Dioxin-like pcb emissions from cement kilns during the use of alternative fuels

Abstract

The substitution of combustion fuels in cement plants is increasing throughout many countries, and its individual performance is constantly assessed against strict regulatory standards. For cement plants within Australia, normal operations remain to use petroleum coal as the dominate energy source at the precalciner, avoiding the opportunity to reduce carbon-based resources and pollutant emissions (such as carbon dioxide, oxides of nitrogen, persistent organic pollutants) whilst providing the necessary energy needs through resource recovery. This paper presents stack emission monitoring of health-critical dl-PCB (dioxin-like polychlorinated biphenyl) congeners during the substitution of alternative fuels at ten Australian cement plants, and to distinguish statistical similarities between other key pollutants (such as polychlorinated dibenzo-p-dioxins and furans (PCDD-F) and hydrogen halogens) and amongst the fuels used. Sampling of plant emissions was performed during normal operations (as baseline trials) and with the varied substitution rates of waste oil, solvents, chipped wood, refuge waste, carbon dust, shredded tyres and black sand (as experimental trials). The extraction of field and analytical data during these trials allowed for determining the total and individual unit mass of dl-PCB and PCDD-F isomers, standardised to 10% O₂ and to World Health Organization (2005) toxicity equivalence (TEQ) values. The findings showed waste co-incineration during cement operations does reduce health-critical congeners of dioxins and dl-PCBs whilst providing the necessary energy and calcination needs. Experimental trials showed all dl-PCBs and PCB TEQ are below the internationally regulated Stockholm Convention article of 10pg TEQ/Nm³. In several cases, an increased rate of substituted fuel also identified a consistent reduction to baseline dl-PCBs. The distribution of toxic isomers (TCDD-F and PeCDD-F) were shown to be predominate during waste oil, wood chips, and solvent trials. Whereas the use of TDFs consistently showed a lower toxicity contribution. The distribution of dl-PCBs toxic congeners showed PCB-126 (3,3',4,4',5-Pentachlorobiphenyl) to be greatly present during the co-incineration of waste oil, wood chips, solvents and TDF trials. Principle component analysis identified a statistical predominance from the 1,2,3,7,8-PeCDF (Pentachlorodibenzofuran) and 1,2,3,4,7,8-HxCDF (Hexachlorodibenzofuran) congeners, while dl-PCBs TEQs had similar correlation amongst combustion fuels with major contributions being from the PCB-126 and PCB-169 (3,3',4,4',5,5'-Hexachlorobiphenyl) congeners.

Keywords: Air emission; Alternative fuel; Cement plant; Co-combustion; Dioxin-like PCBs.