Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) are formed jointly with numerous products of incomplete combustion during waste incineration. Chlorobenzenes (CBz) are often cited as surrogates or precursors of PCDD/Fs. Experiments were conducted to investigate the effect of some key parameters on CBz formation, including moisture (H2O), chlorine gas (Cl2), cupric chloride (CuCl2), urea [(NH2)2CO], ammonia (NH3), and ammonium sulfate [(NH4)2SO4]. Cl2 and CuCl2 promoted CBz formation from fly ash, increasing the chlorination degree. In addition, Cl in cupric compound was more active than chlorine atom of Cl2, and chlorine type significantly affected the chlorination process. Less CBz yield was detected after S- and N-containing compounds [(NH2)2CO, NH3, and (NH4)2SO4] were added into reactive ash. High content of moisture in gas prevented CBz synthesis and reduced chlorination. These experimental results are useful to optimize CBz emission control and realize the mechanism of the correlation between CBz and PCDD/Fs.
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References
1.
AltwickerE.R.1996. Relative rates of formation of polychlorinated dioxins and furans from precursor and de novo reactions. Chemosphere, 33:1897.
2.
BaileyR.E., VanW.D., ThomasP.C.2009. Sources and prevalence of pentachlorobenzene in the environment. Chemosphere, 75:555.
3.
BlumenstockM., ZimmermannR., SchrammK.W., KettrupA.2001. Identification of surrogate compounds for the emission of PCDD/F (I-TEQ value) and evaluation of their on-line real-time detectability in flue gases of waste incineration plants by REMPI-TOFMS mass spectrometry. Chemosphere, 42:507.
4.
CoboM., GávezA., ConesaJ.A., MontesC.2009. Characterization of fly ash from a hazardous waste incinerator in Medellin, Colombia. J. Hazard. Mater., 168:1223.
5.
CunliffeA.M., WilliamsP.T.2007. Influence of temperature on PCDD/PCDF desorption from waste incineration fly ash under nitrogen. Chemosphere, 66:1146.
6.
HuangH., BuekensA.1995. On the mechanisms of dioxin formation in combustion processes. Chemosphere, 31:4099.
7.
IsmoH., KariT., JuhaniR.1997. Formation of aromatic chlorinated compounds catalyzed by copper and iron. Chemosphere, 34:2649.
8.
JayK., StieglitzL.1991. On the mechanism of formation of polychlorinated aromatic compounds with copper (II) chloride. Chemosphere, 22:987.
9.
KhachatryanL., DellingerB. 2003. Formation of chlorinated hydrocarbons from the reaction of chlorine atoms and activated carbon. Chemosphere, 52:709.
10.
KuzuharaS., SatoH., KasaiE., NakamuraT.2003. Influence of metallic chlorides on the formation of PCDD/Fs during low-temperature oxidation of carbon. Environ. Sci. Technol., 37:2431.
11.
KuzuharaS., SatoH., TsubouchiN., OhtsukaY., KasaiE.2005. Effect of nitrogen-containing compounds on polychlorinated dibenzo-p-dioxin/dibenzofuran formation through de Novo synthesis. Environ. Sci. Technol., 39:795.
12.
LavricE.D., KonnovA.A. 2005. Modeling the formation of precursors of dioxins during combustion of woody fuel volatiles. Fuel, 84:323.
13.
LiX.D., ZhangJ., YanJ.H., ChenT., LuS.Y., CenK.F.2006. Effect of water on catalyzed de novo formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans. J. Hazard. Mater., 137:57.
14.
LippertT., WokaunA., LenoirD.1991. Surface-reactions of brominated arenes as a model for the formation of chlorinated dibenzodioxins and dibenzofurans in incineration-inhibition by ethanolamine. Environ. Sci. Technol., 25:1485.
15.
LuS.Y., YanJ.H., LiX.D., NiM.J., CenK.F., DaiH.F.2007. Effects of inorganic chlorine source on dioxin formation using fly ash from a fluidized bed incinerator. J. Environ. Sci., 19:756.
16.
McKayG.2002. Dioxin characterization, formation and minimization during municipal solid waste (MSW) incineration: review. Chem. Eng. J., 86:343.
17.
MüllerE.A., GubbinsK.E.1998. Molecular simulation study of hydrophilic and hydrophobic behavior of activated carbon surfaces. Carbon, 36:1433.
18.
NganaiS., LomnickiS.M., DellingerB.2011. Formation of PCDD/Fs from the copper oxide-mediated pyrolysis and oxidation of 1,2-dichlorobenzene. Environ. Sci. Technol., 45:1034.
19.
ÖbergT., BergstromJ.G.T.1985. Hexachlorobenzene as an indicator of dioxin production from combustion. Chemosphere, 14:1081.
20.
ÖbergT., OhrstromT.2003. Chlorinated aromatics from combustion: Influence of chlorine, combustion conditions and catalytic activity. Environ. Sci. Technol., 37:3995.
21.
PandelovaM.E., LenoirD., KettrupA., SchrammK.W.2005. Primary measures for reduction of PCDD/F in co-combustion of lignite coal and waste: Effect of various inhibitors. Environ. Sci. Technol., 39:3345.
22.
RuokojärviP.H., AatamilaM., TuppurainenK.A., RuuskanenJ.2001. Effect of urea on fly ash PCDD/F concentrations in different particle sizes. Chemosphere, 43:757.
23.
RuokojärviP.H., HalonenI.A., TuppurainenK.A., TarhanenJ., RuuskanenJ.1998. Effect of gaseous suppressants on PCDD/F formation. Environ. Sci. Technol., 32:3099.
24.
Secretariat of the Stockholm Convention. 2007. National Implementation Plan for the Stockholm Convention on Persistent Organic Pollutants. PR China, 2007. www.pops.int
25.
ShaoK., YanJ.H., LiX.D., ChenT., YanJ.H.2010a. Experimental study on the effects of H2O on PCDD/Fs formation by de novo synthesis in carbon/CuCl2 model system. Chemosphere, 78:672.
26.
ShaoK., YanJ.H., LiX.D, LuS.Y., ChenT., YanJ.H.2010b. Inhibition of de novo synthesis of PCDD/Fs by SO2 in a model system. Chemosphere, 78:1230.
27.
StanmoreB.R.2002. Modeling the formation of PCDD/F in solid waste incinerators. Chemosphere, 47:565.
28.
StieglitzL., ZwickG., BeckJ., BautzH., RothW.1990. The role of particulate carbon in the de-novo synthesis of polychlorinated dibenzodioxins and -furans in fly-ash. Chemosphere, 20:1953.
29.
TakacsL., MoilanenG.L.1991. Simultaneous control of PCDD/PCDF, HCl and NOx emissions from municipal solid-waste incinerators with ammonia injection. J. Air Waste Manag. Assoc., 41:716.
30.
TaylorP.H., DellingerB.1999. Pyrolysis and molecular growth of chlorinated hydrocarbons. J. Anal. Appl. Pyrolysis, 49:9.
31.
TaylorP.H., LenoirD.2001. Chloroaromatic formation in incineration processes. Sci. Total Environ., 269:1.
32.
ThomasV.M., MccreightC.M.2008. Relation of chlorine, copper and sulphur to dioxin emission factors. J. Hazard. Mater., 151:164.
33.
TuppurainenK., AatamilaM., RuokojärviP., HalonenI., RuuskanenJ.1999. Effect of liquid inhibitors on PCDD/F formation. Prediction of particle-phase PCDD/F concentrations using PLS modelling with gas-phase chlorophenol concentrations as independent variables. Chemosphere, 38:2205.
34.
United Nations Environment Programme (UNEP). 2005. Standardized Toolkit for Identification and Quantification of Dioxin and Furan Releases. Geneva, Switzerland: UNEP Chemicalswww.pops.int/documents/meetings/cop_2/followup/toolkit
35.
WeberP., DinjusE., StieglitzL.2001. The role of copper (II) chloride in the formation of organic chlorine in fly ash. Chemosphere, 42:579.
36.
WikstromE., RyanS., TouatiA., TelferM., TaborD., GullettB. K.2003. Importance of chlorine speciation on de novo formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans. Environ. Sci. Technol., 37:1108.
37.
YanM., LiX.D., ChenT., LuS.Y., YanJ.H. 2010. Effect of temperature and oxygen on the formation of chlorobenzene as the indicator of PCDD/Fs. J. Environ. Sci., 22:1637.
