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Citations:  Bibtex RefMan EndNote GB/T7714

 ORCID:

Zeng-yi Ma

https://orcid.org/0000-0002-4504-6198

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Journal of Zhejiang University SCIENCE A 2019 Vol.20 No.8 P.564-576

http://doi.org/10.1631/jzus.A1900086


Evolution and distribution characteristics of fluorine during the incineration of fluorine-containing waste in a hazardous waste incinerator


Author(s):  Wen-han Li, Zeng-yi Ma, Jian-hua Yan, Qun-xing Huang, Xu-guang Jiang

Affiliation(s):  State Key Laboratory of Clean Energy Utilization, Institute for Thermal Power Engineering, Zhejiang University, Hangzhou 310027, China

Corresponding email(s):   mazy@zju.edu.cn

Key Words:  Fluorine emission, Hazardous waste incineration, Fluorine-containing waste, Release behavior, Distribution


Wen-han Li, Zeng-yi Ma, Jian-hua Yan, Qun-xing Huang, Xu-guang Jiang. Evolution and distribution characteristics of fluorine during the incineration of fluorine-containing waste in a hazardous waste incinerator[J]. Journal of Zhejiang University Science A, 2019, 20(8): 564-576.

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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%.

I enjoyed reviewing the manuscript. It is important to understand the release behaviors and forms of toxic fluorine. The authors started with introducing the toxicity of fluorine, the importance of studying its release behaviors and distributions, which helped the general reader understand the article. In addition, several techniques and equations have been applied to understand the processes. Overall, this article provided useful information on the understanding the evolution and distribution of fluorine.

危险废物焚烧炉含氟废物焚烧过程中氟的演化及分布特征

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.

关键词:氟污染; 危废焚烧; 含氟废物; 释放特性; 分布特性

Darkslateblue:Affiliate; Royal Blue:Author; Turquoise:Article

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