铁矿球团微波加热煤基直接还原基础与技术研究
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摘要
传统钢铁生产流程长、投资大、能耗高、污染严重,而且焦煤资源日益枯竭,开发一种以煤代焦、节能减排、高效紧凑的炼铁新工艺具有重大的战略意义。本文以铁矿球团和无烟煤为主要研究对象,开展了铁矿球团微波加热煤基直接还原的基础与技术研究。论文研究的主要创新点和结论如下：
研究了铁矿球团和煤的电磁性能及其微波加热升温特性。球团或团块的升温速度快慢顺序是：Fe3O4>FeO≈Fe2O3≈氧化球团>Fe粉；在微波作用下铁矿球团物相及其结构产生了改变,铁氧化物反应活性增强,促进了铁氧化物的还原。无烟煤在微波场中强烈吸收微波,具有还原剂和发热体双重作用,加快了固定碳的气化反应。
采用光学显微镜、XRD和SEM等现代测试技术研究了铁矿球团微波加热煤基非等温还原过程物相和显微结构变化。结果表明,微波作用下球团中的颗粒出现碎裂,促进了铁氧化物还原反应,以及晶格发生变化而产生内应力,造成球团膨胀。当升温到850℃,还原度为43.06%时膨胀率最大,球团强度最低为320N/个,进一步还原时金属铁增多,铁晶粒迁移、聚集、长大,温度上升到1050℃并恒温50min时,球团的还原度达97%,金属化球团的抗压强度达到1035N/个。
揭示了微波作用下铁矿球团煤基还原过程的规律。铁矿氧化球团微波加热煤基还原受CO的内扩散控制；当还原气氛不足,铁矿颗粒碎裂后未能快速还原而形成浑圆状FeO并快速长大,当存在Si02时,形成了大量的FeSiO3,阻碍还原进行。
研究了预还原球团微波加热煤基直接还原新工艺。铁矿氧化球团经预还原后,结构疏松、孔隙发达、体积膨胀小,具有较高的抗压强度；低还原度(金属化率<40%)预还原球团微波加热煤基还原时,表层铁氧化物快速还原形成金属铁壳,阻碍了中心铁氧化物快速还原；对于较高还原度(金属化率>40%)预还原球团微波加热煤基直接还原,球团结构疏松、孔隙发达,提高了CO/CO2扩散速率,加快了铁氧化物还原反应,缩短了还原时间,提高了生产率。当还原度66.90%的预还原球团118g,微波功率1.3kW,配碳量/球团量为0.22,温度上升到1050℃时,球团的还原度和金属化率分别达到94.29%和88.23%。
采用Φ120mm连续式微波竖炉进行了铁矿球团微波加热煤基直接还原中试研究。结果表明：以氧化球团和无烟煤为原料,在温度1050℃,时间65min时,球团金属化率和生产率分别为95.25%和4.08kg/h；以金属化率42.85%的预还原球团和无烟煤为原料,在温度1050℃,时间41min时,球团金属化率和生产率分别为97.68%和6.33kg/h,高温还原时间缩短了36.92%,生产率提高了55.15%。
The traditional iron and steel production has the disadvantages of long process, great investment, high energy consumption and serious pollution issues. Further more, coking coal is increasingly exhausted. Therefore, the development of a new process, which makes the iron making process replacement of coke by coal, energy saving, environment protecting, high-efficiency and compact, has important strategic meanings. In this research, iron ore pellets and anthracite are taken as the objects to investigate the fundamental and technical research of pellets for coal-based direct reduction by microwave heating. The main innovations and conclusions obtained are as follows:
The electromagnetic properties of iron ore pellets and coal, as well as the temperature rising characteristics of microwave heating were studied. The descending order of temperature rising rate of briquettes is Fe3O4>FeO≈Fe2O3≈oxide pellets>Fe. Phase and microstructure of iron ore pellets are changed by microwave heating, activity of iron oxide increases and reduction reaction is promoted. In microwave field, due to the strong absorption ability, anthracite has the dual role of both reducing agent and heating element in microwave field and gasification rate of fixed carbon is increased.
The microstructure and physical phase of iron ore pellets during microwave heating coal-based direct reduction process were researched detailedly by using advanced testing methods, such as optical microscope, SEM, and XRD. It is found that fragmentations appear under the action of microwave and the reduction reaction of iron oxide is promoted. Inner stress is caused due to change of crystal lattice. And the volume of pellet expands. The expansion volume peaks when the reduction degree and temperature is43.06%and850℃and the lowest value of pellet compressive strength is320N/P. Metallic iron increases when the pellets are further reduced; followed with crystal grains migrate, gather and grow. The compressive strength of metallized pellets with a reduction degree of97%is1035N/P after50min of heating at 1050℃。
The restrictive step of coal-based direct reduction of iron ore pellets under the action of microwave is revealed. Microwave heating coal-based direct reduction of oxide pellets is limited by internal diffusion of CO. When the reducing atmosphere is insufficient, FeO with an irregularly perfectly round is formed and grows since iron ore grain is not reduced rapidly after cracking. Lots of FeSiO3forms with the existence of SiO2, and reduction reaction is resisted.
A new iron making process using pre-reduced iron ore pellets by microwave heating has been investigated. The pre-reduced pellet has loose structure, developed pore, small volumetric expansion and high compressive strength. The reduction of center of pre-reduced pellets with lower reduction degree (metallization rate<40%) is limited by the formation of metallic iron shell. The reduction of pre-reduced pellets with higher reduction degree (metallization rate>40%) is promoted because of the higher CO/CO2diffusion rate. The reduction degree and metallization rate are94.29%and88.23%when118g pre-reduced pellets with a reduction degree of66.90%are reduced at1050℃and the power of microwave is1.3kW and ratio of carbon/pellet is0.22.
The study of microwave heating coal-based direct reduction of iron ore pellets was put forward using a φ120mm pilot-sized continuous microwave shaft furnace. The results indicate that the metallization rate and productivity of oxidized pellets is95.25%and4.08kg/h, respectively after65min of reduction at1050℃; the metallization rate and productivity of pre-reducted pellets with a metallization rate of42.85%is97.68%and6.33kg/h, respectively with41min of reduction at1050℃. The reduction time is shortened by36.92%and the productivity increased by55.15%.
研究了铁矿球团和煤的电磁性能及其微波加热升温特性。球团或团块的升温速度快慢顺序是：Fe3O4>FeO≈Fe2O3≈氧化球团>Fe粉；在微波作用下铁矿球团物相及其结构产生了改变,铁氧化物反应活性增强,促进了铁氧化物的还原。无烟煤在微波场中强烈吸收微波,具有还原剂和发热体双重作用,加快了固定碳的气化反应。
采用光学显微镜、XRD和SEM等现代测试技术研究了铁矿球团微波加热煤基非等温还原过程物相和显微结构变化。结果表明,微波作用下球团中的颗粒出现碎裂,促进了铁氧化物还原反应,以及晶格发生变化而产生内应力,造成球团膨胀。当升温到850℃,还原度为43.06%时膨胀率最大,球团强度最低为320N/个,进一步还原时金属铁增多,铁晶粒迁移、聚集、长大,温度上升到1050℃并恒温50min时,球团的还原度达97%,金属化球团的抗压强度达到1035N/个。
揭示了微波作用下铁矿球团煤基还原过程的规律。铁矿氧化球团微波加热煤基还原受CO的内扩散控制；当还原气氛不足,铁矿颗粒碎裂后未能快速还原而形成浑圆状FeO并快速长大,当存在Si02时,形成了大量的FeSiO3,阻碍还原进行。
研究了预还原球团微波加热煤基直接还原新工艺。铁矿氧化球团经预还原后,结构疏松、孔隙发达、体积膨胀小,具有较高的抗压强度；低还原度(金属化率<40%)预还原球团微波加热煤基还原时,表层铁氧化物快速还原形成金属铁壳,阻碍了中心铁氧化物快速还原；对于较高还原度(金属化率>40%)预还原球团微波加热煤基直接还原,球团结构疏松、孔隙发达,提高了CO/CO2扩散速率,加快了铁氧化物还原反应,缩短了还原时间,提高了生产率。当还原度66.90%的预还原球团118g,微波功率1.3kW,配碳量/球团量为0.22,温度上升到1050℃时,球团的还原度和金属化率分别达到94.29%和88.23%。
采用Φ120mm连续式微波竖炉进行了铁矿球团微波加热煤基直接还原中试研究。结果表明：以氧化球团和无烟煤为原料,在温度1050℃,时间65min时,球团金属化率和生产率分别为95.25%和4.08kg/h；以金属化率42.85%的预还原球团和无烟煤为原料,在温度1050℃,时间41min时,球团金属化率和生产率分别为97.68%和6.33kg/h,高温还原时间缩短了36.92%,生产率提高了55.15%。
The traditional iron and steel production has the disadvantages of long process, great investment, high energy consumption and serious pollution issues. Further more, coking coal is increasingly exhausted. Therefore, the development of a new process, which makes the iron making process replacement of coke by coal, energy saving, environment protecting, high-efficiency and compact, has important strategic meanings. In this research, iron ore pellets and anthracite are taken as the objects to investigate the fundamental and technical research of pellets for coal-based direct reduction by microwave heating. The main innovations and conclusions obtained are as follows:
The electromagnetic properties of iron ore pellets and coal, as well as the temperature rising characteristics of microwave heating were studied. The descending order of temperature rising rate of briquettes is Fe3O4>FeO≈Fe2O3≈oxide pellets>Fe. Phase and microstructure of iron ore pellets are changed by microwave heating, activity of iron oxide increases and reduction reaction is promoted. In microwave field, due to the strong absorption ability, anthracite has the dual role of both reducing agent and heating element in microwave field and gasification rate of fixed carbon is increased.
The microstructure and physical phase of iron ore pellets during microwave heating coal-based direct reduction process were researched detailedly by using advanced testing methods, such as optical microscope, SEM, and XRD. It is found that fragmentations appear under the action of microwave and the reduction reaction of iron oxide is promoted. Inner stress is caused due to change of crystal lattice. And the volume of pellet expands. The expansion volume peaks when the reduction degree and temperature is43.06%and850℃and the lowest value of pellet compressive strength is320N/P. Metallic iron increases when the pellets are further reduced; followed with crystal grains migrate, gather and grow. The compressive strength of metallized pellets with a reduction degree of97%is1035N/P after50min of heating at 1050℃。
The restrictive step of coal-based direct reduction of iron ore pellets under the action of microwave is revealed. Microwave heating coal-based direct reduction of oxide pellets is limited by internal diffusion of CO. When the reducing atmosphere is insufficient, FeO with an irregularly perfectly round is formed and grows since iron ore grain is not reduced rapidly after cracking. Lots of FeSiO3forms with the existence of SiO2, and reduction reaction is resisted.
A new iron making process using pre-reduced iron ore pellets by microwave heating has been investigated. The pre-reduced pellet has loose structure, developed pore, small volumetric expansion and high compressive strength. The reduction of center of pre-reduced pellets with lower reduction degree (metallization rate<40%) is limited by the formation of metallic iron shell. The reduction of pre-reduced pellets with higher reduction degree (metallization rate>40%) is promoted because of the higher CO/CO2diffusion rate. The reduction degree and metallization rate are94.29%and88.23%when118g pre-reduced pellets with a reduction degree of66.90%are reduced at1050℃and the power of microwave is1.3kW and ratio of carbon/pellet is0.22.
The study of microwave heating coal-based direct reduction of iron ore pellets was put forward using a φ120mm pilot-sized continuous microwave shaft furnace. The results indicate that the metallization rate and productivity of oxidized pellets is95.25%and4.08kg/h, respectively after65min of reduction at1050℃; the metallization rate and productivity of pre-reducted pellets with a metallization rate of42.85%is97.68%and6.33kg/h, respectively with41min of reduction at1050℃. The reduction time is shortened by36.92%and the productivity increased by55.15%.
引文
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