Abstract
In this study, the evolution and distribution of fluorine during the incineration of fluorine-containing waste in a hazardous waste incinerator were investigated. The evolution characteristics of fluorine during the pyrolysis of the waste were investigated using thermogravimetric analyzer coupled with Fourier transform infrared spectroscopy (TG-FTIR) analysis. The distribution of fluorine in the incineration systems and its form in the incineration residues were studied under two operating conditions. The results showed that fluorine in the waste had strong volatility and hydrogen fluoride (HF) and silicon fluoride (SiF4) were detected as the first fluorine compounds to be released during pyrolysis. The release of HF could be divided into three temperature ranges: 123.5–757.5 °C, 757.5–959.6 °C, and >959.6 °C. The emission of HF between 123.5 °C and 757.5 °C involved loosely bonded organic fluorine and ionic inorganic fluorine, while the HF released between 757.5 °C and 959.6 °C was caused by the crack of fixed carbon and further dehydroxylation, and the HF released above 959.6 °C was due to the decomposition of inorganic minerals. The emission of SiF4 was mainly concentrated between 132.6 °C and 684.0 °C, and almost no SiF4 was emitted from the waste above 684.0 °C. Less than 20.73% of the fluorine was retained in the incineration residues and over 79.17% of fluorine was absorbed in the absorbent solution of a wet flue gas desulfurization (WFGD) system. The amount of fluorine discharged into the atmosphere was below 0.12%. The fluorine in the bottom slag and burn-out chamber ash mainly existed in residual form. The proportions of water-soluble, exchangeable, and acid-soluble fluorine in the boiler ash and bag filter ash were both over 80%.
抽象
目 的
含氟废物焚烧过程排放的氟化物会危害人体健 康, 造成环境污染。 本文旨在探究含氟废物焚烧 过程中氟的析出特性、氟在焚烧系统中的分布特 征以及氟在焚烧灰渣中的赋存形态。 这对评估含 氟废物在焚烧过程中造成的氟污染以及污染控 制具有重要意义。
创新点
1. 系统研究了氟在焚烧过程中的释放特征以及氟 在整个焚烧系统中的质量流, 对评估焚烧过程中 的氟污染及污染控制具有重要意义; 2. 系统研究 了焚烧灰渣中氟的赋存形态, 为后续灰渣中氟污 染控制研究奠定基础。
方 法
1. 采用热重红外联用方法, 分析研究含氟废物热 解过程中氟的析出特性 (图 4 和 6); 2. 采用高温 燃烧水解-离子色谱的方法, 测定焚烧灰渣中的氟 含量, 并结合灰渣量等数据, 得到氟在焚烧系统 的分布特征 (图 10 和11); 3. 采用连续化学萃取 法, 得到焚烧灰渣中氟的赋存形态 (图 12 和 13)。
结 论
1. 热解过程中, 含氟废物中氟主要以氟化氢和氟 化硅形式释放; 氟化氢的释放可以分为3 个温度 区: 123.5~757.5 °C、757.5~959.6 °C 及959.6 °C 以上; 氟化硅的释放主要集中在 132.6~684.0 °C。 2. 焚烧过程中, 超过 79.17% 的氟被湿法脱酸系统 吸收, 不到 20.73% 的氟存在于焚烧灰渣中; 排放 到大气中的氟占比小于0.12%。 3. 底渣和燃尽室 灰中的氟主要以残余态存在; 余热锅炉灰和布袋 飞灰中水溶态、交换态和酸溶态氟的比例之和均 在80%以上。
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Project supported by the National Natural Science Foundation Innovation Research Group of China (No. 51621005)
Contributors
Wen-han LI did the experiment and wrote the first draft of the manuscript. Zeng-yi MA put forward overarching research methodology and revised the final version. Jian-hua YAN was responsible for coordinating the research activity planning and execution. Qun-xing HUANG and Xu-guang JIANG revised and edited the final version.
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Wen-han LI, Zeng-yi MA, Jian-hua YAN, Qun-xing HUANG, and Xu-guang JIANG declare that they have no conflict of interest.
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Li, Wh., Ma, Zy., Yan, Jh. et al. Evolution and distribution characteristics of fluorine during the incineration of fluorine-containing waste in a hazardous waste incinerator. J. Zhejiang Univ. Sci. A 20, 564–576 (2019). https://doi.org/10.1631/jzus.A1900086
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DOI: https://doi.org/10.1631/jzus.A1900086