污泥屏障氧化缓冲容量与重金属再溶出关系研究
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摘要
尾矿堆暴露在自然条件下,其中的硫化矿物不断氧化,产生酸性极强且含有大量重金属的酸性矿山废水(acid mine drainage, AMD),对尾矿堆场周围的土壤和地下水环境造成严重污染。从废弃物包封处置的原理出发,提出了尾矿堆场污泥还原屏障新构想。污泥还原屏障不仅利用污泥的低渗透性阻隔重金属污染,还利用污泥中厌氧微生物导致的还原反应固定重金属污染物,丰富和完善了现有的包封屏障理论与技术。
在风化淋滤条件下形成的AMD溶液,由于自由氧的溶入,表现出比污泥更高的氧化性质。渗入污泥屏障的AMD溶液与污泥发生氧化还原反应,必然会引起污泥屏障向氧化的状态发展。在硫酸盐还原作用下已经固定在污泥中的重金属,可能会由于污泥的氧化而二次释放。本研究的目标是通过实测污泥的氧化缓冲容量,分析污泥氧化缓冲容量的来源,研究氧化缓冲容量消耗过程与重金属溶出之间的关系,模拟计算不同厚度的污泥屏障可以固定重金属的时间,为污泥屏障的实际应用提供理论依据。
本研究首先将污水处理厂污泥与蒸馏水混合,加入营养物质,强化重金属Zn、Cu、Pb的浓度,调节pH值,制备成不同性质的污泥悬液,置于阴暗处水浴恒温厌氧培养。经过一定时间培养后,取一定量的污泥悬液进行氧化滴定实验。在滴定过程中,当悬液Eh值到达一定值时,抽取部分悬液进行化学分析,测定悬液中的重金属含量和主要阴阳离子浓度。通过理论分析法研究污泥氧化缓冲容量的来源以及污泥氧化过程中重金属的释放问题。
实验结果表明,污泥悬液的氧化缓冲容量随着悬液固液比的增大略有减小,随着悬液厌氧培养时间的延长而增加。当污泥进入强烈还原状态后,氧化缓冲容量主要来自Eh≤-150mV的强烈还原区间,可达氧化缓冲容量的50%以上。氧化滴定过程中,当污泥悬液的pH=6.0±0.5,Eh≥-150mV时,Zn首先明显溶出,Eh≥150mV时,Cu和Pb明显溶出；当污泥悬液的pH=5.0±0.5时,目标重金属的溶出量明显要大于pH=6.0±0.5的污泥悬液；当污泥悬液的pH=7.5±0.5时,目标重金属基本不溶出。基于以上实验结果,建立了污泥屏障在AMD渗流条件下氧化缓冲容量消耗的数学模型。模拟计算结果表明,当AMD水头高度为10m时,厚度2m的污泥屏障经历AMD溶液38787a的渗透氧化,仍可保持原有的强烈还原状态,具备对重金属的固定效果。因此,污泥屏障应用于尾矿堆场,具有较强的氧化缓冲容量,可以确保对AMD渗滤液中重金属的长期拦截效果。
Tailings from mining industry can generate acid mine drainage (AMD) containing high-concentration heavy metals. When the sulfide minerals are exposed in an oxidized condition, and result in the contamination of soils and groundwater around the tailings. Benefit from the microbial activities especially the anaerobic sulfate reduction processes, sewage sludge could be used as a barrier to immobilize the heavy metals leached from tailings. Sewage sludge barrier is an enrichment and improvement of the available barriers.
AMD solution, generated from weathering and leaching process, shows a stronger oxidizing capability than the sludge, because of the dissolved of free oxygen in it. Redox reactions between AMD solution and sludge barrier inevitably lead the sludge barrier to an oxidation state. Heavy metals originally immobilized by sulfate reduction in sludge barrier may be released out secondarily because of the oxidation of sludge. The objectives of this research are to analyse the source of the oxidation buffering capacity of sludge, to discuss the relationship between the consumption of oxidation buffer capacity and dissolution of heavy metals, and to calculate the immobilization time of heavy metals in sewage sludge barriers in a simulated thicknesses conditions. This research try to establish a theoretical basis for the practical application of sludge barrier.
At first, specially designed titrations experiments were conducted in this research. Sludge suspensions were prepared by mixing sludge with distilled water, detailed treatment including addition of nutrients, strengthening of the target heavy metals Zn, Cu, Pb, pH adjusting. Followed by an anaerobic cultivation of the sludge suspensions by placing them in water bath with a constant temperature. After anaerobic cultivation for a definite time, a certain quantity of sludge suspension was used for oxidation titration experiment. During the oxidation titration tests, some suspension was taken for chemical analysis at the moment that the Eh of suspension reached a designated Eh value, to determine the concentrations of target heavy metals and inorganic ions in suspension. The source of oxidation buffering capacity (OBC) of sludge and the release characteristics of heavy metals caused by oxidation were discussed based on the test results.
Test results showed that OBC of sludge suspensions was decreased slightly with the solid-liquid ratio of the suspensions, but increased with the anaerobic incubation time. More than 50% of OBC was attributed by the sludge existing in strongly-reduction conditions (Eh≤-150mV). During the oxidation titration tests, it was found that when the pH of sludge was decrease around 6.0±0.5 and Eh≥-150mV, Zn was released obviously, while Cu and Pb released obviously when Eh≥150mV. When the pH of sludge was decrease to 5.0±0.5, the release of target heavy metals were significantly greater than those of pH=6.0±0.5. Especially when the pH of sludge was 7.5±0.5, almost no of heavy metals were found to be released. According to the test results, a mathematical model was established to predict the OBC consumption of the sludge barrier under AMD penetrating conditions. The simulation results showed that a sludge barrier with 2m thickness, even undergone 38787-years oxidation by AMD under 10m water head, keep in a strongly-reduced condition and, therefore, promote an immobilization of heavy metals from AMD in the barrier. As a final conclusions, the sludge barrier can be applied to mine tailings, which has a strong oxidation buffer capacity and ensure a long-term immobilization of heavy metals from AMD solution.
在风化淋滤条件下形成的AMD溶液,由于自由氧的溶入,表现出比污泥更高的氧化性质。渗入污泥屏障的AMD溶液与污泥发生氧化还原反应,必然会引起污泥屏障向氧化的状态发展。在硫酸盐还原作用下已经固定在污泥中的重金属,可能会由于污泥的氧化而二次释放。本研究的目标是通过实测污泥的氧化缓冲容量,分析污泥氧化缓冲容量的来源,研究氧化缓冲容量消耗过程与重金属溶出之间的关系,模拟计算不同厚度的污泥屏障可以固定重金属的时间,为污泥屏障的实际应用提供理论依据。
本研究首先将污水处理厂污泥与蒸馏水混合,加入营养物质,强化重金属Zn、Cu、Pb的浓度,调节pH值,制备成不同性质的污泥悬液,置于阴暗处水浴恒温厌氧培养。经过一定时间培养后,取一定量的污泥悬液进行氧化滴定实验。在滴定过程中,当悬液Eh值到达一定值时,抽取部分悬液进行化学分析,测定悬液中的重金属含量和主要阴阳离子浓度。通过理论分析法研究污泥氧化缓冲容量的来源以及污泥氧化过程中重金属的释放问题。
实验结果表明,污泥悬液的氧化缓冲容量随着悬液固液比的增大略有减小,随着悬液厌氧培养时间的延长而增加。当污泥进入强烈还原状态后,氧化缓冲容量主要来自Eh≤-150mV的强烈还原区间,可达氧化缓冲容量的50%以上。氧化滴定过程中,当污泥悬液的pH=6.0±0.5,Eh≥-150mV时,Zn首先明显溶出,Eh≥150mV时,Cu和Pb明显溶出；当污泥悬液的pH=5.0±0.5时,目标重金属的溶出量明显要大于pH=6.0±0.5的污泥悬液；当污泥悬液的pH=7.5±0.5时,目标重金属基本不溶出。基于以上实验结果,建立了污泥屏障在AMD渗流条件下氧化缓冲容量消耗的数学模型。模拟计算结果表明,当AMD水头高度为10m时,厚度2m的污泥屏障经历AMD溶液38787a的渗透氧化,仍可保持原有的强烈还原状态,具备对重金属的固定效果。因此,污泥屏障应用于尾矿堆场,具有较强的氧化缓冲容量,可以确保对AMD渗滤液中重金属的长期拦截效果。
Tailings from mining industry can generate acid mine drainage (AMD) containing high-concentration heavy metals. When the sulfide minerals are exposed in an oxidized condition, and result in the contamination of soils and groundwater around the tailings. Benefit from the microbial activities especially the anaerobic sulfate reduction processes, sewage sludge could be used as a barrier to immobilize the heavy metals leached from tailings. Sewage sludge barrier is an enrichment and improvement of the available barriers.
AMD solution, generated from weathering and leaching process, shows a stronger oxidizing capability than the sludge, because of the dissolved of free oxygen in it. Redox reactions between AMD solution and sludge barrier inevitably lead the sludge barrier to an oxidation state. Heavy metals originally immobilized by sulfate reduction in sludge barrier may be released out secondarily because of the oxidation of sludge. The objectives of this research are to analyse the source of the oxidation buffering capacity of sludge, to discuss the relationship between the consumption of oxidation buffer capacity and dissolution of heavy metals, and to calculate the immobilization time of heavy metals in sewage sludge barriers in a simulated thicknesses conditions. This research try to establish a theoretical basis for the practical application of sludge barrier.
At first, specially designed titrations experiments were conducted in this research. Sludge suspensions were prepared by mixing sludge with distilled water, detailed treatment including addition of nutrients, strengthening of the target heavy metals Zn, Cu, Pb, pH adjusting. Followed by an anaerobic cultivation of the sludge suspensions by placing them in water bath with a constant temperature. After anaerobic cultivation for a definite time, a certain quantity of sludge suspension was used for oxidation titration experiment. During the oxidation titration tests, some suspension was taken for chemical analysis at the moment that the Eh of suspension reached a designated Eh value, to determine the concentrations of target heavy metals and inorganic ions in suspension. The source of oxidation buffering capacity (OBC) of sludge and the release characteristics of heavy metals caused by oxidation were discussed based on the test results.
Test results showed that OBC of sludge suspensions was decreased slightly with the solid-liquid ratio of the suspensions, but increased with the anaerobic incubation time. More than 50% of OBC was attributed by the sludge existing in strongly-reduction conditions (Eh≤-150mV). During the oxidation titration tests, it was found that when the pH of sludge was decrease around 6.0±0.5 and Eh≥-150mV, Zn was released obviously, while Cu and Pb released obviously when Eh≥150mV. When the pH of sludge was decrease to 5.0±0.5, the release of target heavy metals were significantly greater than those of pH=6.0±0.5. Especially when the pH of sludge was 7.5±0.5, almost no of heavy metals were found to be released. According to the test results, a mathematical model was established to predict the OBC consumption of the sludge barrier under AMD penetrating conditions. The simulation results showed that a sludge barrier with 2m thickness, even undergone 38787-years oxidation by AMD under 10m water head, keep in a strongly-reduced condition and, therefore, promote an immobilization of heavy metals from AMD in the barrier. As a final conclusions, the sludge barrier can be applied to mine tailings, which has a strong oxidation buffer capacity and ensure a long-term immobilization of heavy metals from AMD solution.
引文
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