Compl et e St udy of t he Pyrol ysi s and

Gasi fi cat i on of Scrap Ti res i n a Pi l ot

Pl ant React or
J U A N A . C O N E S A , * I . M A R T I N - G U L L O N ,
R . F O N T , A N D J . J A U H I A I N E N
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 systemfor condensation
of semivolatile matter. The study comprises experiments
at 450, 750, and 1000 C both in nitrogen and 10% oxygen
atmospheres. Analysis of all the products obtained
(gases, liquids, char, and soot) are presented. In the gas
phase only methane and benzene yields increase with
temperatureuntil 1000C. Intheliquids themaincomponents
are styrene, limonene, and isoprene. The solid fraction
(including soot) increases with temperature. Zinc content
of the char decreases with increasing temperature.
I nt roduct i on
One of the ways of recycling organic wastes such as used
tires is the energetic revalorizationby 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), butilerubber (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,
andphysicochemical nature. Tire wastes have a highamount
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 intheoil andgas phase, inadditiontotheresidual
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
formedviaadepropagatingmechanisminthe polymer chain
and that the dipentene dimer was formed by either in-
tramolecular cyclizationfollowedby scissionor 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
suggestedthat bothare producedby depolymerizationfrom
polymer radicals occurring by beta-scissionat double bonds.
The polymer radicals are liable to formsix-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) pyrolyzednatural rubber inheliumat 384Candidentified
isoprene and dipentene as the main products. They also
identified a wide range of other products, including alkane
andalkene gases, toluene, xylene, octene, andhydrocarbons
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.
Thepyrolysis of polybutadienerubber to550Cinnitrogen
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
examinedthepyrolysis of polybutadienerubber andsimilarly
showed that butadiene, vinylcyclohexene, and dipentene
were formed in high concentrations. Other compounds
formedwereethylene, 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 requiredtodegrade 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 CO
2, CO, H2, CH4,
C2H6, C3H6, C3H8, and C4H6, with lower concentrations of
other hydrocarbongases. Bhowmick et al. (4) and Chienand
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-
jugateddouble bonds inthe 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 withsix carbonatoms occurs, producing
single-ring aromatic compounds such as benzene and, as a
* Corresponding author phone: 34+6-590-3400 ext 2324; fax:
34+6-590-3826; e-mail: ja.conesa@ua.es.
Environ. Sci. Technol. 2004, 38, 3189-3194
result of subsequent associative reactions, may lead to the
formation of polycyclic aromatic hydrocarbons such as
naphthaleneandphenanthreneandits substitutedderivates.
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 explainedby 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 theevolutionof gases takes placeinthreedifferent 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 stepof pyrolysis and a stepof combustionof 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 Cfrom6.3 to37.1%. At higher temperatures,
the yield of total gas decreased slightly. The formation of
methane, hydrogen, benzene, andtoluene is favoredby high
residence times, but ethane, ethylene, propane, propylene,
butane, butylene, acetylene, 1,3-butadiene, and pentane
undergocracking todifferent extents at increasing residence
times and/or temperature. Inother work(14), over 100volatile
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
feedingof thematerial. Anexhaustiveanalysis of theproducts
evolved is done, including the quantification and analysis of
the gas, liquid, and solid fractions.
Mat eri al s and Equi pment
The tires usedfor the study were suppliedby 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.
Anscaledscheme of the reactor andcondensationsystem
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:
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. Theappropriateamount of tireis placedinthehopper
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 preheatedby circulating
vertically betweentwocylindrical tubes: the outer one is the
calandria and the inner one is the reactor itself, where the
solids arefed. Thegas flowratewas 1.5L/min. Inthepyrolysis
runs industrial nitrogen (purity = 99.5%) was used. In the
gasificationruns, a nitrogen-synthetic air mixture, with10%
of oxygen, was fed.
III. Reactor. This is thepart that is insidethevertical 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 maximumdifference of 10 Cbetween the furnace and the
inner part of the reactor.
IV. Cooling and condensation system. This was done by
means of ajacket filledwithsolidCO2 (-78C), 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 repeatedtwice inorder tocheck 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.
TABLE 1. Proxi mat e and Ul t i mat e Anal ysi s of t he Ti re
proximateanalysis %weight
moisture 0.9
volatile matter 65.5
fixed carbon 29.4
ash 3.7
ultimateanalysis %weight
C 89.4
H 7.0
N 0.2
S 2.0
FIGURE1. Schematic of thereactor system.
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,
theresiduesolid(char) accumulates insidethereactor during
the experiment.
4. After 1 h, a gas sample is taken directly from the upper
part of the reactor. Atrap for condensable species is inserted
after the probe (water jacket, XAD-2 resinand silica gel), and
apumpis usedtocontrol theflowrateof thesamplingsystem
(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
of the tires is interrupted. In the first runs a gas sample was
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.
5. The furnace is maintained at the reaction temperature
for 2morehours, toget asolidcompletelyreacted. Thecarrier
gas flow rate is also maintained during this time. In a
gasification run performed at 750 C the gas was kept only
during 30 min, to see the effect of this heating.
6. The furnace is switched off and after cooling, and the
solidchar was recoveredfromthereactor. Thetars condensed
in the cold zone are removed by opening valve 8 in Figure
1, and the condensation systemis cleaned with acetone; the
acetone with the rests of tars are also collected, and later the
acetone is evaporated at vacuumand lowtemperature (<40
C); the tars of this fraction are analyzed separately.
Analytical Methods. The gas fraction was analyzed by
gas chromatography withFIDdetector for hydrocarbons and
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-
tionof CO2, CO, methane, andethane. Thelight 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 knownamount
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 COwas 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
with100mLof dichloromethane. Theliquidis totallymiscible
with dichloromethane, and no extraction is required. An
aliquot of 50 L of this solution was diluted to 1.5 mL with
dichoromethane. To the resulting solution, 20 g 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
fromFISONS 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 inthe 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.
Metal content on the solid fractions was measured by
X-ray fluorescence with a Philips model PW1480 apparatus.
Resul t s
Sometests wereperformedintheequipment prior torunning
the complete experiments. On-line measurement of COwas
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 onabove,
the experiments were repeated twice in order to check for
the reproducibility. The results showa good reproducibility.
As canbe seeninTable 2, at 1000 Cthere is no formation
of a liquid fraction. Instead of this, a newfraction composed
by fine particles is formed; these particles are carried away
and seem to be carbonaceous material totally cracked, i.e.,
soot. At this elevatedtemperature, 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.
Animportant 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
FIGURE2. Measurementof theCOinthegasatthebeginningof
arunandat1.1hafter thestart. Pyrolysis at450C.
TABLE 2. Yi el d of t he Di fferent Fract i ons i n t he Runs
Performed
atmosphere T(C) %solids
a
%tars
a
%soot
a
nitrogen 450 36.4 38.6
34.1 37.0
nitrogen 750 36.8 9.23
37.2 12.5
nitrogen 1000 36.7 <0.01 25.3
38.6 <0.01 24.9
10%O
2 450 13.6 27.8
12.4 23.6
10%O2 750 19.8
b
12.3
9.93 13.9
10%O2 1000 14.2
c
<0.01 19.4
18.8
c
<0.01 24.9
a
The % are referred to as the amount of tire (weight) fed. The
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.
respect to the gasification runs. In the pyrolysis runs, this
period means to achieve the total decomposition of the
material at the temperature considered, i.e., at the end a
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 lowtemperature 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. Figure3shows theaverageof theyields obtained
TABLE 3. Gas Anal ysi s
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
isoprene
a
2.93
a
2.80
a
0.368
a
0.351
a
0.79
a
0.65
a
0.31
a
0.29
a
0.015
a
benzene
a
4.16
a
4.53
a
4.30
a
4.72
a
8.32
a
9.10
a
8.10
a
7.35
a
toluene
a
0.003 0.003 1.589
a
1.328
a
2.86
a
2.20
a
2.06
a
2.20
a
0.002 0.003
a
Volatilecompounds arecollectedas gases. Thedatapresentedcorrespondtothegas analysis, but theactual amount obtainedcouldbehigher.
FIGURE3. Yieldofthedifferentfractionsasafunctionoftemperature.
FIGURE4. Gas yields as afunctionof thetemperature.
for the majority compounds. The calculation of these yields
is done by analyzing the nitrogen present in the sample bag,
together with the various compounds. An average yield is
calculated bearing in mind the nitrogen fed to the system
(=1.5 L/min in pyrolysis runs) and the average tire feeding
rate (0.5 g/min).
With respect to the formation of gases in pyrolysis runs,
it should be noted that, at 450 C, the main compound is
isoprene (2-methyl-1,3-butadiene). Other hydrocarbons are
not produced in an important yield, due to the low cracking
occurring in the reactor at this temperature. At 750 C the
yields of all the compounds in this phase increase, and at
1000 C there is a general decrease of the yields, except that
of methane, hydrogen, and benzene. This is a general
behavior of all the materials when being pyrolyzed (15): at
750 C the hydrocarbon yield increases as a consequence of
thecrackingof semivolatilematter, but at 1000Cthecracking
is so intense that it only increases the typical final products,
i.e., methane, benzene, andchar (includingthesoot fraction).
In the pyrolysis runs, the amount of carbon oxides (COx) are
quite constant withtemperature, showing that the formation
of such compounds is possibly due to the oxygen impurities
that present the nitrogen used in the runs.
When oxygen is present in the process, the production of
COx increases considerably withrespect to the pyrolysis run,
and the H2 yield slightly increases in all gasification runs. In
general, there is a decrease of the yields of hydrocarbons,
clearly seen at the highest temperature studied, that is not
so clear at the lower temperatures (at 700 C the yields are
quite similar, and at 400 C some compounds increase their
yields and some other decreases). In gasification runs an
increase of the temperature increases the ratio CO/CO2, due
to the fact that the COis producedat hightemperatures, and
also the chemical equilibrium favors its formation.
Analysis of the Liquid (Tar) Fraction. Table 4 shows the
average results of the analysis of the runs (mg/kg of tire).
Onlythemajor compounds areshown. At 1000Ctheamount
of liquids is negligible.
At a low temperature, as it is 450 C, the composition of
the liquid fraction has as majority compounds styrene,
limonene, and monoaromatic derivates. This compounds
are primary compounds formedinthe decompositionof the
solid. In the presence of oxygen, there is a decrease of all
compounds and also of the total liquid yield as shown in
Table 2.
At 750 C, the styrene emissions are maintained, since it
is an intermediate product in the cracking process. Never-
theless, a decrease in limomene yield is observed, simulta-
neous with an increase in R-methylstyrene and indene. Also
the presence of polyaromatic hydrocarbons (PAHs) couldbe
observed, but at a low extent, as the total liquid fraction is
at this temperature. The presence of oxygen has little effect
in the composition of the liquid.
Analysis of the Solid Residue. Proximate and ultimate
analysis as well as metal analysis has been performed over
TABLE 4. Li qui d Anal ysi s
emissionfactors(mg/kgtire)
450C 750C
compound N2 N2/O2 N2 N2/O2
p-xylene 746 562 65 81
1,2-dimethylbenzene 434 290 160 324
styrene 2780 2152 1022 1857
benzene, (1-methylethyl)- 143 242 0 0
5,5-dimethylhexanal 1635 1427 373 681
R-methylstyrene 336 0 1203 1607
m-methylstyrene 0 0 350 0
2-(1-propenyl)pyrazine 895 890 171 240
limonene 6904 4138 165 1045
indene 344 376 1601 1783
1,2,3,4,5,8-hexahydronaphthalene 206 475 0 0
o-isopropenyltoluene 459 523 258 111
1h-indene,1-methyl- 654 810 337 374
benzene, 1-methyl-4-(1-propynyl)- 295 286 437 463
naphthalene 1225 1087 1456 1791
1,2-benzisothiazole 596 928 102 164
1-ethylidene-1h-indene 627 223 998 0
benzocycloheptatrien 1079 1554 869 941
benzene,3-cyclohexen-1-yl- 660 1237 42 165
naphthalene, 2-ethenyl- 981 1227 826 951
1-phenylcyclohexene 840 1248 146 188
1,8-dimethylnaphthalene 486 491 324 426
2-ethenylnaphthalene 423 0 348 449
2,7-dimethylquinoline 531 1284 436 599
acenaphthylene 680 0 710 868
1,1-biphenyl, 4-methyl- 476 0 397 487
1h-phenalene 560 270 574 684
benzene, 1,1-(1,3-propanediyl)bis- 710 589 0 107
heptadecane, 2,6,10,15-tetramethyl- 520 482 0 0
phenanthrene 204 266 376 783
anthracene 233 278 95 206
2-phenylnaphthalene 150 148 148 332
fluoranthene 130 233 75 198
pyrene 319 121 104 221
bis(2-ethylhexyl) phthalate 0 274 156 0
benz[a]anthracene 0 0 136 0
TABLE 5. Sol i d Propert i es
T (C) 450 450 750 750
b
1000 1000 1000 1000
atmosph N2 10%O2 N2 10%O2 N2 10%O2 FP
a
N2 FP
a
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
NCV
c
kcal/kg 7367.4 7542.3 7671.5
surface area m
2
/g 93 91 139 251
a
FP )fineparticle fraction(soot); all theother datacorrespondto chars.
b
Remember that this runwas performedwithashorter final heating
period.
c
Net calorific value.
the solidfractions collectedinthe runs. Also the surface area
analysis has been performed. Metal content has been
determinedby 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
heatingperiod). Thereasonis thesameas commentedearlier.
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 1000Chas ahigher carboncontent withalmost novolatile
matter, as it was expected, and a surprisingly lower ash
content. Onthe contrary, it seems that all the nitrogeninthe
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
avoidevaporation, it is important tooperate 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.
ComparisonwithLiterature. Intheliteraturesomeresults
obtained in the pyrolysis of tires in different types of
equipment havebeenpreviouslycompared(15). It was shown
that, usingthe appropriate functions, the amount andvariety
of volatile and semivolatile compounds analyzed on one
laboratorys 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,
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.
Acknowl edgment s
Support for this work was provided by Tecnolog as y
Aplicaciones Medioambientales deAlcanar, S. L., acompany
owned by the CEMEX group (http://www.cemex.com).
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Received for review June 16, 2003. Revised manuscript re-
ceived November 10, 2003. Accepted March 9, 2004.
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