Fuel 85 (2006) 2278–2285

www.fuelfirst.com

Chemical composition of fuels and emissions from a coal + tire

combustion experiment in a power station
a,*
Reto Gieré , Katherine Smith b, Mark Blackford b

a
Mineralogisch-Geochemisches Institut, Albert-Ludwigs-Universität, Albertstrasse 23b, D-79104 Freiburg, Germany
b
Institute of Materials and Engineering Science, ANSTO, Menai, NSW 2234, Australia

Received 5 May 2005; received in revised form 23 November 2005; accepted 23 November 2005
Available online 2 June 2006

Abstract

Medium-sulfur bituminous coal and a mixture of 95 wt.% coal plus 5 wt.% tire-derived fuel (TDF) in the form of shredded automo-
tive tires were combusted in a stoker boiler under the same conditions. This paper presents quantitative chemical compositions of the
fuels and of the gaseous and particulate emissions. The coal + TDF mixture is considerably richer in Zn than the pure coal as a result
of the high Zn content of the shredded tires (1 wt.% Zn). Atmospheric emissions of Zn increased from 15 g/h to nearly 2.4 kg/h when
coal + TDF was combusted. Similarly, emissions of most other metals and metalloids, as well as those of HCl increased when TDF
(3000 ppm Cl) was added. The enhanced metal emissions might be due to formation of gaseous metal chloride species in the stack
gases. On the other hand, emissions of CO decreased slightly, whereas those of NOx, SO2, and total particulate matter remained virtually
unchanged. These results help in assessing the environmental impact of energy recovery from scrap tires in stoker boilers.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: Emissions; TDF; Coal-fired power plant

1. Introduction
Accumulation of millions of worn automotive tires
poses a considerable environmental problem. On average,
approximately one scrap tire per person per year accumu-
lates in industrialized countries (see discussion in [1]). As
an important part of the solid waste stream in today’s soci-
ety, worn tires have traditionally been discarded in landfills
or stored in stockpiles. Over the past several decades, how-
ever, innovative alternatives to disposal have been devel-
oped, partly as a result of high tipping fees charged by
landfill operators. Because of their high heat content and
their low levels of moisture and nitrogen compared to coal,
tires are ideally suited for energy recovery through combus-
tion. Consequently combustion of waste tires as supple-
mental or alternate fuel in various industrial combustion
facilities has become the most important alternative to dis-
*
Corresponding author. Tel.: +49 761 302 6409; fax: +49 761 203 6407.
E-mail address: giere@uni-freiburg.de (R. Gieré).
posal [1]. In 2001, for example, 41% of all tires discarded in
the US were used as fuel [2], and in Germany [3] the per-
centage was even higher (Fig. 1).
Because combustion processes generate gaseous pollu-
tants and solid waste materials, which must be disposed
of or reused as secondary raw materials, it is important
to characterize these combustion products in order to
assess the environmental impacts of energy recovery from
scrap tires. Several laboratory studies focused on the emis-
sions resulting from combustion of pure tire fuel and of
blends of coal plus waste tires (see [1] for discussion and
references). The results of these studies revealed that, com-
pared to coal combustion, burning of pure tires or coal +
tire blends under the same conditions generally leads to a
decrease in atmospheric emissions of nitrogen oxides
(NOx), but produces higher emissions of carbon monoxide
(CO), polycyclic aromatic hydrocarbons (PAH), and sub-
micrometer-sized particulate matter (PM). Besides these
laboratory-scale investigations there are only a few
emission studies on controlled tire co-combustion in

0016-2361/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2005.11.024
 R. Gieré et al. / Fuel 85 (2006) 2278–2285 2279

8 2
10 20
14
20
12 5

4
15

USA Germany

41 50
Tire fuel Rubber products Civil engineering

Miscellaneous Landfills Unknown

Fig. 1. Disposition of tires in 2001, shown as percentage of the total number of discarded tires in the USA [2] and in Germany [3]. The category
‘‘Miscellaneous’’ includes used tire exports.

coal-burning industrial facilities. These large-scale studies
have shown that partial replacement of conventional fuels
with waste tires can result in substantial reductions of NOx
emissions, but may also lead to considerable increases in
the levels of other pollutants (e.g., Zn and Pb; see [1]).
In this paper we report an experiment in which two
fuels, pure coal and a blend of coal plus tire-derived fuel
(TDF), were combusted in a commercial power plant.
We will present detailed chemical compositional data of
the fuel as well as of the gases, metals and metalloids emit-
ted into the atmosphere during combustion. Comparison is
made of the emissions generated by combustion of pure
coal and the coal + TDF mixture.
2. Experimental procedure
The Walter Wade Utility Plant provides the Purdue
University campus in West Lafayette (Indiana, USA) with
heating steam, electricity and chilled water for air condi-
tioning. There are four steam generators consisting of
two spreader-stoker coal boilers, one oil/gas-fired unit,
and one fluidized-bed coal boiler. The spreader-stoker boil-
ers are equipped with cyclone-type mechanical collectors
and electrostatic precipitators for air pollution control.
In 2001, Purdue University conducted an experiment
with two different sets of fuel in successive weeks. During
the first week, the power plant combusted pure coal,
whereas a mixture of 95 wt.% coal plus 5 wt.% TDF was
used during the second week. The experiment was carried
out in Unit 2, a Detroit RotoGrate stoker boiler (installed
1967) with a designed maximum load of 12 t coal per hour
and a capacity of 98 t steam per hour (at 440 °C and
4.5 MPa).
Actual fuel consumption during the experiment was, on
average, 9.91 ± 0.07 t/h, and the temperature in the com-
bustion chamber was 1500 °C for both types of fuel.
The TDF was obtained from Entech, Inc. (Michigan)
and consisted of shredded automotive tires. The tire chips
have a nominal size of 2.5 cm and contain abundant syn-
thetic fabric and some wires (Fig. 2). The feed coal was
bituminous coal from Southern Indiana (Table 1) and
consisted of similarly sized chunks (Fig. 2). During this

Fig. 2. Photographs of the fuels used during the experiment at the Purdue University power plant. Left: bituminous coal; right: shredded automotive tires
(TDF). Both pictures have the same scale.
2280 R. Gieré et al. / Fuel 85 (2006) 2278–2285

Table 1 (EPA) Method 3A for oxygen (O2) and carbon dioxide

Characteristics of the coal, the coal + TDF blend, and the TDF (shredded (CO2); Method 6C for sulfur dioxide (SO2); Method 7E
tires) used in the combustion experiment (proximate analyses, as received)
for nitrogen oxides (NOx, i.e. NO + NO2); Method 10
Property Unit Pure coal Coal + TDFa TDF for carbon monoxide (CO); Method 26 for hydrogen chlo-
Average Std. Average Std. (n = 1) ride (HCl) and hydrogen fluoride (HF); Method 25A for
(n = 12) dev. (n = 11) dev. total hydrocarbons (THC); and Method 23 for dioxins
Moisture content wt.% 14.6 1.1 15.9 0.7 2.9 and furans.
Ash content wt.% 7.2 1.5 8.0 0.7 6.2 To sample the stack gases for total particulate matter
Volatile content wt.% 33.6 0.9 33.1 0.6 59.0
Fixed carbon wt.% 43.9 1.2 43.0 0.7 31.9
(PM), a Nutech Corporation (Durham, NC) sampling
content train was used, following the US EPA Method 5 [4]. The
Heat content MJ/kg 25.9 0.5 25.6 0.4 35.1 sample train consisted of a glass-lined, elbow-shaped probe
a
Blend of 95 wt.% coal + 5 wt.% TDF. that pointed downward into the stack and a filtering sys-
tem. The filter media were Whatman 934-AH glass micro-
fiber filters with P99.97% efficiency on 0.3 lm smoke
experiment, the environmental consulting company GE particles (ASTM Method D-2986-71). Samples were col-
Mostardi Platt (Elmhurst, Illinois, USA) performed a gas- lected by washing the train contact surfaces with reagent-
eous and particulate emission test program, which was grade acetone.
observed by the Indiana Department of Environmental Determination of the trace metal content of the stack
Management. gases was performed according to US EPA Method 29
[4], using a comprehensive sampling train based on the
system used in Method 5. The modified system consisted
3. Analytical techniques of three parts: (1) a glass-lined, elbow-shaped probe
wrapped with a heating wire and heated to a temperature
Several analytical methods were used to determine the of 120 ± 4 °C; (2) a high-efficiency (>99.99% on 0.3 lm
bulk composition of the coal, the coal + TDF blend, and smoke particles), heated (120 ± 4 °C) glass-fiber filter
the TDF. The TDF sample was prepared for analysis by (Pallflex 2500 QAT-UP); and (3) a series of six impingers
cryogenically grinding the tire chips with a SPEX CertiPrep placed in an ice bath to induce condensation. The first and
impact grinder (6750-115 freezer/mill), which has a self- second impingers (Greenburg–Smith design) were filled
contained liquid nitrogen tub. All samples of coal and with 200 mL of 5% HNO3 – 10% H2O2 solution; the third
coal + TDF blend were carefully ground, homogenized impinger was left empty to catch any carry-over material,
and split prior to analysis by a commercial geochemical and was followed by two impingers filled with 100 mL of
laboratory (SGS Canada Inc.). Splits of approximately acidic KMnO4 solution. The sixth impinger contained sil-
0.3 g material (as received) were analyzed with the follow- ica gel to absorb any remaining moisture. Sampling time
ing techniques (method codes given in parentheses are was at least 2 h. After each run, all sample contact sur-
those listed in Table 2 for each element): inductively cou- faces of the glass-lined probe and glass-fibre filter as well
pled plasma atomic emission spectroscopy, preceded by as the first three impingers were washed with 0.1 N nitric
LiBO2 fusion (ICP95); inductively coupled plasma mass acid. The fourth and fifth impingers were rinsed with
spectroscopy, preceded by LiBO2 fusion (MS104); induc- acidic KMnO4. A leak check on the sampling train was
tively coupled plasma mass spectroscopy, preceded by performed after each sampling run. Metal contents were
Na2O2 fusion (MS90); aqua regia digestion, followed by determined by atomic absorption spectroscopy (cold-
Na-hydride treatment to liberate the element into a gas vapor atomic absorption method for Hg), inductively cou-
(AAH70), which was then analyzed by flameless atomic pled plasma emission spectroscopy, and inductively cou-
absorption spectrometry; cold vapor atomic absorption pled plasma mass spectrometry at the GE Mostardi
spectrometry (CHM-20); ion-selective electrode potentiom- Platt laboratory.
etry (ISE08); and LECO infrared spectroscopy (CHM119).
All sampling of atmospheric emissions as well as the 4. Results
analytical and calibration procedures used during the Pur-
due University experiment were performed as described in A detailed chemical comparison was made of both types
the appendices of Title 40, Code of Federal Regulations [4]. of fuel, the solid combustion products (bottom ash,
All emission measurements were made by positioning an mechanical collector ash, electrostatic precipitator ash),
inert, temperature-resistant probe into the smoke stack and the atmospheric emissions. It is the aim of this paper
no less than 1 m from the stack wall. Temperature inside to present and discuss the compositional details of both
the stack was measured using K-type thermocouples with fuel types and of the emissions, which have not been
calibrated digital temperature indicators. included in the summary published previously [1]. A com-
The procedures used to determine the gaseous emissions parison of the various types of ash as well as a detailed sin-
are described in the Code of Federal Regulations [4], and gle-particle characterization of emitted particulate matter
included the US Environmental Protection Agency’s will be prepared at a later stage.
 R. Gieré et al. / Fuel 85 (2006) 2278–2285 2281

Table 2
Bulk-chemical composition of the studied fuel materials
Element Methoda Unit Pure coal Coal + TDFb TDFc
Average (n = 5) Std. dev. Average (n = 11) Std. dev. Average (n = 3) Std. dev.
Be MS104 ppm 5.3 0.7 5.0 0.4 <0.5
C CHM119 wt.% 75 1 74 2 83 1
Na ICP95 wt.% 0.02 0.01 0.02 0.01 <0.01
Mg ICP95 wt.% 0.02 0.01 0.03 0.01 0.05 0.00
Al ICP95 wt.% 1.2 0.4 1.4 0.6 0.25 0.01
Si ICP95 wt.% 1.8 0.4 2.2 0.8 0.55 0.01
P ICP95 wt.% 0.01 0.00 0.01 0.00 <0.01
S CHM119 wt.% 1.5 0.2 2.0 0.4 1.69 0.05
Cld ISE08 ppm 215 n.a. 2938
K ICP95 wt.% 0.09 0.03 0.11 0.04 0.03 0.00
Ca ICP95 wt.% 0.04 0.01 0.05 0.02 0.15 0.01
Sc ICP95 ppm n.a. n.a. <10
Ti ICP95 wt.% 0.06 0.02 0.08 0.04 0.15 0.00
V MS104 ppm 33 13 37 15 <5
Cr ICP95 ppm 12 2 13 6 <68
Mn ICP95 wt.% <0.01 <0.01 <0.01
Fe ICP95 wt.% 0.8 0.2 1.2 0.3 0.44 0.02
Co MS104 ppm 10 2 11 2 63 9
Ni MS104 ppm 43 3 41 5 22 1
Cu MS104 ppm 21 6 20 5 38 2
Zn MS104 ppm 36 16 183 42 10900 849
Ga MS104 ppm 5 1 7 1 <1
Ge MS90 ppm 19 3 22 2 n.a.
As AAH70 ppm 7 4 8 2 0.9 0.0
Se AAH70 ppm 2.9 0.8 3.4 0.7 <0.1
Rb MS104 ppm 6 1 8 2 1.7 0.1
Sr MS104 ppm 53 28 78 23 8.5 0.7
Y MS104 ppm 7 1 10 3 <1
Zr MS104 ppm 16 6 22 12 2.5 0.2
Nb MS104 ppm 4 3 3 1 <1
Mo MS104 ppm 2.4 0.9 <2 <2
Ag MS104 ppm <1 <1 <1
Cd MS104 ppm 0.14 0.09 <0.1 0.1 0.0
Sn MS104 ppm 1.8 0.8 2.2 0.8 2.0 0.0
Sb AAH70 ppm 0.3 0.1 0.2 0.0 3.6 0.3
Te AAH70 ppm <0.5 0.52 0.06 <0.1
Cs MS104 ppm 0.6 0.2 0.7 0.2 <0.1
Ba MS104 ppm 26 13 27 8 11.6 0.8
La MS104 ppm 13 3 16 6 1.9 0.2
Ce MS104 ppm 24 7 30 12 3.1 0.3
Pr MS104 ppm 3 1 4 1 0.4 0.1
Nd MS104 ppm 12 5 14 4 1.1 0.1
Sm MS104 ppm 2 1 3.2 0.8 0.2 0.0
Eu MS104 ppm 0.5 0.2 0.6 0.2 <0.05
Gd MS104 ppm 1.9 0.6 2.6 0.8 0.1 0.1
Tb MS104 ppm 0.26 0.09 0.4 0.1 <0.1
Dy MS104 ppm 1.5 0.3 2.0 0.6 0.1 0.0
Ho MS104 ppm 0.26 0.09 0.4 0.1 <0.05
Er MS104 ppm 0.8 0.1 1.1 0.3 <0.1
Tm MS104 ppm 0.1 0.0 0.13 0.05 <0.1
Yb MS104 ppm 0.7 0.1 0.9 0.3 <0.1
Lu MS104 ppm 0.06 0.01 0.08 0.04 <0.05
Hf MS104 ppm <1 <1 <1
Ta MS104 ppm 0.56 0.09 0.6 0.2 <0.5
W MS104 ppm <1 <1 3 1
Hg CHM-20 ppb 68 11 87 36 8 1
Tl MS104 ppm <0.5 0.52 0.04 <0.5
Pb MS104 ppm 12 6 20 10 6 2
Bi AAH70 ppm 0.7 0.4 0.6 0.3 0.2 0.1
Th MS104 ppm 2.1 0.7 2.6 1.0 0.2 0.0
U MS104 ppm 1.1 0.2 1.5 0.7 0.1 0.1
a
See text for abbreviations.
b
Blend of 95 wt.% coal + 5 wt.% TDF.
c
Pure TDF.
d
Only one analysis per sample.
2282 R. Gieré et al. / Fuel 85 (2006) 2278–2285

4.1. Comparison of fuels ence in Zn content, which is approximately three hundred

The Indiana coal used in the Purdue University experi-
ment is a high-volatile C bituminous coal with a moisture
content of approximately 15 wt.% (Table 1). In contrast,
the shredded tires contain only 2.9 wt.% moisture. Such a
low moisture content is typical of scrap tires, and is one
of the important reasons why this material is commonly
used for energy recovery. Other typical properties of waste
tires include high contents of volatiles and heat. The shred-
ded tires used in this experiment contain 59 wt.% volatiles,
a value that is within the range reported for various types
of tires and TDF (52–67 wt.% [1]). The heating value of
the studied TDF, determined at 35.1 MJ/kg, is at the upper
end of the range observed for tire fuels (27–39 MJ/kg [1]),
and is substantially higher than that of the bituminous
Indiana coal (Table 1).
Only few investigations on waste tires provide analytical
data for elements other than C, H, N, and S [1]. These
reports, however, document that tires contain high
amounts of Zn and, for steel-belted tires, Fe. Iron may
be present in concentrations of up to 16 wt.% [5,6]. Of par-
ticular interest for emission studies is the relatively volatile
element Zn, which is added as a vulcanizing agent [7]. The
Zn concentration in tire materials ranges mostly between 1
and 2 wt.% [8,9], but may be as high as 4.3 wt.% in certain
truck tires [10].
The shredded tires used in the Purdue University exper-
iment contain approximately 1.1 wt.% Zn (Table 2), but
only minor amounts of Fe. The Fe concentration is low
because the TDF contains relatively few wire pieces. Table
2 reveals rather large standard deviations for many compo-
nents of the Indiana coal, the TDF, and the blend. This
variability is due to heterogeneity of the two fuel compo-
nents and probably also results from insufficient mixing
of coal and TDF.
The concentrations of most elements detected in TDF
alone are statistically significantly different from those
determined in the Indiana coal. Most dramatic is the differ-
times higher in TDF than in coal. Other elements that
are considerably enriched in TDF relative to the high-vol-
atile C bituminous coal from Indiana include C, Cl, Ca, Ti,
Co, Cu, Sb, and W. The S content of TDF is within error
identical to that of the pure coal, which is a medium-sulfur
coal (1.5 ± 0.2 wt.% S). On the other hand, many elements
are relatively depleted in TDF and occur at levels that are
about five to ten times lower than in coal (e.g., As, Hg, Th,
U, and most light rare earth elements). Several elements are
undetectable in TDF, whereas they are present in coal (e.g.,
Be, V, Ga, Se, and most heavy rare earth elements).
Such statistically significant differences, however, are not
observed when comparing the Indiana coal with the
coal + TDF blend (Table 2). Most of the 61 elements ana-
lyzed have similar concentrations in both types of fuel. This
compositional similarity also includes S. The most impor-
tant difference in chemical composition between the blend
and the pure coal is seen for Zn, which is approximately five
times as abundant in the blend. The increase in Zn is clearly
due to the high Zn content of the scrap tire chips. The Zn
content of the blend, however, was determined at
183 ± 42 ppm, i.e. considerably lower than the 580 ppm,
which would be expected from a 95 wt.% coal + 5 wt.%
TDF mixture (theoretical value = 0.95 * 36 ppm + 0.05 *
11,000 ppm). This inconsistency again supports the
interpretation that the fuels were heterogeneous and/or
the mixing incomplete.
4.2. Comparison of emissions
At the sampling point, the stack gases were emitted with
an average volumetric flow rate of 108 ± 2 million liters per
hour. Temperatures of approximately 183 °C and 195 °C
were measured at the sampling point for the stack gases
emitted from the combustion of pure coal and coal + TDF,
respectively. As indicated in Tables 3 and 4 for each type of
fuel, three two-hour experimental runs were performed dur-
ing which stack gases and PM were chemically analyzed.

Table 3
Temperature of stack gases at sampling point and atmospheric emissions from the combustion of pure coal and a coal + TDF blend
Parameter Unit Pure coal Coal + TDFa
Run 1 Run 2 Run 3 Average Std. dev. Run 1 Run 2 Run 3 Average Std. dev.
Temperature °C 182.6 183.8 183.8 183.4 0.7 196.1 197.6 192.3 195 3
O2 vol% 8.23 7.99 7.89 8.0 0.2 8.58 8.12 8.17 8.3 0.2
CO2 vol% 11.02 11.29 11.32 11.2 0.2 10.78 11.16 11.06 11.0 0.2
COb kg/h 6.4 4.8 3.1 5 2 2.8 2.7 3.6 3.0 0.5
NOx b kg/h 62.8 63.8 63.1 63.2 0.5 69.8 70.4 64.9 68 3
SO2 b kg/h 413.6 388.9 369.7 391 22 358.7 378.6 354.6 364 13
HClb kg/h 0.72 0.62 0.72 0.69 0.06 0.86 1.04 1.40 1.1 0.3
HFb kg/h 0.18 0.20 0.21 0.20 0.01 0.20 0.22 0.26 0.23 0.03
THCb mg/s 142.9 186.5 25.9 118 83 0.0 47.2 26.4 24 24
Dioxins/furansb ng/s <19 <17
Total PM kg/h 13.8 14.5 12.6 13.6 0.9 11.6 13.6 14.9 13 2
a
Blend of 95 wt.% coal + 5 wt.% TDF.
b
Corrected to 7 vol% O2.
 R. Gieré et al. / Fuel 85 (2006) 2278–2285 2283

Table 4
Atmospheric emissions (in g/h) of metals and metalloids from the combustion of pure coal and a coal + TDF blend
Pure coal Coal + TDFa
Run 1 Run 2 Run 3 Average Std. dev. Run 1 Run 2 Run 3 Average Std. dev.
Be 0.18 0.18 0.23 0.20 0.03 0.54 0.73 0.86 0.7 0.2
Al 72.6 48.1 62.6 61 12 576.5 709.0 911.3 732 169
Ca 14.5 7.7 9.5 10 4 29.9 41.3 50.8 41 10
V 1.4 0.5 0.9 0.9 0.4 4.54 5.44 6.80 6 1
Cr 0.91 0.91 0.91 0.91 0.00 3.18 3.63 4.99 3.9 0.9
Mn 77669b 66402b 48.1 48.1c 55.8 44.0 31.3 44 12
Co 0.9 0.9 1.4 1.1 0.3 3.2 4.5 5.4 4 1
Ni 4.5 4.1 5.0 4.5 0.4 10.9 14.5 17.2 14 3
Cu 3.2 2.7 4.1 3.3 0.7 11.3 13.6 15.4 13 2
Zn 16.3 13.2 135.6 15d 2 1672 2360 3153 2395 741
As 4.5 4.5 7.7 6 2 21.8 24.9 30.4 26 4
Se 22.7 8.6 5.4 12e 9 13.6 12.2 6.8 11 4
Mo 1.4 1.4 1.4 1.4 0.0 1.8 1.8 1.8 1.8 0.0
Cd 0.05 0.05 0.05 0.05 0.00 0.18 0.23 0.32 0.24 0.07
In 0.91 0.45 0.45 0.6 0.3 0.45 0.45 0.45 0.45 0.00
Sn <1.4 <1.4 <1.4 <1.4 <1.4 <1.4 < 1.4 <1.4
Sb <0.45 <0.45 0.45 0.45 1.36 1.36 1.81 1.5 0.3
Te <0.9 <0.9 <0.9 <0.9 1.81 1.36 2.27 1.8 0.4
Ba 0.18 0.09 0.32 0.2 0.1 0.50 1.09 0.54 0.7 0.3
W <1.4 <1.4 <1.4 <1.4 <1.4 <1.4 <1.4 <1.4
Hg 0.45 0.45 0.45 0.45 0.00 0.45 0.45 0.45 0.45 0.00
Tl 0.45 0.45 0.45 0.45 0.00 1.36 2.27 1.36 1.7 0.5
Pb 10.4 7.7 6.8 8 2 19.1 27.2 12.7 20 7
U <14 <14 <14 <14 <14 <14 <14 <14
a
Blend of 95 wt.% coal + 5 wt.% TDF.
b
High values for these runs are probably due to contamination, possibly by the acid KMnO4 solution used in the fourth and fifth impingers of the
sampling train.
c
Values from runs 1 and 2 ignored in average.
d
Value from run 3 ignored as it is most likely an outlier.
e
Value from run 1 was not included in average given in the summary of reference [1].

The gaseous emission data measured for a given fuel 2.5

mostly show good reproducibility between runs. For exam-
ple, when pure coal was used as fuel, the volume percent-
ages of CO2 emitted during runs 1, 2, and 3 were 11.02, 2.0
11.29, and 11.32, respectively. On the other hand, repro-
Normalized emissions

ducibility was relatively poor for THC emissions: the 1.5

amounts of emitted THC showed great variation between
runs regardless of whether pure coal or coal + TDF was
used as fuel (Table 3). Fig. 3 displays the normalized emis- 1.0
sions of gases and PM, i.e. the emissions from combustion
of the coal + TDF blend normalized to those from pure 0.5
coal combustion. The data suggest a slight decrease in nor-
malized emissions of CO when the coal + TDF mixture
was combusted instead of pure coal (Table 3, Fig. 3). 0.0
CO NOx SO2 HCl HF THC PM
The high Cl content of the TDF (nearly 3000 ppm; Table
2) used in the Purdue University test is responsible for Fig. 3. Normalized average emissions of gases and total particulate
the considerably higher HCl emissions from the blend rel- matter. Values represent emissions from combustion of the coal + TDF
ative to those from pure coal (Fig. 3), which contains only blend normalized to the respective emissions from combustion of pure
215 ppm Cl. The analytical data for the stack gases further coal. Data without error bars have standard deviations that are smaller
document that the average emissions of NOx, SO2, HF and than the symbols. Data from Table 3. Abbreviations: THC = total
hydrocarbon; PM = particulate matter.
total PM resulting from combustion of the two fuels are
not statistically different.
It is of particular note that the NOx emissions did not ing TDF to coal typically leads to a reduction of NOx emis-
decrease with the addition of TDF. This observation is in sions (cf. discussion in [1]). A decrease of about 80% is
contrast to other studies, some of which reported that add- indicated for the normalized emissions of THC (Fig. 3),
2284
1000
Normalized emissions
100
10
0.1
Be Al Ca V
Fig. 4. Normalized average emissions of metals and metalloids. Values represent emissions from combustion of the coal + TDF blend normalized to the
respective emissions from combustion of pure coal. Data without error bars have standard deviations that are smaller than the symbols. Data from Table 4.
but due to the highly variable emission data for individual
runs, the average THC emission values for coal and
coal + TDF are the same within error (Table 3).
The Purdue University experiment further shows that
combustion of the coal + TDF blend rather than pure coal
leads to significantly enhanced average emissions of many
metals and metalloids (Table 4 and Fig. 4). The normalized
emissions displayed in Fig. 4 clearly show that none of the
analyzed elements was emitted at a statistically lower rate
when TDF was added to the coal. On the other hand, emis-
sions of Mn, Se, Mo, In, Ba, and Hg remained constant or
nearly constant. When considering the uncertainties, the
emission rates more than doubled for many of the studied
elements, including toxic elements such as, Be, As, Cd, and
Sb (Fig. 4). Most dramatic is the increase observed for Zn,
whose emissions averaged nearly 2.4 kg/h for the
coal + TDF blend, compared to 15 g/h for the combustion
of pure coal.
5. Discussion
The results for atmospheric emissions from the Purdue
University test burn correspond closely, both qualitatively
and quantitatively, to those obtained in another study,
which was performed at the University of Iowa with a
blend consisting of 92 wt.% coal plus 8 wt.% TDF [11].
As outlined previously [1], these similarities include the
NOx emissions and thus indicate, that using TDF as sup-
plemental fuel in coal-fired power plants does not necessar-
ily lead to a reduction in the emission of nitrogen oxides.
These emissions are not only dependent on plant operating
conditions but also on the N content of the TDF as com-
pared to that of coal. Typically, coal is considerably richer
in N than TDF [1], but no N data are available for the fuels
used here.
The higher normalized emissions of Ca, Co, Cu, Zn, and
Sb are consistent with the higher concentrations of these
elements in TDF as compared to the Indiana coal. How-
ever, elements such as Be, Al, V, Ni, As, Cd, and Pb are
either not detectable or depleted in TDF relative to the
pure coal, but their normalized emissions are greater than
R. Gieré et al. / Fuel 85 (2006) 2278–2285
Cr Mn Co Ni Cu Zn As Se Mo Cd In Sb Te Ba Hg Tl Pb
unity (Fig. 4). At present, this discrepancy is not yet under-
stood. One possible explanation could be that these
enhanced releases might be due to chlorination reactions
during combustion. In their study of metal behavior under
conditions of incineration furnaces, Verhulst et al. [12]
have shown with thermodynamic equilibrium calculations
that the amounts of some metals volatilized during com-
bustion (e.g., Cu, Zn) depend on the amount of Cl present,
amongst other factors (e.g., redox conditions, presence or
absence of S). These calculations further revealed that tem-
perature has a considerable effect on the metal speciation
and that some metals are present predominantly as gaseous
chlorides over large temperature intervals. For example,
the amount of ZnCl2 (g) increases steadily between 300
and 1100 °C in the S-free system. In the same system, PbCl2
(g) and CdCl2 (g) are the predominant species between
400 and 1000 °C; for Cu, on the other hand, chloride
species only become predominant above 700 °C, and even
higher temperatures (>1080 °C) are required for Sb to
occur mainly as gaseous chloride (SbCl). Based on these
results, we conclude that the high Cl contents of TDF
(Table 2) do not only lead to higher emissions of HCl
(Table 3, Fig. 3) but might also lead to formation of gas-
eous chloride species of some metals which, as a conse-
quence, are then emitted at considerably higher rates.
If the average emission rates determined for the sam-
pling periods of this experiment are extrapolated to longer
time scales, it can be calculated that hundreds of kilograms
of metals and metalloids, some toxic and carcinogenic,
would be emitted per year into the atmosphere when the
coal + TDF blend is combusted. For example, more than
200 kg As and nearly 180 kg Pb are emitted over the course
of a year when 5 wt.% TDF are co-combusted with coal.
For Zn, the yearly emissions would amount to 21 t,
whereas only 130 kg would be emitted when pure coal
is combusted. The 21 t of Zn are equivalent to 31 t of
sphalerite (ZnS), the most important Zn ore. When com-
busting coal blended with only 5 wt.% TDF, the Purdue
University stoker boiler thus releases as much Zn per year
as is contained in one standard four-wheel rail wagon,
which is fully loaded with sphalerite.
 R. Gieré et al. / Fuel 85 (2006) 2278–2285 2285

Table 5 Acknowledgements
Average concentrations of trace metals and metalloids in stack gases (in
mg/m3), calculated from the data given in Table 4 and the measured
volumetric flow rate (108 ± 2 ML/h)
The authors are grateful to D.F. Grabowski (GE Mos-
a
tardi Platt), Dr. J.K. Tishmack (Purdue University), and
Element Pure coal Coal + TDF
Bruce High (Wade Utility Plant, Purdue University) for
Average Std. dev. Average Std. dev. help and information provided both during and after the
Be 0.0018 0.0002 0.007 0.001 TDF test burn. Funding for the experiment was obtained
Al 0.6 0.1 7 2 from Purdue University and from the Indiana Department
Ca 0.10 0.03 0.4 0.1
V 0.008 0.004 0.05 0.01
of Commerce, and travel was supported by the Wissen-
Cr 0.0084 0.0002 0.04 0.01 schaftliche Gesellschaft Freiburg. The constructive com-
Mn 0.44 0.4 0.1 ments and suggestions of two anonymous reviewers are
Co 0.010 0.002 0.04 0.01 gratefully acknowledged.
Ni 0.042 0.004 0.13 0.03
Cu 0.03 0.01 0.12 0.02
Zn 0.14 0.02 22 7 References
As 0.05 0.02 0.24 0.04
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