Environ. Sci. Technol.
2004, 38, 3189-3194
Complete Study of the Pyrolysis and
Gasification of Scrap Tires in a Pilot
Plant Reactor
J U A N A . C O N E S A , * I . M A R T IÄ N - G U L L O
Ä N,
R. FONT, AND J. JAUHIAINEN
Department Chemical Engineering, University of Alicante,
Ap. 99, E-03080 Alicante, Spain
The pyrolysis and gasification of tires was studied in a
pilot plant reactor provided with a system for condensation
of semivolatile matter. The study comprises experiments
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at 450, 750, and 1000 °C both in nitrogen and 10% oxygen
atmospheres. Analysis of all the products obtained
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(gases, liquids, char, and soot) are presented. In the gas
phase only methane and benzene yields increase with
temperature until 1000 °C. In the liquids the main components
are styrene, limonene, and isoprene. The solid fraction
(including soot) increases with temperature. Zinc content
of the char decreases with increasing temperature.
Introduction
One of the ways of recycling organic wastes such as used
tires is the energetic revalorization by combustion, although
another way is its pyrolysis in order to obtain chemicals (1).
Tires are mostly composed of different rubbers, such as
natural rubber (NR), butile rubber (BR), or styrene-butadiene
rubber (SBR) as well as mineral oils and carbon black.
Despite the fact that scrap tires represent slightly more
than 12% of all solid waste, scrap tires present a special
disposal and reuse challenge because of their size, shape,
and physicochemical nature. Tire wastes have a high amount
of energy, so energy recovery could be a good recycling
strategy. Considering the low calorific value of several solid
residues (for example, wood 10 178 kJ/kg, municipal solid
wastes 12 374 kJ/kg, lignite 16 983 kJ/kg, subbituminous coal
24 428 kJ/kg, tires 33 035 kJ/kg), it can be seen that, for
example, tire is more “energetic” than bituminous coal, a
classical energy source.
The thermal degradation of tires produces a wide variety
of products in the oil and gas phase, in addition to the residual
char. The thermal degradation of the individual rubber
components of tires has been analyzed using a variety of
techniques to determine the pyrolysis products and their
degradation mechanism. Groves et al. (2) analyzed the oil
derived from the pyrolysis of natural rubber in a pyrolysis-
gas chromatograph at 500 °C. They showed that the major
products were monomer (isoprene) and dimer (dipentene),
with other oligomers up to hexamer in significant concen-
trations. They suggested that the isoprene monomer was
formed via a depropagating mechanism in the polymer chain
and that the dipentene dimer was formed by either in-
tramolecular cyclization followed by scission or by monomer
recombination via a Diels-Alder reaction. Tamura et al. (3)
have also shown that isoprene and dipentene are formed in
high concentration in natural rubber pyrolysis and have
* Corresponding author phone: 34+6-590-3400 ext 2324; fax:
34+6-590-3826; e-mail: ja.conesa@ua.es.
10.1021/es034608u CCC: $27.50  2004 American Chemical Society
Published on Web 04/23/2004
suggested that both are produced by depolymerization from
polymer radicals occurring by beta-scission at double bonds.
The polymer radicals are liable to form six-membered rings,
especially under mild pyrolysis conditions, so the dipentene
is formed predominantly at lower temperature. Bhowmick
et al. (4) also examined the pyrolysis of natural rubber using
TGA. They showed that degradation started at 330 °C in
nitrogen, with a peak weight loss at 400 °C. They suggested
that decomposition followed from radical generation via
polymer chain scission and the formation of isoprene,
dipentene, and other smaller compounds. Chien and Kiang
(5) pyrolyzed natural rubber in helium at 384 °C and identified
isoprene and dipentene as the main products. They also
identified a wide range of other products, including alkane
and alkene gases, toluene, xylene, octene, and hydrocarbons
up to C16H26. They also suggested a mechanism similar to
that of Bhowmick et al. (4), in which isoprene and dipentene
were formed by polymer chain scission and minor com-
pounds were formed via chain propagation with or without
intramolecular hydrogen transfer.
The pyrolysis of polybutadiene rubber to 550 °C in nitrogen
was examined by Brazier and Schwartz (6) using TGA. They
stated that decomposition took place in two stages, with
maximum decomposition rates at 370 and 470 °C, which
depended on the heating rate and sample size. The material
which did not decompose to yield gaseous products forms
a solid residue by cyclation and cross-linking, which is
degraded in the second stage yielding more gases. The
products of pyrolysis from the second stage were a complex
mixture of hydrocarbons. Madorsky et al. (7) have also
examined the pyrolysis of polybutadiene rubber and similarly
showed that butadiene, vinylcyclohexene, and dipentene
were formed in high concentrations. Other compounds
formed were ethylene, ethane, propylene, propane, butylene,
butane, cyclopentadienes, etc.
The pyrolysis of styrene-butadiene rubber (SBR) between
240 and 450 °C was investigated by Erdogan et al. (8) using
a pyrolysis-mass spectrometer. They identified butadiene
and butadiene fragments at lower pyrolysis temperatures
and styrene and/or benzene at higher temperatures. They
suggested that the thermal degradation of SBR started with
the butadiene elements of the copolymer and that higher
temperatures were required to degrade the styrene elements.
Other compounds identified in tire pyrolysis oils in
significant concentrations have included benzene, toluene,
xylene, styrene, limonene, indane, indene, polycyclic aro-
matic hydrocarbons such as naphthalene, fluorene, and
phenanthrene, vinylalkenes, alkanes. The main gases pro-
duced during the pyrolysis of tires are CO2, CO, H2, CH4,
C2H6, C3H6, C3H8, and C4H6, with lower concentrations of
other hydrocarbon gases. Bhowmick et al. (4) and Chien and
Kiang (9) have suggested that the other products of pyrolysis
can be accounted for by the thermal decomposition of iso-
prene and dipentene. Tamura et al. (3) have also suggested
that benzene may be formed as a direct result of the thermal
degradation of the rubber polymer via the formation of con-
jugated double bonds in the polymer chain. Where extensive
secondary reactions of the pyrolysis vapors occur, the
formation of aromatic and polycyclic aromatic compounds
has been attributed to a Diels-Alder cyclization reaction to
alkenes, particularly at either high temperatures or long
residence times (10, 11). The pyrolysis of tires leads to the
production of ethene, propene, and 1,3-butadiene, which
react to form cyclic alkenes. Dehydrogenation of the cyclic
alkene compounds with six carbon atoms occurs, producing
single-ring aromatic compounds such as benzene and, as a
VOL. 38, NO. 11, 2004 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3189
TABLE 1. Proximate and Ultimate Analysis of the Tire
proximate analysis % weight
moisture 0.9
volatile matter 65.5
fixed carbon 29.4
ash 3.7

ultimate analysis % weight

C 89.4
H 7.0
N 0.2
S 2.0

result of subsequent associative reactions, may lead to the

formation of polycyclic aromatic hydrocarbons such as
naphthalene and phenanthrene and its substituted derivates.
In previous papers of our research group, the kinetics of
the decomposition of tire wastes when heating at different
rates during thermogravimetric measurements was studied,
both in nitrogen and oxygen atmospheres (12, 13), and a
complete kinetic model was also developed. The products
formed during pyrolysis (1) and partial oxygen supply (14)
were also studied. In this last paper, special interest was
placed in the pollutant formation and control. A paper
presenting the gas evolution in different equipments was
published (15). It was shown that the decomposition of tire
wastes at three different heating rates (1, 5, and 25 °C/min)
is explained by means of a kinetic model including 3-organic
fractions that do not form char and an inorganic fraction
that is inert to pyrolysis. The mass spectrometer showed
that the evolution of gases takes place in three different stages,
confirming that three different groups of compounds are
pyrolyzed. The decomposition in an oxidizing atmosphere
was explained by means of a kinetic model including the
first step of pyrolysis and a step of combustion of the residue
formed. On the other hand, the yield of total gas obtained
in the pyrolysis in a fluidized bed reactor increased in the
range 600-800 °C from 6.3 to 37.1%. At higher temperatures,
the yield of total gas decreased slightly. The formation of
methane, hydrogen, benzene, and toluene is favored by high
residence times, but ethane, ethylene, propane, propylene,
butane, butylene, acetylene, 1,3-butadiene, and pentane
undergo cracking to different extents at increasing residence
times and/or temperature. In other work (14), over 100 volatile
and semivolatile compounds evolved in the combustion of
scrap tires in a horizontal laboratory furnace were identified
and quantified by gas chromatography mass spectrometry,
plotting their yields vs the bulk air ratio and temperature.
Five different behaviors considering the bulk air ratio and
the temperature were identified.
The objective of the present study is to investigate the
pyrolysis and gasification of scrap tires in a pilot plant
equipment at different temperatures, with semicontinuous
feeding of the material. An exhaustive analysis of the products
evolved is done, including the quantification and analysis of
the gas, liquid, and solid fractions.
Materials and Equipment
The tires used for the study were supplied by a local recycling
plant. Tires were crushed by physical procedures (no
cryogenic immersion was needed) until a particle size of
approximately 4 mm. Both proximate and ultimate analysis
of the material are presented in Table 1.
An scaled scheme of the reactor and condensation system
can be seen in Figure 1; the length of the reactor that is
inside the furnace is 654 mm. The whole system has four
different zones:
FIGURE 1. Schematic of the reactor system.
I. Solid feeder. The scrap tires are fed to the reactor by a
two-valve manual system. This systems allows the introduc-
tion of the tire particles without gas venting through the
feeder. The appropriate amount of tire is placed in the hopper
and passes first the upper valve, and, after closing it, the
lower valve is opened. The feeding rate has been 5 g each 10
min during at least 2 h.
II. Gas line. The carrier gas is first preheated by circulating
vertically between two cylindrical tubes: the outer one is the
calandria and the inner one is the reactor itself, where the
solids are fed. The gas flow rate was 1.5 L/min. In the pyrolysis
runs industrial nitrogen (purity = 99.5%) was used. In the
gasification runs, a nitrogen-synthetic air mixture, with 10%
of oxygen, was fed.
III. Reactor. This is the part that is inside the vertical electric
furnace. The nominal temperatures used in the runs have
been 450, 750, and 1000 °C. The temperature is controlled
by a type-K thermocouple sited inside the furnace near to
the reactor. Measure of the temperature inside the reactor
has been performed by introducing a thermocouple by its
upper side. The measurements at different positions shows
a maximum difference of 10 °C between the furnace and the
inner part of the reactor.
IV. Cooling and condensation system. This was done by
means of a jacket filled with solid CO2 (-78 °C), approximately
300 g in each run. The temperature inside the system in this
zone is lower than 13 °C in all the runs, so a very good
condensation of semivolatile species is expected.
Description of an Experiment. All the experiments and
analysis of the different fractions (except that of the solid)
were repeated twice in order to check for the reproducibility.
The steps followed to run an experiment are as follows:
1. The temperature is selected in the furnace and begins
the heating. A high flow of air is used during the heating, to
eliminate rests (coke) of the previous run.
2. Dry ice is placed in the condensation jacket.

3190 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 38, NO. 11, 2004
 3. Once the reactor is at the selected temperature, the
flow rate of the gases was fixed at 1.5 L/min. After 15 min
scrap tires were fed 5 g each 10 min. Note that in this way,
the residue solid (char) accumulates inside the reactor during
the experiment.
4. After 1 h, a gas sample is taken directly from the upper
part of the reactor. A trap for condensable species is inserted
after the probe (water jacket, XAD-2 resin and silica gel), and
a pump is used to control the flow rate of the sampling system
(maintained at = 300 mL/min). The gas sample is collected
throughout 15 min (approximately 5 L of gas sample) in a
Tedlar bag sited after the pump. After the second hour of
experiment another gas sample is taken. Later, the feeding FIGURE 2. Measurement of the CO in the gas at the beginning of
of the tires is interrupted. In the first runs a gas sample was a run and at 1.1 h after the start. Pyrolysis at 450 °C.
also taken from the exit of the system, near to the burner;
it was checked that the gas analysis is very similar to that
performed over the sample taken directly from the furnace.
TABLE 2. Yield of the Different Fractions in the Runs
Performed
5. The furnace is maintained at the reaction temperature
for 2 more hours, to get a solid completely reacted. The carrier atmosphere T (°C) % solidsa % tarsa % soota
gas flow rate is also maintained during this time. In a nitrogen 450 36.4 38.6
gasification run performed at 750 °C the gas was kept only 34.1 37.0
during 30 min, to see the effect of this heating. nitrogen 750 36.8 9.23
6. The furnace is switched off and after cooling, and the 37.2 12.5
solid char was recovered from the reactor. The tars condensed nitrogen 1000 36.7 <0.01 25.3
in the cold zone are removed by opening valve 8 in Figure 38.6 <0.01 24.9
10% O2 450 13.6 27.8
1, and the condensation system is cleaned with acetone; the
12.4 23.6
acetone with the rests of tars are also collected, and later the 10% O2 750 19.8b 12.3
acetone is evaporated at vacuum and low temperature (<40 9.93 13.9
°C); the tars of this fraction are analyzed separately. 10% O2 1000 14.2c <0.01 19.4
Analytical Methods. The gas fraction was analyzed by 18.8c <0.01 24.9
gas chromatography with FID detector for hydrocarbons and a The % are referred to as the amount of tire (weight) fed. The

with TCD detector for measuring N2, O2, CO2, CO, and H2.
The analysis is performed by injecting a sample of the gas
collected in the Tedlar bag. Shimadzu GC-14A gas chro-
matograph with a TCD detector was used for the quantifica-
tion of CO2, CO, methane, and ethane. The light hydrocarbons
C1-C6 together with benzene and toluene were analyzed in
Shimadzu GC-17A chromatograph with a FID detector. A
total of six different gas patterns containing a known amount
of hydrocarbons C1-C6 together with CO2 and CO, with the
balance completed with N2, were used to calibrate the gas
chromatographs.
On-line measurement of CO was done in some runs with
a Lancom model 6500 portable gas analyzer.
EPA method 8270 was used for the analysis of the liquid
fraction. The total amount of liquid obtained was diluted
with 100 mL of dichloromethane. The liquid is totally miscible
with dichloromethane, and no extraction is required. An
aliquot of 50 µL of this solution was diluted to 1.5 mL with
dichoromethane. To the resulting solution, 20 µg of each of
the deuterated compounds (1,4-dichlorobenzene-D4, naph-
thalene-D8, acenaphthene-D10, phenanthrene-D10, chrysene-
D12, and perylene-D12) was added. The analysis was per-
formed in a low resolution mass spectrometer (scan mode,
m/z from 50 to 500) connected to a gas chromatograph. For
the analysis the used equipment was a gas chromatograph
GC8000 with a mass spectroscopy detector MD8000, both
from FISONS Instruments. The column used was a DB-5 MS
of length 30 m and an intern diameter of 0.25 mm. For
identifying and quantifying the liquids, the sample was
injected to a chromatograph with a MS Scan mode detector.
The identification of the detected compounds was made by
comparing their mass spectras to ones found in the software
library.
Ultimate analysis were performed in a Carlo Erba Instru-
ment model CHNS-O EA110.
Surface area analysis of carbonaceous materials was
performed in a Autosorb-6 equipment, using CO2 at 273 K
isotherms, after a devolatilization period of 2 h at 200 °C.
percentage of gas can be calculated by the difference. b Experiment
with only 30 min heating after the run. c The char obtained has
appreciable amounts of the reactor structure.
Metal content on the solid fractions was measured by
X-ray fluorescence with a Philips model PW1480 apparatus.
Results
Some tests were performed in the equipment prior to running
the complete experiments. On-line measurement of CO was
done to determine the time after which analysis of the gases
would be representative of the continuous process. Figure
2 shows the CO detected during the first discharge to the
reactor in a pyrolysis run at 450 °C and the same after 1 h
of experiment. As it could be seen, the % of CO in the gas
is quite constant after 1 h of experiment, even taking into
account the addition of tire that is done during this time,
showing that probably the system is stationary.
Yield of the Different Fractions. Table 2 presents the
percentages (in weight basis with respect to the original tire)
of the different fractions collected. As commented on above,
the experiments were repeated twice in order to check for
the reproducibility. The results show a good reproducibility.
As can be seen in Table 2, at 1000 °C there is no formation
of a liquid fraction. Instead of this, a new fraction composed
by fine particles is formed; these particles are carried away
and seem to be carbonaceous material totally cracked, i.e.,
soot. At this elevated temperature, the cracking of the volatile
fraction is much more intense, yielding noncondensable
gases and polycondensate solid carbon. The average weight
yields of each fraction are plotted in Figure 2. The char and
soot yields were added in this figure. An important decrease
in the liquid (tar) fraction when increasing the temperature
is clearly observed, both in the presence and in absence of
oxygen, whereas the solid fraction increases.
An important point is the effect of the final heating period
(point 5 in the description of an experiment) on the solid
sample. The effect is different in the pyrolysis runs with

VOL. 38, NO. 11, 2004 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3191
TABLE 3. Gas Analysis
T (°C) 450 450 750 750 1000 1000
atmosphere nitrogen 10% O2 nitrogen 10% O2 nitrogen 10% O2
flow rate (L/min) 1.56 1.44 1.51 1.56 1.53 1.53 1.51 1.51 1.54 1.56 1.51 1.51
CO2 3.24 3.50 9.12 7.83 4.01 4.22 9.72 10.3 1.28 2.34 4.64 4.31
CO 3.42 5.96 1.19 3.08 4.15 1.37 1.27 8.10 9.69
H2 0.05 0.05 0.28 0.29 0.33 0.36 0.45 0.35 1.05 0.95 1.34 1.42
methane 0.64 0.66 1.20 1.02 4.69 4.55 4.76 4.76 5.08 10.7 3.82 3.84
ethane 0.23 0.24 0.14 0.11 1.13 1.09 1.11 1.16 0.07 0.14 0.04 0.04
ethylene 0.40 0.37 0.15 0.18 2.16 2.67 2.83 2.85 0.45 0.97 0.30 0.32
propane 0.08 0.09 0.11 0.055 0.13 0.14 0.13 0.15 0.002
propylene 0.21 0.23 0.17 0.036 1.00 1.22 1.71 1.54 0.025 0.042 0.007 0.005
acetylene 0.003 0.003 0.012 0.011 0.004 0.011 0.007 0.016 0.046 0.010 0.044 0.042
isobutane 0.002 0.002 0.001 0.017 0.019
n-butane 0.008 0.008 0.053 0.002 0.014 0.051 0.022 0.024
1-butene 0.004 0.004 0.031 0.092 0.080 0.026 0.061
isobutene 0.010 0.010 0.005 0.002 0.017 0.067 0.029
cis-2-butene 0.001 0.001 0.006 0.001 0.021 0.007 0.017
n-pentane 0.004 0.001 0.009 0.004
1,3-butadiene 0.011 0.011 0.058 0.202 0.165 0.068 0.081 0.027 0.001 0.001
1-pentene 0.003 0.001 0.001
2-butyne 0.003
1-butyne 0.012
isoprenea 2.93a 2.80a 0.368a 0.351a 0.79a 0.65a 0.31a 0.29a 0.015a
benzenea 4.16a 4.53a 4.30a 4.72a 8.32a 9.10a 8.10a 7.35a
toluenea 0.003 0.003 1.589a 1.328a 2.86a 2.20a 2.06a 2.20a 0.002 0.003
a Volatile compounds are collected as gases. The data presented correspond to the gas analysis, but the actual amount obtained could be higher.

material at the temperature considered, i.e., at the end a

FIGURE 3. Yield of the different fractions as a function of temperature.
respect to the gasification runs. In the pyrolysis runs, this
period means to achieve the total decomposition of the
solid with no volatile matter at the fixed temperature is
obtained; nevertheless, in reactive atmosphere (oxygen)
during this period the solid char continues reacting with the
gas, so a kind of partially burnt solid is obtained, and
consequently, this fact should be considered for the design
of a continuous process. The solid char fraction obtained in
all the pyrolysis runs is quite similar, indicating that probably
the pyrolysis ends at a low temperature and that the heating
rate has not a great influence. In the gasification runs the
behavior is different: from Table 2, a final heating period of
30 min produces 19.8% of char in the runs performed with
oxygen at 750 °C, while a 2-h period produced 9.93% (while
the liquid fraction coincides). In this way, in 90 min of
difference half of the char produced is burnt.
Analysis of the Gas Fraction. Table 3 shows the results
obtained (yields expressed in wt % of tire fed) produced in
the pyrolysis or gasification process. In this case Table 3
reflects the analysis of the two runs performed at each
temperature. Figure 3 shows the average of the yields obtained

FIGURE 4. Gas yields as a function of the temperature.

3192 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 38, NO. 11, 2004
 isoprene (2-methyl-1,3-butadiene). Other hydrocarbons are
TABLE 4. Liquid Analysis not produced in an important yield, due to the low cracking
emission factors (mg/kg tire) occurring in the reactor at this temperature. At 750 °C the
yields of all the compounds in this phase increase, and at
450 °C 750 °C
1000 °C there is a general decrease of the yields, except that
compound N2 N2/O2 N2 N2/O2 of methane, hydrogen, and benzene. This is a general
p-xylene 746 562 65 81 behavior of all the materials when being pyrolyzed (15): at
1,2-dimethylbenzene 434 290 160 324 750 °C the hydrocarbon yield increases as a consequence of
styrene 2780 2152 1022 1857 the cracking of semivolatile matter, but at 1000 °C the cracking
benzene, (1-methylethyl)- 143 242 0 0 is so intense that it only increases the typical final products,
5,5-dimethylhexanal 1635 1427 373 681 i.e., methane, benzene, and char (including the soot fraction).
R-methylstyrene 336 0 1203 1607
In the pyrolysis runs, the amount of carbon oxides (COx) are
m-methylstyrene 0 0 350 0
2-(1-propenyl)pyrazine 895 890 171 240 quite constant with temperature, showing that the formation
limonene 6904 4138 165 1045 of such compounds is possibly due to the oxygen impurities
indene 344 376 1601 1783 that present the nitrogen used in the runs.
1,2,3,4,5,8-hexahydronaphthalene 206 475 0 0 When oxygen is present in the process, the production of
o-isopropenyltoluene 459 523 258 111 COx increases considerably with respect to the pyrolysis run,
1h-indene,1-methyl- 654 810 337 374
and the H2 yield slightly increases in all gasification runs. In
benzene, 1-methyl-4-(1-propynyl)- 295 286 437 463
naphthalene 1225 1087 1456 1791 general, there is a decrease of the yields of hydrocarbons,
1,2-benzisothiazole 596 928 102 164 clearly seen at the highest temperature studied, that is not
1-ethylidene-1h-indene 627 223 998 0 so clear at the lower temperatures (at 700 °C the yields are
benzocycloheptatrien 1079 1554 869 941 quite similar, and at 400 °C some compounds increase their
benzene,3-cyclohexen-1-yl- 660 1237 42 165 yields and some other decreases). In gasification runs an
naphthalene, 2-ethenyl- 981 1227 826 951
increase of the temperature increases the ratio CO/CO2, due
1-phenylcyclohexene 840 1248 146 188
1,8-dimethylnaphthalene 486 491 324 426 to the fact that the CO is produced at high temperatures, and
2-ethenylnaphthalene 423 0 348 449 also the chemical equilibrium favors its formation.
2,7-dimethylquinoline 531 1284 436 599 Analysis of the Liquid (Tar) Fraction. Table 4 shows the
acenaphthylene 680 0 710 868 average results of the analysis of the runs (mg/kg of tire).
1,1′-biphenyl, 4-methyl- 476 0 397 487 Only the major compounds are shown. At 1000 °C the amount
1h-phenalene 560 270 574 684
of liquids is negligible.
benzene, 1,1′-(1,3-propanediyl)bis- 710 589 0 107
heptadecane, 2,6,10,15-tetramethyl- 520 482 0 0 At a low temperature, as it is 450 °C, the composition of
phenanthrene 204 266 376 783 the liquid fraction has as majority compounds styrene,
anthracene 233 278 95 206 limonene, and monoaromatic derivates. This compounds
2-phenylnaphthalene 150 148 148 332 are primary compounds formed in the decomposition of the
fluoranthene 130 233 75 198 solid. In the presence of oxygen, there is a decrease of all
pyrene 319 121 104 221
compounds and also of the total liquid yield as shown in
bis(2-ethylhexyl) phthalate 0 274 156 0
benz[a]anthracene 0 0 136 0 Table 2.
At 750 °C, the styrene emissions are maintained, since it
is an intermediate product in the cracking process. Never-
for the majority compounds. The calculation of these yields theless, a decrease in limomene yield is observed, simulta-
is done by analyzing the nitrogen present in the sample bag, neous with an increase in R-methylstyrene and indene. Also
together with the various compounds. An average yield is the presence of polyaromatic hydrocarbons (PAHs) could be
calculated bearing in mind the nitrogen fed to the system observed, but at a low extent, as the total liquid fraction is
(=1.5 L/min in pyrolysis runs) and the average tire feeding at this temperature. The presence of oxygen has little effect
rate (0.5 g/min). in the composition of the liquid.
With respect to the formation of gases in pyrolysis runs, Analysis of the Solid Residue. Proximate and ultimate
it should be noted that, at 450 °C, the main compound is analysis as well as metal analysis has been performed over

TABLE 5. Solid Properties

T (°C) 450 450 750 750b 1000 1000 1000 1000
atmosph N2 10% O2 N2 10% O2 N2 10% O2 FPa N2 FPa O2
ultimate analysis %C 88.19 68.27 88.63 83.37 92.13 54.95 90.76 90.92
%H 0.60 0.66 0.31 0.27 0.17 0.15 0.15 0.18
%N 0.10 0.24 0.03 0.00 0.00 0.00 2.64 2.64
%S 1.90 1.29 2.02 3.22 1.23 1.47 1.10 1.17
proximate analysis % moisture 0.37 1.72 0.40 0.61 0.25 0.26
% volatile 7.78 8.82 5.58 0.79 1.06 2.82
% ash 8.27 8.29 5.57
metals (%) Mg 0.147 0.147 0.248 0
Si 1.69 1.64 3.66 0.079
K 0.0969 0.0958 0.225 0.0145
Ca 0.127 0.146 0.29 0.0412
Ti 0.0171 0.0201 0.0384 0.0165
Fe 0.0393 0.057 0.108 0.762
Zn 6.68 6.33 0.935 4.14
Pb 0.0109 0.0019 0.0019 0.0129
NCVc kcal/kg 7367.4 7542.3 7671.5
surface area m2/g 93 91 139 251
aFP ) “fine particle” fraction (soot); all the other data correspond to chars. b Remember that this run was performed with a shorter final heating
period. c Net calorific value.

VOL. 38, NO. 11, 2004 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 3193
the solid fractions collected in the runs. Also the surface area
analysis has been performed. Metal content has been
determined by X-ray fluorescence. The surface area has been
calculated by application of the Dubinin-Radushkievich-
Kaganer method to the CO2 (273 K) isotherm. Table 5 shows
the results.
The carbon content is very high in all the chars obtained
in pyrolysis (88-92%) and also in the soot, but the carbon
content in the chars obtained in the presence of oxygen is
much lower (except of that of the run with a shorter final
heating period). The reason is the same as commented earlier.
The chars obtained at 450 and 750 °C are quite similar
respect to the CHNS composition and also the ultimate
analysis. On the contrary, the char obtained in the pyrolysis
at 1000 °C has a higher carbon content with almost no volatile
matter, as it was expected, and a surprisingly lower ash
content. On the contrary, it seems that all the nitrogen in the
original tire is accumulated in the soot fraction, since the
nitrogen content is quite low in the tire and in the char but
quite high (2.46%) in the soot.
Table 5 shows the metal content for the metals with a
percentage over 0.001%. It is remarkable the similar metal
content for chars obtained at 450 °C and at 750 °C (ap-
proximately 6.4% Zn and 1.6% Si), but the char obtained at
1000 °C (with a very low ash content) has a very low zinc
content, appearing as zinc in the soot. In the literature ZnO
could be transformed to Zn in the presence of hydrogen or
methane (16). Metal Zn has a boiling point of 901 °C, data
that would explain the result obtained. The yield of the
semivolatile fraction is maximum at low temperatures and
practically null at 1000 °C; but from the solid analysis, and
bearing in mind that it is desirable to control the Zn and to
avoid evaporation, it is important to operate at temperatures
under 900 °C.
The surface area of the solids are also shown in Table 5.
The area is similar in all the cases to that of a commercial
carbon black. It should be observed the higher surface of the
soot with respect to the chars.
Comparison with Literature. In the literature some results
obtained in the pyrolysis of tires in different types of
equipment have been previously compared (15). It was shown
that, using the appropriate functions, the amount and variety
of volatile and semivolatile compounds analyzed on one
laboratory’s equipment is given as an estimate of the
production in industrial scale operation.
The kinetic severity function (KSF) has been proposed as
a measure of the cracking undergone by the tars produced,
3194 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 38, NO. 11, 2004
obtaining logical results. Using the method described (15) it
could calculate the KSF in the present work. Values of KSF
are <0.01, 2.5, and 580 at 450, 750, and 1000 °C, respectively.
These values of KSF would produce 0.2% of methane at 450
°C and 4.5% at 750-1000 °C, that coincides with the results
obtained in the present study. From the values of methane
yield some more compounds could be correlated (15). The
present study analyzes with more detail all the products
obtained both in the presence and the absence of oxygen.
Acknowledgments
Support for this work was provided by “Tecnologı́as y
Aplicaciones Medioambientales de Alcanar, S. L.”, a company
owned by the CEMEX group (http://www.cemex.com).
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Received for review June 16, 2003. Revised manuscript re-
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