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Environmental Toxicology and Pharmacology 25 (2008) 128130

Dioxin/furan formation and release in the cement industry


Willem van Loo
Heidelberg Cement, S.A. Cimenteries CBR Cementbedrijven N.V., Chauss ee de La Hulpe 185, Terhulpsesteenweg, B-1170 Brussels, Belgium Available online 25 October 2007

Abstract Cement kilns ring hazardous waste are explicitly mentioned in the Stockholm Convention as an industrial source having the potential for comparatively high formation and release of these chemicals to the environment. The substitution of fossil fuels with alternative waste derived fuels is a well-developed practice in a number of countries. In the European cement industry about 6 million tonnes are used which corresponds to a thermal substitution rate of 17%. The current study evaluates around 2200 dioxin/furan stack emission measurements collected from various sources. It is demonstrated that most cement kilns can meet an emission level of 0.1 ng TEQ/Nm3 if primary measures, i.e. process-integrated measures, are applied. Reducing the temperature to a level lower than 200 C at the inlet of the air pollution control device is the key factor which has shown to limit dioxin formation and emissions at all types of cement kilns, independent of waste feeding. 2007 Elsevier B.V. All rights reserved.
Keywords: Dioxin; Formation; Emission; Cement; Kiln

1. Introduction The Stockholm Convention on persistent organic pollutants requires parties, among other things, to seek the continuing minimization and, where feasible, elimination of the release of unintentionally produced persistent organic pollutants (POPs) such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF). Cement kilns ring hazardous waste are explicitly mentioned in the Stockholm Convention as an industrial source having the potential for comparatively high formation and release of these chemicals to the environment (SC, 2001, Annex C). Emission data from US cement kilns in the 1980s and rst part of the 1990s have indicated that cement kilns ring hazardous waste as a fuel had much higher PCDD/PCDF emissions than kilns co-processing non-hazardous wastes or using conventional fuel only. The cement industry takes any potential release of dioxins and furans seriously. Therefore the Cement Sustainability Initiative (CSI) under the World Business Council for Sustainable Development has given the following mandate to SINTEF, the largest research organization in Scandinavia (Karstensen,

2006): to compile data on the status of PCDD/PCDF emissions from cement kilns ring hazardous wastes, to share state of the art knowledge about PCDD/PCDF formation mechanisms in cement production processes, and to show how it is possible to control and minimize PCDD/PCDF emissions from cement kilns utilizing integrated process optimization (so-called primary measures). 1.1. The cement making process The main constituent of cement is Portland clinker. The basic chemistry of the clinker manufacturing process begins with the decomposition of calcium carbonate (CaCO3 ) at about 900 C to leave calcium oxide (CaO). This is followed by the clinkering process in which the calcium oxide reacts at high temperature (typically 14001500 C) with silica, alumina and ferrous oxide to form the silicates, aluminates and ferrites of calcium which comprise the Portland clinker. The raw feed material, known as raw meal, raw mix, slurry (with a wet process) or kiln feed, is heated in a kiln, typically a large, inclined, rotating cylindrical steel furnace (rotary kiln) (see Fig. 1). Kilns are operated in a counter-current conguration. Gases and solids ow in opposite directions through the kiln, providing for more efcient heat transfer. The raw meal is fed at the upper or cold end of the rotary kiln, and the slope and rotation cause

Tel.: +32 629 091 248. E-mail address: willem.vanloo@heidelbergcement.com.

1382-6689/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.etap.2007.10.031

W. van Loo / Environmental Toxicology and Pharmacology 25 (2008) 128130

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Fig. 2. Thermal substitution: recent CEMBUREAU data. Fig. 1. Rotary kiln with suspension pre-heater and calciner.

the meal to move toward the lower or hot end. The kiln is red at the hot end, usually with coal or petroleum coke as the primary fuel. As the meal moves through the kiln and is heated, it undergoes drying and pyro-processing reactions to form the clinker, which consists of lumps of fused, incombustible material. There are several ways of introducing the fuels (both fossil and alternative) into the kiln. The clinker leaves the hot end of the kiln at a temperature of about 1000 C. It falls into a clinker cooler, typically a moving grate through which cooling air is blown. 1.2. Use of waste-derived alternative fuels The substitution of fossil fuels with alternatives such as rubber tires, animal meal, waste oil, solvents or sludge is a welldeveloped practice in a number of countries. Some countries have been using wastes for almost 30 years, and some national governments actively promote this approach, provided that stringent requirements with regard to input, process and emission control are met. In the European cement industry the share of waste-derived fuel consumption amounts to about 6 million tonnes which corresponds to a thermal substitution rate of 17% (CEMBUREAU, 2006a).
2. Methods 2.1. Survey of dioxin/furan release data
The study by Karstensen (2006) evaluates around 2200 dioxin/furan stack emission measurements collected from public literature, scientic databases and individual company measurements. The data represents emission levels from large capacity processing technologies, including wet and dry process cement kilns, performed under normal and worst case operating conditions, with and without the utilization of a wide range of waste-derived alternative fuel. As a typical example Fig. 2 represents data summarizing PCDD/PCDF emissions of 243 kilns in Europe with different categories of thermal substitution rate (CEMBUREAU, 2006b) (see Fig. 2).

0.1 ng TEQ/Nm3 if primary measures, i.e., process-integrated measures, are applied; that co-processing of alternative fuels and raw materials, fed to the main burner, kiln inlet or the precalciner does not seem to inuence or change the emission of PCDD/PCDF; and that the emissions from modern dry preheater/pre-calciner kilns seem generally to be slightly lower than emissions from wet kilns. These observations are also valid for stack emission data from dry pre-heater and pre-calciner cement kilns in developing countries where according to CEMBUREAU data, the very low emission levels of much below 0.1 ng TEQ/Nm3 were found. The SINTEF study also provides a large number of measurements of PCDD/PCDF in products and residues from the cement industry. The levels are normally low and in the same magnitude (typical average value <10 ng TEQ/kg) as found in foods like sh, butter and breast milk as well as in most soil, sediments and sewage sludge. 4. Discussion The difference between todays measurements at modern cement kilns with the older ndings in the US was explained by the US Environment Protection Agency in that cement kilns burning hazardous waste were normally tested under worst scenario trial burn conditions, i.e. typically high waste feeding rates and high temperatures in the air pollution control device, conditions today known to stimulate PCDD/PCDF formation. Cement kilns burning non-hazardous waste or conventional fossil fuel only were tested under normal conditions, no worst scenario conditions were applied and therefore a direct comparison between results from hazardous waste burning and non-hazardous waste burning kilns cannot be made. In line with this the US EPA concluded in 1999 in the new Maximum Achievable Control Technology regulation that hazardous waste burning in cement kilns does not have an impact on Dioxin/Furan formation because they are formed postcombustion, i.e., in the air pollution control device. 5. Conclusion and recommendation Reducing the temperature at the inlet of the air pollution control device is one factor which has shown to

3. Results The PCDD/PCDF data presented in the SINTEF study shows that most cement kilns can meet an emission level of

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W. van Loo / Environmental Toxicology and Pharmacology 25 (2008) 128130

limit dioxin formation and emissions at all types of cement kilns, independent of waste feeding, as lower temperatures are believed to prevent the post-combustion de-novo synthesis of PCDD/PCDF. Therefore, the most important primary measures to achieve compliance with an emission level of 0.1 ng I-TEQ/Nm3 is quick cooling of the kiln exhaust gases to lower than 200 C in long wet and long dry kilns without pre-heating. Modern pre-heater and pre-calciner kilns have this feature already inherent in the process design. Feeding of alternative raw materials as part of raw-material-mix should be avoided if it includes organic precursors and

no alternative fuels should be fed during start-up and shut down. References
CEMBUREAU, 2006a. Use of Waste as Alternative Fuels & Materials. CEMBUREAU, 2006b. Impact on Emissions Levels when Using Waste. Karstensen, K.H., January 2006. Formation and Release of POPs in the Cement Industry, Second ed. World Business Council for Sustainable Development/SINTEF. SC, 2001. Stockholm Convention on Persistent Organic Pollutants; http:// www.pops.int.

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