低品位微细粒赤铁矿高效富集技术及机理研究
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摘要
随着我国钢铁工业的快速发展,国内各大钢铁企业铁矿石的进口量逐年上升,2009年进口铁矿石6.28亿吨,对进口矿依存度高达69.2%。然而,我国大量的低品位赤铁矿资源由于铁品位低、铁矿物嵌布粒度细小、嵌布关系复杂,常规方法无法有效选别而尚未得到有效利用。在铁矿石价格大幅上涨及我国铁矿资源严重短缺的背景下,采用预选富集-直接还原-磁选新技术对低品位微细粒铁矿的高效利用进行研究,对我国钢铁工业的发展具有十分重要的意义。
本文对涟钢提供的低品位微细粒嵌布赤铁矿高效富集技术及机理进行研究,最佳工艺参数如下：铁品位27.23%Fe的原矿在磨矿细度小于0.074mm占88.72%,pH调整剂NaOH用量200g/t(pH=9.4),抑制剂淀粉用量1000g/t,捕收剂十二胺用量200g/t的条件下,预选粗精矿球团在含钙复合添加剂用量12%,还原温度1200℃,还原时间120min,煤矿质量比2.5的条件下,还原焙烧矿在磨矿细度小于0.043mm占89.20%,磁场强度0.08T的条件下,得到精矿铁品位88.31%Fe,金属化率94.45%,全流程铁回收率69.92%的优质铁精矿。结果表明,含钙复合添加剂能有效改善还原焙烧产品的金属化率,大幅度提高磁选精矿铁品位,铁作业回收率提高1.42个百分点。
对预选粗精矿球团等温还原动力学进行了研究。结果表明,在还原温度900-1050℃范围,还原时间120min,以CO／N2=30／70为还原气体的条件下进行还原,无添加剂球团和含钙复合添加剂球团均受内扩散控制,但含钙复合添加剂使球团直接还原的表观活化能由18.10KJ·mol-1下降到10.15 KJ.mol-1,表观活化能下降幅度达43.92%。表观活化能越低,还原反应越容易进行,即含钙复合添加剂球团的还原性优于无添加剂球团的还原性。
对预选粗精矿球团还原过程金属铁晶粒生长动力学进行了研究。结果表明：在还原温度1000-1200℃,还原时间5-120mmin范围内,无添加剂球团和含钙复合添加剂球团的金属铁晶粒生长速率常数分别为1.155(μm)2·min-1和1.397(μm)2·min-1。无添加剂球团铁晶粒生长表观活化能分别为132.53 KJ·mol-1,含钙复合添加剂球团晶粒生长表观活化能93.27 KJ.mol-1。在还原过程中,含钙复合添加剂在还原诱导期能够快速形成金属铁晶核,诱导晶核周围铁晶粒向晶核扩散、迁移；在还原生长期能够促进晶核周围铁晶粒向晶核扩散、迁移,形成晶粒平均尺寸较大的铁晶粒。在还原稳定期能够不断完善晶粒的晶格缺陷,使晶格结构趋于稳定。铁晶粒的长大有利于其在磨矿时单体解离,降低磨矿成本,提高磁选铁精矿品位和回收率。
With the rapid development of iron and steel industry in China, the demand for imported iron ores has been greatly growing all over the country. In 2009,the import of iron ores was 628 Million tons and the dependence degree had increased to 69.2%.However, large quantities of low grade iron resources are not utilized by conventional beneficiation methods because of low grade iron, main valuable mineral hematite occurring at superfine size and disseminated with gangue minerals.It is significantly important to the development of China iron and steel industry to take the technology of preliminarily upgrade-direct reduction-intensity magnetic separation to treat those resources in the background of the price of iron ores increasing and the reserves of iron resources decreasing in China.
In this paper, the process and mechanism of effective beneficiation on the superfine low grade hematite from Lianyuan steel have been studied.The results show that the final iron concentrate,assaying 88.31% Fe and 94.45% metallization degree was obtained at the iron overall recovery of 69.92% under the conditions of grinding fineness of reduced product at 89.20% passing 0.043mm and magnetic separation at 0.08T field intensity, and the reduced product was achieved under the conditions of rough concentrate at 12% with calcium containing complex additive,reducing for 120min at 1200℃and 2.5 coal-to-pellets mass ratio, and the rough concentrate under the conditions of pH=9.4, 100g/t starch,200g/t dodecylamine and grinding fineness of 88.72% passing 0.074mm of 27.23%Fe ROM ores.The results show that the calcium containing complex additive play an important role in enhancing the metallization degree of reduced product, the iron grade and recovery of the final iron concentrate.
The isothermal reduction kinetics of pellets was studied. The results show that the reduction rate of pellets without additive and pellets with calcium containing complex additive are controlled by internal diffusion when the reduction temperature ranges from 900 to 1050℃,and reduction lasts for 120min in CO/N2=30/70 atmosphere.However, the calcium containing complex additive decreased the apparent activation energy of the pellets from 18.10 KJ-mol"1 to 10.15 KJ·mol-1, dropping 43.92% in reducing. The lower the apparent activation energy, the easier the reduction reaction takes place. So the reduction properties of pellets with calcium containing complex additives are better than that of pellets without additive.
The kinetics of metal ferrous grains growth of pellets without additive and pellets with calcium containing complex additive were studied. The results show that the rate constant of grains growth of pellets without additive and pellets with calcium containing complex additive are 1.155(μm)2·min-1 and 1.397(μm)2·min-1 when reducing at 1000℃to 1200℃for 5min to 120min. The apparent activation energy of metal ferrous grains growth of pellets without additive is 132.53 KJ·mol-1,more than that of pellets with calcium containing complex additive with 93.27 KJ·mol-1.The calcium containing complex additive can effectively improve the growth of the metal ferrous grains.In reduction, the calcium containing complex additive can produce metal ferrous nucleus in the induction period, inducing the metal ferrous grains around nucleus diffusion and movement to the nucleus.In growing period, the metal ferrous grains move to the nucleus, producing the bigger size of metal ferrous grains.The lattice defects are improving and the lattice structures are tending to stability in the steady period. The growth of metal ferrous grains can effectively promote the iron grains liberated in milling, decreasing the cost of milling, upgrading the iron degree and the recovery of concentrate.
本文对涟钢提供的低品位微细粒嵌布赤铁矿高效富集技术及机理进行研究,最佳工艺参数如下：铁品位27.23%Fe的原矿在磨矿细度小于0.074mm占88.72%,pH调整剂NaOH用量200g/t(pH=9.4),抑制剂淀粉用量1000g/t,捕收剂十二胺用量200g/t的条件下,预选粗精矿球团在含钙复合添加剂用量12%,还原温度1200℃,还原时间120min,煤矿质量比2.5的条件下,还原焙烧矿在磨矿细度小于0.043mm占89.20%,磁场强度0.08T的条件下,得到精矿铁品位88.31%Fe,金属化率94.45%,全流程铁回收率69.92%的优质铁精矿。结果表明,含钙复合添加剂能有效改善还原焙烧产品的金属化率,大幅度提高磁选精矿铁品位,铁作业回收率提高1.42个百分点。
对预选粗精矿球团等温还原动力学进行了研究。结果表明,在还原温度900-1050℃范围,还原时间120min,以CO／N2=30／70为还原气体的条件下进行还原,无添加剂球团和含钙复合添加剂球团均受内扩散控制,但含钙复合添加剂使球团直接还原的表观活化能由18.10KJ·mol-1下降到10.15 KJ.mol-1,表观活化能下降幅度达43.92%。表观活化能越低,还原反应越容易进行,即含钙复合添加剂球团的还原性优于无添加剂球团的还原性。
对预选粗精矿球团还原过程金属铁晶粒生长动力学进行了研究。结果表明：在还原温度1000-1200℃,还原时间5-120mmin范围内,无添加剂球团和含钙复合添加剂球团的金属铁晶粒生长速率常数分别为1.155(μm)2·min-1和1.397(μm)2·min-1。无添加剂球团铁晶粒生长表观活化能分别为132.53 KJ·mol-1,含钙复合添加剂球团晶粒生长表观活化能93.27 KJ.mol-1。在还原过程中,含钙复合添加剂在还原诱导期能够快速形成金属铁晶核,诱导晶核周围铁晶粒向晶核扩散、迁移；在还原生长期能够促进晶核周围铁晶粒向晶核扩散、迁移,形成晶粒平均尺寸较大的铁晶粒。在还原稳定期能够不断完善晶粒的晶格缺陷,使晶格结构趋于稳定。铁晶粒的长大有利于其在磨矿时单体解离,降低磨矿成本,提高磁选铁精矿品位和回收率。
With the rapid development of iron and steel industry in China, the demand for imported iron ores has been greatly growing all over the country. In 2009,the import of iron ores was 628 Million tons and the dependence degree had increased to 69.2%.However, large quantities of low grade iron resources are not utilized by conventional beneficiation methods because of low grade iron, main valuable mineral hematite occurring at superfine size and disseminated with gangue minerals.It is significantly important to the development of China iron and steel industry to take the technology of preliminarily upgrade-direct reduction-intensity magnetic separation to treat those resources in the background of the price of iron ores increasing and the reserves of iron resources decreasing in China.
In this paper, the process and mechanism of effective beneficiation on the superfine low grade hematite from Lianyuan steel have been studied.The results show that the final iron concentrate,assaying 88.31% Fe and 94.45% metallization degree was obtained at the iron overall recovery of 69.92% under the conditions of grinding fineness of reduced product at 89.20% passing 0.043mm and magnetic separation at 0.08T field intensity, and the reduced product was achieved under the conditions of rough concentrate at 12% with calcium containing complex additive,reducing for 120min at 1200℃and 2.5 coal-to-pellets mass ratio, and the rough concentrate under the conditions of pH=9.4, 100g/t starch,200g/t dodecylamine and grinding fineness of 88.72% passing 0.074mm of 27.23%Fe ROM ores.The results show that the calcium containing complex additive play an important role in enhancing the metallization degree of reduced product, the iron grade and recovery of the final iron concentrate.
The isothermal reduction kinetics of pellets was studied. The results show that the reduction rate of pellets without additive and pellets with calcium containing complex additive are controlled by internal diffusion when the reduction temperature ranges from 900 to 1050℃,and reduction lasts for 120min in CO/N2=30/70 atmosphere.However, the calcium containing complex additive decreased the apparent activation energy of the pellets from 18.10 KJ-mol"1 to 10.15 KJ·mol-1, dropping 43.92% in reducing. The lower the apparent activation energy, the easier the reduction reaction takes place. So the reduction properties of pellets with calcium containing complex additives are better than that of pellets without additive.
The kinetics of metal ferrous grains growth of pellets without additive and pellets with calcium containing complex additive were studied. The results show that the rate constant of grains growth of pellets without additive and pellets with calcium containing complex additive are 1.155(μm)2·min-1 and 1.397(μm)2·min-1 when reducing at 1000℃to 1200℃for 5min to 120min. The apparent activation energy of metal ferrous grains growth of pellets without additive is 132.53 KJ·mol-1,more than that of pellets with calcium containing complex additive with 93.27 KJ·mol-1.The calcium containing complex additive can effectively improve the growth of the metal ferrous grains.In reduction, the calcium containing complex additive can produce metal ferrous nucleus in the induction period, inducing the metal ferrous grains around nucleus diffusion and movement to the nucleus.In growing period, the metal ferrous grains move to the nucleus, producing the bigger size of metal ferrous grains.The lattice defects are improving and the lattice structures are tending to stability in the steady period. The growth of metal ferrous grains can effectively promote the iron grains liberated in milling, decreasing the cost of milling, upgrading the iron degree and the recovery of concentrate.
引文
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