硫酸盐还原活性污泥矿化固定酸性矿山废水中的镉

doi:10.16085/j.issn.1000-6613.2022-2222

摘要/Abstract

摘要：

为了实现硫酸盐生物还原法处理酸性矿山废水（AMD）中镉（Cd）的稳定去除，受自然界硫酸盐还原菌诱导的生物矿化现象启发，以驯化的硫酸盐还原活性污泥为种泥，在上流式厌氧反应器内，通过维持进水浓度比COD/SO $4 2 -$ =2∶1、水力停留时间（HRT）=72h实现了AMD中Cd的稳定矿化，其固化率为100%，且连续36d未见Cd²⁺的溶出；污泥特性分析表明，硫酸盐还原产生的S^2-将废水中的Cd²⁺转移至污泥中，污泥中的Cd则逐步从不稳定态（可交换态、碳酸盐结合态、铁锰氧化态、硫化物结合态）向稳定态（残渣态）转化，并在污泥表面形成大量离群的微米级镉硫矿；微生物群落结构分析表明，反应器中Desulfovibrio、Desulfuromonas、Acinetobacter、Delftia等丰度明显增加，推测协同代谢实现了Cd的稳定矿化。由此表明，硫酸盐还原活性污泥可通过矿化实现AMD中Cd的稳定去除，为AMD的高效处理及资源回收提供了新思路。

关键词: 硫酸盐还原活性污泥, 酸性矿山废水, 镉, 生物矿化, 镉硫矿

Abstract:

To achieve stable removal of cadmium (Cd) from acid mine drainage (AMD) by sulfate-reducing process, inspired by the phenomenon of sulfate-reducing bacteria-induced biomineralization in nature, we used the domesticated sulfate-reducing activated sludge as seed in an upflow anaerobic reactor to achieve the stable mineralization of Cd in AMD by maintaining the concentration ratio of COD to SO $4 2 -$ at 2∶1 and hydraulic retention time (HRT) for 72h. A stable mineralization of Cd²⁺ in AMD with 100% solidification rate and no leaching of Cd²⁺ was observed for a continuous period of 36d. The sludge characterization showed that the S^2- produced by sulfate reduction transferred Cd²⁺ from the wastewater to the sludge, the Cd in the sludge was gradually transformed from the unstable state (exchangeable, carbonate-bound, Fe-Mn-oxidized or sulfide-bound) to stable state (residue), and formed a large amount of isolated micron Cd-sulfide ore on the sludge surface. The microbial community structure analysis showed that the abundance of Desulfovibrio, Desulfuromonas, Acinetobacter and Delftia in the reactor increased significantly, speculating that these bacteria metabolized synergistically to achieve stable mineralization of Cd. This indicates that sulfate-reducing activated sludge can achieve stable removal of Cd from AMD through mineralization, providing a new idea for the efficient and stable removal of heavy metal and resource recovery from AMD.

Key words: sulfate reduction activated sludge, acid mine wastewater, cadmium, biomineralization, cadmium sulfide ore

中图分类号:

X703

王大为, 毕春梦, 秦永丽, 蒋永荣, 谢华宾, 毛宇昆, 苗雪岩. 硫酸盐还原活性污泥矿化固定酸性矿山废水中的镉[J]. 化工进展, 2023, 42(10): 5509-5519.

WANG Dawei, BI Chunmeng, QIN Yongli, JIANG Yongrong, XIE Huabin, MAO Yukun, MIAO Xueyan. Sulfate-reducing activated sludge for immobilization of cadmium in acid mine drainage by mineralization[J]. Chemical Industry and Engineering Progress, 2023, 42(10): 5509-5519.

图/表 8

图1 上流式厌氧反应器

表1 反应器运行操作参数

阶段	运行时间/d	进水COD浓度/mg·L^-1	进水SO₄^2-浓度/mg·L^-1	进水Cd²⁺浓度/mg·L^-1	进水pH	HRT/h
Ⅰ	1~84	3000	1500	80	6.5 ± 0.2	72
Ⅱ	85~175	3000	1500	100	5.5 ± 0.2	72

图2 反应器运行过程中COD、SO42-、VFA和pH的变化情况

图3 反应器运行过程中S2-和Cd2+的变化情况

图4 污泥中Cd的化学形态转化

图5 污泥的SEM-EDS及XRD图谱

图6 污泥中微生物属水平的变化特征

图7 硫酸盐还原活性污泥矿化固定AMD中Cd的机理

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