I'~U TT E R W Q R T H FuelVol. 74 No. 11, pp.

1589-1594, 1995
I~'IE I N E M A N N Copyright © 1995ElsevierScienceLtd
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0016-2361(95)00165-4 0016-2361/95/$9.50 + 0.00

Characterization of pyrolytic light naphtha

from vacuum pyrolysis of used tyres
Comparison with petroleum naphtha

B. Benallal, C. Roy, H. Pakdel, S. Chabot and M. A. Poirier*

Chemical Engineering Department, Universit~ Lava/, Sainte-Foy, Quebec, Canada G I K 7P4
*Imperial Oil Limited, Samia, Ontario, Canada N7T 7M1
(Received 21 July 1994,"revised 17 January 1995)

Used tyres were thermally decomposed under vacuum in a process development unit. At 510°C and total
pressure 2-20 kPa, the process yielded 50 wt% oil, 25 wt% carbon black, 9 wt% steel, 5 wt% fibres and
11 wt% gas. Distillation of the pyrolytic oil yielded ~20 wt% light naphtha (i.b.p. 160°C), 6.8 wt% heavy
naphtha (160-204°C), 30.7 wt% middle distillate (204-350°C) and 42.5 wt% of bottom residue (>350°C).
D,L-Limonenewas one of the major chemicals in the naphtha fraction, with a concentration of--~7wt%. The
naphtha also had high contents of aromatics, olefins and iso-alkanes (45, 22 and 15 vol. % respectively). Its
relatively high levels of sulfur, nitrogen, olefinic and diolefinic compounds would make it unsuitable as a
blending component for gasoline without hydrofining and reforming. However, ~2 vol. % of the naphtha
could be blended with hydrofiner feedstock without significantly affecting the process requirements.
Approximately 71.1 and 68 wt% of the pyrolytic and petroleum light naphthas respectively were quantified.
(Keywords: tyres; vacuum pyrolysis; naphtha)

The increasing number of discarded tyres in dumps and
landfill sites is a source of environmental and fire hazards.
Environmentally safe and feasible new tyre recycling
technologies are needed.
Each year ,-24 million tyres are disposed of in Canada
and ,-~250 million in the USA. It has been estimated that
one tyre is produced per year per capita in the western
countries. While some of these tyres are recapped or
ground for special uses, most are dumped in rural areas or
in landfills. When buried in landfills, they eventually float
to the surface.
Tyres are made of vulcanized rubber which is a
copolymer of styrene and butadiene (SBR) with ~25%
styrene. Other elastomers such as natural rubber,
synthetic cis-polyisoprene and cis-polybutadiene have
also been used for tyre manufacture with SBR in different
proportionfl. Vehicle tyres are generally a blend of
polybutadiene and SBR; truck and bus tyres are made
of polybutadiene and natural rubber 2. Typically a tyre is
composed of 50% rubber, 27.5% carbon black, 17.5%
extender oil and 5% additives.
Used tyres represent a source of energy and raw
chemical products for the petrochemical industry. By
thermal decomposition of rubber, useful products can be
recovered 3'4. Many processes have been developed for the
thermal decomposition of used tyres to oils, carbon black
and gas1"5.o.,These processes vary depe~_d~ng on the heating
system ' and reactor configuration ' - .
Vacuum pyrolysis, a novel approach based on decom-
position at reduced pressure and low temperature, is
under development in this laboratory. Vacuum pyrolysis
has several advantages over other types of thermal
decomposition methods because of the short organic
vapour residence time in the reactor and low decompo-
sition temperature, which reduces the occurrence and
intensity of secondary reactions. The oil yield is also
considerably higher under vacuum than at atmospheric
pressure. Temperature, pressure and organic vapour
residence time in the reactor are three important factors
influencing the formation of pyrolysis products.
Previous studies have concentrated on engineering
aspects of rubber pyrolysis. The pyrolytic oil obtained
by vacuum pyrolysis of used tyres contains many
aromatic and polyaromatic compounds. Benzene, toluene
and xylenes (BTX) have a high octane number and
typically contribute 15-25% to gasoline. However, it is
important to upgrade the pyrolytic light naphtha to use it
as an octane booster for petroleum naphthas.
This paper reports analyses of tyre pyrolysis light
naphtha fraction, petroleum naphtha and gasoline. The
objective is to compare the quality of the pyrolytic light
naphtha with petroleum naphthas and gasoline and
evaluate it as a blending component for gasoline and
hydro finer feedstock.
EXPERIMENTAL
Vacuum pyrolysis
A schematic of the vacuum pyrolysis process develop-
ment unit (PDU) is shown in Figure 1. The pyrolytic oil
samples used in this investigation were produced from

Fuel 1995 Volume 74 Number 11 1589

Characterization of pyrolytic light naphtha from vacuum pyrolysis." B. Benallal et al.

SCRUBBER
#1 SCRUBBER#2

~ REACTOR I
_I NONCONDENSABLE
GAS

~V/~vAvAx , t

HEAVYOIL LIGHTOIL LIQUIDRING

VACUUMPUMP
CARBON BLACK

Figure 1 Vacuum pyrolysis process flowsheet

used tyres in a horizontal reactor (run No. H03). The Table 1 Refractive index and density of oil samples
reactor was 3 m long and 0.6m in diameter. The system n~20 d415 (gcm -3)
operated in semicontinuous feed mode using punched
cylindrical particles of crossply tyre (12 mm in height and Pyrolytic oil (2) n.d.a 0.9410
6mm in diameter). The feed rate was 19 kgh -1. The Crude oil 1.4454 0.8389
Pyrolytic light naphtha, i.b.p. 160°C 1.4579 0.8357
maximum temperature reached by the feedstock was Petroleum light naphtha, i.b.p. 152°C 1.4169 0.7130
500°C. The system was operated under 13kPa absolute Hydrotreated naphtha 1.4201 0.7453
pressure. The organic vapours were removed from the Mogas GF 711 gasoline 1.4380 0.7244
reactor chamber by means of a liquid ring vacuum pump. Petroleum naphtha +2 vol. % 1.4178 0.7295
pyrolytic light naphtha
The pyrolysis oils were collected in two scrubbers installed Mogas GF 711 +2 vol. % pyrolytic 1.4453 0.7312
in series at the reactor outlet. High-volatile compounds light naphtha
were recovered in the second scrubber, as well as a small
quantity of water. The light oil sample for this study was a Not determined
taken from scrubber No. 2. The heavy oil was recovered
in the first scrubber. The pyrolysis carbon black was
collected separately from the pyrolysis oil and gas. The About 0.15 #1 of the pure sample was injected in split
non-condensable gases were burned. mode (270:1 split/column flow ratio). The injection
temperature was set at 0°C for 15 min, then programmed
Distillation to increase to 50°C at 1Kmin -1, then to 130°C at
Vacuum pyrolysis yielded 50 wt% of a hydrocarbon oil 2 K m i n -l and finally to 180°C at 4 K m i n -1. The oven
from which 20wt% of light naphtha (i.b.p. 160°C) was temperature was set at the final temperature for 20 min.
distilled off. The pyrolytic oil and the crude oil were
distilled under atmospheric pressure up to 160°C to Sulfur analysis
separate the naphtha fraction (ASTM D86 method).
Traces of water were measured in the naphtha fraction Mercaptan analysis by potentiometric method (ASTM
using the Karl Fischer method. The refractive indices D3227). The hydrogen-sulfide-free sample was dis-
and densities of the pyrolytic and petroleum products solved in an alcoholic sodium acetate titration solvent
are given in Table 1. and titrated with silver nitrate, used as an indicator of
the potential between a glass reference electrode and a
PIANO analysis silver/silver sulfide indicating electrode. The mercaptan
Capillary column gas chromatography PIANO was precipitated as silver mercaptide and the titration
analysis (parattins-isoparaffins-aromatics-naphthenes- end point was shown by a large change in cell potential.
olefins) was performed with computer matching of elution
times with those of reference compounds. This method Total sulfur by u.v. fluorescence method. This method
determines hydrocarbon types in naphtha obtained at can be used to determine sulfur in process feeds and may
215°C as defined by ASTM D4057. The operating also be used to control sulfur in the finished product. A
conditions were as follows; the detailed procedure is hydrocarbon sample was directly injected or placed in a
available elsewhere 1233. The g.c. was equipped with a sample boat. The sample was introduced into a high-
flame ionization detector and operated at 250°C, using a temperature combustion tube where the sulfur was oxi-
100 m × 0.25 mm i.d. fused silica capillary column coated dized to SO2 in an oxygen-rich atmosphere. Water pro-
with a 0.50 #m film of methyl silicone gum. Helium was duced during combustion was removed and the gases
used as the carrier gas with 25.6cm s-1 linear velocity. were exposed to ultraviolet light to convert SO2 to the

1590 Fuel 1995 Volume 74 Number 11

 Characterization of pyrolytic light naphtha from vacuum pyrolysis." B. Benallal et al.

Table 2 Elemental analysis of oil samples (wt%)

C H N S Mercaptans
Tyre 88.2 8.5 1.1 1.2 n.d. a
Pyrolytic oil 84.9 13.4 0.8 1.2 n.d.
Crude oil 87.2 10.6 1.6 0.7 n.d.
Pyrolytic light naphtha, i.b.p. 160°C 86.6 10.5 1.8 0.4 0.15
Petroleum light naphtha, i.b.p. 152°C 79.9 19.8 0.1 340 b 216 b
Hydrotreated naphtha 85.0 14.7 <50 b <2 b 1b
Mogas G F 711 gasoline 85.4 14.1 200 b 280 b 4b
Petroleum naphtha, +2 vol. % pyrolytic light naphtha 80.0 19.6 0.2 420 h 245 h
Mogas G F 711 +2 vol. % pyrolytic light naphtha 85.4 14.7 0.1 340 b 56 b

a Not determined
b mg kg -1 (ppm)

excited state, the decay of which was detected by a photo-

multiplier tube.
G.c.-m.s. analysis
Gas chromatography-mass spectrometry analyses
were performed with a gas chromatograph coupled to a
mass-selective quadrupole detector. The g.c. was
equipped with a split injector at 250°C, using a 300:1
split ratio and helium carrier gas at 0.8 ml min -l flow rate.
The analysis was performed on a 30m × 0.25mm i.d.
fused capillary column coated with a 0.25 #m film of DB-
5. The oven temperature was set at 35°C for 10 min, then
programmed to 134oC at 3 K m i n - 1, then to 180°C at
10Kmin- 1 and finally to 250 oC at 30Kmin- 1 . The oven
temperature was set at the final temperature for 5 min.
Typical mass spectrometer operating conditions were as
follows: transfer line 170°C, ion source 270°C and
electron energy 70 eV. Data acquisition was done with
HP-UX ChemStation software and an NBS library data
base. The range m/z 30-600 # was scanned every 1.0 s.
RESULTS AND DISCUSSION
The petroleum naphtha (i.b.p. 152°C) was obtained by
atmospheric distillation of the crude oil. The hydrotreated
naphtha was produced by hydrotreatment of the atmos-
pheric naphtha to remove sulfur, nitrogenous and
oxygenated compounds as well as metallic particles, and
then treated in the reforming unit. Mogas GF 711 is a
regular unleaded gasoline formulated by Imperial Oil.
The elemental analyses of the pyrolysis light naphtha,
petroleum naphtha and gasoline are shown in Table 2.
The carbon content of the pyrolytic light naphtha is
higher than that of the petroleum naphtha and gasoline,
owing to its high content of aromatic and olefinic
hydrocarbons. The petroleum naphtha has lower contents
of sulfur, mercaptans and nitrogenous compounds than
the pyrolytic light naphtha. The formation of sulfur,
nitrogenous and oxygenated compounds is due to the
thermal decomposition of the tyre additives used as
vulcanization agents. The pyrolysis mechanism involves
the formation of free radicals and heteroradicals 14'15.
Sulfur and nitrogen compounds are added as vulcanizing
agents and accelerators during tyre manufacture, and
during compounding and fabricating are continuously
subjected to heat. They are eventually modified and/or
cracked to various sulfur and nitrogen-containing com-
pounds by a free-radical mechanism. Under pyrolysis
(a)
r
13 1'5 30 45 60
minute
Figure 2 Sulfur gas chromatograms: a, pyrolysis oil naphtha; b,
petroleum naphtha
conditions, some heteroatom-containing compounds are
recovered without any further modification and partly
form free radicals. Polymer and polythiyl radicals from
polysulfide cross-linkages are thought to react by addition
to carbon-carbon double bonds, recombination and/or
disproportionation. Nitrogen compounds identified in
the pyrolytic naphtha fraction have already been
reported 16. The reaction pathways change with the
pyrolysis conditions (temperature, pressure and residence
time) and yield various types of compounds. The contents
of heteroatom compounds (S, N, O) are low in the light
fractions of petroleum and are usually concentrated in the
heavy fractions.
Figure 2 compares the gas chromatograms of sulfur
compounds in the pyrolysis and petroleum naphtha
fractions (i.b.p. 204°C). These chromatograms were
recorded with a flame photometric detector. Pyrolytic
sulfur compounds are concentrated in the light portion of
the naphtha fraction (i.b.p. 160°C) but petroleum sulfur
compounds are concentrated in the heavy ends with
boiling point >160°C. The most prominent sulfur com-
pounds identified by g.c.-m.s, in the pyrolitic naphtha are
2-methylthiophene, 3-methylthiophene, 2-ethylthiophene,
2,5-dimethylthiophene, 2,4-dimethylthiophene, 2,3-
dimethylthiophene, 3-ethylthiophene, 2-isopropylthio-
phene, 2-tert-butylthiophene and benzothiazole.
Most naphthas are used as feedstocks for hydrotreat-
ment and catalytic reforming units for the production of
gasoline. Determination of the hydrocarbon types in
naphtha is important in establishing its value as a
feedstock and hence the quality of the end product.

Fuel 1995 Volume 74 Number 11 1591

Characterization of pyrolytic light naphtha from vacuum pyrolysis: B. Benallal et al.

Table 3 PIANO analysis of naphtha fractions (vol. %)

P I A N O Ua

Pyrolytic light naphtha, i.b.p. 160°C 0.7 14.9 45.0 6.6 21.5 11.1
Petroleum naphtha, i.b.p. 152°C 23.1 32.6 11.8 24.6 6.9 1.0
Hydrotreated naphtha 32.7 33.1 7.5 20.4 5.9 0.4
Mogas GF 711 gasoline 25.5 33.9 26.0 5.7 7.8 1.1
Petroleum naphtha +2 vol. % pyrolytic light naphtha 22.7 32.2 12.5 24.2 7.2 1.2
Mogas GF 711 +2vol. % pyrolytic light naphtha 24.2 34.3 27.0 5.7 7.9 0.9

~Unknown

Benzene, toluene and xylene are the major constituents Table 4 Hydrocarbon content of pyrolytic and petroleum naphtha
of the pyrolytic light naphtha fraction. Group composi- (vol. %)
tion analysis of tyre pyrolysis oil produced under N2 has Pyrolytic light Petroleum light
shown than an increase in temperature reduces the Carbon naphtha naphtha
proportion of aliphatic fractions and increases that of number i,b.p. 160°C i.b.p. 152°C
aromatic hydrocarbons 17. It has also been reported that C3 0 0
aliphatic compounds predominate at low temperature but C4 0.1 0
aromatic compounds predominate at high temperature 17-19. C5 2.6 1.3
It has also been suggested that the secondary reactions of C6 6.6 22.2
C7 24.3 26.9
ethylene, propylene and butadiene yield aromatic and C8 31.9 24.3
polyaromatic compounds such as benzene, naphthalene C9 15.1 18.6
and phenanthrene at high temperatures TM.Williams et al. 2° Cl0 7.4 4.9
reported an increase in aromatic compounds having long Cll + 0.7 0.8
Unknown 11.1 1.0
side chains with an increase in pyrolysis temperature. The
role of recombination reactions in the formation of high-
molecular-mass species has been described by Katheklakis
et al. 21 for coal pyrolysis, where pyrolysis vapours increases the octane number. It is interesting to note
condense in the first instance as a fine mist, allowing that the PIANO composition of the pyrolytic light
post-condensation reactions of free radicals to form high- naphtha differs from that of the petroleum naphtha.
molecular-mass species. Since rubber is composed of styrene-butadiene copoly-
During the thermal decomposition of tyres, formation mer, its pyrolytic light naphtha has higher olefinic and
of aromatic hydrocarbons can also be attributed to aromatic hydrocarbon contents than those of the
double bonds produced during scission of the polymer petroleum naphtha. Olefinic and aromatic monomers
chain. Conjugated double bonds tend to form aromatics are formed during the thermal decomposition by scission
after cyclization, and non-conjugated ones tend to form of the polymer chains. The paraffinic hydrocarbons are
olefinic compounds 21- 24 . At high temperature, degrada- obtained by recombination of the alkyl free radicals
tion tends to form many double bonds, including formed.
conjugated bonds, so a high proportion of aromatics is The PIANO analysis also allowed further comparison
produced, whereas at low temperature, olefinic com- of the hydrocarbon distribution of the two naphtha
pounds predominate. fractions. The results are shown in Table 4 according to
It is postulated that if tyres were pyrolysed at ~500°C the number of carbon atoms. Most of the C1-C4 gaseous
under vacuum and with rapid heating (for example components and part of the C5-C6 hydrocarbons were
>100Ks-1), the oil quality would be significantly evacuated from the reactor with the other non-
affected, with reduction in olefinic and an increase in condensable gases and flared. Therefore the C6 content
aromatic content, which would be favourable for a shown in Table 4 is an underestimate. However, vacuum
refining feedstock and production of an octane booster. pyrolysis of tyres produces high yields of toluene and
Table 3 compares the PIANO analyses of the pyrolytic xylene which boost the total C7-C8 content as seen in
light naphtha, petroleum naphtha and gasoline. The Table 4. About 5 wt% of styrene has been reported in
petroleum naphtha and hydrotreated naphtha fraction tyre vacuum pyrolysis naphtha 11 . Dermer and Crynes 25
contain low proportions of olefinic and aromatic hydro- also reported styrene as one of the main vacuum
carbons. This is attributed to the nature of the crude oil. pyrolysis products of polystyrene, but gave no quantita-
The catalytic reforming process increases the content of tive data. However, no styrene was detected under the
aromatic compounds, as shown for the unleaded gasoline conditions reported in this investigation; styrene radicals
in Table 3. It is known that aromatic, low-molecular appear to have contributed to the formation of various
weight olefinic and iso-paraffinic hydrocarbons have a alkylbenzenes--toluene and xylene in particular. Yields
high octane number. The higher the octane number, the of 9.1wt% of toluene and 17.4wt% of xylene were
higher the grade of gasoline. On the other hand, olefinic reported earlier 26 in the total naphtha fraction (i.b.p.
and diolefinic hydrocarbons are undesirable compounds 204°C) using the same PDU at a slightly higher total
in gasoline, owing to their greater oxidation and pressure (run No. H04).
polymerization tendencies which lead to the formation Trimethyl-, isopropyl- and ethylmethylbenzenes (C9
of gum that can damage engine fuel delivery systems. group) are also abundant in the pyrolysis naphtha.
Elimination of the conjugated dienes from gasoline Furthermore, tyre vacuum pyrolysis favours a high yield

1592 Fuel 1995 Volume 74 Number 11

 Characterization of pyrolytic light naphtha from vacuum pyrolysis. B. Benallal et al.

of D,L-limonene, a C10 hydrocarbon, postulated to be the
thermal degradation product of polyisoprene elastomer 27.
Paraffinic hydrocarbons on the other hand are the
principal components of petroleum naphtha, formed by
mild and prolonged thermal alteration of biopolymers.
Based on the PIANO results, the pyrolytic light
naphtha (i.b.p. 160°C) has a higher octane number than
the petroleum naphtha. This is attributed to the high
content of aromatic and low-molecular-mass olefinic
compounds in the former. The addition of 2 vol. % of
the pyrolytic naphtha to the petroleum naphtha (i.b.p.
152°C) and to the gasoline increased the aromaticity of
3 ,3
12
the mixtures, leading to a higher-octane product (Table 3).
However, the increased sulfur and nitrogen contents of
the blended naphtha are still below the hydrofining
process requirement limits. Further study is under way
to evaluate the hydrofining efficiency for the reduction of
heteroatom content.
G.c.-m.s. analyses
Total ion chromatograms of the pyrolysis light naphtha
and the petroleum naphtha are presented in Figure 3.
Comparison of the two chromatograms indicates that the
pyrolysis light naphtha is a more complex mixture than
the petroleum naphtha. Petroleum is basically composed
of homologous series of compounds such as n-alkanes. In
23 (a) contrast, pyrolysis light naphtha is a heterogenous
mixture of various compounds with higher isomerization
14

0 17 20
during the thermal decomposition of the tyres.
Tables 5 and 6 list the main components of both
tO
11 16
22
naphthas as tentatively identified by g.c.-m.s. Analysis
0 15 18 19
based solely on mass spectra usually suffers from isomer-
, , , , , j . . . , , , ,
specific identification problems. Di-, tri- and tetrasubsti-
4 8 12 16 20 tuted benzenes and ethylbenzene are the best examples,
usually showing rather similar isomeric mass spectra that
12
3
9
(b) are difficult to differentiate. However, unambiguous
assignments of isomeric compounds requires co-injection
5 13 16 of standard compounds and simultaneous g.c.-FT-i.r.-
7 m.s. analysis. The relative mass percentages of the
individual compounds were calculated by assuming the
1012 17 10 same response factor from the peak areas of the
22 23 24 25 26
15 19 20
chromatograms shown in Figure 3. Detailed information
4 8 12 16 2'o can be found elsewhere 26.
Time (rain.) Depending on the pyrolysis conditions, vacuum pyro-
lysis of used tyres can yield a high proportion of light
Figure 3 G.c.-m.s. total ion chromatograms: a, pyrolysis naphtha; b, naphtha (~20wt%). In contrast to the petroleum
petroleum naphtha naphtha, the aromatics content of the pyrolytic light

Table 6 Major compounds identified in the petroleum light naphtha

Table 5 Major compounds identified in the pyrolytic light naphtha (i.b.p. 152°C)
(i.b.p. 160°C)
Wt %4 Peak No.
Wt %" Peak No.
Pentane 4.0 1
2-Methyl-l,3-butadiene 0.7 1 2-Methylpentane 4.0 2
1,3-Cyclohexadiene 0.7 2 Hexane 5. l 3
Benzene 2.3 3 Cyclohexane 2.6 4
2,4-Dimethyl-l,3-pentadiene 1.6 4 2-Methylhexane 2.6 5
3-Methyl- 1,3,5-hexatriene 1.0 5 3-Methylhexane 2.9 6
Toluene 15.7 6 1,2-Dimethylcyclopentane 2.1 7
4-Methyl-l,4-hexadiene 1.7 7 Heptane 5.6 8
1-Hexene 1.5 8 2,3-Dimethyl-2-pentene 5.7 9
2-Methylpyridine 0.3 9 Ethylcyclopentane 0.9 10
1,2-Dimethylcyclohexene 1.3 10 1,2,4-Trimethylcyclopentane 1.1 11
4-Ethenylcyclohexene 1.1 11 1,2,3-Trimethylcyclopentane 1.1 12
Ethylbenzene 3.5 12 Toluene + 2,5-dimethylcyclohexane 5.8 13
m + p-Xylene 17.8 13 1,4-Dimet hylcyclohexane 1.9 14
o-Xylene 3.4 14 1,2-Dimethylcyclohexane 1.0 15
2,5-Dimethyl-3-methylene- 1,5-hexadiene 0.8 15 Octane 5.7 16
4-Ethenyl- 1,4-dimethylcyclohexene 1.3 16 1-Ethyl-3-methylcyclopentane 3.2 17
1-Ethyl-4-methylbenzene 3.0 17 m + p-Xylene 3.4 18
1,3,5-Trimethylbenzene 0.9 18 3-Methyloctane 1.3 19
1-Propenylbenzene 0.8 19 o-Xylene 1.0 20
1,2,4-Trimethylbenzene 2.6 20 Nonane 4.6 21
2,3,6-Trimethyl- 1, 5-heptadiene 0.4 21 Bicyclo[3,2,1 ]octane 0.5 22
1,2,3 -Trimethylbenzene 1.5 22 Propylcyclohexane 0.5 23
O,L-Limonene 6.9 23 3-Methylnonane 0.6 24
1-Propenylbenzene 0.2 24 4-(1-Methylethyl)heptane 0.3 25
1-Methyl-2-isopropylbenzene 0.1 25 1-Ethyl-3 -methylbenzene 0.5 26
Total 71.1 - Total 68.0 -
abased on total naphtha a Based on total naphtha

Fuel 1995 Volume 74 Number 11 1593

Characterization of pyrolytic light naphtha from vacuum pyrolysis: B. Benallal et al.
n a p h t h a was a b o u t four times that o f the petroleum
naphtha. B T X were identified with numbers 3, 6, 13 and
14 in Figure 3 and represent the main c o m p o n e n t s o f the
pyrolytic light naphtha. Other benzene derivatives were
also identified (Table 5).
D,L-Limonene, peak 23 (Figure 3a), was also f o u n d at
high concentration. This c o m p o u n d has a high c o m m e r -
cial value. Its concentration is higher under v a c u u m
pyrolysis conditions ( < 20 kPa) than under atmospheric
pressure. The concentration o f paraffinic h y d r o c a r b o n s is
lower in the pyrolytic light n a p h t h a than in the petroleum
naphtha. H o m o l o g o u s series o f n-alkanes in the range
C5-Cll were identified in the petroleum naphtha. M o n o - ,
di- and triolefins were f o u n d to be mainly concentrated in
the range f r o m methylbutadiene to trimethylheptene in
the pyrolytic light naphtha. Cyclopentane and cyclo-
hexane derivatives were the main naphthenic h y d r o c a r b o n
components o f the petroleum naphtha. The pyrolytic oil
on the other hand yielded cyclohexene plus cyclohexadiene
derivatives which could not be well differentiated from
olefinic hydrocarbons by P I A N O analysis.
CONCLUSIONS
V a c u u m pyrolysis oil derived f r o m used tyres contains
,,~20 w t % o f light n a p h t h a fraction (i.b.p. 160°C) which is
rich in aromatic and olefinic c o m p o u n d s . This n a p h t h a
has a higher octane n u m b e r than petroleum n a p h t h a but
must be hydrofined and reformed.
Based on the physical properties and P I A N O analysis
o f the pyrolytic light naphtha, ~ 2 % o f tyre-derived
p r o d u c t can be blended with hydrofiner feedstock without
significantly affecting the process requirements.
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