Table 2.

Yields of identified non aromatic compounds in the C5-C10 fraction

in the pyrolysis of tyres at 500 ºC.
Compound wt%
C5 6.82
isoprene 5.21
3-methyl-1-butene 0.07
2-methylbutane 0.02
1-pentene 0.03
2-methyl-1-butene 0.05
pentane 0.22
2-pentene 0.85
2-methyl-2-butene 0.24
cyclopentene 0.12
C6 1.23
2-methylpentane 0.05
hexane 0.06
1,1,2-trimethylcyclopropane 0.02
3-methyl-2-pentene 0.11
methylcyclopentane 0.04
2-methyl-1,3-pentadiene 0.03
3-hexen-1-yno 0.03
5-methyl-1,3-cyclopentadiene 0.25
1,3-hexadiene 0.08
4-methylcyclopentene 0.16
1,3-cyclohexadiene 0.18
cyclohexene 0.11
unidentified 0.09
.
4 International Journal of Chemical Reactor Engineering Vol. 5 [2007],
Article A96
Table 2. Continued.
Compound wt%C7 1.03
isopropylcyclobutane 0.04
3-methylcyclohexene 0.06
1,3,4-trimethylcyclobutane 0.03
1-ethylcyclopentene 0.01
1-methyl-1,4-cyclohexadiene 0.08
2-methyl-1,3,5-hexatriene 0.14
2,3-dimethyl-1,3-pentadiene 0.23
3-methyl-1,3,5-hexatriene 0.23
5,5-dimethyl-1,3-cyclopentadiene 0.10
unidentified 0.12
C8 2.19
2,5-dimethyl-1,4-hexadiene 0.06
3-methyl-1,5-hexadiene 0.07
2,4,6-octatriene 0.02
3-methyl-1,5-heptadiene 0.03
3-methyl-1,5-heptadiene 0.03
5,5-dimethyl-1,3-hexadiene 0.07
3,5-dimethylcyclohexene 0.05
3-ethyliden-1-methylcyclopentene 0.03
1,3-dimethylcyclohexene 0.13
4-ethenylcyclohexene 1.21
ethenylcyclohexane 0.10
2-methylbicyclo[2.2.1]heptane 0.22
unidentified 0.21
C9 0.76
1,6-dimethylhepta-1,3,5-triene 0.04
5-(1,1-dimethylethyl)-1,3-cyclopentadiene 0.01
1-methylethylidencyclohexane 0.21
2,6-dimethyl-1,3,6-heptatriene 0.19
1,4-dimethyl-2-methylencyclohexane 0.03
1,1-dimethyl-4-methylencyclohexane 0.04
7,7-dimethyl-1,3,5-cycloheptatriene 0.09
2-methylbicyclo[3.2.1]octane 0.05
unidentified 0.11
C10 34.94
2,5,6-trimethyl-1,3,6-heptatriene 0.08
5,5-dimethyl-1-propyl-1,3-cyclopentadiene 0.03
2,7-dimethyl-1,3,7-octatriene 0.28
l-limonene 1.27
1-methyl-3-(1-methylethenyl)cyclohexane 0.51
1,3,5,5-tetramethyl-1,3-cyclohexadiene 0.01
2,6-dimethyl-1,6-octadiene 0.96
3,3,5-trimethyl-1,5-heptadiene 0.34
2,7,7-trimethylbicyclo[2.2.1]hept-2-ene 0.20
2,4,6-trimethyl-1,3,6-heptatriene 0.82
1,2,4,5-pentamethyl-1,3-cyclopentadiene 0.41
1-methyl-4-(1-methylethyl)cyclohexene 0.91
dl-limonene 25.53
1-methylen-4-(1-methylethenyl)cyclohexane 0.40
1,3-butadienylidencyclohexane 1.02
1-methyl-4-(1-methylethyliden)cyclohexene 0.70
3-ethenyl-1,2-dimethyl-1,4-cyclohexadiene 0.16
5-methyl-3-(1-methylethyliden)-1,4-hexadiene 0.34
2,6-dimethyl-2,4,6-octatriene 0.47
5-ethenyl-1,2-dimethyl-1,4-cyclohexadiene 0.13
unidentified 0.37
total C5-C10 non aromatics 46.97
Arabiourrutia et al.: Characterization of the Liquid Obtained in Tyre
Pyrolysis 5
Table 3. Yields of the aromatic compounds in the C5-C10 fraction
obtained in the pyrolysis of tyres at 500 ºC.
Compound wt%
benzene 0.21
toluene 0.78
ethylbenzene 0.53
xylenes 1.23
styrene 2.17
propylbenzene 0.10
1-ethyl-2-methylbenzene 0.05
1-methylethenylbenzene 1.56
1,2,3-trimethylbenzene 0.40
1-methyl-4-(1-methylethyl)benzene 0.69
1H-indene 3.08
1-ethyl-2,3-dimethylbenzene 0.14
1-methyl-4-(1-methylethenyl)benzene 1.13
napthalene 0.24
total C5-C10 aromatics 6.62
The heavy fraction or tar, made up of C11+ components, accounts for 25.6 wt
% of the original tyre. The characterization of the heavier fraction of the
liquid is much more complex than the light fraction. In the C5-C10
fraction the unidentified compounds represent less than 1 wt% but in the
C11+ fraction are about 7 wt%. Tables 4 and5 show the yields of identified
non aromatic and aromatic compounds respectively in the C11+ fraction in
the thermal pyrolysis of tyres at 500 ºC. Figure 3 shows the yield obtained in
the tar fraction according to six groups of components: non-aromatics,
aromatics, sulphur compounds, nitrogen compounds, oxygenates and
unidentified components
To complete the characterization of the pyrolysis liquid Table 6 shows the
hetereoatomic compounds obtained in tyre pyrolysis of tyres at 500 ºC, and
also the simulated distillation and the gross calorific value have
been studied. The simulated distillation has been carried out in a Perkin-
Elmer 8500 gas chromatograph provided with a HT Simdist simulated
distillation column. Figure 4 shows the results obtained. Thus, the light
fraction (boiling point under 200 ºC) is the most important in the pyrolysis
liquid and accounts for 60 wt% of the whole liquid fraction. The medium
fraction, 200 < BP < 350 ºC, accounts for 30 wt% and the heavier fraction
with a boiling point above 350 ºC only accounts for 5 wt%. These results are
similar to those obtained by other authors (Cunliffe and Williams, 1998;
Laresgoiti et al., 2002).The gross calorific value obtained for the tyre
pyrolysis liquid is 43 MJ kg-1, which is a result of the same
order as those reported in the literature (Laresgoiti et al., 2002; Roy et al.,
1990).
The amount of char obtained is slightly higher than the sum of the original
carbon black plus the inorganic components of the tyre. This implies that
there is a certain degree of coking or degraded tyre deposition on the
carbon black. The char obtained is of low quality (surface area of 80 m2g-1)
for its use as carbon black or active carbon. For this purpose, it requires
activation with steam of carbon dioxide (Murillo et al., 2005; Gonzalez et al.,
2006; Pantea et al., 2003).The aforementioned results for yields and
composition of gaseous, liquid and solid products lie between
those of the literature corresponding to the fluidized bed under atmospheric
pressure (Conesa et al., 1996; Kaminsky and Mennerich, 2001) and those of
vacuum pyrolysis (Roy et al., 1999). This is explained by a more efficient
gassolid contact than in a fluidized bed, with higher values for heat and
mass transfer coefficients. In addition to achieving high yields at
temperatures slightly lower than those of a fluidized bed reactor, the
reduced residence time of the gas contributes to minimizing the secondary
reactions, as pursued in vacuum pyrolysis.
6 International Journal of Chemical Reactor Engineering Vol. 5 [2007],

Table 4. Non aromatic compounds in the C11+ fraction.

Compound wt%
6,6-dimethyl-2-vinylidenbicyclo[3.1.1]heptane 0.35
3-[1,3-buthadienyl]-4-vinylcyclopentene 0.32
1,5-diethenil-3-methyl-2-methylencyclohexane 1.60
5,6-diethenylcyclooctene 0.03
1,3-cyclododecadiene 0.90
dodecane 0.04
7-isopropenylbiciylo[4.2.1]nona-2,4,7-triene 0.05
1,2-di-buth-2-enylcyclohexane 0.76
2,3,5,8-tetramethyl-1,5,9-decatriene 0.74
2,6,10-trimethyl-1,5,9-undecatriene 0.43
1-ethenyl-1-methyl-2,4-1-methylethenylcyclohexane 0.59
1,5-diethenyl-2,3-dimethylcyclohexane 0.21
tridecane 0.57
10-methyl-endotricyclo[5.2.1.0(2,6)]decane 0.25
bi-1-cycloocten-1-yl 0.20
tetradecane 0.65
pentadecane 0.65
4-methylen-2,8,8-trimethyl-2-vinylbicyclo[5.2.0]nonane 0.97
hexadecane 1.20
1-ethenyl-1-methyl-2-(1-methylethenyl)-4-(1-methylethyliden)cyclohexane
1.05
octadecane 0.26
nonadecane 0.37
eicosane 0.28
unidentified 10.47
total C11+ non-aromatics 22.92
Table 5. Aromatic compounds in the C11+ fraction.
Compound wt%
4-pentenylbenzene 0.52
1-ethenyl-4-ethylbenzene 0.87
3-pentenylbenzene 0.69
pentylbenzene 0.05
1,2-dimethyl-1-propenylbenzene 0.44
1-methyl-3-(1-methyl-2-propenyl)benzene 0.86
2-methyl-1-butenylbenzene 0.17
cyclopentylbenzene 0.86
4-hexenylbenzene 0.05
3-methylcyclopentylbenzene 0.53
4,7-dimethyl-1H-indene 0.22
hexylbenzene 0.45
3-methyl-4-pentenylbenzene 0.21
4-pentynylbenzene 0.85
1-cyclopentynylbenzene 0.28
1-methylnaphthalene 0.08
1-(1,1-dimethylethyl)-4-ethenylbenzene 0.13
3-cyclohexenylbenzene 0.20
biphenyle 0.03
1-metylpenta-1,3-dienylbenzene 0.01
1-phenylbicyclo[2.1.1]hexane 0.04
2-cyclohexen-1-ylbenzene 0.03
2,3,6-trimethylnaphthalene 0.14
octahydro-3,5,5-trimethyl-9-methylen-1H-benzocycloheptene 0.18
1-phenyl-3,4-divinylcyclohexane 0.43
1,1'-(1,3-propanodiyl)benzene 0.61
1-methyl-7-(1-methylethyl)phenanthrene 0.06
total C11+ aromatics 9.01
Arabiourrutia et al.: Characterization of the Liquid Obtained in Tyre
Pyrolysis 7Published
Table 6. Heteroatomic compounds obtained in tyre pyrolysis at 500 ºC.
Compound wt%
Sulphur Compounds 1.39
2-methylthiophene 0.18
benzothiazol 1.21
Nitrogen compounds 1.33
1,2-dihydro-2,2,4-trimethylquinoline 0.33
4,8,12-trimethyl-3,7,11-tridecatrienonitrile 0.03
N-phenyl-2-naphthalenamine 0.67
N-(1,3-dimethylbuthyl)-N'-phenyl-1,4-benzenediamine 0.30
Oxygen compounds 6.08
Hexadecanoic acid 1.91
Octadecanoic acid 0.47
Octahydro-1,4a-dimethyl-7-(1-methylethyl)-1-phenanthrenocarboxilic acid
0.31
3,7,11-trimethyl-1,6,10-dodecatrien-3-ol 1.72
3,7,11-trimethyl-2,6,10-dodecatrien-1-ol 1.31
ethenylester hexadecanoic acid 0.36
total heteroatomic compounds 8.80
4. CONCLUSIONS
The conical spouted bed reactor (CSBR) is an interesting technology for the
pyrolysis of scrap tyres, due to the excellent hydrodynamic qualities and to
the efficient heat transfer between phases in the spouted bed, apart from
other characteristics of the conical geometry of the reactor, such as its
versatility in gas and solid flowrates under stable and isothermal conditions
in the bed. Moreover, pyrolysis in a CSBR does not have problems related to
particle fusion or agglomerate formation and it only requires a small
amount of sand to help solid flow.
Batch operation at 500 ºC gives way to a yield of 3.1 wt% of gases, 30 wt% of
non aromatic C5-C10 range hydrocarbons, 16.1 wt% of C5-C10 aromatics, 8.8
wt% of tar and 36 wt% of char. Although the liquid fraction has a
rather high amount of aromatic components, its gross calorific value allows
for using as a fuel of suitable quality by blending with standard commercial
fuels.
REFERENCES