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Fuel Processing Technology 72 2001.

922
www.elsevier.comrlocaterfuproc

Pyrolysis of scrap tyres


Isabel de Marco Rodriguez ) , M.F. Laresgoiti, M.A. Cabrero,
B. Caballero
A. Torres, M.J. Chomon,
Escuela Superior de Ingenieros de Bilbao, Alda. Urquijo sr n, 48013 Bilbao, Spain
Received 20 November 2000; received in revised form 5 February 2001; accepted 8 February 2001

Abstract

Cross-section samples 23 cm wide., representative of a whole car tyre, have been pyrolysed
under nitrogen in a 3.5 dm3 autoclave at 3008C, 4008C, 5008C, 6008C and 7008C. The whole solid,
liquid and gaseous products generated during each pyrolysis were collected and characterised. No
significant influence of temperature on the amount and characteristics of pyrolysis products was
observed over 5008C. Tyre-pyrolysis liquids are a complex mixture of C 5 C 20 organic com-
pounds, with a great proportion of aromatics. They have high gross calorific values, GCV ; 42
MJ kgy1 . and N and S contents 0.4% and 1.2%, respectively. within those specified for certain
heating fuels. About 30 wt.% of such liquids is an easily distillable fraction with boiling points
702108C. in the range of commercial petrol, and about 60 wt.% of them have the boiling point
range 1503708C. typical of diesel oil. Pyrolysis gases are composed of hydrocarbons of which
C 1 and C 4 are predominant, together with some CO, CO 2 and SH 2 ; they have very high gross
calorific values 6884 MJ my3 .. Tyre-pyrolysis residues have equal dimensions as the original
tyre portion and are easily disintegrable into black powder and steel cords. The black powder has
surface areas comparable to those of commercial carbon blacks, but it has a great proportion of
ash and impurities ; 12 wt.%., which are the inorganic fillers added to tyre rubber; it may have a
potential use as semireinforcing or nonreinforcing carbon black. q 2001 Elsevier Science B.V. All
rights reserved.

Keywords: Recycling; Pyrolysis; Tyres

1. Introduction

The disposal of used tyres is a major environmental problem in nowadays. It is


estimated that 2.5 = 10 6 tonnesryear are generated in the European Community,
2.5 = 10 6 in North America and 1 = 10 6 in Japan w1x. The complex nature of tyres

)
Corresponding author. Tel.: q34-4-601-4284; fax: q34-4-601-4179.
E-mail address: iapderoi@bi.ehu.es I. de Marco Rodriguez..

0378-3820r01r$ - see front matter q 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 8 - 3 8 2 0 0 1 . 0 0 1 7 4 - 6
10 I. de Marco Rodriguez et al.r Fuel Processing Technology 72 (2001) 922

makes it difficult to recycle them. On one hand, the main component of tyres, rubber, is
a chemically cross-linked polymer and, therefore, is neither fusible nor soluble and,
consequently, cannot be remoulded into other shapes without serious degradation. On
the other hand, tyres are a complex mixture of very different materials, which include
several rubbers, carbon blacks, steel cord and other organic and inorganic minor
components.
Along the years, different alternatives for tyre recycling, such as retreading, reclaim-
ing, incineration, grinding, etc., have been used. However, all of them have significant
drawbacks andror limitations w2,3x. Pyrolysis can be considered as a nonconventional
method for tyre recycling, which is currently receiving renewed attention, and seems to
be very appropriate for complex materials, such as tyres that cannot be remoulded. In
the pyrolysis process heating without oxygen., the organic volatile matter of tyres
mainly the rubber polymerrs. is decomposed to low molecular weight products, liquids
or gases, which can be useful as fuels or chemicals source. The inorganic components
mainly steel. and the nonvolatile carbon black remain as solid residue relatively
unaltered and, therefore, can theoretically be recycled in worthwhile applications.
In the past, several laboratory, pilot plant and even commercial attempts have been
made to establish economical units for pyrolysis of tyres e.g. Kobe Steel in Japan,
Tosco in USA, Tyrolysis in UK, etc... However, the economics of the processes were
not cost-effective. At present, economics is not the fact to be considered, but the rapid
increase in discarded tyre legislation that is being produced in many countries w1,3x. For
instance, the new European Union Landfill Directive bans landfilling whole tyre and its
effective date is 2003. Therefore, advances in the knowledge of the characteristics and
potential uses of the products obtained in tyre pyrolysis is, at present, of the most
interest.
Studies reported in the literature about tyre pyrolysis in commercial plants many
times lack the accuracy of scientific studies carried out in laboratory by qualified
researchers. Gas, liquids and solid samples analysed in commercial plant studies
correspond to samples extracted at certain stages of the pyrolysis process and, therefore,
unless a perfect steady state is maintained, such samples may vary and is difficult to
correlate them with the rubber feedstock, which, in addition, cannot be properly
characterised due to its heterogeneity and bulkiness. This paper reports on an experimen-
tal study of tyre pyrolysis carried out in a 3.5-l laboratory installation, in which the
totality of the solid, liquid and gaseous products generated through the whole pyrolysis
run was collected and thoroughly characterised.
On the other hand, many of the scientific laboratory tyre-pyrolysis studies reported in
the literature e.g. Refs. w410x. were carried out either with steel-free samples extracted
from certain part of the tyre e.g. sidewall., which are not representative of the whole
tyre, or with unspecified rubber mixtures provided by waste managing companies, which
grind tyres both for size reduction and for metallic components recovery. In this study,
the sample used for each experiment was a 23-cm-wide cross-section of a specific car
tyre, which was representative of the whole tyre with all its components steel belt,
synthetic fabrics, etc... Such invariable and representative sample was thoroughly
characterised in order to correlate the characteristics of the pyrolysis products with those
of the original feedstock.
I. de Marco Rodriguez et al.r Fuel Processing Technology 72 (2001) 922 11

2. Experimental

2.1. Characteristics of the samples pyrolysed

Tyres are composed of very different components rubbers, carbon blacks, steel,
fillers, etc.., which additionally are heterogeneously distributed along the tyre. There-
fore, in order to dispose of invariable and representative samples of the whole tyre,
cross-section pieces of 23 cm wide f 175 g. of a commercial car tyre Firestone
155R13, F-570. were used for the pyrolysis experiments. The amount of steel in such
samples was quantified after the pyrolysis experiments, separating it manually from the
solid residue left, and weighing it.
In order to characterise the tyre pieces used for the experiments, a representative
sample was prepared grinding the steel-free rubber once frozen in liquid nitrogen.
Thermogravimetric analyses TGA. were carried out with the prepared samples using a
LECO TGA-500: 1. In nitrogen atmosphere to quantify the amount of organic volatile
components, which are mainly rubbers together with minor components, such as
accelerators, extender oils, etc.; 2. In oxygen atmosphere to quantify the organic
nonvolatile compounds, which are mainly carbon blacks. The solid residue left after the
TGAs corresponded to the inorganic fillers of the tyre. The wt.% of the main
components of the tyre derived from the TGA results are presented in Table 1. The
amount of organic volatile matter 59.3%. should correspond to the amount of gas q
liquids to be obtained in the pyrolysis tests, while the amount of nonvolatile organicsq
inorganics, which adds up to 41.2%, should coincide with the solid residue remaining
after pyrolysis. On the other hand, the elemental composition and gross calorific value
GCV. of the prepared tyre samples were also determined using a LECO CHN-600 and
a LECO SC-132 automatic determinators and a LECO AC 300 automatic calorimetric
bomb. The results are presented in Table 2.

2.2. Pyrolysis experiments

Pyrolysis experiments were carried out at 3008C, 4008C, 5008C, 6008C and 7008C in
nitrogen atmosphere, using an unstirred stainless steel 3.5 dm3 autoclave. In a typical
run, the cross-section tyre portion of about 175 g is placed into the reactor which is
sealed. Then nitrogen is passed through at a rate of 1 dm3 miny1 and the system is
heated at a rate of 158C miny1 to the desired temperature, and maintained there for 30
min. It has been proved by the authors that after 30 min no more pyrolysis products

Table 1
Main components of the tyre section wt.%.
Organic compounds Inorganic compounds
Volatile Nonvolatile Steel Others
mainly rubbers. mainly carbon blacks.
58.8 27.7 9.6 3.9
12 I. de Marco Rodriguez et al.r Fuel Processing Technology 72 (2001) 922

Table 2
Elemental composition wt.%. and gross calorific value GCV. MJ kgy1 . of the whole tyre
C H N S Oa Inorganicsb GCV
74.2 5.8 0.3 1.5 4.7 13.5 31.8
a
Calculated by difference.
b
Steelqinorganic fillers.

evolve from the autoclave. All through the run, the vapours leaving the reactor flowed to
a series of cooled gasliquid separators, where the liquids were condensed and
collected. The uncondensed products were collected in Tedlar plastic bags.
Solid and liquid pyrolysis yields were determined in each experiment by weighing the
amount of each obtained and calculating the corresponding percentage. The gas yields
were determined by difference and, therefore, include all the experimental errors and
inaccuracies. The pyrolysis yields presented in this paper are the mean value of at least
five equivalent experiments; the standard deviation of the data is also presented.

2.3. Liquids characterisation

The tyre-pyrolysis liquids elemental composition was determined using a LECO


CHN-600 and a LECO SC-132 automatic determinator and their gross calorific value
GCV. using a LECO AC-300 automatic calorimetric bomb. The liquids were also
analysed by GCrMS on a Hewlett-Packard HP 5890A gas chromatograph equipped
with a Hewlett-Packard HP 5970A mass selective detector, using a SE-50 capillary
column of methyl silicone.
On the other hand, a distillation automatic test was carried out at atmospheric
pressure with a mixture of the pyrolysis oils obtained in several experiments carried out
at 5008C. The oils were distilled from room temperature to the temperature at which no
more distilled products were collected.

2.4. Gases characterisation

In some of the experiments, the pyrolysis gases were totally collected in Tedlar
plastic bags and analysed by gas chromatography using a Konik KNK-3000-HRGC gas
chromatograph equipped with two detectors Thermal Conductivity Detector, TCD:
Konik KNK-019-501 and Flame Ionisation Detector, FID: Konik KNK-019-421., a
multicolumn system Chromosorb 102: 4.6 m = 2 mm i.d., Molecular Sieve 13X: 3
m = 2 mm i.d. and DC 200 Chromosorb P: 3 m = 2 mm i.d.. and the following
temperature program: initial temperature, 408C; time at initial temperature, 10 min;
heating rate, 68C miny1 ; final temperature, 2008C; time at final temperature, 10 min.
The carrier gas was He of 99.999% purity and the carrier pressure 0.39 MPa. The
injector, TCD and FID temperatures were 1108C, 1108C and 2008C, respectively. The
sample injection was carried out with a 5MDR-VLLMA-GT SGE syringe of 5 ml. The
data were collected and handled using a Perkin-Elmer Turbochrom 4-1 software system.
I. de Marco Rodriguez et al.r Fuel Processing Technology 72 (2001) 922 13

2.5. Solids characterisation

The pyrolysis solid residue was a piece of similar dimensions and shape as the
original tyre section, which was easily disintegrable into black powder and steel cords
and filaments. Both components were thoroughly separated and weighed. The elemental
composition, ash content and GCV of the black powder, were determined using a LECO
CHN-600, a LECO SC-132, a LECO TGA-500 and a LECO AC 300 automatic
determinators.
On the other hand, a mixture of several steel-free 5008C pyrolysis residues was
supplied to a rubber high quality carbon black manufacturer for its characterisation. The
following tests were carried out: iodine absorption number surface area ASTM 1510.,
STSA surface area ASTM D-5816., CTAB surface area ASTM D-3765., tint strength
ASTM D-3265., ash content ASTM D-1506. and sieve residue 325 mesh ASTM
D-1514..

3. Results and discussion

3.1. Pyrolysis yields

The solid, liquid and gas yields wt.%. obtained in the tyre-pyrolysis experiments
carried out at 3008C, 4008C, 5008C, 6008C and 7008C are presented in Table 3. The
results presented in the table include the mean value and the standard deviation of at
least five pyrolysis runs carried out at the same temperature. It can be seen that at 3008C
and 4008C, pyrolysis was incomplete since solid yields 87.6% and 55.9%, respectively.
much higher than the theoretical values expected from the TGA tyre analysis 41.2%.
were obtained; this was corroborated by the heterogeneous sticky-gummy aspect of
those solid residues after pyrolysis. Solid yields obtained at 5008C, 6008C and 7008C are
almost equivalent and somewhat higher than the theoretical value derived from the TGA
analysis 41.2%.. So one might think that not all the volatile matter of tyre has been
decomposed to liquids and gases. However, it has been reported in the literature w1117x
that a certain amount of char or coke-like carbonaceous material is formed in the
pyrolysis of many polymeric materials, due to secondary repolymerisation reactions
among the polymer-derived products. On the other hand, the authors have also proved
that at 5008C, 6008C and 7008C, longer reaction times do not decrease solid yields in
tyre pyrolysis. Therefore, it can be concluded that tyre decomposition at 5008C, 6008C

Table 3
Pyrolysis yields wt.%. mean value"standard deviation of at least five pyrolysis experiments.
Pyrolysis temperature 8C. 300 400 500 600 700
Solid yield 87.6"7.8 55.9"5.5 44.8"0.6 44.2"0.6 43.7"0.4
Liquid yield 4.8"3.9 24.8"6.0 38.0"1.8 38.2"0.5 38.5"1.2
Gas yield 7.7"3.9 19.3"2.2 17.2"1.8 17.5"0.8 17.8"1.2
14 I. de Marco Rodriguez et al.r Fuel Processing Technology 72 (2001) 922

and 7008C is complete and that f 34% of char or carbonaceous material has been
formed.
Concerning the standard deviations of the data, Table 3 shows that for the 5008C to
7008C pyrolysis, they are rather low, which indicates that there is a rather low level of
experimental error. On the contrary, the standard deviations obtained at 3008C and
4008C are much higher. This is due to the fact that at these temperatures pyrolysis is
incomplete together with the fact that the autoclave is an unstirred one and, conse-
quently, there is an uneven temperature distribution inside it; therefore, depending on the
particular disposition of the tyre portion inside the autoclave, it will have more or less
contact with the autoclave sidewalls and, consequently, a greater or lesser amount of
material will be decomposed.
Concerning liquid yields, they increase with temperature from 3008C, to 5008C as
tyre decomposition increases, and then do not vary. Concerning the gas yields, they
increase from 3008C, to 4008C and do not vary above 5008C. It seems that there is a
slight decrease in gas yield from 4008C, to 5008C, but this must not be considered
conclusive, since there is a great dispersion of the data in 4008C pyrolysis, due to its
incompleteness. The lack of influence of temperature in liquids and gas yields above
5008C is somewhat surprising. It might have been expected an increase in the amount of
gases, and a consequent decrease in the amount of liquids, due to the stronger thermal
cracking produced at higher temperatures. However, in the 5007008C interval, such
variation is not produced, which may be attributed to the fact that with the experimental
procedure used, the products generated in tyre decomposition are immediately extracted
from the autoclave and cooled and, therefore, the liquid products are not subsequently
cracked to gaseous products. Similar conclusions concerning the lack of influence of
temperature in tyre-pyrolysis yields have been reported in the literature w6x. Therefore,
concerning pyrolysis yields, it can be concluded that 5008C is the optimum temperature
of those studied for recycling tyres by pyrolysis, since as decomposition is completed,
the same yields are obtained and less energy is required than at higher temperatures.

3.2. Tyre-pyrolysis liquids

The liquids obtained in tyre pyrolysis, which are usually termed oils, are dark-
brown-coloured products, which resemble petroleum fractions. The elemental composi-
tion HrC atomic ratio and GCV of the oils obtained at every temperature are presented
in Table 4. It can be seen that there is almost no effect of pyrolysis temperature on the
composition of the oils. They all have HrC atomic ratios around 1.4, which may be an
indicator that such oils are a mixture of aromatic and aliphatic compounds. This is
logical since the main polymeric component of automotive tyres is styrenebutadiene
rubber SBR., which has both aromatic structure that of the styrene-repetitive unit. and
aliphatic structure that of the butadiene-repetitive unit.. This was corroborated by gas
chromatographyrmass spectroscopy GCrMS. analyses of the oils. Concerning the
contents of polluting elements ; 0.4 wt.% N and ; 1.2 wt.% S., they are both within
those specified for heating fuels, such as commercial No. 1 and No. 2 fuel oils ASTM
240.. Additionally, the oils GCVs are rather high ; 42 MJ kgy1 ., even higher than
those specified for the above-mentioned commercial fuel oils. Therefore, tyre-pyrolysis
I. de Marco Rodriguez et al.r Fuel Processing Technology 72 (2001) 922 15

Table 4
Pyrolysis liquid elemental compositions wt.%. and GCV MJ kgy1 . mean value"standard deviation of at
least five pyrolysis experiments.
Pyrolysis Temperature 8C. 300 400 500 600 700
C 86.5"0.7 85.9"0.7 85.6"0.5 86.2"1.0 86.0"0.9
H 10.7"0.2 10.6"0.3 10.1"0.1 10.2"0.1 10.2"0.2
N 0.3"0.04 0.3"0.06 0.4"0.03 0.4"0.03 0.4"0.04
S 1.0"0.2 1.1"0.2 1.4"0.2 1.2"0.1 1.2"0.2
Oqothers by difference. 1.4"0.8 2.0"0.8 2.5"0.5 2.1"0.9 2.2"0.9
HrC atomic ratio 1.49 1.49 1.42 1.41 1.42
G.C.V 43.2"0.4 42.6"0.4 42.1"0.3 42.2"0.3 42.3"0.4

oils, as a whole, can be considered rather good liquid fuels, with a potential use as
heating fuels.
On the other hand, tyre pyrolytic oils were tested by GCrMS. As a summary of the
results, it can be mentioned that tyre oils are a very complex mixture of organic
compounds of 520 carbons and with a very great proportion of aromatics. Table 7
shows the proportions of the different types of compounds aromatics, aliphatics,
nitrogenated, benzothiazol. present in the pyrolysis oils. It can be seen that at every
temperature, there is a high proportion of aromatics, significantly higher than the
proportion of aromatic structures in the SBR polymer, which has about 25 wt.% styrene
aromatic. and 75 wt.% butadiene aliphatic.. The high proportion of aromatics in tyre
oils is attributed to recombination reactions that take place among aliphatic and aromatic
free radicals and also to cyclation of aliphatic chains. This is coincident with what has
been obtained by some other authors w10,11,1820x that also report that tyre oils are
strongly aromatic. Concerning the effect of temperature, it was observed that there was
no significant influence of temperature on the type of compounds contained in the oils,
but there was on the relative proportion of such compounds. Table 5 shows that the
relative proportion of aromatics increases with temperature up to 6008C with a corre-
sponding decrease of aliphatics. Similar results concerning the increase of aromatics
with temperature have been reported by other authors w20x. Since Table 4 shows that all
the oils have equivalent HrC atomic ratios, it may be inferred that in the low-tempera-
ture pyrolysis, oils there are more free aliphatic compounds, while in the higher-temper-
ature oils, many of such aliphatics are linked to aromatic structures. This may be

Table 5
Pyrolysis liquids types of compounds percent identified area by GCrMS.
Pyrolysis temperature 8C. 300 400 500 600 700
Aromatics 34.7 59.3 62.4 75.6 57.4
Aliphatics 59.2 34.9 31.6 19.8 37.0
Nitrogenated 4.5 3.7 4.2 2.6 3.8
Benzothiazol 1.6 2.1 1.8 2.0 1.8
16 I. de Marco Rodriguez et al.r Fuel Processing Technology 72 (2001) 922

explained as follows. At the lower temperatures, the polymer is more slowly cracked
and the free-radical fragments generated, either aliphatic or aromatic, can be stabilised
by hydrogen coming from potential H-donor structures, while at the higher temperatures,
there are more free radicals, which, in addition, are generated at a greater rate, so that
many of them recombine one another, yielding, as a consequence, more aliphatic chains
linked to aromatic structures. From 6008C, to 7008C, the tendency is inverted; a
significant decrease of aromatics is produced. Since the HrC atomic ratio continues to
be 1.4, the explanation to this change may be that at this higher temperature, the liquid
products initially formed are subsequently cracked, yielding again more free aliphatic
compounds.
On the other hand, Table 5 includes the percentage of nitrogenated compounds,
which is rather low and not temperature-dependent. The origin of this nitrogenated
compounds may be the presence of some nitrile rubber NBR. acrilonitrile butadiene
rubber. mixed with the main component SBR. of the tyre rubber. The presence of
nitrogen in tyre oils has also been reported by other authors w20x. Finally, Table 5 also
includes the proportion of benzothiazol in tyre oils; this is an accelerator typically used
in many rubber formulations, which explains its significant occurrence in tyre pyrolytic
oils.
In order to better analyse the potential uses of pyrolysis oils, an automatic distillation
test at atmospheric pressure was carried out, with a mixture of the oils obtained in
several pyrolysis carried out at 5008C. A summary of the results is presented in Table 6.
It was observed that more than 30 wt.% of such oils was a transparent, easily distillable
fraction with boiling points between 708C, and 2108C, which is the boiling point range
specified for commercial petrol. In order to establish the real potential use of such
fraction mixed with petrol, standard tests typical of petrol, such as induction time,
Amodern gumsB, corrosive properties, octane MON and RON numbers, etc., should be
carried out.

Table 6
Pyrolysis liquids distillation test pyrolysis carried out at 5008C.
Distilled vol.%. Temperature 8C.
0 78
10 114.5
16 155.5
20 168.8
30 198.2
33 214.8
40 249.3
50 296.1
60 333.8
70 359.8
75 370.3
80 373.9
90 386.4
94 388.7
I. de Marco Rodriguez et al.r Fuel Processing Technology 72 (2001) 922 17

On the other hand, Table 6 shows that 75 wt.% of the pyrolytic oils has a boiling
point under 3708C, which is the upper limit specified for the 95% of distilled product in
diesel oils. However, the whole - 3708C tyre oil fraction should not be acceptable as
diesel oil because of its significant proportion of low boiling products. A typical boiling
range for diesel oil is from 1508C, to 3708C. In Table 7, the distillation data that
correspond to the 1503708C pyrolytic oil fraction, which amounts for about 60 wt.% of
the total oil, is presented. For the sake of comparison, the distillation data of a
commercial diesel oil is included in Table 7. It can be seen that up to 1908C, the amount
of distilled product in each 108C interval is greater in the tyre pyrolytic oil fraction than
in the commercial diesel oil; from 1908C to 2208C, there is not a clear tendency; from
2208C to 3208C, the distilled commercial oil fractions are greater than the pyrolytic
fractions; from 3208C to 3408C, the distilled fractions from both oils are similar; and
over 3508C, the fractions from tyre oil are again greater than the diesel oil fractions. So,
to summarize, it may be concluded that the 1503708C tyre pyrolytic oil has a higher
proportion of the lighter and heavier products, and a lower proportion of the middle
boiling range products, than the commercial diesel oil. In order to establish the real
potential use of such tyre oil fraction as diesel oil, a more thorough characterisation of it,
which should include cetane index, corrosive properties, flash point, etc., is needed.

Table 7
Pyrolysis liquids 1503708C fraction distillation data pyrolysis carried out at 5008C.
Temperature 8C. Distilled vol.%.
1503708C Tyre pyrolysis liquids Commercial diesel oil
157.5 1.0 0.0
160 2.2 0.2
170 7.5 2.0
180 13.3 6.5
190 19.8 10.3
200 24.3 14.8
210 27.5 18.8
220 31.4 22.3
230 35.0 26.4
240 37.7 31.6
250 40.9 35.1
260 44.6 39.9
270 47.8 45.3
280 51.2 51.6
290 54.8 59.4
300 59.3 66.3
310 63.6 71.6
320 67.8 79.9
330 72.5 84.3
340 78.0 89.4
350 84.4 91.5
360 91.7 94.8
370 99.7 96.9
18 I. de Marco Rodriguez et al.r Fuel Processing Technology 72 (2001) 922

3.3. Tyre-pyrolysis gases

The composition and GCV of the gases obtained in tyre pyrolysis at 4008C, 5008C,
6008C and 7008C are presented in Table 8. It can be seen that tyre-pyrolysis gases are
mainly composed of hydrocarbons together with some CO, CO 2 and SH 2 . The CO x
components must be derived from oxygenated organic compounds, such as stearic acid,
extender oils, etc., contained in tyres, and even from inorganic components, such as
CaCO 3 , metal oxides, etc. Other authors have also reported the presence of significant
amounts of CO x in tyre-pyrolysis gases w21x. Sulphidric acid comes from the sulphur
links of the vulcanised rubber structure; nevertheless, its concentration is rather low,
even though the tyre sample contains 1.5 wt.% sulphur. Concerning hydrocarbons, Table
8 shows that methane and C 4 butenes and butanes. are the most predominant products;
the latter probably come from the depolymerisation of styrenebutadiene rubber SBR..
Concerning the effect of temperature in gas composition, Table 8 shows that there are
no significant differences above 5008C; the only one worth mentioning is that at 7008C,
more CO x are obtained. This may be attributed to the fact that at this higher-tempera-
ture, inorganic components of tyres, such as CaCO 3 , CaSiO 3 , etc., begin to decompose
generating CO x . A more detailed discussion of this fact has been presented by the
authors elsewhere w22x.
Concerning the composition of the gases obtained at 400 8C, it is clearly different
than that of the gases obtained at G 5008C. Table 8 shows that at 4008C, less light
hydrocarbons C 1 , C 2 and C 3 . and SH 2 , and more heavy hydrocarbons C 4 , C 5 and C 6 .
than at the other temperatures are obtained, while the proportion of CO and CO x are
comparable to those obtained at the other temperatures. The lower SH 2 content is
attributed to the fact that since at 4008C tyre decomposition is incomplete, probably
many of the sulphur atoms remain linked to the nondecomposed solid structure. On the

Table 8
Pyrolysis gas compositions vol.%. and GCV
Pyrolysis temperature 8C. 400 500 600 700
Methane 4.4 19.8 20.0 20.6
Ethene 4.3 9.4 9.7 8.9
Ethane 4.5 9.1 9.0 8.1
Propene 4.1 6.4 6.5 4.5
Propane 4.4 4.4 4.1 3.2
Butene 30.8 17.5 17.9 16.0
Butane 6.1 3.8 4.0 3.8
Pentene 3.7 2.8 3.6 2.1
Pentane 12.8 4.8 3.8 4.6
Hexene 2.2 1.1 0.9 0.9
Hexane 5.1 1.7 1.6 1.6
CO 4.2 4.8 6.5 10.4
CO 2 10.7 9.4 8.8 11.4
SH 2 2.6 5.1 3.6 3.9
GCV MJ my3 . 84.0 75.5 75.3 68.5
GCV MJ kgy1 . 41.7 42.1 42.2 39.4
I. de Marco Rodriguez et al.r Fuel Processing Technology 72 (2001) 922 19

other hand, the higher heavier hydrocarbons content and lower lighter hydrocarbons
content of the 4008C pyrolysis gases may be explained as follows. The heavier
hydrocarbons are predominantly generated earlier, at lower temperatures, and are
derived from the direct breakdown or depolymerisation. of the styrenebutadiene
polymer. While the formation of lighter hydrocarbons is favoured at higher temperatures
due to the stronger thermal cracking and are derived both from the direct breakdown of
the polymer, which is more strongly cracked at higher temperatures, and from secondary
reactions or subsequent cracking of the polymer-derived products previously formed,
which are typical at higher pyrolysis temperatures. A more thorough discussion of the
evolution of tyre gases during the pyrolysis process has been presented by the authors
elsewhere w22x.
Concerning the GCV of the tyre-pyrolysis gases, Table 8 shows that they are very
high 6884 MJ my3 .. There are references in the literature e.g. Refs. w4,23,24x. which
report that tyre-pyrolysis gases have GCV in the range 3040 MJ my3 . These values are
much lower than those presented in this paper; such difference is attributed to the fact
that the gases obtained in this study have a greater proportion of high hydrocarbons
C 4 ) C 4 ., which have the highest GCV, than those reported in the literature. The
greater amount of heavier hydrocarbons obtained in the present study may be due to the
fact that since a high thermal inertia autoclave and a rather low heating rate 158C
miny1 . have been used, most of tyre decomposition and, consequently, the majority of
the gases generated, are produced at 4005008C, even in the 6008C and 7008C pyrolysis
runs. With respect to the variation of GCV with temperature, Table 8 shows that at
7008C, GCV is somewhat lower, both in MJ my3 and in MJ kgy1 , than at the other
temperatures, which may be attributed to the fact that 7008C gases have a greater CO x
content. On the other hand, it can be seen that 4008C gases have similar GCV in MJ
kgy1 , but higher GCV in MJ my3 than the other gases, and this is due to the fact that
4008C gases have a higher content of heavier hydrocarbons, which have greater GCV
per mole than the lighter hydrocarbons.

3.4. Tyre-pyrolysis solid

The solid-pyrolysis residue obtained at 5008C, 6008C and 7008C was a piece of equal
dimensions and shape as the original tyre portion, which was easily disintegrable into
black powder and steel cords and filaments, while the solid residue obtained at 3008C
and 4008C was a sticky-gummy piece of partially decomposed tyre, rather heteroge-
neous, specially that of 3008C, which was for this reason not characterised. The
elemental composition and GCV of the 4008C to 7008C pyrolysis steel-free residues are
presented in Table 9. It can be seen that there are no significant differences among the
solids obtained at the different temperatures, except for the fact that 4008C residue has a
greater hydrogen content than the others, which is due to the incompleteness of pyrolysis
at this temperature.
For the sake of comparison, the elemental composition and GCV of a commercial
carbon black used for automotive tyres is included in Table 9. The most noteworthy fact
concerning tyre pyrolytic residues is that they have a very great proportion of ash,
compared with commercial carbon blacks, which must have at most 0.5 wt.% to be
20 I. de Marco Rodriguez et al.r Fuel Processing Technology 72 (2001) 922

Table 9
Pyrolysis solids elemental compositions wt.%., ash content wt.%. and GCV MJ kgy1 . mean value"
standard deviation of at least five pyrolysis experiments.
Pyrolysis 400 500 600 700 Commercial tyre
temperature 8C. carbon black
C 83.8"0.6 83.5"0.5 83.7"1.0 82.5"2.6 97.1
H 2.4"0.4 0.6"0.04 0.5"0.04 0.5"0.02 0.2
N 0.3"0.06 0.3"0.07 0.3"0.05 0.3"0.08 0.2
S 2.3"0.1 2.4"0.1 2.6"0.2 2.3"0.2 1.0
Ash 9.0 12.1 12.0 13.2 0.4
Oqothers 0.7 1.1 0.9 1.2 1.1
by difference.
GCV 27.3"1.1 28.8"0.6 29.0"0.3 29.1"1.3

admissible for tyre manufacturers. The ash contained in the pyrolytic residues come
from the inorganic fillers steel excluded. of the original tyre. If the percentage of
steel-free inorganics with respect to steel-free nonvolatile material of the tyre, is
calculated with the data presented in Table 1, it results 12.6%, which is quite similar to
the ash contents of the 5008C, 6008C and 7008C pyrolysis solids 1213%.. Also worth
mentioning is the fact that the sulphur content of pyrolysis solids is quite high.
Considering that the original tyre contains 1.5 wt.% sulphur, it can be calculated that
more than 50% of the tyre sulphur is left in the solid residue. Similar ash and sulphur
contents in tyre-pyrolysis solids have been reported by other authors w5,6,25x.
A mixture of tyre pyrolytic carbon blacks obtained in several experiments carried out
at 5008C were characterised by a high-quality carbon black manufacturer; the results are
presented in Table 10. Surface area was determined by three different standard methods:
a. iodine adsorption number ASTM D-1510 I 2 No., which is very much used for
characterising carbon blacks, and the standard states that it is generally in agreement
with nitrogen surface area; b. iodine titration ASTM D-5816 STSA.; and c. ceth-
yltrimethylammonium bromide adsorption ASTM D-3765 CTAB., which covers the
measurement of the specific surface area of carbon black exclusive of area contained in
micropores too small to admit the large CTAB molecule. Table 10 shows that I 2 No
surface area is very high, with a value that corresponds to reinforcing carbon blacks.
However, STSA and CTAB values are comparatively low corresponding to semirein-
forcing or nonreinforcing carbon blacks. On the opinion of the carbon black manufactur-

Table 10
Characteristics of tyre pyrolytic carbon black pyrolysis carried out at 5008C.
Characteristic Standard method Value
I 2 No ASTM D-1510 135.2 mgrg
CTAB ASTM D-3765 59.7 m2 rg
STSA ASTM D-5816 56.2 m2 rg
Tint strength ASTM D-3265 43.3%
Ash content ASTM D-1506 12.6%
Sieve residue 325 mesh. ASTM D-1514 1170 ppm
I. de Marco Rodriguez et al.r Fuel Processing Technology 72 (2001) 922 21

ers, I 2 No test is more reliable than STSA and CTAB; these later give very disperse
results when the samples have a lot of impurities, as is the case of the tyre pyrolytic
carbon black.
The tint strength ASTM D-3265, which is a property that reflects the size distribution
of the primary particles, has a rather low value 43.3%. compared to reinforcing carbon
blacks ; 155%.; however, it must be mentioned that there was a very great dispersion
of the data of the tint strength measurements, which again may be attributed to the high
content of impurities of the pyrolytic carbon blacks.
Concerning the ash and sieve residue 325 mesh., ASTM D-1506 and ASTM
D-1514, respectively, which both reflect the level of impurities, they are very high, and
obviously would not be accepted by tyre manufacturers. However, one must bear in
mind that such impurities are precisely the inorganic fillers ZnO, CaCO 3 , etc.. that are
added to tyre rubbers. Therefore, for a definite conclusion about the potential use of
pyrolytic carbon black as reinforcing carbon black, it was the opinion of the carbon
black manufacturer that it will be necessary to mix the pyrolytic carbon black with
rubber and measure the properties of the vulcanised rubber tensile strength, elongation,
modulus, etc... Nevertheless, it may be ventured that tyre-pyrolysis residues could
partially replace semireinforcing commercial blacks for the preparation of rubber parts,
such as footwear, conveyor belts, dock fenders, etc., which are not so high quality
demanding as automotive tyres. Other potential uses for tyre-pyrolysis solids include
solid fuel, pigments for inks or activated carbon. The potential use as activated carbon
has been studied by other authors w7,8,26x, which have concluded that carbons with high
surface areas, comparable to those of commercial activated carbons, can be obtained
from tyres if proper activation processes of the pyrolysis solids are carried out.

Acknowledgements

The authors thank the Basque Country University UPV 112.345-EA122r94 and
UPV 112.345-631r98. and the Basque Government OD 97UN16 and PI-1998-19. for
financial assistance for this work.

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