Heavy Metals in Pyrolysis of Contaminated Wastes: Phase Distribution and Leaching Behaviour

Erlend Sørmo, Gabrielle Dublet-Adli, Gladys Menlah, Gudny Øyre Flatabø, Valentina Zivanovic, Per Carlsson, Åsgeir Almås, Gerard Cornelissen
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Abstract

Pyrolysis is a recognized alternative for the sustainable management of contaminated organic waste, as it yields energy-rich gas, oil, and a carbon-rich biochar product. Low-volatility compounds, however, such as heavy metals (HMs; As, Cd, Cu, Cr, Ni, Pb, and Zn) typically accumulate in biochars, limiting their application potential, especially for soil improvement. The distribution of HMs in pyrolysis products is influenced by treatment temperature and the properties of both the HMs and the feedstock. There is a significant knowledge gap in our understanding of the mass balances of HMs in full-scale industrial pyrolysis systems. Therefore, the fate of HMs during full-scale relevant pyrolysis (500–800 °C) of seven contaminated feedstocks and a clean wood feedstock were investigated for the first time. Most of the HMs accumulated in the biochar (fixation rates (FR) >70%), but As, Cd, Pb, and Zn partly partitioned into the flue gas at temperatures ≥ 600 °C, as demonstrated by FRs of <30% for some of the feedstocks. Emission factors (EFs, mg per tonne biochar produced) for particle-bound HMs (<0.45 µm) were 0.04–7.7 for As, 0.002–0.41 for Cd, 0.01–208 for Pb, and 0.09–342 for Zn. Only minor fractions of the HMs were found in the condensate (0–11.5%). To investigate the mobility of HMs accumulated in the biochars, a novel leaching test for sustained pH drop (at pH 4, 5.5 and 7) was developed. It was revealed that increasing pyrolysis temperature led to stronger incorporation of HMs in the sludge-based biochar matrix: after pyrolysis at 800 °C, at pH 4, <1% of total Cr, Cu, Ni, and Pb and < 10% of total As and Zn contents in the biochars were leached. Most interestingly, the high HM mobility observed in wood-based biochars compared to sewage-sludge-based biochars indicates the need to develop specific environmental-management thresholds for soil application of sewage-sludge biochars. Accordingly, more research is needed to better understand what governs the mobility of HMs in sewage-sludge biochars to provide a sound basis for future policy-making.
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受污染废物热解过程中的重金属:相分布和浸出行为
热解是一种公认的可持续管理受污染有机废物的替代方法,因为它可以产生富含能量的气体、油和富含碳的生物炭产品。然而,低挥发性化合物,如重金属(HMs;As、Cd、Cu、Cr、Ni、Pb 和 Zn)通常会在生物炭中累积,限制了其应用潜力,尤其是在土壤改良方面。热解产物中 HMs 的分布受处理温度以及 HMs 和原料特性的影响。我们对大规模工业热解系统中 HMs 质量平衡的了解还存在很大的差距。因此,我们首次研究了七种受污染原料和一种清洁木材原料在全规模相关热解(500-800 °C)过程中 HMs 的去向。大部分 HMs 在生物炭中积累(固定率 (FR) >70%),但 As、Cd、Pb 和 Zn 在温度≥ 600 °C 时部分进入烟道气中,部分原料的固定率 <30%。颗粒结合的 HMs(小于 0.45 微米)的排放因子(EF,毫克/吨生物炭)分别为:As 0.04-7.7、Cd 0.002-0.41、Pb 0.01-208、Zn 0.09-342。冷凝液中只发现了少量的 HMs(0-11.5%)。为了研究生物沼渣中积累的 HMs 的流动性,开发了一种新型的持续 pH 值下降(pH 值为 4、5.5 和 7)浸出试验。结果表明,提高热解温度会使 HMs 更强地融入以污泥为基础的生物炭基质中:在 800 °C 高温热解后,pH 值为 4 时,生物炭中的 Cr、Cu、Ni 和 Pb 总含量小于 1%,As 和 Zn 总含量小于 10%。最有趣的是,与污水污泥生物沼渣相比,在木质生物沼渣中观察到的 HM 移动性较高,这表明有必要为污水污泥生物沼渣在土壤中的应用制定特定的环境管理阈值。因此,需要开展更多的研究,以更好地了解污水污泥生物沼渣中的 HMs 移动性,从而为未来的政策制定提供坚实的基础。
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