Research Status of Sulfur Containing Iron Materials Desulfurization Technology
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摘要:
硫在含铁物料的开发利用中是有害杂质元素，因此需要脱除。本文介绍了含铁物料中硫的来源、产出特征与危害，归纳了以浮选法、焙烧法、浸出法处理含铁物料脱硫的技术现状，介绍了此3种脱硫方法的适用条件、应用特色，并比较了各自的优缺点。展望未来含硫铁物料脱硫研究与发展方向，指出浮选法需合理选择磨选流程和药剂制度，注重铜离子复合活化剂、黄药类组合捕收剂提高浮选脱硫指标；焙烧法根据含硫矿物组成和热力学性质选择合适的焙烧炉型、筛选适宜的热工制度；生物浸出应结合多形态硫元素的迁移演变特征，培育良性高效菌种、实施短周期高效浸出，以实现高效脱硫。
Abstract:Sulfur is a harmful impurity element that needs to be removed in the development and utilization of iron-containing materials. The sources, occurrence characteristics and hazards of sulfur in iron-containing materials were introduced successively. The technical status of desulfurization of iron-containing materials from three aspects of flotation, roasting and hydrometallurgy was summarized in proper sequence. Moreover, the applicable conditions and application characteristics of these three desulfurization methods were discussed and the advantages and disadvantages of each other were compared. Looking forward to the future research and development direction of sulfur-containing iron material desulfurization, it is pointed out that the flotation method needs to be chosen the grinding flowsheets and reagent systems reasonably, and pay attention to the copper ion composite activator and the xanthate-type composite collector to improve the flotation desulfurization index. The roasting method will be selected the appropriate roaster type and selected the appropriate thermal system according to the composition and thermodynamic properties of sulfur-containing minerals. Biological leaching should be combined the migration and evolution characteristics of multi-form sulfur elements, by cultivating benign and high-efficiency bacteria, and implementing short-period high-efficiency leaching to achieve high-efficiency desulfurization.
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Key words:
- Iron-containing materials /
- Desulfurization /
- Pyrite /
- Oxidation roasting /
- Bioleaching
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表 1 含铁物料中硫的产出与特征
Table 1. Output and characteristics of sulfur in iron-containing materials
硫的形式 硫化物 硫酸盐 自然硫 硫的产出 黄铁矿、磁黄
铁矿、白铁矿绿矾 硫单质 硫的价态 S2-，S- SO42- S 矿物晶体特性 立方体单晶，粒状，致密块状集合体 浅绿色单斜晶体 斜方晶系 可选性 随矿物表面氧化可浮性逐渐降低 高温分解为氧化铁和二氧化硫 高温下与氧强烈作用生成二氧化硫 
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表 2 含硫矿物的性质与浮选药剂制度
Table 2. Nature and flotation agent system of sulfur-containing iron minerals
含硫矿物 化学式 密度 磁性 矿浆pH值 抑制剂 活化剂 捕收剂 黄铁矿
(白铁矿)FeS2 4.9~5.2 弱磁性 酸性，大于11被抑制 石灰、硫化物、淀粉、CMC 硫酸铜，草酸 组合黄药类 磁黄铁矿 Fe1-xS，FeS，
Fe7S84.6~4.7 强磁性矿物 5~6硫酸活化 石灰、有机抑制剂RC 硫化钠、草酸、
硫酸铵、硫酸铜[8]组合黄药类
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表 3 浮选法脱硫工艺研究现状
Table 3. Flotation desulfurization process research status
矿物来源 选别流程 硫的存在形式 原矿/%
TFe S精矿/%
TFe S铁回收率/% 参考文献作者 江西省 两次反浮选粗选 磁黄铁矿
黄铁矿62.36 1.87 64.03 0.39 95.64 张建超[17] 内蒙古 一次粗选四次精选 磁黄铁矿
黄铁矿63.83 1.59 67.59 0.35 96.51 杨峰涛[20] 山东省 一粗一扫混合浮选 磁黄铁矿 44.47 0.536 68.81 0.201 92.23 韩西鹏[21] 安徽省 浮选强磁再磨再浮选 黄铁矿 43.29 20.58 59.00 0.42 42.00 赵忠花[22] 四川省 一段磨矿一段选别 黄铁矿 14.34 0.378 62.85 0.076 48.45 张敏[23] / 一粗二精一扫 磁黄铁矿
黄铁矿41.55 1.59 67.00 0.078 91.88 彭会清[16] 新疆省 一粗三精三扫 磁黄铁矿
黄铁矿
闪锌矿35.65 1.56 67.40 0.29 86.78 卜显忠[24] 山西省 一次粗选反浮选 磁黄铁矿 66.39 0.32 67.35 0.17 86.91 张洋洋[25]
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表 4 含铁物料中4种含硫矿物的热力学性质
Table 4. Hermodynamic properties of four sulfur-bearing minerals in iron-bearing materials
硫化物 PbS ZnS FeS FeS2 着火温度/K(0.1 mm) 827 920 598 熔点/K 1408 升华 >923 1444 沸点/K 1554 1938 无 △H°/(kJ·mol-1) -94.23 -202.90 △G°/(kJ·mol-1) -92.6 -197.90 放出反应热/ (kJ·kg-1) 146.5 172 92.8
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表 5 生物浸出脱硫的机理与特点
Table 5. Mechanism and characteristics of bioleaching desulfurization
浸出方式 反应式及作用机理 影响因素 微生物直接作用 
利用微生物自身的氧化或还原特性,使矿物的某些组分氧化或还原，接着使硫化物溶解氧化Fe3+的浓度及作用机理、电动电位、pH值、微生物代谢产物层等因素对浸出有明显影响。 微生物间接作用 
利用微生物的代谢产物如三价铁为氧化剂浸出金属硫化物、单质硫作为能量在细菌的作用下生成硫酸根据上述影响因素探究强化生物浸出的途径有：添加催化离子、添加表面活性剂、超声波处理、合理利用菌种等。 微生物复合作用 既有微生物直接作用又有间接作用 黄铁矿生物氧化浸出以直接作用为主。
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