Both hexachlorobenzene and hexabromobenzene were successfully hydrodehalogenated to the monohalogenated derivative and ultimately to benzene (which was subsequently reduced to cyclohexane) using a mixture of metallic Ca, ethanol, and Rh/C, by simple stirring in diethyl ether, at room or mild temperature (60 °C). Various experiments were performed in order to assess the role of the solvent and Rh/C catalyst, as well as for elucidating the reaction pathway.
This is a preview of subscription content, log in to check access.
Buy single article
Instant access to the full article PDF.
Price includes VAT for USA
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
This is the net price. Taxes to be calculated in checkout.
Altwicker ER, Kumar R, Konduri NV, Milligan MS (1990) The role of precursors in formation of polychloro-dibenzo-p-dioxins and polychloro-dibenzofurans during heterogeneous combustion. Chemosphere 20(10–20):1935–1394
Bailey RE (2001) Global hexachlorobenzene emissions. Chemosphere 43(2):167–182
Barbera JL, Sweetmana AJ, van Wijkb D, Jones KC (2005) Hexachlorobenzene in the global environment: emissions, levels, distribution, trends and processes. Sci Total Environ 349:1–44
Berrojalbiz N, Castro-Jiménez J, Mariani G, Wollgast J, Hanke G, Dachs J (2014) Atmospheric occurrence, transport and deposition of polychlorinated biphenyls and hexachlorobenzene in the Mediterranean and Black seas. Atmospheric Chem Phys 14(17):8947–8959
Bossi R, Skjoth CA, Skov H (2013) Three years (2008-2010) of measurements of atmospheric concentrations of organochlorine pesticides (OCPs) at Station Nord, North-East Greenland. Environ Sci Proc Impacts 15(12):2213–2219
Brahushi F, Dorfler U, Schroll R, Munch JC (2004) Stimulation of reductive dechlorination of hexachlorobenzene in soil by inducing the native microbial activity. Chemosphere 55:1477–1484
Covaci A, Harrad S, Abdallah MA-E, Ali N, Law RJ, Herzke D, de Wit CA (2011) Novel brominated flame retardants: a review of their analysis, environmental fate and behavior. Environ Internat 37:532–556
Galban-Malagon C, Cabrerizo A, Caballero G, Dachs J (2013) Atmospheric occurrence and deposition of hexachlorobenzene and hexachlorocyclohexanes in the Southern Ocean and Antarctic Peninsula. Atmospheric Environ 80:41–49
Gao X, Wang W, Liu X (2009) Dechlorination reaction of hexachlorobenzene with calcium oxide at 300–400 °C. J Haz Mater 169(1–3):279–284
Hakk H, Letcher RJ (2003) Metabolism in the toxicokinetics and fate of brominated flame retardants—a review. Environ. Internat. 29:801–828
Huang M, Xue J, Xie L, Ling S, Zhou N, Cai Y, Qian J (2012) Preparation and photoelectrocatalytic activity of CdS particles embedded in highly ordered TiO2 nanotube arrays electrode for HCB degradation. Adv Mater Res 347-353:1894–1897
Lundin L, Marklund S (2007) Thermal degradation of PCDD/F, PCB and HCB in municipal solid waste ash. Chemosphere 67(3):474–481
Ma X, Zheng M, Liu W, Qian Y, Zhang B, Liu W (2005) Dechlorination of hexachlorobenzene using ultrafine Ca–Fe composite oxides. J Haz Mater B127:156–162
Meijer SN, Ockenden WA, Sweetman A, Breivik K, Grimalt JO, Jones KC (2003) Global distribution and budget of PCBs and HCB in background surface soils: implications for sources and environmental processes. Environ. Sci. Technol. 37:667–672
Mitoma Y, Egashira N, Simion C (2009b) Highly effective degradation of polychlorinated biphenyls in soil mediated by a Ca/Rh bicatalytic system. Chemosphere 74:968–973
Mitoma Y, Kakeda M, Simion AM, Egashira N, Simion C (2009a) Metallic Ca−Rh/C-methanol, a high-performing system for the hydrodechlorination/ring reduction of mono- and polychlorinated aromatic substrates. Environ Sci Technol 43(15):5952–5958
Miyoshi K, Nishio T, Yasuhara A, Morita M, Shibamoto T (2004) Detoxification of hexachlorobenzene by dechlorination with potassium–sodium alloy. Chemosphere 55(11):1439–1446
Naso B, Perrone D, Ferrante MC, Zaccaroni A, Lucisano A (2003) Persistent organochlorine pollutants in liver of birds of different trophic levels from coastal areas of Campania, Italy. Arch Environ Contam Toxicol 45:407–414
Nie X, Liu J, Yue D, Zeng X, Nie Y (2013a) Dechlorination of hexachlorobenzene using lead-iron bimetallic particles. Chemosphere 90(9):2403–2407
Nie X, Liu J, Zeng X, Yue D (2013b) Rapid degradation of hexachlorobenzene by micron Ag/Fe bimetal particles. J Environ Sci (China) 25(3):473–478
Shen H, Main KM, Andersson AM, Damgaard IN, Virtanen HE, Skakkebaek NE, Toppari J, Schramm KW (2008) Concentrations of persistent organochlorine compounds in human milk and placenta are higher in Denmark than in Finland. Hum Reprod 23(1):201–210
Shih YH, Hsu CY, Su YF (2011) Reduction of hexachlorobenzene by nanoscale zero-valent iron: kinetics, pH effect, and degradation mechanism. Sep Purif Technol 76(3):268–274
Su G, Liu Y, Huang L, Shi Y, Zhang A, Zhang L, Liu W, Gao L, Zheng M (2013) Synergetic effect of alkaline earth metal oxides and iron oxides on the degradation of hexachlorobenzene and its degradation pathway. Chemosphere 90(1):103–111
Tong M, Yuan S (2012) Physiochemical technologies for HCB remediation and disposal: a review. J Haz Mater:229–230
Watanabe I, Sakai SI (2003) Environmental release and behavior of brominated flame retardants. Environ. Internat. 29(6):665–682
Weber R, Sakurai T, Hagenmaier H (1999) Formation and destruction of PCDD/PCDF during heat treatment of fly ash samples from fluidized bed incinerators. Chemosphere 38:2633–2642
Xiu LF, Hua LX, Bin LX, Ping M (2009) Photodegradation of hexachlorobenzene catalyzed by TiO2. Fresenius Environ Bull 18(5):628–632
Yamada S, Naito Y, Takada M, Nakai S, Hosomi M (2008) Photodegradation of hexachlorobenzene and theoretical prediction of its degradation pathways using quantum chemical calculation. Chemosphere 70(4):731–736
Yan DZ, Mao LQ, Li CZ, Liu J (2015) Biodegradation of hexachlorobenzene by a constructed microbial consortium. World J Microbiol Biotechnol 31(2):371–377
Yang N, Matsuda M, Kawano M, Wakimoto T (2006) PCBs and organochlorine pesticides (OCPs) in edible fish and shellfish from China. Chemosphere 63(8):1342–1352
Yin K, Gao X, Sun Y, Zheng L, Wang W (2013) Thermal degradation of hexachlorobenzene in the presence of calcium oxide at 340–400 °C. Chemosphere 93(8):1600–1606
Yuan S, Zheng Z, Meng XZ, Chen J, Wang L (2010) Surfactant mediated HCB dechlorination in contaminated soils and sediments by micro and nanoscale Cu/Fe Particles. Geoderma 159(1–2):165–173
Zhang Q, Matsumoto H, Saito F, Baron M (2002) Debromination of hexabromobenzene by its co-grinding with CaO. Chemosphere 48(8):787–793
Zhang L, Zheng M, Zhang B, Liu W, Gao L, Ba T, Ren Z, Su G (2008) Decomposition of hexachlorobenzene over Al2O3 supported metal oxide catalysts. J Environ Sci 20(12):1523–1526
Zhao L, Zhu T, Hou H, Qin X, Li F, Terada A, Hosomi M (2015) Removal of PCBs and HCB from contaminated solids using a novel successive self-propagated sintering process. Environ Sci Poll Res 22(22):17527–17539
Zhou X, Zhang C, Zhang D, Awata T, Xiao Z, Yang Q, Katayama A (2015) Polyphasic characterization of an anaerobic hexachlorobenzene-dechlorinating microbial consortium with a wide dechlorination spectrum for chlorobenzenes. J Biosci Bioeng 120(1):62–68
The authors wish to express their thanks to Asuka Takagi and Hiromi Hasegawa from the Mitsubishi Chemical Engineering Corporation as technical experts for measurements by GC and GC-FID.
• Hydrodehalogenation occurs for both hexachloro- and hexabromobenzene, in mild conditions;
• Ultimate reaction product is cyclohexane and/or benzene;
• For the reaction to occur, both Ca and ethanol reagents, as well as Rh/C catalyst are necessary;
• No side-products (e.g., polyaromatic compounds) were recorded.
Responsible editor: Santiago V. Luis
About this article
Cite this article
Katayama, Y., Aoyagi, M., Matsumoto, T. et al. Hydrodehalogenation of hexachloro- and hexabromobenzene by metallic calcium in ethanol, in the presence of Rh/C catalyst. Environ Sci Pollut Res 24, 591–597 (2017). https://doi.org/10.1007/s11356-016-7785-8
- Metallic Ca