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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., Chaussee de La Hulpe 185, Terhulpsesteenweg, B-1170 Brussels, Belgium
Available online 25 October 2007

Abstract
Cement kilns firing 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 firing 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 first part
of the 1990s have indicated that cement kilns firing 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,

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

2006): to compile data on the status of PCDD/PCDF emissions

from cement kilns firing 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 configuration. Gases
and solids flow in opposite directions through the kiln, providing
for more efficient heat transfer. The raw meal is fed at the upper
or cold end of the rotary kiln, and the slope and rotation cause

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

129

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 fired 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).

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 influence 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
fish, butter and breast milk as well as in most soil, sediments and
sewage sludge.
4. Discussion

The study by Karstensen (2006) evaluates around 2200 dioxin/furan stack

emission measurements collected from public literature, scientific 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).

The difference between todays measurements at modern

cement kilns with the older findings 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.

3. Results

5. Conclusion and recommendation

The PCDD/PCDF data presented in the SINTEF study

shows that most cement kilns can meet an emission level of

Reducing the temperature at the inlet of the air pollution control device is one factor which has shown to

2. Methods
2.1. Survey of dioxin/furan release data

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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.