Abstract
The effects of SO2, SO3 on de novo synthesis of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were studied using model fly ashes incorporating copper oxide and activated carbon. It was found that the inhibitive effect of SO2 on PCDD/Fs formation is similar to that of SO3. To investigate the inhibition mechanism, CuSO4 formations from both CuO and CuCl2 were examined. The ability of SO3 to convert CuCl2 and CuO on a silica support into sulfate is much stronger than that of SO2. However, replacing silica by activated carbon leads to a much high conversion of CuCl2 to CuSO4 in the presence of SO2. The promotion by activated carbon is explained by the reduction of CuCl2 to Cu2Cl2 and the eventual conversion of Cu2Cl2 into CuSO4 is the main inhibition mechanism of SO2 on de novo synthesis of PCDD/Fs.
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References
Addink, R., Altwicker, E.R., 1998. Role of copper compounds in the de novo synthesis of polychlorinated dibenzo-p-dioxins/dibenzofurans. Environmental Engineering Science, 15(1):19–27. [doi:10.1089/ees.1998.15.19]
Ba, T., Zheng, M.H., Zhang, B., Liu, W.B., Xiao, K., Zhang, L.F., 2009. Estimation and characterization of PCDD/Fs and dioxin-like PCBs from secondary copper and aluminum metallurgies in China. Chemosphere, 75(9): 1173–1178. [doi:10.1016/j.chemosphere.2009.02.052]
Cunliffe, A.M., Williams, P.T., 2009. De-novo formation of dioxins and furans and the memory effect in waste incineration flue gases. Waste Management, 29(2):739–748. [doi:10.1016/j.masman.2008.04.004]
Griffin, R.D., 1986. A new theory of dioxin formation in municipal solid waste combustion. Chemosphere, 15(9–12): 1987–1990. [doi:10.1016/0045-6535(86)90498-4]
Gullett, B.K., Bruce, K.R., Beach, L.O., 1992. Effect of sulfur dioxide on the formation mechanism of polychlorinated dibenzodioxin in municipal waste combustors. Environmental Science & Technology, 26(10):1938–1943. [doi:10.1021/es00034a009]
Lindbauer, R.L., Wurst, F., Prey, T.H., 1994. PCDD/F-emission control for MSWI by SO3-addition. Organohalogen Compounds, 19:355–359.
Pekarek, V., Puncochar, M., Bures, M., Grabic, R., Fiserova, E., 2007. Effects of sulfur dioxide, hydrogen peroxide and sulfuric acid on the de novo synthesis of PCDD/F and PCB under model laboratory conditions. Chemosphere, 66(10): 1947–1954. [doi:10.1016/j.chemosphere.2006.07.073]
Raghunathan, K., Gullett, B.K., 1996. Role of sulfur in reducing PCDD and PCDF formation. Environmental Science & Technology, 30(6):1827–1834. [doi:10.1021/es950362k]
Ryan, S.P., Li, X.D., Gullett, B.K., Lee, C.W., Clayton, M., Touati, A., 2006. Experimental study on the effect of SO2 on PCDD/F emissions: determination of the importance of gas-phase versus solid-phase reactions in PCDD/F formation. Environmental Science & Technology, 40(22):7040–7047. [doi:10.1021/es0615369]
Stieglitz, L., Zwick, G., Beck, J., Roth, W., Vogg, H., 1989. On the de-novo synthesis of PCDD/PCDF on fly ash of municipal waste incinerators. Chemosphere, 18(1–6): 1219–1226. [doi:10.1016/0045-6535(89)90258-0]
Stieglitz, L., Vogg, H., Zwick, G., Beck, J., Bautz, H., 1991. On formation conditions of organohalogen compounds from particulate carbon of fly ash. Chemosphere, 23(8–10): 1255–1264. [doi:10.1016/0045-6535(91)90150-C]
Stieglitz, L., Bautz, H., Roth, W., Zwick, G., 1997. Investigation of precursor reactions in the de-novo-synthesis of PCDD/PCDF on fly ash. Chemosphere, 34(5–7): 1083–1090. [doi:10.1016/S0045-6535(97)00410-4]
Takaoka, M., Shiono, A., Nishimura, K., Yamamoto, T., Uruga, T., Takeda, N., Tanaka, T., Oshit, K., Matsumoto, T., Harada, H., 2005. Dynamic change of copper in fly ash during de novo synthesis of dioxins. Environmental Science & Technology, 39(15):5878–5884. [doi:10.1021/es048019f]
Tang, G.H., Zhao, Z.T., Zheng, C., 1999. Sulfuric Acid. Chemical Industry Press, Beijing, China, p.206 (in Chinese).
Telfer, M., Gullett, B.K., 2002. Experimental investigations of homogeneous gas-phase SO2 and Cl2 reactions for PCDD/F suppression. Organohalogen Compounds, 56:353–356.
Wang, J.B., Hung, C.H., Hung, C.H., Chang-Chien, G.P., 2009. Polychlorinated dibenzo-p-dioxin and dibenzofuran emissions from an industrial park clustered with metallurgical industries. Journal of Hazardous Materials, 161(2–3):800–807. [doi:10.1016/j.jhazmat.2008.04.026]
Weber, P., Dinjus, E., Stieglitz, L., 2001. The role of copper(II) chloride in the formation of organic chlorine in fly ash. Chemosphere, 42(5–7):579–582. [doi:10.1016/S0045-6535(00)00230-7]
Xu, X., Li, X.D., Yan, J.H., Lu, S.Y., Gu, Y.L., Chi, Y., Cen, K.F., 2001. PCDD/Fs emission in a 150 t/d MSW and coal co-firing fluidized bed incinerator. Journal of Zhejiang University-SCIENCE, 2(3):278–283.
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Project supported by the National High-Tech Research and Development Program (863) of China (Nos. 2007AA061302 and 2007AA06Z336), the National Nature Science Foundation of China (No. 50576082), the Important Project on Science and Technology of Zhejiang Province of China (No. 2007C13084), the Zhejiang Provincial Natural Science Foundation of China (No. R107532), and the Project on Science and Technology of Zhejiang Province of China (No. 2008C23090)
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Shao, K., Yan, Jh., Li, Xd. et al. Effects of SO2 and SO3 on the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans by de novo synthesis. J. Zhejiang Univ. Sci. A 11, 363–369 (2010). https://doi.org/10.1631/jzus.A0900267
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DOI: https://doi.org/10.1631/jzus.A0900267