J. Anal. Appl.

Pyrolysis 72 (2004) 3540

An investigation of sulfur distribution during thermal

plasma pyrolysis of used tires
L. Tang , H. Huang
Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences,
Nengyuan Road, Guangzhou 510640, China

Accepted 9 February 2004

Available online 15 April 2004

Abstract

Plasma pyrolysis of used tires leads to the distribution of sulfur compounds in gas and char generated during the process. Sulfur transformation
and distribution were investigated by analyzing the gas and char at different conditions. Sulfides in the gaseous product were analyzed using
photometric method. It was found that hydrogen sulfide was the main compound containing sulfur. The sulfur content in residual char was
determined using an elemental analyzer and the sulfur forms in char were characterized by the X-ray photoelectron spectroscopy (XPS). It was
found that the sulfur distributed in char was more than 90% of total sulfur and the main sulfur form in char was inorganic sulfide. The results
of this series of experiment have shown that the transformation and the distribution of sulfur in the pyrolysis process is basically affected by
input power, feed rate, addition of steam, and dolomite absorbent to the process.
2004 Elsevier B.V. All rights reserved.

Keywords: Thermal plasma; Pyrolysis; Used tires; Sulfur distribution; Sulfur transformation

1. Introduction
A large amount of used old tires is produced every year
all over the world. It is estimated that 2.5 106 t per year
are generated in the European Community, 2.5 106 t per
year in North America, 1.0 106 t per year in Japan, and
1.0 106 t per year in China [1]. Disposal methods of used
old tires are such as land filling or recycling as raw ma-
terials for lower quality products. The main component of
tires is rubber, a chemically high polymer which is neither
fusible nor soluble in common condition and cannot be re-
moulded into other shapes without serious degradation. The
common disposal method of land filling results in a loss of
valuable chemical. Moreover, the macromolecules of rubber
are not biodegradable when buried in landfills. Currently re-
cycling accounts for only a small fraction of the available
tires. These treatments cannot be considered economical or
environmentally friendly.
Recently, attention has been paid to the incineration and
pyrolysis of used tires, which may be practicable methods
Corresponding author. Tel.: +86-20-87057765;
fax: +86-20-87057761.
E-mail address: tanglan@ms.giec.ac.cn (L. Tang).
for recovering energy from waste tires. Waste tires having
a calorific value of 75008000 kcal/kg can be used as fuel
in incinerators [2]. However, pollution is one of the major
problems from tires incineration. Pyrolysis has the poten-
tial of transforming old tires into useful recyclable products.
There have been many previous laboratory studies of pyrol-
ysis of old tires (e.g. [37]). These studies covered a wide
range of experimental techniques and conditions for the de-
composition of tires. But most focused on pyrolysis at low
temperatures and heating rates, leading to a wide spectrum
of pyrolysis products; it is difficult to separate one from the
others and utilize them. Since the success of the process is
mainly related to the commercial applications of the prod-
ucts, though a number of investigators have reported on tires
pyrolysis, to the authors knowledge, industrial-scale appli-
cations with economic return for the tires pyrolysis has not
been realized so far.
Plasma pyrolysis may be an interesting alternative to clas-
sic pyrolysis process [810]. Plasma technology involves
the creation of a sustained electrical arc by the passage
of electrical current through a gas. Because of the high
electrical resistivity across the stream, significant heat is
generated that strips away electrons from the gas molecules
and results in an ionized gas stream or plasma. It is not a

0165-2370/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2004.02.001
36 L. Tang, H. Huang / J. Anal. Appl. Pyrolysis 72 (2004) 3540
new technology, although for more than 50 years plasma
applications were limited to small chemical processes due
to electrode unreliability. The extremely high temperatures
generated by plasma torches have spurred development of
their application to waste processing, where they are capa-
ble of destroying organic waste, and significantly decreas-
ing waste volume to a non-leachable vitreous slag safe for
landfill. Compared with the conventional pyrolysis, plasma
pyrolysis has a number of unique advantages. For example,
it provides a circumstance of high temperature and high en-
ergy for the reaction, the reaction sample is heated up to a
high temperature rapidly, reaction velocity is fast and some
reaction will take place which would not appear in conven-
tional pyrolysis. It is an appropriate method for polymer
pyrolysis. Chang et al. [8] tested old tires as the raw material
for production of syngas by thermal plasma pyrolysis.
Sulfur is a major factor prohibiting the effective practice
of waste tires disposal. During thermal treatments, the ad-
ditives of sulfur from the process of making tires are trans-
ferred into vapor or liquid phases. Since the heat treatment
or pyrolysis are common step in various disposal processes,
the understanding of physical and chemical transformation
of sulfur in tires during heat treatment is very important for
the rational utilization of used old tires. Moreover, there is
a specific interest in the fate of sulfur compounds due to
environmental concerns.
The present study reports an experimental investigation
of rubber pyrolysis in thermal plasma reactor, and describes
the influence of feed rate, power input, steam injection, and
dolomite addition on sulfur distribution and transformation.
The gaseous and solid products were characterized in order
to obtain an overall diagram of sulfur transformation and
provide some information for development of effective con-
trol method of sulfur compounds.
Fig. 1. Schematic of the plasma reactor. (1) Plasma generator, (2) control system of plasma generator, (3) plasma reaction chamber, (4) control system
of screw feeder, (5) feed hopper, (6) gas sampling system, (7) ash tank, (8) cyclone separator, (9) filter, (10) water scrubber, (11) cooling system, (12)
observational port, (13) water steam generator, (14) nitrogen gas cylinder.
2. Experimental section
The used old tires sample was provided by Guangzhou
Resource Recycling Company. The particle size of the sam-
ple used in this study was 5080 mesh. Sulfur content of
used old tires was evaluated by elemental analyzer Vario EL
CHNOS. The weight percentage is S = 1.57%.
Research on the plasma process has been performed using
a plasma pyrolysis reactor with a maximum electric power
input of 55 kV A. A schematic of the reactor is shown in
Fig. 1. It consists of two main parts: the plasma generator and
the reaction chamber as well as some accessories. In order to
study the degree of pyrolysis in different time so that we can
study the thermal kinetics, four sampling spot were made in
different positions of the reaction chamber corresponding to
different resident times and core temperatures. The spacing
between two sampling point was 200 mm, 5# is the output
exit. Running water was used to cool the system. Detailed
information of the reactor design also can be seen in China
patent 02250661.6 [11].
The working gas (nitrogen) is introduced into the plasma
generator by copper tube. The plasma jet is essentially dc
arc discharge between two electrodes in the nitrogen atmo-
sphere. The nitrogen carrier gas is blown through the arc
zone, it not only ensures smooth feeding of sample particles
by preventing their collection in the feed tube, but also helps
to disperse them as they enter the reactive region and proba-
bly reduce their residence time owing to increased velocity.
Sample particle is put in the reaction chamber by a screw
feeder at an angle of 90 to the reactor axis; adjusting the
speed of the screw feeder can regulate the feed rate. The par-
ticle is heated up very quickly at the speed about 106 K/s by
the plasma. Water steam is generated by a steam generator
and inject into the reaction cavity by a valve when needed.
 L. Tang, H. Huang / J. Anal. Appl. Pyrolysis 72 (2004) 3540
Table 1
Sulfur mass balance for the N2 plasma pyrolysis of used old tires
Number Feed rate N2 flow Power input Char yield Gas yield S content in S content in S content in Share of S in Share of S in Sum of shares
(g/min) rate (m3 /h) (kV A) (g/min) (m3 /min) tires mass (%) char mass (%) gas (mg/m3 ) char mass (%) gas mass (%) mass (%)
F1 44.04 7.92 35.2 17.35 0.166 1.574 3.175 239 79.5 5.8 85.3
F2 89.1 7.92 35.2 51.53 0.186 1.574 2.507 329 92.2 4.4 96.6
F3 96.4 8.1 35.2 55.42 0.201 1.574 2.656 223 97.2 2.96 100.16
F4 122.5 7.92 35.2 85.33 0.195 1.574 2.204 244 97.5 2.5 100
P1 78.06 8.28 30.8 47.08 0.189 1.574 2.55 330 97.7 5.08 102.7
P2 75.36 7.8 39.6 39.94 0.183 1.574 2.78 311 92.8 4.6 97.4
P3 86.6 7.86 44 46.35 0.192 1.574 na 283 na 3.98 na
P4 80.04 7.98 48.4 44 0.189 1.574 2.7 304 94.3 4.35 98.65
S1 75 8.04 35.2 na 0.226 1.574 na 50 na 0.9 na
D1 76 8.1 35.2 31.78 0.196 1.574 na 120 na 1.96 na
SD1 77 8.04 35.2 na 0.258 1.574 na 36.5 na 0.52 na
S1: test with addition of steam (80 ml/min); D1: test with addition of dolomite (10%); SD1: test with addition of steam (80 ml/min) and dolomite (10%); na: not available.

37
38 L. Tang, H. Huang / J. Anal. Appl. Pyrolysis 72 (2004) 3540
Sample particles (sometimes with steam) then travel down-
wards in the reaction chamber and pyrolysis reaction occurs.
Gas product samples were withdrawn through sampling line
and collected by five rubber bags, and then taken by syringes
and analyzed by photometer. Solid residues were saved in
the ash tank and analyzed after the pyrolysis experiments.
The sulfur content in residual char was determined using an
elemental analyzer (Vario EL CHNOS) and the sulfur forms
in char were characterized by the X-ray photoelectron spec-
troscopy (XPS). Nuclear magnetic resonance (NMR) anal-
ysis was also performed on selected samples.
3. Results and discussion
3.1. Distribution of total sulfur in the products
Unlike conventional pyrolysis, which has gaseous, liquid,
and solid products, waste tire particles are transformed only
into gaseous and solid product in the process of thermal
plasma pyrolysis. In order to investigate the effect of the
process parameters on the distribution of sulfur compounds
in pyrolysis gas and char, a series of experiments have been
done; the results are summarized in Table 1.
The share of total sulfur in the plasma pyrolysis products
are calculated as follows:
Sp Mp
SS (%) = 100
St M t
where SS is the percentage of total sulfur in product (%),
Sp the content of total sulfur in product of pyrolysis process
(%), St the content of total sulfur in tires (%), Mp the product
yield (g/min); Mt is the tires feed rate (g/min).
The change of the share of total sulfur in the gaseous
products can be found in Table 1. As a main parameter,
power input has an important effect on tires plasma pyrol-
ysis. In power input ranging from 30.8 to 48.4 kV A, the
share of total sulfur in the gaseous products decreased from
500
450
400
350
300
3
H2 S,mg/m
250
200
150
100
50
0
1#
Fig. 2. H2 S concentration at different sampling positions as a function of power input (feed rate: 80 g/min).
5.08 to 4.35%. Another important factor is feed rate, as we
can see that the share of total sulfur in the gaseous products
decreases with increasing feed rate. These tendencies could
be explained as that increasing the input power can increase
the amount of energy. Thereby the pyrolysis is more rapid;
while increasing the feed rate may decrease the amount of
energy available to heat each particle and likely decrease
the average temperature reached by each particle, leading
to decreased gaseous product volume and increased carbon
residues. The share of total sulfur in the gaseous products
decreased consequently.
Addition of steam or dolomite all decreases the share of
total sulfur in the gaseous products when the other parame-
ters are coincident. Dolomite binds the sulfur from the gas
phase, and after the reactions it is collected together with
char, so there is a decrease of the share of total sulfur in the
gaseous products.
From Table 1, we can see that the deposit sulfur in the
solid residue can reach 8098%, indicating that the sulfur in
tires plasma pyrolysis is mainly distributed in solid phase. In
char, sulfur probably is chemically bonded mainly in form of
non-volatile inorganic sulfides and elemental sulfur as well
as trace organic sulfides, as suggested by other workers [8].
3.2. Distribution of H2 S in the plasma reactor
Gaseous samples were collected and analyzed by photo-
metric method. As expected, hydrogen sulfide was the main
sulfur-containing component of gaseous products. On the
other hand, sulfur dioxide could not be found from our ex-
periments. This is in agreement with the reductive condi-
tions in the nitrogen plasma reactor. So we choose, H2 S as
a representation to describe gaseous sulfide content changes
in the pyrolysis process.
The H2 S evolution curves during plasma pyrolysis as a
function of power input and tires feed rate are illustrated
in Figs. 2 and 3, respectively. We can see that all curves
show a maximum at sampling point 3#. Take the experiment
30.8kVA
35.2kVA
39.6kVA
44kVA
2# 3# 4# 5#
Sampling spot
 L. Tang, H. Huang / J. Anal. Appl. Pyrolysis 72 (2004) 3540 39

600
40g/min
500 80g/min
100g/min
400 120g/min
H2S,mg/m3

300

200

100

0
1# 2# 3# 4# 5#
Sampling spot

Fig. 3. H2 S concentration at different sampling positions as a function of feed rate (power input: 35.2 kV A).

of power input 35.2 kV A, feed rate 80 g/min for example,
from 1# to 3#, the concentration of H2 S increased from 114
to 324 mg/m3 , whereas from 3# to the output exit, the con-
centration of H2 S decreased to 205 mg/m3 . It is suggested
that the formation of hydrogen atoms H during the first
step of the plasma pyrolysis benefits the formation of H2 S,
these hydrogen atoms come from hydrogen containing com-
pounds in tires, so most of the sulfur is released in the gas
phase as H2 S during the first stage of the process. During the
later stage, it is possible that large amount of these radicals
recombine to form hydrocarbon or other stable structures
which are subsequently difficult to remove.
Comparing the different curves of H2 S evolution, it can
be seen that increasing the input power tends to decrease
H2 S concentration in the gaseous product; the converse is
observed for increasing the feed rate. Possible explanations
are that increasing the tires feed rate may provide a larger
amount of sulfur in the system while increasing the input
power can increase the amount of energy. Most sulfur in
the gas phase may ulteriorly be deposited in the solid phase
(Table 1).
3.3. NMR and XPS analysis
Samples CBP1 and CBP2 obtained from plasma pyroly-
sis of tires at 35.2 kV A, feed rate 80 g/min, without steam
injection and with steam injection 80 ml/min, respectively,
were selected for characterization analysis.
The bulk carbon chemistry was studied by 13 C-MAS
NMR performed with a Bruker DSX 300 spectrometer at a
carbon frequency of 75.47 MHz and a spinning frequency of
10 kHz. The 90 pulse width was 4 s and high power pro-
ton decoupling was performed during recording of spectra.
The chemical shifts , expressed in ppm were referenced
relative to the signal of admantane at c = 38.3 ppm. The
recycle delay was 20s and 1800 scans were co-added for
each spectrum. 13 C NMR spectra of samples CBP1 and
CBP2 are shown in Fig. 4, all of the sample are dominated
by the aromatic C=C bonds at about 116 ppm, the inten-
sities of the C=C peaks is about 90% of total area. There
are indications that the CBP surface chemistry is slightly
modified upon pyrolysis, while the bulk of the pyrolysis
carbon black is not changed obviously. This conclusion was

350 250 150 50 -50 -150 350 250 150 50 -50 -150

CBP1 CBP2
Fig. 4. 13 C-MAS NMR spectra of CBP1 and CBP2 .
40 L. Tang, H. Huang / J. Anal. Appl. Pyrolysis 72 (2004) 3540
2200
-S2p
2000
Intensity (counts)
1800
1600
CBp2
1400
1200
1000 CBp1
155 160 165 170
Bind energy (eV)
Fig. 5. XPS narrow scan spectra of S2p .
also obtained by Roy et al. [7]. They studied vacuum py-
rolysis of used tires and found that the CBP yield matches
the concentration of the virgin carbon black in the tires; it
is suggested that the morphology of the carbon black did
not change or changed only slightly; only a limited amount
of carbonaceous deposits are produced on the carbon black
surface during the pyrolysis. Therefore, by XPS analysis,
we preliminarily estimate the configuration of the sulfide
produced in the process.
XPS spectra were obtained with a PHI-5300/ESCA
equipped with an aluminum anode (bombarded with 250 VA
electron beam). The analyzer energy was 100 eV for sur-
vey scans (01000 eV) and 50 eV for the detailed analysis
of each peak. The binding energy (BE) was referenced
to C1s peak, which was set at 285 eV for carbon black
samples. The pressure during the XPS experiment was
<2.9 107 Pa.
The narrow scan spectra of S2p region are shown in Fig. 5.
A major peak occurred at binding energy about 162 eV,
which is close to that of FeS2 and ZnS, this can be attributed
to the fixation of S by the mineral in the tires. Mineral matter
in tires can fix H2 S produced in the process to form higher
sulfur content char. The portion BE = 164 eV in the spectra
is from elemental S signal according to the high binding en-
ergy peak occurred at 164 eV; this is in agreement with the
formation of elemental S under nitrogen plasma conditions.
Further investigation of sulfur compounds originating from
pyrolyzed char is needed.
4. Conclusions
The distribution and transformation of sulfur in char and
gas obtained from plasma pyrolysis of used tires have been
studied. The parameters having influence on the distribution
of total sulfur in products of thermal plasma pyrolysis are:
power input, feed rate, addition of water steam and addition
of dolomite absorbent to the process. Increasing power in-
put or feed rate tends to decrease the share of total sulfur in
gas and increase the share of total sulfur in char correspond-
ingly. Addition of steam or absorbent in the plasma pyroly-
sis process result in the decrease of share of total sulfur in
gas and increase the share of total sulfur in char correspond-
175 180
ingly. The content of sulfur in tires plasma pyrolysis char
can reach more than 80% of total sulfur in tires. Inorganic
sulfide such as FeS2 and ZnS as well as element sulfur have
been identified in the char.
Acknowledgements
We thank Guangdong Science Foundation (project no.
010875).
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