Energy Vol 20, No. 10, pp.

969-976, 1995

Pergamon

0360-5442(9S)00049-6

Copyright 1995 Elsevter Sctence Ltd

Pnnted in Great Britain. All nghts reserved
0360-5442/95 $9 50 + 0 00

PYROLYSIS OF WASTE TIRES WITH PARTIAL OXIDATION IN

A FLUIDIZED-BED REACTOR
JONG MIN LEE, JUNG SOO LEE, JUNG RAE KIM, and SANG DONE K I M t
Department of Chemical Engineering and Energy & Enwronment Research Center, Korea Advanced
Institute of Science and Technology, Taejon 305-701, Korea
(Received 22 February 1995)

Abstract--The effects of feed rate of waste t~res (0.21-0.52 kg/h), oxygen concentration (0l 1%), pyrolysis temperature (700-880C), and fluidizing gas velocity (1.5-3.0 Umf) on product
(gas, oil, char) yield, composition, energy recovery, and heating value of the product gas have
been determined in a fluidized-bed reactor (0.076 m i.d. x 1.2 m-high). The product yield, composition and heating value of the product-gas, and energy recovery are found to be independent of
the feed rate of waste tires. The effects of oxygen concentration (0-6.5%) on the yield and producuon rate of product gas (H2, CI-L) are small but both decrease with oxygen concentrauons
above 6.5%. With increasing pyrolysis temperature, the gas yield and energy recovery increase,
oil yield decreases, whereas the char yield remains constant. With increasing fluidlzlng gas velocity
(Uo), the heating value of the product gas increases linearly, the total gas-producaon rate decreases,
but energy recovery remains almost constant.

INTRODUCTION
Numerous studies have been carried out to find efficient treatment processes for waste tires since large
amounts of scrap tires become available annually (1.5 x 106t/yr in the European Community,
2.5 x 106 t/yr in North America, ~,2 0.8 x 106 t/yr in Japan, 3 1.7 x 105 t/yr in Korea4). Most of the waste
tires have been dumped in landfill sites, thereby discarding the large energy potential of scrap tires.
Furthermore, open dumping may result in accidental fires with high pollutant emissions. 2,5,6 Therefore,
several utilization processes for waste tires such as incineration, pyrolysis and gasification have been
developed to maximize potential economic recovery of energy and chemical materials from waste tires.
Among the utilization alternatives, various types of pyrolysis processes have been developed since they
have the following advantage: production of valuable liquid fuels which are easily handled, stored and
transported and hence do not have to be used at or near the recycling plant, while simultaneously
reducing the amount of gas to be cleaned. 2,7,8 Pyrolysis of waste tires in a fluidized-bed reactor attains
high heating rates of the tire in a continuous process operation with easy control. 9,1 Published studies
on gas recovery from pyrolysis of waste tires at high temperatures in fluidized-bed reactors are relatively
sparse. In the present study, the effects of pyrolysis temperature (700-880C), fluidizing velocity (1.53.0 Umf) and oxygen concentration (0-11%) on product yield, gas composition and energy recovery
have been determined.
EXPERIMENTAL STUDIES
Feed material

Waste tires were crushed in a shredder to remove steel cords and textiles to obtain granule sizes of

1.4-2.3 mm. The proximate and ultimate analyses of the tires are summarized in Table 1. Since the
tires have large amounts of volatile matter (67.3 wt %) with high heating values, pyrolysis of the tires
is an efficient method for utilizing waste tires.

tTo whom all correspondence should be addressed.

969

970

Jong Min Lee et al

Table 1. Proximateand ulumate analyses of waste tires.

Proximate analysis

wt. %

Ultimate analysis

wt.%

Volatile matter

67.3

Fixed

28.5

H
O
N

83.8
7.6
3.1
0.4
1.4
3.7

Carbon

Ash

3.7

Moisture

0.5

H.H.V. (kJ/kg)

36450

S
Ash

Facilities
A schematic of the apparatus is shown in Fig. 1. The system has five components: (i) a variable
speed rotary feeder, ( i i ) a reactor assembly with a cyclone separator, (iii)air and nitrogen supplies,
(iv) a flue-gas treatment unit, ( v ) a n instrumentation and control panel. The fluidized-bed reactor was
constructed from a heat-resistant 316 stainless-steel pipe of 76.2 mm i.d. The distributor plate was made
of a 6 mm thick stainless steel plate having 14 holes of 1.5 mm i.d. The reactor height from the distributor to the gas exit was 0.8 m, which provided gas-residence times of more than 2 sec. Electrical heating
jackets of 3 kW were equipped to supply supplementary heat to the windbox, the main bed and freeboard
sections separately; the heat inputs were controlled by on-off controllers. The reactor was insulated
with 100-ram thick ceramic wool. Pressure taps were mounted flush with the column wall 15 mm above
the distributor and gas-exit points in the reactor. The temperature profile along the reactor was measured
with K-type (chromel-alumel) thermowells 0.04, 0.10, 0.25, 0.40, 0.6, and 0.8 m above the distributor.
Flue gas passed through a cyclone in which the entrained solid particles were collected.

/ PF
...............~--~0t A
p~NDONO
]

. . . . . . .

E~EC'I'RI~

HOT
nu
='-->WATER

I~AIID

TO VEl~
. . . . . .

N.IIIDILEI

iiiiiii OOO!
.......~

'H O L E
COLD

W
BO
INX
D
FILTER
RF.~EIVER

Fig. 1. Schematicdiagram of the fluidized-bedreactor.

Pyrolysis of waste ttres

971

Expertmental procedure
Shredded waste tires were fed by using a calibrated rotary feeder with a variable speed motor from
a sealed hopper. Sand in the size range 0.25-0.36 mm (dp=0.31 mm, Umf=0.1 m/sec) as fluidizing
medium was charged into the main bed to provide a static bed height of 150 mm. The amount of nitrogen
gas mixed with compressed air depends on the stoichiometric oxygen concentration (0-11.5 wt %) and
fluidlzmg gas velocity. Experimental conditions for pyrolysis of shredded waste tires in the present
study are hsted in Table 2. The compositions of product gases after pyrolysis were measured by using
gas chromatography (HP 5890). The gas compositions (CO, H2, CI-L, and 02) were analyzed by using
a molecular sieve 5A column with argon carder gas and a thermal conductivity detector. Nitrogen was
the carrier gas m the fluidized-bed reactor for which the composition was also determined by using
this column. The flow rates of other gases were also calculated. The concentrations of CO2 and gaseous
hydrocarbons up to C4 were determined by using a Porapark Q column with argon carder gas and a
thermal conductivity detector. To confirm steady-state condition for the reactor, temperature profiles
and product gases after pyrolysis were measured. The reactor reached steady-state conditions 30 minutes
after the tires had been fed. To determine the char yield, the char weight in the main bed and char
collected m the cyclone were measured by separating char from the bed material of the sand mixture
and from that in the cyclone.
RESULTS AND DISCUSSION

Energy recovery and yields (gas, oil and char) from pyrolysis of waste tires are defined as 7

Energy recovery =

Heating value of product gas

Heating value of tires fed

Y= TY/TF,

(1)
(2)

where Y is the yield, TY the production rate of materials (gas, oil and char) and TF the feed rate of
waste tires.
The effect of feed rate of waste tires (0.21-0.52 kg/h) on the product-gas composition from the
pyrolysis of waste tires is shown in Fig. 2; the primary gaseous components are H2, CH4, C2H4, C2H6,
CO, and CO2 Gas compositions do not change appreciably with the feed rates of waste tires since the
heating rate is very high in the fluldized-bed reactor, although the heating rates of tire rubber are reduced
with increasing feed rates of waste tires. The feed rate was maintained constant at 0.32 kg/h to prevent
tar formation

Effect of oxygen concentration

The production rates of various gas components at different oxygen concentrations are shown in
Fig. 3. With increasing 02 concentration, the production rate of CO2 increases due to char and productgas combustion and consequent decrease in C2H4 production rate. However, production rates of H2 and
CH4 do not change appreciably with 02 concentration up to 6.5% and decrease with a further increase
of 02 concentration up to 11%. The production rates of C2H6 and c 3 n 6 do not change with variations
Table 2 Experimental condmons for pyrolysts of shredded waste tires.

Experimental conditions
Bed temperature (C)
Fluidizing gas velocity (Uo/Um~)
Static bed height (mm)
Oxygen concentration (wt.%)
Feed rate (kg/h)
Sand size (ram)
Tire size (mm)

Operation range
700 - 880
15-30
150
0-115
0.21 - 0.52
0.25 - 0.36
1.4 - 2.3

972

Jong Min Lee et al

60
rn CI!4
ZX C=I-i4

$o

v c~
o co

40

o co2

0
"

C..i

O-

30

O
1:3

20

I0
1.0
05
~7

O0
Ol

~7

0.2

0.3

~7
I

04

05

0.6

Feedl~m (ks/h)
Fig. 2. Effect of feed rates of tires on the product-gas composition (850C, 2.5 Umf,6.5% 02).
0

0:t

n
,x

0
0

c~
c~
qlt,
co
co=

40

2o

6
8
10
o, ce.c. (%)

12

14

Fig. 3. Effect of 02 concentration on gas-productionrate (800C, 0.32 kg/h, 2.5 umf).

of 02 concentration. Differences in the amounts of combustion-product gases may indicate that pyrolysis
gases are evolved at different axial locations of the fluidized-bed reactor. For example, C2H6 and C31-16
are generated at the upper part and H2 and CI-I4 are evolved at the surface of the fluidized-bed reactor.
The gas yield and energy recovery with variations of O2 concentration are shown in Fig. 4. With
increasing O2 concentration, the gas yield increases from 22 to 43% since CO2 generation increases.
Energy recovery is about 0.32 with O2 concentrations up to 6.5%; thereafter, energy recovery is reduced
to 0.24. We conclude that there are optimum operating conditions at which the supplied 02 mainly
contributes to char oxidation. In this study, the stoichiometric 02 concentration was maintained at 6.5%.

Effect of pyrolysis temperature

The effects of pyrolysis temperature on gas yield and on char and oil produced on a dry, ash-free
basis are shown in Fig. 5. As the pyrolysis temperature increases from 700 to 880C, the yield of char
is nearly constant at 32%, while the yield of gas increases from 30 to 40% and oil decreases to 25%.
Araki et alu found the same trend for pyrolysis of tires between 350 and 600C in which the oil yield
had a maximum value of about 50% at 450C. Raman et al7 reported that the char yield ranged between
25 and 29%, the gas yield varied between 20 and 52% and the oil yield ranged between 51 and 17%
at temperatures from 625 to 750C in the steam gasification of fires.
The effects of temperature on the production rates of gases from pyrolysis of waste tires are shown
in Fig. 6. As can be seen, the production rates of H2 and CI-I4 increase but C3 components decrease

Pyrolyms of waste tires

973

70

0.5
60
i0.4
50
40

"o

"6

30

03

0.2

0.1

20 (

10

0.0

'

10

12

14

o2c,~ e/,)
Fig 4 Effect of O~ concentraUon on gas yield and energy recovery (800C, 0 32 kg/h, 2 5 u.,,t)

60

0
n

50

Gas
011

z~ Char

o~

40

m
o

30

20

650

700

750

800

850

900

950

Temp (oC)
Ftg 5 Effect of pyrolyms temperature on gas, od and char yields (0 32 kg/h, 2 5 u,,,t, 6.5% 02)

80

60

CH~

C3I-~

40

20

0
650

700

750

800

850

900

950

Temp ((2)
Fig 6 Effect of pyrolysis temperature on gas-production rate (0.32 kg/h, 2 5 urn, 6.5% 02)
EGY 20/10-8

974

Jong Min Lee et al

with pyrolysis temperature. At pyrolysis temperatures above 800C, C2H4 production begins to decrease
and Ca components do not appear in the product gas. On the other hand, the production of unsaturated
hydrocarbon gases (C2H4 and C3H6) exceeds that of saturated hydrocarbons (C2H6 and C3H8). With
increasing pyrolysis temperature, the production rate of CO increases due to oil decomposition.2 Thus,
the pyrolysis mechanism 7,1.~2.~3 of waste tire may be described as follows:
waste tires - . oil, gas, char,
oil - . heavy and light hydrocarbons, CO, CO2, H2,
gas --. light gas, H2,
saturated hydrocarbons ---, unsaturated hydrocarbons + H2,
heavy hydrocarbons ---, light hydrocarbons + CH4, H2,
light hydrocarbons - . CH4, H 2.
The heating values of the product gases and energy recovery from pyrolysis of tires as a function
of reaction temperature are shown in Fig. 7. As the pyrolysis temperature increases, the heating value
of the product gases decrease from 25.1 to 22.8 MJ/Nm 3 due to decomposition of heavy hydrocarbons
to light hydrocarbons and hydrogen, whereas energy recovery increases from 0.20 to 0.32. Therefore,
about 32% of the energy content in the feed can be converted to gas through pyrolysis of waste tires
with partial oxidation. On the other hand, Raman et al 7 reported that about 40% of the energy contents
of tires can be recovered as gas by steam gasification of tires.

Effect of gas velocity

The effects of gas velocity on the gas-production rates from pyrolysis of waste tires are shown in
Fig. 8. As the fluidizing gas velocity increases from 1.5 to 3.0 Umf (Umf of sand = 0.1 m/sec), the production rates of H2, C H 4 and CO decrease slightly, but the production rate of C 3 H 6 increases from 0.7
to 3.0 l/h. The decomposition of oil and heavy hydrocarbons decreases with increasing fluidizing gas
velocity due to the reduction of residence time of oil and of heavy hydrocarbons in the fluidized-bed
reactor. When the gas velocity is increased from 1.5 to 3.0 Urnf, the gas yield decreases from 44 to
38%, but the heating value of the produced gas increases from 23.1 to 25.2 MJ/Nm 3 due to an increase
of C 3 H 6 yield which has a relatively high heating value. Energy recovery does not change appreciably
at the given fluidizing gas velocity since the decrease of gas yield compensates for the increase of
heating value of the product gas (Fig. 9).
The gas compositions for waste-tire treatments in fluidized-bed reactors in the present and previous
studies 7"12-j4 are listed in Table 3. As can be seen, the maximum yield of gaseous components is
different for different processes. For example, the volume percentage of C H 4 exhibits a maximum value
in the pyrolysis process of Kaminsky and S i n n , 1'12A3 the maximum H2 yield comes from steam gasification of tires by Raman et al,7 whereas in the REG (Refuse Energy Gasifier) process of Saito et al, 14
36

0.6

32

0.5
0.4

28

0.3
24
0.2

2O
0.1
16 ~
I

700

750

800

850

900

0.0
95O

Temp.(~5')
Fig. 7 Effect of pyrolysis temperature on the heating value of gas and energy recovery (0.32 kg/h, 2.5 umf,
6.5% 02).

Pyrolysis of waste tires

975

80

oc4-~

60

o %8,
o co
o CO a

40
o

20

I
1.5

I
10

I
i
2.0
2.5
u,/u,a

t
3.5

30

Fig. 8. Effect of Uo/Umfon gas-production rate (0.32 kg/h, 800C, 6.5% 02).

1.0

55
"el

50

0.8

45
06

4o
0.4
~7

.._.$._-.--

0.2

2O
I

I0

1.5

2.0
2.5
udu~

30

3.5

0.0

Fig. 9 Effect of Uo/Umfo n the gas yield, heating value of the product-gas and energy recovery (0.32 kg/h,
800C, 6.5% 02)

Table 3 Comparison of gas composmon between the present and previous studies.

Glme$

(voL%)
a t 7500C

Kaminsky

Raman et al7 Saito et !1114

This work

and
S i n n ha3
30.8

38.4

I 1.8

22.3

45.0

22 1

16.4

24.8

C2H4

6.6

I 1.4

8.2

I 1.8

C2I-~

4.7

0.5

1.3

C3I-I6

2.8

1.4

C3Hs

C~-I~

0.3
0.8

C4I-Is
CO
C02

1.1
6.4
1.4

H2
C~

3.3
12.4

1.2
3.7

17.3
43.6

10.9
25.3

976

Jong Min Lee et al

is the main component of the product gases since the heating method and the oxidant used in the
reaction are different in different processes. In the pyrolysis process of Kaminsky and S inn, l.'2.13 some
of the product gases are circulated to the fluidize-bed materials and the bed is heated indirectly. In the
steam gasification of Raman et al, 7 the bed is heated directly and indirectly and steam is used as an
oxidant, which leads to steam reforming, shift reaction and steam--char reaction from which increased
yields of H2 are attained. On the other hand, air was used as an oxidant in the directly heated REG
process of Saito et al. 14 In the present study, most gaseous components have comparable yields but the
yields of C2H4 and C3H6 are higher without C4 components than for other processes. Thus, selection
of the optimum process depends on yields of gases or liquid, with proper consideration of the initial
and operating costs for the processes.
CO 2

CONCLUSIONS
The product yield, composition, heating value of the product gas, and energy recovery are independent
of the feed rate of waste tires. The effects of oxygen concentration (06.5%) on the yields and production rates of H2 and CH 4 are small but both decrease with oxygen concentrations above 6.5%. With
increasing pyrolysis temperature (7000880C), the gas yield (30-M0%) and energy recovery increase
(0.2000.32), oil yield decreases, and heating value of the product gas decreases (25.1-22.8 MJ/Nm3),
whereas the char yield remains constant (32%). With increasing fluidizing gas velocity (1.5-3.0 Umf),
the heating value of product gas increases linearly, the total gas-production rate decreases, but energy
recovery remains almost constant (0.32).
Acknowledgement--We acknowledgefinancial aid from the Tong Yang Central Laboratoryof the Tong Yang CementCo, Korea

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1. C. Roy and J. Unsworth, Pyrolysis and Gasification, Elsevier Applied Science, London (1989).
2. P. T. Williams, S. Besler, and D. T. Taylor, Fuel, 69, 1474 (1990)
3 M Inaba, F. Nakagawa, K. Fukm, and K. Ikeda, The Cement Manufacturmg Tech. Syrup., p. 86, Osaka,
Japan (1992).
4. J. S. Lee, K. S. Lee, and J. K. Ku, Korean J. Solid Wastes 10, 117 (1993).
5. R. K. Anand and G. A. Marker, Proc. 13th Natlonal Waste Process Conf., ASME, p. 335, New York, NY
(1988).
6. Y. Nakajima and M Matsuyulo, Conserv. Recychng 4, 145 (1981)
7. K. P. Raman, W. P. Walawender, and L. T. Fan, Conserv. Recycling 4, 79 (1981).
8. J. R. Kim, J. M. Lee, and S. D. Kim, Proc. 4th. Astan Conf. on Fluidized-bed & Three Phase Reactors, p. 128,
Fukuoka, Japan (1994).
9. J. R. Kim, J. S. Lee, and S. D. Kim, Energy--The International Journal 19, 845 (1994).
10. W. Kaminsky and H. Stun, ACS Syrup. Ser. 130, 423 (1980).
11. T. Araka, K. Nnkawa, H. Hosoda, H. Nlshlzaki, S. Mttsm, K. Endo, and K. Yoshida, Conserv. Recycling 3,
155 (1979).
12. W. Kaminsky and H. Stun, Hydrocarbon Processmg 59, 187 (1980)
13. W. Kammsky, Resource Recovery Conserv. 5, 205 (1980).
14. I. Smto, K. Sakae, T. Ogre, and Y. Ueda, World Cement, p. 764 (1987).