Anda di halaman 1dari 6

20

th
European Symposium on Computer Aided Process Engineering ESCAPE20
S. Pierucci and G. Buzzi Ferraris (Editors)
2010 Elsevier B.V. All rights reserved.
Optimization of Multi-Stage Waste Tyre Pyrolysis
Process
King Lung Lee
a
, Kwok Yuen Cheung
a
, Ka Leung Lam
a
, Chi Wai Hui
a
a
Department of Chemical and Biomolecular Engineering, The Hong Kong University of
Science and Technology, Clear Water Bay, Kowloon, Hong Kong, kehui@ust.hk

Abstract
Waste tyre pyrolysis is a Waste to Energy (WtE) technology for converting waste tyre
into hydrocarbon fuels and high carbon content char. The heating rate of tyre is an
important parameter affecting the reaction time, product yield, product quality and
energy requirement of the waste tyre pyrolysis process. In this study, the effects of
heating rate on the kinetics and heat flow of the waste tyre pyrolysis were studied by
modeling the experimental results of thermogravimetric analysis and differential
thermal analysis. The model results of the kinetics and heat flow of waste tyre pyrolysis
were applied for the development of a quantitative numerical model for batch waste tyre
pyrolysis reactor. Effects of tyre size and reactor temperature on the heating rates of
waste tyre inside the pyrolysis reactor were investigated by using the developed
quantitative numerical model. Based on the model results, a patent-pending multi-stage
pyrolysis process was proposed, modeled and optimized. The optimized multi-stage
pyrolysis reactor shows advantages in minimizing the energy requirement of the waste
tyre pyrolysis by improving the control of heating rates of tyre and providing heat
integration between stages. Besides saving the energy for the waste tyre pyrolysis
process, multi-stage pyrolysis also provided a larger throughput than that of the
conventional batch pyrolysis reactor at a fixed reactor volume.

Keywords: Waste tyre; Energy; Heating rate
1. Introduction
Pyrolysis of waste tyre can be one of the possible solutions to the waste tyre disposal
problem. Pyrolysis of waste tyre involves the decomposition of organic matters of
waste tyre at elevated temperatures in the absence of oxygen. Through pyrolysis, three
fractions, non-condensable gas, pyrolysis oil and carbon-rich char, can be produced.
All three fractions have high potential to be used as fuel substitutes. The feedstock
compositions and operating conditions of the pyrolysis process are two major factors,
which affect affecting the economic viability of waste tyre pyrolysis process. The
operating condition of pyrolysis process is easier to be controlled. Heating rate of the
tyre, |
tyre
, is an important operating condition of the pyrolysis process as mentioned by
Semino and Tognotti [1]. Prior investigations suggested that heating rate of the tyre,
|
tyre
, can affect the kinetics and heat flow of the pyrolysis process.the total mass loss
during the waste tyre pyrolysis process [2-4]. This study involves the modeling of
effects of |
tyre
on the kinetics and heat flow of waste tyre pyrolysis. Based on the
kinetics and heat flow results, the temperature profile of single piece of tyre was
modeled and furthermore, a novel multi-stage pyrolysis process is proposed, modeled
and optimized.
K.L. Lee et al.
2. Paper approach
2.1. Experimental arrangement
The pyrolysis kinetics and heat flow are analyzed by using the common analytical
technique. Waste tyre samples of 10, 20 and 30mg were pyrolyzed in a nitrogen
atmosphere at heating rates of 2, 5, 10 and 20 K/min using TGA/DTA 92 Setaram II.

2.2. Methodology
Modeling of pyrolysis kinetics involves the utilization of equation (1) to regress the
experimental thermogravimetric analysis results with the following assumptions:
Pyrolysis mechanism follows the mechanism proposed by Senneca et al. [2].
Three different mass loss reactions (MLR), including MLR
1
representing the
pyrolysis of tyre additives; MLR
2
representing the pyrolysis of depolymerized
rubbers and MLR
3
representing Pyrolysis of crosslinked/cyclized rubbers
Amount of mass loss through MLR
1
is independent of heating rate, whereas mass
losses due to MLR
2
and MLR
3
depend on heating rate

Based on the above assumptions, mass loss kinetics was formulated as follows:
( ) ( )

= =
|
.
|

\
|
= |
.
|

\
|
=
3
1
3
1
1 exp Z
1
T
1 exp Z
i
n
i
i
i i
tyre i
n
i
i
i i
i i
RT
E
w
d
d
RT
E
w
dt
d
o
|
o
o
o
(1)
In equation (1), represents the fraction of the cumulative mass loss over the total
possible mass loss,
i
is of specific mass loss reaction i; t is the time (s); w
i
is the mass
loss percentage due to the mass loss reaction i; Z
i
is the pre-exponential constant of
mass loss reaction i (min
-1
), E
i
is the activation energy of the mass loss reaction i
(kJ/mol), R is the universal gas constant, T is the tyre temperature (K), and n
i
is the
order of mass loss reaction i. The heat flow of tyre pyrolysis at different heating rates
were obtained by modeling the thermal analysis results through utilization of Yang and
Roy [3-4] method. The governing equation for each of the three heat flow categories is
shown as follows:

= =
dt
T C dm
q heat ensible
t p t
s
,
S
(2)

= =
dt
dm
h q heat c Endothermi
t i
i g endo
,
,
(3)

= =
dt
dN
h q heat Exothermic
t j
j d exo
,
,
(4)
In equations (2) (7), m
t
is the total mass at time t (g), C
p,t
is the specific heat capacity
(kJ/kg-K), h
g,i
is the heat of the mass loss reaction i (J/g tyre), m
i,t
is the amount of mass
loss due to mass loss reaction i at time t, h
d,j
is the heat of the exothermic reaction j (J/g
tyre), N
j,t
is the normalized mass undergoes exothermic reaction j at time t. The
temperature profiles of the pyrolyzing tyre under different heating profiles were
modeled by solving the energy balance using explicit finite difference method.
Assuming the pyrolyzing tyre is spherical, the energy balance is expressed as follows:

+
c
c
+ c
c
c
=
c
c
dt
dN
h
t
m
h T UA
r t
T C m
t j
j d
t i
i g
t p t ,
,
,
,
, (5)
rubber p f t f p f t p t
C m m C m C m
, , ,
) ( + - =
(6)
Optimization of Multi-Stage Waste Tyre Pyrolysis Process
( )
(

|
.
|

\
|
- = |
.
|

\
|
- =

=
3
1
0 0
1 exp Z 1 1
i
n
i
i
i i t
i
RT
E
w m
dt
d
m m o
o (7)
U is the overall heat transfer coefficient (W/m
2
-K), A is the particle surface area (m
2
),
m
0
is the initial mass (kg), m
f
is the final mass (kg), C
p,f
is the specific heat capacity of
final residue (1.8 kJ/kg-K [5] ) and C
p,rubber
is the specific heat capacity of tyre rubber
(1.23 kJ/kg-K [5]).

In order to solve equations (5) (7), some assumptions are made as follows:
Conduction is the only heat transfer phenomena of intraparticle heat transfer.
Gaseous pyrolysis products transfer through the particles in short time (from
solid/semi-solid/liquid to gas implies great volume change), i.e., negligible [5].
The thermal conductivity of the tyre are expressed as equation (8) [5].
Boundary conditions are complex heat transfers phenomenon, U is assumed to be
50W/m
2
K.
cb tyre t
k k k o o + = ) 1 ( (8)

2.3. Results & discussions
The experimental and model results of pyrolysis kinetics are shown in figure 1(a) and
table 1, whereas the experimental and model results of pyrolysis heat flow are show in
figure 1(b) and table 2. As seen from figure 1(a) and table 1, different |
tyre
imply
different kinetics, the increase of |
tyre
generally shift the mass loss to the higher
temperature. Although mass loss happens in higher temperature for cases with higher
|
tyre
, the time required for completing the reaction should be shorter. As seen from
figure 1(b) and table 2, different |
tyre
can lead to different energy requirements, higher
the |
tyre
implies higher energy requirement. This should relate to the change of product
distribution and product composition. Thus, |
tyre
is an important parameter affecting the
time, energy required for the pyrolysis process. Furthermore, |
tyre
can also affects the
product distribution and product quality [6-7].

0%
10%
20%
30%
40%
50%
60%
70%
0 100 200 300 400 500 600
Temperature ()
C
u
m
u
l a
t
i v
e

M
a
s
s

L
o
s
s
Model -Heating Rate = 2K/min
Model -Heating Rate = 5K/min
Model -Heating Rate = 10K/min
Model -Heating Rate = 20K/min
Experimental-Heating Rate = 2K/min
Experimental-Heating Rate = 5K/min
Experimental-Heating Rate = 10K/min
Experimental-Heating Rate = 20K/min
-6
-5
-4
-3
-2
-1
0
1
2
3
4
5
0 100 200 300 400 500 600
Temperature ()
H
e
a
t

f
l
o
w

(
m
J
/

)
Model -Heating Rate = 2/min Model -Heating Rate = 5/min
Model -Heating Rate = 10/min Model -Heating Rate = 20/min
Experimental-Heating Rate = 2/min Experimental-Heating Rate = 5/min
Experimental-Heating Rate = 10/min Experimental-Heating Rate = 20/min

Figure 1. Experimental and modeled pyrolysis kinetics and heat flows; (a) kinetics; (b) heat flows

Table 1. Model results of waste tyre pyrolysis kinetics

Z (min
-1
) E
i
(kJ mol
-1
) n
i
w
i
at different |
tyre

2K/min 5K/min 10K/min 20K/min
MLR
1
4.62x10
6
69.73 2.26 4.81% 4.81% 4.81% 4.81%
MLR
2
5.03 x10
8
118.04 0.93 20.65% 22.16% 24.22% 50.98%
MLR
3
1.24 x10
9
128.92 0.90 31.54% 27.01% 26.50% 0.00%
(a)
(b)
K.L. Lee et al.
Table 2. Model results of heat flow of waste tyre pyrolysis
|
tyre
(K/min) 2 5 10 20
Exothermic heat (J/g tyre) -468 -325 -238 -114
Heat related to MLR
1
(J/g tyre) 27 31 27 28
Heat related to MLR
2
(J/g tyre) 19 44 61 266
Heat related to MLR
3
(J/g tyre) 70 72 186 0
Sensible heat 303K to 783K (J/g tyre) 599 621 661 673
Overall heat flow (J/g tyre) 248 440 699 853

2.4. Batch pyrolysis process
It is assumed that the fluid temperature inside a batch reactor can be controlled. Thus,
by using equations (1) (8), the temperature profiles of pyrolyzing spherical tyre with
different sizes under different heating conditions inside a batch reactor with fluid inside
the reactor as heating medium were modeled and the results are shown in figure 2.
0
100
200
300
400
500
600
0 10 20 30 40 50 60
Time (min)
T
e
m
p
e
r
a
t
u
r
e

(

)
Radial position = 0.20cm
Radial position = 0.15cm
Radial position = 0.10cm
Radial position = 0.05cm
Environment temperature (+10/min)
0
100
200
300
400
500
600
0 20 40 60 80 100 120 140 160
Time (min)
T
e
m
p
e
r
a
t
u
r
e

(
)
Radial position 2.4 - 2.5 cm
Radial position 1.9 - 2.0 cm
Radial position 1.4 - 1.5cm
Radial position 0.9 - 1.0cm
Radial position 0.4 - 0.5cm
Radial position 0.0 - 0.1cm
Environment temperature (+10/min)

0
100
200
300
400
500
600
0 20 40 60 80 100 120 140
Time (min)
T
e
m
p
e
r
a
t
u
r
e

(
)
Radial position 2.4 - 2.5 cm
Radial position 1.9 - 2.0 cm
Radial position 1.4 - 1.5cm
Radial position 0.9 - 1.0cm
Radial position 0.4 - 0.5cm
Radial position 0.0 - 0.1cm
0
100
200
300
400
500
600
0 100 200 300 400 500 600
Time (min)
T
e
m
p
e
r
a
t
u
r
e

(
)
Radial position 2.4 - 2.5 cm
Radial position 1.9 - 2.0 cm
Radial position 1.4 - 1.5cm
Radial position 0.9 - 1.0cm
Radial position 0.4 - 0.5cm
Radial position 0.0 - 0.1cm
Environment temperature (+2/min)

Figure 2. Modeled temperature profiles of tyre with different sizes inside a batch reactor under
different heating conditions ((a) Spherical tyre with 2mm radius heated by reactor fluid with
heating rate of 10K/min, i.e., |
fluid
= 10K/min; (b) Spherical tyre with 25mm radius and |
fluid
=
10K/min; (c) Spherical tyre with 25mm radius heated by constant fluid temperature of 783K; (d)
Spherical tyre with 25mm radius and |
fluid
= 2K/min)

It was found that although |
fluid
were kept constants in figure 2(a), (b) and (d), |
tyre

inside the tyre particle varies according to the time and radical positions. Figures 2(a)
and (b) showed the effects of different tyre sizes, for a tyre particle smaller than 2mm in
radius, the temperature profiles of all positions of a tyre shred are nearly identical. Yet,
the temperature profiles of tyre shred with larger than 2mm in radius shows significant
differences at different radical positions. Figures 2(b), (c) and (d) show the influences
of the fluid temperature inside the reactor. When the heating rate is low, the
temperature profiles of different radical positions of a single tyre shreds are similar. As
shown in figure 1, the pyrolysis of tyre should be finished before 773K, the overall
energy usage of the pyrolysis for figures 2(a), (b), (c) and (d) are 720, 867, 962 and 583
(a) (b)
(c) (d)
Optimization of Multi-Stage Waste Tyre Pyrolysis Process
J/g tyre respectively. Although tyre with smaller size requires less energy for
completing the pyrolysis process, the shredding of tyre can be an energy intensive
process. Although lower |
fluid
gives lower energy required for completing the pyrolysis
process, longer reaction time is needed and heat loss may also be larger. Another
important implication from the modeling results is that the tyre may not be completely
pyrolyzed even if the fluid inside the reactor reached 783K, a longer time is needed for
tyre with larger size to complete the pyrolysis.

2.5. Multi-stage pyrolysis process
If spherical tyres with 25mm radius have to be pyrolyzed completely within 100
minutes and at around |
tyre
= 10K/min for a specific product composition and
distribution, according to figure 2, the conventional pyrolysis process is not applicable
as |
tyre
at different radical positions are different. A novel multi-stage pyrolysis process
was proposed to tackle the problem and improve both the throughput and the energy
efficiency of the waste tyre pyrolysis. As shown in figure 3, pyroylsis process was
divided into two stages. The first stage of the process keeps |
fluid
at 10K/min, once the
fluid temperature reached 773K, i.e, the temperature at which pyrolysis should have
finished, the second-stage pyrolysis process aimed at pyrolyzing the core part of the tyre
at |
tyre
=10K/min, thus, |
fluid
and the maximum temperature of the heating fluid were
varied. One of the optimized results are |
fluid
= 40K/min and maximum fluid
temperature = 1083K. The multi-stage pyrolysis process gives better control of |
tyre
and
requires less time for completing the pyrolysis compared with the conventional method.
0
100
200
300
400
500
600
700
800
900
0 20 40 60 80 100 120 140 160
Time (min)
T
e
m
p
e
r
a
t
u
r
e

(
)
Radial position 2.4 - 2.5 cm
Radial position 1.4 - 1.5cm
Radial position 0.4 - 0.5cm
Radial position 0.0 - 0.1cm
+10/min

Figure 3. Modeled temperature profiles of spherical tyre with 25mm radius pyrolyzed using two-
stage pyrolysis process

Higher maximum fluid phase temperature implies higher energy usage, thus, heat
integration between the stages is crucial. The energy required for the process showed in
figure 3 is 1173J/g tyre, the energy required for the first stage and second stage of the
pyrolysis process are 617 and 556 J/g tyre respectively. ASPEN PLUS simulation of
condensing 773K tyre pyrolysis oil from the second stage pyrolysis process to 353K
gives a waste heat of 219J/g tyre. Thus, recovering the waste heat, the two stage
pyrolysis process required only 954J/g tyre, which is lower than the case shown in
figure 2(c) and with a shorter process time. Thus, multi-stage pyrolysis process with
heat integration gives advantages in throughput, energy requirement and control of |
tyre
.
3. Conclusions
The kinetics and heat flows of the waste tyre pyrolysis at different heating rates of tyre
were modeled. It was found that a high heating rate of tyre implies a pyrolysis with
Stage 1:
|fluid = 10K/min
Stage 2:
|fluid = 40K/min
Time at which pyrolysis of specific
radical position completed
K.L. Lee et al.
shorter time and higher energy requirement. The temperature profiles of a pyrolyzing
tyre shred were modeled and the effect of tyre size and reactor heating profile was
studied. A novel multi-stage pyrolysis process was model to demonstrate its advantages
in the throughput, energy requirement and the control of the heating rate of tyre.
4. Acknowledgements
The project is supported by the Hong Kong RGC research grant no. 613808 and Hong
Kong Innovation Technology Fund UIM/189. The authors would also like to thanks
Global Power and Energy Company Limited for their financial and technical supports.

Notation
w
i
: Mass loss percentage due to mass loss reaction i;
Z
i
: Pre-exponential constant of mass loss reaction i (min
-1
);
E
i
: Activation energy of mass loss reaction i (kJ/mol);
n
i
: Order of reaction of mass loss reaction i; R: Universal gas constant = 8.314 J/mol-K;
T: Temperature (K); t: Time (s); m
t
: Total mass at time t (g)
C
p,t
: Heat capacity (kJ/kg-K); m
0
: Initial mass (kg); m
f
: Final mass (kg) ;
m
i,t
: Amount of mass loss due to mass loss reaction i at time t;
h
g,i
:

Specific heat due to mass loss reaction i (j/g tyre);
h
d,j
: Specific heat due to exothermic reaction j (j/g tyre) ;
N
j,t
: Normalized mass undergoes exothermic reaction j at time t;
C
p,f
: Specific heat capacity of final residue = 1.8 kJ/kg-K [5] ;
C
p,rubber
: Specific heat capacity of tyre rubber = 1.23 kJ/kg-K [5] ;
U: Overall heat transfer coefficient (W/m
2
-K); A: Area (m
2
)
k
t
: Thermal conductivity at time t (W/m-K) ;
k
tyre
: Thermal conductivity of tyre = 0.38 W/m-K [5] ;
k
cb
: Thermal conductivity of carbon black = 0.20 W/m-K [5] ;
: Cumulative mass loss percentage;

i
: Cumulative mass loss percentage through mass loss reaction I;
|
tyre
: Heating rate of tyre; |
fluid
: Heating rate of fluid inside the reactor;
References
[1] D. Semino and L. Tognotti, 1998, Modelling and sensitivity analysis of pyrolysis of
biomass particle in a fluidised bed, Computers & Chemical Engineering, 22,
Supplement 1, S699-S702.
[2] O. Senneca, P. Salatino, and R. Chirone, 1999, A fast heating-rate thermogravimetric
study of the pyrolysis of scrap tyres, Fuel, 78, 13, 1575-1581.
[3] J. Yang and C. Roy, 1999, Using DTA to quantitatively determine enthalpy change over
a wide temperature range by the "mass-difference baseline method", Thermochimica
Acta, 333, 2, 131-140.
[4] J. Yang and C. Roy, 1996, A new method for DTA measurement of enthalpy change
during the pyrolysis of rubbers, Thermochimica Acta, 288, 1-2, 155-168.
[5] J. Yang, P.A. Tanguy, and C. Roy, 1995, Heat transfer, mass transfer and kinetics study
of the vacuum pyrolysis of a large used tire particle, Chemical Engineering Science, 50,
12, 1909-1922.
[6] J.F. Gonzlez, J.M. Encinar, J.L. Canito, and J.J. Rodriguez, 2001, Pyrolysis of
automobile tyre waste. Influence of operating variables and kinetics study, Journal of
Analytical and Applied Pyrolysis, 58-59, 667-683.
[7] P.T. Williams, S. Besler, and D.T. Taylor, 1990, The pyrolysis of scrap automotive
tyres : The influence of temperature and heating rate on product composition, Fuel, 69,
12, 1474-1482.