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松桃地区电解锰渣制备烧结砖的实验研究

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周友连, 黄雷鸣, 姬云波, 左金星, 魏祥松. 松桃地区电解锰渣制备烧结砖的实验研究[J]. 矿产综合利用, 2025, 46(3): 57-64, 96. doi: 10.12476/kczhly.202210200665
引用本文: 周友连, 黄雷鸣, 姬云波, 左金星, 魏祥松. 松桃地区电解锰渣制备烧结砖的实验研究[J]. 矿产综合利用, 2025, 46(3): 57-64, 96. doi: 10.12476/kczhly.202210200665
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ZHOU Youlian, HUANG Leiming, JI Yunbo, ZUO Jinxing, WEI Xiangsong. Preparation of Sintered Brick from Electrolytic Manganese Residue in Songtao[J]. Multipurpose Utilization of Mineral Resources, 2025, 46(3): 57-64, 96. doi: 10.12476/kczhly.202210200665
Citation: ZHOU Youlian, HUANG Leiming, JI Yunbo, ZUO Jinxing, WEI Xiangsong. Preparation of Sintered Brick from Electrolytic Manganese Residue in Songtao[J]. Multipurpose Utilization of Mineral Resources, 2025, 46(3): 57-64, 96. doi: 10.12476/kczhly.202210200665
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松桃地区电解锰渣制备烧结砖的实验研究

  • 中化地质矿山总局地质研究院，北京　100101

  • 基金项目: 国家自然科学基金（52104282）；自然资源部矿区生态修复工程技术创新中心、中化地质矿山总局资源高效清洁利用技术研究团队联合基金（ZHTD202104）
详细信息
    作者简介: 周友连（1985-），女，高级工程师，主要从事矿产资源综合利用研究
    通讯作者: 魏祥松（1963-），男，教授级高工，主要从事选矿技术研究

  • 中图分类号: TD985；X7

Preparation of Sintered Brick from Electrolytic Manganese Residue in Songtao

  • Geology Institute of China Chemical Geology and Mine Bureau, Beijing 100101, China

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    摘要

  • 针对松桃地区的电解锰渣，采用页岩、石灰石和粉煤灰协同电解锰渣制备烧结砖。以松桃地区富含的页岩和石灰石及电厂粉煤灰为配矿原料，协同电解锰渣进行了成型、预热、焙烧实验。结果表明，电解锰渣掺量可为50%～70%，其掺量过高或过低均降低坯块强度。烧制过程中可通过调整温度和时间，使得固体颗粒之间形成有效固相和液相黏结，避免坯块内部应力聚集形成裂纹降低强度。冷却时应避免急冷产生的不均匀收缩和低强度玻璃相。综合考虑推荐配比为电解锰渣∶页岩∶石灰石∶粉煤灰=6∶2∶1∶1，热工制度为预热温度500 ℃，时间30 min。焙烧温度1 000 ℃，时间120 min，随炉冷却，可得平均抗压强度28.84 MPa的焙烧坯块，达到了烧结普通砖MU25的强度指标，坯块浸出毒性也满足污水综合排放标准。该研究为松桃地区电解锰渣的无害化和资源化提供了新的技术思路。

    Aiming at electrolytic manganese residue in Songtao, sintered bricks were prepared by using shale, limestone and fly ash in coordination with electrolytic manganese residue. With the shale and limestone which are rich in Songtao and the fly ash from the local power plant as ore blending materials in coordination with electrolytic manganese residue, the experiments of briquetting, preheating and roasting were carried out. The results show that the dosage of electrolytic manganese residue can be 50%～70%, and the briquet strength will be reduced when the dosage is too high or too low. In the firing process, the effective solid binding and liquid binding can be obtained, and the briquet cracks due to internal stress gathering can be avoided by adjusting the firing temperature and time. The uneven shrinkage and glass phase of low strength resulting from rapid cooling should be avoided during cooling down. The recommended ratio iselectrolytic manganese residue∶shale∶limestone∶fly ash= 6∶2∶1∶1, and the firing system is as follows: preheating temperature 500 ℃, preheating time 30 min, roasting temperature 1 000 ℃, roasting time 120 min, cooling down in a furnace. At this condition, the roasted briquets with the average strength of 28.84 MPa can be obtained, which reaches the MU25 strength index of common sintered brick, and its leaching toxicity also meets the comprehensive standards of sewage discharge. This study provides a new technical idea for the detoxification and recycle of electrolytic manganese residue in Songtao.

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  • 图 1  电解锰渣SEM

    Figure 1. 

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    图 2  电解锰渣热重分析结果

    Figure 2. 

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    图 3  电解锰渣掺量对焙烧坯块抗压强度的影响

    Figure 3. 

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    图 4  电解锰渣掺量与焙烧坯块失重率的关系

    Figure 4. 

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    图 5  预热温度对焙烧坯块抗压强度的影响

    Figure 5. 

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    图 6  预热时间对焙烧坯块抗压强度的影响

    Figure 6. 

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    图 7  焙烧温度对焙烧坯块抗压强度的影响

    Figure 7. 

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    图 8  焙烧时间对焙烧坯块抗压强度的影响

    Figure 8. 

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    图 9  冷却方式对焙烧坯块抗压强度的影响

    Figure 9. 

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    表 1  主要元素组成/%

    Table 1.  Composition of major elements

    原料Al2O3CaOFe2O3MgOMnOSO42-SiO2K2ONa2OLOI
    电解锰渣12.395.124.822.383.0719.8647.482.661.1923.23
    页岩12.222.833.751.435.567.1357.302.671.9010.52
    石灰石0.09354.530.0950.4190.0300.0670.3090.0110.05443.04
    粉煤灰33.545.134.860.760.0410.44750.210.7300.2453.58
    下载: 导出CSV

    表 2  原料配比

    Table 2.  Ratio of raw materials

    序号电解锰渣页岩石灰石粉煤灰
    17111
    26211
    36121
    45311
    55221
    64411
    74141
    84231
    94321
    1071.501.5
    下载: 导出CSV

    表 3  不同原料配比对焙烧坯块强度的影响

    Table 3.  Effect of different raw material ratio on strength of roasted briquet

    序号 原料配比 焙烧块
    抗压强度/
    MPa    		 焙烧过程
    中失重率/
    %
    电解锰渣 页岩 石灰石 粉煤灰
    1 7 1 1 1 21.06 26.27
    2 6 2 1 1 28.84 23.96
    3 6 1 2 1 27.79 21.67
    4 5 3 1 1 40.25 22.21
    5 5 2 2 1 29.08 21.68
    6 4 4 1 1 37.03 20.73
    7 4 1 4 1 8.21 26.47
    8 4 2 3 1 16.66 24.08
    9 4 3 2 1 32.27 21.27
    10 7 1.5 0 1.5 14.42 27.60
    下载: 导出CSV

    表 4  不同配比的烧结坯块浸出毒性检测结果/%

    Table 4.  Test results of leaching toxicity of sintered briquet with different raw material ratio

    序号砷镉钴铬铜铁汞锰镍铅硒锌硫化物氨氮SO42-
    00.115 10.001 91.257 40.048 30.064 50.167 60.000 21 439.363 10.713 30.005 80.130 30.730 3<0.02613.210 280
    10.058 10.000 30.002 60.001 40.000 50.287 80.001 40.314 60.064 10.003 60.012 00.047 90.050.051 250
    20.029 70.000 40.002 40.001 80.000 40.261 50.001 30.016 20.046 30.000 60.010 90.065 00.04<0.021 282
    30.002 70.000 20.002 50.013 30.001 30.252 90.000 90.004 10.05050.001 00.008 00.026 5＜0.02<0.021 372
    40.026 80.000 50.002 40.003 20.004 10.228 50.001 20.007 40.053 30.001 70.006 90.088 2＜0.02<0.021 156
    50.002 40.000 30.002 60.014 20.005 60.225 20.000 90.000 10.050 10.001 80.006 60.027 6＜0.020.2211 200
    60.019 00.000 40.002 30.004 90.002 40.201 70.001 20.006 30.047 80.001 10.008 90.314 3＜0.02<0.021 180
    70.000 30.000 20.005 10.181 50.016 30.513 50.000 10.000 90.140 50.009 90.060 90.019 4＜0.020.12936
    80.000 30.000 30.005 10.128 90.020 70.487 60.000 10.020 10.130 20.009 20.027 20.026 7＜0.020.061 232
    90.002 40.000 40.002 70.021 20.001 40.217 10.001 00.006 60.048 40.000 60.010 00.106 3＜0.020.061 326
    100.458 70.000 80.004 40.001 10.012 10.122 90.000 85.595 90.037 40.003 30.002 90.062 0＜0.020.06956
    下载: 导出CSV

    表 5  固相反应开始温度

    Table 5.  Starting temperature of solid phase reaction

    反应物固相反应产物开始反应的温度/℃
    2CaO+SiO22CaO·SiO2500，510，690
    2MgO+SiO22MgO·SiO2680
    SiO2+Fe2O3Fe2O3在SiO2中的固溶体575
    MgO+Fe2O3MgO·Fe2O3600
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收稿日期:  2022-10-20
刊出日期:  2025-06-25

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