The thermal degradation of decabromodiphenyl ether (BDE-209) was studied at the temperature range of 400~600℃. The types and contents of its degradation products were determined using GC and GC/MS techniques. The effects of temperature, time, and alkaline- and sulfur-containing compounds on the thermal degradation of BDE-209, as well as the formation of brominated dioxins, were discussed in this study. The results showed that both temperature and time were the two key factors for both the thermal degradation of BDE-209 and the formation of brominated dioxins. When BDE-209 was pyrolyzed at 450℃ for 40minutes, the brominated dioxins were generated to the maximum extent. The types of the products confirmed that alkaline compounds promoted the thermal degradation of BDE-209 by reaction with HBr formed from the BDE-209 debromination, and inhibited the formation of dioxins. Similarly, the sulfur compounds also promoted the degradation of BDE-209 and inhibited the formation of dioxins. However, the detailed inhibition mechanism needs to be further investigated in the future study. There are two kinds of degradation reactions for BDE-209, namely, debromination of phenyl rings and cleavage of ether bond. This research may provide a theoretical basis for the safe disposal of BDE-209-contained products and the reduction of secondary pollution.
刘芃岩, 高兰, 张雅婧, 李占圣, 李牧原. 碱性及含硫化合物对十溴联苯醚热降解的影响[J]. 中国环境科学, 2020, 40(6): 2658-2663.
LIU Peng-yan, GAO Lan, ZHANG Ya-jing, LI Zhan-sheng, LI Mu-yuan. Influence of alkaline and sulfur-containing compounds on the thermal degradation of decabromodiphenyl ether. CHINA ENVIRONMENTAL SCIENCECE, 2020, 40(6): 2658-2663.
Huang Y, Zhang D, Yang Y, et al.Distribution and partitioning of polybrominated diphenyl ethers in sediments from the Pearl River Delta and Guiyu, South China [J].Environmental Pollution, 2018,235: 104-112.
[2]
English K, Toms L-M L, Gallen C, et al.BDE-209 in the Australian Environment: Desktop review [J].Journal of Hazardous Materials, 2016,320:194-203.
[3]
韦朝海,廖建波,刘浔,等.PBDEs的来源特征、环境分布及污染控制[J].环境科学学报, 2015,35(10):3025-3041. Wei C, Liao J, Liu X, et al.Source, characteristics, environmental distribution and pollution control of PBDEs [J].Acta Scientiae Circumstantiae, 2015,35(10):3025-3041.
[4]
赵金平,何群华,钟英立,等.典型电子垃圾拆解区二噁英污染特征、相分配及暴露风险[J].生态环境学报, 2014,23(8):1338-1343. Zhao J, He Q, Zhong Y, et al.Pollution characteristics, gas/particle partitioning and inhalation risk assessment of dioxin in the typical E-waste dismantling region [J].Ecology and Environmental, Sciences, 2014,23(8):1338-1343.
[5]
Zennegg M, Schluep M, Streicher-Porte P, et al.Formation of PBDD/F from PBDE in electronic waste in recycling processes and under simulated extruding conditions Markus [J].Chemosphere, 2014, 116:34-39.
[6]
苍大强,魏汝飞,张玲玲,等.钢铁工业烧结过程二噁英的产生机理与减排研究进展[J].钢铁, 2014,49(8):1-8. Cang D, Wei R, Zhang L, et al.Formation mechanism and emission reduction of PCDD/Fs in iron ore sintering [J].Iron & Steel, 2014,49(8):1-8.
[7]
Ebert J, Bahadir M.Formation of PBDD/F from flame-retarded plastic materials under thermal stress [J].Environment International, 2003, 29(6):711-716.
[8]
Ortuño N, Lundstedt S, Lundin L.Emissions of PBDD/Fs, PCDD/Fs and PBDEs from ?ame-retarded high-impact polystyrene under thermal stress [J].Chemosphere, 2015,123:64-70.
[9]
Brian K, Barbara W, Emanuela G, et al.PCDD/F, PBDD/F, and PBDE Emissions from Open Burning of a Residential Waste Dump [J].Environmental science & technology, 2010,44(1):394-399.
[10]
冯涛,严建华,李晓东,等.典型废弃物焚烧炉飞灰中溴代二噁英和呋喃的分析研究[J].环境污染与防治, 2011,33(5):40-49. Feng T, Yan J, Li X, et al.Analytical research on the PBDD/Fs in typical waste incinerators flyash [J].Environmental Pollution & Control, 2011,33(5):40-49.
[11]
Altarawneh M, Dlugogorski B Z.A Mechanistic and Kinetic Study on the Formation of PBDD/Fs from PBDEs [J].Environmental science & technology, 2013,47(10):5118-5127.
[12]
Altarawneh M, Saeed A, Al-Harahsheh M, et al.Thermal decomposition of brominated flame retardants (BFRs): Products and mechanisms [J].Progress in Energy and Combustion Science, 2019, 70:212-259.
[13]
Mei J, Wang X, Xiao X, et al.Characterization and inventory of PBDD/F emissions from deca-BDE, polyethylene (PE) and metal blends during the pyrolysis process [J].Waste Management, 2017,62: 84-90.
[14]
Zhang M, Buekens A, Li X.Brominated flame retardants and the formation of dioxins and furans in fires and combustion [J].Journal of Hazardous Materials, 2016,304:26-39.
[15]
刘芃岩,张雅婧,张彦娜,等.十溴联苯醚的热解及其影响因素研究[J].中国环境科学, 2016,36(4):1099-1105. Liu P, Zhang Y, Zhang Y, et al.Pyrolysis and its influence factors of decabromodiphenyl ether [J].China Environmental Science, 2016, 36(4):1099-1105.
[16]
Cai C Y, Yu S Y, Liu Y, et al.PBDE emission from E-wastes during the pyrolytic process: Emission factor, compositional profile, size distribution, and gas-particle partitioning [J].Environmental Pollution, 2018,235:419-428.
[17]
Cai C Y, Chen L Y, Huang H J, et al.Effects of temperature on the emission of particulate matter, polycyclic aromatic hydrocarbons, and polybrominated diphenyl ethers from the thermal treatment of printed wiring boards [J].Journal of Hazardous Materials, 2019,380:120849.
[18]
Jin Y, Tao L, Chi Y, et al.Conversion of bromine during thermal decomposition of printed circuit boards at high temperature [J].Journal of Hazardous Materials, 2011,186(1):707-712.
[19]
Jung S-H, Kim S-J, Kim J-S.Thermal degradation of acrylonitrile-butadiene-styrene (ABS) containing flame retardants using a fluidized bed reactor: The effects of Ca-based additives on halogen removal [J].Fuel Processing Technology, 2012,96:265-270.
[20]
Sun J, Wang W, Liu Z, et al.Study of the transference rules for bromine in waste printed circuit boards during microwave-induced pyrolysis [J].Journal of the Air & Waste Management Association [J].2011,61(5):535-542.
[21]
Terakado O, Ohhashi R, Hirasawa M.Thermal degradation study of tetrabromobisphenol A under the presence metal oxide: Comparison of bromine fixation ability [J].Journal of Analytical and Applied Pyrolysis 2011,91(2):303-309.
[22]
Griffin R D.A new theory of dioxin formation in municipal solid waste combustion [J].Chemosphere, 1986,15(9-12):1987-1990.
[23]
Gullett B K, Bruce K R, Beach L O.Effect of sulfur-dioxin on the formation mechanism of poly-chlorinated dibenzodionxin and dibenzofuran in municipal waste combustors [J].Environmental Science & Technology, 1992,26(10):1938-1943.
[24]
Raghunathan K, Gullett B K.Role of sulfur in reducing PCDD and PCDF formation [J].Environmental Science & Technology, 1996, 30(6):1827-1834.
[25]
Ryan S P, Li X, Gullett B K, et al.Experimental study on the effect of SO2on PCDD/F emissions: determination of the importance of gas-phase versus solid-phase reactions in PCDD/F formation [J].Environmental Science & Technology, 2006,40(22):7040-7047.