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黄金科学技术 ›› 2020, Vol. 28 ›› Issue (5): 621-636.doi: 10.11872/j.issn.1005-2518.2020.05.128

• 绿色胶凝材料专栏 • 上一篇    下一篇

有色冶金渣制备胶凝材料研究现状与展望

郭利杰1,2(),张雷1,2,李文臣1,2   

  1. 1.矿冶科技集团有限公司,北京 100160
    2.国家金属矿绿色开采国际联合研究中心,北京 102628
  • 收稿日期:2020-07-17 修回日期:2020-08-25 出版日期:2020-10-31 发布日期:2020-11-05
  • 作者简介:郭利杰(1980-),男,河南南乐人,教授,博士,从事矿山充填技术与矿冶固废资源化利用方面的研究工作。guolijie@bgrimm.com
  • 基金资助:
    国家重点研发计划项目“基于有色冶炼渣的绿色充填胶凝材料制备及其性能合作研究”(2017YFE0107000)

Progress and Prospects of the Preparation of Cementitious Materials Based on Nonferrous Metallurgical Slags

Lijie GUO1,2(),Lei ZHANG1,2,Wenchen LI1,2   

  1. 1.BGRIMM Technology Group,Beijing 100160,China
    2.National Centre for International Research on Green Metal Mining,Beijing 102628,China
  • Received:2020-07-17 Revised:2020-08-25 Online:2020-10-31 Published:2020-11-05

摘要:

有色冶金渣是有色金属冶炼的副产品,利用有色冶金渣制备可替代水泥的胶凝材料,是实现有色冶金固废大宗量资源化利用的重要途径之一。本文从有色冶金渣成分与结构特征、潜在的胶凝活性及其评价、活性激发方法、胶凝材料制备工艺和胶结体性能5个方面,系统总结了国内外有关有色冶金渣制备胶凝材料的研究进展和成果。目前有色冶金渣制备胶凝材料以试验研究阶段为主,大规模工业化应用案例较少,究其根本原因是尚未彻底突破有色冶金渣低活性有效激发的瓶颈难题。基于此研究,提出了从源头改变有色冶金渣结构,是破解大宗固废规模化利用的关键,讨论了其制备胶凝材料过程中应深入研究的重要问题,阐明了未来应重点关注的研究方向,加快拓展有色冶金渣胶凝材料制备技术的工业化应用。

关键词: 有色冶金渣, 胶凝材料, 铜渣, 镍渣, 铅锌渣, 活性激发, 水化反应

Abstract:

Nonferrous slag,a by-product of the nonferrous metal smelting process,can be used as a replacement for cement in the preparation of cementitious materials,which is a critical way to utilize large amounts of non-ferrous metallurgical solid waste resources.This study systematically analyzed to shed light on the latest research progress and achievements on the cementitious materials mainly prepared with the non-ferrous metallurgical slags both in China and abroad.Particularly,five aspects are emphasized in this paper,which are the composition and structural characteristics of nonferrous slag,potential cementitious properties,the activation method of slag,the preparation methods of cementitious materials,and the performance of its cemented body,respectively.The results showed as below:First,the mineral composition and structures of nonferrous slag differed widely.The crystallization of silicate mineral is almost complete and has high chemical stability,but the content of the vitreous body is lower.Second,the evaluation method of nonferrous slag potential gelling activity and the activity evaluation criteria are inconsistent.Third,the combination of phase modification and compound activation method could effectively improve the gelling activity of nonferrous slag.Fourth,nonferrous slag cementitious materials has good durability and high-temperature resistance and has certain properties of heavy metal solidification.At present,the preparation of cementitious materials based on nonferrous slag is mainly laboratory-based with few examples of large-scale industrial applications.The fundamental reason is that the problem of low and insufficient activity of nonferrous metallurgical slag has not yet been completely solved.As such,changing the structural characteristics of non-ferrous metallurgical slag is the key to overcoming the obstacles to its large-scale industrial utilization.Followed by this,the paper next discussed some important issues involved in the preparation process of cementitious materials and highlights the importance of the establishment of a non-ferrous metallurgical slag cementing system configuration database,the use of molecular research on simulation optimization of activation methods,and the development of simple and efficient activation methods,all in an effort to hasten the expansion of the future industrial application of non-ferrous slag cementitious materials preparation technology.

Key words: nonferrous slag, cementitious materials, copper slag, nickel slag, lead-zinc slag, activation, hydration reaction

中图分类号: 

  • TU526

图1

不同种类有色冶金渣形貌"

表1

不同类型铜渣化学组成"

冶金渣类型化学成分/%资料来源
SiO2Al2O3Fe2O3CaOMgOSO3Na2O
铜渣33.623.6555.601.121.511.120.37Gupta等[14]
39.147.7630.4813.412.090.461.05Nazer等[15]
38.338.1720.4026.102.140.260.64Nazer等[15]
33.052.7953.456.061.561.890.28Al-Jabri等[16]
34.603.2039.002.205.303.700.60李文臣等[17]
35.466.7138.9311.522.83-0.43李峰[18]
17.886.6456.165.864.660.160.70杜海云等[19]

表2

不同类型镍渣化学组成"

冶金渣类型化学成分/%资料来源
SiO2Al2O3Fe2O3CaOMgOSO3Na2O
电炉镍渣52.276.194.208.7726.93--Yang等[20]
48.653.418.051.3531.28--Qi等[21]
52.653.4111.361.9427.92--齐太山等[22]
高炉镍渣34.618.2642.013.378.86-0.02Wang[23]
30.5426.741.5421.6112.471.58-齐太山等[22]
29.9526.311.5525.318.930.851.01Huang等[24]

表3

不同类型铅锌渣化学组成"

冶金渣类型化学成分/%资料来源
SiO2Al2O3Fe2O3CaOMgONa2OSO3
铅锌渣27.107.6535.3017.954.70--Nath[25]
30.677.2729.7312.483.270.723.06Zhang等[26]
18.484.0410.906.300.510.264.20史采星等[27]
30.767.2830.0911.801.931.652.41Xia等[28]

图2

典型有色冶金渣化学成分分布"

图3

不同种类有色冶金渣矿物组成[27,30-31]"

图4

中钙复合体系微粉XRD图谱[38]"

图5

不同粉磨时间铜渣状态[45]"

图6

研磨时间对铜渣强度和比表面积的影响[45]"

图7

Glukhovsky机理模型[55]"

图8

有色冶金渣水淬粒化系统[56]1-水箱;2-水箱盖;3-受渣管;4-管道进水;5-排水管;6-感应炉"

图9

增钙水淬后玻璃相结构示意图[56]"

图10

有色冶金渣胶凝材料制备方法"

图11

复合胶凝材料水化放热曲线[68]GGBS5-50%水泥+50%矿粉;BFFN3-70%水泥+30%高炉镍铁渣;BFFN5-50%水泥+50%高炉镍铁渣"

图12

不同掺量铜渣砂浆抗压强度[71]注:掺量为铜渣用量与水泥的质量比"

图13

水泥和碱激发铜渣砂浆中碱集料反应膨胀现象随时间的发展[74]注:图中A4S1.5表示碱掺量为4%,水玻璃模数为1.5,其他依此类推;OPC为水泥"

图14

高温下碱激发铜渣及水泥铜渣砂浆质量损失[30]CCM0-水泥;CCM5-95%水泥+5%铜渣;CCM10-90%水泥+10%铜渣;CCM15-85%水泥+15%铜渣;AACM6-碱激发铜渣,碱浓度为6 M;AACM8-碱激发铜渣,碱浓度为8 M;AACM10-碱激发铜渣,碱浓度为10 M;AACM12-碱激发铜渣,碱浓度为12 M"

图15

固化样品中重金属的浸出浓度[28]"

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