NaCl-CaCl2熔盐热处理危险废物焚烧飞灰的重金属转化/稳定化研究

Transformation and stabilization of heavy metals in hazardous waste incineration fly ash treated by NaCl-CaCl2 molten salt thermal process

  • 摘要: 利用NaCl-CaCl2混合熔盐体系对危险废物焚烧飞灰进行低温(600~700 ℃)热处理,研究了热处理工艺参数(时间、温度、飞灰/熔盐配比)对产物中重金属迁移规律及浸出特性的影响,以揭示重金属的转化与稳定化机制。研究发现:飞灰中的重金属在熔盐或飞灰所含氯化物(NaCl、KCl等)的作用下发生直接或间接氯化反应,并最终在熔盐相中富集,其余留存于熔渣。熔盐中重金属占比与其本身的挥发性及热处理温度显著相关。飞灰在温度为600 ℃、飞灰与熔盐比为1∶5的条件下熔盐热处理1 h后,Cu、Zn、Cr、Cd、Pb在熔盐中占比分别为84.45%、82.28%、75.35%、93.08%、96.39%,减量63%。硫酸硝酸法熔渣中Cu和Pb浸出率与原灰相比分别下降了88.4%和97.3%,浸出液中未检出Zn、Cd和Cr,满足GB 18598—2019《危险废物填埋污染控制标准》规定限值。醋酸缓冲溶液法熔渣中Cr、Zn、Cd、Cu、Pb的浸出率与原灰相比分别下降了90.5%、99.9%、99.8%、98.4%、79.6%,可通过进一步添加CaO(4%)调配NaCl-CaCl2熔盐体系,提升熔渣中Pb稳定性。

     

    Abstract: The low-temperature (600-700 ℃) heat treatment of hazardous waste incineration fly ash was carried out using a NaCl-CaCl2 mixed molten salt system. The effects of heat treatment process parameters (time, temperature, fly ash/molten salt ratio) on the migration and leaching characteristics of heavy metals in the product were studied to reveal the transformation and stabilization mechanism of heavy metals. The results indicated that heavy metals in fly ash underwent direct or indirect chlorination reactions under the action of molten salt or chlorides (NaCl, KCl, etc.) contained in fly ash, and ultimately accumulated in the molten salt phase, while the rest remained in the slag. The proportion of heavy metals in molten salt was significantly correlated with their volatility and heat treatment temperature. After 1 hour of molten salt heat treatment at a temperature of 600 ℃ and a fly ash to molten salt ratio of 1∶5, the proportions of Cu, Zn, Cr, Cd, and Pb in the molten salt were 84.45%, 82.28%, 75.35%, 93.08%, and 96.39%, respectively, resulting in a 63% reduction in the fly ash volume. The leaching rates of Cu and Pb in the sulfuric acid-nitric acid method slag decreased by 88.4% and 97.3%, respectively, compared to the original ash. Zn, Cd, and Cr were not detected in the leachate, meeting the limit values specified in the Standard for Pollution Control on the Hazardous Waste Landfill (GB 18598-2019). The leaching rates of Cr, Zn, Cd, Cu, and Pb in the slag produced by the acetic acid buffer solution method decreased by 90.5%, 99.9%, 99.8%, 98.4%, and 79.6%, respectively, compared to the original ash. The stability of Pb in the slag can be improved by further adding CaO (4%) to the NaCl-CaCl2 molten salt system.

     

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