanium-rich materials) in which V2O5content was1.64%, TiO2content was28.4%. It is conducive to choose vanadium acid extraction technology to utilize vanadium-titanium-rich materials, in which the leaching rate of vanadium reached70.18%and the purity of V2O5product was more than98%under proper conditions.
(4) As the study of another new process of vanadium-titanium magnetite concentrate, the pre-reduction-electric furnace process based on coal-based rotary kiln, we found that the suitable metallization rate of the pre-reduction products was70%in the process. Pre-oxidation was used to enhance the pre-reduction process, and adjusting the alkalinity and MgO content were used to moderate slag in the electric furnace. Under the appropriate conditions of pre-reduction and slag type in smelting furnace, we gained the pig iron in which vanadium grade was0.253%and the vanadium recovery was85.36%, and titanium slag in which TiO2content was35.97%.
(5) It is suitable for areas that are lack of power resources and have small amounts of vanadium-titanium magnetite to deal with to choose reduction-grinding, which has many benefits, including small power consumption, easy controlling of vanadium and titanium in the reduction. Taking advantages of pre-reduction-electric furnace, production of large-scale, high efficiency, heavy power consumption, we recommended this process is suitable for the areas that are rich in electric power resource and have large amounts of vanadium-titanium magnetite to deal with. Pre-reduction-electric furnace weighs more than other processes in dealing with vanadium-titanium magnetite, when the production scale, production efficiency and pollution control are taken into account.
The thermodynamics of the carbothermic reduction of vanadium-titanium magnetite concentrate was systematically researched in this paper, and we identified the thermodynamic conditions to realize the selective reductions of iron oxide, vanadium oxide and titanium oxide. By studying the solid-state reduction behavior and slag type in electric furnace, we developed the technologies to enhance the solid-state reduction of vanadium-titanium magnetite concentrate and control the vanadium and titanium in the smelting of electric furnace, optimizing the new comprehensive utilization processes, reduction-grinding and pre-reduction-electric furnace, leading train of novel thoughts to select and develop new processes to utilize vanadium-titanium magnetite.
引文
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