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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 for recovering energy from waste tires. Waste tires having
a calorific value of 75008000 kcal/kg can be used as fuel
A large amount of used old tires is produced every year in incinerators [2]. However, pollution is one of the major
all over the world. It is estimated that 2.5 106 t per year problems from tires incineration. Pyrolysis has the poten-
are generated in the European Community, 2.5 106 t per tial of transforming old tires into useful recyclable products.
year in North America, 1.0 106 t per year in Japan, and There have been many previous laboratory studies of pyrol-
1.0 106 t per year in China [1]. Disposal methods of used ysis of old tires (e.g. [37]). These studies covered a wide
old tires are such as land filling or recycling as raw ma- range of experimental techniques and conditions for the de-
terials for lower quality products. The main component of composition of tires. But most focused on pyrolysis at low
tires is rubber, a chemically high polymer which is neither temperatures and heating rates, leading to a wide spectrum
fusible nor soluble in common condition and cannot be re- of pyrolysis products; it is difficult to separate one from the
moulded into other shapes without serious degradation. The others and utilize them. Since the success of the process is
common disposal method of land filling results in a loss of mainly related to the commercial applications of the prod-
valuable chemical. Moreover, the macromolecules of rubber ucts, though a number of investigators have reported on tires
are not biodegradable when buried in landfills. Currently re- pyrolysis, to the authors knowledge, industrial-scale appli-
cycling accounts for only a small fraction of the available cations with economic return for the tires pyrolysis has not
tires. These treatments cannot be considered economical or been realized so far.
environmentally friendly. Plasma pyrolysis may be an interesting alternative to clas-
Recently, attention has been paid to the incineration and sic pyrolysis process [810]. Plasma technology involves
pyrolysis of used tires, which may be practicable methods the creation of a sustained electrical arc by the passage
of electrical current through a gas. Because of the high
Corresponding author. Tel.: +86-20-87057765; electrical resistivity across the stream, significant heat is
fax: +86-20-87057761. generated that strips away electrons from the gas molecules
E-mail address: tanglan@ms.giec.ac.cn (L. Tang). 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 2. Experimental section
applications were limited to small chemical processes due
to electrode unreliability. The extremely high temperatures The used old tires sample was provided by Guangzhou
generated by plasma torches have spurred development of Resource Recycling Company. The particle size of the sam-
their application to waste processing, where they are capa- ple used in this study was 5080 mesh. Sulfur content of
ble of destroying organic waste, and significantly decreas- used old tires was evaluated by elemental analyzer Vario EL
ing waste volume to a non-leachable vitreous slag safe for CHNOS. The weight percentage is S = 1.57%.
landfill. Compared with the conventional pyrolysis, plasma Research on the plasma process has been performed using
pyrolysis has a number of unique advantages. For example, a plasma pyrolysis reactor with a maximum electric power
it provides a circumstance of high temperature and high en- input of 55 kV A. A schematic of the reactor is shown in
ergy for the reaction, the reaction sample is heated up to a Fig. 1. It consists of two main parts: the plasma generator and
high temperature rapidly, reaction velocity is fast and some the reaction chamber as well as some accessories. In order to
reaction will take place which would not appear in conven- study the degree of pyrolysis in different time so that we can
tional pyrolysis. It is an appropriate method for polymer study the thermal kinetics, four sampling spot were made in
pyrolysis. Chang et al. [8] tested old tires as the raw material different positions of the reaction chamber corresponding to
for production of syngas by thermal plasma pyrolysis. different resident times and core temperatures. The spacing
Sulfur is a major factor prohibiting the effective practice between two sampling point was 200 mm, 5# is the output
of waste tires disposal. During thermal treatments, the ad- exit. Running water was used to cool the system. Detailed
ditives of sulfur from the process of making tires are trans- information of the reactor design also can be seen in China
ferred into vapor or liquid phases. Since the heat treatment patent 02250661.6 [11].
or pyrolysis are common step in various disposal processes, The working gas (nitrogen) is introduced into the plasma
the understanding of physical and chemical transformation generator by copper tube. The plasma jet is essentially dc
of sulfur in tires during heat treatment is very important for arc discharge between two electrodes in the nitrogen atmo-
the rational utilization of used old tires. Moreover, there is sphere. The nitrogen carrier gas is blown through the arc
a specific interest in the fate of sulfur compounds due to zone, it not only ensures smooth feeding of sample particles
environmental concerns. by preventing their collection in the feed tube, but also helps
The present study reports an experimental investigation to disperse them as they enter the reactive region and proba-
of rubber pyrolysis in thermal plasma reactor, and describes bly reduce their residence time owing to increased velocity.
the influence of feed rate, power input, steam injection, and Sample particle is put in the reaction chamber by a screw
dolomite addition on sulfur distribution and transformation. feeder at an angle of 90 to the reactor axis; adjusting the
The gaseous and solid products were characterized in order speed of the screw feeder can regulate the feed rate. The par-
to obtain an overall diagram of sulfur transformation and ticle is heated up very quickly at the speed about 106 K/s by
provide some information for development of effective con- the plasma. Water steam is generated by a steam generator
trol method of sulfur compounds. and inject into the reaction cavity by a valve when needed.

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

500
450
400
350
300
3
H2 S,mg/m

250
200
30.8kVA
150
35.2kVA
100
39.6kVA
50
44kVA
0
1# 2# 3# 4# 5#
Sampling spot

Fig. 2. H2 S concentration at different sampling positions as a function of power input (feed rate: 80 g/min).
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, 3.3. NMR and XPS analysis
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- Samples CBP1 and CBP2 obtained from plasma pyroly-
centration of H2 S decreased to 205 mg/m3 . It is suggested sis of tires at 35.2 kV A, feed rate 80 g/min, without steam
that the formation of hydrogen atoms H during the first injection and with steam injection 80 ml/min, respectively,
step of the plasma pyrolysis benefits the formation of H2 S, were selected for characterization analysis.
these hydrogen atoms come from hydrogen containing com- The bulk carbon chemistry was studied by 13 C-MAS
pounds in tires, so most of the sulfur is released in the gas NMR performed with a Bruker DSX 300 spectrometer at a
phase as H2 S during the first stage of the process. During the carbon frequency of 75.47 MHz and a spinning frequency of
later stage, it is possible that large amount of these radicals 10 kHz. The 90 pulse width was 4 s and high power pro-
recombine to form hydrocarbon or other stable structures ton decoupling was performed during recording of spectra.
which are subsequently difficult to remove. The chemical shifts , expressed in ppm were referenced
Comparing the different curves of H2 S evolution, it can relative to the signal of admantane at c = 38.3 ppm. The
be seen that increasing the input power tends to decrease recycle delay was 20s and 1800 scans were co-added for
H2 S concentration in the gaseous product; the converse is each spectrum. 13 C NMR spectra of samples CBP1 and
observed for increasing the feed rate. Possible explanations CBP2 are shown in Fig. 4, all of the sample are dominated
are that increasing the tires feed rate may provide a larger by the aromatic C=C bonds at about 116 ppm, the inten-
amount of sulfur in the system while increasing the input sities of the C=C peaks is about 90% of total area. There
power can increase the amount of energy. Most sulfur in are indications that the CBP surface chemistry is slightly
the gas phase may ulteriorly be deposited in the solid phase modified upon pyrolysis, while the bulk of the pyrolysis
(Table 1). 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 4. Conclusions
-S2p

2000 The distribution and transformation of sulfur in char and


gas obtained from plasma pyrolysis of used tires have been
Intensity (counts)

1800
studied. The parameters having influence on the distribution
of total sulfur in products of thermal plasma pyrolysis are:
1600
power input, feed rate, addition of water steam and addition
CBp2 of dolomite absorbent to the process. Increasing power in-
1400
put or feed rate tends to decrease the share of total sulfur in
1200
gas and increase the share of total sulfur in char correspond-
ingly. Addition of steam or absorbent in the plasma pyroly-
1000 CBp1 sis process result in the decrease of share of total sulfur in
gas and increase the share of total sulfur in char correspond-
155 160 165 170 175 180
ingly. The content of sulfur in tires plasma pyrolysis char
Bind energy (eV)
can reach more than 80% of total sulfur in tires. Inorganic
Fig. 5. XPS narrow scan spectra of S2p . sulfide such as FeS2 and ZnS as well as element sulfur have
been identified in the char.

also obtained by Roy et al. [7]. They studied vacuum py-


rolysis of used tires and found that the CBP yield matches Acknowledgements
the concentration of the virgin carbon black in the tires; it
is suggested that the morphology of the carbon black did We thank Guangdong Science Foundation (project no.
not change or changed only slightly; only a limited amount 010875).
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 References
produced in the process.
[1] V.L. Shulman, The Recycling in the EU Member States, Gestin
XPS spectra were obtained with a PHI-5300/ESCA
Europea de Residuos Especiales: Vehculos Fuera de Uso, Aceites
equipped with an aluminum anode (bombarded with 250 VA Usados y Neumticos, Club Espaol de los Residuos, Madrid, 2000.
electron beam). The analyzer energy was 100 eV for sur- [2] V.K. Shaarma, F. Fortuna, M. Mincarini, M. Berillo, G. Cornacchia,
vey scans (01000 eV) and 50 eV for the detailed analysis Appl. Energy 65 (2000) 381394.
of each peak. The binding energy (BE) was referenced [3] H. Pakdel, D.M. Pantea, C. Roy, J. Anal. Appl. Pyrolysis 57 (2001)
91107.
to C1s peak, which was set at 285 eV for carbon black
[4] W. Kaminsky, C. Mennerich, J. Anal. Appl. Pyrolysis 5859 (2001)
samples. The pressure during the XPS experiment was 803811.
<2.9 107 Pa. [5] R. Helleur, N. Popovic, M. Ikura, M. Stanciulescu, D. Liu, J. Anal.
The narrow scan spectra of S2p region are shown in Fig. 5. Appl. Pyrolysis 5859 (2001) 813824.
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Ramaswamy, Carbon 38 (2000) 12791287.
which is close to that of FeS2 and ZnS, this can be attributed
[7] C. Roy, A. Chaala, H. Darmstadt, J. Anal. Appl. Pyrolysis 51 (1999)
to the fixation of S by the mineral in the tires. Mineral matter 201221.
in tires can fix H2 S produced in the process to form higher [8] J.S. Chang, B.W. Gu, P.C. Looy, F.Y. Chu, C.J. Simpson, J. Environ.
sulfur content char. The portion BE = 164 eV in the spectra Sci. Health A31 (1996) 17811799.
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[10] L. Tang, H. Huang, Z. Zhao, C. Wu, Y. Chen, Ind. Eng. Chem. Res.
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pyrolyzed char is needed. 02250661.6, December 2002.