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Journal of Analytical and Applied Pyrolysis

55 (2000) 43 54
www.elsevier.com/locate/jaap

Chromatographic analysis of the gases obtained


in tyre pyrolysis
M. Felisa Laresgoiti, Isabel de Marco *, Amelia Torres,
Blanca Caballero, Miguel A. Cabrero, M. Jesus Chomon
Escuela de Ingenieros de Bilbao, Alda. de Urquijo s/n, 48013 Bilbao, Spain

Received 5 May 1999; received in revised form 21 June 1999; accepted 28 September 1999

Abstract

Representative samples of a whole car tyre have been pyrolysed under nitrogen in a 3.5
dm3 autoclave at 400, 500, 600 and 700C. The whole gas generated during each pyrolysis
run was collected in several plastic bags all of which were analysed, and so the composition
of tyre pyrolysis gas and its evolution during the process were determined reliably. Tyre
pyrolysis gases are composed of CO, CO2, H2S, and hydrocarbons such as CH4, C2H4, C3H6,
C4H8, etc. and its unsaturated derivatives. Multidimensional gas chromatography using three
capillary columns installed in a sole furnace have been used, together with a Thermal
Conductivity Detector (TCD) and a Flame Ionisation Detector (FID) connected on-line. The
gas components have been quantified collecting and handling the data with an appropriate
software system. This assembly (three columns + two detectors +software system) enables
easy and automatic analysis of tyre pyrolysis gases with only one sample injection. No
significant influence of temperature on tyre pyrolysis solid, liquid and gas yields was
observed over 500C; however there was an influence of temperature on gas composition and
its evolution. At higher temperatures, more COx (CO +CO2) was produced, derived from
inorganic components, and more lighter gases were produced, generated in secondary
reactions. 2000 Elsevier Science B.V. All rights reserved.

Keywords: Pyrolysis; Recycling; Tyres; Gases

* Corresponding author. Tel.: + 34-4-6014-284; fax: +34-4-4414-041.


E-mail address: iapderoi@bi.ehu.es (I. de Marco)

0165-2370/00/$ - see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 5 - 2 3 7 0 ( 9 9 ) 0 0 0 7 3 - X
44 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 55 (2000) 4354

1. Introduction

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


complex nature of tyres makes it difficult to recycle them. On the 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.
Different alternatives for tyre recycling such as retreading, reclaiming, incinera-
tion, grinding, etc., have been used. However all have significant drawbacks and/or
limitations [1]. Pyrolysis can be considered a non-conventional 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 polymer/s) is decomposed to low molecular weight products,
liquids or gases, which can be useful as fuels or a source of chemicals. The
inorganic components (mainly steel) and the non-volatile carbon black remain as a
solid residue which is relatively unaltered, and therefore can be recycled in
worthwhile applications.
The pyrolysis process is not new; it has been applied in the past to carbonaceous
materials such as coal or wood. At present it is being considered as a non-conven-
tional method of reusing polymeric materials. Over the last 2030 years, several
laboratory, pilot-plant and even commercial attempts have been made to establish
economical units for pyrolysis of such materials (e.g. Kobe Steel in Japan, Tosco in
USA, Tyrolysis in UK, Ebenhausen in Germany and many more).
Concerning tyre pyrolysis it has been reported [25] that the main components of
the gases generated are carbon monoxide (CO), carbon dioxide (CO2), hydrogen
sulphide (SH2), methane (CH4), ethane (C2H4), ethene (C2H4), propane (C3H8),
propene (C3H6), butane (C4H10), butenes (C4H8) and butadiene (C4H6), that they
have gross calorific values about 30 40 MJ N m 3 and that are more than
sufficient to provide the energy requirements of the process plant. However, scarce
information is given in the literature about the variation of gas composition
throughout the whole pyrolysis process. Additionally the data reported in the
mentioned references correspond to analysis carried out with gas samples taken at
certain stages of the pyrolysis run, and since there is a continuous variation of the
amount and composition of the gases during the pyrolysis run, such data may be
somewhat misleading. In the present study, all the gases generated were collected
throughout the process in successive plastic bags, and therefore a reliable determi-
nation of gas composition and its evolution during pyrolysis runs at different
temperatures, could be carried out, and so information of how tyre components are
decomposed at the different temperatures, may be inferred. A somewhat similar
work, which also analyses the evolution of gas composition throughout the process,
has been published [6]; however such work only reports on pyrolysis carried out at
low temperatures (380 550C) and only considers COx, SH2, H2, CH4, C2H4 and
C2H6 as the main constituents of the gas.
M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 55 (2000) 4354 45

On the other hand, since it is not possible to separate all the components of tyre
pyrolysis gases using a single column, multidimensional gas chromatography using
three capillary columns installed in a gas chromatograph was used. As far as
detection devices are concerned, given that Thermal Conductivity Detectors (TCD)
have low sensibility for the higher molecular weight components of the pyrolysis
gases, a Flame Ionisation Detector (FID), which has very high sensibility for
hydrocarbons, was used together with the TCD. In order to quantify the gas
components the chromatographic data were collected and handled using an appro-
priate software system. The whole assembly (three columns, two detectors and the
software system), has enabled quantification, with ease and confidence, of all the
components of tyre pyrolysis gases with only one sample injection.

2. Experimental

2.1. Pyrolysis experiments

Pyrolysis experiments of automotive tyres were carried out at 400, 500, 600 and
700C in a nitrogen atmosphere, using an unstirred stainless steel 3.5 dm3 auto-
clave. In a typical run, a radial car 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 min 1
and the system is heated at a rate of 15C min 1 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 evolve from the autoclave. All through the run the
vapours leaving the reactor flowed to a gasliquid separator where the liquids
condensed by simple cooling in the outlets of the reactor and were collected, and
then to a second separator where the liquids condensed in a water-cooled heat
exchanger and were collected. The uncondensed products were collected in succes-
sive Tedlar plastic bags. In the experiments devoted to follow the evolution of gas
composition through the process, 10 dm3 plastic bags were used.
Solid and liquid pyrolysis yields (wt.%) were determined in each experiment by
weighing the amount of each obtained, while gas yields were determined by
quantifying the amount (g) of each component of the gases by gas chromatography.

2.2. Chromatographic analysis

Tyre pyrolysis gases have been analysed by gas chromatography using three
columns coupled in series. The temperature programs and the analysis conditions
were as follows:
Packed columns:
Chromosorb 102 (C102): 4.6 m 2 mm i.d.
Molecular Sieve 13X (MS13X): 3 m 2 mm i.d.
DC 200 Chromosorb P (DC200): 3 m 2 mm i.d.; 25% DC 200 (12 500 cstk).
Column switches:
From 0 to 2.8 min through C102, MS13X, DC200;
46 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 55 (2000) 4354

From 2.8 to 11.8 min through MS13X, DC200;


From 11.8 to 55 min through C102, DC200.
Temperature program:
Initial temperature: 40C;
Time at initial temperature: 10 min;
Heating rate: 6C min 1;
Final temperature: 200C;
Time at final temperature: 10 min.
Detectors:
Thermal Conductivity Detector (TCD): Konik KNK-019-501 coupled to C102
and MS13X;
Flame Ionisation Detector (FID): Konik KNK-019-421 coupled to DC200;
Gas chromatograph: Konik KNK-3000-HRGC;
Carrier gas: He, purity: 99.999% supplied by Air Liquide Espana S.A. (Spain);
Carrier pressure: 0.390 MPa;
Injector temperature: 110C;
TCD temperature: 110C;
FID temperature: 200C;
Sample injection: with a 5MDR-VLLMA-GT SGE syringe of 5 ml;
Standard gas mixtures for calibration: supplied by Air Liquide Espana S.A.
(Spain);
Software system for collecting and handling the data: Perkin-Elmer Turbochrom
4-1.

2.3. 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.
Therefore in order to dispose of invariable and representative samples of the whole
tyre, radial pieces 2 3 cm wide ( : 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 radial 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 non-volatile compounds, which are mainly carbon blacks.
The solid residue left after the TGAs correspond 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 + liquids obtained in the pyrolysis tests, while the
amount of non-volatile organics+ inorganics, which adds up to 40.7%, should
M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 55 (2000) 4354 47

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 analyser, and a LECO AC 300 automatic calorimetric bomb. The results
are presented in Table 2.

3. Results and discussion

The solid, liquid and gas pyrolysis yields (wt.%) obtained in the pyrolysis
experiments carried out at 400, 500, 600 and 700C are presented in Table 3. It can
be seen that the three yields at 500, 600 and 700C are almost equivalent, while at
400C solid yield is higher and liquid and gas yields are lower than at the other
temperatures. The 500 700C solid yields are somewhat higher than the theoretical
value derived from the TGA analysis (40.7%). So one might think that not all the
volatile matter of the tyre has been decomposed to liquids and gases. However it
has been proved by the authors [7] and by other research groups [2,811], that a

Table 1
Main components of the whole tyre (wt.%) (determined by TGA at 500C in N2 and O2 atmospheres)

Organic compounds Inorganic compounds

Volatile (mainly rubbers) Non-volatile (mainly carbon blacks) Steel Others

59.3 27.6 9.6 3.5

Table 2
Elemental composition (wt.%) and gross calorific value (GCV) (MJ kg1) of the whole tyre (deter-
mined by CHN, S and GCV automatic analysers)

C H N S Oa Inorganicsb GCV

74.2 5.8 0.3 1.5 5.1 13.1 31.8

a
Calculated by difference.
b
Steel+inorganic fillers.

Table 3
Pyrolysis yields (wt.%)

Temperature (C)

400 500 600 700

Solid yield 53.4 44.1 44.5 43.4


Liquid yield 28.3 41.1 39.4 40.5
Gas yield 6.8 8.0 8.1 8.8
48 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 55 (2000) 4354

certain amount of coke-like carbonaceous material is formed in the pyrolysis of


many polymeric materials, due to secondary repolymerisation reactions among the
polymer-derived products. The authors have also proved that at every temperature
longer reaction times do not decrease solid yields in tyre pyrolysis. So it can be
concluded that pyrolysis at 500, 600 and 700C is complete and that : 34% of
coke or carbonaceous material has been formed. On the other hand, at 400C
pyrolysis is clearly incomplete since a solid yield (53.4%) much higher than the
theoretical value derived from TGA (40.7%), was obtained; this was corroborated
by the heterogeneous sticky-gummy aspect of the solid residue after pyrolysis.
Concerning liquid and gas yields it seems surprising that they do not vary with
temperature above 500C. An increase in the amount of gases might have been
expected, and a consequent decrease in the amount of liquids, due to the stronger
thermal cracking produced at higher temperatures. However in the temperature
interval explored (500 700C), 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 [12,13]. Therefore concern-
ing pyrolysis yields, it can be concluded that 500C is the optimum temperature for
recycling tyres by pyrolysis, since decomposition is complete and the same yields
are obtained and less energy is required than at higher temperatures.
With respect to pyrolysis liquids, they have been thoroughly characterised
(elemental composition, gas chromatography/mass spectroscopy, GCV). The results
have been presented elsewhere [14], but in summary, tyre pyrolytic oils are a very
complex mixture of organic compounds of 520 carbons and with a very great
proportion of aromatics; their GCV is very high (: 42 MJ kg 1), and their sulphur
content (: 1%) is within the E.U. specifications for heating fuels.
As far as tyre pyrolysis gases are concerned, the following gases were determined
and quantified: CO, CO2, H2S, CH4, C2 (ethane, ethene), C3 (propane, propene), C4
(butano, butenes, etc.), C5 (pentane, pentenes, etc.), C6 (hexane, hexenes, etc.). An
example of a chromatogram obtained with the TCD detector is presented in Fig. 1.
The global compositions of the gases obtained in tyre pyrolysis at 400, 500, 600
and 700C are presented in Fig. 2. Such compositions are given as grams of gas
component with respect to grams of tyre pyrolysed, so that the results at different
temperatures can be compared and information on how tyre components have
decomposed may be inferred. It can be seen that tyre pyrolysis gases are mainly
composed of hydrocarbons together with some COx (CO, CO2) and H2S. The COx
components must be mostly derived from the oxygenated organic compounds
which are contained in tyres, such as stearic acid, extender oils, etc. Sulphidric acid
comes from the decomposition of 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 it can be seen that C4 and
\ C4 gases are the most predominant products; these come from the depolymerisa-
tion of styrene butadiene (SBR) rubber, which normally is the main component of
automotive tyres.
M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 55 (2000) 4354 49

Fig. 1. Example of a chromatogram of 500C tyre pyrolysis gases with the TCD detector.

Fig. 2. Compositions of the gases obtained in tyre pyrolysis at different temperatures.


50 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 55 (2000) 4354

The evolution of gas composition during tyre pyrolysis runs at 400, 500, 600 and
700C are presented in Figs. 3 6 respectively. Each point in such figures is the
concentration of a component in the gas collected in a 10-l bag during the pyrolysis

Fig. 3. Evolution of gas composition in a pyrolysis run at 400C.

Fig. 4. Evolution of gas composition in a pyrolysis run at 500C.


M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 55 (2000) 4354 51

Fig. 5. Evolution of gas composition in a pyrolysis run at 600C.

Fig. 6. Evolution of gas composition in a pyrolysis run at 700C.

run along the time interval labelled on the horizontal axis. The temperature
inside the autoclave throughout such a time interval is also labelled on the
horizontal axis.
52 M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 55 (2000) 4354

Figs. 4 6 show that in the pyrolysis runs carried out at 500, 600 and 700C, H2S,
COx and the heavier hydrocarbons (C4, \ C4) present the maximum concentration
in the 21.5 29 min time interval, while the lighter hydrocarbons (C1 and C2)
present their maxima later (29 37.5 min). This difference between the maxima of
the heavier and lighter hydrocarbons may be explained as follows. The majority of
the heavier hydrocarbons (C4, \C4) are generated earlier, because they are
probably derived from the direct breakdown of the polymer, which in Firestone car
tyres is mainly styrene butadiene rubber (SBR). The lighter hydrocarbons (C1 and
C2) are generated both directly from the breakdown of the polymer and by
secondary reactions, that take place later, among the polymer-derived products
already formed; these products contain shorter aliphatic chains than the original
SBR, and consequently when they are cracked or react generate more lighter
hydrocarbon gases (C1, C2), giving as a result the delay in the maxima of the lighter
gases. In relation to this, Cypres and Bettens [15] have suggested that the lighter
gases (methane and hydrogen) are derived from secondary aromatisation reactions.
The authors have determined by GC/MS [14] that many of the components of tyre
pyrolysis oils are aromatics, and since the proportion of styrene (aromatic) to
butadiene (non-aromatic) is normally just 25/75 in SBR, it is obvious that aromati-
sation reactions have had to take place throughout the pyrolysis process.
Concerning the evolution of C3, the maximum concentration is obtained in the
later interval (29 37 min) in the 500 and 600C runs, while it is obtained in the
earlier interval (21.5 29 min) in the 700C run; this difference may be attributed to
the fact that at 700C, the initial cracking of SBR is stronger than at the lower
temperatures and yields products with shorter aliphatic chains than those yielded at
500 and 600C, that in secondary reactions will hardly generate C3. The fact that at
higher temperatures there is a stronger thermal cracking, which yields more lighter
hydrocarbons, is corroborated by the data presented in Fig. 2 which show higher
concentrations of C1 and C2 at 600 and 700C than at 500C, and higher
concentrations of C4 and \ C4 at 500C than at the higher temperatures.
Concerning the evolution of COx there is also a difference in the 700C gases;
two maxima appear, one in the same time interval (21.529 min) as at the other
pyrolysis temperatures, and the other one in the later 37.550 min time interval, at
temperatures between 663 and 701C; the latter may correspond to CO and CO2
derived from inorganic tyre components, such as CaCO3, ZnO, CaSiO3, etc., which
suffer decompositions and/or reactions at higher temperatures than the organic
components. This also explains the fact that total COx (Fig. 2) at 700C is
significantly higher than at the other temperatures.
With respect to the 400C pyrolysis run, Fig. 2 shows that most of the gas
components are less abundant than at the higher temperatures, and Fig. 3 that the
maximum concentration of all the gas components is produced in the earlier
interval (21 31.5 min). At this lower temperature the decomposition of tyre is
incomplete, and less cracking and secondary reactions are produced; therefore on
the one hand, a smaller total amount of gases is generated and on the other, no
delay in the maxima of the lighter products (C1, C2 and C3) is produced.
M.F. Laresgoiti et al. / J. Anal. Appl. Pyrolysis 55 (2000) 4354 53

Table 4
Gross calorific values (GCV) of the gases obtained in tyre pyrolysis at different temperatures

Temperature (C)

400 500 600 700

GCV (MJ N m3) 81.6 76.7 73.8 69.5

The gross calorific values (GCV) of the total of the gases generated in tyre
pyrolysis at each temperature have been calculated and are presented in Table 4. It
can be seen that the GCVs of the gases obtained are in general very high (69.581.6
MJ N m 3), and that there is a decrease of GCV with temperature; this is
attributed to the facts that COx increase with temperature and that the proportion
of longer hydrocarbons, which have the greatest calorific values, is lower at the
higher temperatures.
There are references in the literature [35] which report that tyre pyrolysis gases
have GCVs in the range 30 40 MJ N m 3. These values are much lower than those
presented in this paper; such a difference is attributed to the fact that the gases
obtained in this study have a greater proportion of high hydrocarbons (C4, \ C4),
which have the highest GCVs, 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 (15C
min 1) have been used, most tyre decomposition and consequently the majority of
the gases generated, are produced at 400500C, even in the 600 and 700C
pyrolysis runs, as can be seen in Figs. 36. In fact Williams et al. [3] have reported
that there is a great influence of heating rate on the amount and composition, and
consequently in GCVs, of tyre pyrolysis gases. Another important reason is that the
data presented here correspond to the analysis of the gas collected throughout the
whole pyrolysis run, while the data reported in the literature correspond to gas
samples extracted at certain stages of the pyrolysis process.

Acknowledgements

The authors wish to express thanks to the Basque Country University (UPV
112.345-EA122/94) and the Basque Government (PI-1998-19) for financial support
for this work.

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